Patent Application
20090214976
1. Field of the Invention
The present invention relates to a method of producing a liquid developer and a liquid developer produced by the method.
2. Description of the Background Art
As a developer used for developing an electrostatic latent image formed on a latent image carrier, there are known two types. One type of such a developer is known as a dry toner which is formed of a material containing a coloring agent such as a pigment or the like and a binder resin, and such a dry toner is used in a dry condition thereof. The other type of such a developer is known as a liquid developer which is obtained by dispersing toner particles into a carrier liquid having electric insulation properties.
In the developing method using such a dry toner, since a solid state toner is used, there is an advantage in handleability thereof. On the other hand, however, there is fear of an adverse effect on human body and the like caused by toner powder. Further, this method also involves problems such as contamination caused by dispersal of toner and insufficient uniformity of toner particles when dispersed in the insulation liquid. Further, in such a dry toner, aggregation of toner particles is likely to occur during the preservation thereof, and thus it is difficult to make the size of each toner particle sufficiently small. This means that it is difficult to form a toner image having high resolution. Furthermore, there is also a problem in that when the size of the toner particle is made to be relatively small, the problems resulted from the powder form of the dry toner described above becomes more serious.
On the other hand, in the developing method using the liquid developer, since aggregation of toner particles in the liquid developer during the preservation thereof is effectively prevented, it is possible to use very fine toner particles and it is also possible to use a binder resin having a low softening point (a low softening temperature). As a result, the method using the liquid developer has the advantages such as good reproductivity of an image composed of thin lines, good tone reproductivity as well as good reproductivity of colors. Further, the method using the liquid developer is also superior as a method for forming an image at high speed.
Conventionally, such a liquid developer is produced by a grinding method in which toner particles are produced by grinding a resin (see JP-A No. 07-234551, for example), a polymerization method in which monomer components are polymerized in a solution having electric insulation to produce resin fine particles which are not soluble in the electric insulation solution (see JP-B No. 08-7470, for example), or a precipitation method in which a solution is obtained by dissolving a resin material and a pigment in a non-water-based solvent, and then a solvent which is insoluble to the resin material is added to the thus obtained solution with being stirred to thereby precipitate the resin material (see JP-A No. 2003-345071, for example).
However, these conventional liquid developer producing methods involve such problems as described below.
Namely, in the grinding method, it is difficult to grind a resin material so that toner particles can have sufficiently small size (e.g. 5 μm or less). This means that it takes very long time or it requires very large energy to obtain toner particles having a sufficiently small size that can exhibit properly the effects resulted by the use of the liquid developer as described above, thus leading to extremely low productivity of a liquid developer. Further, in the grinding method, a particle size distribution of toner particles is likely to be large (that is, there is large variations in particle sizes), and the shapes of the toner particles are liable to be nonuniform. As a result, obtained toner particles are likely to have variations in their properties (e.g. charge properties). Further, it may be conceived that a resin material is to be subjected to dry grinding instead of wet grinding in a nonpolar solvent (insulation liquid). In this case, however, even if very fine particles are obtained by the dry grinding, these particles are likely to get aggregated with each other, thus it is difficult to make the size of each toner particle sufficiently small.
Further, in the polymerization method, it is difficult to set polymerization conditions appropriately. This means that it is difficult to produce a resin material having a desired molecular weight and form toner particles having a desired size. Further, it is also difficult to make the variations in the size of the toner particles sufficiently small. As a result, stability of quality of a toner and reliability thereof are likely to be low. Further, since the polymerization method requires a relatively long time for the formation of the toner particles, the productivity of the liquid developer is not so high. In addition, the polymerization method generally requires large production machines and facilities.
Furthermore, in the precipitation method, each of the materials (especially, a pigment) is likely to get aggregated when precipitating a resin material. Therefore, there is a problem in that obtained toner particles are likely to have variations in compositions and properties among the toner particles. In addition, since a pigment is likely to get aggregated in this precipitation method as described above, it is difficult to form an image having sufficient transparency (a clear image) using an obtained liquid developer.
Moreover, the liquid developers produced by the conventional methods involve a problem in that toner particles generally have poor fixing properties to recording mediums such as papers.
Accordingly, it is an object of the present invention to provide a liquid developer constituted from toner particles having excellent fixing properties to a recording medium, a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed and a liquid developer producing method which can produce such a liquid developer effectively. In particular, it is an object of the present invention to provide such a liquid developer as described above by a method harmless to the environment.
These objects are achieved by the present invention described below.
One aspect of the present invention is directed to a method of producing a liquid developer which comprises an insulation liquid and toner particles dispersed in the insulation liquid. The method comprises the steps of: a water-based dispersion liquid preparing step for preparing a water-based dispersion liquid, the water-based dispersion liquid comprising a dispersoid composed of a material containing a resin material and a water-based dispersion medium constituted from a water-based liquid in which the dispersoid is dispersed;
a dispersion medium removal step for removing the dispersion medium to obtain toner particles; and
a dispersing step for dispersing the toner particles into the insulation liquid.
According to the liquid developer producing method described above, it is possible to produce effectively (with good productivity) a liquid developer constituted from toner particles having excellent fixing properties to a recording medium. Further, it is also possible to produce effectively (with good productivity) a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed. In particular, it is possible to provide a liquid developer producing method which makes it possible to produce a liquid developer by a method harmless to the environment
In the liquid developer producing method according to the present invention, it is preferred that the toner particles obtained in the water-based dispersion medium removal step are directly dispersed in the insulation liquid without intervening any step of collecting the obtained toner particles between the dispersin medium removal step and the dispersing step.
According to this method, it is possible to produce effectively (with good productivity) a liquid developer constituted from toner particles having excellent fixing properties to a recording medium. In particular, it is possible to provide a liquid developer producing method which makes it possible to produce a liquid developer constituted from toner particles having excellent fixing properties to a recording medium by a method harmless to the environment.
In the liquid developer producing method according to the present invention, it is preferred that the toner particles contain water whose amount is more than a water absorption amount of the resin material.
This enables the fixing properties of the toner particles to a recording medium to become particularly excellent.
In the liquid developer producing method according to the present invention, it is preferred that a water content of the toner particles is in the range of 0.3 to 5.0 wt %.
According to this method, it is possible to make dispersibility of the toner particles excellent while making charge properties of the toner particles sufficiently excellent, thus enabling the toner particles to have particularly excellent fixing properties to a recording medium.
In the liquid developer producing method according to the present invention, it is preferred that the dispersoid constituting the water-based dispersion liquid is composed of a plurality of particles and the respective toner particles correspond to the particles of the dispersoid.
This makes it possible to make variations in size of the toner particles especially small as well as make the size of the toner particles smaller.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion liquid contains fine particles manufactured by an emulsion polymerization method as the dispersoid.
This makes it possible to form the particles each having an uniform particle diameter.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion liquid is prepared using fine particles obtained by a grinding method.
This makes it possible to make size of the particles of the dispersoid constituting the water-based dispersion liquid sufficiently small, whereby size of the toner particles can be made sufficiently small.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion liquid is prepared using a kneaded material containing the resin material and a coloring agent.
According to this method, variations in compositions and properties of the respective toner particles can be made particularly small.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion liquid is prepared through a method which comprises the steps of: dissolving the kneaded material into a solvent which can dissolve at least a part of the kneaded material to obtain a solution; and dispersing the solution into the water-based liquid.
According to this method, it is possible to make variations in shape and size of the toner particles small, and thus variations in properties (such as charge properties) of the toner particles can be made small. Further, it is also possible to make the diameter of each toner particle smaller.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion liquid is obtained by removing the solvent after the solution is dispersed in the water-based liquid.
This makes to possible to prevent undesirable aggregation between the particles of the dispersoid and between the toner particles more effectively, and as a result thereof, uniformity in shape and size of the toner particles can be made especially excellent. Further, since a deairing treatment can be performed together with the removal of the solvent, it is possible to prevent formation of toner particles having irregular shapes effectively even in a case where the toner particles are obtained in the form of aggregation of a plurality of particles of the dispersoid. Further, the water-based dispersion medium (water) can enter the inside of the particles of the dispersoid effectively, thus it is possible to obtain the toner particles containing appropriate amount of water.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion liquid is sprayed by intermittently ejecting droplets of the water-based dispersion liquid.
This makes it possible to remove the water-based dispersion medium more efficiently while preventing undesirable aggregation of the particles of the dispersoid effectively.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion liquid is ejected by a pressure pulse generated by a piezoelectric element.
This makes it possible to remove the water-based dispersion medium more efficiently while preventing undesirable aggregation of the particles of the dispersoid effectively. Further, it is possible to intermittently eject the water-based dispersion liquid in the form of droplets having uniform size more reliably. Namely, stability of the shape of the water-based dispersion liquid to be ejected can be improved. As a result of this, in a case where the toner particles are obtained in the form of aggregation of a plurality of particles of the dispersoid, for example, it is possible to obtain a liquid developer in which variations in shape and size of the toner particles are small. Further, it is also possible to produce toner particles having high sphericity (a shape close to a geometrically perfect spherical shape) relatively easily.
In the liquid developer producing method according to the present invention, it is preferred that an average particle size of the droplets is in the range of 1.0 to 100 μm.
In this case, the water-based dispersion medium can be removed more efficiently. Further, in a case where the toner particles are obtained in the form of aggregation of a plurality of particles of the dispersoid, for example, it is possible to form toner particles having appropriate particle diameter more reliably.
In the liquid developer producing method according to the present invention, it is preferred that an antiaggregation agent for preventing aggregation of the dispersoid is added in the water-based dispersion medium removal step when removing the water-based dispersion medium from the water-based dispersion liquid.
This makes it possible to prevent aggregation of the particles of the dispersoid more reliably in the water-based dispersion medium removal step so that toner particles each of which is derived from one particle of the dispersoid can be obtained. Accordingly, by simply forming the dispersoid using an emulsion as a water-based dispersion liquid so that particles of the dispersoid have uniform shape and small particle size distribution, the dry fine particles to be obtained can also have uniform shape and small particles size distribution. Namely, it is possible to provide a liquid developer producing method which makes it possible to produce effectively (with good productivity) a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed.
In particular, since the water-based dispersion liquid is used, it is possible to provide a liquid developer producing method which makes it possible to produce effectively (with good productivity) a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed by a method harmless to the environment. In addition to this, since the toner particles contain water, they have excellent dispersibility in the insulation liquid. As a result, the obtained liquid developer has excellent storage stability.
In the liquid developer producing method according to the present invention, it is preferred that the antiaggregation agent is constituted from inorganic particles.
According to this method, it is possible to prevent aggregation of the particles of the dispersoid more reliably in the water-based dispersion medium removal step to thereby obtain toner particles each of which is derived from one particle of the dispersoid. As a result of this, it is possible to obtain a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed more reliably.
In the liquid developer producing method according to the present invention, it is preferred that the inorganic particles are mainly comprised of silica and/or titanium oxide.
This makes it possible to prevent undesirable effect on properties of the finally obtained toner particles while preventing aggregation of the particles of the dispersoid in the dispersion liquid in the form of droplets more reliably. Further, in a case where such an antiaggregation agent adheres to the surfaces of the toner particles formed from the dispersoid and collected as the toner particles with the agent adhering thereto, the antiaggregation agent can serve as a part of external additives.
In the liquid developer producing method according to the present invention, it is preferred that when Dm (μm) represents an average particle size of the particles of the dispersoid and Dc (μm) represents an average particle size of the particles of the antiaggregation agent, a relation of 1×10−3<Dc/Dm<1×10−1 is satisfied.
This makes it possible to prevent aggregation of the particles of the dispersoid in the dispersion liquid in the form of droplets effectively, whereby enabling each particle derived from the dispersoid to become a toner particle more reliably. Accordingly, it is possible to obtain a liquid developer in which toner particles having excellent mechanical strength and uniform shape are dispersed.
In the liquid developer producing method according to the present invention, it is preferred that the average particle size of the particles of the antiaggregation agent is in the range of 0.02 to 1.0 μm.
This makes it possible to prevent aggregation of the particles of the dispersoid in the dispersion liquid in the form of droplets effectively, whereby enabling each particle of the dispersoid to become a toner particle more reliably.
Accordingly, a liquid developer in which toner particles having excellent mechanical strength and uniform shape are dispersed can be obtained.
Moreover, in the liquid developer producing method according to the present invention, it is preferred that an average particle size of the particles of the dispersoid contained in the water-based dispersion liquid is in the range of 0.01 to 5 μm.
This makes it possible to obtain toner particles having sufficiently high roundness and uniformity in properties, size and shape of the respective particles (toner particles). Further, it is also possible to raise the resolution of an image formed using the liquid developer to an extremely high level.
In the liquid developer producing method according to the present invention, it is preferred that in the water-based dispersion medium removal step droplets the toner particles are obtained by ejecting the water-based dispersion liquid from nozzles to form droplets and then removing the water-based dispersion medium from the droplets.
This makes it possible to remove the water-based dispersion medium efficiently while preventing aggregation and the like of the particles of the dispersoid effectively.
In the liquid developer producing method according to the present invention, it is preferred that in the water-based dispersion medium removal step the antiaggregation agent is added to the droplets so that the antiaggregation agent are present between the particles of the dispersoid.
This makes it possible to prevent aggregation of the particles of the dispersoid in the dispersion liquid in the form of droplets more reliably.
In the liquid developer producing method according to the present invention, it is preferred that the antiaggregation agent is added to the droplets by injecting the antiaggregation agent in a direction opposite to an ejection direction of the droplets.
This makes it possible to add the antiaggregation agent homogeneously between the droplets, thus aggregation of the particles of the dispersoid in the dispersion liquid in the form of droplets can be prevented more reliably.
In the liquid developer producing method according to the present invention, it is preferred that in the water-based dispersion medium removal step the droplets are formed by using a pressure pulse generated by a piezoelectric element.
This makes it possible to remove the water-based dispersion medium more efficiently while preventing aggregation and the like of the particles of the dispersoid effectively. Further, it is possible to intermittently eject the dispersion liquid in which the dispersoid is dispersed in the water-based dispersion medium (water-based dispersion liquid) in the form of droplets having uniform size more reliably. Namely, stability of the shape of the water-based dispersion liquid to be ejected can be improved. As a result thereof, in a case where the toner particles are obtained in the form of aggregation of a plurality of particles of the dispersoid, for example, it is possible to obtain a liquid developer in which variations in shape and size of the toner particles are small. Further, it is possible to produce toner particles having high sphericity (a shape close to a geometrically perfect spherical shape) relatively easily.
In the liquid developer producing method according to the present invention, it is preferred that an ejection opening of the nozzle has a circular or substantially circular shape and an inner diameter of the nozzle is in the range of 5 to 500 μm.
This enables stable formation of the droplets of the dispersion liquid with reducing variations in the particle size of the droplets. As a result of this, it is possible to reduce variations in the particle size of the toner particles to be obtained more effectively.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion medium removal step is carried out at a temperature equal to or lower than a glass transition point of the dispersoid.
According to this, since droplets of the dispersoid are unlikely to stick with each other when forming the droplets of the dispersion liquid, it is possible to prevent bonding between the toner particles each of which is derived from the dispersoid.
In the liquid developer producing method according to the present invention, it is preferred that the water-based dispersion liquid is an emulsion or a suspension obtained through the emulsion.
This makes if possible to provide a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed.
In the liquid developer producing method according to the present invention, it is preferred that volume resistivity of the insulation liquid is in the range of 1×109 to 1×1018 Ω·cm.
According to this, the toner particles in the liquid developer to be obtained can exhibit excellent charge properties.
In the liquid developer producing method according to the present invention, it is preferred that the insulation liquid includes at least one of a saturated hydrocarbon compound, silicone oil, vegetable oil and a denaturation compound of one of these materials, wherein these materials are used singly or in combination of two of them.
According to this method, the toner particles in the liquid developer to be obtained can exhibit excellent charge properties.
Another aspect of the present invention is directed to a liquid developer produced using the liquid developer producing method as described above.
This makes it possible to provide a liquid developer constituted from toner particles having excellent fixing properties to a recording medium. Further, it is possible to provide a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed.
In the liquid developer according to the present invention, it is preferred that an average particle size of toner particles is in the range of 0.1 to 5 μm.
This makes it possible to make variations in properties of the toner particles such as charge properties and fixing properties, and therefore the reliability of the liquid developer as a whole can be made especially high, and the resolution of an image to be formed using the liquid developer (toner) can also be made especially high.
Further, in the liquid developer according to the present invention, it is preferred that the standard deviation in the particle size among the toner particles is 1.0 μm or less.
This makes it possible to make variations in properties such as charge properties and fixing properties particularly small, thereby enabling to improve reliability of the liquid developer as a whole.
Hereinbelow, with reference to the accompanying drawings, a preferred embodiment of a method of producing a liquid developer according to the present invention and a liquid developer manufactured by the method will be described in details.
First, the first embodiment of the present invention will be described.
The liquid developer producing method according to the first embodiment of the present invention is characterized by comprising:
a water-based dispersion liquid preparing step for preparing a water-based dispersion liquid comprising a dispersoid composed of a material containing a resin material and a water-based dispersion medium constituted from a water-based liquid in which the dispersoid is dispersed;
a dispersion medium removal step for removing the dispersion medium by spraying the water-based dispersion liquid to obtain toner particles; and
a dispersing step for dispersing the toner particles directly into an insulation liquid.
Although the water-based dispersion liquid used in the present invention can be prepared by any methods, the one prepared using a kneaded material containing a coloring agent and a resin material is used in this embodiment.
<Constituent Material of Kneaded Material>
A kneaded material obtained in the kneading step described below contains a component which forms a toner particle of a liquid developer, and the kneaded material contains at least a binder resin (resin material) and a coloring agent.
First, a description will be made with regard to a constituent material used for preparing the kneaded material.
1. Resin (Binder Resin)
Generally, toner particles contained in a liquid developer are constituted from a material which contains a resin (binder resin) as its main component.
In the present invention, although a type of a resin (binder resin) constituting the kneaded material is not particularly limited, it is preferred to use a self-dispersible type resin which has dispersibility to a water-based liquid described later.
By using the self-dispersible type resin, dispersibility of a dispersoid in the water-based dispersion liquid becomes particularly excellent and an appropriate amount of water (moisture) can be contained in the dispersoid. As a result of this, it is possible to obtain toner particles having appropriate water content (moisture content).
In this regard, it is to be noted that in this specification, the term “self-dispersible” means properties having dispersibility to a dispersion medium without using a dispersant, and the term “self-dispersible type resin” means a resin material having such self-dispersibility.
No particular limitation is imposed on the self-dispersible type resin, and examples of such a self-dispersible type resin include a resin having a plurality of groups which are lyophilic (hydrophilic) to a water-based liquid described below.
Examples of groups (functional groups) having such lyophilic property (hydrophilic property) include —COO− group, —SO3− group, —CO group, —OH group, —OSO3− group, —COO-group, —SO3—, —OSO3-group, —PO3H2, —PO32−), —PO4-group, and quaternary ammonium, and salts thereof. Since such a self-dispersible type resin has particularly excellent dispersibility to a water-based liquid, it is possible to prepare a water-based dispersion liquid (water-based emulsion and water-based suspension) described later without using any dispersant or by using an extremely small amount of dispersant. As a result, it is possible to prevent effectively occurrence of a problem resulted from the fact that a dispersant is contained in a liquid developer finally obtained. In more details, it is possible to effectively prevent a dispersant from giving an adverse effect to a charge property of toner particles. Further, it is also possible to prevent foam formation by a lowered antifoaming property resulted from the use of a dispersant for preparation of a dispersion liquid, thereby enabling to improve an ejection stability when the water-based dispersion liquid (water-based suspension) described later is ejected.
Furthermore, since a dispersant or charge control agent are likely to be absorbed when resin particles are dispersed into a carrier solution which constitutes a liquid developer, it is possible to further stabilize dispersibility and charge properties.
The above-mentioned groups themselves have properties which are easily charged. Therefore, use of such groups is advantageous in improving charge properties of toner particles themselves.
Further, among the groups mentioned above, —COO-group and —SO3-group are particularly preferred. A self-dispersible type resin having such a group has particularly superior dispersibility against the water-based liquid as well as appropriate water retention ability. Further, it can be manufactured relatively easily and be available at a relatively low cost. As a result, it is possible to further reduce production cost of the liquid developer.
It is preferred that the group mentioned above exists at a side chain of a polymer constituting a resin material. This makes it possible to make hydrophilic property against the water-based liquid more excellent, and thereby to make dispersibility of a dispersoid constituted from a self-dispersible type resin in a water-based dispersion liquid (water-based emulsion and water-based suspension) especially excellent. Furthermore, it is also possible to obtain a dispersion liquid of particularly excellent dispersion state without using a polar organic solvent.
The self-dispersible type resin described above can be manufactured by bonding the material having the functional group described above to a raw resin material (raw resin) or its monomer, dimer, oligomer, and the like.
For example, a self-dispersible type resin having —COO-group can be manufactured by graft copolymerization or block copolymerization of a low water-soluble or water-insoluble resin (raw resin) with unsaturated carboxylic acids, or random copolymerization of a monomer constituting a thermoplastic resin with unsaturated carboxylic acids.
Example of such unsaturated carboxylic acids include unsaturated monocarboxylic acids, unsaturated dicarboxylic acid or anhydrides thereof such as (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nagic acid, maleic anhydride, citraconic anhydride; ester compounds such as monoester and diester of methyl, ethyl, and propyl of the unsaturated carboxylic acids; salts of unsaturated carboxylic acids such as alkali metal salts, alkaline earth metal salts, ammonium salts, and the like.
Further, the self-dispersible type resin having —SO3-group can be manufactured by, for example, graft copolymerization or block copolymerization of a thermoplastic resin (raw resin) with unsaturated sulfonic acids, random copolymerization of an unsaturated monomer constituting an addition polymerization type thermoplastic resin with a monomer containing unsaturated sulfonic acids, or polycondensation of a monomer constituting a polycondensation type thermoplastic resin with a monomer containing unsaturated sulfonic acids.
Examples of such unsaturated sulfonic acids include styrene sulfonic acids, sulfoalkyl (meth)acrylate, metal salts thereof, and ammonium salts, and the like. Further, examples of a monomer containing sulfonic acids include sulufo-isophthalic acid, sulufo-terephthalic acid, sulfo-phthalic acid, sulfo-succinic acid, sulfo-benzoic acid, sulfo-salicylic acid, and metal salts thereof, and ammonium salts, and the like.
Examples of a resin (raw resin) which can be used as a constituent material of the self-dispersible type resin include (meth)acrylic resin; polycarbonate resin; a homopolymer or a copolymer of styrene resin that includes styrene or a styrene substitution product, such as polystyrene, poly-α-methylstyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylate ester copolymer, styrene-methacrylate ester copolymer, styrene-acrylate ester-methacrylate ester copolymer, styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate ester copolymer, styrene-vinylmethylether copolymer, or the like; polyester resin; epoxy resin; urethane modified epoxy resin; silicone modified epoxy resin; vinyl chloride resin; rosin modified maleic acid resin; phenyl resin; polyethylene-based resin; polypropylene; ionomer resin; polyurethane resin; silicone resin; ketone resin; ethylene-ethyl acrylate copolymer; xylene resin; polyvinyl butyral resin; terpene resin; phenol resin; aliphatic or alicyclic hydrocarbon resin; or the like. These resin components can be used alone or in combination of two or more.
As described above, the self-dispersible type resin can be manufactured, for example, by polymerizing a precursor having a functional group described above (that is, corresponding monomer, dimmer, oligomer, and the like).
The number of the functional groups (hydrophilic groups) contained in the self-dispersible type resin is preferably in the range of 0.001 to 0.050 mol with respect to 100 g of the self-dispersible type resin, and more preferably in the range of 0.005 to 0.030 mol. This makes it possible to improve dispersibility of the dispersoid mainly formed of the self-dispersible type resin while maintaining effectively properties necessary as a toner particle.
The content of the self-dispersible type resin in the kneaded material (that is, the content of the self-dispersible type resin in the composition used for preparing the kneaded material) is not particularly limited to any specific value, but it is preferably in the range of 55 to 95 wt %, more preferably in the range of 60 to 90 wt %, and even more preferably in the range of 65 to 85 wt %. If the content of the self-dispersible type resin is less than the above lower limit value, there is a case that it is not possible to raise the dispersibility of the dispersoid in the water-based dispersion liquid (water-based emulsion and water-based suspension) sufficiently. On the other hand, if the content of the self-dispersible type resin exceeds the above upper limit value, the amount of the coloring agent is relatively decreased so that it becomes difficult to form a visible image having a sufficient contrast when a resultant liquid developer is actually used.
The kneaded material may contain other resin materials in addition to the self-dispersible type resin described above. As for such resin materials (that is, resin materials other than the self-dispersible type resin), resin materials such as those mentioned above as the raw material resins can be used.
The softening point of the resin (resin material) is not particularly limited to any specific value, but it is preferably in the range of 50 to 120° C., more preferably in the range of 60 to 115° C., still more preferably in the range of 65 to 115° C. In this specification, the term “softening point” means a temperature at which softening begins under the conditions that a temperature raising speed is 5° C./min and a diameter of a die hole is 1.0 mm in a high-floored flow tester.
Further, in a case where the resin material contains two or more types of resins, the softening point of the resin material is determined by the weighted average of these resins.
2. Coloring Agent
A toner contains a coloring agent. As for a coloring agent, pigments, dyes or the like can be used. Examples of such pigments and dyes include Carbon Black, Spirit Black, Lamp Black (C.I. No. 77266), Magnetite, Titanium Black, Chrome Yellow, Cadmium Yellow, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Benzidine Yellow, Quinoline Yellow, Tartrazine Lake, Chrome Orange, Molybdenum orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosine Lake, Brilliant Carmine 3B, Manganese Violet, Fast Violet B, Methyl Violet Lake, Prussian Blue, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Fast Sky Blue, Indanthrene Blue BC, Ultramarine Blue, Aniline Blue, Phthalocyanine Blue, Chalco Oil Blue, Chrome Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Phthalocyanine Green, Final Yellow Green G, Rhodamine 6G, Quinacridone, Rose Bengal (C.I. No. 45432), C.I. Direct Red 1, C.I. Direct Red 4, C.I. Acid Red 1, C.I. Basic Red 1, C.I. Mordant Red 30, C.I. Pigment Red 48:1, C.I. Pigment Red 57:1, C.I. PigmentRed122, C.I. Pigment Red 184, C.I. Direct Blue 1, C.I. Direct Blue 2, C.I. Acid Blue 9, C.I. Acid Blue 15, C.I. Basic Blue 3, C.I. Basic Blue 5, C.I. Mordant Blue 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:3, C.I. Pigment Blue 5:1, C.I. Direct Green 6, C.I. Basic Green 4, C.I. Basic Green 6, C.I. Pigment Yellow 17, C.I. Pigment Yellow 93, C.I. Pigment Yellow 97, C.I. Pigment Yellow 12, C.I. Pigment Yellow 180, C.I. Pigment Yellow 162, and Nigrosine Dye (C.I. No. 50415B); metal oxides such as metal complex dyes, silica, aluminum oxide, magnetite, maghemite, various kinds of ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, magnesium oxide, and the like, and magnetic materials including magnetic metals such as Fe, Co, and Ni; and the like. These pigments and dyes can be used singly or in combination of two or more of them.
3. Other Components
In preparing the kneaded material, additional components other than the above components may be used. Examples of such other components include a wax, a charge control agent, a magnetic powder, and the like.
Examples of such a wax include hydrocarbon wax such as ozokerite, ceresin, paraffin wax, micro wax, microcrystalline wax, petrolatum, Fischer-Tropsch wax, or the like; ester wax such as carnauba wax, rice wax, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, butyl stearate, candelilla wax, cotton wax, Japan wax, beeswax, lanolin, montan wax, fatty ester, or the like; olefin wax such as polyethylene wax, polypropylene wax, oxidized polyethylene wax, oxidized polypropylene wax, or the like; amide wax such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, or the like; ketone wax such as laurone, stearone, or the like; ether wax; and the like. These waxes can be used singly or in combination of two or more.
Examples of the charge control agent include a metallic salt of benzoic acid, a metallic salt of salicylic acid, a metallic salt of alkylsalicylic acid, a metallic salt of catechol, a metal-containing bisazo dye, a nigrosine dye, tetraphenyl borate derivatives, a quaternary ammonium salt, an alkylpyridinium salt, chlorinated polyester, nitrohumic acid, and the like.
Further, examples of the magnetic powder include a powder made of a magnetic material containing a metal oxide such as magnetite, maghemite, various kinds of ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, magnesium oxide, or the like, and/or magnetic metal such as Fe, Co or Ni.
Further, the constituent material of the kneaded material may further contain zinc stearate, zinc oxide, cerium oxide, silica, titanium oxide, iron oxide, aliphatic acid, or aliphatic metal salt, or the like in addition to the materials described above.
Furthermore, the constituent material of the kneaded material may further contain materials used as a solvent such as inorganic solvent, organic solvent and the like. This makes it possible to improve kneading efficiency so that the kneaded material in which each component thereof is mixed with each other more homogeneously can be obtained.
<Kneaded Material>
Hereinbelow, a description will be made with regard to one example of a method for obtaining a kneaded material K7 by kneading a material K5 which contains the above-mentioned components.
The kneaded material K7 can be manufactured using a kneading apparatus as shown in
<Kneading Step>
The material K5 to be kneaded contains the components as described above. By containing a coloring agent, air such as air contained by the coloring agent is also contained in the material K5, which means that there is a possibility that air bubble could enter the inside of the toner particle. However, since the material K5 is subjected to the kneading process in this step, it is possible to eliminate air contained in the material K5 efficiently, and therefore it is possible to prevent air bubble from entering the inside of the toner particle effectively, that is, prevent air bubble from remaining inside the toner particle effectively. Therefore, it is preferred that the material K5 to be kneaded is prepared in advance by mixing the above-mentioned various components.
In this embodiment, a biaxial kneader-extruder is used as the kneading machine, a detail of which will be described below.
The kneading machine K1 includes a process section K2 which kneads the material K5 with conveying it, a head section K3 which extrudes a kneaded material K7 so that an extruded kneaded material can have a prescribed cross-sectional shape, and a feeder K4 which supplies the material K5 into the process section K2.
The process section K2 has a barrel K21, screws K22 and K23 inserted into the barrel 21, and a fixing member K24 for fixing the head section K3 to the front portion of the barrel K21.
In the process section K2, a shearing force is applied to the material K5 supplied from the feeder K4 by the rotation of the screws K22 and K23 so that a homogeneous kneaded material K7 is obtained.
In this embodiment, it is preferred that the total length of the process section K2 is in the range of 50 to 300 cm, and more preferably in the range of 100 to 250 cm. If the total length of the process section K2 is less than the above lower limit value, there is a case that it is difficult to mix and knead the components contained in the material K5 homogeneously. On the other hand, if the total length of the process section K2 exceeds the above upper limit value, there is a case that thermal modification of the material K5 is likely to occur depending on the temperature inside the process section K2, or the number of revolutions of the screws K22 and K23, or the like, thus leading to a possibility that it becomes difficult to control the physical properties of a finally obtained liquid developer (that is, resultant toner) sufficiently.
In this connection, when the temperature of the material (material temperature) during the kneading step is preferably in the range of 80 to 260° C., and more preferably in the range of 90 to 230° C. though it varies depending on the composition of the material K5 and the like. In this regard, it is to be noted that the temperature of the material inside the process section K2 may be constant throughout the process section K2 or different depending on positions inside the process section K2. For example, the process section K2 may include a first region in which an internal temperature is set to be relatively low, and a second region which is provided at the base side of the first region and in which an internal temperature is set to be higher than the internal temperature of the first region.
Moreover, it is preferred that the residence time of the material K5 in the process section K2, that is the time required for the material K5 to pass through the process section K2, is 0.5 to 12 minutes, and more preferably 1 to 7 minutes. If the residence time of the material K5 in the process section K2 is less than the above lower limit value, there is a possibility that it is difficult to mix the components contained in the material K5 homogeneously. On the other hand, if the residence time of the material K5 in the process section K2 exceeds the above upper limit value, there is a possibility that production efficiency is lowered, and thermal modification of the material K5 is likely to occur depending on the temperature inside the process section K2 or the number of revolutions of the screws K22 and K23, or the like, thus resulting in a case that it is difficult to control the physical properties of a finally obtained liquid developer (that is, a resultant toner) satisfactorily.
Although the number of revolutions of the screws K22 and K23 varies depending on the compositions of the binder resin or the like, 50 to 600 rpm is preferable. If the number of revolutions of the screws K22 and K23 is less than the above lower limit value, there is a case that it is difficult to mix the components of the material K5 homogeneously. On the other hand, if the number of revolutions of the screws K22 and K23 exceeds the above upper limit value, there is a case that molecular chains of the resin are cut due to a shearing force, thus resulting in the deterioration of the characteristics of the resin.
In the kneading machine K1 used in this embodiment, the inside of the process section K2 is connected to a pump P through a duct K25. This makes it possible to deaerate the inside of the process section K2, thereby enabling to prevent the pressure inside the process section K2 from raising due to heated-up or heat generation of the material K5 (kneaded material K7). As a result, the kneading step can be carried out safely and effectively. Further, since the inside of the process section K2 is connected to the pump P through the duct K25, it is possible to prevent air bubble (in particular, relatively large air bubble) from being contained in the obtained kneaded material 17 effectively, so that it becomes possible to obtain a liquid developer (that is, a toner) having excellent properties.
<Extrusion Process>
The kneaded material K7 which has been kneaded in the process section K2 is extruded to the outside of the kneading machine 11 via the head section K3 by the rotation of the screws K22 and K23.
The head section K3 has an internal space K31 to which the kneaded material K7 is sent from the process section K2, and an extrusion port K32 through which the kneaded material K7 is extruded.
In this connection, it is preferred that the temperature (temperature at least in the vicinity of the extrusion port K32) of the kneaded material K7 in the internal space K31 is higher than a softening temperature of the resin materials contained in the material K5. When the temperature of the kneaded material K7 is such a temperature, it is possible to obtain a toner particle in which the components thereof are more homogeneously mixed, thereby enabling to make variations in its properties such as charge properties, fixing properties, and the like particularly small.
The concrete temperature of the kneaded material K7 inside the internal space K31 (that is, the temperature of the kneaded material K7 at least in the vicinity of the extrusion port K32) is not particularly limited to a specific temperature, but is preferably in the range of 80 to 150° C., and more preferably in the range of 90 to 140° C. In the case where the temperature of the kneaded material K7 in the internal space K31 is within the above range, the kneaded material K7 is not solidified inside the internal space K31 so that it can be extruded from the extrusion port K32 easily.
The internal space K31 having a structure as shown in
<Cooling Process>
The kneaded material K7 in a softened state extruded from the extrusion port K32 of the head section K3 is cooled by a cooler K6 and thereby it is solidified.
The cooler K6 has rolls K61, K62, K63 and K64, and belts K65 and K66.
The belt K65 is wound around the rolls K61 and K62, and similarly, the belt K66 is wound around the rolls K63 and K64.
The rolls K61, K62, K63 and K64 rotate in directions shown by the arrows e, f, g and h in the drawing about rotary shafts K611, K621, K631 and K641, respectively. With this arrangement, the kneaded material K7 extruded from the extrusion port K32 of the kneading machine K1 is introduced into the space between the belts K65 and K66. The kneaded material K7 is then cooled while being molded into a plate-like object with a nearly uniform thickness, and is ejected from an ejection part K67. The belts K65 and K66 are cooled by, for example, an air cooling or water cooling method. By using such a belt type cooler, it is possible to extend a contact time between the kneaded material extruded from the kneading machine and the cooling members (belts), thereby enabling the cooling efficiency for the kneaded material to be especially excellent.
Now, during the kneading process, since the material K5 is subjected to a shearing force, phase separation (in particular, macro-phase separation) and the like can be sufficiently prevented. However, since the kneaded material K7 which went through the kneading process is free from the shearing force, there is a possibility that phase separation (in particular, macro-phase separation) will occur again if such a kneaded material is being left standing for a long period of time. Accordingly, it is preferable to cool the thus obtained kneaded material K7 as quickly as possible. More specifically, it is preferred that the cooling rate of the kneaded material K7 (for example, the cooling rate when the kneaded material K7 is cooled down to about 60° C.) is faster than −3° C./s, and more preferably in the range of −5 to −100° C./s. Moreover, the time between the completion of the kneading process (at which a shearing force has been eliminated) and the completion of the cooling process (time required to decrease the temperature of the kneaded material K7 to 60° C. or lower, for example) is preferably 20 seconds or less, and more preferably 3 to 12 seconds.
In the above embodiment, a description has been made in terms of an example using a continuous biaxial kneader-extruder as the kneading machine, but the kneading machine used for kneading the material is not limited to this type. For kneading the material, it is possible to use various kinds of kneading machines, for example, a kneader, a batch type triaxial roll, a continuous biaxial roll, a wheel mixer, a blade mixer, or the like.
Further, although in the embodiment shown in the drawing the kneading machine is of the type that has two screws, the number of screws may be one or three or more. Further, the kneading machine may have a disc section (kneading disc section).
Furthermore, in the embodiment described above, one kneading machine is used for kneading the material, but kneading may be carried out by using two kneading machines. In this case, the heating temperature of the material and the rotational speed of the screws of one kneading machine may be different from those of the other kneading machine.
Moreover, in the above embodiment, the belt type cooler is used, but a roll type (cooling roll type) cooler may be used. Furthermore, cooling of the kneaded material extruded from the extrusion port K32 of the kneading machine is not limited to the way using the cooler described above, and it may be carried out by air cooling, for example.
<Grinding Process>
The kneaded material K7 obtained through the cooling process described above is ground. By grinding the kneaded material K7, it is possible to obtain a water-based dispersion liquid (water-based emulsion and water-based suspension) (described later) in which a finer dispersoid is dispersed relatively easily. As a result, it becomes possible to make the size of the toner particles smaller in a liquid developer finally obtained, and such a liquid developer can be preferably used in forming a high resolution image.
The method of grinding is not particularly limited. For example, such grinding may be carried out by employing various kinds of grinding machines or crushing machines such as a ball mill, a vibration mill, a jet mill, a pin mill, or the like.
The grinding process may be carried out by dividing it into a plurality of stages (for example, two stages of coarse and fine grinding processes). Further, after the grinding process, other treatment such as classification treatment may be carried out as needed. Such classification treatment may be carried out using a sieve or an air flow type classifier or the like.
By subjecting the material K5 to the kneading process as described above, it is possible to eliminate air contained in the material K5 effectively. In other words, the kneaded material K7 obtained through such a kneading process hardly contains air (air bubble) in the inside thereof. By using such kneaded material K7, it is possible to prevent generation of toner particles of irregular shape (such as void particles, defect particles, fused particles, and the like) effectively in a water-based dispersion liquid spraying step which will be described later. As a result, in a liquid developer finally obtained, it is possible to prevent occurrence of a problem such as lowered transfer property and cleaning property which are caused by such toner particles having irregular shape.
In the present embodiment, a water-based dispersion liquid is prepared using the kneaded material described above. In particular, a water-based emulsion is firstly prepared using the kneaded material described above and a water-based suspension is then prepared using the water-based emulsion.
By using the kneaded material K7 in preparing the water-based dispersion liquid (water-based emulsion), the following effects can be obtained. Namely, even in a case where a constituent material of toner particles contains components which are difficult to be dispersed in a dispersion medium or difficult to be mutually soluble to each other, these components are mutually soluble to each other satisfactorily and finely dispersed in the obtained kneaded material by way of the kneading step described above. In particular, most of pigments (coloring agent) have poor dispersibility to a liquid used as a solvent described later. However, in this embodiment, because the kneading step has been carried out before the kneaded material is dispersed into a solvent, the outer periphery of each particle of a pigment is coated with a resin component effectively. Therefore, dispersibility of the pigment to the solvent is improved (particularly, the pigment can be finely dispersed in the solvent), color development of a finally obtained liquid developer becomes excellent. For these reasons, even in a case where a constituent material of toner particles contains a component having poor dispersibility to a dispersion medium of a water-based dispersion liquid (water base-emulsion and water-based suspension) (water-based dispersion medium) which will be described later (hereinafter, this component will be referred to as “poor dispersibility component”) or a component having poor solubility to a solvent contained in a dispersion medium of a water-based emulsion (hereinafter, this component will be referred to as “poor solubility component”), it is possible to make dispersibility of a dispersoid in the water-based dispersion liquid (water base-emulsion or water-based suspension) more excellent. With these results, in a finally obtained liquid developer, variations in compositions and properties of respective toner particles can be made small, and therefore the liquid developer can have excellent properties as a whole.
<Water-based Emulsion Preparing Step>
Next, by using the kneaded material K7, a water-based emulsion comprised of a water-based dispersion medium constituted from a water-based liquid in which a dispersoid constituted from a toner material is dispersed is prepared (water-based emulsion preparing step).
Further, in the water-based emulsion used in the present invention, since a dispersoid is in a liquid sate (that is, a dispersoid has fluidity so that it can be deformed relatively easily), there is a tendency that each particle of the dispersoid is formed into a shape having a relatively high roundness (sphericity) due to its surface tension. Accordingly, in a suspension (water-based suspension) prepared using the water-based emulsion, there is also a tendency that each particle of the dispersoid is formed into a shape having a relatively high roundness (sphericity). As a result, it is possible to finally obtain toner particles having a relatively high roundness (sphericity). Further, in the emulsion containing a dispersoid in a liquid state (that is, a dispersoid having fluidity so that it can be deformed relatively easily), it is possible to raise uniformity in the size of the dispersoid relatively easily by stirring the emulsion.
The method for preparing the water-based emulsion is not particularly limited, but in the present embodiment, a water-based emulsion is prepared by obtaining a solution in which at least a part of the kneaded material K7 is dissolved, and then by dispersing such a solution into a water-based liquid In this connection, it should be noted that in this specification the term “emulsion” means a dispersion liquid comprised of a liquid state dispersion medium and a liquid state dispersoid (dispersion particles) dispersed in the dispersion medium, and the term “suspension” means a suspension liquid (including suspension colloid) comprised of a liquid state dispersion medium and a solid state dispersoid (suspension particles) dispersed in the dispersion medium. Further, in a case where both a liquid state dispersoid and a solid state dispersoid exist in a dispersion liquid, the term “emulsion” means a dispersion liquid in which the total volume of the liquid state dispersoid is larger than the total volume of the solid state dispersoid, while the term “suspension” means a dispersion liquid in which the total volume of the solid state dispersoid is larger than the total volume of the liquid state dispersoid.
Hereinbelow, a description will be made with regard to the method for preparing the water-based emulsion.
<Preparation of Kneaded Material Solution>
In the present embodiment, a kneaded material solution (a solution of the kneaded material) in which at least a part of the kneaded material is dissolved is obtained.
The solution is prepared by mixing the kneaded material with a solvent in which at least a part of the kneaded material can be dissolved.
As for the solvent used for preparing the solution, various solvents can be used so long as at least a part of the kneaded material can be dissolved thereinto, but normally, solvents which have low mutual solubility to a water-based liquid described later (that is, a water-based liquid used for preparing the water-based emulsion) are used. For example, a liquid having a solubility of 10 g or less with respect to 100 g of a water-based liquid at a temperature of 25° C. is used.
Examples of such solvents include inorganic solvents such as carbon disulfide, and carbon tetrachloride, and organic solvents such as ketone-based solvents (e.g., methyl ethyl ketone (MEK), methyl isopropyl ketone (MIPK), and 2-heptanone), alcohol-based solvents (e.g., pentanol, n-hexanol, 1-octanol, and 2-octanol), ether-based solvents (e.g., diethyl ether, and anisole), aliphatic hydrocarbon-based solvents (e.g., hexane, pentane, heptane, cyclohexane, octane, and isoprene), aromatic hydrocarbon-based solvents (e.g., toluene, xylene, benzene, ethyl benzene, and naphthalene) aromatic heterocyclic compound-based solvents (e.g., furan, and thiophene), halide-based solvents (e.g., chloroform), ester-based solvents (e.g., ethyl acetate, isopropyl acetate, isobutyl acetate, and ethyl acrylate), nitrile-based solvents (e.g., acrylonitrile), and nitro-based solvents (e.g., nitromethane and nitroethane). These materials can be used singly or in combination of two or more of them.
The amount of the solvent contained in the solution is not limited to any specific value, but is preferably in the range of 5 to 75 wt %, more preferably in the range of 10 to 70 wt %, and even more preferably in the range of 15 to 65 wt %. If the amount of the solvent contained in the solution is less than the above lower limit value, there is a possibility that it is difficult to dissolve the kneaded material sufficiently depending on the solubility of the kneaded material to the solvent. On the other hand, if the amount of the solvent exceeds the above upper limit value, a time required for removing the solvent in the subsequent step becomes long, the productivity of the liquid development is lowered. Further, if the amount of the solvent is too much, there is a possibility that the components which were sufficiently and homogeneously mixed to each other in the kneading step described above are phase-separated, and thereby making it difficult to make variations in the properties of the toner particles of a finally obtained liquid developer sufficiently small.
In this regard, it is to be noted that it is sufficient if at least a part of the components which constitute the kneaded material is dissolved (including a swelling state), and therefore components which were not dissolved may exist in the solution.
<Preparation of Water-Based Emulsion>
Next, a water-based emulsion is obtained by mixing the above mentioned solution with a water-based liquid. Normally, in the thus obtained water-based emulsion, a dispersoid which contains the solvent and the constituent material of the kneaded material are dispersed in the water-based dispersion medium formed from the water-based liquid.
In the present invention, the term “water-based liquid” means a liquid which contains at least water (H2O), and it is preferred that the water-based liquid is mainly constituted from water. The water content of the water-based liquid is preferably 50 wt % or higher, more preferably 80 wt % or higher, and even more preferably 90 wt % or higher. In this regard, the water-based liquid may contain components other than water. It may contain, for example, a component having excellent mutual solubility with water (for example, a material which has solubility of 30 g or higher with respect to 100 g of water at a temperature of 25° C.). Examples of such components include alcohol-based solvents such as methanol, ethanol, propanol, and the like, ether-based solvents such as 1,4-dioxane, tetrahydrofuran (THF), and the like, aromatic heterocyclic compound-based solvents such as pyridine, pyrazine, pyrrole, and the like, amide-based solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and the like, nitrile-based solvents such as acetonitrile and the like, and aldehyde-based solvents such as acetaldehyde, and the like.
Further, in preparing the water-based emulsion (water-based dispersion liquid), a dispersant or the like may be used for the purpose of improving the dispersibility of the dispersoid. Examples of such a dispersant include: inorganic dispersants such as tricalcium phosphate, and the like; nonionic organic dispersants such as polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, and the like; anionic organic dispersants such as tristearic acid metal salts (e.g., aluminum salts), distearic acid metal salts (e.g., aluminum salts and barium salts), stearic acid metal salts (e.g. calcium salts, lead salts, and zinc salts), linolenic acid metal salts (e.g., cobalt salts, manganese salts, lead salts, and zinc salts), octanoic acid metal salts (e.g., aluminum salts, calcium salts, and cobalt salts), oleic acid metal salts (e.g., calcium salts and cobalt salts), palmitic acid metal salts (e.g., zinc salts), dodecylbenzenesulfonic acid metal salts (e.g., sodium salts), naphthenic acid metal salts (e.g., calcium salts, cobalt salts, manganese salts, lead salts, and zinc salts), resin acid metal salts (e.g., calcium salts, cobalt salts, manganese salts, lead salts, and zinc salts), polyacrylic acid metal salts (e.g., sodium salts), polymethacrylic acid metal salts (e.g., sodium salts), polymaleic acid metal salts (e.g., sodium salts), metal salts of acrylic acid-maleic acid copolymers (e.g., sodium salts), polystyrenesulfonic acid metal salts (e.g., sodium salts); and cationic organic dispersants such as quaternary ammonium salts (e.g., dodecyltrimethylammonium chloride); and the like. By using the dispersant as described above in preparing the water-based emulsion, it is possible to improve the dispersibility of the dispersoid. Further, it is also possible to make variations in shape and size of the dispersoid in the water-based emulsion particularly small relatively easily, and also possible to make the shape of each particle of the dispersoid roughly spherical shape. With these results, it is possible to obtain a liquid developer which is comprised of toner particles each formed into a roughly spherical shape and having uniform shape and size. Further, it is possible to make storage stability of the water-based emulsion particularly excellent by using the above-mentioned dispersant in the preparation of the water-based emulsion.
It is preferred that the solution is mixed with the water-based liquid while at least either the solution or the water-based liquid is being stirred. This makes it possible to obtain an emulsion (a water-based emulsion) in which a dispersoid having small variations in size and shape is homogeneously dispersed easily and reliably.
Examples of methods for mixing the solution and the water-based liquid include a method in which the solution is added (for example, dropped) into the water-based liquid contained in a container, a method in which the water-based liquid is added (for example, dropped) into the solution contained in a container, and the like. In these methods, the water-based liquid or the solution which is contained in a container is preferably being stirred. This makes it possible to exhibit the above effect more conspicuously.
The amount of the dispersoid in the water-based emulsion is not particularly limited, but preferably in the range of 5 to 55 wt %, and more preferably in the range of 10 to 50 wt %. This makes it possible to prevent undesirable bonding or aggregation of particles of the dispersoid more reliably, thereby enabling to make productivity of the toner particles (liquid developer) particularly superior.
The average particle diameter of the dispersoid in the water-based emulsion is not particularly limited, but preferably in the range of 0.01 to 5 μm, and more preferably in the range of 0.1 to 3 μm. This makes it possible to prevent undesirable bonding or aggregation of particles of the dispersoid in the water-based emulsion more reliably, thereby enabling to make the size of the toner particles finally obtained optimum. In this regard, it is to be noted that the term “average particle diameter” means an average particle diameter per the volume of particles.
Further, although the above description was made with regard to the case that the components of the kneaded material are contained in the dispersoid in the water-based emulsion, a part of the components of the kneaded material may be contained in the dispersion medium.
Furthermore, the water-based emulsion may contain additional components other than the above-mentioned components. Examples of such additional components include a charge control agent, magnetic powder and the like.
Example of the charge control agent include metal salts of benzoic acid, metal salts of salicylic acid, metal salts of alkyl salicylic acid, metal salts of catechol, metal-containing bisazo dyes, nigrosine dyes, tetraphenylborate derivatives, quaternary ammonium salts, alkyl pyridinium salts, chlorinated polyesters, nitrohumic acid, and the like.
Examples of the magnetic powders include powders of metal oxides such as magnetite, maghemite, various ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, magnesium oxide, and the like, and powders of magnetic materials containing magnetic metals such as Fe, Co, and Ni.
The water-based emulsion may further contain, for example, zinc stearate, zinc oxide, or cerium oxide, in addition to the above-mentioned materials.
<Water-Based Suspension Preparing Step>
The thus obtained water-based emulsion may be used as a spray liquid for producing toner particles as it is. However, in the present embodiment, a water-based suspension 3 comprised of a dispersion medium (water-based dispersion medium) 32 and a solid state dispersoid 31 dispersed in the dispersion medium 32 is obtained based on the water-based emulsion (in which the liquid state dispersoid is dispersed in the water-based dispersion medium), and the thus obtained water-based suspension is used as a spray liquid for producing toner particles. This makes it possible to prevent undesirable aggregation between particles of the dispersoid or between the toner particles more effectively, and as a result thereof, the uniformity in the shape and size of the toner particles can be made especially excellent. Further, a deaerating treatment can be carried in addition to the removal of the solvent, which means that it is possible to prevent formation of toner particles having irregular shape more effectively in a case where toner particles are obtained in the form of aggregation of a plurality of particles of the dispersoid. Furthermore, since the water-based dispersion medium (water) can enter the inside of particles of the dispersoid effectively when removing the solvent, it is possible to obtain toner particles having appropriate water content (moisture content).
Hereinbelow, a detailed description will be made with regard to a method for preparing the water-based suspension 3.
The water-based suspension 3 can be prepared by removing the solvent which constitutes the dispersoid from the water-based emulsion.
The removal of the solvent can be carried out, for example, by heating or warming the water-based emulsion or placing it in an atmosphere under reduced pressure. However, it is preferred that the water-based emulsion is heated under reduced pressure. This makes it possible to obtain a water-based suspension 3 containing a dispersoid 31 having particularly small variations in size and shape thereof relatively easily. Further, by removing the solvent as described above, it is possible to carry out a deaerating treatment in addition to the removal of the solvent. By the deaerating treatment, it is possible to reduce the amount of the dissolved air in the water-based suspension 3, and therefore when the dispersion medium 32 is removed from the droplets 5 of the water-based suspension 3 in the water-based dispersion medium removal section M3 of the liquid developer producing apparatus M1, it is possible to prevent generation of air bubble in the water-based suspension 3 in an effective manner. As a result, it is possible to prevent toner particles having irregular shapes (such as void particles and defect particles) from entering (or being mixed into) a finally obtained liquid developer effectively.
When the water-based emulsion is heated (or warmed) the heating temperature is preferably in the range of 30 to 110° C., and more preferably in the range of 40 to 100° C. If the heating temperature is set to a value within the above range, it is possible to remove the solvent immediately while preventing generation of a dispersoid 31 having irregular shapes effectively (that is, preventing rapid vaporization (boiling) of a solvent from the inside of the dispersoid of the water-based emulsion).
Further, when the water-based emulsion is placed in an atmosphere under reduced pressure, the pressure of the atmosphere in which the water-based emulsion is placed is preferably in the range of 0.1 to 50 kPa, and more preferably in the range of 0.5 to 5 kPa. If the pressure of the atmosphere in which the water-based emulsion is placed is within the above range, it is possible to remove the solvent immediately while preventing generation of a dispersoid 31 having irregular shapes effectively (that is, preventing rapid vaporization (boiling) of a solvent from the inside of the dispersoid of the water-based emulsion).
In this regard, it should be noted that it is sufficient that the removal of the solvent is carried out to the extent that at least the dispersoid is transformed into a solid state. It is not necessary to remove substantially all the solvent contained in the water-based emulsion.
The average particle diameter of the dispersoid 31 contained in the water-based suspension 3 is not limited to any specific value, but preferably in the range of 0.01 to 5 μm, and more preferably in the range of 0.1 to 3 μm. This makes it possible to prevent undesirable bonding (aggregation) of the particles of the dispersoid reliably, thereby enabling the size of finally obtained toner particles to be optimum size.
<Water-Based Dispersion Liquid Spraying Step>
Next, the water-based suspension (water-based dispersion liquid) 3 is sprayed. By spraying the water-based suspension 3, the dispersion medium (water-based dispersion medium) 32 is removed from the water-based suspension 3 (droplets 5) to thereby form toner particles 8 and the thus formed toner particles 8 are directly dispersed into an insulation liquid 9 (water-based dispersion liquid spraying step). By this process, a liquid developer 10 in which the toner particles 8 are dispersed in the insulation liquid 9 is obtained. Further, since the dispersion medium in the dispersion liquid used as a spray liquid is constituted from a water-based liquid, it is possible to obtain a liquid developer by a method which is harmless to the environment.
The spray of the water-based suspension (water-based dispersion liquid) may be carried out by any methods, but preferably carried out by intermittently ejecting droplets of the water-based suspension. This makes it possible to carry out the removal of the water-based dispersion medium efficiently while preventing undesirable aggregation of the dispersoid effectively, whereby the productivity of the liquid developer is improved. Further, since the removal of the water-based dispersion medium is carried out by intermittently ejecting droplets of the water-based suspension, even in the case where a part of the solvent remains in preparing the water-based suspension, it is possible to remove the remaining solvent together with the water-based dispersion medium in an effective manner.
In particular, in the present embodiment, the removal of the water-based dispersion medium is carried out using a liquid developer production apparatus as shown in
<Liquid Developer Production Apparatus>
As shown in
The water-based suspension supply portion M4 is not particularly limited as long as it has the function of supplying the water-based suspension 3 to the head portions M2. The water-based suspension supply portion M4 may be provided with a stirring means M41 for stirring the water-based suspension 3 as shown in
Each of the head portions M2 has a function of ejecting the water-based suspension 3 in the form of fine droplets (fine particles) 5.
Further, each of the head portions M2 has a dispersion liquid storage portion M21, a piezoelectric device (element) M22, and an ejection port (nozzle) M23.
In the dispersion liquid storage portion M21, the water-based suspension 3 is stored.
The water-based suspension 3 stored in the dispersion liquid storage portion M21 is ejected from the ejection port M23 in the form of droplets 5 into the dispersion medium removal portion M3 when a pressure pulse (piezoelectric pulse) is applied by the piezoelectric device M22.
The shape of the ejection portion M23 is not particularly limited, but preferably it is formed into a substantially circular shape. By forming the ejection portion M23 into such a shape, it is possible to raise sphericity of the ejected water-based suspension 3 and the toner particle 8 formed in the dispersion medium removal portion M3.
When the ejection portion M23 has such a substantially circular shape, the diameter thereof (that is, nozzle diameter) is preferably in the range of 0.5 to 100 μm, more preferably in the range of 0.8 to 50 μm, and even more preferably in the range of 0.8 to 15 μm. If the diameter of the ejection portion M23 is less than the above lower limit value, clogging is likely to occur and therefore there is a case that variations in the size of the droplets 5 to be ejected become larger. On the other hand, if the diameter of the ejection portion M23 exceeds the above upper limit value, there is a possibility that the water-based suspension 3 (droplets 5) to be ejected contains air bubbles inside thereof depending on the relative power balance between the negative pressure of the dispersion liquid storage portion M21 and the surface tension of the nozzle.
Further, it is preferred that the a portion in the vicinity of the ejection portion M23 of each head portion M2 (that is, an inner surface of the nozzle aperture of each ejection portion M23 and a surface of the head portions M2 in which the ejection portions M23 are provided (the lower surface in the drawing)) has a liquid repellency (water repellency). This makes it possible to prevent the water-based suspension 3 from adhering around the ejection portion effectively. As a result, it is possible to prevent a poor formation of droplets and occurrence of defective ejection of the water-based suspension 3. Further, since adhering of the water-based suspension 3 around the ejection portion is prevented effectively, the shape stability of the droplets to be ejected is improved (variations in shape and size of the respective droplets are made small), and thus variations in shape and size of toner particles to be finally obtained can also be made small.
Examples of a material having such a liquid repellency include fluoro-based resins such as polytetrafluoroethylene (PTFE) and silicone-based materials.
As shown in
The piezoelectric device M22 functions as a vibration source, and the diaphragm M24 is vibrated by the piezoelectric device (vibration source) M22 to instantaneously increase the internal pressure of the dispersion liquid storage portion M21.
In particular, in each of the head portions M2, the piezoelectric element M222 keeps its original shape in a state where a predetermined eject signal from a piezoelectric device driving circuit (not shown in the drawings) is not inputted, that is, in a state where a voltage is not applied across the lower electrode M221 and the upper electrode M223 of the piezoelectric device M22. At this time, since the diaphragm M24 also keeps its original shape, the volume of the dispersion liquid storage portion M21 is not changed. That is, the water-based suspension 3 is not ejected through the ejection portion M23.
On the other hand, the piezoelectric element M222 changes its shape when a predetermined eject signal from the piezoelectric device driving circuit is inputted, that is, when a predetermined voltage is applied across the lower electrode M221 and the upper electrode M223 of the piezoelectric device M22. As a result, the diaphragm M24 is significantly bent (toward the lower side in
When single ejection of the water-based suspension 3 is finished, namely one droplet is formed, the piezoelectric device driving circuit stops a voltage from being applied across the lower electrode M221 and the upper electrode M223. As a result, the piezoelectric device M22 is returned to its almost original shape so that the volume of the dispersion liquid storage portion M21 is increased. At this time, since pressure is exerted on the water-based suspension 3 in the direction from the water-based suspension supply portion M4 to the ejection portion M23 (that is, in the positive direction), it is possible to prevent air from entering the dispersion liquid storage portion M21 through the ejection portion M23. Then, the water-based suspension 3 in an amount equal to the ejected amount thereof is supplied to the dispersion liquid storage portion M21 from the water-based suspension supply portion M4.
By carrying out predetermined periodic application of a voltage in such a manner as described above, the water-based suspension 3 in the form of a droplet is repeatedly ejected due to vibration of the piezoelectric device M22.
As described above, by carrying out ejection (discharge) of the water-based suspension 3 by the use of a pressure pulse due to vibration of the piezoelectric element M222, it is possible to eject the water-based suspension 3 intermittently drop by drop with the shape of each droplet 5 being stable. As a result, it is possible to make variations in shape and size of respective toner particles extremely small, thereby enabling to produce toner particles having high sphericity (a shape close to a geometrically perfect spherical shape) relatively easily.
Further, by ejecting the dispersion liquid (water-based dispersion liquid) by the use of vibration of the piezoelectric element, it is possible to eject the dispersion liquid at predetermined intervals more reliably. This makes it possible to effectively prevent collision or aggregation between the ejected droplets 5 of the dispersion liquid, thus resulting in preventing formation of defective toner particles 8 effectively.
The initial velocity of the water-based suspension 3 (droplets 5) at the time when the water-based suspension 3 is ejected from the head portions M2 into the dispersion medium removal portion M3 is preferably in the range of, for example, 0.1 to 10 m/sec, more preferably in the range of 2 to 8 m/sec. If the initial velocity of the water-based suspension 3 is less than the above lower limit value, productivity of toner particles is lowered. On the other hand, the initial velocity of the water-based suspension 3 exceeds the above upper limit value, the finally obtained toner particles tend to have a lower degree of sphericity.
The viscosity of the water-based suspension (water-based dispersion liquid) 3 ejected from the head portions M2 is not limited to any specific value, but is preferably in the range of, for example, 0.5 to 200 (mPa·s), and more preferably in the range of 1 to 25 (mPa·s). If the viscosity of the water-based suspension 3 is less than the above lower limit value, it is difficult to control the size of each droplet of the water-based suspension to be ejected properly, thus resulting in a case where the finally obtained toner particles have large variations in size. On the other hand, if the viscosity of the water-based suspension 3 exceeds the above upper limit value, there is a tendency that each of the formed droplets has a larger diameter, the ejecting velocity of the water-based suspension 3 becomes low, and the amount of energy required to eject the water-based suspension 3 becomes large. In a case where the viscosity of the water-based suspension 3 is especially high, it is impossible to eject the water-based suspension 3 in the form of droplets.
The water-based suspension (water-based dispersion liquid) 3 to be ejected from the head portions M2 may be cooled in advance. By cooling the water-based suspension 3 in such a manner, it is possible to prevent undesirable evaporation (volatilization) of the dispersion medium 32 from the water-based suspension 3 at the vicinity of the ejection portions M23 effectively. As a result, it is possible to prevent changes in the ejected amount of the water-based suspension 3 which are caused by the fact that the diameter of each ejection portion is reduced with the elapse of time, thereby enabling to obtain toner particles having small variations in shape and size of respective particles.
Further, the average diameter of the droplets 5 ejected from the head portions M2 also varies depending on the content of the dispersoid 31 in the water-based suspension (water-based dispersion liquid) 3, but is preferably in the range of 1.0 to 100 μm, more preferably in the range of 1.0 to 50 μm, and even more preferably in the range of 1.0 to 15 μm. By setting the average diameter of the droplets 5 of the water-based suspension 3 to a value within the above range, it is possible to obtain toner particles 8 each having an appropriate diameter.
Furthermore, when Dd (μm) denotes the average particle diameter of the droplets 5 and Dm (μm) denotes the average particle diameter of the dispersoid 31, it is preferred that the relation of 0.1<Dm/Dd<1.0 is satisfied and more preferred that the relation of 0.2<Dm/Dd<0.5 is satisfied. By satisfying such a relation, it is possible to prevent each of the droplets 5 ejected from the ejection portion M23 from containing two or more particles of the dispersoid 31, which means that each of the droplets 5 to be formed is constructed from the dispersion medium 32 which contains only one particle of the dispersoid 31 therein or each of the droplets 5 is substantially constructed from only the dispersion medium 32 without containing any dispersoid 31. This makes it possible to form the toner particles 8 each of which corresponds to each particle of the dispersoid 31. In other word, the respective toner particles 8 can be made to have a substantially same size and shape as each particle of the dispersoid 31. As a result of this, it is possible to form the toner particles 8 each having a smaller size as well as to make variations in size of the toner particles 8 sufficiently small. The above-mentioned relation can be satisfied easily and reliably by adjusting the size of the ejection portion M23 and the like.
The frequency of the piezoelectric device M22 (the frequency of an piezoelectric pulse) is not limited to any specific value, but is preferably in the range of 1 kHz to 500 MHz, and more preferably in the range of 5 kHz to 200 MHz. If the frequency of the piezoelectric device M22 is less than the above lower limit value, productivity of toner particles is lowered. On the other hand, if the frequency of the piezoelectric device M22 exceeds the above upper limit value, there is a possibility that the ejection of the water-based suspension 3 cannot follow the frequency of the piezoelectric device M22 so that the sizes of the droplets of the water-based suspension 3 become different from each other. As a result, there is a possibility that toner particles 8 finally obtained have large variations in their size.
The liquid developer production apparatus M1 shown in
The water-based suspension 3 may be ejected at substantially the same time from all the head portions M2, but it is preferred that the water-based suspension 3 is ejected in such a manner that the timing of ejection is different in at least two adjacent head portions M2. This makes it possible to prevent collision and undesirable aggregation effectively between the water-based suspension 3 in the form of droplets 5, namely between the droplets 5 ejected from the adjacent head portions M2, before the toner particles 8 are formed.
Further, as shown in
Further, by injecting gas supplied from the gas stream supply means M10 through the gas injection openings M7, it is possible to form an air stream flowing in substantially one direction (that is, in a downward direction in
Furthermore, by injecting gas through the gas injection openings M7, an air flow curtain is formed between the droplets 5 ejected from the adjacent head portions M2. Such an air curtain makes it possible to prevent collision and aggregation between the droplets more effectively.
The gas stream supply means M10 is equipped with a heat exchanger M11. By providing such a heat exchanger M11, it is possible to set the temperature of gas to be injected from the gas injection openings M7 to an appropriate value, thereby enabling to efficiently remove the dispersion medium 32 from the water-based suspension 3 in the form of droplets which have been ejected into the dispersion medium removal portion M3.
Further, by providing such a gas stream supply means M10, it is possible to control the dispersion medium removal rate for removing the dispersion medium 32 from the droplets of the water-based suspension 3 ejected from the ejection portions M23 easily by adjusting the amount of a gas stream to be supplied.
The temperature of gas to be injected from the gas injection openings M7 varies depending on the compositions of the dispersoid 31 and the dispersion medium 32 contained in the water-based suspension (water-based dispersion liquid) 3, but is preferably in the range of 0 to 70° C., and more preferably in the range of 15 to 60° C. By setting the temperature of gas to be injected from the gas injection openings M7 to a value within the above range, it is possible to remove the dispersion medium 32 effectively from the droplets 5 while maintaining shape uniformity and shape stability of the obtained toner particles 8 at a sufficiently high level.
The humidity of gas to be injected from the gas injection openings M7 is preferably 50% RH or less, and more preferably 30% RH or less. By setting the humidity of gas to be injected from the gas injection openings M7 to 50% RH or less, it is possible to remove the dispersion medium 32 contained in the water-based suspension 3 efficiently in the dispersion medium removal portion M3, thereby further improving the productivity of the toner particles 8.
The dispersion medium removal portion M3 is constructed from a tubular housing M31. In order to maintain the inside of the dispersion medium removal portion M3 at a temperature within a predetermined range, a heat source or a cooling source may be provided inside or outside the housing M31, or the housing M31 may be formed as a jacket having a passage of a heat medium or a cooling medium.
In the liquid developer production apparatus shown in
The pressure inside the housing M31 is not limited to any specific value, but is preferably 150 kPa or less, more preferably in the range of 100 to 120 kPa, and even more preferably in the range of 100 to 110 kPa. By setting the pressure inside the housing M31 to a value within the above range, it is possible to prevent effectively the dispersion medium 32 from being removed rapidly from the droplets 5 (that is, boiling phenomenon of the droplets 5). As a result, it is possible to produce the toner particles 8 effectively while preventing formation of defective toner particles 8 reliably. In this connection, it is to be noted that the pressure inside the housing M31 may be substantially the same or different from each other at various positions thereof.
Further, a voltage apply means M8 for applying a voltage to the inner surface of the housing M31 is connected to the housing M31. By applying a voltage of the same polarity as the toner particles 8 (droplets 5) to the inner surface of the housing M31 by the use of the voltage apply means M8, it is possible to obtain such effects as described below.
Generally, the toner particles 8 are positively or negatively charged. Therefore, when there is any charged matter of polarity opposite to that of the toner particles 8, the phenomenon in which the toner particles 8 are electrostatically attracted and adhere to the charged matter occurs. On the other hand, when there is any charged matter of the same polarity as that of the toner particles 8, the charged matter repels each another, thereby effectively preventing the phenomenon in which the toner particles 8 adhere to the surface of the charged matter. For this reason, by applying a voltage of the same polarity as that of the toner particles 8 to the side of the inner surface of the housing M31, it is possible to prevent effectively the toner particles 8 from adhering to the inner surface of the housing M31. As a result, it is also possible to prevent effectively the formation of defective toner particles 8 as well as to improve the collection efficiency of the toner particles B.
The housing M31 further includes an expanded-diameter portion M311 in the bottom portion thereof. In the expanded-diameter portion M311, the inner diameter thereof is expanded toward the lower side in
Normally, the respective toner particles 8 formed in the dispersion medium removal portion M3 (housing M31) as described above has a size corresponding to each particle of the dispersoid 31 contained in the droplets 5. Therefore, a finally obtained liquid developer contains toner particles each having a relatively small diameter and a high degree of roundness (sphericity) and having small variations in shape and size of the respective particles.
Further, as described in the above, the toner particles 8 are produced using the water-based dispersion liquid (water-based emulsion and water based suspension) which contains the dispersion medium constructed from the water-based liquid. Water constituting the water-based liquid has a relatively high boiling point and relatively low vapor pressure at around room temperature among various types of liquids. Therefore, the toner particles 8 formed in the dispersion medium removal portion M3 (housing M31) contain predetermined amount of water while maintaining sufficient shape stability. In addition, the inventors discovered that the toner particles containing predetermined amount of water as above have excellent fixing properties to recording mediums such as papers and the like. This is because of the reasons described below.
Namely, since an insulation liquid (carrier) which constitutes a liquid developer needs to have insulation properties and low dielectric constant, it is normally constructed from molecule having no functional group of high polarity. On the other hand, a recording medium such as papers and the like used for image forming with a liquid developer is normally constructed from a material having hydrophilic functional group (e.g., hydroxyl group) such as cellulose. Therefore, in a conventional liquid developer, if an insulation liquid remains in surfaces of toner particles, the insulation liquid impairs fixing properties of the toner particles (adhesion between the toner particles and the recording medium). On the other hand, in the liquid developer of the present invention, since the toner particles contain predetermined amount of water, the water contained in the toner particles exhibits a function of improving adhesion between the toner particles and the recording medium, whereby resulting in excellent fixing properties of the toner particles.
The toner particles 8 are not particularly limited to any specific one as long as the respective toner particles 8 contains predetermined amount of water therein, but it preferably contains water more than the amount of water absorption of a resin material which constitutes the toner particles 8. According to this, fixing properties of the toner particles 8 to a recording medium can be made particularly excellent. In this regard, the term “amount of water absorption” in the present invention means the largest amount of water which can be contained in the toner material (resin material) itself and it does not include the amount of water adsorption (amount of water adsorbed in the surface of the resin material by functional group).
Further, the water content of the toner particles 8 is not particularly limited to any specific value, but is preferably in the range of 0.3 to 5.0 wt %, more preferably in the range of 1.0 to 4.0 wt %, and even more preferably in the range of 1.0 to 2.5 wt %. When the water content of the toner particles 8 is set to a value within the above range, it is possible to make charge properties of the toner particles 8 sufficiently good as well as to make fixing properties of the toner particles 8 to a recording medium particularly excellent.
The toner particles 8 produced in the above manner are introduced into the insulation liquid storage portion M5 and mixed with the insulation liquid 9. In this way, a liquid developer 10 comprised of the insulation liquid 9 and the toner particles 8 dispersed in the insulation liquid 9 is obtained. As described in the above, in the present invention, the formed toner particles 8 are directly mixed with the insulation liquid 9 without being collected as fine particles. This makes it possible to prevent aggregation and the like of the toner particles sufficiently as well as to make productivity of the liquid developer excellent.
In the structure shown in the drawing, the insulation liquid storage portion M5 includes a stirring means M51 for stirring the insulation liquid 9. The stirring means M51 enables the toner particles 8 to be dispersed in the insulation liquid 9 homogeneously enough even in a case where a difference of specific gravity between the insulation liquid 9 and the toner particles 3 is relatively large (for example, absolute value of the difference is 0.3 g/cm3 or more). Further, it becomes possible to keep an excellent dispersion state of the toner particles 8 stably for a long period of time in the obtained liquid developer 10. Furthermore, it is possible to prevent effectively the toner particles 8 from being suspended in the vicinity of the surface of the insulation liquid 9 as well as to prevent the aggregation and the like of the toner particles 8 in an efficient manner.
Various liquids may be used as the insulation liquid 9 if the liquids have sufficiently high insulation properties. Specifically, a liquid having an electric resistance of 109 Ωcm or more at room temperature (20° C.) is preferably used, more preferably a liquid having an electric resistance of 1011 Ωcm or more is used, and even more preferably a liquid having an electric resistance of 1013 Ωcm or more is used.
Further, it is preferred that the insulation liquid 9 has a dielectric constant of 3.5 or less.
Examples of such insulation liquids 9 that satisfy the above conditions include octane, isooctane, decane, isodecane, decaline, nonane, dodecane, isodecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, various types of silicone oils, vegetable oils (e.g., linseed oil, soybean oil), ISOPAR E, ISOPAR G, ISOPAR H, ISOPAR L (“ISOPAR” is a product name of Exxon Mobil Corporation), SHELLSOL 70, SHELLSOL 71 (“SHELLSOL” is a product name of Shell Oil), Amsco OMS, Amsco 460 solvent (“Amsco” is a product name of Spirit Co., Ltd.).
<Liquid Developer>
The liquid developer obtained as described above is constituted from toner particles having superior fixing properties to a recording medium. Further, in the liquid developer obtained as described above, variations in shape and size of the toner particles are small. Therefore, in such a liquid developer, toner particles are easy to migrate in the insulation liquid (that is, in the liquid developer), and thus it is advantageous in high speed development. Further, since the toner particles have small variations in their shape and size and thus they have superior dispersibility, so that settle down and floating of the toner particles in the liquid developer are prevented effectively. Therefore, such a liquid developer can keep superior storage stability for a long period of time.
The average particle size (diameter) of the toner particles 8 in the liquid developer 10 obtained as described above is preferably in the range of 0.1 to 5 μm, more preferably in the range of 0.4 to 4 μm, and even more preferably in the range of 0.5 to 3 μm. If the average particle size of the toner particles 8 is within the above range, it is possible to make resolution of a toner image formed from the liquid developer (toner) sufficiently high with small variations in properties of the toner particles 8 such as chargeable properties or fixing properties, and especially high reliability as a whole of a liquid developer 10.
Further, it is preferred that the standard deviation of particle size among the toner particles 8 which constitute the liquid developer 10 is 1.0 μm or less, and more preferably in the range of 0.1 to 1.0 μm. When the standard deviation of particle size lies within the above range, variations in charge properties, fixing properties and the like of the toner particles 8 become especially small, thereby further improving the reliability of the liquid developer 10 as a whole.
Next, the second embodiment of the method of producing the liquid developer according to the present invention will be described in detail.
In the following description, the left side in
The liquid developer producing method according to the second embodiment of the present invention is characterized by comprising:
a water-based dispersion liquid preparing step for preparing a water-based dispersion liquid comprising a dispersoid containing a resin material and a coloring agent and a water-based dispersion medium constituted from a water-based liquid in which the dispersoid is dispersed;
a dry fine particle producing step in which the water-based dispersion medium is removed from the water-based dispersion liquid and an antiaggregation agent for preventing aggregation of the dispersoid is added thereto to thereby obtain dry fine particles (toner particles); and
a dispersion step for dispersing the dry fine particles into an insulation liquid.
In the second embodiment, a description will be made with regard to a case where a material containing a resin and a coloring agent is kneaded to obtain a kneaded material and a dispersion liquid is obtained using the kneaded material in the water-based dispersion liquid preparing step. In this regard, it is to be noted that a dispersion liquid may be obtained without using the kneaded material in the present invention.
<Constituent Material of Kneaded Material>
A kneaded material obtained in a kneading step described below contains a component which forms toner particles of a liquid developer, and the kneaded material contains at least a binder resin (resin material) and a coloring agent.
First, a description will be made with regard to a constituent material used for preparing the kneaded material.
1. Resin (Binder Resin)
Toner particles which constitute a liquid developer are constituted from a material which contains a resin (binder resin) as its main component.
In the present invention, a type of a resin (binder resin) is not particularly limited to any specific one. Examples of a resin that can be used include a monomer or a copolymer of styrene resin that includes styrene or a styrene substitution product, such as polystyrene, poly-α-methylstyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylate ester copolymer, styrene-methacrylate ester copolymer, styrene-acrylate ester-methacrylate ester copolymer, styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate ester copolymer, styrene-vinylmethylether copolymer, or the like; polyester resin; epoxy resin; urethane modified epoxy resin; silicone modified epoxy resin; vinyl chloride resin; rosin modified maleic acid resin; phenyl resin; polyethylene-based resin; polypropylene; ionomer resin; polyurethane resin; silicone resin; ketone resin; ethylene-ethyl acrylate copolymer; xylene resin; polyvinyl butyral resin; terpene resin; phenol resin; aliphatic or alicyclic hydrocarbon resin; or the like. These resin components can be used alone or in combination of two or more of them.
The softening point of the resin (resin material) is not limited to any specific value, but it is preferably in the range of 50 to 130° C., more preferably in the range of 55 to 120° C., and still more preferably in the range of 60 to 115° C. In this specification, the term “softening point” means a temperature at which softening begins under the conditions that a temperature raising speed is 5° C./mm and a diameter of a die hole is 1.0 mm in a high-floored flow tester.
2. Coloring Agent
Further, the toner particles include a coloring agent. The same coloring agent as the one used in the first embodiment can be used in this second embodiment.
3. Other Components
In preparing the kneaded material, additional components other than the above components may be contained. As such components, the same components as those mentioned listed in the first embodiment described above can be used in the second embodiment.
<Kneaded Material>
Next, a kneaded material K7 is obtained by kneading a material K5 which contains the above-mentioned components in the same manner as in the first embodiment described above.
<Grinding Process>
Next, the thus obtained kneaded material K7 is ground. By grinding the kneaded material K7, it is possible to obtain a water-based emulsion (described later) in which a finer dispersoid is dispersed relatively easily. As a result, it becomes possible to make the size of the toner particles smaller in a liquid developer finally obtained, and such a liquid developer can be preferably used in forming a high resolution image.
The method of grinding is not particularly limited. For example, such grinding may be carried out by employing various kinds of grinding machines or crushing machines such as a ball mill, a vibration mill, a jet mill, a pin mill, or the like.
The grinding process may be carried out by dividing it into a plurality of stages (for example, two stages including a coarse grinding process and a fine grinding process). Further, after the grinding process, other treatment such as classification treatment may be carried out as needed. Such classification treatment may be carried out using a sieve or an air flow type classifier or the like.
By subjecting the material K5 to the kneading process as described above, it is possible to eliminate air contained in the material K5 effectively. In other words, the kneaded material K7 obtained through such a kneading process hardly contains air (air bubble) therein. By using such kneaded material K7, it is possible to prevent generation of toner particles having irregular shapes (such as void particles, defect particles, fused particles, and the like) effectively in a dry fine particle producing step which will be described later. As a result, in a liquid developer finally obtained, it is possible to prevent occurrence of a problem such as lowered transfer property and cleaning property which are caused by such toner particles having irregular shapes.
In the present embodiment, a water-based emulsion is prepared using the kneaded material described above.
By using the kneaded material K7 in preparing the water-based emulsion, the following effects can be obtained. Namely, even in the case where a constituent material of toner particles contains components which are difficult to be dispersed in a dispersion medium or difficult to be mutually soluble to each other, these components are mutually soluble to each other satisfactorily and finely dispersed in an obtained kneaded material by way of the kneading step described above. In particular, most of pigments (coloring agent) have poor dispersibility to a liquid used as a solvent. However, in this embodiment, because the kneading step has been carried out before the kneaded material is dispersed into a solvent, the outer periphery of each particle of a pigment is coated with a resin component effectively. Therefore, dispersibility of the pigment to the solvent is improved (particularly, the pigment can be finely dispersed in the solvent), color development of a finally obtained liquid developer becomes excellent. For these reasons, even in a case where a constituent material of toner particles contains a component having poor dispersibility to a dispersion medium of a water base-emulsion (water-based dispersion medium) which will be described later (hereinafter, this component will be referred to as “poor dispersibility component”) or a component having poor solubility to a solvent contained in a dispersion medium of a water-based emulsion (hereinafter, this component will be referred to as “poor solubility component”), it is possible to make dispersibility of a dispersoid in a water-based emulsion more excellent. Further, in a water-based suspension 3 (droplets 5′), dispersibility of a dispersoid 31 becomes excellent. With these results, in a finally obtained liquid developer, variations in compositions and properties of respective toner particles can be made small, and therefore the liquid developer can have excellent properties as a whole.
Further, according to the present invention, since the kneaded material described above is used in preparing a water-based emulsion, it is possible to obtain toner particles in which the respective components are dispersed (finely dispersed) or mutually dissolved sufficiently homogeneously.
Further, in the water-based emulsion, a dispersoid is in a liquid sate, there is a tendency that each particle of the dispersoid is formed into a shape having a relatively high roundness (sphericity) due to its surface tension. Accordingly, in a suspension (water-based suspension) prepared using the water-based emulsion, there is also a tendency that each particle of the dispersoid is formed into a shape having a relatively high roundness (sphericity). In contrast, in the case where resin particles which are prepared without the water-based emulsion process are used in a suspension which is used for producing dry fine particles described later, each particle of a dispersoid contained in the suspension is likely to have low roundness, so that variations in the shape of the respective particles become larger. In this connection, in order to suppress such variations in their shape, it may be conceived that a heat spheronization treatment is carried out when dry fine particles are being formed or after dry fine particles have been formed. However, in such a case (particularly, when such a heat spheronization treatment is carried out when dry fine particles are being formed), it is difficult to make the variations in shapes of the obtained particles sufficiently small unless otherwise conditions for the heat spheronization treatment are set to be relatively severe. Further, such severe conditions for the heat spheronization treatment in turn involve such problems in that deterioration of the constituent material of the dry fine particles is likely to occur and a mutually dissolved state and a finely dispersed state of the components in the respective dry fine particles are likely to get worse, and thereby it becomes difficult for a finally obtained liquid developer to exhibit sufficient properties.
<Water-Based Dispersion Liquid Preparing Step>
In this step, by using the kneaded material K7, a water-based emulsion comprised of a water-based dispersion medium constituted from a water-based liquid in which a dispersoid constituted from a toner material is dispersed is prepared (water-based emulsion preparing step) at first.
The method for preparing the water-based emulsion is not particularly limited, but in the present embodiment, a water-based emulsion is prepared by obtaining a solution in which at least a part of the kneaded material K7 is dissolved, and then by dispersing such a solution into a water-based liquid. In this connection, it should be noted that in this specification the term “emulsion” means a dispersion liquid comprised of a liquid state dispersion medium and a liquid state dispersoid (dispersion particles) dispersed in the dispersion medium, and the term “suspension” means a suspension liquid (including suspension colloid) comprised of a liquid state dispersion medium and a solid state dispersoid (suspension particles) dispersed in the dispersion medium. Further, in the case where both a liquid state dispersoid and a solid state dispersoid exist in a dispersion liquid, the term “emulsion” means a dispersion liquid in which the total volume of the liquid state dispersoid is larger than the total volume of the solid state dispersoid, while the term “suspension” means a dispersion liquid in which the total volume of the solid state dispersoid is larger than the total volume of the liquid state dispersoid.
Hereinbelow, a description will be made with regard to the method for preparing the water-based emulsion.
<Preparation of Kneaded Material Solution>
In the present embodiment, a kneaded material solution (a solution of the kneaded material) in which at least a part of the kneaded material is dissolved is obtained.
The solution is prepared by mixing the kneaded material with a solvent in which at least a part of the kneaded material can be dissolved.
As for the solvent used for preparing the solution, various solvents can be used so long as at least a part of the kneaded material can be dissolved thereinto, but normally, solvents which have low mutual solubility to a water-based liquid described later (that is, a water-based liquid used for preparing the water-based emulsion) are used. For example, a liquid having a solubility of 10 g or less with respect to 100 g of a water-based liquid at a temperature of 25° C. is used.
Examples of such solvents include inorganic solvents such as carbon disulfide, and carbon tetrachloride, and organic solvents such as ketone-based solvents (e.g., methyl ethyl ketone (MEK), methyl isopropyl ketone (MIPK), and 2-heptanone), alcohol-based solvents (e.g., pentanol, n-hexanol, 1-octanol, and 2-octanol), ether-based solvents (e.g., diethyl ether, and anisole), aliphatic hydrocarbon-based solvents (e.g., hexane, pentane, heptane, cyclohexane, octane, and isoprene), aromatic hydrocarbon-based solvents (e.g., toluene, xylene, benzene, ethyl benzene, and naphthalene), aromatic heterocyclic compound-based solvents (e.g., furan, and thiophene), halide-based solvents (e.g., chloroform), ester-based solvents (e.g., ethyl acetate, isopropyl acetate, isobutyl acetate, and ethyl acrylate), nitrile-based solvents (e.g., acrylonitrile), and nitro-based solvents (e.g., nitromethane and nitroethane). These materials can be used singly or in combination of two or more of them.
The amount of the solvent contained in the solution is not limited to any specific value, but is preferably in the range of 25 to 95 wt %, more preferably in the range of 30 to 90 wt %, and even more preferably in the range of 35 to 85 wt %. If the amount of the solvent contained in the solution is less than the above lower limit value, there is a possibility that it is difficult to dissolve the kneaded material sufficiently depending on the solubility of the kneaded material to the solvent. On the other hand, if the amount of the solvent exceeds the above upper limit value, a time required for removing the solvent in the subsequent step becomes long, the productivity of the liquid development is lowered. Further, if the amount of the solvent is too much, there is a possibility that the components which were sufficiently and homogeneously mixed to each other in the kneading step described above are phase-separated, and thereby making it difficult to make variations in the properties of the toner particles of a finally obtained liquid developer sufficiently small.
In this regard, it is to be noted that it is sufficient that at least a part of the components which constitute the kneaded material is dissolved (including a swelling state), and therefore components which were not dissolved may exist in the solution.
<Preparation of Water-Based Emulsion>
Next, a water-based emulsion is obtained by mixing the above mentioned solution with a water-based liquid. Normally, in the thus obtained water-based emulsion, a dispersoid which contains the solvent and the constituent material of the kneaded material are dispersed in the water-based dispersion medium formed from the water-based liquid.
In this specification, the term “water-based liquid” means a liquid constituted from water and/or a liquid having good compatibility with water (for example, a liquid which has solubility of 30 g or higher with respect to 100 g of water at a temperature of 25° C.). As described above, the water-based liquid is constituted from water and/or a liquid having good compatibility with water, but it is preferable that the water-based liquid is mainly constituted from water, more preferably constituted from a liquid of which water content is 70 wt % or higher, and even more preferably constituted from a liquid of which water content is 90 wt % or higher. By using such a water-based liquid, it is possible to simplify a liquid collecting apparatus.
Examples of the water-based liquid include alcohol-based solvents such as methanol, ethanol, propanol, and the like, ether-based solvents such as 1,4-dioxane, tetrahydrofuran (THF), and the like, aromatic heterocyclic compound-based solvents such as pyridine, pyrazine, pyrrole, and the like, amide-based solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and the like, nitrile-based solvents such as acetonitrile and the like, and aldehyde-based solvents such as acetaldehyde, and the like.
Further, in preparing the water-based emulsion, a dispersant or the like may be used for the purpose of improving the dispersibility of the dispersoid. Examples of such a dispersant include: inorganic dispersants such as tricalcium phosphate, and the like; nonionic organic dispersants such as polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, and the like; anionic organic dispersants such as tristearic acid metal salts (e.g., aluminum salts), distearic acid metal salts (e.g., aluminum salts and barium salts), stearic acid metal salts (e.g., calcium salts, lead salts, and zinc salts), linolenic acid metal salts (e.g., cobalt salts, manganese salts, lead salts, and zinc salts), octanoic acid metal salts (e.g., aluminum salts, calcium salts, and cobalt salts), oleic acid metal salts (e.g., calcium salts and cobalt salts), palmitic acid metal salts (e.g., zinc salts), dodecylbenzenesulfonic acid metal salts (e.g., sodium salts), naphthenic acid metal salts (e.g., calcium salts, cobalt salts, manganese salts, lead salts, and zinc salts), resin acid metal salts (e.g., calcium salts, cobalt salts, manganese salts, lead salts, and zinc salts), polyacrylic acid metal salts (e.g., sodium salts), polymethacrylic acid metal salts (e.g., sodium salts), polymaleic acid metal salts (e.g., sodium salts), metal salts of acrylic acid-maleic acid copolymers (e.g., sodium salts), polystyrenesulfonic acid metal salts (e.g., sodium salts); and cationic organic dispersants such as quaternary ammonium salts; and the like. By using the dispersant as described above in preparing the water-based emulsion, it is possible to improve the dispersibility of the dispersoid. Further, it is also possible to make variations in shape and size of the dispersoid in the water-based emulsion particularly small relatively easily, and also possible to make the shape of each particle of the dispersoid roughly spherical shape. With these results, it is possible to obtain a liquid developer which is comprised of toner particles each formed into a roughly spherical shape and having uniform shape and size.
It is preferred that the solution is mixed with the water-based liquid while at least either the solution or the water-based liquid is being stirred. This makes it possible to obtain an emulsion (a water-based emulsion) in which a dispersoid having small variations in its size and shape is homogeneously dispersed easily and reliably.
Examples of methods for mixing the solution and the water-based liquid include a method in which the solution is added (for example, dropped) into the water-based liquid contained in a container, a method in which the water-based liquid is added (for example, dropped) into the solution contained in a container, and the like. In these methods, the water-based liquid or the solution which is contained in a container is preferably being stirred. This makes it possible to exhibit the above effect more conspicuously.
The amount of the dispersoid in the water-based emulsion is not particularly limited, but preferably in the range of 5 to 55 wt %, and more preferably in the range of 10 to 50 wt %. This makes it possible to prevent bonding or aggregation of particles of the dispersoid more reliably, thereby enabling to make productivity of the toner particles (liquid developer) particularly superior.
The average particle diameter of the dispersoid in the water-based emulsion is not particularly limited, but preferably in the range of 0.01 to 5 μm, and more preferably in the range of 0.1 to 3 μm. This makes it possible to obtain toner particles having sufficiently high roundness. Further, uniformity in the characteristics, size and shape of the respective particles (toner particles) can be made particularly excellent. In addition, resolution of an image which is formed using the liquid developer becomes particularly high. In this regard, it is to be noted that the term “average particle diameter” means an average particle diameter per the reference number of particles.
Further, although the above description was made with regard to the case that the components of the kneaded material are contained in the dispersoid in the water-based emulsion, a part of the components of the kneaded material may be contained in the dispersion medium.
Furthermore, the water-based emulsion may contain additional components other than the above-mentioned components. Examples of such additional components include a charge controlling agent, magnetic powder and the like.
Example of the charge controlling agent include metal salts of benzoic acid, metal salts of salicylic acid, metal salts of alkyl salicylic acid, metal salts of catechol, metal-containing bisazo dyes, nigrosine dyes, tetraphenylborate derivatives, quaternary ammonium salts, alkyl pyridinium salts, chlorinated polyesters, nitrohumic acid, and the like.
Examples of the magnetic powders include powders of metal oxides such as magnetite, maghemite, various ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, magnesium oxide, and the like, and powders of magnetic materials containing magnetic metals such as Fe, Co, and Ni.
The water-based emulsion may further contain, for example, zinc stearate, zinc oxide, or cerium oxide, in addition to the above-mentioned materials.
<Water-Based Suspension Preparing Step>
The thus obtained water-based emulsion may be brought to a dry fine particle producing step described below as it is. However, in the present embodiment, a water-based suspension 3 comprised of a dispersion medium (water-based dispersion medium) 32 and a solid state dispersoid 31 dispersed in the dispersion medium 32 is obtained based on the water-based emulsion (in which the liquid state dispersoid is dispersed in the water-based dispersion medium), and the thus obtained water-based suspension is used in the dry fine particle producing step.
Hereinbelow, a detailed description will be made with regard to a method for preparing the water-based suspension 3.
The water-based suspension 3 can be prepared by removing the solvent which constitutes the disperoid from the water-based emulsion.
The removal of the solvent can be carried out, for example, by heating or warming the water-based emulsion or placing it in an atmosphere under reduced pressure. However, it is preferred that the water-based emulsion is heated under reduced pressure. This makes it possible to obtain a water-based suspension 3 containing a dispersoid 31 having particularly small variations in size and shape thereof relatively easily. Further, by removing the solvent as described above, it is possible to carry out a deaerating treatment in addition to the removal of the solvent. By the deaerating treatment, it is possible to reduce the amount of the dissolved air in the water-based suspension 3, and therefore when the dispersion medium 32 is removed from the droplets 5′ of the water-based suspension 3 in the water-based dispersion medium removal section M3 of the dry fine particle production apparatus M1, it is possible to prevent generation of air bubble in the water-based suspension 3 in an effective manner. As a result, it is possible to prevent toner particles having irregular shapes (such as void particles and defect particles) from entering (or being mixed into) a finally obtained liquid developer effectively.
When the water-based emulsion is heated (or warmed), the heating temperature is preferably in the range of 30 to 110° C., and more preferably in the range of 40 to 100° C. If the heating temperature is set to a value within the above range, it is possible to remove the solvent immediately while preventing generation of a dispersoid 31 having irregular shapes effectively (that is, preventing rapid vaporization (boiling) of a solvent from the inside of the dispersoid of the water-based emulsion).
Further, when the water-based emulsion is placed in an atmosphere under reduced pressure, the pressure of the atmosphere in which the water-based emulsion is placed is preferably in the range of 0.1 to 50 kPa, and more preferably in the range of 0.5 to 5 kPa. If the pressure of the atmosphere in which the water-based emulsion is placed is within the above range, it is possible to remove the solvent immediately while preventing generation of a dispersoid 31 having irregular shapes effectively (that is, preventing rapid vaporization (boiling) of a solvent from the inside of the dispersoid of the water-based emulsion).
In this regard, it should be noted that it is sufficient that the removal of the solvent is carried out to the extent that at least the dispersoid is transformed into a solid state. It is not necessary to remove substantially all the solvent contained in the water-based emulsion.
The average particle diameter of the dispersoid 31 contained in the water-based suspension 3 is not limited to a specific value, but preferably in the range of 0.01 to 5 μm, and more preferably in the range of 0.1 to 3 μm. This makes it possible to obtain toner particles having sufficiently high roundness as well as having superior uniformity in their characteristics, sizes and shapes. In addition, resolution of an image formed using the liquid developer becomes particularly high.
<Dry Fine Particle Producing Step (Water-Based Dispersion Medium Removal Step)>
Next, by removing the water-based dispersion medium from the water-based dispersion liquid (water-based suspension 3), dry fine particles corresponding to the dispersoid of the water-based dispersion liquid (water-based suspension 3) are obtained (dry fine particle producing step). The dry fine particles obtained in this way are used as toner particles of a liquid developer.
The removal of the water-based dispersion medium may be carried out by any method, but it is carried out by intermittently ejecting droplets of a dispersion liquid (water-based dispersion liquid) comprised of a water-based dispersion medium and a dispersoid dispersed in the dispersion medium in this embodiment. This makes it possible to carry out the removal of the water-based dispersion medium efficiently while preventing aggregation of the dispersoid effectively. Further, in this embodiment, the removal of the water-based dispersion medium is carried out by intermittently ejecting droplets of the water-based dispersion liquid. Therefore, even in the case where a part of the solvent remains in preparing the water-based suspension, it is possible to remove the remaining solvent together with the water-based dispersion medium in an effective manner.
In particular, in the present embodiment, the removal of the water-based dispersion medium is carried out using a dry fine particle production apparatus (toner particle production apparatus) as shown in
<Dry Fine Particle Production Apparatus (Toner Particle Production Apparatus)>
As shown in
The water-base suspension supply portion M4′ is not particularly limited as long as it has the function of supplying the water-based suspension 3 to the head portions M2′. In the present embodiment, the water-based suspension supply portion M4′ is provided with a stirring means M41′ for stirring the water-based suspension 3 as shown in
Each of the head portions M2′ has a function of ejecting the water-based suspension 3 in the form of fine droplets (fine particles) 5′.
Further, each of the head portions M2′ has a dispersion liquid storage portion M21′, a piezoelectric device (element) M22′, and an ejection port (nozzle) M23′.
In the dispersion liquid storage portion M21′, the water-based suspension 3 is stored.
The water-based suspension 3 stored in the dispersion liquid storage portion M21′ is ejected from the ejection port (nozzle) M23′ in the form of droplets 5′ into the dispersion medium removal portion M3′ when a pressure pulse (piezoelectric pulse) is applied.
The shape of the ejection portion M23′ (the ejection aperture of the nozzle) is not particularly limited, but preferably it is formed into a substantially circular shape. By forming the ejection portion M23′ into such a shape, it is possible to raise sphericity of the ejected water-based suspension 3 and the dry fine particle (toner particle) 8 formed in the dispersion medium removal portion M3′.
When the ejection portion M23′ has such a substantially circular shape, the diameter thereof (that is, nozzle diameter) is preferably in the range of 5 to 500 μm, and more preferably in the range of 10 to 200 μm. If the diameter of the ejection portion M23′ is less than the above lower limit value, clogging is likely to occur and therefore there is a case that variations in the size of the droplets 5′ to be ejected become larger. On the other hand, if the diameter of the ejection portion M23 exceeds the above upper limit value, there is a possibility that the water-based suspension 3 (droplets 5′) to be ejected contains air bubbles inside thereof depending on the relative power balance between the negative pressure of the dispersion liquid storage portion M21′ and the surface tension of the nozzle.
Further, it is preferred that the a portion in the vicinity of the ejection portion M23′ of each head portion M2, (that is, an inner surface of the nozzle aperture of each ejection portion M23′ and a surface of the head portions M2′ in which the ejection portions M23′ are provided (the lower surface in the drawing)) has a liquid repellency (water repellency). This makes it possible to prevent the water-based suspension 3 from adhering around the ejection portion effectively. As a result, it is possible to prevent poor formation of droplets and occurrence of defective ejection of the water-based suspension 3. Further, since adhering of the water-based suspension 3 around the ejection portion is prevented effectively, the shape stability of the droplets to be ejected is improved (variations in the shape and size of the respective droplets are made small), and thus variations in shape and size of toner particles to be finally obtained can be made small.
Examples of a material having such a liquid repellency include fluorobased resins such as polytetrafluoroethylene (PTFE) and silicone-based materials.
As shown in
The piezoelectric device M22′ functions as a vibration source, and the diaphragm M24′ is vibrated by the piezoelectric device (vibration source) M22′ to instantaneously increase the internal pressure of the dispersion liquid storage portion M21′.
In particular, in each of the head portions M2′, the piezoelectric element M222′ keeps its original shape in a state where a predetermined eject signal from a piezoelectric device driving circuit (not shown in the drawings) is not inputted, that is, in a state where a voltage is not applied across the lower electrode M221′ and the upper electrode M223′ of the piezoelectric device M22′. At this time, since the diaphragm M24′ also keeps its original shape, the volume of the dispersion liquid storage portion M21′ is not changed. That is, the water-based suspension 3 is not ejected through the ejection portion M23′.
On the other hand, the piezoelectric element M222′ changes its shape when a predetermined eject signal from the piezoelectric device driving circuit is inputted, that is, when a predetermined voltage is applied across the lower electrode M221′ and the upper electrode M223′ of the piezoelectric device M22′. As a result, the diaphragm M24′ is significantly bent (toward the lower side in
When single ejection of the water-based suspension 3 is finished, namely one droplet is formed, the piezoelectric device driving circuit stops a voltage from being applied across the lower electrode M221′ and the upper electrode M223′. As a result, the piezoelectric device M221 is returned to its almost original shape so that the volume of the dispersion liquid storage portion M21′ is increased. At this time, since pressure is exerted on the water-based suspension 3 in the direction from the water-based suspension supply portion M4′ to the ejection portion M23′ (that is, in the positive direction), it is possible to prevent air from entering the dispersion liquid storage portion M21′ through the ejection portion M23′. Then, the water-based suspension 3 in an amount equal to the ejected amount thereof is supplied to the dispersion liquid storage portion M21′ from the water-based suspension supply portion M4′.
By carrying out predetermined periodic application of a voltage in such a manner as described above, the water-based suspension 3 in the form of a droplet is repeatedly ejected due to vibration of the piezoelectric device M22′.
As described above, by carrying out ejection (discharge) of the water-based suspension 3 by the use of a pressure pulse due to vibration of the piezoelectric element M222′, it is possible to eject the water-based suspension 3 intermittently drop by drop with the shape of each droplet 5′ being stable. As a result, it is possible to make variations in shape and size of respective toner particles extremely small, thereby enabling to produce toner particles having high sphericity (a shape close to a geometrically perfect spherical shape) relatively easily.
Further, by ejecting the dispersion liquid by the use of vibration of the piezoelectric element, it is possible to eject the dispersion liquid at predetermined intervals more reliably. This makes it possible to effectively prevent collision or aggregation between the ejected droplets 5′ of the dispersion liquid, thus resulting in preventing formation of defective dry fine particles 8 effectively.
The initial velocity of the water-based suspension 3 (droplets 5′) at the time when the water-based suspension 3 is ejected from the head portions M2′ into the dispersion medium removal portion M3′ is preferably in the range of, for example, 0.1 to 10 m/sec, more preferably in the range of 2 to 8 m/sec. If the initial velocity of the water-based suspension 3 is less than the above lower limit value, productivity of toner particles is lowered. On the other hand, the initial velocity of the water-based suspension 3 exceeds the above upper limit value, the finally obtained toner particles tend to have a lower degree of sphericity.
The viscosity of the water-based suspension 3 ejected from the head portions M2′ is not limited to any specific value, but is preferably in the range of, for example, 0.5 to 200 (mPa·s) more preferably in the range of 1 to 25 (mPa·s). If the viscosity of the water-based suspension 3 is less than the above lower limit value, it is difficult to control the size of each droplet of the water-based suspension to be ejected properly, thus resulting in a case where the finally obtained toner particles have large variations in size. On the other hand, if the viscosity of the water-based suspension 3 exceeds the above upper limit value, there is a tendency that each of the formed droplets has a larger diameter, the ejecting velocity of the water-based suspension 3 becomes low, and the amount of energy required to eject the water-based suspension 3 becomes large. In a case where the viscosity of the water-based suspension 3 is especially high, it is impossible to eject the water-based suspension 3 in the form of droplets.
The water-based suspension 3 to be ejected from the head portions M2′ may be cooled in advance. By cooling the water-based suspension 3 in such a manner, it is possible to prevent undesirable evaporation (volatilization) of the dispersion medium 32 from the water-based suspension 3 at the vicinity of the ejection portions M23′ effectively. As a result, it is possible to prevent changes in the ejected amount of the water-based suspension 3 which are caused by the fact that the diameter of each ejection portion is reduced with the elapse of time, thereby enabling to obtain toner particles having small variations in shape and size of respective particles.
The ejected amount of one droplet of the water-based suspension 3 slightly varies depending on the content of the dispersoid 31 in the water-base suspension 3, but is preferably in the range of 0.05 to 500 pl, more preferably in the range of 0.5 to 50 pl. By setting the ejected amount of one droplet of the water-based suspension 3 to a value within the above range, it is possible to obtain the dry fine particles 8 each having an appropriate diameter.
Further, in the present embodiment, the content and the particle size of the dispersoid 31 in the water-based dispersion liquid 3 are determined so as to prevent the respective droplets 5′ ejected from the ejection portions (nozzles) M23′ from containing two or more particles of the dispersoid 31. Accordingly, the thus formed droplets 5′ are droplets each formed from the dispersion medium 32 containing one particle of the dispersoid 31 as shown in
By removing the dispersion medium 32 from the droplet 5′ which is formed from the dispersion medium 32 containing one particle of the dispersoid 31, a dry fine particle 8 which is derived from one particle of the dispersoid 31 is obtained. Therefore, by simply forming the dispersoid 31 so that particles of the dispersoid 31 have uniform shape and small particle size distribution, the dry fine particles 8 to be obtained can also have uniform shape and small particles size distribution.
On the other hand, the droplet which is formed from only the dispersion medium 32 without containing the dispersoid 31 disappears during the process of removing the dispersion medium 32. Further, the particles size of the dispersoid 31 is not so small with respect to the particle size of the droplet 5′. Therefore, even in a case where a sub-droplet whose particle size is smaller than that of a necessary main-droplet in the formation of the droplet 5′, it is possible to prevent a particle of the dispersoid 31 from being contained in the sub-droplet. Since such a sub-droplet is formed from only the dispersion medium 32 without containing the dispersoid 31, it disappears during the process of removing the dispersion medium. Therefore, existence of such sub-droplets does not affect to the particles size distribution of the obtained dry fine particles 8.
The frequency of the piezoelectric device M22′ (the frequency of an piezoelectric pulse) is not limited to any specific value, but is preferably in the range of 1 kHz to 500 MHz, more preferably in the range of 5 kHz to 200 MHz. If the frequency of the piezoelectric device M22′ is less than the above lower limit value, productivity of toner particles is lowered. On the other hand, if the frequency of the piezoelectric device M22′ exceeds the above upper limit value, there is a possibility that the ejection of the water-based suspension 3 cannot follow the frequency of the piezoelectric device M22′ so that the sizes of the droplets of the water-based suspension 3 become different from each other. As a result, there is a possibility that the dry fine particles 8 (toner particles) finally obtained have large variations in their size.
The dry fine particle production apparatus M1′ shown in
The water-based suspension 3 may be ejected at substantially the same time from all the head portions M2′, but it is preferred that the water-based suspension 3 is ejected in such a manner that the timing of ejection is different in at least two adjacent head portions M2′. This makes it possible to prevent collision and undesirable aggregation effectively between the water-based suspension 3 in the form of droplets 5′, namely between the droplets 5′ ejected from the adjacent head portions M2′, before the dry fine particles 8 are formed.
Further, as shown in
Further, by injecting gas supplied from the gas stream supply means M10′ through the gas injection openings M7′, it is possible to form an air stream flowing in substantially one direction (that is, in a downward direction in
Furthermore, by injecting gas through the gas injection openings M7′, an air flow curtain is formed between the droplets 5′ ejected from the adjacent head portions M2′. Such an air curtain makes it possible to prevent collision and aggregation between the droplets effectively.
The gas stream supply means M10′ is equipped with a heat exchanger M11′. By providing such a heat exchanger M11′, it is possible to set a temperature of gas to be injected from the gas injection openings M7′ to an appropriate value, thereby enabling to efficiently remove the dispersion medium 32 from the water-based suspension 3 in the form of droplets which have been ejected into the dispersion medium removal portion M3′.
Further, by providing such gas stream supply means M10′, it is possible to control the dispersion medium removal rate for removing the dispersion medium 32 from the droplets of the water-based suspension 3 ejected from the ejection portions M23′ easily by adjusting the amount of a gas stream to be supplied.
The temperature of gas to be injected from the gas injection openings M7′ varies depending on the compositions of the dispersoid 31 and the dispersion medium 32 contained in the water-based suspension 3, but is preferably in the range of 0 to 70° C., and more preferably in the range of 15 to 60° C. By setting the temperature of gas to be injected from the gas injection openings M7′ to a value within the above range, it is possible to remove the dispersion medium 32 effectively from the droplets 5′ while maintaining shape uniformity and shape stability of the dry fine particles 8 obtained at a sufficiently high level.
The humidity of gas to be injected from the gas injection openings M7′ is preferably 50% RH or less, more preferably 30% RH or less. By setting the humidity of gas to be injected from the gas injection openings M7′ to 50% RH or less, it is possible to remove the dispersion medium 32 contained in the water-based suspension 3 efficiently in the dispersion medium removal portion M3′, thereby further improving the productivity of the dry fine particles 8.
An antiaggregation agent 14 for preventing or controlling aggregation and granulation of the dispersoid 31 is added to the droplets 5′ which are formed as described above.
As shown in
Such an antiaggregation agent 14 lies between the respective particles of the dispersoid 31 contained in the droplets 5′ to thereby prevent the respective particles of the dispersoid 31 from making direct contact with each other. Thus, aggregation and granulation between the particles of the dispersoid 31 are prevented. As a result, each of the fine particles derived from the dispersoid 31 is formed into each of the respective dry fine particles (toner particles) 8 in the dry fine particle producing step. Since the respective dry fine particles 8 obtained in this manner are not aggregated to each other, each fine particle 8 can have excellent mechanical strength. Further, since the respective dry fine particles 8 are not in the form of aggregation of the fine particles, it is possible to prevent generation of particles having void or irregular shape. Thus, it is possible to manufacture dry fine particles 8 having uniform shape and small particle size distribution in an effective manner. Furthermore, since it is not necessary to fuse or join fine particles derived from the dispersoid 31 at a high temperature to obtain sufficient mechanical strength, it is possible to prevent undesirable modification of a resin constituting the dry fine particles B.
Examples of a material constituting the antiaggregation agent 14 include fine particles constituted from an inorganic material such as metal oxide (e.g., silica, aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chrome oxide, titania, zinc oxide, alumina, magnetite), nitride (e.g., silicon nitride), carbide (e.g., silicon carbide), calcium sulfate, calcium carbonate, aliphatic metal salt and the like, fine particles constituted from an organic material such as acrylic resin, fluorine resin, polystyrene resin, polyester resin, aliphatic metal salt and the like, and fine particles constituted from a compound of these materials. These materials can be used singly or in combination of two or more of them.
Among these materials described above, it is preferable to use inorganic fine particles and more preferable to use inorganic fine particles constituted from silica and/or titanium oxide as a material constituting the antiaggregation agent 14. By using such inorganic fine particles as the antiaggregation agent 14, it is possible to prevent aggregation and granulation among the particles of the dispersoid 31 in the droplets 5′ more reliably, whereby making it possible to prevent undesirable affects on characteristics of finally obtained dry fine particles 8. Further, in a case where such an antiaggregation agent 14 is collected with a state that it adheres to the surface of the fine particle derived from the dispersoid 31, the antiaggregation agent 14 can serve as a part of external additives.
Further, it is preferred that a lyophilic treatment (hydrophilic treatment) is applied to the surface of the antiaggregation agent 14. This enables the antiaggregation agent 14 to be added to the dispersion liquid 3 (droplets 5′) described above easily. As a result, it is possible to prevent aggregation and granulation between the particles of the dispersoid 31 in the dispersion liquid 3 more reliably.
Examples of such a lyophilic treatment include a physical treatment such as a plasma treatment, a chemical treatment for hydroxylating the surface thereof, and the like.
The addition of the antiaggregation agent 14 may be carried out in a cooled area which is provided near the head portions M2′, for example. This makes it possible to add the antiaggregation agent 14 to the ejected dispersion liquid 3 before starting the substantial removal of the dispersion medium 32, thus granulation of the dispersoid 31 can be prevented more reliably. In this regard, the ambient temperature of this cooled area is preferably in the range of 10 to 35° C., and more preferably in the range of 20 to 25° C.
When Dc (μm) denotes the average particles size of the antiaggregation agent 14 and Dm (μm) denotes the average particles size of the dispersoid 31, it is preferred to satisfy the relation of 1×10−3≦Dc/Dm≦1×10−1, and more preferred to satisfy the relation of 5×10−3≦Dc/Dm≦2×10−2. If the average particle size of the particles of the antiaggregation agent 14 and the average particle size of the particles of the dispersoid 31 satisfy such a relation, it is possible to prevent aggregation between the particles of the dispersoid 31 in the droplets 5′ effectively, thus enabling respective particles derived from the dispersoid 31 to be formed into each of the dry fine particles 8 more reliably. Accordingly, it is possible to obtain dry fine particles 8 having uniform shape and excellent mechanical strength.
In particular, the average particle size of particles of the antiaggregation agent 14 is preferably in the range of 0.02 to 1.0 μm, and more preferably in the range of 0.02 to 0.5 μm. This makes it possible to prevent aggregation between the particles of the dispersoid 31 in the droplets 5′ effectively, thus enabling respective particles derived from the dispersoid 31 to be formed into each of the dry fine particles 8 more reliably. Accordingly, it is possible to obtain dry fine particles 8 having uniform shape and excellent mechanical strength.
It is preferred that the antiaggregation agent 14 is added such that the amount of the antiaggregation agent 14 contained in the finally obtained dry fine particles 8 is in the range of about 0.1 to 1.0 wt %, more preferred in the range of about 0.1 to 0.8 wt %. This makes it possible for the finally obtained dry fine particles 8 to exhibit their functions sufficiently while preventing aggregation between the particles of the dispersoid 31 contained in the droplets 5′ more reliably.
The dispersion medium removal portion M3′ is constructed from a tubular housing M31′. In order to maintain the inside of the dispersion medium removal portion M3′ at a temperature within a predetermined range, a heat source or a cooling source may be provided inside or outside the housing M31′, or the housing M31′ may be formed as a jacket having a passage of a heat medium or a cooling medium.
The temperature inside the housing M31′ is preferably equal to or lower than the glass transition point of the dispersoid 31. In other words, the dry fine particle producing step is preferably carried out under the temperature equal to or lower than the glass transition point of the dispersoid 31. According to this, since droplets of the dispersoid 31 are unlikely to stick with each other when forming the droplets 5′ of the dispersion liquid 3, it is possible to prevent bonding between dry fine particles 8 derived from the dispersoid 31.
In the dry fine particle production apparatus shown in
The pressure inside the housing M31′ is not limited to any specific value, but is preferably 150 kPa or less, more preferably in the range of 100 to 120 kPa, even more preferably in the range of 100 to 110 kPa. By setting the pressure inside the housing M31 to a value within the above range, it is possible to prevent effectively the dispersion medium 32 from being removed rapidly from the droplets 5′ (that is, boiling phenomenon of the droplets 5′). As a result, it is possible to produce the dry fine particles 8 effectively while preventing formation of defective dry fine particles 8 reliably. In this connection, it is to be noted that the pressure inside the housing M31′ may be substantially the same or different from each other at various positions thereof.
Further, voltage apply means M8′ for applying a voltage to the inner surface of the housing M31′ is connected to the housing M31′. By applying a voltage of the same polarity as the dry fine particles 8 (droplets 5′) to the inner surface of the housing M31′ by the use of the voltage apply means M8′, it is possible to obtain such effects as described below.
Generally, the dry fine particles 8 are positively or negatively charged. Therefore, when there is any charged matter of polarity opposite to that of the dry fine particles 8, the phenomenon in which the dry fine particles 8 are electrostatically attracted and adhere to the charged matter occurs. On the other hand, when there is any charged matter of the same polarity as that of the dry fine particles 8, the charged matter repels each another, thereby effectively preventing the phenomenon in which the dry fine particles 8 adhere to the surface of the charged matter. For this reason, by applying a voltage of the same polarity as that of the dry fine particles 8 to the side of the inner surface of the housing M31′, it is possible to prevent effectively the dry fine particles 8 from adhering to the inner surface of the housing M31′. As a result, it is also possible to prevent effectively the formation of defective dry fine particles 8 as well as to improve the collection efficiency of the dry fine particles 8.
The housing M31′ further includes a reduced-diameter portion M311′ in the bottom portion thereof. In the reduced-diameter portion M311′, the inner diameter thereof is reduced toward the lower side in
The dry fine particles 8 obtained in this way are collected in the collection portion M5′.
Normally, the thus obtained dry fine particles 8 have size and shape corresponding to each particle of the dispersoid 31. Therefore, a finally obtained liquid developer contains toner particles each having a relatively small diameter and a high degree of roundness (sphericity) and having small variations in shape and size of the respective particles.
Further, the thus obtained dry fine particles 8 may be particles obtained by removing the dispersion medium 32 of the water-based suspension 3, and in such a case a part of the dispersion medium may remain inside thereof.
Furthermore, the thus obtained dry fine particles 8 may be subjected to the dispersion step described later as they are or subjected to various treatments such as a heat treatment. This makes it possible to further enhance the mechanical strength (shape stability) of the dry fine particles and decrease the water content in the dry fine particles. Further, it is also possible to decrease the water content of the dry fine particles 8 as is the same as the above by subjecting the thus obtained dry fine particles to a treatment such as aeration, or placing the dry fine particles 8 in an atmosphere under reduced pressure.
Moreover, the thus obtained dry fine particles 8 may be subjected to other various treatments such as classification, and external addition and the like.
<Dispersing Step>
Next, the dry fine particles 8 obtained through the processes described above are dispersed into an insulation liquid 9 as toner particles (dispersing step). In this way, it is possible to obtain a liquid developer in which toner particles comprised of the dry fine particles 8 are dispersed in the insulation liquid 9. In this embodiment, the dry fine particles 8 taken out from the collection portion M5′ are put in a container M6′ which stores the insulation liquid 9 and then stirred to thereby obtain the liquid developer.
Various liquids may be used as the insulation liquid if the liquids have insulation properties, and a liquid used in a known liquid developer can be used. Specifically, a liquid having an electric resistance of 109 Ωcm or more at room temperature (20° C.) is preferably used, more preferably a liquid having an electric resistance of 1011 Ωcm or more is used, and even more preferably a liquid having an electric resistance of 1013 Ωcm or more is used.
Further, it is preferred that the insulation liquid has a dielectric constant of 3.5 or less.
More specifically, examples of the insulation liquid include a hydrocarbon saturation compound, silicone oil, vegetable oil and the like.
Examples of a hydrocarbon saturation compound include octane, isooctane, decane, isodecane, decaline, nonane, dodecane, isodecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoparaffin, normal paraffin and the like. Examples of silicone oil include dimethyl silicone, methylphenyl silicone, cyclic dimethyl polysiloxane, phlorosilicone and the like. Examples of vegetable oil include soybean oil, sunflower oil, rapeseed oil, ricinus oil, linseed oil and denatured oil of these oils. These materials can be used singly or in combination of two or more of them.
Examples of a specific commercially-available product for the insulation liquid include ISOPAR G, H, L and M (product name of Exxon Mobil Corporation), NORPAR 12 (product name of Exxon Mobil Corporation), SHELLSOL 70, SHELLSOL 71 (“SHELLSOL” is a product name of Shell Oil), Amsco OMS, Amsco 460 solvent (“Amsco” is a product name of Spirit Co., Ltd.) and the like as a petroleum hydrocarbon saturation compound and SH-200 (product name of Dow Corning Tray Co., Ltd.), KF-96 (product name of Shin-Etsu Chemical Co., Ltd.), L-45 (product name of Nippon Unicar Company Limited) and the like as silicone oil.
By the use of the insulation liquid as described above, the toner particles in the obtained liquid developer can have excellent charge properties.
Further, the insulation liquid may contain a well-known charge adjustment agent such as a metal soup including metal salt of octylic acid, metal salt of naphthenic acid and the like, a chelate compound containing titanium alkoxide and aluminum, and the like or may contain additives such as surfactant including dodecyltrimethylammonium chloride, alkyl benzene sulfonate and the like, a fatty acid ester compound and its derivatives, solid fine particles which are insoluble to the insulation liquid including silica fine particles, alumina fine particles, titania fine particles and the like for the purpose of improving the dispersibility of the toner particles, adjusting the charge of the toner particles, adjusting the viscosity of the liquid developer and the like.
Furthermore, the volume resistivity of the insulation liquid is preferably in the range of 1×109 to 1×1018 Ω·cm, and more preferably in the range of 1×1011 to 1×1018 Ω·cm. This makes it possible for the toner particles in the obtained liquid developer to have excellent charge properties.
Moreover, the viscosity of the insulation liquid is not particularly limited to any specific value, but is preferably in the range of 10 to 10000 (mPa·s), and even more preferably in the range of 50 to 1000 (mPa·s), for example. This makes it possible to make the dispersibility of the dry fine particles 8 excellent while making the handleability of the liquid developer when manufacturing and using it excellent.
Various methods can be used for dispersing the dry fine particles 8 into the insulation liquid. However, it is preferred that the dispersion is carried out by adding the dry fine particles 8 into the insulation liquid that is being stirred. This makes it possible to prevent undesirable aggregation of the dry fine particles 8 in preparing the liquid developer, so that the obtained liquid developer can keep a satisfactory dispersing state of the toner particles 8 for a long period of time in a stable manner.
<Liquid Developer>
The average particle size (diameter) of the toner particles in the liquid developer obtained as described above is preferably in the range of 0.1 to 5 μm, more preferably in the range of 0.4 to 4 μm, and even more preferably in the range of 0.5 to 3 μm. If the average particle size of the toner particles is within the above range, it is possible to make resolution of a toner image formed from the liquid developer (toner) sufficiently high with small variations in properties of the toner particles such as charge properties and fixing properties. Further, the liquid developer can have especially high reliability as a whole thereof.
Further, it is preferred that a standard deviation of particle size among the toner particles which constitute the liquid developer is 3.0 μm or less, more preferably in the range of 0.1 to 2.0 μm, and even more preferably in the range of 0.1 to 1.0 μm. When the standard deviation of particle size lies within the above range, variations in charge properties, fixing properties, etc can be made especially small, thereby further improving the reliability of the liquid developer.
Furthermore, it is also preferred that an average roundness R represented by the following formula (I) is 0.85 or higher, more preferably in the range of 0.90 to 0.99, and even more preferably 0.95 to 0.99.
R=L
0
/L
1 (I)
wherein L1 (μm) represents the circumference of projected image of a toner particle that is a subject of measurement, and L0 (μm) represents the circumference of a perfect circle (a geometrically perfect circle) having the same area as that of the projected image of the toner particle that is a subject of measurement.
When the average roundness R of the toner particles is within the above range, the transfer efficiency and the mechanical strength of the toner particles can be made excellent while the particle size of the toner particles are made sufficiently small.
In this case, it is preferred that a standard deviation of the average roundness among the toner particles is 0.15 or less, more preferably in the range of 0.001 to 0.10, and even more preferably 0.001 to 0.05. When the standard deviation of average roundness among the toner particles lies within the above range, variations in charge properties, fixing properties, etc can be made especially small, thereby further improving the reliability of the liquid developer.
Further, the amount of the toner particles (dry fine particles 8) contained in the liquid developer is preferably in the range of 5 to 50 wt % or less, and more preferably in the range of 10 to 35 wt %.
This assures sufficient image density and stable dispersion of the toner particles in the liquid developer, whereby making it possible to obtain such an effect that image quality remains stable for a long period of time.
As described above, in the present invention, it is possible to obtain dry fine particles 8 each of which is derived from one particle of the dispersoid 31 in the dry fine particle producing step.
Therefore, by simply forming the dispersoid 31 so that particles of the dispersoid 31 have uniform shape and small particle size distribution using an emulsion as the water-based dispersion liquid (water-based suspension 3), the dry fine particles 8 to be obtained can also have uniform shape and small particles size distribution.
Namely, it is possible to manufacture a liquid developer in which toner particles (dry fine particles 8) having uniform shape and small particle size distribution are dispersed effectively (with good productivity).
In particular, since the water-based dispersion liquid (water-based suspension 3) is used, it is possible to manufacture a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed by a method which is harmless to the environment. Further, since the dry fine particles B contain water, dispersibility thereof in the insulation liquid 9 becomes excellent. As a result, the obtained liquid developer has excellent storage stability.
In this regard, it is to be noted that in the present invention the toner particles may be obtained in the form of aggregation of a plurality of particles of the dispersoid 31. In such a case, even if there are variations in size and shape of the dispersoid 31, the total amount of the dispersoid 31 contained in the respective droplets 5′ can be made to be substantially the same among the droplets 5′. Consequently, even in a case where there are variations in size and shape of the dispersoid 31, it is possible to uniform size and shape of the toner particles. As a result, it is possible to manufacture a liquid developer in which toner particles having uniform shape and small particle size distribution are dispersed effectively (with good productivity).
Next, a description will be made with regard to preferred embodiments of an image forming apparatus to which the liquid developer of the present invention can be applied.
A developer P10 has an application roller P12 apart of which is immersed in a developer container P11 and a development roller P13. The application roller P12 is formed form, for example, a gravure roller made of stainless steel or the like, which rotates with opposing to the development roller P13. On the surface of the application roller P12, a liquid developer application layer P14 is formed, and the thickness of the layer is adapted to be kept constant by a metering blade P15.
Further, a liquid developer is transferred from the application roller P12 to the development roller P13. The development roller P13 is constructed from a metallic roller core member P16 made from stainless steel or the like, a low hardness silicone rubber layer provided on the metallic core member P16, and a resin layer made of a conductive PFA (polytetrafluoroetylene-perfluorovinylether copolymer) formed on the silicone rubber layer. The development roller P13 is adapted to rotate at the same speed as the photoreceptor P2 to transfer the liquid developer to a latent image section. A part of the liquid developer remaining on the development roller P13 after it has been transferred to the photoreceptor P2 is removed by a development roller cleaning blade P17 and then collected in the developer container P11.
Further, after a toner image is transferred from the photoreceptor to an intermediate transfer roller P18, the photoreceptor is discharged with discharging light P21, and a toner which has not been transferred and remains on the photoreceptor P2 is removed by a cleaning blade P22 made of a urethane rubber or the like.
In a similar manner, a toner which is not transferred and remains on the intermediate transfer roller P18 after the toner image has been transferred to an information recording medium P20 is removed by a cleaning blade P23 made of a urethane rubber or the like.
The toner image formed on the photoreceptor P2 is transferred to the intermediate transfer roller P18. Then, a transfer current is supplied to a secondary transfer roller P19, and the toner image transferred on the intermediate roller P18 is transferred onto the information recording medium P20 such as a paper which passes between the intermediate transfer rollers P18 and the secondary transfer roller P19. Thereafter, the toner image on the information recording medium P20 is fixed thereto using a fixing unit shown in
Preferably, between the development roller P13 and the photoreceptor P2, there is formed a gap whose width is 200 μm to 800 μm, and an AC voltage having 500 to 3000 Vpp and a frequency of 50 to 3000 Hz which is superimposed on a DC voltage of 200 to 800 V is applied across the development roller P13 and the photoreceptor P2. Other structures of this non-contact type image forming apparatus are the same as those of the contact type image forming apparatus shown in
In the foregoing, the description was made with regard to the image formation by the embodiments shown in
As shown in this figure, the fixing unit F40 includes the heat fixing roller (hereinafter, also referred to as “heat fuser roller”) F1, the pressure roller F2, the heat resistant belt F3, the belt tension member F4, and the cleaning member F6.
The heat fixing roller F1 has the roller base F1b formed from a pipe member having an outer diameter of about 25 mm and a thickness of about 0.7 mm. The roller base F1b is coated with the elastic body F1c having a thickness of about 0.4 mm. Further, inside the roller base F1b, two halogen lamps F1a which act as a heat source are provided. Each of the halogen lamps F1a has a tubular shape and an output of 1,050W. The heat fixing roller F1 is rotatable in an anticlockwise direction shown by the arrow in
As described above, since each of the heat fixing roller F1 and the pressure roller F2 is formed to have a small outer diameter of about 25 mm, there is less possibility that a sheet material F5 after the fixing process is wound around the heat fixing roller F1 or the heat resistant belt F3, and thus it is not necessary to have any means for peeling off the sheet material F5 forcibly. Further, since the PFA layer having a thickness of about 30 μm is provided on the surface of the elastic member F1c of the heat fixing roller F1, the strength thereof is improved. By providing such a PFA layer, both the elastic members F1c and F2c are elastically deformed substantially uniformly though their thicknesses are different from each other, thereby forming a so-called horizontal nip. Further, there is no difference between the circumferential velocity of the heat fixing roller F1 and the conveying speed of the heat resistant belt F3 or the sheet material F5. For these reasons, it is possible to perform an extremely stable image fixation.
Further, as described above, the two halogen lamps F1a, F1a which act as a heat source are provided inside the heat fixing roller F1. These halogen lamps F1a, F1a are provided with heating elements, respectively, which are arranged at different positions. With this arrangement, by selectively lighting up any one or both of the halogen lamps F1a, F1a, it is possible to easily carry out a temperature control under different conditions such as a case where a wide sheet material is used or a narrow sheet material is used, and/or a case where a fixing nip part at which the heat resistant belt F3 is wound around the heat fixing roller F1 is to be heated or a part at which the belt tension member F4 is in slidably contact with the heat fixing roller F1 is to be heated.
The heat resistant belt F3 is a ring-shaped endless belt, and it is wound around the outer circumferences of the pressure roller F2 and the belt tension member F4 so that it can be moved with being held between the heat fixing roller F1 and the pressure roller F2 in a pressed state. The heat resistant belt F3 is formed from a seamless tube having a thickness of 0.03 mm or more. Further, the seamless tube has a two layered structure in which its surface (which is the surface thereof that makes contact with the sheet material F5) is formed of PFA, and the opposite surface thereof (that is, the surface thereof that makes contact with the pressure roller F2 and the belt tension member F4) is formed of polyimide. However, the structure of the heat resistant belt F3 is not limited to the structure described above, and it may be formed from other materials. Examples of tubes formed from other materials include a metallic tube such as a stainless tube or a nickel electrocasting tube, a heat-resistance resin tube such as a silicone tube, and the like.
The belt tension member F4 is disposed on the upstream side of the fixing nip part between the heat fixing roller F1 and the pressure roller F2 in the sheet material F5 conveying direction. Further, the belt tension member F4 is pivotally disposed about the rotation shaft F2a of the pressure roller F2 so as to be movable along the arrow P. The belt tension member F4 is constructed so that the heat resistant belt F3 is extended with tension in the tangential direction of the heat fixing roller F1 in a state that the sheet material P5 does not pass through the fixing nip part. When the fixing pressure is large at an initial position where the sheet material F5 enters the fixing nip part, there is a case that the sheet material F5 can not enter the fixing nip part smoothly and thereby fixation is performed in a state that a tip part of the sheet material F5 is folded. However, in this embodiment, the belt tension member F4 is provided so that the heat resistant belt F3 is extended with tension in the tangential direction of the heat fixing roller F1 as described above, there is formed an introducing portion for smoothly introducing the sheet material F5, so that the sheet material F5 can be introduced into the fixing nip part in a stable manner.
The belt tension member F4 is a roughly semi-circular member for slidably guiding the heat resistant belt F3 (the heat resistant belt F3 slidably moves on the belt tension member F4). The belt tension member F4 is fitted into the inside of the heat resistant belt F3 so as to impart tension f to the heat resistant belt F3 in cooperation with the pressure roller F2. The belt tension member F4 is arranged at a position where a nip part is formed by pressing a part of the heat resistant belt F3 toward the heat fixing roller F1 over the tangential line L on the pressing portion at which the heat fixing roller F1 is pressed against the pressure roller F2. The protruding wall F4a is formed on any one or both of the end surfaces of the belt tension member F4 which are located in the axial direction thereof. The protruding wall F4a is provided for restricting the heat resistant belt F3 from being off to the side by abutment thereto in a case that the heat resistant belt F3 is deviated in any one of the sides. Further, a spring F9 is provided between the frame and an end portion of the protruding wall F4a which is located at an opposite side from the heat fixing roller F1 so as to slightly press the protruding wall F4a of the belt tension member F4 against the heat fixing roller F1. In this way, the belt tension member F4 is positioned with respect to the heat fixing roll F1 in slidably contact with the heat fixing roller F1.
In order to stably drive the heat resistant belt F3 by the pressure roller F2 in a state that the heat resistant belt F3 is wound around the pressure roller F2 and the belt tension member F4, the frictional coefficient between the pressure roll F2 and the heat resistant belt F3 is set to be larger than the frictional coefficient between the belt tension member F4 and the heat resistant belt F3. However, there is a case that these frictional coefficients become unstable due to enter of foreign substances between the heat resistant belt F3 and the pressure roller F2 or between the heat resistant belt F3 and the belt tension member F4, or due to the abrasion of the contacting part between the heat resistant belt F3 and the pressure roller F2 or the belt tension member F4.
Accordingly, the winding angle of the heat resistant belt F3 with respect to the belt tension member F4 is set to be smaller than the winding angle of the heat resistant belt F3 with respect to the pressure roller F2, and the diameter of the belt tension member F4 is set to be smaller than the diameter of the pressure roller F2. With this structure, the distance that the heat resistant belt F3 moves on the belt tension member F4 becomes short so that unstable factors due to deterioration with the elapse of time and disturbance can be avoided or reduced. As a result, it is possible to drive the heat resistant belt F3 with the pressure roller F2 in a stable manner.
The cleaning member F6 is disposed between the pressure roller F2 and the belt tension member F4. The cleaning member F6 is provided for cleaning foreign substances or wear debris on the inner surface of the heat resistant belt F3 by slidably contacting with the inner surface of the heat resistant belt F3. By cleaning the foreign substances and wear debris in this way, it is possible to refresh the heat resistant belt F3 to eliminate the unstable factors on the frictional coefficients described above. Further, the belt tension member F4 is formed with a concave portion F4f, and this concave portion F4f is preferably used for collecting the foreign substances or wear debris eliminated from the heat resistant belt F3.
A position where the belt tension member F4 is slightly pressed against the heat fixing roller F1 is set as a nip beginning position and a position where the pressure roller F2 is pressed against the heat fixing roller F1 is set as a nip ending position. The sheet material F5 enters the fixing nip part from the nip beginning position to passes through between the heat resistant belt F3 and the heat fixing roller F1, and then fed out from the nip ending position, and during these processes an unfixed toner image F5a is fixed on the sheet material F5 and then the sheet material F5 is discharged along the tangential line L of the pressing part between the heat fixing roller F1 and the pressing roller F2.
In the foregoing, the present invention was described based on the preferred embodiments, but the present invention is not limited to these embodiments.
For example, each element constituting the liquid developer production apparatus may be replaced with other element that exhibits the same or similar function, or additional element may be added to the apparatus.
Further, the liquid developer of the present invention is not limited to the one that is used in the image forming apparatus as described above.
Furthermore, as shown in
As described above, by the use of the head portion as shown in
Further, by the use of the head portions as shown in
In this regard, although in the head portions as shown in
Further, head portions as shown in
Furthermore, although in each of the embodiments described above the constituent material of the toner particles is contained in a dispersoid as a solid component thereof, but at least a part of the constituent material of the toner particles may be contained in a dispersion medium.
Further, although each of the embodiments described above has a structure in which the dispersion liquid (water-based suspension) is intermittently ejected from the head portions by the use of a piezoelectric pulse, the dispersion liquid may be ejected (sprayed) by other methods. Examples of such other methods include a spray dry method, the so-called Bubble Jet method (“Bubble Jet” is a trademark) and a method disclosed in Japanese Patent Application No. 2002-321889, and the like. In the method disclosed in the Japanese Patent Application, a dispersion liquid is ejected in the form of droplets using a specific nozzle in which a dispersion liquid is transformed into a thin laminar flow by thinly expanding the dispersion liquid by forcing it onto a smooth flat surface using a gas flow, and then separating the thin laminar flow from the flat smooth surface to eject it in the form of droplets. The spray dry method is a method which obtains droplets by ejecting (spraying) a liquid (a dispersion liquid) using high pressure gas. Further, as an example of a method using the Bubble Jet method (“Bubble Jet” is a trademark) a method disclosed in Japanese Patent Application No. 2002-169348 and the like can be mentioned. Namely, the dispersion liquid may be ejected (sprayed) by a method in which a dispersion liquid is intermittently ejected from a head portion using a volume change of gas.
Further, although the toner particles are obtained so that the respective toner particles has size and shape corresponding to each particle of the dispersoid in the water-based suspension in the first embodiment described above, the toner particles may be formed from aggregates which are formed by aggregation (bonding) between fine particles each corresponding to a plurality of particles of a dispersoid in the water-based suspension (water-based dispersion liquid). In such as case, since the adjustment range of the amount of water is large, the amount of water can be adjusted easily. In addition, it is possible to deal with water retention of a resin which does not have any functional group of water adsorption easily.
Furthermore, the method for preparing the water-based dispersion liquid as a spray liquid is not limited to the one described above. For example, the water-based suspension as a spray liquid may be obtained in the following manner. Namely, a dispersion liquid (suspension) in which a dispersoid in a solid state is dispersed is heated such that the dispersoid once becomes a liquid state to obtain a water-based emulsion, and the water-based emulsion is then cooled to thereby obtain the water-based suspension as a spray liquid. Further, the water-based emulsion may be used as a spray liquid as it is without being changed to the suspension. Alternatively, even in a case where the suspension is used as a spray liquid, the suspension may be prepared without going through the emulsion (water-based emulsion). For example, the suspension which is obtained by dispersing the ground kneaded material into the water-based liquid as described above may be used as a spray liquid. Further, the water-based dispersion liquid as a spray liquid may contain fine particles produced by an emulsion polymerization method as a dispersoid. This makes it possible for the particles to contain the most appropriate amount of water therein while maintaining sufficient particle strength. Additionally, the particles having stable size can be obtained.
Moreover, formation of the toner particles (dry fine particles) may be carried out without using the ejection of the water-based dispersion liquid (water-based suspension). For example, it is possible to obtain dry fine particles by filtering the water-based suspension to filter out fine particles corresponding to a dispersoid.
Moreover, in the second embodiment, dry fine particles each having shape and size corresponding to each particle of the dispersoid contained in the water-based suspension are obtained. However, the dry fine particles of the present invention may be formed from aggregates which are formed by aggregating (or bonding) a plurality of particles of a dispersoid contained in the water-based suspension.
Moreover, in the second embodiment, a water-based emulsion is prepared using ground particles obtained by grinding the kneaded material, but such a grinding step of the kneaded material may be omitted.
Moreover, a method for preparing the water-based emulsion and the water-based suspension is not limited to the method described above. For example, it is possible to obtain a water-based emulsion by heating a dispersion liquid in which a solid state dispersoid is dispersed to transform the dispersoid into a liquid state, and then by cooling the water-based to obtain a water-based suspension.
Moreover, in the second embodiment described above, once after a water-based suspension is obtained using a water-based emulsion, dry fine particles are produced using the water-based suspension. However, the dry fine particles may be produced directly from the water-based emulsion without using the water-based suspension. For example, it is possible to obtain dry fine particles by ejecting the water-based emulsion in the form of droplets, and then removing the dispersion medium together with the solvent contained in the dispersoid from the droplets.
First, 80 parts by weight of a polyester resin (glass transition point was 58° C.; softening point was 120° C.; amount of water absorption was 0.2 wt %) which is a self-dispersible type resin having a side chain of a plurality of —SO3− groups (sulfone acid Na group) and 20 parts by weight of a cyanogen-based pigment (“Pigment Blue 15:3”, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) as a coloring agent were prepared. The self-dispersible type resin contains 0.1 mol of —SO3− group in 100 g of the self-dispersible type resin.
These components were mixed using a 20 L type Henschel mixer to obtain a material for producing toner particles.
Next, the material (mixture) was kneaded using a biaxial kneader-extruder shown in
The entire length of a process section of the biaxial kneader-extruder was 160 cm.
Further, the material temperature in the process section was set to be 125 to 135° C.
Furthermore, the rotational speed of the screw was 120 rpm, and the speed for feeding the material into the kneader-extruder was 20 kg/hour.
Under these conditions, a time required for the material to pass through the process section was about 4 minutes.
The kneading was carried out with deairing the inside of the process section by driving a vacuum pump connected to the process section through a deairing port.
The material (kneaded material) kneaded in the process section was extruded outside the biaxial kneader-extruder from the head portion. The temperature of the kneaded material at the head portion was adjusted to be 130° C.
The kneaded material extruded from the extruding port of the biaxial kneader-extruder was cooled by a cooling machine as shown in
The cooling rate of the kneaded material was −9° C./sec. Further, a time required for the completion of the cooling process from the end of the kneading process was 10 seconds.
The kneaded material cooled as described above was coarsely ground to be formed into powder having an average particle size of 1.5 mm. The coarse grinding of the kneaded material was carried out using a hammer mil.
Next, 250 parts by weight of toluene was added to 100 parts by weight of the coarse kneaded material, and then it was subjected to a treatment using an ultrasound homogenizer (output: 400 μA) for 1 hour to obtain a solution in which the self-dispersible type resin of the kneaded material was dissolved. In the solution, the pigment was finely dispersed homogeneously.
Further, a water-based liquid comprised of 700 parts by weight of ion-exchanged water was prepared.
The water-based liquid was stirred with a homomixer (PRIMIX Corporation) with the number of stirring being adjusted.
The above-mentioned solution (that is, the toluene solution of the kneaded material) was dropped in the water-based liquid which is being stirred. In this way, a water-based emulsion in which a dispersoid comprised of particles having an average particle size of 3 μm was homogeneously dispersed was obtained.
Thereafter, the toluene in the water-based emulsion was removed under the conditions in which a temperature was 100° C. and an ambience pressure was 80 kPa, and then it was cooled to room temperature to thereby obtain a water-based suspension in which solid fine particles were dispersed. In the thus obtained water-based suspension, substantially no toluene remained. The concentration of the solid component (dispersoid) of the thus obtained water-based suspension was 30.5 wt %. Further, the average particle size of the particles of the dispersoid (solid fine particles) dispersed in the suspension was 1.6 μm. The measurement of the average particle size was carried out using a laser diffraction/scattering type particle size distribution measurement apparatus (“LA-920”, a product name of HORIBA Ltd.).
The thus obtained suspension was put into a water-based suspension supply section of a toner particle production apparatus shown in
The water-based suspension in the water-based suspension supply section was being stirred with a stirring means, and it was supplied to head portions by a metering pump so that the suspension was ejected (discharged) to a dispersion medium removal section through ejection portions. Each ejection portion was formed into a circular opening having a diameter of 25 μm. The head portions were of the type that a hydrophobic treatment was made around the ejection portions thereof with a fluorine resin (polytetrafluoroethylene) coating. Further, the temperature of the water-based suspension in the water-based suspension supply section was adjusted to be 35° C.
The ejection of the water-based suspension was carried out under the conditions that the temperature of the dispersion liquid in the head portions was 35° C., the frequency of vibration of each piezoelectric element was 10 kHz, the initial velocity of the dispersion liquid ejected from the ejection portions was 3 m/sec, and the size of one droplet ejected from each head portion was 2 μl (the diameter of the droplet was 15 μm). Further, the ejection of the water-based suspension was carried out so that the ejection timing of the water-based suspension was changed at least in the adjacent head portions in the plural head portions.
Further, when the water-based suspension was ejected, air was also ejected from the gas injection openings downwardly in a vertical direction, wherein the temperature of the air was 35° C., the humidity of the air was 27% RH, and the flow rate of the air was 3 m/sec. Further, the temperature of the inside of the housing (that is, the ambient temperature) was set to be 40° C., the pressure of the inside of the housing was about 103 kPa, and the length of the dispersion medium removal section (in the direction of conveying the dispersoid) was 1.5 m.
Furthermore, a voltage was applied to a part of the housing which constitutes the dispersion medium removal section so that an electrical potential at the side of the inner surface thereof was −100 V, thereby preventing the water-based suspension (toner particles) from adhering to the inner surface of the housing.
Then, the dispersion medium was removed from the ejected water-based suspension in the dispersion medium removal section to thereby obtain a plurality of toner particles each having shape and size corresponding to each particle of the dispersoid. The thus obtained toner particles were introduced into an insulation liquid storing section which stores ISOPAR H (product of Exxon Mobil Corporation) as an insulation liquid and stirred with a stirring means to thereby obtain a liquid developer. The water content of the toner particles formed in the dispersion medium removal section was 1.58 wt %. Further, the electrical resistance of the insulation liquid (ISOPAR H) at room temperature (20° C.) was 1014 Ωcm and the dielectric constant of the insulation liquid was 2.3. Further, the amount of the toner particles contained in the liquid developer was 20 wt %.
In each of Examples 2 to 4, a liquid developer was prepared in the same manner as in the Example 1 excepting that the average particle size of the particles of the dispersoid, the amount thereof and the water content of the toner particles were changed as shown in Table 1 by changing the amount of toluene in preparing the toluene solution of the kneaded material, the stirring condition of the water-based liquid in preparing the water-based emulsion, the rate of dropping the solution, the temperature of the water-based suspension in the head portions, the temperature of the air ejected from the gas injection openings, respectively.
A liquid developer was prepared in the same manner as in the Example 1 excepting that a polyester resin having a side chain of a plurality of —PO4− groups (softening point thereof was 115° C.) was used as a self-dispersible type resin in preparing the kneaded material, The self-dispersible type resin had 0.1 mol of —PO4− group in 100 g of the self-dispersible type resin.
A liquid developer was prepared in the same manner as in the Example 1 excepting that an epoxy resin (which is not a self-dispersible type resin) was used instead of the self-dispersible type resin, and 0.5 parts by weight of dodecyltrimethylammonium chloride as a dispersant was used in the preparation of the material for producing a toner particles (kneaded material).
A water-based suspension was prepared by an emulsion polymerization method described below.
A mixed solution comprised of 100 g of octadecylmethacrylate, 150 g of toluene, and 50 g of isopropanol was heated to a temperature of 75° C. with being stirred in a nitrogen gas stream. Then, 30 g of 2,2′-azobis (4-cyanovaleric acid) was added thereto to make reaction for 8 hours, and after being cooled, it was settled out in 2 liter of methanol so that white powder was aggregated and then it was dried. Then, a mixture comprised of 50 g of the thus obtained white powder, 3.3 g of vinyl acetate, 0.2 g of hydroquinone, and 100 g of toluene was heated to a temperature of 40° C. to make reaction for 3 hours. Then, it was heated to 70° C. and 3.8×10−3 ml of 100% sulfuric acid was added thereto to make reaction for 10 hours. Thereafter, it was cooled to a temperature of 25° C., and 0.02 g of sodium acetate trihyddrate was added thereto. Thereafter, it was stirred for 30 minutes, and then it was settled out in 1 liter of methanol to aggregate, and then it was dried, to thereby obtain a resin for stabilizing dispersion.
Next, a mixed solution comprised of 12 g of the thus obtained resin for stabilizing dispersion, 100 g of vinyl acetate, 1.0 g of octadecylmethacrylate, 384 g of ISOPAR H was heated to a temperature of 70° C. with being stirred in a nitride gas stream. Then, 0.8 g of 2,2-azobis (isovalernitryl) was added to make reaction for 6 hours. After 20 minutes of addition of an initiator, white turbidity was caused, and then the reaction temperature was raised to 88° C. Thereafter, the temperature was raised to 100° C., and then it was being stirred for 2 hours to distil away the unreacted vinyl acetate. After being cooled, it was passed through a nylon cloth of 200 meshes to thereby obtain white latex particles. The average particle size of the white latex particles was 0.3 μm.
Then, 30 g of the white latex particles were dispersed in water.
A liquid developer was prepared in the same manner as in the Example 1 excepting that the thus obtained water-based suspension was used as a spray liquid.
A dispersion liquid in which fine particles mainly composed of a resin material were dispersed in an insulation liquid was obtained in the same manner as in the Example 1 excepting that the toluene solution prepared in the Example 1 was used as a spray liquid instead of the water-based suspension.
Then, the dispersion liquid was placed under the atmosphere of which temperature was 100° C. and ambience pressure was 80 kPa with being stirred to thereby obtain a liquid developer from which toluene was removed.
First, in the same manner as in the Example 1, a coarsely ground kneaded material having an average particle size of 1.5 mm was obtained.
Then, the coarsely ground kneaded material was finely ground by a jet mill to thereby obtain fine particles having an average particle size of 5.2 μm.
Then, 20 parts by weight of the thus obtained finely ground material was dispersed into the mixture of 100 parts by weight of ISOPAR H (product of Exxon Mobil Corporation) and 1 part by weight of a dispersant (dodecyltrimethylammonium chloride) using a ball mill to thereby obtain a liquid developer.
First, in the same manner as in the Example 6, a coarsely ground kneaded material having an average particle size of 1.5 mm was obtained.
Then, the coarsely ground kneaded material was finely ground by a jet mill to thereby obtain fine particles having an average particle size of 5.4 μm.
Then, 20 parts by weight of the thus obtained finely ground material was dispersed into the mixture of 100 parts by weight of ISOPAR H (product of Exxon Mobil Corporation) and 1 part by weight of a dispersant (dodecyltrimethylammonium chloride) using a ball mill to thereby obtain a liquid developer.
First, ISOPAR H (product of Exxon Mobil Corporation) was prepared as an electrical insulation liquid. The electrical resistance of the electrical insulation liquid at room temperature (20° C.) was 1014 Ωcm and the dielectric constant thereof was 2.3.
A mixed solution comprised of 100 g of octadecylmethacrylate, 150 g of toluene, and 50 g of isopropanol was heated to a temperature of 75° C. with being stirred in a nitrogen gas stream. Then, 30 g of 2,2′-azobis (4-cyanovaleric acid) was added thereto to make reaction for 8 hours, and after being cooled, it was settled out in 2 liter of methanol so that white powder was aggregated and then it was dried. Then, a mixture comprised of 50 g of the thus obtained white powder, 3.3 g of vinyl acetate, 0.2 g of hydroquinone, and 100 g of toluene was heated to a temperature of 40° C. to make reaction for 2 hours. Then, it was heated to 70° C. and 3.8×10−3 ml of 100% sulfuric acid was added thereto to made reaction for 10 hours. Thereafter, it was cooled to a temperature of 25° C., and 0.02 g of sodium acetate trihydrate was added thereto. Thereafter, it was stirred for 30 minutes, and then it was settled out in 1 liter of methanol to aggregate, and then it was dried, to thereby obtain a resin for stabilizing dispersion.
Next, a mixed solution comprised of 12 g of the thus obtained resin for stabilizing dispersion, 100 g of vinyl acetate, 1.0 g of octadecylmethacrylate, 384 g of ISOPAR H was heated to a temperature of 70° C. with being stirred in a nitride gas stream. Then, 0.8 g of 2,2-azobis (isovalernitryl) was added to make reaction for 6 hours. After 20 minutes of addition of an initiator, white turbidity was caused, and then the reaction temperature was raised to 88° C. Thereafter, the temperature was raised to 100° C., and then it was being stirred for 2 hours to distil away the unreacted vinyl acetate. After being cooled, it was diluted with ISOPAR to thereby obtain a liquid developer.
80 parts by weight of a partially saponified resin of ethylene-vinyl acetate copolymer (“Dumiran C-2280”, product name of Takeda Pharmaceutical Company Limited) was dissolved in 200 parts by weight 2-ethylhexanoate ester (“EXCEPARL HO”, product name of KAO CORPORATION) with being heated. Then, it was mixed with 20 parts by weight of a cyanogen-based pigment (“Pigment Blue 15:3”, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) and then they were dispersed using a three roll mill (manufactured by INOUE MFG., INC.) heated at a temperature of 80° C. Then, 70 parts by weight of ISOPAR H (Exxon Mobil Corporation) was added to 30 parts by weight of the thus obtained pigment dispersed liquid which has been heated at 40° C. with being stirred and mixed using a homogenizer at 7000 rpm. Then, it was further stirred and mixed using a homogenizer at 7000 rpm for 30 minutes. Thereafter, a solution in which 1 part by weight of salicylic acid aluminum salt (“Bontron E-88”, product name of Orient Chemical Industries, Ltd.) was dissolved in 100 parts by weight of ISOPAR H was added thereto with being stirred and dispersed using a homogenizer at 7000 rpm. Then, it was further stirred and dispersed using a homogenizer at 7000 rpm for 30 minutes to thereby obtain a liquid developer.
The conditions for producing the liquid developers of the Examples 1 to 7 and the Comparative Examples 1 to 5 are shown in the following Table 1 with the evaluation concerning the ejection stability of the droplets of the dispersion liquid. In Table 1, the evaluation concerning the ejection stability of the droplets of the dispersion liquid was made as follows. Namely, in the case where droplets whose variations in the average particle size was 20% or less could be ejected stably for more than 6 hours, “A” evaluation was made, in the case where variations in the average particle size was in the range of 20% to 40% within 6 hours from the start of the ejection of the dispersion liquid, “B” evaluation was made, and in the case where variations in the average particle size was 40% or more within 6 hours from the start of the ejection of the dispersion liquid, “C” evaluation was made.
As shown in Table 1, in the present invention the ejection of droplets could be carried out stably. In particular, although no dispersant was used in the Examples 1 to 5, the ejection of droplets could be carried out in a particularly stable manner.
For each of the respective liquid developers obtained as described above, fixing strength, transparency, and storage stability were evaluated.
(2.1) Fixing Strength
By using the image forming apparatus shown in
Thereafter, after it was confirmed as to whether or not a non-offset area was present, the fixed image on each of the papers was rubbed out twice using a sand eraser (“LION 261-11”, product of LION OFFICE PRODUCTS CORP.) with a pressure loading of 1.0 kgf/cm2. Then, the residual rate of the image density of each recording paper was measured by a calorimeter “X-Rite model 404” (manufactured by X-Rite Incorporated), and the measurement results were evaluated according to the following three criteria.
A: Residual rate of the image density was 90% or higher.
B: Residual rate of the image density was 70% or higher but lower than 90%.
C: Residual rate of the image density was lower than 70%.
(2.2) Transparency
By using the image forming apparatus shown in
Then, the HAZE value was measured by a haze meter (“MODEL 1001DP”, product of Nippon Denshoku Industries Co., Ltd.), and the measurement results were evaluated according to the following four criteria. In this regard, the HAZE value is a value which is calculated by dividing diffuse transmittance by total transmittance. The HAZE value becomes smaller if the dispersibility of the respective components of the toner particles is better.
A: HAZE value was less than 47.
B: HAZE value was more than 47, but less than 50.
C: HAZE value was more than 50, but less than 53.
D: HAZE value was more than 53.
(2.3) Storage Stability
The liquid developers obtained in the Examples and the Comparative Examples were being placed under the atmosphere of which temperature was in the range of 15 to 20° C. for 6 months. Thereafter, the toner particles in the liquid developers were observed with naked eyes, and the observation results were evaluated by the following four criteria.
A: Aggregation and settling of toner particles were not observed at all.
B: Aggregation and settling of toner particles were scarcely observed.
C: Aggregation and settling of toner particles were slightly observed.
D: Aggregation and settling of toner particles were clearly observed.
These results are shown in the following Table 2 together with the water content, the average particle size based on volume of particles, and the standard deviation in the particle size of the toner particles.
As shown in Table 2, the liquid developers of the present invention had excellent fixing strength, excellent transparency, and excellent storage stability. In contrast, in the liquid developers of the Comparative Examples, satisfactory results could not be obtained.
Further, liquid developers which are the same as those described above were produced excepting that as a coloring agent a pigment red 122, a pigment yellow 180, and a carbon black (“Printex L”, product name of Degussa AG) were used instead of a cyanogen-based pigment, and they were evaluated in the same manner as described above. As a result, substantially the same results could be obtained.
Furthermore, liquid developers which are the same as those described above were produced using a different liquid developer production apparatus in which the structure of the head portions was changed from the structure shown in
First, 80 parts by weight of a polyester resin having a side chain of a plurality of —SO3− groups (sulfone acid Na group) (weight-average molecular weight was 7500; glass transition point Tg was 58° C.; and softening point was 84° C.) as a binder resin, 20 parts by weight of a cyanogen-based pigment (“Pigment Blue 15:3”, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) as a coloring agent were prepared.
These components were mixed using a 20 L type Henschel mixer to obtain a material for producing toner particles.
Next, the material (mixture) was kneaded using a biaxial kneader-extruder (“PCM-30”, product name of IKEGAI Ltd.) shown in
The entire length of a process section of the biaxial kneader-extruder was 160 cm.
Further, the material temperature in the process section was set to be 130 to 140° C.
Furthermore, the rotational speed of the screw was 120 rpm, and the speed for feeding the material into the kneader-extruder was 20 kg/hour.
Under these conditions, a time required for the material to pass through the process section was about four minutes.
The kneading was carried out with deairing the inside of the process section by driving a vacuum pump connected to the process section through a deairing port.
The material (kneaded material) kneaded in the process section was extruded outside the biaxial kneader-extruder from the head portion. The temperature of the kneaded material at the head portion was adjusted to be 110° C.
The kneaded material extruded from the extruding port of the biaxial kneader-extruder was cooled by a cooling machine as shown in
The cooling rate of the kneaded material was −9° C./sec. Further, the time required for the completion of the cooling process from the end of the kneading process was 10 seconds.
The kneaded material cooled as described above was coarsely ground to be formed into powder having an average particle size of 1.5 mm. The coarse grinding of the kneaded material was carried out using a hammer mil.
Next, 250 parts by weight of toluene was added to 100 parts by weight of the coarse kneaded material, and then it was subjected to a treatment using an ultrasound homogenizer (output: 400 μA) for one hour to obtain a solution in which the epoxy resin of the kneaded material was dissolved. In the solution, the pigment was finely dispersed homogeneously.
Further, a water-based liquid constituted from 700 parts by weight of ion-exchanged water was prepared.
The water-based liquid was stirred with a homomixer (PRIMIX Corporation) with the number of stirring being adjusted.
The above-mentioned solution (that is, the toluene solution of the kneaded material) was dropped in the water-based liquid which is being stirred. In this way, a water-based emulsion in which a dispersoid comprised of particles having an average particle size of 2.6 μm was homogeneously dispersed was obtained.
Thereafter, the toluene in the water-based emulsion was removed under the conditions in which a temperature was 100° C. and an ambience pressure was 80 kPa, and then it was cooled to room temperature to thereby obtain a water-based suspension in which solid fine particles were dispersed. In the thus obtained water-based suspension, substantially no toluene remained. The concentration of the solid component (dispersoid) of the thus obtained water-based suspension was 28.8 wt %. Further, the average particle size of the particles of the dispersoid (solid fine particles) dispersed in the suspension was 1.5 μm. The measurement of the average particle size was carried out using a laser diffraction/scattering type particle size distribution measurement apparatus (“LA-920” which is a product name of HORIBA Ltd.).
The thus obtained suspension was put into a water-based suspension supply section of a dry fine particle production apparatus shown in
The ejection of the water-based suspension was carried out under the conditions that the temperature of the dispersion liquid in the head portions was 25° C., the frequency of vibration of each piezoelectric element was 10 kHz, the initial velocity of the dispersion liquid ejected from the ejection portions was 3 m/sec, and the size of one droplet ejected from each head portion was 0.4 pl (the diameter thereof was 2.08 μm). Further, the ejection of the water-based suspension was carried out so that the ejection timing of the water-based suspension was changed at least in the adjacent head portions in the plural head portions.
Further, when the water-based suspension was ejected, air was also ejected from the gas injection openings downwardly in a vertical direction, wherein the temperature of the air was 25° C., the humidity of the air was 27% RH, and the flow rate of the air was 3 m/sec. Further, the temperature of the inside of the housing (that is, the ambient temperature) was set to be 45° C., the pressure of the inside of the housing was about 1.5 kPa, and the length of the dispersion medium removal section (in the direction of conveying the dispersoid) was 1.0 m.
Furthermore, a voltage was applied to a part of the housing which constitutes the dispersion medium removal section so that an electrical potential at the side of the inner surface thereof was −200 V, thereby preventing the water-based suspension (dry fine particles) from adhering to the inner surface of the housing.
An antiaggregation agent is added to the ejected dispersion liquid in a cooled area by injecting it using an antiaggregation agent supply means shown in
In this regard, silica having an average particle size of 50 nm which has been subjected to hydrophilic treatment was used as the antiaggregation agent.
Further, the antiaggregation agent was injected so that the amount of the antiaggregation agent contained in the finally obtained toner particles became 0.5 wt %.
Then, the dispersion medium was removed from the ejected water-based suspension in the dispersion medium removal section to thereby obtain a plurality of dry fine particles (toner particles) each having shape and size corresponding to each particle of the dispersoid.
Thereafter, the dry fine particles formed in the dispersion medium removal section were collected at the cyclone. The water content of the collected dry fine particles was 0.48 wt %.
The collected dry fine particles were dispersed in an insulation liquid to thereby obtain a liquid developer. As the insulation liquid, a liquid in which 1 part by weight of surfactant (dodecyltrimethylammonium chloride) was added to 360 parts by weight of ISOPAR H (Exxon Mobil Corporation) was used. The electrical resistance (resistivity) of the insulation liquid at room temperature (20° C.) was 1.5×1015 Ωcm, the dielectric constant was 2.2, and the viscosity was 180 mPa·s. Further, the amount of the dry fine particles contained in the obtained liquid developer was 15 wt %.
A liquid developer was prepared in the same manner as in the Example 8 excepting that dry fine particles were obtained by removing a dispersion medium from a water-based suspension using a spray dryer (“Micro Mist Spray Dryer MDL-050B”, product name of Fujisaki Electric Co., Ltd.) instead of the dry fine particle production apparatus shown in
A liquid developer was prepared in the same manner as in the Example 8 excepting that a water-based suspension was filtrated and then dried in an oven at a temperature of 50° C. to thereby obtain dry fine particles without using the dry fine particle production apparatus shown in
A liquid developer was prepared in the same manner as in the Example 8 excepting that the particle size of the particles of the dispersoid was changed as shown in Table 3.
A liquid developer was prepared in the same manner as in the Example 8 excepting that an epoxy resin (softening point thereof was 117° C.) was used as a binder resin.
A liquid developer was prepared in the same manner as in the Example 8 excepting that titanium oxide having an average particle size of 30 nm which has been subjected to hydrophilic treatment was used as the antiaggregation agent and it was injected so that the amount of the antiaggregation agent contained in the finally obtained toner particles became 1.0 wt %.
A liquid developer was prepared in the same manner as in the Example 8 excepting that the antiaggregation agent was added to a deaerated resin dispersed liquid so that the concentration thereof became 0.1 wt % instead of spraying the antiaggregation agent.
A liquid developer was prepared in the same manner as in the Example 8 excepting that isododecane (volume resistivity was 1.6×1011 Ω·cm; dielectric constant was 2.0) was used as the insulation liquid.
A mixed solution comprised of 100 g of octadecylmethacrylate, 150 g of toluene, and 50 g of isopropanol was heated to a temperature of 75° C. with being stirred in a nitrogen gas stream. Then, 30 g of 2,2′-azobis (4-cyanovaleric acid) was added thereto to make reaction for 8 hours, and after being cooled, it was settled out in 2 liter of methanol so that white powder was aggregated and then it was dried. Then, a mixture comprised of 50 g of the thus obtained white powder, 3.3 g of vinyl acetate, 0.2 g of hydroquinone, and 100 g of toluene was heated to a temperature of 40° C. to make reaction for 2 hours. Then, it was heated to 70° C. and 3.8×10−3 ml of 100% sulfuric acid was added thereto to make reaction for 10 hours. Thereafter, it was cooled to a temperature of 25° C., and 0.02 g of sodium acetate trihydrate was added thereto. Thereafter, it was stirred for 30 minutes, and then it was settled out in 1 liter of methanol to aggregate, and then it was dried, to thereby obtain a resin for stabilizing dispersion.
Next, a mixed solution comprised of 12 g of the resin for stabilizing dispersion, 100 g of vinyl acetate, 1.0 g of octadecylmethacrylate, and 384 g of ISOPAR H was heated to a temperature of 70° C. with being stirred in a nitride gas stream. Then, 0.8 g of 2,2-azobis (isovalernitryl) was added to make reaction for 6 hours. After 20 minutes of addition of an initiator, white turbidity was caused, and then the reaction temperature was raised to 88° C. Thereafter, the temperature was raised to 100° c., and then it was being stirred for 2 hours to distil away the unreacted vinylacetate. After being cooled, it was passed through a nylon cloth of 200 meshes to thereby obtain white latex particles. The average particle size of the white latex particles was 0.26 μm.
Next, 10 g of a copolymer of dodecylmethacrylate/acrylic acid, 10 g of nigrosine, and 30 g of ISOPAR G were put in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads, and then dispersion was being continued for 4 hours to thereby obtain fine dispersed substances of nigrosine.
Next, 30 g of the white latex particles, 2.5 g of the dispersed substances of nigrosine, and 0.07 g of a copolymer of octadecene/maleate octadecylamide were diluted with 1 liter of ISOPAR G, to thereby obtain a liquid developer.
First, in the same manner as in the Example 8, a coarsely ground kneaded material was obtained.
Then, the coarsely ground kneaded material was finely ground to obtain fine particles constituting toner particles. A jet mill (“200AFG,” product of HOSOKAWA MICRON CORPORATION) was used for finely grinding the kneaded material. In this regard, the fine grinding was carried out under the conditions in which the grinding air pressure was 500 (kPa) and the rotor revolution was 7000 (rpm).
Then, the thus obtained toner particles were dispersed in an insulation liquid to thereby obtain a liquid developer. As the insulation liquid, a mixture of 360 parts by weight of ISOPAR H (Exxon Mobil Corporation) and 1 part by weight of surfactant (dodecyltrimethylammonium chloride) was used. The electrical resistance (resistivity) of the insulation liquid at room temperature (20° C.) was 1.5×1015 Ω·cm, the dielectric constant was 2.2 and the viscosity was 180 mPa·s. Further, the amount of the dry fine particles contained in the obtained liquid developer was 15 wt %.
The conditions for producing the liquid developers of the Examples and the Comparative Examples described above are shown in the following Table 3 together with the average roundness R, the standard deviation in the roundness, the average particle size per volume of particles, and the standard deviation in the particle size of the toner particles. In this connection, it is to be noted that the roundness R was measured by the use of a flow system particle image analyzer (FPIA-2000, manufactured by SYSMEX CORPORATION). The roundness R was determined by the following formula (I):
R=L
0
/L
1 (I)
where L1 (μm) represents the circumference of projected image of a particle that is a subject of measurement, and L0 (μm) represents the circumference of a perfect circle having the same area as that of the projected image of the particle that is a subject of measurement.
For the respective liquid developers obtained as described above, image density, resolution, and storage stability were evaluated.
(4.1) Image Density
By using the image forming apparatus shown in
(4.2) Resolution
By using the image forming apparatus shown in
(4.3) Storage Stability
The liquid developers obtained in the Examples and the Comparative Examples were being placed under the atmosphere of which temperature was in the range of 15 to 25° C. for 6 months. Thereafter, the toner particles in the liquid developers were visually observed, and the observation results were evaluated by the following four criteria.
A: Suspension of toner particles and aggregation and settling of toner particles were not observed at all.
B: Suspension of toner particles and aggregation and settling of toner particles were scarcely observed.
C: Suspension of toner particles and aggregation and settling of toner particles were slightly observed.
D: Suspension of toner particles and aggregation and settling of toner particles were clearly observed.
These results are shown in the following Table 4.
As shown in Table 3, in each of the liquid developers of the present invention, the roundness of the toner particles was large and the particle size distribution was small. Further, the toner particles had small variations in shape thereof (that is, the standard deviation of the roundness was small).
In contrast, in each of the liquid developers of the Comparative Examples, the toner particles had large variations in shape and size thereof. Further, in each of the liquid developers of the Comparative Examples, the toner particles had the unstable shapes, and the roundness thereof was low.
Further, as shown in Table 4, each of the liquid developers of the present invention had excellent image density, excellent resolution, and excellent storage stability. In contrast, in each of the liquid developers of the Comparative Examples, satisfactory results could not be obtained.
Furthermore, liquid developers which are the same as those described above were produced excepting that as a coloring agent a pigment red 122, a pigment yellow 180, and a carbon black (“Printex L”, product of Degussa AG) were used instead of a cyanogen-based pigment, and they were evaluated in the same manner as described above. As a result, substantially the same results could be obtained.
Moreover, liquid developers which are the same as those described above were produced using a different dry fine particle production apparatus in which the structure of the head portions was changed from the structure shown in
Finally, this application claims priorities to Japanese Patent Applications No. 2005-005744 filed on Jan. 12, 2005 and No. 2005-008404 filed on Jan. 14, 2005 which are hereby expressly incorporated by reference herein in its entirety.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-005744 | Jan 2005 | JP | national |
| 2005-008404 | Jan 2005 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2006/300283 | 1/12/2006 | WO | 00 | 10/31/2008 |
