JP2009282426A - Method of manufacturing color filter, color filter, and image display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing color filter, by which peeling property of a light-curing ink composition from a temporary supporting body and transferability are improved, and adhesion to a transparent substrate is improved when the light-curing ink composition is transferred from the temporary supporting body to form a pattern on the transparent substrate and to provide a color filter having excellent color characteristics and an image display which yields a high quality image. <P>SOLUTION: The method of manufacturing the color filter include a pattern forming process comprising hardening the light-curing ink composition, which includes: (i) a step in which the pattern of the light-curing ink composition is given on the temporary supporting body and the given light-curing ink composition pattern is brought into contact with the transparent substrate; (ii) a step in which printing pressure is applied to the transparent substrate; (iii) a step in which the light-curing ink composition pattern on the transparent substrate is exposed to light from the face opposite to the contact face with the transparent substrate and the light-curing ink composition pattern is hardened; and (iv) a step in which the temporary supporting body is peeled off and the hardened light-curing ink composition pattern is transferred to the transparent substrate, in this order. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a color filter in which a photocurable ink composition is applied to a substrate by printing to form a colored pattern, and to a color filter and an image display device obtained thereby.

  In recent years, liquid crystal display devices are used from televisions to information terminal interfaces, from industrial device interfaces to portable information devices, and are at the center of thin display devices. In particular, as the display area of liquid crystal display devices has increased in size and definition, the mother glass substrate area of color filters has been steadily expanding in order to increase productivity and reduce manufacturing costs. On the other hand, color filters that are indispensable for colorization of liquid crystal display devices are required to improve quality, and high optical characteristics such as high contrast, high color purity, and high transmittance are required.

  In the production of color filters, a dyeing method, an electrodeposition method, a photolithographic method using a photocurable composition in which a pigment is dispersed or a photocurable composition in which a dye is dissolved, an inkjet method, screen printing, or gravure printing. A number of manufacturing methods such as a printing method using the above have been proposed, but from the viewpoint of quality, a photolithography method using a photocurable composition in which a pigment is dispersed has become mainstream.

  However, in the photolithography method, a color filter is manufactured by repeating coating, drying, exposure, development, and post-baking, so there are many processes, a large number of facilities are required, the footprint is increased, and it is difficult to improve productivity. In addition, a large capital investment was required. In particular, the increase in the size of the mother glass substrate has led to an increase in the size of the line and the associated increase in the price of production equipment, and it is difficult to meet the demand for cost reduction.

  When forming a multicolor pattern, apply a photocurable composition of a different color on the pattern once formed and repeat the pattern formation process again. May remain as scum, causing color mixing and a decrease in color purity. In order to suppress this phenomenon, it is necessary to further cure the pattern once formed at a high temperature. On the other hand, the pigment used is miniaturized for high contrast. Since many heating steps are repeated in the photolithography method, the miniaturized pigment is easily deteriorated by heat, easily changes in hue, and it is difficult to maintain high optical characteristics.

  On the other hand, the color filter manufacturing method based on the printing method, which has high productivity but is difficult in terms of quality, particularly the gravure printing method and the gravure offset printing method, improve the accuracy of the printing apparatus and make the plate making technology ( For example, refer to Cited Document 1), suggesting the possibility of producing a high quality color filter at low cost. When a color filter is produced by a printing method, it is important that the ink is completely transferred from the intaglio to the transfer target (substrate) and that the ink adheres to the transfer target. As a device for complete transfer, a release layer is provided on the surface of the intaglio and a device for improving the adhesion of ink to the transfer target (for example, Patent Document 2) has been made. It is incomplete and transfer residue is likely to occur on the blanket roll, etc., and if the continuous printing process is repeated, stains due to the ink composition accumulate on the blanket roll, and the problem that it is not possible to maintain a good printing situation cannot be solved. It was.

Further, in order to improve the transfer from the concave portion of the intaglio plate to the blanket roll, a proposal has been made to cure the ink composition in the concave portion by exposing from the back side of the concave printing plate (see Patent Document 3). However, in this method, the surface portion of the ink filled in the concave portion, that is, the surface in contact with the blanket roll is not cured, so that the ink composition applied to the blanket roll is not left on the blanket roll and is printed. It cannot be retransferred to the substrate. For this reason, the ink transferred onto the substrate to be printed has unevenness or hue unevenness, and a preferable chromaticity characteristic cannot be obtained.
JP 2007-118593 A JP-A-8-072384 JP 2007-256334 A

The present invention relates to a method for producing a color filter comprising a cured pattern forming step of forming a pattern formed by curing a photocurable ink composition on a transparent substrate, and the releasability of the photocurable ink composition on a temporary support. In addition to improving the transferability of the photocurable ink composition from the temporary support to the transparent substrate, further improving the adhesion of the photocurable ink composition to the transparent substrate, for image display devices, etc. It is an object of the present invention to provide a method for manufacturing a color filter that has high productivity and can be continuously produced even when applied to a large substrate.
A further object of the present invention is to provide a color filter excellent in color characteristics obtained by the method for producing a color filter and a high-quality image display device including such a color filter.

As a result of intensive studies, the present inventor has found that the above problems can be solved by the following method.
<1> A method for producing a color filter comprising a cured pattern forming step of forming a pattern formed by curing a photocurable ink composition on a transparent substrate,
The cured pattern forming step includes (i) applying the photocurable ink composition in a pattern on a temporary support, and bringing the applied photocurable ink composition pattern into contact with the transparent substrate; and (ii) Applying a printing pressure to the transparent substrate; and (iii) exposing the photocurable ink composition pattern on the transparent substrate from a surface opposite to the contact surface with the transparent substrate to form a photocurable ink composition. A method for producing a color filter, comprising: a step of curing an object pattern; and (iv) a step of peeling a temporary support and transferring the cured photocurable ink composition pattern to the transparent substrate.

<2> The method for producing a color filter according to <1>, wherein the temporary support is a printing plate or an intermediate transfer member.
<3> The method for producing a color filter according to <1>, wherein the temporary support is a blanket roll.

<4> The method for producing a color filter according to <3>, wherein the temporary support is a blanket roll in which a photocurable ink composition is formed in a pattern using an intaglio.

<5> The method for producing a color filter according to any one of <1> to <4>, wherein a printing pressure applied to the transparent substrate is in a range of 0.001 MPa to 50 MPa.
<6> exposure in the step of curing the exposure to the ^pattern, the method for producing a color filter according range of 1mJ / cm ² ~3000mJ / cm 2 from <1> to 1 wherein one of <5> .

<7> In the step (i), the amount of the solvent contained in the applied photocurable ink composition pattern is 5% by mass to 80% by mass with respect to the total mass of the photocurable ink composition pattern. The method for producing a color filter according to any one of <1> to <6>, which is a range.
<8> A color filter manufactured by the manufacturing method according to any one of <1> to <7>.
<9> An image display device using the color filter according to <8>.

In the present invention, a transparent substrate (transfer object) is brought into contact with a temporary support formed with a photocurable ink composition in a pattern, and printing pressure is applied to the transparent substrate. Although it has a step of exposing to radiation (preferably ultraviolet rays), this allows the photocurable ink composition to be exposed through the transparent substrate from the side in contact with the transparent substrate and sufficiently cured to impart film properties. At the same time, it is considered that the adhesion to the transparent substrate is improved. By such an action, the pattern-like ink composition has improved transferability from the temporary support to the transparent substrate, the temporary support after transfer has no residue, and the substrate and photocurable ink composition pattern. It is considered that productivity and continuous productivity were improved.
This improvement in transferability is not only due to the application of film properties by curing as described above, but also the temperature of the photocurable ink composition rises due to exposure, and the solvent in the photocurable ink composition is appropriately dried. Or, by raising the temperature, the solvent contained in the photocurable ink composition pattern is likely to evaporate, and the entire photocurable ink composition pattern is more uniformly dried. Estimated.

According to the present invention, in a method for producing a color filter comprising a cured pattern forming step of forming a pattern formed by curing a photocurable ink composition on a transparent substrate, the releasability of the photocurable ink composition on a temporary support. In addition to improving the transferability of the photocurable ink composition from the temporary support to the transparent substrate, further improving the adhesion of the photocurable ink composition to the transparent substrate, for image display devices, etc. Even when applied to a large substrate, it is possible to provide a method for manufacturing a color filter having high productivity and capable of continuous production.
Furthermore, it is possible to provide a color filter excellent in color characteristics obtained by the method for producing a color filter and a high-quality image display device including such a color filter.

Hereinafter, the best mode for carrying out the invention will be described in detail.
In the present invention, the term “temporary support” refers to a support that forms an ink composition pattern on the surface and holds the pattern until it is transferred onto a transparent substrate. It corresponds to.
That is, when performing direct printing in which a photocurable ink composition pattern is printed directly on a transparent substrate, which is a transfer target, from a printing plate, a “printing plate” such as an ordinary intaglio or letterpress is used as a temporary support. . The printing plate may be a flat plate or a roll plate.
In addition, when the ink composition pattern is not directly transferred onto the substrate, but once transferred to the intermediate transfer member and then printed on the transparent substrate, the “intermediate transfer member” serves as a temporary support. In this case, first, the ink composition is transferred to the "intermediate transfer member" such as a blanket roll from the printing plate, and further transferred to the transparent substrate from the blanket roll and printed by offset printing. A pattern is formed on the transparent substrate.

  A method for producing a color filter comprising a cured pattern forming step of forming a pattern formed by curing a photocurable ink composition on a transparent substrate, the cured pattern forming step comprising: (i) a photocurable ink composition In a pattern on a temporary support, contacting the applied photocurable ink composition pattern with a transparent substrate, (ii) applying a printing pressure to the transparent substrate, and (iii) the transparent Exposing the photocurable ink composition pattern on the substrate from the surface opposite to the contact surface with the transparent substrate to cure the photocurable ink composition pattern; and (iv) peeling the temporary support. And the color filter which has a fine pattern on the said transparent substrate can be manufactured by having sequentially the process of transferring this hardened | cured photocurable ink composition pattern to this transparent substrate.

The transparent substrate used in the present invention is not limited as long as it can transmit visible light and transmit active light, and various glass substrates and plastic resin substrates can be used.
The transparent substrate, which is a transfer target in the present invention, may be supplied in sheet form as a single sheet, or may be supplied as a web in the form of a long product wound in a roll.

  The glass substrate can be used as long as it is printable and is not particularly damaged or deformed by the printing pressure during printing. As a color filter application for a liquid crystal display device, a glass substrate having a thickness of 1.0 mm or less can be used. Preferably, it is a glass substrate having a thickness in the range of 0.7 mm to 0.03 mm, and when supplied in the form of a web, a thickness in the range of 0.3 mm to 0.03 mm is particularly preferable.

  The properties required for plastic resin substrates include low thermal expansion (preventing deterioration of display accuracy associated with the curing process during color filter creation), gas barrier properties (ensuring liquid crystal stability), light transmittance and optical isotropy, etc. There are optical characteristics, surface smoothness and the like. Regarding thermal expansion, the thermal expansion coefficient is preferably 10-4 or less. In particular, it is preferable that the printing process of the present invention has high dimensional stability and does not swell with a solvent. Moreover, it is preferable that it is a board | substrate which does not deform | transform by the heating after printing, and restore | restores even if it bends in a printing process. In the case of a plastic resin substrate, as a color filter application for a liquid crystal display device, the thickness is preferably in the range of 1.0 mm to 0.02 mm, and when supplied in the form of a web, the thickness is 0.7 mm to 0.01 mm. A thickness in the range is preferred.

  Examples of the transparent substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and solid-state imaging devices. Examples of the photoelectric conversion element substrate to be used include a silicon substrate and a plastic resin substrate. On these substrates, a black matrix for isolating each pixel is usually formed, or a transparent resin layer is provided for promoting adhesion.

  Plastic resin substrate materials include amorphous polyolefin, polyethersulfone, polyglutarimide, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, norbornene polymer, and bisaniline fluorene as diamines in terms of optical properties, heat resistance, and mechanical strength. Examples include polyimide as a component, polyester composed of bisphenolfluorene and dibasic acid, and the like. Among these, polyethersulfone, polycarbonate, polyethylene terephthalate, and norbornene polymer are preferable. The raw materials are particularly preferable for liquid crystal display devices.

  For these transparent substrates, chemical treatment with silane coupling agent, application of various primers, EB surface modification treatment, flame treatment, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc. It is also possible to perform appropriate pretreatment. Thereby, the affinity between the photocurable ink composition and the transparent substrate is improved, and the transferability is improved. The plastic resin substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  In addition, a color filter can be formed on the driving substrate on which the thin film transistor of the thin film transistor type color liquid crystal display device is arranged according to the present invention.

  As a printing method that can be used in the present invention, any existing method such as a planographic plate, a relief plate, an intaglio plate, and a stencil plate can be used. In the case of a lithographic plate, a plate in which an ink repellent ink repellent portion and a parent ink portion where the ink gets wet can be used. As the relief plate, a photosensitive resin relief plate (flexo) capable of forming a precise shape with light is preferable. As the stencil, the mesh material and the number of lines are not limited, but a screen printing method using a stainless mesh is preferable in consideration of the elongation of the plate.

As the intaglio, an intaglio capable of measuring a precise transfer ink amount is particularly preferable. The intaglio may be a method of engraving a metal plate with a high hardness stylus (needle), laser engraving, or etching (etching). In order to form a precise recess, an etching method is preferred in which a resist is applied, a mask having a desired shape is formed by exposure and development, and then a groove is formed in the substrate with a corrosive liquid or gas.
As long as the intaglio can form a groove for measuring the photocurable ink composition in a cylinder or a plane, the plate material may be a resin or a metal. The plate material is preferably a metal for precise weighing, particularly copper that is easy to etch. The plate surface is preferably subjected to a surface treatment for controlling the wettability of the photocurable ink composition. Various platings such as Cr and vacuum film formation can be used, but a DLC film as disclosed in Japanese Patent Application Laid-Open No. 2007-118593 is preferable in terms of plate durability.

  In the present invention, regarding the method of transferring the photocurable ink composition to the transparent substrate, the photocurable ink composition can be transferred directly from the printing plate to an intermediate transfer member such as a blanket roll. An offset method in which the pattern is transferred and then re-transferred to the transparent substrate may be used.

  The present invention can be applied to any printing method as long as printing is performed by transferring using a printing plate. Among them, the intaglio method is particularly preferable because of excellent dimensional stability and reproducibility in repeated printing of fine lines. In addition, the offset method, in which an image is transferred from a plate to an intermediate transfer member such as a blanket roll and then re-transferred from the intermediate transfer member to a transparent substrate, deforms or breaks a pattern that has already been printed when multiple colors are superimposed. Since the transfer can be performed without performing the process, it is the most suitable method for manufacturing the color filter of the present invention.

In the manufacturing method of a color filter, it is common to provide a black black matrix for the purpose of preventing reflection and a pixel composed of three primary colors of red, blue and green for color display. Further, in order to improve the transmittance, white, or yellow, indigo, orange, magenta, or other pixels may be provided in order to improve color reproducibility. For white pixels, there are cases where no colored pixels are provided and pixels are formed with transparent ink having no colorant.
In the method for producing a color filter of the present invention, it is preferable to create a black matrix or the like for the first color with respect to the transparent substrate. As a transfer method in forming the black matrix, a direct method in which the photocurable ink composition is directly transferred from the printing plate is preferable. Since this is the first layer, it is possible to form a uniform layer, and the linearity and dimensional stability of the formed pattern are good. By printing. Since the second and subsequent colors after forming the black matrix are superposed with colored layers, the offset method is preferred from the viewpoint of ink transferability.

  When a blanket roll is used, an elastic roll is disposed on the transfer surface of the transparent substrate at a point where the transparent substrate contacts the blanket roll, and the transparent substrate is guided so as to uniformly contact the blanket roll. Next, a printing pressure is applied. This can be performed using the above-described induction roll, but preferably a roll for applying the printing pressure is provided after the induction roll.

(I) Step of applying a photocurable ink composition in a pattern on a temporary support and bringing the applied photocurable ink composition pattern into contact with a transparent substrate Next, the steps of the present invention will be sequentially described. For example, the method shown in FIGS. 1 and 2 can be used. (FIG. 1, FIG. 2 has illustrated the case of the intaglio.)
The photocurable ink composition is applied in a pattern on a temporary support. This method is performed using the above-described relief printing, intaglio printing, lithographic printing, stencil printing, etc., and in many cases, is measured and leveled with a blade or the like. Arbitrary shapes and sizes can be adopted as the pattern shape in the design of the printing plate. Usually, an arbitrary shape such as a lattice shape, a rectangular shape, or a stripe shape can be used, but the colored pixel is preferably a stripe shape, and in the case of a black matrix, the lattice shape is preferable.

  Thus, the temporary support body provided with the photocurable ink composition in a pattern is brought into contact with the transparent substrate. The solvent amount of the photocurable ink composition at the time immediately before the temporary support and the transparent substrate come into contact with each other is preferably in the range of 5% by mass to 80% by mass with respect to the total mass of the photocurable ink composition. More preferably, it is the range of 30 mass%-75 mass%. If the amount of the solvent is within this range, moderate curing can be obtained by exposure, transferability to a transparent substrate is good, adhesion to the substrate is good, and the temporary support is hardly contaminated with high continuous productivity. Is obtained.

(Ii) Step of applying printing pressure to the transparent substrate Next, the temporary support and the transparent substrate which are in contact with each other are subjected to printing pressure so that the contact is uniform. As a result, the ink composition pattern on the temporary support is deformed by pressure.
The magnitude of the printing pressure is preferably in the range of 0.001 MPa to 50 MPa, more preferably in the range of 0.1 MPa to 10 MPa. When the printing pressure exceeds this range, the shape of the photocurable ink composition formed into a fine pattern is compressed and crushed, and the shape cannot be maintained. On the other hand, if the printing pressure is too small, a space is partially formed between the transparent substrate and the ink composition pattern, and it is not preferable because it is affected by oxygen in the exposure process and causes uneven curing.

  Examples of the material of the roll for applying the printing pressure include metals, glass, resins and rubbers. Especially, rubbers include natural rubber, butadiene rubber, styrene rubber, chloroprene rubber, butyl rubber, nitrile rubber, ethylene / propylene rubber, Silicone rubber, acrylic rubber / urethane rubber, fluorine rubber, polysulfide rubber, etc. In a preferred embodiment, various rubber composites and a plurality of layers are provided to give uniform printing pressure in view of necessary physical properties such as hardness, elasticity, wettability, and dust generation properties. Silicone rubber is used for the outermost layer. Is preferred.

(Iii) A step of exposing the photocurable ink composition pattern on the transparent substrate from a surface opposite to the contact surface with the transparent substrate to cure the photocurable ink composition pattern. The photocurable ink composition pattern is exposed with actinic rays through the transparent substrate from the surface opposite to the contact surface with the transparent substrate. By this step, at least a part of the photocurable ink composition pattern formed between the temporary support and the transparent substrate reacts to promote transfer to the transparent substrate.

The exposure means is not limited as long as the photocurable ink composition is transferred to the transparent substrate and exposed by irradiation with actinic rays through the transparent substrate from the surface opposite to the contact surface with the transparent substrate.
The light source for exposure may be any wavelength as long as the photopolymerization initiator generates radicals, and a mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an LED, and an LD (laser diode) are preferable. The exposure wavelength is preferably 200 to 480 nm. More preferably, the wavelength is in the range of 300 nm to 400 nm.
The exposure amount in the range of ^{1mJ / cm 2 ~3000mJ / cm 2} , preferably in the range of ^{2mJ / cm 2 ~500mJ / cm 2} .

(Iv) Peeling the temporary support and transferring the cured photocurable ink composition pattern to the transparent substrate After the exposure, the transparent substrate and the temporary support are peeled off and photocured on the transparent substrate. The ink composition pattern is transferred. A peeling roll is disposed at the separation point between the transparent substrate and the temporary support to prevent the transparent substrate from swinging.
After the temporary support is released, the transferred photocurable ink composition pattern may be further exposed.

  While the transparent substrate and the temporary support are in contact, at least an induction roll, a printing pressure roll (which may also serve as an induction roll), an exposure light source, and a peeling roll are installed. If there is a space for this, there is no particular limitation on the contact length between the transparent substrate and the temporary support. By using glass fiber, mirror, prism, etc. as the exposure light source, it is possible to guide the actinic rays by separating the light source device of the exposure machine, and the exposure area can be designed freely.

The speed (printing speed) when producing a color filter using the present invention is preferably in the range of 2 mm / sec to 300 mm / sec, more preferably in the range of 5 mm / sec to 15 mm / sec. Within this range, the transferred photocurable ink composition pattern is smooth, smooth, and the color characteristics of the colored pixels are good.
When you want to increase the speed, you can adopt an exposure light source with high illuminance, increase the number of exposure light sources, increase the contact length between the transparent substrate and the temporary support, and a large diameter blanket roll Should be adopted.

  The transferred photocurable ink composition pattern is preferably heated in order to improve the surface smoothness. The photocurable ink composition preferably has fluidity in this heating step. The photocurable ink composition transferred to the transparent substrate has an effect of improving the surface smoothness by flowing in the heating step.

Furthermore, it is preferable that the transferred photocurable ink composition pattern promotes drying and curing of the solvent remaining in the photocurable ink composition.
The surface of the ink composition pattern thus transferred should have a center line average roughness of 200 nm or less as measured by AFM, preferably 100 nm or less, more preferably 50 nm or less. It is preferable from the viewpoint of suppressing optical scattering on the surface and improving optical characteristics.

  For the above-described heating for improving smoothness, drying of the remaining solvent, and heating for promoting curing, a thermostatic bath, a hot plate, a high-frequency infrared heating device, or the like can be used. Heating for improving smoothness is preferably in the range of 80 ° C to 180 ° C, more preferably in the range of 90 ° C to 160 ° C, and the residence time is 40 seconds to 180 seconds. Within this range, the surface of the transferred photocurable ink composition tends to be smooth, and a colored pixel with good optical properties can be obtained.

  Further, the heating for promoting the drying and curing of the remaining solvent is preferably in the range of 160 ° C. to 260 ° C., more preferably in the range of 180 ° C. to 240 ° C., and the residence time is 180 seconds to 3600 seconds. . Within this range, the degree of cure of the photocurable ink composition is improved, black matrix or colored pixels are formed, and adverse effects such as transfer of the composition to other layers in contact with these pixels can be reduced. .

  The photocurable ink composition used in the present invention is printed on a transparent substrate by a printing method using various printing machines to create a color filter. During the transfer to the transparent substrate, at least a part reacts by exposure with actinic rays through the transparent substrate, the transferability is improved, the adhesion of the pixels is improved, and the pattern formability is good. The photocurable ink composition suitable for the present invention is described in detail below.

  The photocurable ink composition preferable for the present invention can adjust the viscosity of the ink according to the printing method. The range of the viscosity is preferably 100 to 1000000 mPa · s for lithographic printing, preferably 30 to 10000 mPa · s for relief printing (photosensitive resin relief printing), and if it is a stencil (screen), The range of 10 to 1000000 mPa · s is preferable, and if intaglio printing (gravure), the range of 5 to 1000 mPa · s is preferable, the range of 5 to 300 mPa · s is more preferable, and the range of 7 to 200 mPa · s is more preferable. It is.

  The method of adjusting the viscosity to the above range is not particularly limited, and examples thereof include a method of adjusting the solid content concentration, a method of adjusting the molecular weight of the polymer compound, and blending of various monomers / oligomers.

The photocurable ink composition used in the present invention comprises (a) a colorant, (b) a polymer compound, (c) a polymerizable compound, (d) a photopolymerization initiator, and (e) if necessary. It is comprised with the composition containing a solvent.

<(A) Colorant>
(A) As the colorant, organic and inorganic pigments, dyes, or mixtures thereof can be used. As the pigment, various conventionally known inorganic pigments or organic pigments can be appropriately selected and used. As the particle size of the pigment, considering that it is preferable to have high contrast and high transmittance, an organic pigment is preferable, and it is preferable to use a pigment having a particle size as small as possible. Considering the handling properties of the photocurable ink composition, the average primary particle diameter of the pigment is preferably 100 nm or less, more preferably 30 nm or less, and most preferably 5 to 25 nm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast. The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 4, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7

  These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. The above range is preferable from the viewpoints of light transmittance, color purity, and coloring power. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. The above range is preferable from the viewpoints of light transmittance, color purity, and NTSC target hue. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

  Further, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable. Carbon black and titanium black Is preferably in the range of 100: 0 to 100: 60. The above range is preferable from the viewpoint of dispersion stability.

  The pigment used in the present invention can be finely used for improving color purity, increasing transmittance, improving contrast, and the like. Such fine pigments are produced by mixing i) a pigment, ii) a water-soluble inorganic salt, iii) a small amount of a water-soluble organic solvent that does not substantially dissolve ii), and, if necessary, iv) a dispersion resin. A step of mechanically kneading with a kneader or the like (this pigment refining step is called salt milling), a step of putting this mixture into water and stirring it with a high-speed mixer or the like to form a slurry, and this slurry Is filtered, washed with water, and dried if necessary. By such a production method, a finely processed pigment can be obtained which is fine and has little aggregation of the pigment when dried.

  The salt milling described above will be described more specifically. First, a small amount of iii) a water-soluble organic solvent is added as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, and iv) if necessary, after kneading the dispersion resin with a kneader, etc. This mixture is put into water and stirred with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. In addition, when using it disperse | distributing to an oil-based varnish, it is also possible to disperse | distribute the process pigment (it is called a filter cake) before drying to an oil-based varnish, removing water by the method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.

By using iv) a dispersion resin in combination with the above iii) organic solvent at the time of salt milling, a finer processed pigment with a finer surface and coated with the dispersion resin iv) and less agglomeration of the pigment upon drying can be obtained. .
Note that iv) the timing of adding the dispersed resin may be added all at the beginning of the salt milling step, or may be added in divided portions.

ii) Water-soluble inorganic salt The water-soluble inorganic salt is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used. Sodium chloride or sodium sulfate is preferably used.
The amount of the inorganic salt used for salt milling is preferably 1 to 30 times, particularly 5 to 25 times, that of the organic pigment from the viewpoint of both processing efficiency and production efficiency. The larger the ratio of the inorganic salt to the organic pigment is, the higher the refinement efficiency is.

iii) A small amount of a water-soluble organic solvent that does not substantially dissolve ii) A water-soluble organic solvent serves to wet organic pigments and inorganic salts, and is an inorganic salt that is dissolved (mixed) in water and used. If it does not melt | dissolve substantially, it will not specifically limit. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol or the like is used.

The addition amount of the water-soluble organic solvent is preferably 5% by mass to 50% by mass with respect to the inorganic salt. More preferably, it is 10 mass%-40 mass% with respect to an inorganic salt, and optimally it is 15 mass%-35 mass% with respect to an inorganic salt. The above range is preferable from the viewpoint of physical properties suitable for kneading.
iii) The water-soluble organic solvent may be added in the initial stage of salt milling, or may be added separately. A water-soluble organic solvent may be used independently and can also use 2 or more types together.

  If necessary, iv) a dispersion resin can be used in the above-described finer process, and as the dispersion resin, natural resins, synthetic resins or polymer compounds having a specific structure as described below can be used. The polymer compound having a specific structure shown in (1) has a strong adsorptivity to the pigment and can coat the pigment. It is effective to ensure the dispersion stability of the pigment dispersion and the photocurable ink composition by dispersing the fine pigment coated with a resin having a specific structure as primary particles.

  The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.

  The above-mentioned covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent shown below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed, but in the case of a surface-coated pigment, the liberation rate is extremely small. 30% or less.

  The pigment after the coating treatment is washed with 1-methoxy-2-propanol, and the free amount is calculated. In this method, 10 g of a pigment is put into 100 ml of 1-methoxy-2-propanol, shaken with a shaker at room temperature for 3 hours, and then precipitated with a centrifuge at 80,000 rpm for 8 hours. The solid content of the supernatant can be determined from the drying method. The mass of the polymer compound released from the pigment is obtained, and the liberation rate (%) can be calculated from the ratio to the mass of the polymer compound used in the initial treatment.

The liberation rate of commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. And calculated as “mass of the polymer compound used in the initial treatment”. Separately, the pigment is washed with 1-methoxy-2-propanol, and the obtained liberation amount is divided by the “mass of the polymer compound used in the initial treatment” to obtain the liberation rate (%). .
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. The preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The polymer compound having a specific structure used for coating the pigment is a polymer containing a polymerization unit derived from a monomer represented by the following general formula (1) or a monomer comprising a maleimide or a maleimide derivative. It is particularly preferable that the polymer contains a polymer unit derived from the monomer represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
As the alkyl group for R ¹ , an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific examples of preferable alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.
R ¹ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R ² represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
The alkylene group represented by R ² may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ² has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the terminal of the above alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z via the heteroatom or a partial structure containing a heteroatom.

  In general formula (1), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, indanthrone series, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

  Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

  In general formulas (2), (3), and (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring C in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formulas (2), (3) and (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  Specific examples of these compounds include [0029] to [0030] of Japanese Patent Application No. 2006-259673, [0044] to [0047] of Japanese Patent Application No. 2007-85382, and [0045] to [0047] of Japanese Patent Application No. 2007-231695. And those disclosed in [0075] to [0076] can be used.

  A preferred photocurable ink composition used in the present invention is preferably a photocurable ink composition after a pigment is previously dispersed with the polymer compound having the specific structure described above to prepare a pigment dispersion. In preparing the pigment dispersion, it is more preferable to disperse the pigment by using a dispersant and a pigment derivative in addition to the polymer compound having the specific structure described above and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility and dispersion stability of the pigment can be further improved.

  Dispersion is performed mainly using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., and finely dispersed with beads made of glass having a particle diameter of 0.01 to 1 mm, zirconia, etc. A dispersion composition is obtained. Before performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.
Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15. Disperse aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L12 P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162 , 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie Co., Ltd.). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  As content in the pigment dispersion composition of a dispersing agent, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of a pigment derivative, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The solvent in the pigment dispersion composition is not particularly limited as long as it is an organic solvent, and can be appropriately selected from known ones such as 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, (Poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and their acetates; ethyl acetate Acetates such as n-propyl acetate, i-propyl acetate, n-butyl acetate and i-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl ethyl keto , Acetone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, alcohols such as glycerin, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, alkylene glycol monoalkyl ethers and their acetates, acetates, methyl ethyl ketone, and the like are preferable.

  The content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition. When the pigment dispersion composition is used for the preparation of a photocurable ink composition to be described later, from the viewpoint of handleability, it is contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass. be able to.

In the present invention, when a dye is used as the colorant, a uniformly curable photocurable ink composition is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

  As content of the coloring agent in the photocurable ink composition preferable for this invention, it is 5-70 mass% with respect to the total solid (mass) of this composition, and 10-60 mass% is more preferable. . When the content of the colorant is within the above range, the color density is sufficient to ensure excellent color characteristics.

<Photocurable ink composition>
A photocurable ink composition preferable for the present invention comprises the pigment dispersion composition described above, (b) a polymer compound, (c) a photopolymerizable compound, and (d) a photopolymerization initiator. If necessary, (e) other components such as a solvent may be contained. Hereinafter, each component will be described in detail.

<(B) polymer compound>
A preferred photocurable ink composition for the present invention comprises (b) a polymer compound. The addition of the polymer compound is preferable because the peelability of the photocurable ink composition pattern from the temporary support is improved and the adhesion to a transparent substrate and the like is improved. Further, it is desirable that the polymer compound has an appropriate polar group such as a carboxyl group or a hydroxyl group, and this improves the dispersion stability when a pigment is used as the colorant.
A silicon resin having a siloxane structure can also be used. By using a silicon resin, the color filter can be prevented from being discolored over time due to yellowing or the like, and since it is highly insulating, image burn-in can be prevented when used as a color filter for a liquid crystal display.

  As the polymer compound that can be used in the photocurable ink composition preferable for the present invention, in addition to the above-described dispersion resin, a polymer compound having another structure can be used when preparing the photocurable ink composition. . The polymer compound that can be added when preparing the photocurable ink composition includes, in addition to the above-described dispersion resin, a linear organic polymer, and a molecule (preferably an acrylic copolymer). And a molecule having at least one polar group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) in a molecule having a styrene copolymer as the main chain).

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, polymers having a hydroxyl group, an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  The specific structural unit of the polymer compound that can be used in the photocurable ink composition preferred in the present invention is, in particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith. Is preferred. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ¹¹ R ¹² , CH ₂ = C (R ¹¹ ) (COOR ¹³ ) [wherein R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ¹³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹¹ R ¹² , CH ₂ ═C (R ¹¹ ) (COOR ¹³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. At least one.

  In the present invention, it is also a preferred embodiment that (b) a polymer compound having at least one fluorene ring and one epoxy ring in the molecule (hereinafter appropriately referred to as a specific epoxy compound) is used as the polymer compound. Particularly preferred are compounds having one or more fluorene rings and two or more epoxy rings in the molecule. By having two or more epoxy rings, a crosslinked product is formed after curing, so that toughness is improved and a strong pixel can be obtained, which is preferable.

  The specific epoxy compound is more preferably a compound having a structure represented by the following general formula (I).

  In the general formula (I), R represents ethylene or propylene, and n and m each independently represent an integer having a relationship in which m + n is 0 to 12.

  The specific epoxy compound is a low molecular compound having a molecular weight of 2000 or less, but from the viewpoint of thermal polymerization at the time of heating for curing, the molecular weight is preferably 1500 or less, and more preferably 1000 or less. .

The specific epoxy compound may have an alkyleneoxy group. In the general formula (I), R represents ethylene or propylene. The alkyleneoxy group is an ethyleneoxy group or a propyleneoxy group. It is preferable from the viewpoint of thermal polymerizability during post-baking that the alkyleneoxy group selected from these is repeatedly in the range of 0 to 12. The alkyleneoxy group may further have a substituent.
As said substituent, hydrophilic groups, such as a hydroxy group, an amino group, and a carboxy group, can be mentioned. Further, the alkyleneoxy group may have both an ethyleneoxy group and a propyleneoxy group in one molecule.

  Examples of the specific epoxy compound include Ogsol EG-210 and PG-100 manufactured by Osaka Gas Chemical Co., Ltd., ESF-300 manufactured by Nippon Steel Chemical Co., Ltd., and in particular, Ogsol EG-210 manufactured by Osaka Gas Chemical Co., Ltd. is a glass substrate. This is preferable because the transfer rate can be improved.

  As content in the photocurable ink composition of the high molecular compound which can be used for the photocurable ink composition preferable for this invention, 1-60 mass% is preferable with respect to the total solid of this composition, More Preferably, it is 2-50 mass%, Most preferably, it is 5-40 mass%. When the content is in the range of 5 to 40% by mass, high transferability is obtained, the thixotropic property is low, and the change in the viscosity of the ink on the printing press (ink supply system) is small, which is preferable.

<(C) Photopolymerizable compound>
(C) As the photopolymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable. Among them, a tetrafunctional or higher acrylate compound is more preferable. preferable.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

  Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.

Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition having a very high photosensitive speed. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T. UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

The photopolymerizable compound can be used in combination of two or more, in addition to being used alone.
As content in the photocurable ink composition of a photopolymerizable compound, 3-55 mass parts is preferable with respect to 100 mass parts of total solid of this composition, More preferably, it is 10-50 mass parts. . When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently performed.

<(D) Photopolymerization initiator>
(D) As the photopolymerization initiator, for example, halomethyl oxadiazole described in JP-A-57-6096, halomethyl-oxa described in JP-B-59-1281, JP-A-53-133428, etc. active halogen compounds such as s-triazine, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318,791 and European Patent Application No. 88050 Aromatic ketone compounds such as benzophenones described in Japanese Patent No. 4199420, (thio) xanthone-based or acridine-based compounds described in French Patent No. 2456741, and coumarin described in JP-A-10-62986 Or biimidazole compounds, sulfos such as JP-A-8-015521 Umm organic boron complex, etc., etc. can be mentioned.

  Examples of the photopolymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, active halogen compounds (triazine series, halomethyloxadiazole series, coumarin series), acridine series, biimidazole series. And oxime ester systems are preferred.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Suitable examples include 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. be able to.

  Preferred examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. Can do.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen photopolymerization initiator (triazine, oxadiazole, coumarin) include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis. (Trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2, 4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (Trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxy Tyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- ( Diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) ) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloro Methyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl- -Amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl A preferred example is -5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

  Preferable examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the photocurable ink composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, 0.5-5. 0% by mass. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

-Sensitizing dye-
It is preferable to add a sensitizing dye to the photocurable ink composition as necessary. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the polymerization initiator component and polymerization reaction of the polymerizable compound thereby. Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

  Preferred spectral sensitizing dyes or dyes as sensitizing dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines ( For example, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), Phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll, chlorophyllin, Heart metal-substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having a maximum absorption wavelength at 350 to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

-Solvent-
A pigment dispersion composition and a photocurable ink composition suitable for the present invention can be suitably prepared using a solvent together with the above components as necessary.
Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, lactic acid 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ter, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

  In the photocurable ink composition suitable for the present invention, if necessary, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, other fillers, Various additives such as a polymer compound other than the above-described polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

  By containing the fluorinated organic compound, the smoothness can be improved when the photocurable ink composition is applied to the temporary support and after the transfer. That is, it is effective in that the interfacial tension between the plate or the transparent substrate and the photocurable ink composition is lowered to improve the wettability to the temporary support or the transparent substrate, and a film having a smooth surface can be formed. It is.

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within the above range, the surface smoothness of the photocurable ink composition is improved, and the solubility in the composition is also good.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R- 61, R-90 (Dainippon Ink Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 8 2 (manufactured by JEMCO (Ltd.)), and the like.

  0.001-2.0 mass% is preferable with respect to the total mass of a photocurable ink composition, and, as for the addition amount of a fluorine-type organic compound, More preferably, it is 0.005-1.0 mass%.

The photocurable ink composition suitable for the present invention contains a thermal polymerization initiator, stabilizes the shape of the colored pixel after transfer, and leaches the photocurable ink composition into each layer in contact with the colored pixel. It is effective in preventing image deterioration.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

  It is also effective to contain a thermopolymerizable compound in the photocurable ink composition suitable for the present invention. If necessary, an epoxy compound can be added to increase the strength of the coating film. The epoxy compound is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103, etc. (more from Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (more from Daicel Chemical) and their similarities The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above manufactured by Nagase Kasei), Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT- 401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

  The photocurable ink composition suitable for the present invention is preferably composed of various surfactants. In addition to the aforementioned fluorosurfactants, various nonionic, cationic and anionic surfactants are used. Agents can be used. Among these, the above-mentioned fluorine-based surfactants and nonionic surfactants are preferable.

  Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Kasei Co., Ltd. It can be used as appropriate. In addition to the above, the aforementioned dispersants can also be used.

  In addition to the above, various additives can be added to the photocurable ink composition. Specific examples of additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate. Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers Resin, such as phenoxy resin formed from alcohol-soluble nylon, bisphenol A and epichlorohydrin.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photocurable ink composition suitable for the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol Pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzo Imidazole and the like are useful.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.
(Dispersion adjustment)

<Synthesis example of polymer compound having heterocycle in side chain>
(Synthesis of polymer 1)
M-11 (27.0 g), methyl methacrylate (126.0 g), methacrylic acid (27.0 g), and 1-methoxy-2-propanol (420.0 g) were introduced into a nitrogen-substituted three-necked flask and a stirrer (Shinto Kagaku Co., Ltd.). ): Three-one motor), and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 1 was obtained. As a result of measuring the weight average molecular weight of the obtained polymer compound by a gel permeation chromatography method (GPC) using polystyrene as a standard substance, it was 20,000. Moreover, the acid value per solid content was 98 mgKOH / g from the titration using sodium hydroxide.

(Synthesis of polymer 2)
M-6 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: The mixture is stirred with a three-one motor, and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred with heating at 90 ° C. for 2 hours. Two hours later, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. From the titration with sodium hydroxide, the acid value per solid content was 99 mgKOH / g.

(Preparation of Red Pigment 1)
50 g of pigment (CI Pigment Red254), 500 g of sodium chloride, 25 g of the above-described polymer 1 solution, and 100 g of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare Red pigment 1.

(Preparation of Green Pigment 2)
In the adjustment of Red pigment 1, instead of Pigment Red254, C.I. I. Green Pigment 36 was prepared in the same manner as Red Pigment 1 except that Pigment Green 36 was used, and Polymer 2 was used instead of Polymer 1.

(Preparation of Blue Pigment 3)
In the adjustment of Green Pigment 2, instead of Pigment Green 36, C.I. I. Blue Pigment 3 was prepared in the same manner as Green Pigment 2 except that Pigment Blue 15: 6 was used.

(Preparation of Black pigment 4)
In the adjustment of Green Pigment 2, instead of Pigment Green 36, C.I. I. Black Pigment 4 was prepared in the same manner as Green Pigment 2 except that Pigment Black 7 was used.

(Preparation of Red Dispersion 1)
120 parts of Red Pigment 1, 80 parts of a dispersant (Disperbyk 166, manufactured by Big Chemie Co., Ltd.) and 800 parts of a solvent propylene glycol monomethyl ether acetate were stirred for 3 hours at a rotational speed of 3,000 rpm using a homogenizer. The mixture was mixed to prepare a mixed solution, and further subjected to a dispersion treatment for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads to obtain Red dispersion 1.

(Preparation of Green dispersion 2)
In the preparation of Red Dispersion 1, the composition was dispersed in the same manner as Red Dispersion 1 instead of 150 parts of Green Pigment 2, 90 parts of a dispersant (Disperbyk 161, manufactured by Big Chemie Co., Ltd.), and 760 parts of the solvent propylene glycol monomethyl ether acetate. Green dispersion 2 was obtained.

(Preparation of Blue dispersion 3)
In the preparation of Red Dispersion 1, the composition was dispersed in the same manner as Red Dispersion 1 instead of 120 parts of Blue Pigment 3, 60 parts of a dispersant (Disperbyk 166 manufactured by Big Chemie Co., Ltd.), and 820 parts of the solvent propylene glycol monomethyl ether acetate. , Blue dispersion 3 was obtained.

(Preparation of Black dispersion 4)
In the preparation of Red Dispersion 1, the composition was replaced with Black Pigment 427 parts, Dispersant (Disperbyk 130, manufactured by Big Chemie Co., Ltd.), 20 parts of cyclohexanone as a solvent, and 45 parts of propylene glycol monomethyl ether acetate. Dispersion was conducted in the same manner as in Example 1 to obtain Black dispersion 4.

<Create a black matrix>
(Plate making)
Plate making was performed using a boomerang line (a gravure plate making apparatus manufactured by Sink Laboratory Co., Ltd.). A body circumference of 720 mm An aluminum alloy cylinder (manufactured by Nikkin Act Corporation) having a body width of 600 mm was used. The aluminum alloy cylinder was degreased with 3.0 wt% dilute sulfuric acid and washed with water, followed by ballad plating for degreasing and removal of the oxide film. Further, the roll was polished and mirror finished.

  Thermal resist: TSER-2104E4 was applied to a cylinder using a fountain coater, dried, and then exposed with a laser stream FX (manufactured by Sink Laboratory Co., Ltd.).

As the pattern, the repeating pattern of FIG. 3 was created. The white portion corresponds to the saw portion at the exposed portion, and the black portion corresponds to the unexposed portion at the exposed portion.
After exposure, the TLD developer (manufactured by Sink Laboratory Co., Ltd.) was developed using a developer diluted to 12.5% with pure water, burned, and then stepped (cell depth) between the nuki part and the saw part Was etched to 4.4 μm.

  Further, cylinder etching was performed to form a gravure cell. Further, after removing the resist image, Cr plating was applied to obtain a gravure plate.

(Photocurable ink composition = adjustment of Black ink composition)
Polymer compound: benzyl methacrylate / acrylic acid (7/3 mol ratio) copolymer weight average molecular weight 5000 24 parts Polymerizable compound (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) 38 parts Polymerizable compound (Shin Nakamura Chemical Co., Ltd.) Company A-BPE-20) 36 parts Solvent Propylene glycol monomethyl ether acetate 140 parts Solvent Ethyl 3-ethoxypropionate 65 parts Polymerization initiator Etanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (OXE-02 manufactured by Ciba Specialty Chemicals Co., Ltd.) 8 parts Surfactant Abycia Solsperse 20000 9 parts Thermally polymerizable compound (Epiclon N-695 manufactured by DIC Corporation) Shinto Science Co., Ltd .: Three-One Motor)
-Black dispersion 4 638 parts was added and it fully stirred, and obtained 1000 parts of photocurable ink compositions.

(printing)
Experiments were performed using a gravure direct printing method (see FIG. 1). The glass substrate used was Corning EAGLE XG 0.5 mm thick.
The Black ink composition was supplied to the plate using a doctor chamber and an anilox roller, and transferred (printed) directly from the plate to the glass substrate. Immediately before being transferred to the glass substrate, the excess ink is scraped off with a doctor blade, the printing speed is 24 mm / sec, and the glass substrate has a length of 80 mm wound around the plate (contact area: 440 cm ² ), and the printing pressure. 4.4 MPa (= 0.102 kgf / cm ² ), the exposure light source is an LED array with a wavelength of 365 nm (LED: Nichia Chemical Industries NSHU590B peak wavelength 365 nm), and the exposure is 80 mJ / cm ² from the back surface of the transparent substrate. did.

The glass substrate and the gravure plate are peeled off, and the glass substrate to which the black ink composition is applied is heated on a hot plate at 100 ° C. for 120 seconds, and then an LED array (LED: Nichia Corporation NSHU590B peak wavelength 365 nm) is further applied from the top surface of the substrate. It was exposed to 80 mJ / cm ² and heated in an oven at 230 ° C. for 30 minutes to obtain a glass substrate on which a black matrix was printed. When the film thickness of the obtained black matrix was measured with a stylus type step difference measuring machine (Dektak Nippon Beiko Co., Ltd.), it was 1.1 μm.

<Create Green pattern>
(Plate making)
Ballard plating was applied in the same manner as the black matrix plate, a resist was applied, and a pattern as shown in FIG. 4 was exposed. Etching was performed to obtain a stripe pattern having a width of 60 μm and a cell depth of 11.9 μm. The gravure offset method shown in FIG. 2 is used as a printing method, and the width of the printing plate is designed in consideration of the fact that the photocurable ink composition layer is compressed by the printing pressure at the offset and the width is widened. Further, Cr plating was applied in the same manner as the black matrix plate to obtain a green printing plate.

(Photocurable ink composition = Adjustment of Green ink composition)
・ High molecular compound: benzyl methacrylate / acrylic acid (7/3 mol ratio) copolymer weight average molecular weight 5000 26 parts ・ Polymerizable compound (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) ・ Polymerizable compound (Shin Nakamura Chemical Co., Ltd.) Company A-BPE-20) 40 parts Solvent Propylene glycol monomethyl ether acetate 98 parts Solvent Ethyl 3-ethoxypropionate 137 parts Polymerization initiator (B-CIM manufactured by Hodogaya Chemical Co., Ltd.) 12 Part / sensitizing dye diethylaminobenzophenone (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.)
2 parts ・ Surfactant (Solsperse 20000) 9 parts ・ Thermopolymerizable compound (EPICLON N-695, manufactured by DIC Corporation) 30 parts are added, and with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor) Stir,
-606 parts of Green Dispersion 2 were added and further sufficiently stirred to obtain 1000 parts of a photocurable ink composition = Green ink composition.

(printing)
Experiments were performed using the gravure offset printing method (see FIG. 2). The green ink composition was supplied to the plate using a doctor chamber and an anilox roller, and the pattern transferred to the silicone rubber blanket roller was printed on the glass substrate provided with the black matrix obtained above. That is, the silicone rubber bracket roller has a silicone rubber layer thickness of 0.6 mm and its surface is mirror-finished. Spring hardness Hs (JISA)
60, using a doctor blade to wipe off excess ink immediately before being transferred to the silicone rubber blanket roller, printing speed of 24 mm / sec, and a glass substrate provided with a black matrix is 80 mm long on the silicone rubber blanket roller. It is is wound around so as to contact (a contact area: 440 cm ^2), an exposure light source was exposed from the substrate backside at an exposure amount 80 mJ / cm ² by using a LED array having a wavelength of 365 nm.

Using a plurality of alignment scopes from the back of the substrate, reading was performed using the black matrix (alignment mark) as a reference, and the printing pressure and the printing pressure balance were adjusted. After the exposure, the glass substrate and the silicone rubber blanket roller are peeled off, heated on a hot plate at 100 ° C. for 120 seconds, and further, 80 mJ / cm ² using an LED array (LED: Nichia Chemical NSHU590B) having a wavelength of 365 nm from the upper surface of the substrate. Exposed.

<Create Blue Pattern>
(Plate making)
Ballade plating was applied in the same manner as the black matrix plate, and after applying a resist, the stripe pattern was the same as the Green pattern, and the position was between the Green patterns. Etching was performed to create a stripe pattern having a width of 60 μm and a cell depth of 10.7 μm. The gravure offset method shown in FIG. 2 is used as a printing method, and the width of the printing plate is designed in consideration of the fact that the photocurable ink composition layer is compressed by the printing pressure at the offset and the width is widened. Further, similarly to the black matrix plate, Cr plating was performed to obtain a blue printing plate.

(Photocurable ink composition = Adjustment of Blue ink composition)
Polymer compound: benzyl methacrylate / acrylic acid (7/3 mol ratio) copolymer weight average molecular weight 5000 65 parts Polymerizable compound (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) 47 parts Polymerizable compound (Shin Nakamura Chemical Co., Ltd.) Company A-BPE-20) 47 parts Solvent Propylene glycol monomethyl ether acetate 120 parts Solvent Ethyl 3-ethoxypropionate 140 parts Polymerization initiator (OXE01 made by Ciba Specialty Chemicals) 8 parts Surfactant (Solsperse 20000) 9 parts · Thermopolymerizable compound (EPICLON N-695, manufactured by DIC Corporation) 30 parts were added and stirred thoroughly with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor).
-534 parts of Blue dispersion liquid 3 was added and further sufficiently stirred to obtain 1000 parts of a photocurable ink composition = Blue ink composition.

(printing)
Experiments were performed using the gravure offset printing method (see FIG. 2). The blue ink composition is supplied to the plate using a doctor chamber and an anilox roller, and the pattern transferred to the silicone rubber blanket roller is printed on the glass substrate provided with the black matrix and the green stripe pattern obtained above. did. That is, the silicone rubber bracket roller uses a silicone rubber layer having a thickness of 0.6 mm and a mirror-finished surface, and has a spring hardness of Hs (JISA) 60, and immediately before being transferred to the silicone rubber blanket roller, the doctor blade Excess ink was removed, the printing speed was 24 mm / sec, the glass substrate provided with the black matrix was wound around the silicone rubber blanket roller with a length of 80 mm (contact area: 440 cm ² ), and the light source for exposure Were exposed from the back of the substrate using an LED array with a wavelength of 365 nm at an exposure dose of 80 mJ / cm ² .

Using a plurality of alignment scopes from the back of the substrate, reading was performed using the black matrix (alignment mark) as a reference, and the printing pressure and the printing pressure balance were adjusted. After the exposure, the glass substrate and the silicone rubber blanket roller are peeled off, heated on a hot plate at 100 ° C. for 120 seconds, and further, 80 mJ / cm using an LED array with a wavelength of 365 nm (LED: Nichia Chemical NSHU590B) from the upper surface of the substrate. ² exposures.

<Create red pattern>
(Plate making)
Ballard plating was applied in the same manner as the black matrix plate, and after applying a resist, the stripe pattern was the same as the Green pattern, and the position was between the Green and Blue patterns. Etching was performed to create a stripe pattern having a width of 60 μm and a cell depth of 12.8 μm. The gravure offset method shown in FIG. 2 is used as a printing method, and the width of the printing plate is designed in consideration of the fact that the photocurable ink composition layer is compressed by the printing pressure at the offset and the width is widened. Further, similarly to the black matrix plate, Cr plating was performed to obtain a red printing plate.

(Photocurable ink composition = Red ink composition adjustment)
-Polymer compound: benzyl methacrylate / acrylic acid (7/3 mol ratio) copolymer weight average molecular weight 5000 5 parts-Polymerizable compound (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)-Polymerizable compound (Shin Nakamura Chemical Co., Ltd.) Company A-BPE-20) 30 parts / solvent 17 parts propylene glycol monomethyl ether acetate / solvent ethyl, 3-ethoxypropionate 148 parts / polymerization initiator (B-CIM manufactured by Hodogaya Chemical Co., Ltd.) 13 Part / surfactant (Arvasia Corp. Solsperse 20000) 8 parts thermopolymerizable compound (DIC Corporation EPICLON N-695) Add 25 parts and stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor) Stir in
-724 parts of Red dispersion 1 were added and further sufficiently stirred to obtain 1000 parts of a photocurable ink composition = Red ink composition.

(printing)
Experiments were performed using the gravure offset printing method (see FIG. 2). The red ink composition was supplied to the plate using a doctor chamber and an anilox roller, and the pattern transferred to the silicone rubber blanket roller was transferred onto the glass substrate provided with the black matrix obtained above and the green and blue stripe patterns. Printed on. That is, the silicone rubber bracket roller uses a silicone rubber layer having a thickness of 0.6 mm and a mirror-finished surface, and has a spring hardness of Hs (JISA) 60, and immediately before being transferred to the silicone rubber blanket roller, the doctor blade Excess ink was removed, the printing speed was 24 mm / sec, the glass substrate provided with the black matrix was wound around the silicone rubber blanket roller with a length of 80 mm (contact area: 440 cm ² ), and the light source for exposure Were exposed from the back of the substrate using an LED array with a wavelength of 365 nm at an exposure dose of 80 mJ / cm ² .

Using a plurality of alignment scopes from the back of the substrate, reading was performed using the black matrix (alignment mark) as a reference, and the printing pressure and the printing pressure balance were adjusted. After the exposure, the glass substrate and the silicone rubber blanket roller are peeled off, heated on a hot plate at 100 ° C. for 120 seconds, and further, 80 mJ / cm using an LED array with a wavelength of 365 nm (LED: Nichia Chemical NSHU590B) from the upper surface of the substrate. ² was exposed to light.

(Post bake)
The substrate on which the black matrix and the green, blue, and red stripe patterns were formed was heated in an oven at 220 ° C. for 30 minutes, and post-baked to obtain a color filter.

(Comparative example)
In the pattern formation of the black matrix, green, blue, and red in the examples, except that the exposure was not performed from the surface opposite to the contact surface of the transparent substrate that the photocurable ink composition contacts at the time of transfer. A color filter was created in the same manner as in the example. About the exposure after transfer, it implemented similarly to the Example.

  Using the color filters obtained in the Examples and Comparative Examples, the film thickness, chromaticity, and surface roughness for each color were measured by the method described below, respectively, the transfer rate of the photocurable ink composition, The color characteristics and surface smoothness as a color filter were evaluated. In addition, the adhesion strength of the pattern as a whole color filter and the stain on the plate were evaluated.

Evaluation Method and Results (1) Transfer Rate The film thickness for each color was measured, and the transfer rate was determined and defined as follows. The results are shown in Table 1.
Transfer rate (%) = Finish thickness of finished color filter / (cell depth × solid content) × 100
The film thickness was measured with a stylus type step difference measuring machine (Dektak Nihon Beco Co., Ltd.).

  From Table 1, the comparative example that was not exposed during the transfer of the present invention showed a transfer rate of 35% or less for each color. However, when the exposure of the present invention was applied, the transfer rate was 57-72%. It can be seen that the value is high. Further, the in-plane film thickness variation was about 5% in the comparative example, but the example is within 2%, and it can be seen that the transfer rate is improved and the film thickness unevenness is small according to the present invention.

(2) Color characteristics The photocurable ink composition of each color was applied onto a glass substrate by a spin coating method instead of the printing method in Examples and Comparative Examples to prepare a single color filter substrate. However, the film thickness was made to be the same film thickness (finished film thickness described in Table 1) as the color filters prepared in Examples and Comparative Examples. The spectrum of the obtained monochromatic color filter was measured with a spectrophotometer (MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.), and the Y value, x value, and y value as CIE chromaticity were determined and summarized in Table 2.

  From Table 2, it can be seen that the color of each example is lighter than that of the comparative example and is not sufficiently transferred.

(3) Surface roughness The surface roughness of each color of the produced color filter was measured with an atomic force microscope (NanoScope III manufactured by Digital Instruments). The results are shown in Table 3. The unit is nm.

  There was no significant difference in surface smoothness between the examples and the comparative examples, and no adverse effects due to the practice of the present invention were observed. Further, even when compared with a color filter manufactured using a normal pigment dispersion type color resist, the value was inferior.

(4) Adhesion strength Adhesive (STRUCT BOND XN-651 made by ThreeBond) was dropped onto a color filter provided with a black matrix, green, blue, and red pattern, and the washed glass substrate 24 was pressure-bonded at 180 ° C. Cured in an oven for 4 hours. As schematically shown in FIG. 7, a transparent substrate 21 with a colored layer is held using a tensile / compression tester (SV-200-0 manufactured by Imada Seisakusho), and a load is applied to the glass substrate 24 in the direction of arrow 25. Then, the load applied when the transparent substrate having the colored layer and the glass substrate peeled was evaluated as the adhesion strength. Moreover, the peeling location was investigated by observing a peeling surface. The results are shown in Table 4.

  From Table 4, it can be seen that the adhesion strength of the examples according to the present invention is more than double the value of the comparative examples. Further, in the comparative example, the peeled portion is between the colored layer made of the photocurable ink composition and the transparent substrate of the printing material, whereas in the example of the present invention, the adhesive layer and the cleaning glass substrate. It was peeling between. That is, in the examples of the present invention, it can be seen that peeling does not occur in the color filter (transparent substrate and colored layer), and the colored layer formed by the present invention is firmly adhered to the transparent substrate.

(5) Stains on the plate After printing, the plate and the blanket roll were washed, and the washing liquid was observed. The cleaning liquid after carrying out the examples of the present invention was less colored than the cleaning liquid after carrying out the comparative examples. Thereby, it is estimated that the Example of this invention has few photocurable ink compositions which remained on the printing plate and the blanket roll rather than the comparative example.

FIG. 1 is a schematic view of gravure printing of the present invention. (A): Step of applying a photocurable ink composition to a printing plate (intaglio) (b): Step of transferring the photocurable ink composition from the printing plate (intaglio) to a transparent substrate FIG. 2 is a schematic diagram of gravure offset printing of the present invention. (A): Overall view (b): Detailed view of transfer section FIG. 3 is a black matrix printing plate. FIG. 4 is a printing plate of the first colored layer (green). FIG. 5 is a printing plate of the second colored layer (blue). FIG. 6 is a printing plate of the third colored layer (red). FIG. 7 shows a method of adhesion test.

Explanation of symbols

1: Printing plate (intaglio)
2: concave portion 3: blade 4: photocurable ink composition 5: transparent substrate 6: induction roll 7: printing pressure roll 8: exposure light source 9: peeling roll 10: 10a: ink IN, 10b: ink OUT
11: Photocurable ink composition 12: Anilox roller 13: Intaglio 14: Blanket roll 15: Doctor blade 16: Transparent substrate 17: Induction roll 18: Printing pressure roll 19: Exposure light source 20: Peeling roll 21: Transparent substrate 22: Colored layer 23: Adhesive 24: Glass substrate 25: Load

Claims (9)

A method for producing a color filter comprising a cured pattern forming step of forming a pattern formed by curing a photocurable ink composition on a transparent substrate,
The cured pattern forming step includes (i) applying the photocurable ink composition in a pattern on a temporary support, and bringing the applied photocurable ink composition pattern into contact with the transparent substrate; and (ii) Applying a printing pressure to the transparent substrate; and (iii) exposing the photocurable ink composition pattern on the transparent substrate from a surface opposite to the contact surface with the transparent substrate to form a photocurable ink composition. A method for producing a color filter, comprising: a step of curing an object pattern; and (iv) a step of peeling a temporary support and transferring the cured photocurable ink composition pattern to the transparent substrate.   The method for producing a color filter according to claim 1, wherein the temporary support is a printing plate or an intermediate transfer member.   The method for producing a color filter according to claim 1, wherein the temporary support is a blanket roll.   The method for producing a color filter according to claim 3, wherein the temporary support is a blanket roll in which a photocurable ink composition is formed in a pattern using an intaglio.   The method for producing a color filter according to claim 1, wherein a printing pressure applied to the transparent substrate is in a range of 0.001 MPa to 50 MPa. Exposure in curing the pattern the exposure to ^the, 1mJ / cm 2 ^~3000mJ / method of producing a color filter according to any one of cm ² of claims 1 to 5 in the range.   In the step (i), the amount of the solvent contained in the applied photocurable ink composition pattern is in the range of 5% by mass to 80% by mass with respect to the total mass of the photocurable ink composition pattern. The manufacturing method of the color filter of any one of Claims 1-6.   The color filter manufactured by the manufacturing method of any one of Claims 1-7.   An image display device using the color filter according to claim 8.