Patent Grant
7946699
This application claims priority under 35 USC 119 from Japanese Patent Application Nos. 2006-171732 and 2007-120744, the disclosure of which are incorporated by reference herein.
1. Field of the Invention
The invention relates to an ink jet recording method and an ink jet recording device, and specifically relates to an ink jet recording method and an ink jet recording device favorably used for forming a high-quality image at high-speed.
2. Description of the Related Art
An ink jet method of ejecting ink in the form of liquid droplets from an ink ejector has been used in various kinds of printers for the reasons of being compact and less expensive, capable of forming an image without contacting a recording medium, or the like. Among these ink jet methods, there are a piezo ink jet method utilizing deformation of piezoelectric elements to eject ink and a thermal ink jet method utilizing boiling phenomenon of ink due to thermal energy to eject ink in droplets, which have the characteristics of high resolution and high-speed printability.
Improvements of speed and image quality have currently become important objectives, upon printing by ejecting ink droplets onto a plain paper sheet or a non-water absorbing recording medium made of plastics or the like with an ink jet printer.
Ink jet recording is a method of ejecting ink droplets according to image data to form a line or an image on a recording medium with the liquid droplets. However, there have been problems in practical use, particularly in the case of recording on the above described non-absorbing recording medium, e.g., bleeding of an image easily occurs, or mixing of adjacent ink droplets occurs on the recording medium to inhibit formation of a sharp image, when it takes time for the liquid droplets to dry or penetrate into the recording medium after being ejected. When the liquid droplets mix with each other, ejected adjacent liquid droplets coalesce with each other to shift from the positions at which they have landed, thereby causing unevenness in line width in a case of forming fine lines or unevenness in color in a case of forming a colored area, or the like. Further, since the degree of occurrence of unevenness in line width or color unevenness in a colored area varies depending on ink absorption and wettability of the surface of the recording medium, there has also been a problem that different images are formed among various types of recording media, even though the same ink is used under the same ejection conditions.
As a method of suppressing image bleeding or nonuniformity of line width, there is a method of promoting fixation of liquid droplets. For example, there have been disclosed the methods of using inks of two-liquid type having reactivity and allowing them to react with each other on a recording medium to achieve a describing property with high definition, such as a method of recording with ink containing an anionic dye after application of a liquid containing a basic polymer (for example, refer to Japanese Patent Application Laid-Open (JP-A) No. 63-60783), or a method of applying ink containing an anionic compound and a coloring material after application of a liquid composition containing a cationic substance (for example, refer to JP-A No. 8-174997).
An ink jet recording method has also been proposed in which an ultraviolet-curable ink is used as the ink, and the ejected ink dots on a recording medium are irradiated with an ultraviolet ray in conformity with the timing of ejection, then the dots are pre-cured to be thickened to such an extent that the adjacent dots do not mix with each other, and thereafter the dots are further irradiated with an ultraviolet ray to complete curing (for example, refer to JP-A No. 2004-42548).
Further, a method has been proposed that improves visibility or bleeding of color ink and the problem such as variation in the obtained images formed on different types of recording media, by applying a radiation curable white ink to form a uniform undercoating layer onto a transparent or a semi-transparent non-absorbing recording medium, then curing or thickening the layer by irradiating with a radiation ray, thereafter recording with a radiation curable color ink (for example, refer to JP-A No. 2003-145745 and JP-A No. 2004-42525). There has also been proposed a method in which a substantially transparent active ray-curable ink is applied onto a recording medium in place of the radiation curable white ink by an ink jet head (for example, refer to JP-A No. 2005-96254).
However, in the method described in JP-A No. 2004-42548, although blurring can be suppressed, there still remains the problem of variation in images among various types of recording media, and thus the problem of unevenness in line width, color or the like due to mixing of ink droplets are not sufficiently solved. This problem of unevenness in line width, color or the like due to mixing of ink droplets are also not sufficiently solved by any of the methods described in JP-A No. 2003-145745, JP-A No. 2004-42525. Further, there sill remains a problem of unevenness in line width, color or the like due to mixing of ink droplets in the method described in JP-A No. 2005-96254.
The invention has been made in view of the above problems and provides an ink jet recording method and an ink jet recording device.
According to a first aspect of the invention, there is provided an ink jet recording method that records an image by ejecting, onto a recording medium, an ink that is cured by irradiation of an active energy ray, the method comprising:
applying an undercoating liquid onto the recording medium;
half-curing the undercoating liquid; and
forming an image by ejecting an ink onto the half-cured undercoating liquid.
According to a second aspect of the invention, there is provided an ink jet recording device comprising:
an undercoating liquid application unit that applies an undercoating liquid onto a recording medium;
an undercoating liquid curing unit that is provided downstream of the undercoating liquid application unit and that half-cures of the undercoating liquid by applying energy; and
an image forming unit that is provided downstream of the undercoating liquid curing unit and that forms an image by ejecting, onto the undercoating liquid, an ink that is curable by irradiation of an active energy ray.
Exemplary embodiments of the present invention will be described in detail based on the following figures, wherein:
The ink jet recording method of the invention is a method of forming an image by half-curing at least one kind of undercoating liquid applied onto a recording medium and ejecting at least one kind of ink capable of curing by irradiation with an active energy ray, onto the half-cured undercoating liquid.
Generally, in an ink jet recording method, ink droplets are ejected so as to partly overlap each other to obtain a high degree of image density and the adjacent ink droplets before being dried stay on a recording medium and coalesce with each other. Therefore, image bleeding or unevenness in line width of fine lines may easily occur, thereby impairing formation of an image having high sharpness. However, in the ink jet recording method of the invention, an undercoating liquid is applied onto a recording medium and half-cured, and even when ink droplets are applied so as to partly overlap each other onto the half-cured undercoating liquid, image bleeding or unevenness in line width of fine lines can be effectively prevented by the interaction between the undercoating liquid and the ink droplets.
Therefore, the ink jet recording method of the invention enables formation of sharp lines with uniform width and recording of an ink jet image with high image density, i.e., a reverse character, with favorable reproducibility of fine images such as fine lines.
The ink jet recording method of the invention is particularly effective, for example, in the case of recording an image onto a non-permeable or slow permeable recording medium having low liquid absorption.
In the invention, the description “adjacent ink droplets” refers to the liquid droplets ejected from an ink ejecting port with an ink of a single color so as to have an overlapping portion, or the liquid droplets ejected from an ink ejecting port with inks of different colors to have an overlapping portion. The adjacent ink droplets may be the liquid droplets that are ejected at the same time, or may be composed of the preceding liquid droplets and the following liquid droplets where the former are ejected prior to the ejection of the latter.
In the invention, at least one kind of ink and at least one kind of undercoating liquid are used as the liquids for formation of an image. The undercoating liquid preferably has a different composition from that of the ink. The undercoating liquid is preferably applied onto the region that is equal to, or larger than, the region on which an image is formed by ejecting ink droplets onto a recording medium.
Further, the ink in the invention is preferably used as inks of plural colors in a multicolor ink set. In the case of using the multicolor ink set, it is preferable that after each ejection of the ink of each color, half-curing is further performed.
One of the specific configurations of the ink jet recording method of the invention includes the steps of applying, onto a recording medium, an undercoating liquid containing a polymerizable or crosslinkable material in advance in the region that is equal to, or larger than, the region on which an image is formed with ink; applying an energy ray or heat to the undercoating liquid applied onto the recording medium; and ejecting the ink droplets of plural colors on the side of the recording medium onto which the undercoating liquid has been applied, after half-curing the undercoating liquid by the active energy ray or heat, wherein the ink droplets contain a polymerizable or crosslinkable material for formation of the image and have a different composition from that of the undercoating liquid.
In the above method, it is preferable to provide a step of fixing the recorded image by applying energy, after the undercoating liquid has been applied and at least all of the inks of plural colors have been ejected, from the viewpoint of achieving excellent fixing properties. By applying energy, curing reaction caused by polymerization or crosslinking of the polymerizable or crosslinkable material contained in the undercoating liquid or the ink is promoted, thereby enabling formation of a tougher image with more efficiency. For example, in a system containing a polymerization initiator, generation of active species is promoted due to decomposition of the polymerization initiator by applying of active energy such as an active energy ray or heat, and the curing reaction, which is due to polymerization or crosslinking of the polymerizable or crosslinkable material caused by the active species, is promoted by the increase in the amount of the active species or the increase in temperature.
Application of energy can favorably be performed by irradiation with an active energy ray or heating. As the active energy, similar ones to the later discussed active lights for image fixation can be used, such as ultraviolet rays, visible rays, α rays, γ rays, X rays and electron beams, wherein ultraviolet rays and visible rays are preferable and ultraviolet rays are particularly preferable, from the viewpoint of cost and safety.
Further, the heating can be performed using a non-contact type heating device, and preferable ones include a heating device in which the recording medium passes through, such as an oven, or a heating device in which exposure is performed over the whole area with light in the range of ultraviolet light-visible light-infrared light, or the like. Examples of the preferable light sources for use in exposure as a heating device include a metal halide lamp, xenon lamp, tungsten lamp, carbon arc lamp and a mercury lamp.
When the energy is applied by irradiation with active light, the amount of the energy required for curing reaction varies depending on the type or content of the polymerization initiator, but is generally preferably from about 100 to about 10000 mJ/cm2. When the energy is applied by heating, it is preferable to heat a recording medium under such conditions that the surface temperature of the recording medium becomes from 40 to 80° C., for the time period of from 0.1 to 1 second.
—Curing Process of Undercoating Liquid—
The invention is provided with a step of half-curing the applied undercoating liquid after the application of the undercoating liquid and before the ejection of at least one kind of ink droplets. Details of the application of the undercoating liquid and the ink droplets will be described later.
In the invention, the description “half-curing” refers to a state in which the undercoating liquid is partially but not completely cured. When the undercoating liquid that has been applied onto a recording medium (substrate) is half-cured, the degree of the curing may be uneven. For example, the curing is preferably more developed at a deeper point in a depth direction.
When a radical polymerizable undercoating liquid is used in the air or the air that has partly substituted by an inert gas, the radial polymerization at the surface of the undercoating liquid tends to be inhibited by the action of oxygen to inhibit the radial polymerization. As a result, the degree of the curing becomes uneven and the curing tends to be more developed in the inside of the undercoating liquid than at the surface thereof.
In the case where a cationic polymerization liquid is used in the air containing moisture, the curing also tends to be more developed in the inside of the undercoating liquid than at the surface thereof, due to the action of the moisture to inhibit the cationic polymerization.
In the invention, when a radical photopolymerizable undercoating liquid is used under coexistence of oxygen that tends to inhibit radical polymerization and partially photo-cured, the curing degree of the undercoating liquid becomes higher at the outside than in the inside thereof.
When an ink (hereinafter, referred to as “colored liquid” sometimes) is ejected onto an undercoating liquid that has not been cured, favorable effects can be achieved in the quality of an image that has been formed onto a recording medium. The mechanism of this action can be determined by observing a section of the recording medium.
Hereinafter, explanation will be given taking the case where an ink of about 12 pL (picoliter, hereinafter the same) is ejected onto a half-cured undercoating liquid layer having a thickness of 5 μm as an example, by reference with
As shown in
On the other hand, as shown in
When the colored liquid 24 is ejected onto a completely cured undercoating liquid 20, the colored liquid 24 does not submerge in the undercoating liquid 20, as shown in
It is preferable that the amount per area of the uncured part of the undercoating liquid is sufficiently smaller than the largest amount per area of the applied colored liquid, from the viewpoint that when the droplets of the colored liquid are applied with high density, they do not remain independent of each other and form a uniform liquid layer of the colored liquid; and that the occurrence of interdroplet interference is prevented. Therefore, the mass per area of the uncured part of the undercoating liquid “M (undercoating liquid)” and the largest mass per area of the applied ink droplets “m (colored liquid)” preferably satisfies a relation “m (colored liquid)/30<M (undercoating liquid)<m (colored liquid)”, further preferably satisfies a relation “m (colored liquid)/20<M (undercoating liquid)<m (colored liquid)/3”, and still more preferably satisfies a relation “m (colored liquid)/10<M (undercoating liquid)<m (colored liquid)/5”. The largest mass per area of the colored liquid to be ejected here refers to the largest mass of each case of respective colors. When a relation “m (colored liquid)/30<M (undercoating liquid)” is satisfied, occurrence of interdroplet interference can be prevented and excellent dot size reproducibility can be achieved. Further, when a relation “M (undercoating liquid)<m (colored liquid)” is satisfied, uniform liquid layer of the colored liquid can be formed and high density can be obtained.
The mass per area of the uncured part of the undercoating liquid can be determined by a transferring test, in which a permeable medium such as a plain paper sheet is pressed against the half-cured undercoating liquid, at a point after the completion of the half-curing process (e.g., after irradiation with an active energy ray) and prior to the ejection of the colored liquid droplets, and the mass of the undercoating liquid that has been transferred onto the permeable medium from the undercoating layer is measured.
For example, when the largest ejection amount of the colored liquid droplets in an ejection density of 600×600 dpi is 12 pL per pixel, the largest mass per area of the ejected colored liquid “m (colored liquid)” is determined to be 7.4 g/cm2 (here, the density of the colored liquid is assumed to be 1.1 g/cm3). Therefore, the preferable mass per area of the uncured part of the undercoating liquid is greater than 0.25 g/cm2 and less than 7.4 g/cm2, more preferably greater than 0.37 g/cm2 and less than 2.5 g/cm2, and still more preferably greater than 0.74 g/cm2 and less than 1.48 g/cm2.
Further, in a case of forming a secondary color from the inks of two colors (hereinafter, referred to as an ink A and an ink B) by applying one of the inks onto the other ink that has been half-cured, e.g., applying the ink B onto the half-cured ink A. When the ink B is ejected onto the half-cured ink A, a part of the ink B28 submerges in the ink A24, and at the same time, the ink A24 exists under the ink B28. Therefore, a recording medium on which an image is formed by applying the ink B28 onto the half-cured ink A24 has a section as schematically shown in
On the other hand, when the ink B is ejected onto the uncured ink A, the ink B28 submerges entirely in the ink A24 as shown in
When the ink B is ejected onto the completely cured ink A, ink B28 does not submerge in the ink A24, as shown in
It is preferable that the amount per area of the uncured part of the ink A is sufficiently smaller than the largest amount per area of the applied ink B, from the viewpoint that the droplets of the ink B applied with high density does not remain independent of each other and form a uniform liquid layer of ink B, and that occurrence of interdroplet interference is prevented. Therefore, the mass per area of the uncured part of ink A layer “M (ink A)” and the largest mass per area of the applied droplets of the ink B “m (ink B)” preferably satisfies a relation “m (ink B)/30<M (ink A)<m (ink B)”, further preferably satisfies a relation “m (ink B)/20<M (ink A)<m (ink B)/3”, and still more preferably satisfies a relation “m (ink B)/10<M (ink A)<m (ink B)/5”. When a relation “m (ink B)/30<M (ink A)” is satisfied, occurrence of interdroplet interference can be prevented, and excellent dot size reproducibility can be achieved. Further, when a relation “M (ink A)<m (ink B)” is satisfied, uniform liquid layer of an ink can be formed and high density can be obtained.
The mass per area of the uncured part of the ink A can be determined by a transferring test, in which a permeable medium such as a plain paper sheet is pressed against the half-cured layer of ink A, at the point after the completion of the half-curing process (e.g., after irradiation with an active energy ray) and prior to the ejection of the droplets of ink B, and the mass of the liquid that has been transferred onto the permeable medium from the layer of the ink A is measured.
For example, when the largest ejection amount of the droplets of the ink B in an ejection density of 600×600 dpi is 12 pL per pixel, the largest mass per area of the ejected ink B “m (ink)” is determined to be 7.4 g/cm2 (here, the density of the ink B is assumed to be 1.1 g/cm3). Therefore, the mass per area of the uncured part of the layer of the ink A is preferably greater than 0.25 g/cm2 and less than 7.4 g/cm2, more preferably greater than 0.37 g/cm2 and less than 2.5 g/cm2, and still more preferably greater than 0.74 g/cm2 and less than 1.48 g/cm2.
When the curing reaction is based on an ethylene unsaturated compound or a cyclic ether, the unpolymerization rate can be quantitatively measured from the reaction rate of the ethylene unsaturated compound or the cyclic ether.
When the above-described half-cured state of the undercoating liquid and/or the ink is achieved by polymerization reaction of a polymerizable compound that starts polymerization by irradiation with an active energy ray or heating, the unpolymerization rate defined as “A (after polymerization)/A (before polymerization)” is preferably from 0.2 to 0.9, more preferably from 0.3 to 0.9, and still more preferably from 0.5 to 0.9, in terms of improving abrasion resistance of a printed material.
In the above discussion, “A (after polymerization)” indicates an absorbance at an infrared absorption peak of a polymerizable group after polymerization, and “A (before polymerization)” indicates an absorbance at an infrared absorption peak of a polymerizable group before polymerization. For example, when the polymerizable compound contained in the undercoating liquid and/or the colored liquid is an acrylate monomer or a methacrylate monomer, an absorption peak based on a polymerizable group (acrylate group or methacrylate group) can be observed in the vicinity of 810 cm−1, and the unpolymerizaion rate is preferably determined by the absorbance at this peak. On the other hand, when the polymerizable compound is an oxetane compound, an absorption peak based on a polymerizable group (oxetane group) can be observed in the vicinity of 986 cm−1, and the unpolymerizaion rate is preferably determined by the absorbance at this peak. Further, when the polymerizable compound is an epoxy compound, an absorption peak based on a polymerizable group (epoxy group) can be observed in the vicinity of 750 cm−1, and the unpolymerizaion rate is preferably determined by the absorbance at this peak.
As the device for measuring an infrared absorption spectrum, any commercially available infrared spectrometer of transmission type or reflection type may be used and selected according to the form of the sample. For example, an infrared spectrometer (FTS-6000, manufactured by BIO-RAD Laboratories, Inc.) can be used for the measurement.
The methods for half-curing the undercoating layer can be exemplified by known methods for increasing viscosity, such as: (1) a method of utilizing a so-called aggregation phenomenon performed by adding a basic compound to an acidic polymer, or adding an acidic compound or metallic compound to a basic polymer; (2) a method of adjusting the viscosity of the undercoating liquid by preliminarily preparing an undercoating liquid to have high viscosity, then adding a low boiling point organic solvent to the undercoating liquid to decrease the viscosity thereof, and thereafter bringing the undercoating liquid back to have high viscosity by evaporating the low boiling point organic solvent; (3) a method of adjusting the viscosity of the undercoating liquid by heating the undercoating liquid which has previously been prepared to have high viscosity, then cooling the undercoating liquid back to have high viscosity; and (4) a method of causing a curing reaction by applying an active energy ray or heat to the undercoating liquid. Among these, (4) a method of causing a curing reaction by applying an active energy ray or heat to the undercoating liquid is most preferable.
The method of causing a curing reaction by applying an active energy ray or heat to an undercoating liquid is a method of causing an insufficient polymerization reaction of a polymerizable compound at the surface of the undercoating liquid applied onto a recording medium. At the surface of the undercoating layer, the polymerization reaction is easily inhibited under the influences of oxygen in the air, as compared with the inside of the undercoating layer. Therefore, half-curing of the undercoating layer can be caused by regulating the conditions of application of an active energy ray or heat.
The amount of the energy required for the half-curing of the undercoating liquid varies depending on the type or content of the polymerization initiator, but is generally preferably from about 1 to about 500 mJ/cm2 when energy is applied by an active energy ray. When energy is applied by heating, it is preferable to heat a recording medium under the conditions where the surface temperature of the recording medium becomes in the range of from 40 to 80° C., for a period of from 0.1 to 1 second.
By applying an active energy ray or heat such as active light or heat, generation of active species can be promoted by decomposition of the polymerization initiator, and the curing reaction due to polymerization or crosslinking of a polymerizable or crosslinkable material resulting from the active species can be promoted, by the increased active species or elevated temperature. Increasing of viscosity can also be favorably performed by irradiating with active light or heating.
Further preferable half-cured state can be determined by observing the section of ink droplet that has been ejected onto a half-cured undercoating liquid. The method of observation is not particularly limited, but for example, a commercially available microtome or optical microscope can be used. The size of the ink droplet that has been ejected onto a half-cured undercoating liquid is preferably in the range of from 1 pL to 100 pL, and is further preferably equal to the size of the ink droplet which is practically used. Further, the half-cured film is preferably fixed by a method of some kind, at the time of observation. The method for fixation is not particularly limited, but may be a method of utilizing freezing, polymerization or the like.
In the above, the half-curing of the undercoating liquid has been discussed, but the same will apply to the cases of half-curing of the ink (hereinafter, referred to as “ink liquid” sometimes).
—Application of Undercoating Liquid and Ink Droplets—
In the ink jet recording method of the invention, the undercoating liquid can be applied onto the recording medium using a coating device, an ink jet nozzle, and the like. The ink jet liquid droplets are ejected using an ink jet nozzle or the like, and are applied onto the half-cured undercoating liquid.
(i) Application Using an Application Device
In the invention, an embodiment is preferable in which an image is recorded by applying an undercoating liquid onto a recording medium using an application device, and thereafter ink droplets are ejected using an ink jet nozzle. Details of the ink jet nozzle will be discussed later.
The application device is not particularly limited and can be selected from known application devices as appropriate according to purposes. Examples of the application devices include an air doctor coater, blade coater, lot coater, knife coater, squeeze coater, immersion coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater and an extruding coater. Details of these coating devices can be referred to Yuji Harasaki, “Coating Engineering”, (1978).
(ii) Ejection by Ink Jet Nozzle
In the invention, an embodiment is also preferable in which an image is recorded by ejecting an undercoating liquid by an ink jet nozzle, and thereafter ink droplets are ejected by the ink jet nozzle. Details of the ink jet nozzle will be discussed later.
As the conditions for applying of the undercoating liquid by the ink jet nozzle, it is preferable that the undercoating liquid is ejected by a head capable of ejecting a greater amount per droplet and having lower nozzle density as compared with the head for an ink, and the head is arranged as a full-line head unit in a width direction of the recording medium. Such a head having a greater amount per droplets to be ejected generally has a high degree of ejection power, and is therefore compatible with an undercoating liquid having high viscosity, and is also advantageous in terms of avoiding nozzle clogging. Further, using of a head capable of ejecting a greater amount per droplet is also advantageous from the viewpoint that an inexpensive head having lower driving frequency can be applied, since the droplet resolution of the undercoating liquid in a conveyance direction of a recording medium can reduced.
In either case of the above embodiments, liquids other than the undercoating liquid and ink can be further applied. Any means such as an application device or an ink jet nozzle can be applied to the application of such liquids, and the timing thereof is also not particularly limited. When a colorant is contained in the liquid other than the undercoating liquid and ink, the liquid is preferably applied by ejecting with an ink jet nozzle, and is preferably applied after the undercoating liquid has been applied.
Next, a method of ejecting by an ink jet nozzle (ink jet recording method) will be discussed.
In the invention, known ink jet recording methods are preferably used, such as an electrostatic induction method in which an ink is ejected by means of electrostatic power, drop-on-demand method (pressure-pulse method) utilizing vibration pressure of a piezoelectric element, acoustic ink jet method in which ink is ejected by means of radiation pressure caused by irradiating the ink with an acoustic beam which has been converted from an electric signal, and a thermal ink jet method of utilizing the pressure generated by heating ink to form air bubbles.
In the invention, the ink is preferably ejected onto the half-cured undercoating liquid to a droplet size of from 0.1 pL to 100 pL. When the droplet size is within the above range, an image with high sharpness and density can be effectively formed. The droplet size is more preferably in the range of from 0.5 pL to 50 pL.
The amount of the undercoating liquid to be applied in terms of mass ratio per area is preferably from 0.05 to 5, more preferably from 0.07 to 4, and still more preferably from 0.1 to 3.
The ejection interval between the application of the undercoating liquid and the ejection of the ink droplet is preferably in the range of from 5μ seconds to 10 seconds. When the ejection interval is within the above range, the effect of the invention can be remarkably achieved. The ejection interval of the ink droplet is more preferably in the range of from 10μ seconds to 5 seconds, and particularly preferably from 20μ seconds to 5 seconds.
(Physical Properties of Ink and Undercoating Liquid)
Regarding the physical properties of the ink (liquid droplet) to be ejected onto a recording medium in an ink jet recording method, the viscosity at 25° C. thereof is preferably in the range of from 5 to 100 mPa·s, and more preferably in the range of from 10 to 80 mPa·s, although the value may vary dependent on the type of the devices. The viscosity at 25° C. of the undercoating liquid before being subjected to half-curing is preferably in the range of from 100 to 5000 mPa·s, and more preferably in the range of from 200 to 3000 mPa·s.
In the invention, the undercoating liquid preferably contains a surfactant from the viewpoint of forming the dots with the desired size onto a recording medium, and preferably satisfies all of the conditions (A), (B), and (C) described below:
(A) The surface tension of the undercoating liquid is smaller than that of at least one of the inks.
(B) At least one surfactant contained in the undercoating liquid satisfies the following relation:
γs(0)−γs(saturated)>0 (mN/m).
(C) The surface tension of the undercoating liquid satisfies the following relation:
γs<(γs(0)+γs(saturated)max)/2.
In the above relations, γs is the value of the surface tension of the undercoating liquid; γs (0) is the value of the surface tension of the liquid having a composition of the undercoating liquid from which all surfactants are excluded; γs (saturated) is the value of the surface tension of the liquid, wherein the liquid is obtained by adding one of the surfactants contained in the undercoating liquid to the above “liquid excluding all of the surfactants”, the value being measured when the surface tension reaches a point of saturation as the density of the surfactant is increased; and γs (saturated)max is the maximum value among the values of γs (saturated) respectively measured for all kinds of the surfactants which are contained in the undercoating liquid that satisfy the above condition (B).
<Condition (A)>
In the invention, the surface tension γs of the undercoating liquid is preferably smaller than the surface tension γk of at least one of the inks in order to form ink dots of desired size onto the recording medium as described above.
Further, from the viewpoint of preventing the spreading of the ink dots during the period from the landing of the ink droplets up to the exposure more effectively, the values of γs and γk preferably satisfy the relation of γs<γk−3 (mN/m), and more preferably satisfy the relation of γs<γk−5 (mN/m).
In the case of printing a full-color image, from the viewpoint of improving sharpness of the image, the surface tension of the undercoating liquid γs is preferably at least smaller than the surface tension of the ink containing a coloring agent with high visibility, and more preferably smaller than the surface tensions of all of the inks. The coloring agent with high visibility is, for example, a coloring agent that exhibits the color of magenta, black, or cyan.
Even though the values of the surface tension of the ink γk and the surface tension of the undercoating liquid γs satisfy the above-described relations, when both of the values are less than 15 mN/m, formation of the liquid droplets may become difficult at the time of ejecting the ink, and the ejection may not be carried out. On the other hand, when the above values are greater than 50 mN/m, wettability with the ink jet head may be deteriorated to cause a failure in ejection. Therefore, it is preferable that each of the surface tension of the ink γk and the surface tension of the undercoating liquid γs is within the range of from 15 mN/m to 50 mN/m, more preferably in the range of from 18 mN/m to 40 mN/m, and particularly preferably in the range of from 20 mN/m to 38 mN/m.
The surface tension mentioned here is a value measured in accordance with a Wilhelmy method at a liquid temperature of 20° C. and at 60% RH, by a commonly used surface tensiometer (for example, surface tensiometer CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.).
<Conditions (B) and (C)>
In the invention, the undercoating liquid preferably contains at least one kind of surfactant in order to form the ink dots of desired size onto a recording medium. In this case, it is preferable that at least one kind of surfactant contained in the undercoating liquid satisfies the condition (B) described below:
γs(0)−γs(saturated)>0 (mN/m) Condition (B)
Further, it is preferable that the surface tension of the undercoating liquid preferably satisfies the condition (C) described below:
γs<(γs(0)+γs(saturated)max)/2 Condition (C)
As mentioned above, γs is the value of the surface tension of the undercoating liquid; γs (0) is the value of the surface tension of the liquid having a composition of the undercoating liquid from which all surfactants are excluded; γs (saturated) is the value of the surface tension of the liquid, wherein the liquid is obtained by adding one kind of the surfactants contained in the undercoating liquid to the above “liquid excluding all of the surfactants”, and wherein the value is measured when the surface tension reaches a point of saturation as the density of the surfactant is increased; and γs (saturated)max is the maximum value among the values of γs (saturated) respectively measured for all kinds of surfactants contained in the undercoating liquid that satisfy the above condition (B).
The value γs (0) can be obtained by measuring the value of the surface tension of the liquid having the composition of the undercoating liquid from which all surfactants are excluded. The value γs (saturated) can be obtained by adding one kind of the surfactant contained in the undercoating liquid to the “liquid excluding all of the surfactants”, then increasing the concentration of the surfactant by the increment of 0.01% by mass, and measuring the surface tension at the point where the change in the degree of the surface tension relative to the change in the concentration of the surfactant becomes 0.01 mN/m or less.
Details of the values γs (0), γs (saturated) and γs (saturated)max will be discussed below by reference with the case where components of the undercoating liquid (Example 1) are: a high boiling point solvent (diethyl phthalate, manufactured by Wako Pure Chemical Industries, Ltd.); a polymerizable material (dipropylene glycol diacrylate, manufactured by Akcros Chemicals Ltd.), a polymerization initiator (TPO, shown below as “Initiator-1”); a fluorine-based surfactant (MEGAFAC F475, manufactured by Dainippon Ink and Chemicals, Inc.); and a hydrocarbon-based surfactant (sodium di-2-ethylhexyl sulfosuccinate).
In the above example, the values of γs (0), γs (saturated)1 (when the fluorine-based surfactant is added), γs (saturated)2 (when the hydrocarbon-based surfactant is added), γs (saturated), and γs (saturated)max are determined as follows.
The value of γs (0), indicating the surface tension of the liquid having a composition of the undercoating liquid from which all surfactants are excluded, is determined as 36.7 mN/m.
The value of γs (saturated)1, which is the saturated value of the surface tension of the liquid when the fluorine-based surfactant is added and the concentration thereof is increased, is determined as 20.2 mN/m.
The value of γs (saturated)2, which is the saturated value of the surface tension of the liquid when the hydrocarbon-based surfactant is added and the concentration thereof is increased, is determined as 30.5 mN/m.
Since the undercoating liquid (Example 1) contains two kinds of the surfactants that satisfy the above-described condition (B), there are two values of γs (saturated), i.e., the value when the fluorine-based surfactant is added (γs (saturated)1) and the value when the hydrocarbon-based surfactant is added (γs (saturated)2). Here, the value of γs (saturated)max, i.e., the maximum value between γs (saturated)1 and γs (saturated)2, is determined as the value of γs (saturated)2.
The above results are summarized as follows:
γs (0)=36.7 mN/m
γs (saturated)1=20.2 mN/m (when the fluorine-based surfactant is added)
γs (saturated)2=30.5 mN/m (when the hydrocarbon-based surfactant is added)
γs (saturated)max=30.5 mN/m
From the above results, the surface tension of the undercoating liquid γs preferably satisfies the relationship:
γs<(γs(0)+γs(saturated)max)/2=33.6 mN/m.
As for the above-described condition (C), from the viewpoint of preventing spreading of the ink droplets during the period from the landing of the liquid droplets up to the exposure, the surface tension of the undercoating liquid more preferably satisfies the relationship:
γs<γs(0)−3×{γs(0)+γs(saturated)max}/4
and particularly preferably satisfies the relationship:
γs≦γs(saturated)max.
The compositions of the ink and the undercoating liquid may be selected so that the desired surface tension can be obtained, but it is preferable that these liquids contain a surfactant. As described above, in order to form the ink dots of desired size onto a recording medium, the undercoating liquid preferably contains at least one kind of surfactant. Details of the surfactants will be explained below.
(Surfactant)
The surfactant in the invention is a substance having strong surface activity to at least one solvent selected from hexane, cyclohexane, p-xylene, toluene, ethyl acetate, methylethylketone, butyl carbitol, cyclohexanone, triethylene glycol monobutyl ether, 1,2-hexanediol, propylene glycol monomethyl ether, isopropanol, methanol, water, isobornyl acrylate, 1,6-hexane diacrylate, and polyethylene glycol diacrylate; preferably a substance having strong surface activity to at least one kind of solvent from hexane, toluene, propylene glycol monomethylether, isobonylacrylate, 1,6-hexanediacrylate, and polyethylene glycol diacrylate, more preferably a substance having a strong surface activity to at least one solvent selected from propylene glycol monomethyl ether, isobornyl acrylate, 1,6-hexane diacrylate, and polyethylene glycol diacrylate; and particularly preferably a substance having strong surface activity to at least one solvent selected from isobornyl acrylate, 1,6-hexane diacrylate, and polyethylene glycol diacylate.
Whether a compound has strong surface activity to the solvents listed above can be determined by the procedures as described below.
(Procedures)
One solvent is selected from the solvents listed above and measure the surface tension thereof. γsolvent (0). Add the objective compound in the same solvent used to measure the γsolvent (0), increase the concentration of the compound by the increment of 0.01% by mass, and measure the surface tension of the solution γsolvent (saturated) at the point when the change in the surface tension with respect to the change in the concentration of the compound becomes 0.01 mN/m or less.
If the relationship between the γsolvent (0) and the γsolvent (saturated) satisfies the following relation, the compound can be determined to have strong surface activity to the solvent:
γsolvent(0)−γsolvent(saturated)>1 (mN/m).
Specific examples of the surfactants contained in the undercoating liquid include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenensulfonates and fatty acid salts; nonionic surfactants such as polyoxyethylenealkyl ethers, polyoxyethylenealkylallyl ethers, acetylene glycols and polyoxyethylene-polyoxypropylene block copolymers; cationic surfactants such as alkylamine salts and quaternary ammonium salts; and fluorine-based surfactants. Examples of other surfactants include the surfactants described in JP-A No. 62-173463 and JP-A No. 62-183457.
(Curing Sensitivity of Ink and Undercoating Liquid)
In the invention, the curing sensitivity of the ink is preferably equal to or higher than the curing sensitivity of the undercoating liquid. More preferably, the curing sensitivity of the ink is not less than the curing sensitivity of the undercoating liquid and not more than 4 times as high as the curing sensitivity of the undercoating liquid. Further preferably, the curing sensitivity of the ink is not less than the curing sensitivity of the undercoating liquid and not more than twice as high as the curing sensitivity of the undercoating liquid or less.
The curing sensitivity here refers to the amount of the energy necessary to completely cure the ink and/or the undercoating liquid using a mercury lamp of super high pressure, high pressure, medium pressure or the like, preferably a super high pressure mercury lamp. Smaller amount of the energy indicates that the sensitivity is higher. Therefore, the curing sensitivity being twice as high indicates that the amount of energy is ½ as much.
When one of the two curing sensitivities is not more than twice as high as the other, preferably not more than 1.5 times as high as the other, the two curing sensitivities are regarded as being equal.
—Recording Medium—
Any recording medium of permeable, non-permeable or slow permeable can be used as the recording medium in the ink jet recording method in the invention. Among these, a non-permeable and a slow permeable recording medium are preferable from the viewpoint that the effect of the invention can be remarkably displayed. The permeable recording medium refers to, for example, a recording medium having such properties that when a liquid droplet of 10 pL is dropped onto the recording medium, the permeation time for the total amount of the droplet is 100 ms or less. The description “substantially does not permeate” refers to, for example, the conditions where the permeability of the liquid droplets after the lapse of one minute is 5% or less. The slow permeable recording medium refers to a recording medium having such properties that when a liquid droplet of 10 pL (pico liter) is dropped onto the recording medium, the permeating time for the total amount of the droplet is 100 ms or more.
Examples of the permeable recording media include plain paper, porous paper, and other recording media that are capable of absorbing a liquid.
Examples of the materials of the recording media which are non-permeable or slow permeable include art paper, synthetic resin, rubber, resin coated paper, glass, metal, ceramic, and wood. In the invention, a composite recording medium composed of some of the above materials in combination can also be used for the purpose of adding functions.
Any kind of synthetic resin can be used as the synthetic resin, and examples thereof include polyesters such as polyethylene terephthalate and polybutadiene terephthalate, polyolefins such as polyvinyl chloride, polystyrene, polyethylene, polyurethane, and polypropylene, acrylic resins, polycarbonate, acrylonitrile-butadiene-styrene copolymers, diacetate, triacetate, polyimide, cellophane, and celluloid. The thickness and shape of the recording medium when a synthetic resin is used are not particularly limited and the medium may be any shape of film, card and block, and may be either transparent or opaque.
As to the form of usage, the synthetic resin is preferably used in the form of a film for so-called light wrapping, and various non-absorbing plastics and a film thereof can be used. Examples of the plastic films include a PET film, an OPS film, an OPP film, a PNy film, a PVC film, a PE film, a TAC film, and a PP film. Examples of other plastics include polycarbonate resins, acrylic resins, ABS resins, polyacetal resins, PVA resins, and rubbers.
Examples of the resin coated papers include a transparent polyester film, an opaque polyester film, an opaque polyolefin resin film, and a paper supporting body having both sides laminated with a polyolefin resin. A paper supporting body having both sides laminated with a polyolefin resin is particularly preferable.
The kind of the metals is not particularly limited and preferable examples thereof include aluminum, iron, gold, silver, copper, nickel, titanium, chromium, molybdenum, silicon, lead, zinc, stainless steel, and composite materials thereof.
Further, ink jet recording can be performed on the label side of read-only optical disks such as CD-ROM and DVD-ROM, write-once optical disks such as CD-R and DVD-R, rewritable optical disks and the like.
—Ink and Undercoating Liquid—
The ink and the undercoating liquid used in the ink jet recording method in the invention will be explained in detail.
The ink is composed so as to at least form an image. The ink contains at least one polyerizable or crosslinkable material, and further a polymerization initiator, a lipophilic solvent, a coloring agent, and other components depending on the necessity.
The undercoating liquid is preferably composed so as to have a different composition from that of the ink. The undercoating liquid contains at least one polyerizable or crosslinkable material, and preferably contains a polymerization initiator, a lipophilic solvent, a coloring agent, and other components depending on the necessity.
The polymerization initiator is preferably capable of initiating a polymerization reaction or a crosslinking reaction with an active energy ray. By using the polymerization initiator, the undercoating liquid applied onto the recording medium can be cured by irradiation with an active energy ray.
The undercoating liquid preferably contains a radical polymerizable composition. The radical polymerizable composition in the invention contains at least one radical polymerizable material and at least one radical polymerization initiator. By using the radical polymerizable composition, the curing reaction of the undercoating liquid can be performed with high sensitivity in a short time.
The ink in the invention is preferably contains a coloring agent. The undercoating liquid to be used in combination preferably contains no coloring agent; contains a coloring agent to the amount of less than 1% by mass; or contains a white pigment as a coloring agent. Each component constituting each liquid will be described in detail.
(Polymerizable or Crosslinkable Material)
The polymerizable or crosslinkable material in the invention causes polymerization or crosslinking by the action of an initiating species such as a radical generated from a polymerization initiator described later, or the like, and has a function to cure a composition containing the initiating species.
Known polymerizable or crosslinkable materials that cause polymerization or crosslinking reaction such as a radical polymerization reaction or dimerization reaction can be applied as the polymerizable or crosslinkable material. Examples of the polymerizable or crosslinkable materials include an addition polymerizable compound having at least one ethylenically unsaturated double bond, a polymer compound having a maleimide group in the side chain, and a polymer having a group having an unsaturated double bond positioned adjacent to an aromatic core and is capable of photo-dimerization, such as a cinnamyl group, a cinnamylidene group, a chalcone group or the like, in a side chain. Among these, an addition polymerizable compound having at least one ethylenically unsaturated double bond is more preferable, and particularly preferably a compound selected from the compounds having at least one and more preferably two or more of terminal ethylenically unsaturated bonds (monofunctional or multifunctional compound). It can be appropriately selected from the widely known compounds in the industrial field to which the invention is related, and examples thereof include a compound having a chemical form of a monomer, a prepolymer (i.e., a dimer, a trimer, and an oligomer), a mixture thereof, and a copolymer of these compounds.
The polymerizable or crosslinkable materials may be used alone, or in combination of two or more kinds.
The polymerizable or the crosslinkable material in the invention is particularly preferably various known radical polymerizable monomers that cause a polymerization reaction by initiating species generated from a radical initiator.
Examples of the radical polymerization monomers include (meth)acrylates, (meth)acrylamides, aromatic vinyls, vinyl ethers, and a compound having an inner double bond (maleic acid, etc.). In this case, “(meth)acrylate” refers to both or either one of “acrylate” and “methacrylate,” and “(meth)acryl” refers to both or either one of “acryl” and “methacryl.”
Specific examples of the (metha)acrylates include the following compounds.
Specific examples of the monofunctional (meth)acrylates include hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, tert-octyl(meth)acrylate), isoamyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate, cyclohexyl(meth)acrylate, 4-n-butylcyclohexyl(meth)acrylate, bornyl(meth)acrylate, isobornyl(meth)acrylate, benzyl(meth)acrylate, 2-ethylhexyl diglycol(meth)acrylate, butoxyethyl(meth)acrylate, 2-chloroethyl(meth)acrylate, 4-bromobutyl(meth)acrylate, cyanoethyl(meth)acrylate, benzyl(meth)acrylate, butoxymethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate, alkoxymethyl(meth)acrylate, alkoxyethyl(meth)acrylate, 2-(2-methoxyethoxy)ethyl(meth)acrylate, 2-(2-butoxyethoxy)ethyl(meth)acrylate, 2,2,2-trifluoroethyl(meth)acrylate, 1H, 1H,2H,2H-perfluorodecyl(meth)acrylate, 4-butylphenyl(meth)acrylate, phenyl(meth)acrylate, 2,3,5,6-tetramethylphenyl(meth)acrylate, 4-chlorophenyl(meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl(meth)acrylate, glycidyl(meth)acrylate, glycidyloxybutyl (meth)acrylate, glycidyloxyethyl(meth)acrylate, glycidyloxypropyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, hydroxyalkyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate,
2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, dimethyaminopropyl(meth)acrylate, diethylaminopropyl(meth)acrylate, trimethoxysilylpropyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, polyethyleneoxide monomethyether (meth)acrylate, oligoethyleneoxide monomethylether (meth)acrylate, polyethyleneoxide (meth)acrylate, oligoethylenoxide (meth)acrylate, oligoethyleneoxide monoalkylether (meth)acrylate, polyethyleneoxide monoalkylether (meth)acrylate, dipropylene glycol (meth)acrylate, polypropyleneoxide monoalkylether (meth)acrylate, oligopropyleneoxide monoalkylether (meth)acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol (meth)acrylate, trifluoroethyl(meth)acrylate, perfluorooctylethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, EO-modified phenol (meth)acrylate, EO-modified cresol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, and EO-modified-2-ethyhexyl (meth)acrylate.
Specific examples of the bifunctional (meth)acrylates include 1,6-hexadiol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,4-dimethyl-1,5-pentanediol di(meth)acrylate, butylethylpropanediol (meth)acrylate, ethoxylated cyclohexanemethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, 2-ethyl-2-butyl-butanediol di(meth)acrylate, hydroxypivalic neopentyl glycol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, polypropylene glycol di(meth)acrylate, oligopropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 2-ethyl-2-butylpropanediol di(meth)acrylate, 1,9-nonane di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, and tricyclodecane di(meth)acrylate.
Specific examples of the trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, alkyleneoxide-modified tri(meth)acrylate of trimethylolpropane, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tris((meth)acryloyloxypropyl)ether, isocyanuric alkyleneoxide-modified tri(meth)acrylate, propionic dipentaerythritol tri(meth)acrylate, tris((meth)acryloyloxyethyl)isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri(meth)acrylate, sorbitol tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and ethoxylated glycerin triacrylate.
Specific examples of the tetrafunctional (meth)acrylates include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, propionic dipentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.
Specific examples of the pentafunctional (meth)acrylates include sorbitol penta(meth)acrylate and dipentaerythritol penta(meth)acrylate.
Specific examples of the hexafunctional (meth)acrylates include dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkyleneoxide-modified hexa(meth)acrylate of phosphazene, and captolactone-modified dipentaerythritol hexa(meth)acrylate.
Examples of the (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-n-butyl(meth)acrylamide, N-t-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl(meth)acrylamide, and (meth)acryloylmorphorine.
Specific examples of the aromatic vinyls include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chlormethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorstyrene, bromstyrene, methyl vinylbenzoate, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethyhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octenylstyrene, 4-t-butoxycarbonylstyrene, 4-methoxystyrene, and 4-t-butoxystyrene.
Specific examples of the vinylethers include the following compounds.
Specific examples of the monofunctional vinylethers include methylvinylether, ethylvinylether, propylvinylether, n-butylvinylether, t-butylvinylether, 2-ethylhexylvinylether, n-nonylvinylether, laurylvinylether, cyclohexylvinylether, cyclohexylmethylvinylether, 4-methylcyclohexylmethylvinylether, benzylvinylether, dicyclopentenylvinylether, 2-dicyclopentenoxyethylvinylether, methoxyethylvinylether, ethoxyethylvinylether, butoxyethylvinylether, methoxyethoxyethylvinylether, ethoxyethoxyethylvinylether, methoxypolyethylene glycol vinylether, tetrahydrofurfurylvinylether, 2-hydroxyetylvinylether, 2-hydroxypropylvinylether, 4-hydroxybutylvinylether, 4-hydroxymethylcyclohexylmethylvinylether, diethylene glycol monovinylether, polyethylene glycol vinylether, chlorethylvinylether, chlorbutylvinylether, chlorethoxyethylvinylether, phenylethylvinylether, and phenoxypolyethylene glycol vinylether.
Examples of the multifunctional vinylethers include divinylethers such as ethylene glycol divinylether, diethylene glycol divinylether, polyethylene glycol divinylether, propylene glycol divinylether, butylene glycol divinylether, hexanediol divinylether, bisphenol A alkyleneoxide divinylether and bisphenol F alkyleneoxide divinylether; and multifunctional vinylethers such as trimethylolethane trivinylether, trimethylolpropane trivinylether, ditrimethylolpropane tetravinylether, glycerin trivinylether, pentaerythritol tetravinylether, dipentaerythritol pentavinylether, dipentaerythritol hexavinylether, ethyleneoxide added trimethylolpropane trivinylether, propyleneoxide added trimethylolpropane trivinylether, ethyleneoxide added ditrimethylolpropane tetravinylether, propyleneoxide added ditrymethylolpropane tetravinylether, ethyleneoxide added pentaerythritol tetravinylether, propyleneoxide added pentaerythritol tetravinylether, ethyleneoxide added dipentaerythritol hexavinylether, and propyleneoxide added dipentaerythritol hexavinylether.
The vinylether compound is preferably a di- or tri-vinylether compound from the viewpoint of curing property, adhesion to a recording medium, surface hardness of the formed image or the like, and particularly preferably a divinylether compound.
Other examples of the radical polymerizable monomers in the invention include vinylesters such as vinyl acetate, vinyl propionate and vinyl versatate; allylesters such as allyl acetate; halogen-containing monomers such as vinylidene chloride and vinyl chloride, cyanide vinyls such as (metha)acrylonitrile; and olefins such as ethylene and propylene.
Among the above, the radical polymerizable monomer is preferably a (metha)acrylate and (metha)acrylamides in view of curing speed, and particularly preferably a (metha)acrylate of tetrafunctional or more in view of curing speed. From the viewpoint of the viscosity of the ink composition, it is preferable to use a multifunctional (metha)acrylate in combination with a monofunctional or bifunctional (metha)acrylate or (metha)acrylamide.
The content of the polymerizable or crosslinkable material in the ink and the undercoating liquid is preferably in the range of from 50 to 99.6% by mass with respect to the total solid content (mass) in each liquid droplet, more preferably in the range of from 70 to 99.0% by mass, and further preferably in the range of from 80 to 99.0% by mass.
The content of the polymerizable or crosslinkable material in the liquid droplet is preferably in the range of from 20 to 98% by mass with respect to the total mass of each liquid droplet, more preferably in the range of from 40 to 95% by mass, and particularly preferably in the range of from 50 to 90% by mass.
(Polymerization Initiator)
The ink and the undercoating liquid can be preferably composed using at least one polymerization initiator, and it is preferable that at least the undercoating liquid contains the polymerization initiator. This polymerization initiator is a compound that generates initiating species such as a radical by application of active light, heat, or both of these, and allow the polymerization or crosslinking reaction of the above-described polymerizable or crosslinkable materials to initiate, promote and cure.
From the aspect of the polymerizability, the polymerization initiator preferably causes a radical polymerization, and is particularly preferably a photopolymerization initiator.
The photopolymerization initiator is a compound that causes a chemical change by the action of light and an interaction with a sensitizing dye in an electronically excited state and produces at least any one of a radical, acid and base, and a photoradical generator is preferable from the viewpoint that the polymerization can be initiated with a simple means as exposure.
The photopolymerization initiator in the invention can be selected from the photopolymerization initiators having sensitivity to active light rays such as an ultraviolet ray of from 400 to 200 nm, far ultraviolet ray, g-ray, h-ray, i-ray, KrF excimer laser beam, ArF excimer laser beam, electron beam, X-ray, molecular beam or an ion beam.
Specifically, known photopolymerization initiators in the art can be used without limitation, such as the ones described in Bruce M. Monroe et al., Chemical Reviews, 93, 435 (1993); R. S. Davidson, Journal of Photochemistry and Biology A: Chemistry, 73. 81 (1993); J. P. Faussier, “Photoinitiated Polymerization—Theory and Applications”, Rapra Review Report, vol. 9, Rapra Technology (1998); and M. Tsunooka et al., Prog. Polym. Sci., 21, 1 (1996). Further, a group of compounds that oxidatively or reductively generates a bond cleavage through interaction with a sensitizing dye in an electronically excited state as described in F. D. Saeva, Topics in Current Chemistry, 156, 59 (1990); G. G. Maslak, Topics in Current Chemistry, 168, 1 (1993); H. B. Shuster et al., JACS, 112, 6329 (1990); I. D. F. Eaton et al., JACS, 102, 3298 (1980), and the like.
Preferable photopolymerization initiators can be exemplified by: (a) aromatic ketones; (b) aromatic onium salt compounds; (c) organic peroxides; (d) hexaarylbiimidazole compounds; (e) ketoxime ester compounds; (f) borate compounds; (g) azinium compounds; (h) metallocene compounds; (i) active ester compounds; and (j) compounds having a carbon-halogen bond.
Preferable examples of the (a) aromatic ketones include a compound having a benzophenone skeleton or a thioxanthone skelton described in J. P. Fouassier, J. F. Rabek, “Radiation Curing in Polymer Science and Technology”, pp. 77-117 (1993). More preferable examples of the (a) aromatic ketones include α-thiobenzophenone compounds described in Japanese Patent Publication (JP-B) No. 47-6416, benzoin ether compounds described in JP-B No. 47-3981, α-substituted benzoin compounds described in JP-B No. 47-22326, benzoin derivatives described in JP-B No. 47-23664, aroylphosphonic esters described in JP-A No. 57-30704, dialkoxybenzophenone described in JP-B No. 60-26483, benzoinethers described in JP-B No. 60-26403 and JP-B No. 62-81345, α-aminobenzophenones described in JP-B No. 1-34242, U.S. Pat. No. 4,318,791 and EP No. 0284561A1, p-di(dimethylaminozenzoyl)benzene described in JP-A No. 2-211452, thio-substituted aromatic ketones described in JP-A No. 61-194062, acylphosphine sulfides described in JP-B No. 2-9597, acylphosphines described in JP-B No. 2-9596, thioxantones described in JP-B No. 63-61950, and coumarins described in JP-B No. 59-42864.
Examples of the (b) aromatic onium salt compounds include aromatic omium salts of the elements in the groups of V, VI, and VII in the periodic table, specifically N, P, As, Sb, Bi, O, S, Se, Te or I. Preferable examples thereof include iodonium salts described in EP No. 104143, U.S. Pat. No. 4,837,124, JP-A No. 2-150848 and JP-A No. 2-96514; sulfonium salts described in EP Nos. 370693, 233567, 297443, 297442, 279210 and 422570, U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760,013, 4,734,444 and 2,833,827; diazonium salts (such as benzene diazoniums that may have a substituent); diazonium salt resins (such as formaldehyde resins of diazophenylamine); N-alkoxypyridium salts (examples thereof include compounds described in U.S. Pat. No. 4,743,528, JP-A Nos. 63-138345, 63-142345, 63-142346 and JP-B No. 46-42363; and specific examples thereof include 1-methoxy-4-phenylpyridium and tetrafluoroborate), and compounds described in JP-B Nos. 52-147277, 52-14278 and 52-14279. Radicals and acids are produced as the active species.
Examples of the (c) “organic peroxides” includes almost all of the organic compounds having one or more oxygen-oxygen bonds in the molecule and can be exemplified by ester peroxide type compounds such as
Examples of the (d) hexaarylbiimidazoles include the lophin dimers described in JP-B Nos. 45-37377 and 44-86516 such as
Examples of the (e) ketoxime esters include 3-benzoyloxyiminobutane-2-one, 3-acetoxyimonobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-p-toluenesulfonyloxyiminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.
Examples of the (f) borate compounds include the compounds described in U.S. Pat. Nos. 3,567,453 and 4,343,891, and EP Nos. 109,772 and 109,773.
Examples of the (g) azinium compounds are include the compounds having a N—O bond described in JP-A Nos. 63-138345, 63-142345, No. 63-142346 and 63-143537, and JP-B No. 46-42363.
Examples of the (h) metallocene compounds include the titanocene compounds described in JP-A Nos. 59-152396, 61-151197, 63-41484, 2-249, and 2-4705; and the iron-arene complexes described in JP-A Nos. 1-304453 and 1-152109.
Specific examples of the titanocene compounds include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoropheny-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluoropheny-1-yl, di-cyclopentadienyl-Ti-2,6-difluoropheny-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluoropheny-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoropheny-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluoropheny-1-yl, bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyri-1-yl)phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(methylsulfoneamide)phenyl]titanium, and bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbiaroyl-amino)phenyl]titanium.
Examples of the (i) active ester compounds include the nitrobenzylester compounds described in EP Nos. 0290750, 046083, 156153, 271851 and 0388343, U.S. Pat. Nos. 3,901,710 and 4,181,531, JP-A Nos. 60-198538 and 53-133022; iminosulfonate compounds described in EP Nos. 0199672, 84515, 044115 and 0101122, U.S. Pat. Nos. 4,618,564, 4,371,605 and 4,431,774, JP-A Nos. 64-18143, 2-245756 and 4-365048; and the compounds described in JP-B No. 62-6223, JP-B No. 63-14340, and JP-A No. 59-174831.
Preferable examples of the (j) compounds having a carbon-halogen bond include the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in U.K. Patent No. 1388492, compounds described in JP-A No. 53-133428, and the compounds described in German Patent No. 3337024.
Further, preferable examples of the compounds also include the compounds described in F. C. Schaefer et al., J. Org. Chem., 29, 1527 (1964), compounds described in JP-A Nos. 62-58241 and 5-281728, compounds described in German Patent Nos. 2641100 and 3333450, and the compounds described in German Patent Nos. 3021590 and 3021599.
Examples of the photopolymerization initiator in the invention may be the compounds as shown below, but are not limited thereto. In the following formulae, Ar represents an aromatic group.
The polymerization initiator preferably has a high degree of sensitivity. However, from the viewpoint of storage stability, the polymerization initiator that does not cause thermal decomposition at a temperature up to 80° C. is preferably selected.
The polymerization initiator may be used alone or in combination of two or more kinds. Known sensitizers may be also used in combination for the purpose of improving the sensitivity as long as the effect of invention is not spoiled.
The content of the polymerization initiator in the undercoating liquid is preferably in the range of from 0.5 to 20% by mass with respect to the amount of the polymerizable material contained in the undercoating liquid, more preferably from 1 to 15% by mass, and particularly preferably from 3 to 10% by mass, from the viewpoint of temporal stability, curing property and curing speed. By containing the polymerization initiator of the amount in the above-described range, occurrence of precipitation or separation with the lapse of time and deterioration in the performances such as ink strength or rubbing resistance after curing can be suppressed.
The polymerization initiator may be contained in the ink as well as in the undercoating liquid, and the content thereof can be appropriately determined in the range where the storage stability of the ink can be maintained at the desired level. The content of the polymerization initiator in the ink droplet is preferably from 0.5 to 20% by mass with respect to the polymerizable or crosslinkable compound in the ink, and more preferably from 1 to 15% by mass.
(Sensitizing Dye)
A sensitizing dye may be added for the purpose of improving the sensitivity of the photopolymerization initiator in the invention. Preferred examples of the sensitizing dyes are the compounds included in the following compounds below and have an absorption wavelength in the range of from 350 nm to 450 nm.
Polynuclear aromatics (for example, pyrene, perylene, and triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, and rose bengal), cyanines (for example, thiacarbocyanine and oxacarbocyanine), merocyanines (for example, merocyanine and carbomerocyanine), thiazines (for example, thionine, methylene blue, and toluyzine blue), acridines (for examples, acridine orange, chloroflavin, and acriflavin), anthraquinones (for example, anthraquinone), squaryliums (for example, squarylium), and cumarins (for example, 7-diethylamino-4-methylcumarin).
Examples of the preferred sensitizing dyes are the compounds represented by the following Formulas (IX) to (XIII).
In Formula (IX), A1 represents a sulfur atom or —NR50—, R50 represents an alkyl group or an aryl group, L2 represents a non-metal atomic group that forms a basic nucleus of a dye together with the adjacent A1 and the adjacent carbon atom, R51 and R52 each independently represent a hydrogen atom or a monovalent non-metal atomic group, wherein R51 and R52 may form an acid nucleus of a dye by bonding to each other. W represents an oxygen atom or a sulfur atom.
In Formula (X), Ar1 and Ar2 each independently represent an aryl group, and connect with each other via a bond by -L3-, wherein L3 represents —O— or —S—. W represents an oxygen atom or a sulfur atom.
In Formula (XI), A2 represents a sulfur atom or —NR59—, L4 represents a non-metal atomic group that forms a basic nucleus of a dye together with the adjacent A2 and the carbon atom. R53, R54, R55, R56, R57, and R58 each independently represent a group of a monovalent non-metal atomic group, and R59 represents an alkyl group or an aryl group.
In Formula (XII), A3 and A4 each independently represent —S—, —NR62—, or —NR63—, R62 and R63 each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, L5 and L6 each independently represent a non-metal atomic group that forms a basic nucleus of a dye together with the adjacent A3, A4, and the adjacent carbon atom, and R60 and R61 each independently represent a hydrogen atom or a monovalent non-metal atomic group, or can form an aliphatic or aromatic ring by bonding to each other.
In Formula (XIII), R66 represents an aromatic ring or a hetero ring that may have a substituent, and A5 represents an oxygen atom, a sulfur atom, or —NR67—. R64, R65, and R67 each independently represent a hydrogen atom or a monovalent non-metal atomic group, and R67 and R64, and R65 and R67 can bond to each other to form an aliphatic or an aromatic ring.
Specific examples of the compounds represented with the Formulas (IX) to (XIII) include Exemplified Compounds (A-1) to (A-20) shown as follows.
(Cosensitizer)
Known compounds having the capacity to further improve sensitivity or suppress the inhibition of polymerization by oxygen may be added as a cosensitizer.
Examples of the cosensitizers include amines such as the compounds described in M. R. Sander et al., Journal of Polymer Society, vol. 10, 3173 (1972), JP-B No. 44-20189, JP-A Nos. 51-82102, 52-134692, 59-138205, 60-84305, 62-18537 and 64-33104, and Research Disclosure No. 33825. Specific compounds thereof include triethanolamine, p-dimethylaminobenzenethylester, p-formyldimethyaniline, and p-methylthiodimethylaniline.
Other examples of the cosensitizers include thiols and sulfides such as the thiol compounds described in JP-A No. 53-702, JP-B No. 55-500806, and JP-A No. 5-142772, and the disulfide compounds described in JP-A No. 56-75643. Specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4-(3H)-quinazoline, and β-mercaptonaphthalene.
Other examples of the cosensitizers further include amino acid compounds (for example, N-phenylglycine), the organic metal compounds described in JP-B No. 48-42965 (for example, tributyl tin acetate), the hydrogen donors described in JP-B No. 55-34414, the sulfur compounds described in JP-A No. 6-308727 (for example, trithiane), the phosphor compounds described in JP-A No. 6-250387 (for example, diethylphosphite), and the compounds of Si—H and Ge—H described in JP-A No. 8-65779.
(Coloring Agent)
The ink and the undercoating liquid preferably contain at least one coloring agent, and more preferably a coloring agent is contained at least in the ink. The coloring agent may be included in the undercoating liquid and other liquids other than the ink.
The coloring agent is not particularly limited, and may be appropriately selected from known water-soluble dyes, oil-soluble dyes, and pigments. The ink and the undercoating liquid in the invention are preferably composed as a non-water soluble organic solvent system from the viewpoint of the effect of the invention, and oil-soluble dyes or pigments that readily dissolve and uniformly disperse in a non-water soluble medium are preferably used.
The content of the coloring agent in the ink is preferably from 1 to 30% by mass, more preferably from 1.5 to 25% by mass, and particularly preferably from 2 to 15% by mass. When the undercoating liquid contains a white pigment, the content thereof in the undercoating liquid is preferably from 2 to 45% by mass, and more preferably from 4 to 35% by mass.
Details of the pigments will be explained focusing on the preferable examples thereof in the invention.
(Pigment)
In the invention, it is preferable that a pigment is used as the coloring agent. Either of organic pigments and inorganic pigments can be used as the pigment, but a carbon black pigment can be named as a preferable black pigment. The pigments of black and the three basic colors of cyan, magenta, and yellow are generally used, but pigments having other hues such as red, green, blue, brown and white, metallic-glossy pigments such as gold and silver, and body pigments of colorless or a light color can also be used depending on the purposes.
Examples of the organic pigments are not limited by the hues thereof, and include the pigments of perylene, perynone, quinacridone, quinacridone quinone, anthraquinone, anthoanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxadine, aminoanthraquinone, diketopyrrolopyrrole, thio indigo, isoindoline, isoindolinone, pyranthrone and isoviolanthrone, and mixtures thereof.
Further specific examples of the pigments include perylene-based pigments such as C. I. Pigment Red 190 (C. I. No. 71140), C. I. Pigment Red 224 (C. I. No. 71127), and C. I. Pigment Violet 29 (C. I. No. 71129); perynone-based pigments such as C. I. Pigment Orange 43 (C. I. No. 71105) and C. I. Pigment Red 194 (C. I. No. 71100); quinacridone-based pigments such as C. I. Pigment Violet 19 (C. I. No. 73900), C. I. Pigment Violet 42, C.I. Pigment Red 122 (C. I. No. 73915), C. I. Pigment Red 192, C. I. Pigment Red 202 (C. I. No. 73907), C. I. Pigment Red 207 (C. I. No. 73900 and No. 73906), and C. I. Pigment Red 209 (C. I. No. 73905); quinacridone quinone-based pigments such as C. I. Pigment Red 206 (C. I. No. 73900/73920), C. I. Pigment Orange 48 (C. I. No. 73900/73920), and C. I. Pigment Orange 49 (C. I. No. 73900/73920); anthraquinone-based pigments such as C. I. Pigment Yellow 147 (C. I. No. 60645); anthoanthrone-based pigments such as C. I. Pigment Red 168 (C. I. No. 59300); benzimidazolone-based pigments such as C. I. Pigment Brown 25 (C. I. No. 12510), C. I. Pigment Violet 32 (C. I. No. 12517), C. I. Pigment Yellow 180 (C. I. No. 21290), C. I. Pigment Yellow 181 (C. I. No. 11777), C. I. Pigment Orange 62 (C. I. No. 11775), and C. I. Pigment Red 185 (C. I. No. 12516); disazo condensation-based pigments such as C. I. Pigment Yellow 93 (C. I. No. 20710), C. I. Pigment Yellow 94 (C. I. No. 20038), C. I. Pigment Yellow 95 (C. I. No. 20034), C. I. Pigment yellow 128 (C. I. No. 20037), C. I. Pigment Yellow 166 (C. I. No. 20035), C. I. Pigment Orange 34 (C. I. No. 21115), C. I. Pigment Orange 13 (C. I. No. 21110), C. I. Pigment Orange 31 (C. I. No. 20050), C. I. Pigment Red 144 (C. I. No. 20735), C. I. Pigment Red 166 (C. I. No. 20730), C. I. Pigment Red 220 (C. I. No. 20055), C. I. Pigment Red 221 (C. I. No. 20065), C. I. Pigment Red 242 (C. I. No. 20067), C. I. Pigment Red 248, C.I. Pigment Red 262, and C. I. Pigment Brown 23 (C. I. No. 20060);
Disazo-based pigments such as C. I. Pigment Yellow 13 (C. I. No. 21100), C. I. Pigment Yellow 83 (C. I. No. 21108), and C. I. Pigment Yellow 188 (C. I. No. 21094); azo-based pigments such as C. I. Pigment Red 187 (C. I. No. 12486), C. I. Pigment Red 170 (C. I. No. 12475), C. I. Pigment Yellow 74 (C. I. No. 11714), C. I. Pigment Yellow 150 (C. I. No. 48545), C. I. Pigment Red 48 (C. I. No. 15865), C. I. Pigment Red 53 (C. I. No. 15585), C. I. Pigment Orange 64 (C. I. No. 12760), and C. I. Pigment Red 247 (C. I. No. 15915); indanthrone-based pigments such as C. I. Pigment Blue 60 (C. I. No. 69800); phthalocyanine-based pigments such as C. I. Pigment Green 7 (C. I. No. 74260), C. I. Pigment Green 36 (C. I. No. 74265), C. I. Pigment Green 37 (C. I. No. 74255), C. I. Pigment Blue 16 (C. I. No. 74100), C. I. Pigment Blue 75 (C. I. No. 74160:2), and 15 (C. I. No. 74160); triarylcarbonium-based pigments such as C. I. Pigment Blue 56 (C. I. No. 42800) and C.I. Pigment Blue 61 (C. I. No. 42765:1); dioxadine-based pigments such as C. I. Pigment Violet 23 (C. I. No. 51319) and C. I. Pigment Violet 37 (C. I. No. 51345); aminoanthraquinone-based pigments such as C. I. Pigment Red 177 (C. I. No. 65300); diketopyrrolopyrrole-based pigments such as C. I. Pigment Red 254 (C. I. No. 56110), C. I. Pigment 255 (C. I. No. 561050), C. I. Pigment Red 264, C. I. Pigment Red 272 (C. I. No. 561150), C. I. Pigment Orange 71, and C. I. Pigment Orange 73; thio indigo-based pigments such as C. I. Pigment Red 88 (C. I. No. 73312); isoindoline-based pigments such as C. I. Pigment Yellow 139 (C. I. No. 56298) and C. I. Pigment Orange 66 (C. I. No. 48210); isoindolinone-based pigments such as C. I. Pigment Yellow 109 (C. I. No. 56284) and C. I. Pigment Orange 61 (C. I. No. 11295); pyranthrone-based pigments such as C. I. Pigment Orange 40 (C. I. No. 59700) and C. I. Pigment Red 216 (C. I. No. 59710); and isoviolanthrone-based pigments such as C. I. Pigment Violet 31 (60010).
In the invention, two or more kinds of the organic pigments or solid solutions of the organic pigments can be combined and used.
Other materials such as particles composed of a core of silica, alumina, resin or the like having a dye or a pigment fixed on the surface, an insoluble laked compound of a dye, colored emulsion and colored latex can also be used as the pigment. Further, a pigment coated with a resin can be also used, which is called a micro capsule pigment and the products thereof are commercially available from Dainippon Ink and Chemicals, Inc., Toyo Ink MFG. Co., Ltd. and the like.
The volume average particle diameter of the pigment particles contained in the liquid is preferably in the range of from 10 to 250 nm, from the viewpoint of the balance between optical concentration and storage stability, and further preferably from 50 to 200 nm. The volume average particle diameter of the pigment particles can be measured with a particle diameter distribution analyzer such as LB-500 (manufactured by HORIBA, Ltd.).
The coloring agents may be used alone or in the form of a mixture of two or more kinds thereof. Further, different coloring agents may be used in different liquid droplets to be ejected and liquids, or the same coloring agent may be used therein.
(Other Components)
Components other than the ones described above such as known additives can also be used as appropriate according to usage.
<Storage Stabilizer>
A storage stabilizer can be added in the ink and the undercoating liquid according to the invention (preferably in the ink) for the purpose of suppressing undesired polymerization during storage. The storage stabilizer is preferably used together with the polymerizable or crosslinkable material, and is preferably soluble in the liquid droplets or liquid or other coexistent components in which the storage stabilizer is contained.
Examples of the storage stabilizers include a quaternary ammonium salt, hydroxylamines, cyclic amides, nitrites, substituted ureas, heterocyclic compounds, organic acids, hydroquinone, hydroquinone monoethers, organic phosphines and copper compounds, and specific examples thereof include benzyltrimethylammonium chloride, diethylhydroxylamine, benzothiazole, 4-amino-2,2,6,6-tetramethylpiperizine, citric acid, hydroquinone monomethyether, hydroquinone monobutylether and copper naphthenate.
The addition amount of the storage stabilizer is preferably adjusted as appropriate according to the activity of the polymerization initiator, polymerization capability of the polymerizable or crosslinkable material, or the type of the storage stabilizer, but is preferably from 0.005 to 1% by mass in terms of the solid content, more preferably from 0.01 to 0.5% by mass, and further preferably 0.01 to 0.2% by mass, in view of the balance between storage stability and curing property.
<Conductive Salt>
Conductive salts are solid compounds that improve conductivity. In the invention, it is preferable that the conductive salt is not substantially used since there is a large possibility that they deposit at the time of storage, but appropriate amount thereof may be added when the solubility is in good condition by enhancing the solubility of the conductive salt or using a substance having high solubility in the liquid component, and the like.
Examples of the conductive salts include potassium thiocyanate, lithium nitrate, ammonium thiocyanate and dimethylamine hydrochloride.
<Solvent>
Known solvents can be used in the invention, as necessary. The solvent can be used for the purpose of improving the polarity, viscosity or the surface tension of the liquid (ink), improving the solubility or dispersibility of the coloring agent, adjusting the conductivity, or adjusting the printing performance.
The solvent in the invention is preferably a non-water soluble liquid that does not contain an aqueous solvent from the viewpoint of recording a high quality image that dries quickly and is uniform in line width, and is more preferably a solvent composed of a high boiling point organic solvent. The high boiling point organic solvent used in the invention preferably has a good compatibility with the constituent materials, especially with the monomers.
Preferable examples of the solvents include tripropylene glycol monomethyether, dipropylene glycol monomethylether, propylene glycol monomethylether, ethylene glycol monobutylether, diethylene glycol monobutylether, triethylene glycol monobutylether, ethylene glycol monobenzylether and diethylene glycol monobenzylether.
Although there are known low boiling point organic solvents having a boiling point of 100° C. or less, it is preferable to avoid using such solvents in consideration of unfavorable effects on the curing ability and the possibility of causing environmental pollution. In the case of using these solvents, it is preferable to select a solvent with high safety, i.e., a solvent with high control concentration (the index indicated according to the working environment evaluation standard), which is preferably 100 ppm or more and further preferably 200 ppm or more. Examples of such solvents include alcohols, ketones, esters, ethers and hydro carbons, and specifically include methanol, 2-butanol, acetone, methylethylketone, ethyl acetate, tetrahydrofuran.
The solvent can be used alone or in combination of two or more kinds. However, when water and/or a low boiling point organic solvent are used, the total amount thereof in each liquid is preferably from 0 to 20% by mass, more preferably from 0 to 10% by mass, and it is further preferable that they are substantially not contained. It is preferable that the ink and the undercoating liquid in the invention substantially does not contain water from the viewpoint of achieving temporal stability without decreasing the uniformity or increasing the turbidity of the liquid due to precipitation of a dye and the like, with the lapse of time, and from the viewpoint of securing the drying property when an impermeable or slow permeable recording medium is used. The term “Substantially does not contain” here means that the admissible level of inevitable impurities may exist.
<Other Additives>
Known additives such as a polymer, a surface tension regulator, an ultraviolet absorber, an antioxidant, an anti-fading agent, and a pH regulator can be used in combination.
Known compounds may be appropriately selected and used as the above additives, and specific examples thereof include the additives described in JP-A 2001-181549.
Further, a pair of compounds that generate an aggregate or increase viscosity when they react with each other upon mixing can be contained separately in the ink and the undercoating liquid in the invention. The above pair of compounds has a characteristic of rapidly forming the aggregate or rapidly increasing viscosity of the liquid, thereby suppressing coalescence of adjacent liquid droplets more effectively.
Examples of the reaction of the above pair of compounds include an acid/base reaction, a hydrogen bonding reaction by a carbonic acid/amide group containing compound, a crosslinking reaction such as a reaction of boronic acid/diol, and a reaction by electrostatic interaction by cation/anion.
—Mechanism of Image Recording and Recording Device of Images—
One example of the mechanism of the invention to form an image on a recording medium while avoiding interdroplet interference will be explained by referring to
The undercoating liquid that does not contain a coloring agent is applied onto a recording medium 16 to form a liquid film 81 consisting of the undercoating liquid on the surface of the recording medium 16, as shown in
The thickness of the liquid film of the applied undercoating liquid is determined as an average thickness obtained by dividing the value of the volume of the applied undercoating liquid by the value of the area onto which the undercoating liquid is applied. In the case where the undercoating liquid is applied by ejection, the thickness of the liquid film can be obtained from the value of the ejected volume and the value of the area onto which the undercoating liquid has been ejected. The thickness of the liquid film of the undercoating liquid is desirably uniform with no local unevenness. From this viewpoint, the undercoating liquid preferably wets the recording medium well and spreads thereon, i.e., has a small degree of static surface tension, as long as the liquid can be ejected stably from the ink jet head.
After the undercoating liquid is half-cured by irradiation with active light from a light source W (half-cured undercoating liquid (layer); 81a), an ink droplet 82a is ejected as shown in
Subsequently, another ink droplet 82b is ejected onto the recording medium 16 in the region where the liquid film 81 of the undercoating liquid is formed and near the position where the first liquid droplet 82a has been ejected, as shown in
A substance that causes a chemical reaction that makes coloring material contained in the ink to aggregate or become insoluble has conventionally been contained in the undercoating liquid, in order to avoid the interdroplet interference. However, according to the invention, the interdroplet interference can be avoided without containing such a substance in the undercoating liquid.
While the interdroplet interference is avoided and the shapes of the ink droplets of 82a and 82b are maintained (in the case of the invention, during a period of from a few hundred milliseconds to 5 seconds) as shown in
Next, the entire configuration of an inline label printer, an example of the image recording device provided with the ink jet recording device in the invention, will be explained by reference with the figures.
The ink jet recording device in the invention is applied to the ink jet recording part 100A. The ink jet recording part 100A consists of an undercoating liquid film forming unit 100A1 that forms a half-cured undercoating liquid film that does not contain a coloring agent on the recording medium (label) 16, and an image forming unit 100A2 that forms a desired image on the recording medium 16 by applying four inks containing a coloring material on the prescribed position of the recording medium 16.
The preferred images can be formed particularly when a recording medium that does not have permeability (for example, OPP (Oriented Polypropylene Film), CPP (Casted Polypropylene Film), PE (Polyethylene), PET (Polyethylene Terephthalate), PP (Polypropylene), a soft wrapping material with low permeability, laminate paper, coated paper and art paper is used as the recording medium.
In
The image recording device 100 is provided with a liquid storage/loading unit that is prevented from light-transmittance (not shown) and store the undercoating liquid and the ink to be supplied to the undercoating liquid film forming part 100A1 and the image forming part 100A2; a paper supplying unit 101 that supplies the recording medium 16; an image detecting unit 104c that reads an image as a result of ejection of the ink (the state of the deposited ink droplets) by the image forming part 100A2; and a rewinding unit 109 that rewinds the recorded recording medium.
The paper supplying unit 101 is described in
Further details of the ink jet recording unit 100A will now be explained. The ink jet recording unit 100A has the image forming part 100A2 including ejecting heads 102Y, 102C, 102M, and 102K that eject ink onto the recording medium 16 in a single pass, pinning light sources 103Y, 103C, and 103M, and a final curing light source 103F; and the undercoating liquid film forming part 100A1 including the roll coater 102P and a light source for the half-curing 103P. Specifically, it is a so-called full line-formation head which is a line-formation head having a length corresponding to the entire width of the recordable area of the recording medium 16, the head being arranged in a direction perpendicular to a direction of conveying the recording medium (shown by an arrow S in
The roll coater 102P and the ejecting heads 102Y, 102C, 102M, and 102K having plural nozzles (liquid ejecting ports) are arranged in the length longer than at least one side of the recording medium 16 of the maximum size for which the ink jet recording part 100A is intended.
The ejecting heads 102Y, 102C, 102M, and 102K corresponding to each liquid are arranged in the order of yellow ink (Y), cyan ink (C), magenta ink (M), and black ink (K) from the upstream side (the left side of
Specifically, the undercoating liquid is first uniformly applied onto the recording medium 16 with the roll coater (102P), then half-curing of the undercoating liquid is performed by the ultraviolet light source for half-curing 103P. Next, the ink is ejected from the ejecting head for yellow ink 102Y toward the recording medium 16, then the yellow ink on the recording medium is half-cured to such a level that the surface thereof is not cured and the shape thereof is kept by the pinning light source 103Y arranged downstream of the ejecting head 102Y Subsequently, the same processes as that of the yellow ink are repeated with the heads 102C and 102M, and after the ejection by the ejecting head for black ink 102K, curing is completed by the final curing light source 103F capable of completely curing the undercoating liquid and all of the inks. In this process, by half-curing the undercoating liquid and the inks after application, interdroplet interference can be avoided.
According to the image forming part 100A2 consisting of a full line-formation ejecting head, an image can be recorded on the entire surface of the recording medium 16 at one operation of relatively moving the recording medium 16 and the image forming part 100A2 in a direction of conveying the recording medium. Therefore, high-speed printing can be performed as compared with a case of using a shuttle type head in which the ejecting head moves back and forth in a direction perpendicular to the direction of conveying the recording medium while conveying the recording medium, thereby improving the productivity.
In the embodiments, inks of the standard colors YCMK (4 colors) are used, but the number of the colors or the combination thereof is not limited to the examples shown here, and other inks of a light color, dark color, white or other spot colors, or transparent inks may also be used depending on necessity. Examples of the possible constitutions thereof include using an ejecting head that ejects an ink of light colored type such as light cyan and light magenta in combination; delineating the background with a white ink; and adjusting the glossiness with a transparent ink.
UV light sources 103P, 103Y, 103C, 103M, and 103F irradiate ultraviolet rays to the recording medium 16 in order to cure the ink containing a polymerizable compound. Known light sources such as a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal-halide lamp, a xenon lamp, a carbon arc lamp, an ultraviolet fluorescent lamp, an ultraviolet LED, and an ultraviolet LD can be used as the ultraviolet light source. Among these, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal-halide lamp are preferably used from the aspect of practicality. The UV light source preferably has the peak amount of light in the wavelength range of from 200 nm to 400 nm, and preferably has an irradiation light intensity in the range of from 1 to 500 mW/cm2 in the wavelength at the peak amount of light. The UV light source is preferably constituted using a cold mirror in a reflector and an infrared cut glass in a cover glass so as to prevent the increase in temperature of the recording medium by the irradiation with a heat ray. In the case of an ink containing a radical based polymerizable compound, by substituting the curing atmosphere created by the final curing light source 103F with an inert gas such as nitrogen (not shown), hindrance of the polymerization due to oxygen can be suppressed and curing and fixing of the ink can be performed more favorably.
An electron beam irradiation device (not shown) may also be used as a means of curing the ink containing a polymerizable compound.
In the above, the use of a UV light source and an electron beam irradiation device is discussed as a means of curing the polymerizable compound, but the means is not limited to thereto and other radiant rays such as an α-ray, a γ-ray, and an X-ray may also be used.
The image detecting unit 104c includes an image sensor (such as a line sensor) to pick up the image of the result of the ejection by the image forming part 100A2, and functions as a means of checking the presence of ejection abnormalities such as clogging of the nozzles from the image read by the image sensor.
A buffer 104 is provided as a cushioning unit between the ink jet recording part 100A and the post-processing part 100B. The recording medium that has been subjected to ink jet recording passes through the buffer 104 consisting of several upper rollers 104a and several lower rollers 104b, while repeating going up and down a few times. The buffer 104 serves as a regulator that absorbs the difference between the operation speeds (the speeds for conveying the recording medium 16) in the ink jet recording part 100A positioned upstream of the buffer and in a later-described post-processing part 100B positioned in the downstream of the buffer.
In the downstream of the buffer 104 is provided a varnish coater 105. In the varnish coater 105, the surface of a label is slightly coated with a varnish to improve scratch-resistance of the label surface.
A drier X is provided downstream of the varnish coater 105. For example, a UV lamp (same as the final curing light source 103F) can be used for the drier X when a UV varnish is used.
A label cutting unit 106 provided in the downstream of the varnish coater 105 is composed of a marking reader 106a, a die cutter driver 106b, a dye cutter 106c equipped with a roll (a plate) 106e having a blade, and a facing roller 106d.
A label cut by the die cutter 106c in the label cutting unit 106 is wound up by a label winding unit 109 into the form of a product, and other parts are peeled off by a scrap removing unit 108 and disposed as a waste.
Structure of Ejecting Head
The ejecting head 50 shown as one example in
In the ejecting head 50, plural pressure chamber units 54 each consisting of a nozzle 51, a pressure chamber 52 communicating to the nozzle 51 and a liquid supplying port 53 are arranged along two directions, i.e., the main scanning direction M and the inclined direction at a prescribed acute angle θ (0 degree<θ<90 degrees) with the main scanning direction M. For illustration purpose, only a part of the pressure chamber unit 54 is shown in
The nozzles 51 are arranged at a regular pitch d in the inclined direction at a prescribed acute angle θ with the main scanning direction M, which can be equated to that in which the nozzles are arranged in a straight line along with the main scanning direction M at an interval of “d×cos θ”.
Each pressure chamber 52 communicates with a common liquid chamber 55 via the liquid supplying port 53. The common liquid chamber 55 communicates with a tank as a liquid supplying source (not shown), from which the liquid is supplied and distributed to each pressure chamber 52 via the common liquid chamber 55.
A piezoelectric body 58a is positioned on a vibrating plate 56 that forms a top face of the pressure chamber 52, and an individual electrode 57 is positioned on the piezoelectric body 58a. The vibrating plate 56 is grounded and functions as a common electrode. These vibrating plate 56, individual electrode 57 and piezoelectric body 58a constitute a piezoelectric actuator 58 that serves as a means of generating liquid ejection force.
When a prescribed driving voltage is applied to the individual electrode 57 in the piezoelectric actuator 58, the piezoelectric body 58a is deformed to change the volume of the pressure chamber 52, resulting in the change in pressure in the pressure chamber 52, and thereby a liquid is ejected from the nozzle 51. When the volume of the pressure chamber 52 returns back to the initial state after the ejection of the liquid, a new liquid is supplied to the pressure chamber 52 from the common liquid chamber 55 via the liquid supplying port 53.
In
In the ink jet recording device in the invention, other means such as ejection of the undercoating liquid from the nozzle may also be used for the application of the undercoating liquid onto the recording medium, instead of coating.
The device used for the coating is not particularly limited, and known coating devices can be selected as appropriate according to usage. Examples thereof include an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, an impregnating coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a cast coater, a spray coater, a curtain coater, and an extruding coater.
Liquid Supply System
A liquid tank 60 supplies a liquid to the ejecting head 50 as a base tank. In the midstream of a tube that connects the liquid tank 60 and the ejecting head 50, a liquid supplying pump 62 that sends the liquid to the ejecting head 50 is provided. The tube, liquid tank 60 and the ejecting head 50 preferably have a temperature which is regulated together with the ink contained therein, by a temperature detecting means and a heater. The ink temperature is preferably regulated to a range of from 40° C. to 80° C.
The image recording device 100 is provided with a cap 64 as a means for preventing a meniscus of the nozzle 51 from drying during the intermission of ejection, or from increasing in viscosity in the vicinity of the meniscus, and a cleaning blade 66 as a means for cleaning the ejection face 50a. A maintenance unit including the cap 64 and the cleaning blade 66 can be transferred relatively to the ejecting head 50 by a transfer system (not shown), and can be transferred to a maintenance position positioned below the ejecting head 50 from a prescribed retracting position as necessary.
The cap 64 is elevated relatively to the ejecting head 50 with an elevation mechanism (not shown). The elevation mechanism is designed to cover at least the region of the nozzle in the ejection face 50a with the cap 64 by elevating the cap 64 up to a prescribed position and attaching the cap 64 to the ejecting head 50.
The cap 64 preferably has the inside thereof divided into plural areas each corresponding to each row of the nozzles by dividing walls, and each of the divided areas can be selectively suctioned using a selector or the like.
The cleaning blade is composed of an elastic member such as rubber, and is capable of sliding on the ejection face 50a of the ejecting head 50 with a transfer mechanism for the cleaning blade (not shown). When the liquid droplets or foreign materials are attached onto the ejection face 50a, the ejection face 50a is wiped off by sliding the cleaning blade 66 on the ejection face 50a and cleaned.
A suction pump 67 sucks a liquid from the nozzle 51 of the ejecting head 50 while the ejection face 50a of the ejecting head 50 is covered with the cap 64, and sends the sucked liquid to a collection tank 68.
The above suction operation is also performed when the liquid tank 60 is loaded in the image recording device 100 and the liquid tank 60 is filled with a liquid from the liquid tank 60 (at the time of the initial filling) or when the liquid having viscosity that has been increased during the long-term cessation is removed (at the time of starting the operation after a long-term intermission).
Note that there are two types of ejections from the nozzle: first, a normal ejection performed onto a recording medium such as paper in order to form an image; and second, a purge performed onto the cap 64 serving as a liquid receiver (also referred to as a blank ejection).
Further, when air bubbles are mixed into the nozzle 51 or the pressure chamber 52 in the ejecting head 50 or increase in the viscosity in the nozzle 51 exceeds a certain level, the liquid cannot be ejected from the nozzle 51 by the above-described blank ejection. In this case, the liquid with the air bubbles or increased viscosity in the pressure chamber 52 in the ejecting head 50 is sucked by the suction pump 67 by applying the cap 64 onto the ejection face 50a in the ejecting head 50.
The ejecting head 50, liquid tank 60, liquid supplying pump 62, cap 64, cleaning blade 66, suction pump 67, collection tank 68 and an ink flowing route that connects these units, as well as other members and equipments with which the ink directly contact, preferably have dissolution resistance and swelling resistance. Further, these members and equipments preferably have a light shielding property.
Control System
In
Since the image forming unit 102 is shown as a representative of the ejecting heads 102Y, 102C, 102M and 102K shown in
The communication interface 110 is an image data inputting means that receives the image data sent from a host computer 300. For the communication interface 110, wired interfaces such as USB (Universal Serial Bus) or IEEE1394, or wireless interfaces can be applied. The image data inputted into the image recording device 100 via the communication interface 110 are temporarily memorized in a first memory 114 for memorizing image data.
The system controller 112 is composed of a central processing unit (CPU), its surrounding circuit, and the like, and is a main controlling means of controlling the entire image recording device 100 according to a prescribed program that has been previously memorized in the first memory 114. That is, the system controller 112 controls each unit of the communication interface 110, motor driver 118, heater driver 124, medium type detecting unit 132, ink type detecting unit 134, printing control unit 150 and the like.
The motor for transportation 116 imparts a driving force to rollers, belts or the like that transport a recording medium. By this motor for transportation 116, the ejecting head 50 that constitutes the image forming unit 102 and the recording medium move relatively to each other. The motor driver 118 is a circuit that drives the motor for transportation 116 in accordance with the instructions given from the system controller 112.
The heater 122 is a circuit that drives a heater (or a cooling element) 122 which is not shown in the Figure, and maintains the temperature of the recording medium to be constant. The heater driver 124 is a circuit that drives the heater 122 in accordance with the instructions given from the system controller 112.
The medium type detecting unit 132 detects the type of the recording medium. There are various embodiments of detecting the type of the recording medium and examples thereof include an embodiment of detecting the type by a sensor provided at a paper supplying unit which is not shown in the Figure; an embodiment of inputting the type by the operation of a user; an embodiment of inputting the type from the host computer 300; and an embodiment in which the type is automatically detected by analyzing the image data (for example, resolution or color) inputted from the host computer 300 or supplemental data of the image data.
The ink type detecting unit 134 detects the type of the ink. There are various embodiments of detecting the type of the ink and examples thereof include an embodiment of detecting by a sensor provided in the liquid storage/loading unit which is not shown in the Figure; an embodiment of inputting the type by the operation of a user; an embodiment of inputting the type from the host computer 300; and an embodiment in which the type is automatically detected by analyzing the image data (for example, resolution or color) inputted from the host computer 300 or supplemental data of the image data.
The illumination intensity detecting unit 135 detects the illumination intensity of the UV rays emitted from the UV light source 103. Examples of the embodiments of detecting the illumination intensity include an embodiment of detecting the illumination intensity by a sensor provided near the UV light source 103 shown in
The environmental temperature detecting unit 136 detects the temperatures of the outside air and the inside of the image recording device. Examples of the embodiments of detecting the environmental temperature include an embodiment of detecting the environmental temperature by a sensor provided at the outside or inside of the device.
The environmental humidity detecting unit 137 detects the humidity of the outside air and the inside of the image recording device. Examples of the embodiments of detecting the environmental humidity include an embodiment of detecting the humidity by a sensor provided at the outside or the inside of the device.
The medium temperature detecting unit 138 detects the temperature of the recording medium at the time of forming an image. There are various embodiments of detecting the medium temperature and examples thereof include an embodiment of detecting the temperature by a contact type temperature sensor and an embodiment of detecting the temperature by a non-contact type temperature sensor provided above the recording medium 16. The temperature of the recording medium is maintained constant by the heater 122.
The liquid supplying unit 142 is composed of a tube through which the ink flows from the liquid tank 60 shown in
The liquid supplying driver 144 is a circuit that drives the liquid supplying pump that constitutes the liquid supplying unit and the like so that the liquid can be supplied to the image forming unit 102.
The printing control unit 150 produces the data (ejection data) necessary for each ejecting head 50 that constitute the image forming unit 102 to perform ejection (jetting) toward the recording medium based on the image data inputted in the image recording device 100. That is, the printing control unit 150 functions as an image processing means that performs image processing such as various processes, corrections or the like to generate the ejection data from the image data stored in the first memory 114 in accordance with the control of the system controller 112, and supplies the generated ejection data to the head driver 154.
The printing control unit 150 is accompanied with a second memory 152, and the ejection data and the like are temporarily stored in the second memory 152 at the time of performing the image processing in the printing control unit 150.
The second memory 152 is shown as an embodiment in which it accompanies the printing control unit 150 in
The head driver 154 outputs a driving signal for the ejection to each ejecting head 50 that constitute the image forming unit 12 based on the ejection data given from the printing control unit 150 (practically, it is the ejection data stored in the second memory 152). The driving signal for the ejection outputted from this head driver 154 is given to each ejecting head 50 (specifically, the actuator 58 shown in
A light source driver 156 is a circuit that controls the voltage, time and the timing to be inputted in the UV light source 103 based on the instructions given from the printing control unit 150, illumination intensity detected by the illumination intensity detecting unit 135, environmental temperature detected by the environmental temperature detecting unit 136, environmental humidity detected by the environmental humidity detecting unit 137 and the medium temperature detected by the medium temperature detecting unit 138, and drives the UV light source 103.
Hereinafter, exemplary embodiments of the invention will be described:
1. An ink jet recording method that records an image by ejecting, onto a recording medium, an ink that is cured by irradiation of an active energy ray, the method comprising:
applying an undercoating liquid onto the recording medium;
half-curing the undercoating liquid; and
forming an image by ejecting an ink onto the half-cured undercoating liquid.
2. The ink jet recording method of 1, wherein the undercoating liquid is cured by irradiation of an active energy ray.
3. The ink jet recording method of 2, wherein the active energy ray is an ultraviolet ray.
4. The ink jet recording method of 1, wherein the undercoating liquid contains a radical polymerizable composition.
5. The ink jet recording method of 1, wherein the undercoating liquid contains a surfactant.
6. The ink jet recording method of 1, wherein the ink is a multi-color ink set, and the method further comprises curing only the inside of the ink of at least one color ejected onto the recording medium.
7. The ink jet recording method of 1, further comprising completely curing the ink and the undercoating liquid.
8. The ink jet recording method of 1, wherein the surface tension of the undercoating liquid is smaller than the surface tension of at least one ink of the ink.
9. The ink jet recording method of 1, wherein the curing sensitivity of the ink is equal to or higher than the curing sensitivity of the undercoating liquid.
10. The ink jet recording method of 1, wherein the recording medium has low liquid absorbability.
11. The ink jet recording method of 1, wherein the undercoating liquid is applied by a coater.
12. An ink jet recording device comprising:
an undercoating liquid application unit that applies an undercoating liquid onto a recording medium;
an undercoating liquid curing unit that is provided downstream of the undercoating liquid application unit and that half-cures the undercoating liquid by applying energy; and
an image forming unit that is provided downstream of the undercoating liquid curing unit and that forms an image by ejecting, onto the undercoating liquid, an ink that is curable by irradiation of an active energy ray.
13 The ink jet recording device of 12, further comprising:
a conveyance unit that conveys the recording medium; and
an active energy irradiation unit that is provided downstream of the image forming unit and that irradiates, with an active energy ray, the recording medium on which an image is formed by the image forming unit and cures the ink and the undercoating liquid, wherein:
the image forming unit is an image forming unit that ejects the ink from at least one line-formation ink jet head, the head having a length corresponding to the entire width of a recordable width of the recording medium and being arranged in a direction perpendicular to a direction in which the recording medium is conveyed.
14. The ink jet recording device of 12, wherein the undercoating liquid is cured by irradiation of an active energy ray.
15. The ink jet recording device of 14, wherein the active energy ray is an ultraviolet ray.
16. The ink jet recording device of 12, wherein the interval between the application of the undercoating liquid and the ejection of the ink is in the range of from 5 microseconds to 10 seconds.
17. The ink jet recording device of 12, wherein the ink is a multi-color ink set.
18. The ink jet recording device of 12, wherein the undercoating liquid is applied by a coater.
Further details of the invention will now be explained by Examples. However, the invention is not limited to the following examples as long as its main purport is not exceeded.
Cromophtal Yellow LA (a pigment manufactured by Ciba Specialty Chemicals K.K.) 16g, dipropylene glycol diacrylate (DPGDA, manufactured by Akcros Chemicals Ltd.) 48g, and DISPERBYK-168 (manufactured by BYK-Chemie Japan K.K.) 16g were mixed and stirred for 1 hour with a Silverson high-speed stirrer. The mixture after stirring was dispersed with Disper Matte Mill and a pigment dispersion P-1 was obtained.
The dispersion conditions are that the mill was filled with zirconia beads having a diameter of from 0.4 to 0.5 mm at a filling rate of 80%, the peripheral velocity was 9 m/s, and the dispersion time was 6 hours.
<Preparation of Cyan Pigment Dispersion>
PB15:3 (trade name: IRGALITE BLUE GLO, manufactured by Ciba Specialty Chemicals K.K.) 16 g, dipropylene glycol diacrylate (DPGDA, manufactured by Akcros Chemicals Ltd.) 48 g, and DISPERBYK-168 (manufactured by BYK-Chemie Japan K.K.) 16 g were mixed, and a pigment dispersion P-2 was obtained according to the same method as that for the preparation of yellow pigment dispersion.
<Preparation of Magenta Pigment Dispersion>
Cinquasia Mazenta RT-355D (pigment manufactured by Ciba Specialty Chemicals K.K.) 16 g, dipropylene glycol diacrylate (DPGDA, manufactured by Akcros Chemicals Ltd.) 48 g, and DISPERBYK-168 (manufactured by BYK-Chemie Japan K.K.) 16 g were mixed, and a pigment dispersion P-3 was obtained according to the same method as that for the preparation of yellow pigment dispersion.
<Preparation of Black Pigment Dispersion>
Microlith Black C-K (pigment manufactured by Ciba Specialty Chemicals K.K.) 16 g, dipropylene glycol diacrylate (DPGDA, manufactured by Akcros Chemicals Ltd.) 48 g, and DISPERBYK-168 (manufactured by BYK-Chemie Japan K.K.) 16 g were mixed, and a pigment dispersion P-4 was obtained according to the same method as that for the preparation of yellow pigment dispersion.
<Preparation of Liquid I-1 for Yellow Ink Jet Recording>
The following components were mixed by high-speed stirring and dissolved, and a liquid I-1 for ink jet recording was prepared. The surface tension of the liquid I-1 for ink jet recording was 32 mN/m.
<Preparation of Liquid I-2 for Cyan Ink Jet Recording>
The following components were mixed by high-speed stirring and dissolved, and a liquid I-2 for ink jet recording was prepared. The surface tension of the liquid I-2 for ink jet recording was 31 mN/m.
<Preparation of Liquid I-3 for Magenta Ink Jet Recording>
The following components were mixed by high-speed stirring and dissolved, and a liquid I-3 for ink jet recording was prepared. The surface tension of the liquid I-3 for ink jet recording was 32 mN/m.
<Preparation of Liquid I-4 for Black Ink Jet Recording>
The following components were mixed by high-speed stirring and dissolved, and a liquid I-4 for ink jet recording was prepared. The surface tension of the liquid I-4 for ink jet recording was 33 mN/m.
<Preparation of Undercoating Liquid>
The following components were mixed by stirring and dissolved, and the undercoating liquid of the ink for ink jet recording was prepared. The surface tension of the undercoating liquid was 23 mN/m.
<Preparation of Comparative Ink I-0 for One-Liquid Type Ink Jet Recording>
The following components were mixed by stirring and dissolved, and a comparative ink I-0 for one-liquid type ink jet recording was prepared. The sp value of the comparative ink I-0 was 20 and the surface tension of the comparative ink I-0 liquid was 32 mN/m.
<Composition>
<Image Recording and Evaluation>
The obtained liquids of four colors for ink jet recording I-1 to 4 were loaded into an ink jet printer equipped with heads manufactured by TOSHIBA TEC CORPORATION. Four of the head sets were loaded in the ink jet printer, wherein each head set consists of two heads being arranged in full-line to have a droplet density of 600 npi, and wherein each head has an ejection frequency of 6.2 KHz, number of nozzles of 636, nozzle density of 300 npi (nozzle/inch, hereinafter the same), and a drop size of from 6 pl to 42 pl which is changeable in seven steps. The heads were fixed in the machine body in the order of yellow, cyan, magenta, and black from the upstream in the direction of conveying the recording medium, and a roll coater for the undercoating liquid and a half-curing light source (a number of ultra-high pressure mercury lamps were arranged in the width direction of the recording medium) were installed downstream of the head for yellow ink. Further, the position directly beneath the head was designed so that the recording medium can move, and the above-mentioned ultra-high pressure mercury lamps were respectively arranged in the direction in which the recording medium is conveyed, for each head of yellow, cyan, and magenta filled with the liquids I-1 to 3 for ink jet recording. In the downstream of the black ink head filled with the liquid I-4 for ink jet recording was installed a metal halide lamp. In this way, an experimental machine was prepared. The recording medium was conveyed by a roll conveyance and an image of 600 dpi×600 dpi was formed on the recording medium.
The undercoating liquid was applied uniformly to a thickness of 5 μm using the experimental machine (coating speed; 400 mm/s). Subsequent processes were then performed in two ways: 1) after the application of the undercoating liquid, exposure was performed with the light source for half-curing to half-cure the applied undercoating liquid; and 2) exposure with the light source for half-curing was not performed. Thereafter, by ejecting the liquids I-1 to 4 for ink jet recording onto the recording medium onto which the undercoating liquid has been applied with the heads loaded with the liquids I-1 to 4 for ink jet recording and performing pinning exposure after every ejections of each color (light intensity; 500 mW/cm2), thereby forming a full-color image and reversal characters of 5 pt of Hiragana characters “AIUEO” (conveying speed of the recording medium was 400 mm/s; four-scale image formation of from 6 to 18 pL (line evaluation was conducted at 6 pL); and an anti-aliasing treatment was performed on the characters.). The images were then fixed by irradiating with an ultraviolet ray (wavelength; 365 nm) at a light intensity of 3000 mW/cm2 with a metal halide lamp.
Here, the exposure intensity by the ultra-high pressure mercury lamp at the time before the image is formed with the liquid I-1 for ink jet recording and after the undercoating liquid has been applied was set in two ways, i.e., at 500 mW/cm2 and at 2000 mW/cm2, and the interval between the application of the undercoating liquid and the ejection of the liquid I-1 for yellow ink jet recording was set to be 0.2 second. LINTEC YUPO 80 (manufactured by Lintec Corporation) was used for the recording medium.
The measurement of the viscosity of the undercoating liquid that has been applied onto the entire surface of the recording medium was performed on the undercoating liquid that has been scraped up after exposure and kept at 25° C., using a portable laboratory-use digital viscometer VISCOSTICK (manufactured by Maruyasu Industries Co., Ltd.). When the exposure was performed at 500 mW/cm2, the inside was cured almost completely, but the surface was not cured and the viscosity at the surface was 1200 mPa s. When the exposure was performed at 2000 mW/cm2, the undercoating liquid was completely cured, including the surface layer.
Further, an image was recorded by performing the same operation as that described above except that the liquid I-2 for ink jet recording was changed to the comparative ink liquid I-0 and that the undercoating liquid was not used.
The evaluation below was performed on the obtained images, the liquid I-2 for ink jet recording, the undercoating liquid, and the comparative ink I-0. The evaluation result are shown in Table 1.
1. Evaluation of Line Quality
The quality of the image formed in the shape of a line having a width of 100 μm and an interval between the dots of 84 μm was determined by observing a 50 times magnified photograph by eye and evaluated according to the evaluation standard shown below. As for the comparative ink I-0, only one liquid was ejected in the form of a line.
<Evaluation Standard>
A: The shape of the dots was maintained, and a uniform shape of a line was obtained.
B: Each dot lacked its independency and disorder in line width due to the coalescence of adjacent liquid droplets was observed in places.
C: Each dot lacked its independency and disorder in line width due to the coalescence of adjacent liquid droplets was observed over the whole line.
2. Evaluation of Line Width
The line width of the image formed in the shape of a line with one droplet (6 pL) of the liquid droplet in the line width direction, at intervals of 84 μm between the dots, and at intervals of 175 μm between the nozzles was measured with a five-point average method based on a 50 times magnified photograph by a microscope. The line width consisting of one liquid droplet (6 pL) in the line width direction is ideally 40 μm.
3. Character Quality of Reversal Characters
The character quality of the reversal character was evaluated using the characters ejected onto a paper for photography (trade name: Gasai, manufactured by FujiFilm Corporation) as a benchmark, in accordance with the evaluation standard shown below by comparing a part where the void part was most narrowed in the Hiragana characters “AIUEO” shown with the original character.
<Evaluation Standard>
A: The shape of the image is favorable and the void part was not narrowed.
B: The void part was narrowed by 10 to 30%.
C: The void part was narrowed by 30% or more.
4. Evaluation of Stickiness
The stickiness was evaluated right after the irradiation of an ultraviolet ray, by touching the image face (recording face) with a finger, in accordance with the evaluation standard shown below.
<Evaluation Standard>
A: There was no stickiness.
B: Stickiness was felt to some extent.
C: Stickiness was remarkably felt.
5. Evaluation of Scratch Resistance
The change in the recording medium on which the line-shaped image was recorded was evaluated by observing the image that has been rubbed back and forth with an eraser for 10 times after the lapse of 30 minutes from the irradiation with an ultraviolet ray was, in accordance with the evaluation standard shown below.
<Evaluation Standard>
A: Decrease in the density due to scratching was not observed.
B: Decrease in the density due to scratching was slightly observed.
C: Decrease in the density due to scratching was remarkably observed.
6. Evaluation of Light Resistance
A residual ratio of a pigment [%] was obtained by recording the line-shaped image on a PET sheet, performing the irradiation with xenon light (85,000 Lux) using a weather meter (Atlas C. I65) for one week, and measuring the densities before and after the irradiation with a microdensitometer (trade name: MICRO-PHOTO METHER MPM-No. 172, manufactured by Union Optical Co., Ltd.), and a five-step evaluation was performed in accordance with the evaluation standard shown below. The evaluation of the light resistance was performed only on the image on the PET sheet.
<Evaluation Standard>
A: The residual ratio of a pigment was 90% or more.
B: The residual ratio of a pigment was from 89 to 80%.
C: The residual ratio of a pigment was from 79 to 70%.
D: The residual ratio of a pigment was from 69 to 50%.
E: The residual ratio of a pigment was 49% or less.
7. Evaluation of Ozone Resistance
A residual pigment ratio (%) was obtained by recording the line shaped image on a PET sheet, storing for one week under a condition of ozone concentration 5.0 ppm, and measuring the concentration before and after the storage with a microdensitometer (trade name: MICRO-PHOTO METHER MPM-No. 172, manufactured by Union Optical Co., Ltd.), and the 5 step evaluation was performed following the evaluation standard below. The evaluation of the ozone resistance was performed only on the image on the PET sheet.
<Evaluation Standard>
A: The residual pigment ratio was 90% or more.
B: The residual pigment ratio was 89 to 80%.
C: The residual pigment ratio was 79 to 70%.
D: The residual pigment ratio was 69 to 50%.
E: The residual pigment ratio was 49% or less.
8. Evaluation of [A (after Polymerization)/A (Before Polymerization)]
The ratio of unpolymerization ratio [A (after polymerization)/A (before polymerization)] was calculated by measuring the infrared absorbing spectra of the undercoating liquid, after the application of the undercoating liquid has been completed, before and after the exposure by a half-curing light source for curing the undercoating liquid. The measurement of the infrared absorbing spectra was performed by an infrared spectrometer (FTS-6000, manufactured by BIO-RAD Laboratories, Inc.). “A (after polymerization)” indicates an absorbance at an infrared absorption peak of a polymerizable group after polymerization, and “A (before polymerization)” indicates an absorbance at an infrared absorption peak of a polymerizable group before polymerization. An infrared absorption peak in the vicinity of 810 cm−1 was used as the infrared absorption peak.
9. Cross-Section Observation
The obtained image was sliced by a microtome (RM2255, manufactured by Leica Mycrosystems Japan) and the slice was observed by an optical microscopic (measuring microscope MM-40, manufactured by NIKON Corporation).
10. Measurement of Transferred Amount of Half-Cured Undercoating Liquid
The mass of the transferred half-cured undercoating liquid was obtained by pressing a plain paper sheet (copy paper C2, commodity code; V436, manufactured by Fuji Xerox Co., Ltd.) onto an undercoating liquid with a uniform pressure of 500 mN/cm2. The transferred amount of the half-cured undercoating liquid was then calculated as the mass per area of the uncured part of the undercoating liquid (uncured liquid amount). The above process was performed after the undercoating liquid has been applied and the exposure by a half-curing light source has been performed thereon, and prior to ejection of the ink.
Subsequently, the uncured liquid amount of the ink liquid of each color after the half-curing process was measured, after the application of the ink of each color and the exposure by a pinning light source (half-curing), in accordance with the same method as that in the above.
As shown in Table 1, in the Example according to the invention, a favorable line quality was obtained and the disorder of the characters was avoided by half-curing the undercoating liquid, and images with high reproducibility were recorded, as compared with the cases of Comparative Examples. In the Comparative Examples, the line quality was deteriorated, and the area of the void part was decreased in case of a pattern in which a fine non-image area is formed in a wide area such as a reversal character. In the case of curing the undercoating liquid completely, the undercoating liquid became just like plastics and the dot shape could not be maintained and a bleeding was caused, the uniform line width was not obtained, stickiness and scratch resistance were inferior, and the advantages of using two types of liquids could not be achieved.
The value of the ratio [A (after polymerization)/A (before polymerization)] in the Examples were in the range of from 0.3 to 0.7, respectively, by which the state of being half-cured was determined (the quantitative accuracy is presumed to be about +20% considering the unevenness in application or stability of the light source).
In the image parts obtained in Examples, as shown in
In Examples of the invention, the maximum application amount per area of the ink liquid was in the range of from 0.74 mg/cm2 to 0.87 mg/cm2, in the case where the ink droplet amount was 12 pL, in each case of the ink liquid of each color.
Further, the transferred amount of the half-cured undercoating liquid (the mass per area of the uncured part) was in the range of from 0.10 mg/cm2 to 0.12 mg/cm2, in the case where the ink droplet amount was 12 pL.
Therefore, the mass per area of the uncured part of the undercoating liquid, “M (undercoating liquid)”, and the maximum mass per area of the ejected ink liquid (colored liquid), “m (colored liquid)”, satisfied the following relation: “m(colored liquid)/10<M(undercoating liquid)<m(colored liquid)/5”.
Further, the uncured liquid amount of the ink liquid of each color was in the range of from 0.15 mg/cm2 to 0.18 mg/cm2.
Accordingly, in the case where the ink liquids (colored liquids) having different color phases were used in combination, the mass per area of the uncured part of a colored liquid A that was applied first onto a recording medium, “M(colored liquid A)”, and the mass per area of the uncured part of a colored liquid B that was applied subsequently onto the recording medium, “m(colored liquid B)”, satisfied the following relation: “m(colored liquid B)/10<M(colored liquid A)<m(colored liquid B)/5”.
A graph showing the effect of the invention will be further shown in
Fair: No unevenness in line width or color was observed.
Bad: Unevenness in line width was not observed, but in color was observed.
Worse: Unevenness in both line width and color was observed.
The diamond-shaped plots in the graph indicate results of performing the image formation on various recording media without performing undercoating. In the recording medium having the surface onto which an ink wets well, there is a tendency that the interdroplet interference is suppressed whereas the bleeding is worsened; On the other hand, in the recording medium having the surface onto which an ink hardly wets, there is a tendency that the bleeding is suppressed wherein the interdroplet interference is worsened. Therefore, the interdroplet interference and the bleeding are in such a trading-off relationship that the image quality varies depending on the types of the recording medium, and both of them cannot be satisfied at the same time.
The triangle-shaped plot indicates a result of the case that the undercoating liquid was applied and the exposure was not performed (equivalent to the comparative example shown in Table 1), and both of the interdroplet interference and the bleeding are not achieved at the same time.
The square-shaped plot indicates a result of performing half-curing of the undercoating liquid in the invention, where the bleeding can be suppressed without generating the interdroplet interference.
In this system, it is presumed that such an effect is achieved because the curing is hard to proceed on the oxygen-rich surface since a radical monomer as a curing component contained in the undercoating liquid is prevented from polymerizing under the existence of oxygen when the light irradiation is performed on the undercoating liquid, and a low intensity light from the light source for half-curing only causes the half-curing of the undercoating liquid. On the other hand, the oxygen-rich surface of the undercoating layer is also cured by the final curing light source having high light intensity. However, the above mechanism does not limit the invention. The same action also works in a case of the ink, and both of the interdroplet interference and the bleeding of an ink ejected onto another ink that has been ejected in advance can be prevented at a high level. In the case of recording an image on a non-absorbing recording medium having uneven surface such as Yupo paper, when the undercoating liquid was applied, and the exposure was not performed (corresponding to the Comparative Example shown in Table 1), unevenness in the medium tone was observed due to the change in the thickness of the undercoating liquid layer due to the unevenness in the surface thereof. When the half-curing of the undercoating liquid according to the invention is performed, unevenness was not observed at all and a high quality image having a uniform medium tone was obtained.
The liquids I-1 to I-4 and the undercoating liquid was prepared in the same manner as in Example 1, and the image recording and the evaluation of the character quality of the reversal characters were performed, except that the liquids I-1 to I-4 and DPGDA (manufactured by Akcros Chemicals Ltd.) used for the preparation of the undercoating liquid used in Example 1 were changed to the same mass of an organic high boiling point solvent S-15 as shown below. The same results as that in Example 1 were also obtained in Example 2.
The image recording and the evaluation of the character quality of the reversal characters were performed using the same ink and undercoating liquid and in the same manner as Example 1, except the light source 103P for half-curing of the undercoating liquid was removed and the undercoating liquid and the yellow ink provided on the recording medium were half-cured at the same time by the pinning light source provided downstream of the yellow ink head with low visibility. The same results as that in Example 1 were also obtained in Example 3. By removing the light source 103P for half-curing of the undercoating liquid, bleeding was caused in the yellow ink. However, it does not lead to the deterioration in the image quality because of the low visibility of the yellow ink, and the cost for the light source could be reduced.
The image recording was performed in the same manner as that in Example 1 except the undercoating liquid used in Example 1 was changed to the substance containing the following components, and the same evaluation as that in Example 1 was performed.
<Preparation of Undercoating Liquid>
The components of the following compositions were mixed by stirring and dissolved, and the white undercoating liquid was prepared. The surface tension of the white undercoating liquid was 23 mN/m.
According to the invention, an ink jet recording method and an ink jet recording device can be provided in which ink bleeding can be effectively suppressed even in the case of using any type of non-absorbing recording media, a high degree of uniformity in an image between various recording media can be obtained, and unevenness in line width or color caused by mixing between the liquid droplets can be suppressed.
Further, the ink jet recording method and the ink jet recording device can also be provided that are capable of high-speed recording of a high quality image.
All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-171732 | Jun 2006 | JP | national |
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| 20070296790 A1 | Dec 2007 | US |
