Patent Application
20150086919
This application is based on Japanese Patent Application No. 2013-195142 filed with the Japan Patent Office on Sep. 20, 2013, the entire content of which is hereby incorporated by reference.
1. Field of the Invention
The present invention relates to a liquid developer having an insulating liquid and toner particles which are dispersed in the insulating liquid and contain a resin and a coloring agent and an image formation method with the use of the liquid developer.
2. Description of the Related Art
From a point of view of prevention of fly-off of toner particles during handling, a liquid developer has increasingly been used. A liquid developer has been required to have low-temperature fixability, fixability, and heat resistance, and various studies have been conducted (for example, Japanese Laid-Open Patent Publication No. 2009-042730 and Japanese Laid-Open Patent Publication No. 2009-096994).
It has been found that it may be difficult to improve fixability when low-temperature fixability and heat resistance are improved.
The present invention was made in view of such aspects, and an object of the present invention is to provide a liquid developer having excellent low-temperature fixability and heat resistance and also excellent fixability. Another object of the present invention is to provide a method of forming an image with the use of the liquid developer according to the present invention.
A liquid developer according to the present invention has an insulating liquid and toner particles which are dispersed in the insulating liquid and contain a resin and a coloring agent. The resin contains 80 mass % or more of a first resin which is a urethane-modified polyester resin resulting from increase in chain length of a component derived from a polyester resin by a compound containing an isocyanate group. The component derived from the polyester resin contains a constitutional unit derived from an acid component and a constitutional unit derived from an alcohol component. A ratio of a constitutional unit derived from an aliphatic monomer occupied in the constitutional unit derived from the acid component and the constitutional unit derived from the alcohol component is not lower than 90 mass %. Relation of |Tm1−Tm5|≧20° C. (70° C.≦Tm1≦170° C., 60° C.≦Tm5≦120° C.) is satisfied, where Tm1 (° C.) represents a softening temperature T1/2 of toner particles measured with a flow tester under a load of 1 kg and Tm5 (° C.) represents a softening temperature T1/2 of toner particles measured with a flow tester under a load of 5 kg.
The “component derived from the polyester resin” means a polyester resin from which one or more atoms have been removed from terminal end(s), and it includes a polyester resin from which one hydrogen atom has been removed from each of opposing terminal ends and a polyester resin from which one hydrogen atom has been removed from one terminal end. A “chain length” means bonding between a component derived from a polyester resin and a compound containing an isocyanate group such that the urethane-modified polyester resin is linear. The “aliphatic monomer” is a monomer constituting the polyester resin and it preferably has a straight chain alkyl skeleton having a carbon number not smaller than 2.
The first resin preferably has a concentration of a urethane group not lower than 0.8 mass % and not higher than 5 mass %. A concentration of a urethane group in the first resin can be calculated as (a mass of a urethane group in a urethane-modified polyester resin)/(a mass of the urethane-modified polyester resin)×100.
An image formation method according to the present invention preferably includes the steps of transferring the liquid developer according to the present invention to a recording medium and fixing toner particles contained in the liquid developer transferred to the recording medium to the recording medium at a pressure not lower than 200 kPa and not higher than 700 kPa.
The step of fixing the toner particles to the recording medium preferably includes the step of heating the recording medium. A heating condition in the step of heating the recording medium preferably satisfies relation of Tm5≦T1≦(Tm1+10° C.), where T1 (° C.) represents a temperature of the recording medium after the toner particles are fixed to the recording medium. As the recording medium is heated, toner particles on the recording medium are heated.
The step of heating the recording medium preferably includes a first heating step of heating the recording medium while a heat source is not in contact with the recording medium and a second heating step following the first heating step, of heating the recording medium while the heat source is in contact with the recording medium. Preferably, a heating condition in the first heating step satisfies relation of Tms5≦T2≦Tm1 and a heating condition in the second heating step satisfies relation of Tms5≦T3≦(Tm1+10° C.), where T2 (° C.) represents a temperature of the recording medium after the first heating step and before the second heating step, T3 (° C.) represents a temperature of the recording medium after the second heating step, and Tms5 (° C.) represents a melt start temperature of the toner particles measured with a flow tester under a load of 5 kg. The “heat source” preferably has a function to heat a recording medium and also a function to fix toner particles contained in the liquid developer to the recording medium, and it is implemented, for example, by a heated fixation roller.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
<Liquid Developer>
A liquid developer according to the present embodiment is useful as a liquid developer for electrophotography used in an image formation apparatus of an electrophotography type (which will be described later) such as a copying machine, a printer, a digital printer, or a simple printer, a paint, a liquid developer for electrostatic recording, an oil-based ink for ink jet printer, or an ink for electronic paper. The liquid developer according to the present embodiment contains an insulating liquid and toner particles dispersed in the insulating liquid, and preferably contains 10 to 50 mass % of toner particles and 50 to 90 mass % of the insulating liquid. The liquid developer according to the present embodiment may contain any component other than the toner particles and the insulating liquid. Any component other than the toner particles and the insulating liquid is, preferably, for example, a charge control agent, a thickener, or a dispersant.
<Toner Particles>
Toner particles in the present embodiment contain a resin and a coloring agent dispersed in the resin. A content of each of the resin and the coloring agent in the toner particles is preferably determined such that desired image density is obtained when an amount of adhesion of toner particles to such a recording medium as paper is within a prescribed range. The toner particles according to the present embodiment may contain any component other than the resin and the coloring agent. Any component other than the resin and the coloring agent is, preferably, for example, a dispersant for a pigment, a wax, or a charge control agent.
<Resin>
The resin in the present embodiment contains the first resin by not lower than 80 mass % and the second resin preferably different from the first resin by not higher than 20 mass %. The second resin may be composed of one type of resin or two or more types of resins as mixed. A content of the first resin or the second resin in the resin can be found, for example, based on an infrared absorption spectrum, also on a spectrum obtained from nuclear magnetic resonance, or also on a GCMS (gas chromatograph mass spectrometer).
<First Resin>
The first resin is a urethane-modified polyester resin. A component derived from a polyester resin contains a constitutional unit derived from an acid component and a constitutional unit derived from an alcohol component. A ratio of a constitutional unit derived from an aliphatic monomer occupied in the constitutional unit derived form the acid component and the constitutional unit derived from the alcohol component is not lower than 90 mass %, preferably not lower than 95 mass %, and more preferably 100 mass %. This ratio may be found based on a spectrum obtained from nuclear magnetic resonance or with a GCMS.
<Crystallinity>
Since a ratio of the constitutional unit derived from the aliphatic monomer occupied in the constitutional unit derived from the acid component and the constitutional unit derived from the alcohol component is not lower than 90 mass %, the first resin is considered to be excellent in crystallinity. Here, “crystallinity” means that a ratio between a softening point of the resin (hereinafter abbreviated as “Tmp”) and a maximum peak temperature (hereinafter abbreviated as “Ta”) of heat of fusion of the resin (Tmp/Ta) is not lower than 0.8 and not higher than 1.55 and that a result of change in amount of heat obtained in differential scanning calorimetry (DSC) does not show stepwise change in amount of heat absorption but has a clear heat absorption peak. A ratio between Tmp and Ta (Tmp/Ta) being higher than 1.55 can mean that such a resin is not excellent in crystallinity and also that such a resin has non-crystallinity.
A flow tester (capillary rheometer) (such as CFT-500D manufactured by Shimadzu Corporation) can be used to measure Tmp. Specifically, while 1 g of a sample is heated at a temperature increase rate of 6° C./min., a plunger applies load of 1.96 MPa to the sample to thereby extrude the sample from a nozzle having a diameter of 1 mm and a length of 1 mm. Relation between “an amount of lowering of the plunger (a value of flow)” and a “temperature” is plotted in a graph. A temperature at the time when an amount of lowering of the plunger is ½ of a maximum value of the amount of lowering is read from the graph, and this value (a temperature at which half of the measurement sample was extruded from the nozzle) is adopted as Tmp. In the present embodiment, a softening temperature of the first resin is preferably not lower than 40° C. from a point of view of prevention of occurrence of document offset and preferably not higher than 80° C. from a point of view of low-temperature fixability.
A differential scanning calorimeter (such as “DSC210” manufactured by Seiko Instruments, Inc.) can be used to measure Ta. Specifically, a sample is molten at 130° C., thereafter a temperature is lowered from 130° C. to 70° C. at a rate of 1.0° C./min., and thereafter a temperature is lowered from 70° C. to 10° C. at a rate of 0.5° C./min. Thereafter, with the DSC method, a temperature of the sample is raised at a temperature increase rate of 20° C./min., change in heat absorption and generation of the sample is measured, and relation between an “amount of heat absorption and generation” and a “temperature” is plotted in a graph. Here, a temperature of a heat absorption peak observed in a range from 20 to 100° C. is defined as Ta′. When there are a plurality of heat absorption peaks, a temperature of a peak largest in amount of heat absorption is defined as Ta′. After the sample was stored for 6 hours at (Ta′−10)° C., it is in turn stored for 6 hours at (Ta′−15)° C.
After pre-treatment of the sample ends, with the DSC method, the sample subjected to the pre-treatment above is cooled to 0° C. at a temperature lowering rate of 10° C./min., and then a temperature is raised at a temperature increase rate of 20° C./min. Based on change in heat absorption and generation thus measured, relation between an “amount of heat absorption and generation” and a “temperature” is plotted in a graph. A temperature at which an amount of heat absorption attains to a maximum value is defined as a maximum peak temperature (Ta) of heat of fusion.
<Mn>
A number average molecular weight (hereinafter denoted as “Mn”) of the first resin is preferably not smaller than 10000 and not greater than 50000. When relation of 10000≦Mn is satisfied, excessive softening of the first resin during fixation can be prevented, and hence occurrence of high-temperature offset can be prevented. When relation of Mn≦50000 is satisfied, less likeliness of softening of the first resin during fixation can be prevented, and hence fixability can be ensured. Preferably, relation of 10000≦Mn≦30000 is satisfied. Thus, fixability can be improved.
Mn of the first resin can be measured with gel permeation chromatography (GPC) under conditions below, with respect to solubles in tetrahydrofuran (THF). Mn and Mw of a resin other than the polyester resin can also be measured under conditions shown below.
Measurement apparatus: “HLC-8120” manufactured by Tosoh Corporation
Column: “TSKgel GMHXL” (two) manufactured by Tosoh Corporation and “TSKgel Multipore HXL-M” (one) manufactured by Tosoh Corporation
Sample solution: 0.25 mass % of THF solution
Amount of injection of sample solution into column: 100 μl
Flow rate: 1 ml/min.
Measurement temperature: 40° C.
Detection apparatus: Refraction index detector
Reference material: 12 standard polystyrenes manufactured by Tosoh Corporation (TSK standard POLYSTYRENE) (molecular weight: 500, 1050, 2800, 5970, 9100, 18100, 37900, 96400, 190000, 355000, 1090000, 2890000)
A number average molecular weight of a polyester resin can be measured with the use of GPC under conditions below.
Measurement apparatus: “HLC-8220GPC” manufactured by Tosoh Corporation
Column: “Guardcolumn α” (one) and “TSKgel α-M” (one)
Sample solution: 0.125 mass % of dimethylformamide solution
Amount of injection of dimethylformamide solution into column: 100 μl
Flow rate: 1 ml/min.
Measurement temperature: 40° C.
Detection apparatus: Refraction index detector
Reference material: 12 standard polystyrenes manufactured by Tosoh Corporation (TSK standard POLYSTYRENE) (molecular weight: 500, 1050, 2800, 5970, 9100, 18100, 37900, 96400, 190000, 355000, 1090000, 2890000)
<Constitutional Unit>
The first resin is obtained in accordance with a method shown below. Initially, a polyester resin (a skeleton) is obtained by polymerizing polyol (an alcohol component) with polycarboxylic acid (an acid component), acid anhydride of polycarboxylic acid (an acid component), or ester of lower alkyl of polycarboxylic acid (an acid component). The obtained polyester resin is increased in chain length by di(tri)isocyanate. Di(tri)isocyanate means diisocyanate and/or triisocyanate.
A polyester resin obtained in a process for manufacturing the first resin is preferably a polycondensed product of polyol and polycarboxylic acid, acid anhydride of polycarboxylic acid, or ester of lower alkyl of polycarboxylic acid (having a carbon number of an alkyl group from 1 to 4). A known polycondensation catalyst can be used for polycondensation reaction. A ratio between polyol and polycarboxylic acid is not particularly limited. A ratio between polyol and polycarboxylic acid should only be set such that an equivalent ratio between a hydroxyl group [OH] and a carboxyl group [COOH] ([OH]/[COOH]) is set preferably to 2/1 to 1/5, more preferably to 1.5/1 to 1/4, and further preferably to 1.3/1 to 1/3.
In the present embodiment, polyol preferably has a straight chain alkyl skeleton having a carbon number not smaller than 2 and more preferably it is aliphatic diol. Polycarboxylic acid preferably has a straight chain alkyl skeleton having a carbon number not smaller than 2 and more preferably it is aliphatic dicarboxylic acid. This is also the case with “polycarboxylic acid” in each of acid anhydride of polycarboxylic acid and lower alkyl of polycarboxylic acid. Thus, the first resin will express crystallinity. So long as the first resin expresses crystallinity, the first resin may contain aromatic polyol or aromatic polycarboxylic acid.
Aliphatic diol is one type of an aliphatic monomer, it is preferably alkane diol having a carbon number from 4 to 10, and it is more preferably, for example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, or 1,10-decanediol.
Aliphatic dicarboxylic acid is one type of an aliphatic monomer, and it is preferably, for example, alkane dicarboxylic acid having a carbon number from 4 to 20, alkene dicarboxylic acid having a carbon number from 4 to 36, or an ester-forming derivative thereof. Aliphatic dicarboxylic acid is more preferably succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, or an ester-forming derivative thereof.
A compound containing an isocyanate group is preferably a compound having a plurality of isocyanate groups in a molecule, and it is more preferably chain aliphatic polyisocyanate or cyclic aliphatic polyisocyanate.
Chain aliphatic polyisocyanate is preferably, for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, or the like. Two or more of these may be used together.
Cyclic aliphatic polyisocyanate is preferably, for example, isophoron diisocyanate (hereinafter abbreviated as “IPDI”), dicyclohexylmethane-4,4′-diisocyanate (hereinafter also denoted as “hydrogenated MDI”), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hereinafter also denoted as “hydrogenated TDI”), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, or 2,6-norbornane diisocyanate. Two or more of these may be used together.
<Second Resin>
The second resin is preferably, for example, a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin, a polyamide resin, a polyimide resin, a silicon resin, a phenol resin, a melamine resin, a urea resin, an aniline resin, an ionomer resin, or a polycarbonate resin. The second resin is more preferably a vinyl resin, a polyester resin, a polyurethane resin, or an epoxy resin, and further preferably a vinyl resin. Thus, a median diameter D50 (which will be described later) of toner particles and circularity (which will be described later) of toner particles are readily controlled. The second resin preferably also has crystallinity.
The vinyl resin may be a homopolymer obtained by homopolymerizing a monomer having polymeric double bond or a copolymer obtained by copolymerizing two or more types of monomers having polymeric double bond. A monomer having polymeric double bond is, for example, (1) to (9) below.
(1) Hydrocarbon Having Polymeric Double Bond
Hydrocarbon having polymeric double bond is preferably, for example, aliphatic hydrocarbon having polymeric double bond shown in (1-1) below, aromatic hydrocarbon having polymeric double bond shown in (1-2) below, or the like.
(1-1) Aliphatic Hydrocarbon Having Polymeric Double Bond
Aliphatic hydrocarbon having polymeric double bond is preferably, for example, chain hydrocarbon having polymeric double bond shown in (1-1-1) below, cyclic hydrocarbon having polymeric double bond shown in (1-1-2) below, or the like.
(1-1-1) Chain Hydrocarbon Having Polymeric Double Bond
Chain hydrocarbon having polymeric double bond is preferably, for example, alkene having a carbon number from 2 to 30 (such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, or octadecene); alkadiene having a carbon number from 4 to 30 (such as butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, or 1,7-octadiene); or the like.
(1-1-2) Cyclic Hydrocarbon Having Polymeric Double Bond
Cyclic hydrocarbon having polymeric double bond is preferably, for example, mono- or di-cycloalkene having a carbon number from 6 to 30 (such as cyclohexene, vinyl cyclohexane, or ethylidene bicycloheptane); mono- or di-cycloalkadiene having a carbon number from 5 to 30 (such as cyclopentadiene or dicyclopentadiene); or the like.
(1-2) Aromatic Hydrocarbon Having Polymeric Double Bond
Aromatic hydrocarbon having polymeric double bond is preferably, for example, styrene; hydrocarbyl (such as alkyl, cycloalkyl, aralkyl, and/or alkenyl having a carbon number from 1 to 30) substitute of styrene (such as α-methylstyrene, vinyl toluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinyl benzene, divinyl toluene, divinyl xylene, or trivinyl benzene); vinyl naphthalene; or the like.
(2) Monomer Having Carboxyl Group and Polymeric Double Bond and Salt Thereof
A monomer having a carboxyl group and polymeric double bond is preferably, for example, unsaturated monocarboxylic acid having a carbon number from 3 to 15 [such as (meth)acrylic acid, crotonic acid, isocrotonic acid, or cinnamic acid]; unsaturated dicarboxylic acid (unsaturated dicarboxylic anhydride) having a carbon number from 3 to 30 [such as maleic acid (maleic anhydride), fumaric acid, itaconic acid, citraconic acid (citraconic anhydride), or mesaconic acid]; monoalkyl (having a carbon number from 1 to 10) ester of unsaturated dicarboxylic acid having a carbon number from 3 to 10 (such as maleic acid monomethyl ester, maleic acid monodecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester, or citraconic acid monodecyl ester); or the like. “(Meth)acrylic” herein means acrylic and/or methacrylic.
The salt of the monomer above is preferably, for example, alkali metal salt (such as sodium salt or potassium salt), alkaline earth metal salt (such as calcium salt or magnesium salt), ammonium salt, amine salt, or quaternary ammonium salt, or the like.
Amine salt is not particularly limited so long as it is an amine compound. Amine salt is preferably, for example, primary amine salt (such as ethylamine salt, butylamine salt, or octylamine salt); secondary amine salt (such as diethylamine salt or dibutylamine salt); tertiary amine salt (such as triethylamine salt or tributylamine salt); or the like.
Quaternary ammonium salt is preferably, for example, tetraethyl ammonium salt, triethyl lauryl ammonium salt, tetrabutyl ammonium salt, or tributyl lauryl ammonium salt, or the like.
Salt of the monomer having a carboxyl group and polymeric double bond is preferably, for example, sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, lithium acrylate, cesium acrylate, ammonium acrylate, calcium acrylate, or aluminum acrylate, or the like.
(3) Monomer Having Sulfo Group and Polymeric Double Bond and Salt Thereof
A monomer having a sulfo group and polymeric double bond is preferably, for example, vinyl sulfonic acid, α-methylstyrene sulfonic acid, sulfopropyl (meth)acrylate, or 2-(meth)acryloylamino-2,2-dimethylethane sulfonic acid. Salt of a monomer having a sulfo group and polymeric double bond is preferably, for example, salts listed as the “salt of the monomer above” in “(2) Monomer Having Carboxyl Group and Polymeric Double Bond” above.
(4) Monomer Having Phosphono Group and Polymeric Double Bond and Salt Thereof
A monomer having a phosphono group and polymeric double bond is preferably, for example, 2-hydroxyethyl (meth)acryloyl phosphate or 2-acryloyloxy ethyl phosphonic acid. Salt of the monomer having a phosphono group and polymeric double bond is preferably, for example, salts listed as the “salt of the monomer above” in “(2) Monomer Having Carboxyl Group and Polymeric Double Bond” above.
(5) Monomer Having Hydroxyl Group and Polymeric Double Bond
A monomer having a hydroxyl group and polymeric double bond is preferably, for example, hydroxystyrene, N-methylol (meth)acrylamide, or hydroxyethyl (meth)acrylate.
(6) Nitrogen-Containing Monomer Having Polymeric Double Bond
A nitrogen-containing monomer having polymeric double bond is preferably, for example, a monomer shown in (6-1) to (6-4) below.
(6-1) Monomer Having Amino Group and Polymeric Double Bond
A monomer having an amino group and polymeric double bond is preferably, for example, aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, N-aminoethyl (meth)acrylamide, (meth)allyl amine, morpholinoethyl (meth)acrylate, 4-vinylpyridine, 2-vinylpyridine, crotyl amine, N,N-dimethylamino styrene, methyl-α-acetamino acrylate, vinylimidazole, N-vinylpyrrole, N-vinyl thiopyrrolidone, N-aryl phenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, or the like. The monomer having an amino group and polymeric double bond may be the salts of the monomer listed above. The salts of the monomer listed above are exemplified, for example, by salts listed as the “salt of the monomer above” in “(2) Monomer Having Carboxyl Group and Polymeric Double Bond and Salt Thereof” above.
(6-2) Monomer Having Amide Group and Polymeric Double Bond
A monomer having an amide group and polymeric double bond is preferably, for example, (meth)acrylamide, N-methyl (meth)acrylamide, N-butyl (meth)acrylamide, diacetone acrylamide, N-methylol (meth)acrylamide, N,N′-methylene-bis(meth)acrylamide, cinnamic acid amide, N,N-dimethyl (meth)acrylamide, N,N-dibenzyl (meth)acrylamide, (meth)acrylformamide, N-methyl-N-vinylacetamide, or N-vinylpyrrolidone, or the like.
(6-3) Monomer Having Carbon Number from 3 to 10 and Having Nitrile Group and Polymeric Double Bond
A monomer having a carbon number from 3 to 10 and having a nitrile group and polymeric double bond is preferably, for example, (meth)acrylonitrile, cyanostyrene, or cyanoacrylate, or the like.
(6-4) Monomer Having Carbon Number from 8 to 12 and Having Nitro Group and Polymeric Double Bond
A monomer having a carbon number from 8 to 12 and having a nitro group and polymeric double bond is preferably, for example, nitrostyrene or the like.
(7) Monomer Having Carbon Number from 6 to 18 and Having Epoxy Group and Polymeric Double Bond
A monomer having a carbon number from 6 to 18 and having an epoxy group and polymeric double bond is preferably, for example, glycidyl (meth)acrylate or the like.
(8) Monomer Having Carbon Number from 2 to 16 and Having Halogen Element and Polymeric Double Bond
A monomer having a carbon number from 2 to 16 and having a halogen element and polymeric double bond is preferably, for example, vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, or chloroprene, or the like.
(9) Ester Having Carbon Number from 4 to 16 and Having Polymeric Double Bond
An ester having a carbon number from 4 to 16 and having polymeric double bond is preferably, for example, vinyl acetate; vinyl propionate; vinyl butyrate; diallyl phthalate; diallyl adipate; isopropenyl acetate; vinyl methacrylate; methyl-4-vinyl benzoate; cyclohexyl methacrylate; benzyl methacrylate; phenyl (meth)acrylate; vinyl methoxy acetate; vinyl benzoate; ethyl-α-ethoxy acrylate; alkyl (meth)acrylate having an alkyl group having a carbon number from 1 to 11 [such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, or 2-ethylhexyl (meth)acrylate]; dialkyl fumarate (two alkyl groups being straight-chain alkyl groups, branched alkyl groups, or alicyclic alkyl groups, having a carbon number from 2 to 8); dialkyl maleate (two alkyl groups being straight-chain alkyl groups, branched alkyl groups, or alicyclic alkyl groups, having a carbon number from 2 to 8); poly(meth)allyloxy alkanes (such as diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, or tetramethallyloxyethane); a monomer having a polyalkylene glycol chain and polymeric double bond [such as polyethylene glycol (Mn=300) mono(meth)acrylate, polypropylene glycol (Mn=500) mono(meth)acrylate, a 10-mole adduct (meth)acrylate of ethylene oxide (hereinafter “ethylene oxide” being abbreviated as “EO”) to methyl alcohol, or a 30-mole adduct (meth)acrylate of EO to lauryl alcohol]; poly(meth)acrylates {such as poly(meth)acrylate of polyhydric alcohols [such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylol propane tri(meth)acrylate, or polyethylene glycol di(meth)acrylate]}, or the like. “(Meth)allylo” herein means allylo and/or methallylo.
A vinyl resin is preferably, for example, a styrene-(meth)acrylic acid ester copolymer, a styrene-butadiene copolymer, a (meth)acrylic acid-(meth)acrylic acid ester copolymer, a styrene-acrylonitrile copolymer, a styrene-maleic acid (maleic anhydride) copolymer, a styrene-(meth)acrylic acid copolymer, a styrene-(meth)acrylic acid-divinylbenzene copolymer, a styrene-styrene sulfonic acid-(meth)acrylic acid ester copolymer, or the like.
The vinyl resin may be a homopolymer or a copolymer of a monomer having polymeric double bond in (1) to (9) above, or it may be a polymerized product of a monomer having polymeric double bond in (1) to (9) above and a monomer (m) having a molecular chain (k) and having polymeric double bond. The molecular chain (k) is preferably, for example, a straight-chain hydrocarbon chain having a carbon number from 12 to 27, a branched hydrocarbon chain having a carbon number from 12 to 27, a fluoro-alkyl chain having a carbon number from 4 to 20, a polydimethylsiloxane chain, or the like. A difference in SP value between the molecular chain (k) in the monomer (m) and the insulating liquid is preferably 2 or smaller. The “SP value” herein is a numeric value calculated with a Fedors' method [Polym. Eng. Sci. 14(2) 152, (1974)].
Though the monomer (m) having the molecular chain (k) and polymeric double bond is preferably, for example, monomers (m1) to (m3) below. Two or more of the monomers (m1) to (m3) may be used together as the monomer (m).
The monomer (m1) having straight-chain hydrocarbon chain having carbon number from 12 to 27 (preferably from 16 to 25) and polymeric double bond is preferably, for example, mono-straight-chain alkyl (a carbon number of alkyl being from 12 to 27) ester of unsaturated monocarboxylic acid, mono-straight-chain alkyl (a carbon number of alkyl being from 12 to 27) ester of unsaturated dicarboxylic acid, or the like. Unsaturated monocarboxylic acid and unsaturated dicarboxylic acid above are, for example, a carboxyl group containing vinyl monomer having a carbon number from 3 to 24 such as (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, or citraconic acid. A specific example of the monomer (m1) is, for example, dodecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, eicosyl (meth)acrylate, or the like.
The monomer (m2) having branched hydrocarbon chain having carbon number from 12 to 27 (preferably from 16 to 25) and polymeric double bond is preferably, for example, branched alkyl (a carbon number of alkyl being from 12 to 27) ester of unsaturated monocarboxylic acid, mono-branched alkyl (a carbon number of alkyl being from 12 to 27) ester of unsaturated dicarboxylic acid, or the like. Unsaturated monocarboxylic acid and unsaturated dicarboxylic acid are exemplified, for example, by those the same as listed as specific examples of unsaturated monocarboxylic acid and unsaturated dicarboxylic acid with regard to the monomer (m1). A specific example of the monomer (m2) is exemplified by 2-decyltetradecyl (meth)acrylate or the like.
The monomer (m3) preferably has a fluoro-alkyl chain having carbon number from 4 to 20 and polymeric double bond.
The second resin has a melting point preferably from 0 to 220° C., more preferably from 30 to 200° C., and further preferably from 40 to 80° C. From a point of view of particle size distribution and a shape of toner particles, as well as powder fluidity, heat-resistant storage stability, and resistance to stress of the liquid developer, the second resin has a melting point preferably not lower than a temperature during manufacturing of the liquid developer. If a melting point of the second resin is lower than a temperature during manufacturing of the liquid developer, it may be difficult to prevent toner particles from uniting with each other and it may be difficult to prevent the toner particles from breaking. In addition, it may be difficult to achieve a narrow width of distribution in particle size distribution of the toner particles. In other words, variation in particle size of toner particles may be great. The “melting point” can be measured with a differential scanning calorimeter (such as “DSC20” or “SSC/580” manufactured by Seiko Instruments, Inc.) in compliance with a method defined under ASTM D3418-82.
Mn of the second resin (obtained through measurement with GPC) is preferably from 100 to 5000000, more preferably from 200 to 5000000, and further preferably from 500 to 500000. The second resin has an SP value preferably from 7 to 18 (cal/cm3)1/2 and more preferably from 8 to 14 (cal/cm3)1/2.
<Coloring Agent>
A coloring agent has a particle size preferably not larger than 0.3 μm. When a coloring agent has a particle size exceeding 0.3 μm, dispersibility of the coloring agent may become poor, which may result in lowering in degree of gloss. Consequently, a desired color cannot be realized in some cases.
Though a known pigment can be employed as a coloring agent without being particularly limited, from a point of view of cost, light resistance, coloring capability, and the like, pigments below are preferably employed. In terms of color construction, these pigments are normally categorized into a black pigment, a yellow pigment, a magenta pigment, or a cyan pigment, and colors (color images) other than black are basically toned by subtractive color mixture of a yellow pigment, a magenta pigment, or a cyan pigment. A pigment shown below may be used alone, or two or more types of pigments shown below may be used together as necessary.
A pigment contained in a black coloring agent (a black pigment) may be, for example, carbon black such as furnace black, channel black, acetylene black, thermal black, or lamp black, carbon black derived from biomass, or magnetic powders of magnetite or ferrite. Nigrosine (an azine-based compound) which is a purple-black dye may be used alone or in combination. As nigrosine, C. I. Solvent Black 7 or C. I. Solvent Black 5 can be employed.
A pigment contained in a magenta coloring agent (a magenta pigment) is preferably, for example, C. I. Pigment Red 2, C. I. Pigment Red 3, C. I. Pigment Red 5, C. I. Pigment Red 6, C. I. Pigment Red 7, C. I. Pigment Red 15, C. I. Pigment Red 16, C. I. Pigment Red 48:1, C. I. Pigment Red 53:1, C. I. Pigment Red 57:1, C. I. Pigment Red 122, C. I. Pigment Red 123, C. I. Pigment Red 139, C. I. Pigment Red 144, C. I. Pigment Red 149, C. I. Pigment Red 166, C. I. Pigment Red 177, C. I. Pigment Red 178, or C. I. Pigment Red 222.
A pigment contained in a yellow coloring agent (a yellow pigment) is preferably, for example, C. I. Pigment Orange 31, C. I. Pigment Orange 43, C. I. Pigment Yellow 12, C. I. Pigment Yellow 13, C. I. Pigment Yellow 14, C. I. Pigment Yellow 15, C. I. Pigment Yellow 17, C. I. Pigment Yellow 74, C. I. Pigment Yellow 93, C. I. Pigment Yellow 94, C. I. Pigment Yellow 138, C. I. Pigment Yellow 155, C. I. Pigment Yellow 180, or C. I. Pigment Yellow 185.
A pigment contained in a cyan coloring agent (a cyan pigment) is preferably, for example, C. I. Pigment Blue 15, C. I. Pigment Blue 15:2, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:4, C. I. Pigment Blue 16, C. I. Pigment Blue 60, C. I. Pigment Blue 62, C. I. Pigment Blue 66, or C. I. Pigment Green 7.
<Dispersant for Pigment>
A dispersant for pigment is exemplified as one example of an additive to toner particles. A dispersant for pigment has a function to uniformly disperse a coloring agent (a pigment) in toner particles and it is preferably a basic dispersant. Here, the basic dispersant refers to a dispersant defined below. Namely, 0.5 g of a dispersant for pigment and 20 ml of distilled water are introduced in a screw bottle made of glass, the screw bottle is shaken for 30 minutes with the use of a paint shaker, and the resultant product is filtered. pH of a filtrate obtained through filtration is measured with a pH meter (trade name: “D-51” manufactured by Horiba, Ltd.), and a filtrate of which pH is higher than 7 is defined as a basic dispersant. It is noted that a filtrate of which pH is lower than 7 is referred to as an acid dispersant.
A type of such a basic dispersant is not particularly limited. For example, a basic dispersant is preferably a compound (dispersant) having a functional group such as an amine group, an amino group, an amide group, a pyrrolidone group, an imine group, an imino group, a urethane group, a quaternary ammonium group, an ammonium group, a pyridino group, a pyridium group, an imidazolino group, or an imidazolium group in a molecule. It is noted that what is called a surfactant having a hydrophilic portion and a hydrophobic portion in a molecule normally falls under the dispersant, however, various compounds can be employed, so long as they have a function to disperse a coloring agent (a pigment) as described above.
A commercially available product of such a basic dispersant may be, for example, “Ajisper PB-821” (trade name), “Ajisper PB-822” (trade name), or “Ajisper PB-881” (trade name), manufactured by Ajinomoto Fine-Techno Co., Inc., or “Solsperse 28000” (trade name), “Solsperse 32000” (trade name), “Solsperse 32500” (trade name), “Solsperse 35100” (trade name), or “Solsperse 37500” (trade name), manufactured by Japan Lubrizol Limited. Since a dispersant for pigment is more preferably not dissolved in an insulating liquid, for example, “Ajisper PB-821” (trade name), “Ajisper PB-822” (trade name), or “Ajisper PB-881” (trade name), manufactured by Ajinomoto Fine-Techno Co., Inc. is more preferred. By using such a dispersant for pigment, it becomes easier to obtain toner particles having a desired shape, although a reason is not known.
Preferably 1 to 100 mass % and more preferably 1 to 40 mass % of such a dispersant for pigment is added to the coloring agent (pigment). When an amount of addition of the dispersant for pigment is lower than 1 mass %, dispersibility of the coloring agent (pigment) may be insufficient, and hence necessary ID (image density) cannot be achieved in some cases and fixation strength of toner particles may be lowered. When an amount of addition of the dispersant for pigment exceeds 100 mass %, the dispersant for pigment in an amount more than necessary for dispersing the pigment is added. Therefore, the excessive dispersant for pigment may be dissolved in the insulating liquid, which adversely affects chargeability or fixation strength of toner particles. One type alone of such a dispersant for pigment may be used or two or more types may be mixed for use.
<Shape of Toner Particles>
A median diameter D50 found through measurement of particle size distribution of toner particles based on volume (hereinafter denoted as “median diameter D50 of toner particles”) is preferably not smaller than 0.5 μm and not greater than 5.0 μm. This particle size is smaller than a particle size of toner particles contained in a dry developer which has conventionally been used and represents one of the features of the present invention. If median diameter D50 of toner particles is smaller than 0.5 μm, toner particles have too small a particle size and hence mobility of toner particles in electric field may become poor, which may hence lead to lowering in development performance. If median diameter D50 of toner particles exceeds 5.0 μm, uniformity in particle size of toner particles may be lowered, which may hence lead to lowering in image quality. More preferably, toner particles have median diameter D50 not smaller than 0.5 μm and not greater than 2.0 μm.
Median diameter D50 of toner particles can be measured, for example, with a flow particle image analyzer (FPIA-3000S manufactured by Sysmex Corporation). This analyzer can use a solvent as it is as a dispersion medium. Therefore, this analyzer can measure a state of toner particles in a state closer to an actually dispersed state, as compared with a system in which measurement is conducted in a water system.
<Core/Shell Structure>
Toner particles in the present embodiment preferably have a core/shell structure. The “core/shell structure” is such a structure as having the first resin as a core and the second resin as a shell. The core/shell structure includes not only such a structure that the second resin covers at least a part of surfaces of first particles (the first particles containing the first resin) but also such a structure that the second resin adheres to at least a part of surfaces of the first particles. When the toner particles have the core/shell structure, median diameter D50 of toner particles and circularity of toner particles are readily controlled. In the core/shell structure, a mass ratio between a shell resin (the second resin) and a core resin (the first resin) is preferably from 1:99 to 80:20. When a content of the second resin in the resin contained in the toner particles is lower than 1 mass %, formation of particles having the core/shell structure may become difficult. When a content of the second resin in the resin contained in the toner particles exceeds 20 mass %, fixability may lower.
In the core/shell structure, a coloring agent may be contained in the core resin or the shell resin, or in both of the core resin and the shell resin. This is also the case with an additive (for example, a dispersant for pigment) to toner particles.
<Softening Temperature T1/2 of Toner Particles>
In the following, matters studied by the present inventors in completing the liquid developer according to the present embodiment are shown, and then toner particles in the present embodiment are further shown.
With the liquid developer, fly-off of toner particles during handling can be prevented. Therefore, the toner particles can be smaller in particle size than in a dry developer and hence an amount of adhesion of toner particles to a recording medium can be decreased. When an amount of adhesion of toner particles to a recording medium is decreased, however, image density is lowered, which leads to necessity for increase in content of a coloring agent. When a content of a coloring agent is increased on the other hand, melt viscosity of the liquid developer becomes higher and fixation at a low temperature becomes difficult. Therefore, conventionally, melt viscosity of the liquid developer has been lowered by adjusting a molecular weight of a non-linear polyester resin contained in toner particles.
The non-linear polyester resin does not have excellent crystallinity but has a glass transition point. Though a resin contained in toner particles is swollen with an insulating liquid, a non-linear polyester resin is lower in glass transition point when it is contained in a liquid than when it is contained in a dry state, which leads to lowering in heat resistance of the liquid developer. As a method of enhancing heat resistance of the liquid developer, it is possible to adjust a molecular weight of the non-linear polyester resin so as to raise a glass transition point thereof. Adoption of this method, however, results in difficulty in fixation at a low temperature.
As another method of enhancing heat resistance of the liquid developer, it is possible to employ a resin having excellent crystallinity as a resin to be contained in toner particles. As a result of dedicated studies conducted by the present inventors, it has been found that use of a urethane-modified polyester resin as a resin to be contained in toner particles can provide a liquid developer excellent in low-temperature fixability and heat resistance, which will be detailed below.
As shown in
As shown in
In general, when fixation is carried out with a contact-type fixer (a fixer for fixing by being in contact with a recording medium) such as a heated fixation roller, a temperature of the fixation roller may be lowered by consecutive paper feed. Lowering in temperature of the fixation roller is noticeable when thick paper is fed or when a system speed (a speed of processing for image formation) is high. Viscoelasticity (for example, melt viscosity) of a resin different from the urethane-modified polyester resin is varied in a melt region of the resin. Therefore, when a temperature of the fixation roller is lowered while an image is being formed with the liquid developer not containing the urethane-modified polyester resin, quality of the resin may lower. The urethane-modified polyester resin, however, has a stable region in that melt region (a high-temperature region). Therefore, even though a temperature of the fixation roller lowers while an image is being formed with the liquid developer containing the urethane-modified polyester resin, lowering in quality of the resin can be prevented.
The present inventors have recently found, however, that a new problem arises when an image is formed with the liquid developer containing the urethane-modified polyester resin. As described above, the liquid developer containing the urethane-modified polyester resin has the stable region in the melt region (the high-temperature region) of the liquid developer. Therefore, it is difficult to control quality of the liquid developer by varying a temperature of the liquid developer. For example, since viscoelasticity of toner particles does not significantly vary in spite of increase in temperature, it is difficult to improve fixability by increasing a temperature.
As a result of dedicated studies for solving the problem above, the present inventors have found that the problem above is solved by satisfying relation of |Tm1−Tm5|≧20° C. (70° C.≦Tm1≦170° C., 60° C.≦Tm5≦120° C.), where Tm1 (° C.) represents a softening temperature T1/2 of toner particles measured with a flow tester under a load of 1 kg and Tm5 (° C.) represents a softening temperature T1/2 of toner particles measured with a flow tester under a load of 5 kg. When Tm1 and Tm5 satisfy the temperature range above, less likeliness of melt of toner particles can be prevented and occurrence of high-temperature offset due to excessive melt of toner particles can be prevented.
Regarding the conventional toner particles, a temperature corresponding to Tm1 (° C.) and a temperature corresponding to Tm5 (° C.) are substantially the same. In other words, viscoelasticity of toner particles is substantially the same even when a load onto toner particles is varied. Therefore, regarding the conventional toner particles, it is difficult to improve fixability in spite of fixation with a load being varied. Since viscoelasticity of the conventional toner particles greatly varies when a temperature of the toner particles is varied, they can be fixed with a temperature of the toner particles being varied.
Regarding the toner particles in the present embodiment, on the other hand, a difference between Tm1 (° C.) and Tm5 (° C.) is not less than 20° C. In other words, viscoelasticity of the toner particles greatly varies when a load onto the toner particles is varied. Therefore, fixability can be improved when the toner particles are fixed with a load onto the toner particles being optimized.
As |Tm1−Tm5| is greater, viscoelasticity of the toner particles greatly varies depending on a load onto the toner particles. Therefore, a liquid developer excellent in fixability regardless of a temperature during fixation can be provided. It is difficult, however, to manufacture toner particles satisfying relation of |Tm1−Tm5|>100° C. Therefore, the toner particles in the present embodiment preferably satisfy relation of 50° C.≧|Tm1−Tm5|≧20° C. Further preferably, the toner particles in the present embodiment satisfy relation of 50° C.≧|Tm1−Tm5|≧25° C.
When relation of Tm1≦120° C. is satisfied, a liquid developer excellent in low-temperature fixability can be provided. Therefore, relation of Tm1≦120° C. is preferably satisfied.
Varying a load onto toner particles in a range from 1 kg to 5 kg in a flow tester corresponds to varying a range of a pressure of a fixation roller within a defined range in a common fixation method.
Tm1 and Tm5 herein refer to a softening temperature T1/2 of toner particles measured with a flow tester (capillary rheometer) (such as “CFT-500D” manufactured by Shimadzu Corporation) under conditions shown below.
Initially, 5 g of the liquid developer is subjected to solid-liquid separation for 5 minutes in a centrifugal separator (a revolution speed of 10000 rpm). After the supernatant was discarded, 10 g of a hexane solution is added for preparing reslurry. The reslurry is subjected to solid-liquid separation for 5 minutes in a centrifugal separator (a revolution speed of 10000 rpm). After the supernatant was discarded, a hexane solution is added for preparing reslurry. The reslurry is subjected to solid-liquid separation for 5 minutes in a centrifugal separator (a revolution speed of 10000 rpm). After the supernatant was discarded, slurry is recovered. The recovered slurry is dried under vacuum for 2 hours at room temperature. Thus, 1 to 2 g of a powder sample (toner) is obtained.
The obtained powder sample is introduced in a cylinder of a flow tester (capillary rheometer). The powder sample is heated and a load is applied to the powder sample with the use of a piston. Thus, the powder sample is molten and flows out of a die of the flow tester (capillary rheometer). A temperature Tms at the time when the powder sample starts to flow out of the die corresponds to a melt start temperature of the powder sample. Softening temperature T1/2 of the toner particles is a temperature at the time when the piston was present at a position intermediate between a position (Ss) of the piston at the time of start of melt of the powder sample and a position (Se) of the piston at the time of end of flow-out of the powder sample.
Powder sample: 1 g
Rate of temperature increase: 5° C./min.
Cross-sectional area A of piston: 1 cm2
Diameter D of hole in die: 0.5 mm
Length L of die: 1 mm
Load at the time of measurement of Tm1: 1 kg (test force: 15 kgf)
Load at the time of measurement of Tm5: 5 kg (test force: 55 kgf)
Apparent viscosity η(Pa·S) of sample powders is calculated with the following equation:
Apparent viscosity η(Pa·S) of sample powders=(πD4P)/(128LQ)×10−3
where D and L are as described above. P represents a load (unit of Pa) applied to the sample powders. Q represents a rate of flow-out of the sample powders, and is calculated with the following equation:
Rate of flow-out Q of sample powders=(X/10)×(A/t)
where X represents an amount of travel (unit of mm) of the piston, t represents a measurement time period (unit of second), and A is as described above.
In order to obtain toner particles satisfying relation of |Tm1−Tm5|≧20° C., for example, a concentration of a urethane group in the first resin is preferably not lower than 0.8 mass % and not higher than 5 mass %. When the concentration of a urethane group in the first resin is not lower than 0.8 mass %, occurrence of high-temperature offset can also be prevented. The concentration of a urethane group in the first resin is more preferably not lower than 1 mass % and not higher than 3 mass %.
A concentration of a urethane group in the first resin can be measured with a gas chromatograph mass spectrometer (GCMS). Specifically, under conditions shown below (conditions for pyrolysis of a urethane-modified polyester resin), a urethane-modified polyester resin is pyrolyzed. Then, a concentration of a urethane group is measured with a GCMS under conditions shown below (conditions for measurement of a concentration of a urethane group in the urethane-modified polyester resin). Then, a concentration of a urethane group in the first resin is calculated by using a ratio of ion intensity detected from the thermally decomposed urethane-modified polyester resin.
(Conditions for Pyrolysis of Urethane-Modified Polyester Resin)
Apparatus: PY-2020iD manufactured by Frontier Laboratories Ltd.
Mass of sample: 0.1 mg
Heating temperature: 550° C.
Heating time period: 0.5 minute
(Conditions for Measurement of Concentration of Urethane Group in Urethane-Modified Polyester Resin)
Apparatus: GCMS-QP2010 manufactured by Shimadzu Corporation
Column: UltraALLOY-5 manufactured by Frontier Laboratories Ltd. (inner diameter: 0.25 mm, length: 30 m, thickness: 0.25 μm)
Temperature increase condition: Temperature Increase Range: 100° C. to 320° C. (held at 320° C.), Rate of Temperature Increase: 20° C./min.
<Insulating Liquid>
The insulating liquid in the present embodiment has a resistance value preferably to such an extent as not distorting an electrostatic latent image (approximately from 1011 to 1016 Ω·cm) and preferably it is a solvent having low odor and toxicity. The insulating liquid is generally exemplified by aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon, or polysiloxane. In particular from a point of view of low odor and toxicity as well as low cost, the insulating liquid is preferably a normal paraffin based solvent or an isoparaffin based solvent, and preferably Moresco White (trade name, manufactured by MORESCO Corporation), Isopar (trade name, manufactured by Exxon Mobil Corporation), Shellsol (trade name, manufactured by Shell Chemicals Japan Ltd.), or IP Solvent 1620, IP Solvent 2028, or IP Solvent 2835 (each of which is trade name and manufactured by Idemitsu Kosan Co., Ltd.).
<Manufacturing of Liquid Developer>
The liquid developer according to the present embodiment is preferably manufactured by dispersing toner particles in an insulating liquid. Toner particles are preferably manufactured in accordance with a method shown below.
<Method of Manufacturing Toner Particles>
Toner particles are preferably manufactured based on such a known technique as a crushing method or a granulation method. In the crushing method, resin particles and a pigment are mixed and kneaded, and then the mixture is crushed. Crushing is preferably carried out in a dry state or a wet state such as in oil.
The granulation method is exemplified, for example, by a suspension polymerization method, an emulsion polymerization method, a fine particle aggregation method, a method of adding a poor solvent to a resin solution for precipitation, a spray drying method, or a method of forming a core/shell structure with two different types of resins.
In order to obtain toner particles having a small diameter and sharp particle size distribution, the granulation method rather than the crushing method is preferably employed. A resin high in meltability or a resin high in crystallinity is soft even at a room temperature and less likely to be crushed. Therefore, with the granulation method, a desired toner particle size is obtained more easily than with the crushing method. Among the granulation methods, toner particles are preferably manufactured with a method shown below. Initially, a core resin solution is obtained by dissolving a resin in a good solvent. Then, the core resin solution described above is mixed, together with an interfacial tension adjuster, in a poor solvent different in SP value from the good solvent, shear is provided, and thus a droplet is formed. Thereafter, by volatilizing the good solvent, toner particles are obtained. With this method, controllability of a particle size or a shape of toner particles based on variation in how to provide shear, difference in interfacial tension, or an interfacial tension adjuster (a material for the shell resin) is high. Therefore, toner particles having desired particle size distribution are likely to be obtained.
<Image Formation Apparatus>
A construction of an apparatus for forming an image (image formation apparatus) which is formed by a liquid developer according to the present embodiment is not particularly limited. An image formation apparatus is preferably, for example, a monochrome image formation apparatus in which a monochrome liquid developer is primarily transferred from a photoconductor to an intermediate transfer element and thereafter secondarily transferred to a recording medium, an image formation apparatus in which a monochrome liquid developer is directly transferred from a photoconductor to a recording medium, or a multi-color image formation apparatus forming a color image by layering a plurality of types of liquid developers. Preferably, the image formation apparatus according to the present embodiment includes a transfer mechanism shown in
<Image Formation Method>
The image formation method according to the present embodiment is a method of forming an image with the use of the liquid developer according to the present embodiment, and it preferably includes the steps of transferring the liquid developer according to the present embodiment to a recording medium and fixing the toner particles contained in the liquid developer transferred to the recording medium to the recording medium. The step of transferring the liquid developer to the recording medium is preferably performed in accordance with a known transfer method. The fixing step will mainly be shown below.
<Fixing Step>
The toner particles contained in the liquid developer transferred to the recording medium are preferably fixed to the recording medium at a pressure not lower than 200 kPa and not higher than 700 kPa. More preferably, a pressure during fixation is not lower than 250 kPa and not higher than 600 kPa. When a pressure during fixation is lower than 200 kPa, sufficient load may not be applied to the toner particles during fixation, and hence the toner particles may be less likely to soften during fixation. When a pressure during fixation is higher than 700 kPa, an image (in particular, a line image) may collapse. Here, a pressure during fixation is calculated by dividing the total load onto the toner particles by an area of a nipping portion formed between fixation rollers.
In order to set a pressure during fixation not lower than 200 kPa and not higher than 700 kPa, the total load onto a roller or hardness of a roller is preferably adjusted.
<Heating Step>
The fixing step preferably includes the step of heating the recording medium. Thus, the toner particles on the recording medium are heated and softened by pressurization.
A heating condition in the step of heating the recording medium preferably satisfies relation of Tm5≦T1≦(Tm1+10° C.), where T1 (° C.) represents a temperature of the recording medium after the toner particles are fixed to the recording medium. Thus, it is considered that a temperature of the recording medium during fixation is not lower than Tm5 (° C.) and not higher than (Tm1+10° C.) and hence a temperature of the toner particles during fixation is considered to be not lower than Tm5 (° C.) and not higher than (Tm1+10° C.). Therefore, occurrence of high-temperature offset can be prevented while fixability and glossiness are ensured. When Tm5 is higher than T1 (Tm5>T1), a temperature of the recording medium during fixation is considered to be lower than Tm5 (° C.) and hence a temperature of the toner particles during fixation is considered to be lower than Tm5 (° C.). Therefore, the toner particles may be less likely to soften during fixation, and hence fixability may be lowered. When T1 is higher than (Tm1+10° C.) (T1>(Tm1+10° C.)), a temperature of the recording medium during fixation is considered to be higher than (Tm1+10° C.) and hence a temperature of the toner particles during fixation is considered to be higher than (Tm1+10° C.). Therefore, the toner particles may excessively soften during fixation, and hence high-temperature offset may occur.
T1 (° C.) herein represents a temperature of a recording medium 2 (a portion where an image has not yet been formed) after lapse of 0.025 second since passage through the nipping portion formed between the fixation rollers, and it can be measured with a method shown below.
Then, a digital radiation temperature sensor 13, a digital amplifier 14, and a personal computer 15 are used to find T1 (° C.). Here, digital radiation temperature sensor 13 is arranged at a point distant by 35 mm from a surface of recording medium 2 (D shown in
The recording medium may be heated only through contact heating, or may be heated through non-contact heating followed by contact heating.
<Contact Heating>
Contact heating means heating of a recording medium while a heat source is in contact with the recording medium, and it can be carried out, for example, with the use of the fixers shown in
In the fixer shown in
In the fixer shown in
In the fixer shown in
A heating condition in contact heating preferably satisfies relation of Tm5≦T1≦(Tm1+10° C.). To that end, for example, a temperature of first fixation roller 4 or second fixation roller 5 is preferably not lower than 80° C. and not higher than 200° C.
<Non-Contact Heating Followed by Contact Heating>
Non-contact heating means heating of a recording medium while a heat source is not in contact with the recording medium. In the following, the step of non-contact heating is denoted as a “first heating step” and the step of contact heating is denoted as a “second heating step.”
When toner particles are fixed to a recording medium by performing the second heating step after the first heating step, the heating step is performed twice. Therefore, even when a sufficient amount of heat could not be provided to toner particles on recording medium 2 in the second heating step, lowering in fixability can be prevented. Therefore, when image formation processing is performed at a high speed or when two or more toner layers are formed as layered on a recording medium, the second heating step is preferably performed after the first heating step.
When the image formation processing is performed at a high speed by performing the second heating step after the first heating step, an effect shown below can also be obtained. In performing image formation processing at a high speed, a sufficient nip time is less likely to be given in the second heating step. Therefore, if only the second heating step is performed without performing the first heating step, low-temperature offset (removal of a part of a toner image formed on a recording medium due to adhesive force or electrostatic attraction force between a fixation roller and toner particles in fixation of toner particles with the use of a heating roller) may occur in the second heating step. By performing the second heating step after the first heating step, however, occurrence of low-temperature offset in the second heating step can be prevented because the toner particles have been heated also in the first heating step.
When the second heating step is performed after the first heating step, a heating condition in the first heating step preferably satisfies relation of Tms5≦T2≦Tm1 and a heating condition in the second heating step preferably satisfies relation of Tm5≦T3≦(Tm1+10° C.). Here, T2 (° C.) represents a temperature of a recording medium after the first heating step and before the second heating step, T3 (° C.) represents a temperature of a recording medium after the second heating step, and Tms5 (° C.) represents a melt start temperature of toner particles measured with a flow tester under a load of 5 kg.
When relation of Tms5≦T2≦Tm1 is satisfied, a temperature of the toner particles in the first heating step is considered to be not lower than Tms5 (° C.) and not higher than Tm1 (° C.). Thus, since toner particles are sufficiently softened and aggregate with one another in the first heating step, an insulating liquid is readily discharged from between the toner particles. Therefore, in the second heating step, the insulating liquid is likely to permeate through the recording medium, and the insulating liquid is readily volatilized. Therefore, since density of toner particles fixed to the recording medium increases, occurrence of low-temperature offset is prevented and image deletion (a phenomenon that a toner image formed on a recording medium is blurred or is deleted as being rubbed) is also less likely.
When Tms5 is higher than T2 (Tms5>T2), a temperature of the toner particles in the first heating step is considered to be lower than Tms5 (° C.). Therefore, in the first heating step, the toner particles may not sufficiently be softened. Thus, in the second heating step, low-temperature offset or image deletion may occur. When T2 is higher than Tm1 (T2>Tm1), a temperature of the toner particles in the first heating step is considered to be higher than T2 (° C.). Therefore, in the first heating step, the toner particles are readily softened. Therefore, in the second heating step, high-temperature offset may occur.
Regarding Tm5≦T3≦(Tm1+10° C.), the discussion for Tm5≦T1≦(Tm1+10° C.) also applies thereto.
T2 (° C.) herein represents a temperature of recording medium 2 (a portion where an image has not yet been formed) 0.1 second before passage through the nipping portion formed between the fixation rollers, and it can be measured with the method of measuring T1 (° C.) above, except that a position reached 0.1 second before passage of recording medium 2 through the nipping portion is defined as a point of measurement. T3(° C.) herein represents a temperature of recording medium 2 (a portion where an image has not yet been formed) reached after lapse of 0.025 second since passage through the nipping portion formed between the fixation rollers, and it can be measured in accordance with the method of measuring T1 (° C.) above.
The second heating step is preferably performed after the first heating step, with the use of the fixer shown in
Though the present invention will be described hereinafter in further detail with reference to Examples, the present invention is not limited thereto.
In a beaker made of glass, 100 parts by mass of 2-decyltetradecyl (meth)acrylate, 30 parts by mass of methacrylic acid, 70 parts by mass of an equimolar reactant with hydroxyethyl methacrylate and phenyl isocyanate, and 0.5 part by mass of azobis methoxy dimethyl valeronitrile were introduced, and stirred and mixed at 20° C. Thus, a monomer solution was obtained.
Then, a reaction vessel provided with a stirrer, a heating and cooling apparatus, a thermometer, a dropping funnel, a desolventizer, and a nitrogen introduction pipe was prepared. In that reaction vessel, 195 parts by mass of THF were introduced, and the monomer solution above was introduced in the dropping funnel provided in the reaction vessel. After a vapor phase portion of the reaction vessel was replaced with nitrogen, the monomer solution was dropped in THE in the reaction vessel for 1 hour at 70° C. in a sealed condition. Three hours after the end of dropping of the monomer solution, a mixture of 0.05 part by mass of azobis methoxy dimethyl valeronitrile and 5 parts by mass of THF was introduced in the reaction vessel and caused to react for 3 hours at 70° C. Thereafter, cooling to room temperature was carried out. Thus, a copolymer solution was obtained.
Four hundred parts by mass of the obtained copolymer solution were dropped in 600 parts by mass of IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.) which was being stirred, and THF was distilled out at 40° C. at a reduced pressure of 0.039 MPa. Thus, a dispersion liquid (W1) of shell particles was obtained. A volume average particle size of the shell particles in the dispersion liquid (W1) was measured with a laser particle size distribution analyzer (“LA-920” manufactured by Horiba, Ltd.), which was 0.12 μm.
In a reaction vessel provided with a stirrer, a heating and cooling apparatus, and a thermometer, 937 parts by mass of polyester resin (Mn: 6000) obtained from sebacic acid, adipic acid, and ethylene glycol (a molar ratio of 0.8:0.2:1) and 300 parts by mass of acetone were introduced and dissolved uniformly in acetone by stirring. In the obtained solution, 63 parts by mass of IPDI were introduced and caused to react for 6 hours at 80° C. When an NCO value attained to 0, 28 parts by mass of terephthalic acid were further added and caused to react for 1 hour at 180° C. Thus, a core resin which was a urethane-modified polyester resin was obtained. Eight hundred parts by mass of the obtained core resin and 1200 parts by mass of acetone were stirred in a beaker, to thereby uniformly dissolve the core resin in acetone. Thus, a solution (Y1) for forming a core resin was obtained.
The core resin obtained in the present Manufacturing Example had Mn of 25000, Mw of 45000, and a concentration of a urethane group of 1.44 mass %.
A solution for forming a core resin in Manufacturing Example 3 was obtained in accordance with the method in Manufacturing Example 2 above except that a polyester resin obtained from sebacic acid, adipic acid, and ethylene glycol (a molar ratio of 0.8:0.2:1) had Mn of 3500. The core resin obtained in the present Manufacturing Example had Mn of 18000 and a concentration of a urethane group of 2.55 mass %.
A solution for forming a core resin in Manufacturing Example 4 was obtained in accordance with the method in Manufacturing Example 2 above except that a polyester resin obtained from sebacic acid, adipic acid, and ethylene glycol (a molar ratio of 0.8:0.2:1) had Mn of 7000. The core resin obtained in the present Manufacturing Example had Mn of 22000 and a concentration of a urethane group of 1.11 mass %.
A solution for forming a core resin in Manufacturing Example 5 was obtained in accordance with the method in Manufacturing Example 2 above except that a polyester resin obtained from sebacic acid, adipic acid, and ethylene glycol (a molar ratio of 0.8:0.2:1) had Mn of 8800. The core resin obtained in the present Manufacturing Example had Mn of 22000 and a concentration of a urethane group of 0.78 mass %.
In a reaction vessel provided with a stirrer, a heating and cooling apparatus, and a thermometer, 937 parts by mass of polyester resin (Mn: 3500) obtained from terephthalic acid and an adduct of propylene oxide to bisphenol A (a molar ratio of 1:1) and 300 parts by mass of acetone were introduced and stirred for uniform solution. Eight hundred parts by mass of the obtained core resin and 1200 parts by mass of acetone were introduced and stirred in a beaker, to thereby uniformly dissolve the core resin in acetone. Thus, a solution for forming a core resin in Manufacturing Example 6 was obtained.
In a reaction vessel provided with a stirrer, a heating and cooling apparatus, and a thermometer, 937 parts by mass of polyester resin (Mn: 2000) obtained from terephthalic acid, fumaric acid, and an adduct of propylene oxide to bisphenol A (a molar ratio of 0.8:0.2:1) and 300 parts by mass of acetone were introduced and stirred for uniform solution. Eight hundred parts by mass of the obtained core resin and 1200 parts by mass of acetone were introduced and stirred in a beaker, to thereby uniformly dissolve the core resin in acetone. Thus, a solution for forming a core resin in Manufacturing Example 7 was obtained.
In a beaker, 20 parts by mass of acid-treated copper phthalocyanine (“FASTGEN Blue FDB-14” manufactured by DIC Corporation), 5 parts by mass of a dispersant for pigment “Ajisper PB-821” (manufactured by Ajinomoto Fine-Techno Co., Inc.), and 75 parts by mass of acetone were introduced and stirred to uniformly disperse acid-treated copper phthalocyanine. Thereafter, copper phthalocyanine was finely dispersed with the use of a bead mill. Thus, a dispersion liquid of a pigment was obtained. A volume average particle size of the pigment (copper phthalocyanine) in the dispersion liquid of the pigment was 0.2 μm
Forty parts by mass of the solution (Y1) for forming the core resin and 20 parts by mass of the dispersion liquid of the pigment obtained in Manufacturing Example 8 were introduced in a beaker and stirred at 8000 rpm with the use of TK Auto Homo Mixer (manufactured by PRIMIX Corporation) at 25° C. Thus, a resin solution (Y11) in which the pigment was uniformly dispersed was obtained.
In another beaker, 67 parts by mass of IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.) and 11 parts by mass of the dispersion liquid (W1) of the shell particles were introduced to uniformly disperse the shell particles. Then, while TK Auto Homo Mixer was used at 25° C. to perform stirring at 10000 rpm, 60 parts by mass of the resin solution (Y11) was introduced and stirred for 2 minutes. Then, the obtained liquid mixture was introduced in a reaction vessel provided with a stirrer, a heating and cooling apparatus, a thermometer, and a desolventizer, and a temperature was raised to 35° C. At a reduced pressure of 0.039 MPa at that temperature, acetone was distilled out until a concentration of acetone was not higher than 0.5 mass %. Thus, a liquid developer was obtained.
Liquid developers in Manufacturing Examples 10 to 14 were obtained in accordance with the method in Manufacturing Example 9 above, except that the solution (Y1) for forming the core resin was changed to solutions for forming a core resin shown in Table 2.
The transfer mechanism shown in
Liquid developer 21 on leveling roller 25 is sent to a development roller 26. The excessive liquid developer on development roller 26 is scraped off by a development cleaning blade 27, and remaining liquid developer 21 is charged by a development charger 28 and developed on a photoconductor 29. Specifically, a surface of photoconductor 29 is evenly charged by a charging portion 30, and an exposure portion 31 arranged around photoconductor 29 emits light based on prescribed image information to the surface of photoconductor 29. Thus, an electrostatic latent image based on the prescribed image information is formed on the surface of photoconductor 29. As the formed electrostatic latent image is developed, a toner image is formed on photoconductor 29. The excessive liquid developer on photoconductor 29 is scraped off by a cleaning blade 32.
The toner image formed on photoconductor 29 is primarily transferred to an intermediate transfer element 33 at a primary transfer portion 37, and the liquid developer transferred to intermediate transfer element 33 is secondarily transferred to recording medium 2 at a secondary transfer portion 38. The liquid developer transferred to recording medium 2 is fixed, and the liquid developer which remained on intermediate transfer element 33 without being secondarily transferred is scraped off by an intermediate transfer element cleaning portion 34.
In the present Example, Z-1 shown in Table 2 was employed as the liquid developer, OK top coat (manufactured by Oji Paper Co., Ltd., 128 g/m2) was employed as recording medium 2, and a velocity of transportation of recording medium 2 was set to 400 mm/s. During transfer, the surface of photoconductor 29 was positively charged by charging portion 30, a potential of intermediate transfer element 33 was set to −400 V, and a potential of a secondary transfer roller 35 was set to −1200 V. During fixation, a fixation NIP time was set to 50 milliseconds, a temperature of each of first fixation roller 4 and second fixation roller 5 was set to 130° C., and a set pressure of first fixation roller 4 and second fixation roller 5 was set to 680 kPa. Thus, a solid image of which amount of toner adhesion was 1.0 g/m2 was obtained.
An image in Example 2 was obtained under conditions shown in Table 3. Specifically, an image in the present Example was obtained in accordance with the method described in Example 1 above, except that Z-2 shown in Table 2 was employed as the liquid developer, a temperature of each of first fixation roller 4 and second fixation roller 5 was set to 120° C., and a set pressure of first fixation roller 4 and second fixation roller 5 was set to 220 kPa.
An image in Example 3 was obtained under conditions shown in Table 3. Specifically, an image in the present Example was obtained in accordance with the method described in Example 1 above, except that Z-3 shown in Table 2 was employed as the liquid developer, a fixation NIP time was set to 40 milliseconds, and a set pressure of first fixation roller 4 and second fixation roller 5 was set to 430 kPa.
An image in Example 4 was obtained under conditions shown in Table 3. Specifically, an image in the present Example was obtained in accordance with the method described in Example 3 above, except that a solid image of which amount of toner adhesion was 3.0 g/m2 was obtained.
An image in Example 5 was obtained under conditions shown in Table 3. Specifically, fixation was carried out with the use of the apparatus shown in
An image in Example 6 was obtained under conditions shown in Table 3. Specifically, an image in the present Example was obtained in accordance with the method described in Example 5 above, except that a set pressure of first fixation roller 4 and second fixation roller 5 was set to 150 kPa.
An image in Example 7 was obtained under conditions shown in Table 3. Specifically, an image in the present Example was obtained in accordance with the method described in Example 1 above, except that Z-4 shown in Table 2 was employed as the liquid developer and a set pressure of first fixation roller 4 and second fixation roller 5 was set to 430 kPa.
An image in Comparative Example 1 was obtained under conditions shown in Table 3. Specifically, an image in the present Comparative Example was obtained in accordance with the method described in Example 5 above, except that Z-5 shown in Table 2 was employed as the liquid developer, a fixation NIP time was set to 50 milliseconds, and a solid image of which amount of toner adhesion was 1.0 g/m2 was obtained.
An image in Comparative Example 2 was obtained under conditions shown in Table 3. Specifically, an image in the present Comparative Example was obtained in accordance with the method described in Comparative Example 1 above, except that Z-6 shown in Table 2 was employed as the liquid developer.
<Measurement of Tm1 (° C.), Tm5 (° C.), and Tms5 (° C.)>
A flow tester (capillary rheometer) (“CFT-500D” manufactured by Shimadzu Corporation) was used to measure Tm1 (° C.), Tm5 (° C.), and Tms5 (° C.). Table 4 shows results.
<Measurement of T1, T2, and T3>
T1, T2, and T3 were measured with the method shown in
<Measurement of Degree of Gloss>
Seventy-five-degree Gloss Meter (VG-2000 manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure a degree of gloss of a solid portion of a fixed image. Table 4 shows results. In Table 4, a degree of gloss not lower than 70 is denoted as A1, a degree of gloss not lower than 60 and lower than 70 is denoted as B1, and a degree of gloss lower than 60 is denoted as C1. As a degree of gloss is higher, it can be concluded that such a liquid developer is excellent in glossiness.
<Measurement of Fixation Strength>
An obtained image was subjected to a tape peel test. Initially, a tape (“Scotch® mending tape” manufactured by Sumitomo 3M Limited) was stuck to a site of interest of measurement on coated paper to which the image had been fixed, and thereafter the tape was peeled off. Density of an image (ID) peeled by the tape was then determined with a reflection density meter (trade name: “X-Rite model 404”, manufactured by X-Rite, Incorporated.). Table 4 shows results. In Table 4, image density less than 0.1 is denoted as A2, image density not less than 0.1 and less than 0.15 is denoted as B2, and image density not less than 0.15 is denoted as C2. It can be concluded that lower image density indicates less likeliness of peel-off of a fixed image by the tape and hence such a liquid developer is excellent in fixability.
<Evaluation of High-Temperature Offset>
Whether or not high-temperature offset occurred was observed by feeding white paper immediately after feeding of coated paper. Table 4 shows results. In Table 4, a case where white paper was not contaminated with toner is denoted as A3, a case where white paper was slightly contaminated with toner is denoted as B3, and a case where white paper was significantly contaminated with toner is denoted as C3. When high-temperature offset occurs, first fixation roller 4 or second fixation roller 5 is contaminated and contamination is transferred to white paper. Therefore, unless white paper is contaminated with toner, it can be concluded that high-temperature offset has not occurred.
As shown in Table 4, in Examples 1 to 7, fixation strength and glossiness did not lower or high-temperature offset did not occur either even after 1K consecutive paper feed. On the other hand, in Comparative Example 1, glossiness and fixation strength lowered after 1K consecutive paper feed. The reason may be |Tm1−Tm5| was less than 20° C. (|Tm1−Tm5|<20° C.). In Comparative Example 2, high-temperature offset occurred, which seems to have resulted from adjustment of a molecular weight of the resin for increase in glossiness and fixation strength.
Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the scope of the present invention being interpreted by the terms of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-195142 | Sep 2013 | JP | national |
