JP2009058546A - Manufacturing method of color filter and liquid crystal display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a color filter which uses ink jet ink excellent in a straightly advancing property and stability when ejected from a head and by which high color purity and high color reproducibility can be given and to provide a liquid crystal display apparatus which uses the color filter manufactured by the method. <P>SOLUTION: Pigment dispersion liquid is selectively applied to a clearance between partition sections on a transparent insulating substrate by an ink jet system (a pigment dispersion liquid applying process), then a transparent resin solution is selectively applied to the clearance between partition sections by the ink jet system to form a mixed liquid layer by mixing the pigment dispersion liquid and the transparent resin solution in the clearance (a transparent resin solution applying process). Then the mixed liquid layer formed at the process described above is hardened (a hardening process) to manufacture the color filter. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an inkjet ink for a color filter used for forming a cured layer having a predetermined pattern such as a pixel portion (colored layer), a method for producing the inkjet ink, and a color filter using the inkjet ink. And a method of manufacturing a liquid crystal display device using the color filter.

  In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. However, since this color liquid crystal display is expensive, there is an increasing demand for cost reduction, and in particular, there is a high demand for cost reduction for a color filter having high specific gravity.

  In such a color filter, for example, a colored layer of three primary colors of red (R), green (G), and blue (B) is usually formed on the surface of a transparent substrate formed of glass or plastic. In general, a protective film is formed on the surface as necessary. Each of the three colored layers constitutes a pixel, and the liquid crystal operates as a shutter by turning on and off the electrodes corresponding to each of the R, G, and B pixels, and appropriately transmits light to each pixel. As a result, color display is performed.

  Further, a black matrix made of a light shielding layer is provided between the pixels. Furthermore, a transparent electrode layer made of an ITO film or the like is provided on the protective film. The protective film is formed for the purpose of filling and flattening the surface level difference in the state where the colored layer is formed, and preventing thermal deterioration of the colored layer in the process of forming the transparent electrode layer.

  As a conventional method for producing a color filter, for example, a dyeing method may be mentioned. In this dyeing method, first, a water-soluble polymer material, which is a dyeing material, is formed on a glass substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To get a colored pattern. By repeating this three times, R, G, and B color filter layers are formed.

Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers.
Still other methods include an electrodeposition method, a method in which a pigment is dispersed in a thermosetting resin, R, G, and B are printed three times, and then the resin is thermoset.

However, in any method, in order to color three colors of R, G, and B, it is necessary to repeat the same process three times, which causes a problem of high cost, and the yield decreases because the same process is repeated. There is a problem of doing.
As a method of manufacturing a color filter that solves these problems, a method of forming a colored layer (pixel portion) on a substrate surface by an inkjet method has been proposed.

  In the coloring process by the ink jet method, one of R, G, or B ink is ejected from the nozzle tip of the ink jet ejection head, and the ink is sprayed onto the substrate surface in accordance with the pattern to form a colored layer. According to the ink jet system, the R, G, and B coloring steps can be performed once, and thus attention is focused on the reduction of manufacturing costs.

  In order to form pixels by spraying ink in accordance with an accurate pattern by an inkjet method, it is required to have straightness and stability of the ink when ejected from the ejection head. However, if the ink evaporation rate is too fast, the viscosity of the ink will increase sharply at the tip of the nozzle of the discharge head, causing ink droplets to be bent, and if the ink is ejected intermittently after a while, clogging will occur. It may become impossible to re-discharge. In addition, a pigment is often used as a colorant for the color filter. However, if the pigment dispersibility of the color filter ink is poor, clogging occurs at the nozzle portion of the ejection head due to aggregation of pigment particles. Therefore, when a pigment is used as the colorant, the pigment dispersibility also affects the ink ejection performance.

  In Patent Document 1, in a method of manufacturing a color filter by spraying colored ink by an inkjet method to form a colored layer (pixel portion), a resin (photocurable resin) that has radiation curability by visible light, ultraviolet light, or the like. It is described that a colored ink (photo-curable ink) having a binder resin may be used. However, if such a conventional photocurable ink is used as it is in an ink jet system, the ink is dried at the tip of the ink jet head while the colored ink is being sprayed, and the viscosity gradually increases, resulting in poor ejection properties. Become. As a result, the discharge amount and the discharge direction of the colored ink may become unstable, or the inkjet head may be clogged. As described above, when an ink containing a colorant and a binder component is used, the discharge stability as an ink jet is lowered due to the fixing of the ink in the nozzle, or in a severe case, the discharge becomes impossible immediately. There was a problem.

  In Patent Document 2, a resin composition layer having ink absorption ability is formed on a transparent substrate, and the resin composition layer is colored by applying ink along a predetermined coloring pattern by an ink jet method. A method for producing a color filter is disclosed in which a colored layer is formed by laminating a plurality of colored resin composition layers by repeating the process of forming a physical layer twice or more. However, in the manufacturing method disclosed here, since the pigment concentration of the colored ink is low, it is necessary to take a complicated process of repeating the ink filling process in order to obtain color purity and color reproducibility as a color filter, resulting in a decrease in yield. To do.

  The color filter constituting the liquid crystal element is required to have a high color purity and color reproducibility, that is, a high colorant concentration in the colored portion. There is a method of increasing the amount of ink to be applied. However, if the amount of ink to be applied is increased, it becomes difficult to suppress the occurrence of color mixing due to the protrusion of ink, and a color filter cannot be manufactured with high yield.

  As described above, this is a method for producing a color filter by forming a colored layer by an ink jet method, which is excellent in straightness and stability when ejected from the head of an ink jet nozzle, and high in one color component application. A method capable of obtaining color purity and color reproducibility has not yet been obtained.

Japanese Patent Laid-Open No. 11-295520 JP 2002-31224 A

  The present invention is excellent in straightness and stability when ejected from the head, and the landed ink droplets are easily spread to every corner of the entire ink layer forming region, and high color purity and color can be obtained by applying a single color component. To provide a method for producing a color filter using an inkjet ink capable of providing reproducibility, a method for producing a color filter using the inkjet ink, and a method for producing a liquid crystal display device using the method for producing the color filter Is an issue.

  As a result of intensive studies to solve the above problems, the present inventors have divided the pigment as a coloring component and the transparent resin as a binder component into a pigment dispersion and a transparent resin solution, respectively, and applied the above problems. The present invention has been found.

That is, the present invention provides a method for producing a color filter shown in the following (1) to (9) and a liquid crystal display device using the same.
(1) A step of selectively applying the pigment dispersion liquid to the gaps of the partition portions on the transparent insulating substrate by an inkjet method (pigment dispersion liquid application step), and a gap between the partition portions after the pigment dispersion liquid application step. A transparent resin solution is selectively applied by an ink jet method, and the pigment dispersion and the transparent resin solution are mixed in the gap (transparent resin solution application step), and the pigment dispersion formed in the transparent resin solution application step The manufacturing method of a color filter including the process (curing process) of hardening the liquid mixture layer of a liquid and a transparent resin solution.

(2) The method for producing a color filter according to claim 1, wherein the color liquid layer formed in the pigment dispersion application step has a thickness of 0.4 to 2 μm.
(3) The method for producing a color filter according to claim 1 or 2, wherein the mixed liquid layer is formed so as to have the same film thickness as the partition portion.
(4) In the pigment dispersion application step, the colored liquid layer formed by applying the pigment dispersion is dried at a temperature of 40 to 160 ° C. Manufacturing method of color filter.

(5) In the transparent resin solution application step, the mixed liquid layer obtained by mixing the pigment dispersion and the transparent resin solution is dried at a temperature of 80 to 200 ° C. A method for producing a color filter according to claim 1.
(6) The solid content ratio of the pigment and the transparent resin in the mixed liquid layer after the mixed liquid layer is cured is 1: 0.4 to 1, wherein any one of claims 1 to 5 is characterized. A method for producing a color filter according to claim 1.
(7) The color filter according to any one of claims 1 to 6, wherein the pigment dispersion is composed of at least a pigment, a pigment dispersant, and a solvent, and the boiling point of the solvent is 200 ° C or higher. Manufacturing method.

(8) The method for producing a color filter according to any one of claims 1 to 7, wherein the transparent resin composition contained in the transparent resin solution comprises a photocurable resin composition.
(9) A color filter manufactured by the manufacturing method according to any one of claims 1 to 8, a counter substrate, and a liquid crystal composition sandwiched between the color filter and the counter substrate. A liquid crystal display device comprising:

  According to the present invention, the pigment as the coloring component and the transparent resin as the binder component are each prepared by dividing the pigment dispersion into a relatively low viscosity pigment dispersion and a transparent resin solution, and each liquid is transparent in separate steps. By applying on the conductive insulating substrate, the following effects can be obtained.

(1) Since the pigment dispersion and the transparent resin solution have an appropriate viscosity, they are excellent in straightness and stability when discharged from the discharge head. Therefore, the viscosity of the ink rapidly increases at the tip of the nozzle of the ejection head, causing flying bends of the ink droplets, or clogging when intermittent ejection is carried out at a time, making it impossible to eject again. There is no, and it is excellent in colored layer formation workability | operativity.

(2) Since it is possible to print a pigment dispersion having a low viscosity and a high pigment concentration, it is possible to print once without applying a coloring component several times in order to obtain color purity and color reproducibility as a color filter. In this coloring component application step, it is possible to apply a necessary amount of the coloring component, and a liquid crystal element excellent in color display characteristics can be manufactured with a higher yield.

(3) Without causing problems such as color mixing, the landed ink droplets tend to wet and spread to every corner of the entire ink layer formation region.
Therefore, according to the present invention, a highly reliable color filter having superior performance can be manufactured at a low cost, and in particular, a pixel portion having a high transmission density, a uniform density, and no color loss is precisely formed. A color filter with improved brightness can be manufactured. In addition, according to the present invention, since a color filter having better performance is used, a liquid crystal display element having excellent color display characteristics can be provided with a high yield, and a high-quality liquid crystal display device can be manufactured.

1. Method for Producing Color Filter The method for producing a color filter of the present invention comprises a step of selectively applying a pigment dispersion liquid in a gap between partitions on a transparent insulating substrate by an inkjet method (pigment dispersion application step), and the pigment After the dispersion liquid coating step, a step of selectively applying a transparent resin solution to the gap of the partition portion by an ink jet method and mixing the pigment dispersion and the transparent resin solution in the gap (transparent resin solution coating step); A step (curing step) of curing a mixed liquid layer of the pigment dispersion formed in the transparent resin solution applying step and the transparent resin solution.

(1) Pigment dispersion In the production method of the present invention, the pigment dispersion used in the pigment dispersion coating step comprises at least a pigment and a solvent, and other components are blended as necessary.

(A) Pigment The pigment as the colorant is selected from organic colorants and inorganic colorants according to the color required by the pixel (pixel portion) R, G, B, etc. and the black matrix layer. Can be used. As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Moreover, as an inorganic coloring agent, an inorganic pigment, an extender pigment, etc. can be used, for example.

  Among these, organic pigments are preferably used because they have high color developability and high heat resistance. As organic pigments, for example, compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), specifically, the following Color Index (CI) numbers are attached. Can be mentioned.

CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment .... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Buy Olet 32, C.I. pigment violet 36, C.I. pigment violet 38;

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58 : 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI pigmentless 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 77, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red . 64, C.I Pigment Red 265;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25 CI pigment black 1, pigment black 7.

  Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In this invention, a pigment can be used individually or in mixture of 2 or more types.

  In the case of forming pixels, the pigment is usually blended in a proportion of 1 to 60% by weight, preferably 15 to 40% by weight, based on the total solid content of the inkjet ink. When there are too few pigments, there exists a possibility that the permeation | transmission density | concentration at the time of apply | coating an inkjet ink to predetermined | prescribed film thickness (usually 0.1-2.0 micrometers) may not be enough. Moreover, when there are too many pigments, the characteristics as a coating film such as adhesion to the substrate when the ink-jet ink is applied and cured on the substrate, surface roughness of the cured film, and coating film hardness may be insufficient. There is.

(B) Solvent The solvent of the pigment dispersion used in the present invention is selected depending on the printability of the ink jet apparatus. Preferably, it is selected from those having a boiling point of 200 ° C. or higher, more preferably 240 ° C. or higher. Since the solvent has a boiling point of 200 ° C. or higher, it has moderate drying and evaporating properties, so it has excellent straightness and stability when ejected from the head, and can be dried more efficiently. It is easy for the droplet to wet and spread to every corner of the entire ink layer formation region. As a result, even when the substrate is diversified, it is possible to spread the ink that has landed on the wrinkled portion of the black matrix, thereby preventing color loss and a decrease in luminance of the pixel. When the boiling point is less than 200 ° C., the drying property in the vicinity of the nozzle becomes remarkably high, and as a result, the occurrence of defects such as nozzle clogging may occur.

  The solvent preferably has a surface tension range of 25 to 35 mN / m, more preferably 26 to 32 mN / m. If the surface tension is too high, there may be a disadvantage that the dot shape stability at the time of ink jet ejection is significantly adversely affected, or that the ink does not spread and spread in the partition gap. If the surface tension is too low, there may be a disadvantage that the dot shape stability at the time of inkjet ejection is significantly adversely affected, or that the ink diffuses beyond the partition portion and the possibility of color mixing increases.

  Specific examples of solvents that satisfy these conditions include diethylene glycol ethyl ether, diethylene glycol n-butyl ether, diethylene glycol n-butyl ether acetate, diethylene glycol hexyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol n-propyl ether, and dipropylene glycol. n-butyl ether or the like can be used. Moreover, what was mixed and adjusted so that two or more types of solvent may meet the said conditions as needed can be used. Among these, particularly preferred solvents include dipropylene glycol methyl ether acetate and diethylene glycol n-butyl ether acetate.

(C) Other components The pigment dispersion of the present invention may contain a pigment dispersant, a filler, a polymer compound aggregation inhibitor other than the binder polymer, and the like as other components.

(Pigment dispersant)
The pigment dispersant is blended in the ink as necessary to satisfactorily disperse the pigment. Examples of the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.
That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Polymeric surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.

(2) Transparent resin solution The transparent resin solution used in the transparent resin solution coating step of the present invention comprises at least a transparent resin component and a solvent, and other components are blended as necessary. Examples of the transparent resin component include a photocurable resin composition and a thermosetting resin composition.

(A) Photocurable resin composition The photocurable resin composition includes a polymer having a relatively high molecular weight (high molecular weight polymer), a polyfunctional monomer having two or more photopolymerizable functional groups, an oligomer, and photopolymerization. It comprises a bifunctional monomer having two functional functional groups, a monofunctional monomer having one photopolymerizable functional group, and a photopolymerization initiator activated by light. It is also possible to mix a relatively low viscosity reactive monomer as a reactive diluent. Examples of other additives include fillers, polymer compounds other than binder polymers, surfactants, adhesion promoters, anti-aggregation agents, organic acids, and curing agents. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

(High molecular weight polymer)
A polymer having a relatively high molecular weight (high molecular weight polymer) means a polymer having a molecular weight higher than that of a so-called monomer or oligomer, and a weight average molecular weight of 5,000 or more can be used as a guide. As the polymer, any of a polymer having no polymerization reactivity per se and a polymer having a polymerization reactivity per se may be used, or two or more kinds may be used in combination.

  The said polymer is normally mix | blended in the ratio of 1 to 50 weight% with respect to the solid content whole quantity of a transparent resin solution. Here, the solid content of the ink for specifying the blending ratio includes all components except the solvent, and liquid polymerizable monomers and the like are also included in the solid content.

  In the present invention, a polymer having a relatively high molecular weight is blended in the transparent resin solution for a color filter. Among these, oligomers that are polymers having polymerization reactivity are most easily available on the market, such as ester acrylates, ether acrylates, urethane acrylates, epoxy acrylates, amino resin acrylates, Examples thereof include acrylic resin acrylates and unsaturated polyesters.

  The molecular weight of the ethylenic double bond-containing compound used as a polymer having polymerization reactivity per se is so that the viscosity of the ink according to the present invention is not too high to adversely affect the discharge performance from the discharge head. The average molecular weight is preferably 25,000 or less.

(Polymer without polymerization reactivity)
As the polymer having no polymerization reactivity per se, for example, a copolymer comprising two or more of the following monomers can be used: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate. 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

  More specifically, acrylic acid / benzyl acrylate copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer, Acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl Acrylate / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate macromono -Copolymer, Acrylic acid / Benzyl methacrylate copolymer, Acrylic acid / Methyl methacrylate / Styrene copolymer, Acrylic acid / Benzyl methacrylate / Styrene copolymer, Acrylic acid / Methyl methacrylate / Polystyrene macromonomer copolymer, Acrylic Acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / Benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethylmeta It can be used acrylic acid copolymers such as Li rate macromonomer copolymer.

  Further specific examples include methacrylic acid / benzyl acrylate copolymer, methacrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer. , Methacrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxy Ethyl acrylate / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl Methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer , Methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxy Ethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate It can be exemplified DOO / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers methacrylic acid copolymers such as such.

(Polyfunctional monomer)
In the present invention, a polyfunctional monomer is blended in the transparent resin solution. Conventionally, in order to increase the film strength of a cured layer obtained by curing a photocurable composition and the adhesion to a substrate, a monomer (polyfunctional monomer) having two or more polymerizable functional groups in the photocurable composition However, in order to obtain sufficient film strength and adhesion, a polyfunctional monomer having 3 or more functional groups is usually used.

However, when a polyfunctional monomer having a large number of functional groups is blended in a photocurable composition and sprayed onto a substrate by an inkjet method, the ink is dried at the tip of the inkjet head during the spraying operation, and the viscosity gradually increases. The ink becomes larger and the ink ejection property becomes worse.
The blending ratio of the polyfunctional monomer is usually 20 to 70% by weight based on the total solid content of the transparent resin solution.

  Here, when the blending ratio of the polyfunctional monomer is less than 20% by weight of the total solid content, the crosslinking density of the coating film becomes low, and the solvent resistance, adhesion, and hardness of the coating film are inferior and sufficient. May not be able to obtain proper characteristics. Further, when the blending ratio of the polyfunctional monomer exceeds 70% by weight of the total solid content, the ink composition (transparent resin solution) is not sufficiently diluted with the monomer, and the viscosity of the ink is high from the beginning, or the solvent It becomes higher after volatilization, and there is a risk of clogging the inkjet head.

(Monofunctional monomer)
Examples of the monofunctional monomer (monofunctional polymerizable compound) include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. It is done.

(Bifunctional and trifunctional monomers)
Examples of the polyfunctional monomer having two or more photopolymerizable functional groups include a bifunctional monomer and a trifunctional or more polyfunctional monomer.
Examples of the bifunctional monomer include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, and 1,10-decanediol. Diacrylate, 1,10-decanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, hydroxypivalate neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol dimethacrylate, polytetramethylene glycol diacrylate, polytetramethylene Glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene Lenglycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) Diacrylate, polyethylene glycol (400) dimethacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (600) dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methyl Pentanediol dimethacrylate, dimethylol-tricyclodecane diacryl , Dimethylol - such as tricyclodecane methacrylate.

  Examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide modified trimethylpropane triacrylate, ethylene oxide modified trimethylpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Tris (2-hydroxyethyl) isocyanurate triacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, propoxylated glyceryl triacrylate, propoxylated glyceryl trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetra Acrylate, dito Examples include dimethylolpropane tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate dipentaerythritol hydroxypentaacrylate, dipentaerythritol hydroxypentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

(Reactive diluent)
A “reactive diluent” is a monomer having at least one reactive group having a double bond in the molecule. Examples of reactive diluents include monofunctional caprolactone acrylate, tridecyl acrylate, isodecyl acrylate, isooctyl acrylate, isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl-diglycol acrylate, 2-hydroxybutyl acrylate, 2- Acryloyloxyethyl hexahydrophthalic acid, neopentyl glycol acrylic acid benzoate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxy-polyethylene glycol acrylate, methoxy Dipropylene glycol acrylate, phenoxy ethyl Acrylate, phenoxy-polyethylene glycol acrylate, nonylphenol ethylene oxide adduct acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyl Examples include loxyethyl-succinic acid, 2-acryloyloxyethyl-phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

(Photopolymerization initiator)
The photopolymerization initiator is appropriately determined in consideration of the difference in the reaction format (for example, radical polymerization or cationic polymerization) of a relatively high molecular weight polymer, polyfunctional monomer, bifunctional monomer or monofunctional monomer, and the type of each material. Although selected, it is added as necessary to cure the colored ink.

  Examples of the polymerization initiator include active radical generators that generate active radicals by light or heat. Examples of the photopolymerization initiator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, and triazine compounds.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxy Ethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- And oligomers of (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxy). Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can also be used.

  A commercially available thing can also be used as an active radical generator. Examples of commercially available polymerization initiators include trade name “Irgacure-369” (acetophenone photopolymerization initiator, manufactured by Ciba Specialty Chemicals).

Examples of the thermal polymerization initiator include azo compounds and peroxide compounds.
As azo compounds, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (4-methyl-2,4-dimethylvaleronitrile), dimethyl 2 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N-2 (propenyl) -2-methyl-propionamide], 1, [(cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), polymer azo polymerization initiator containing polydimethylsiloxane unit (Wako Pure Chemical Industries, VPS series), polymer polymerization initiator containing polyethylene glycol unit Light pure drug Work, VPE series), and the like.

  Examples of peroxide compounds include peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. Peroxyesters include t-butyl-peroxy-lactate (Nippon Yushi Co., Ltd., trade name “Perbutyl L”), t-butyl-peroxy-3,5,5-trimethyl-hexanoate (Nippon Yushi Co., Ltd.) Product name "Perbutyl 355"), t-hexyl-peroxy-isopropyl-monocarbonate (manufactured by NOF Corporation, trade name "Perhexyl I") and the like.

  These polymerization initiators can be used alone or in combination of two or more. The usage-amount of a polymerization initiator is 1 mass part or more and 30 mass parts or less normally with respect to 100 mass parts of total amounts of a binder polymer and a polymeric compound, Preferably they are 3 mass parts or more and 20 mass parts or less.

(Other additives)
Examples of other additives include fillers, polymer compounds other than binder polymers, surfactants, adhesion promoters, anti-aggregation agents, organic acids, and curing agents. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

(B) Thermosetting resin composition The thermosetting resin composition according to the present invention is characterized by containing at least a thermopolymerizable binder and a bifunctional to trifunctional epoxy group-containing monomer. You may mix | blend a coloring agent, a dispersing agent, a hardening accelerator, or another additive with a thermosetting resin composition as needed. Moreover, in order to provide the thermosetting transparent resin composition with appropriate fluidity and dischargeability for application to the ink jet system, each of the above components may be dissolved or dispersed in a solvent (diluent). In addition, a bifunctional or trifunctional epoxy group-containing monomer may be used in combination with a tetrafunctional or higher functional epoxy group-containing resin.

(binder)
As the thermopolymerizable binder, for example, a homopolymer or copolymer obtained by polymerizing one or more monomers containing an ethylenically unsaturated bond and an epoxy group as shown below can be used. : Glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4 -Epoxybutyl, methacrylic acid-4,5-epoxypentyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, etc. ) Acrylates; o-vinylphenylglycidyl ether, m-vinylphenylglycidyl ether Ter, p-vinylphenyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc .; 2,3-diglycidyloxystyrene, 3,4-di Glycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether, vinyl phlorog Ricinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl Ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, and 1,3,5-trihydroxymethylstyrene Triglycidyl ether.

  Further, a copolymer obtained by polymerizing one or more monomers containing an ethylenically unsaturated bond and an epoxy group as described above and a monomer not containing an epoxy group as described below is also thermally polymerizable. Can be used as a binder: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

A binder is normally mix | blended in the ratio of 1 to 50 weight% with respect to the solid content whole quantity of a thermosetting resin composition. Here, the solid content of the thermosetting resin composition for specifying the blending ratio includes all components except the solvent, and a liquid polymerizable monomer is also included in the solid content.
If the blending amount of the binder is less than the above range, the solvent resistance, adhesion, and hardness of the coating film are inferior, and there may be a disadvantage that sufficient characteristics cannot be obtained. When the above range is exceeded, the ink composition (transparent resin solution) is not sufficiently diluted with the monomer, and the viscosity of the ink is high from the beginning or becomes high after volatilization of the solvent, which may cause clogging of the inkjet head.

(Epoxy group-containing monomer)
In the thermosetting resin composition, a bifunctional to trifunctional epoxy group-containing monomer is used as a thermosetting component, or one or more of them are used in combination. A bifunctional to trifunctional epoxy group-containing monomer has a relatively low viscosity among thermosetting resins and has a small increase in viscosity due to drying. The ink used as the curable component hardly raises the viscosity at the tip of the head during the spraying operation by the ink jet method, does not cause clogging of the head, and stabilizes the ink ejection property during the operation. Therefore, the discharge amount and discharge direction of the ink are kept constant, and the ink can be adhered to the substrate accurately and uniformly according to a predetermined pattern.

  Examples of the bifunctional to trifunctional epoxy group-containing monomer include, for example, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2, 3 -Diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4 Dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene Examples thereof include triglycidyl ether and 1,3,5-trihydroxymethylstyrene triglycidyl ether, and one of these can be used alone or two or more can be used in combination.

The blending ratio of the bifunctional to trifunctional epoxy group-containing monomer is usually 20 to 70% by weight based on the total solid content of the thermosetting resin composition.
Here, when the blending ratio of the bifunctional to trifunctional epoxy group-containing monomer is less than 20% by weight of the total solid content (all components other than the solvent), the transparent resin solution is not sufficiently diluted with the monomer, There is a possibility that the viscosity of the ink is high from the beginning or becomes high after the solvent is volatilized, and the ink jet head is clogged. Moreover, when the blending ratio of the bifunctional to trifunctional epoxy group-containing monomer exceeds 70% by weight of the total solid content, the crosslinking density of the coating film is lowered, and the solvent resistance, adhesion, and hardness of the coating film are reduced. Is inferior, and sufficient characteristics may not be obtained.

(Other thermosetting components)
In addition, the thermosetting resin composition includes a monofunctional epoxy group-containing monomer and / or a tetrafunctional or higher functional epoxy group-containing resin, if necessary, together with the above bifunctional to trifunctional epoxy group-containing monomer. And / or a thermosetting component other than the epoxy group-containing monomer may be blended.

  Monofunctional epoxy group-containing monomers include methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butyl phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, polypropylene glycol glycidyl ether Examples include ether and butoxypolyethylene glycol monoglycidyl ether.

  Examples of the thermosetting component other than the epoxy group-containing monomer include melamine resin, urea resin, alkyd resin, phenol resin, and cyclopentadiene resin.

  It is preferable to blend a tetrafunctional or higher functional epoxy group-containing resin together with a bifunctional to trifunctional epoxy group-containing monomer. When all of the epoxy group-containing components blended in the thermosetting resin composition are bifunctional to trifunctional, the viscosity increase due to drying of the ink is unlikely to occur, so that the ejection performance of the inkjet head is stable. On the other hand, the film strength of the cured layer obtained by curing the ink layer and the adhesion to the substrate may be insufficient. Therefore, by blending an appropriate amount of a tetrafunctional or higher functional epoxy group-containing resin together with the bifunctional to trifunctional epoxy group-containing monomer, sufficient film strength and adhesion can be imparted to the pattern of the cured layer.

  Examples of the tetrafunctional or higher functional epoxy group-containing resin include novolak resins such as phenol novolac epoxy and cresol novolac epoxy, glycidyl amine resins such as tetraglycidyldiaminodiphenylmethane and tetraglycidylmetaxylenediamine, tetraphenylglycidyl ether ethane, Glycidyl ether resins such as phenyl glycidyl ether methane can be used.

  It is preferable that the tetrafunctional or higher functional epoxy group-containing resin is usually blended at a ratio of 1 to 30% by weight with respect to the total solid content of the thermosetting transparent resin composition. In addition, in order to balance discharge stability by containing a bi- or tri-functional epoxy group and improvement in strength and adhesion by a tetra- or higher-functional epoxy group-containing resin, it is based on 100 parts by weight of a bi- to trifunctional monomer. The blending ratio of the tetrafunctional or higher epoxy group-containing resin is usually 1 to 50 parts by weight, preferably the lower limit of the blending ratio is 2 parts by weight and / or the upper limit of the blending ratio is 35 parts by weight. The following.

  Here, when the blending ratio of the tetrafunctional or higher functional epoxy group-containing resin is less than 1 part by weight with respect to 100 parts by weight of the bi- to tri-functional monomer, the hardness and solvent resistance after the ink is cured There is a possibility that characteristics such as property cannot be obtained sufficiently. Moreover, when the said mixing | blending ratio of the epoxy group containing resin more than tetrafunctional exceeds 50 weight part, there exists a possibility that the cure rate of an ink may become slow and process speed may become slow.

(Curing agent)
A curing agent is usually blended in the thermosetting resin composition used in the present invention. As the curing agent, for example, a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid is used.
Specific examples of polyhydric carboxylic acid anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Containing acid anhydrides, particularly preferably aromatic poly It may be mentioned carboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.

Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.
These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids can be used singly or in combination of two or more. The compounding quantity of the hardening | curing agent used for this invention is the range of 1-100 weight part normally per 100 weight part of components (monomer and resin) containing an epoxy group, Preferably it is 5-50 weight part. When the blending amount of the curing agent is less than 1 part by weight, curing may be insufficient and a tough coating film may not be formed. Moreover, when the compounding quantity of a hardening | curing agent exceeds 100 weight part, while the adhesiveness with respect to the board | substrate of a coating film is inferior, a uniform and smooth coating film may be unable to be formed.

(Other additives)
Examples of other additives include fillers, polymer compounds other than binder polymers, surfactants, adhesion promoters, anti-aggregation agents, organic acids, and curing agents. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

(C) Solvent The solvent of the transparent resin solution is selected according to the printability of the ink jet apparatus, similarly to the solvent of the pigment dispersion. Preferably, a solvent having a boiling point of 200 ° C. or higher is used. Further, a solvent having a surface tension range of 25 to 35 mN / m is preferably used. Particularly preferably, a solvent having a surface tension range of 25 to 35 mN / m and a boiling point of 200 ° C. or higher is used. When the boiling point is less than 200 ° C., the drying property in the vicinity of the nozzle becomes remarkably high, and as a result, the occurrence of defects such as nozzle clogging may occur. In addition, if the surface tension exceeds 35 mN / m, the dot shape stability at the time of ink jet ejection will be significantly adversely affected, or the transparent resin solution will not wet and spread to every corner of the entire colored layer when applied on the colored layer. There is a risk of

  Specific examples of solvents that satisfy these conditions include diethylene glycol ethyl ether, diethylene glycol n-butyl ether, diethylene glycol n-butyl ether acetate, diethylene glycol hexyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol n-propyl ether, and dipropylene glycol. n-butyl ether or the like can be used. Moreover, what was mixed and adjusted so that two or more types of solvent may meet the said conditions as needed can be used. Of these, dipropylene glycol methyl ether acetate and diethylene glycol n-butyl ether acetate are most preferred.

(3) Production of color filter The method for producing a color filter of the present invention comprises a step of selectively applying a pigment dispersion by a inkjet method in a gap between partitioning portions on a transparent insulating substrate (pigment dispersion application step), After the pigment dispersion application step, a step of selectively applying a transparent resin solution to the gap of the partition portion by an ink jet method and mixing the pigment dispersion and the transparent resin solution in the gap (transparent resin solution application step) And a step (curing step) of curing the mixed liquid layer of the pigment dispersion formed in the transparent resin solution applying step and the transparent resin solution.

(A) Pigment dispersion application step In the pigment dispersion application step of the present invention, first, a partition (black matrix) is formed on the transparent insulating substrate of the color filter.
Examples of the transparent insulating substrate used for the color filter in the present invention include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. In addition, these transparent insulating substrates may be appropriately subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum deposition as necessary. You can also.

  The material forming the partitioning portion is a mixture of a resin component and a black pigment (such as carbon black) and / or a pigment such as R (red), G (green), B (blue), Y (yellow), or V (violet). And a mixed resin black pigment and a photosensitive resin containing a solvent for decomposing and dissolving these components. The resin material may be a negative type or a positive type such as an acrylic resin used for a general black photosensitive resin. The height of the partition portion is about the same as that of the transparent colored resin film, and when used as a color filter with a high chromaticity range specification, it is 1.5 μm or more and 5.0 μm or less, more preferably 2.0 μm or more and 4.0 μm or less. is there. The width of the partition portion is set to 10 μm or more and 30 μm or less, and the light transmission region partitioned by the partition portion is generally a rectangle or a bent shape having a width of 60 μm to 250 μm.

  In order to form the partition portion on the transparent insulating substrate using this photosensitive resin, a thin film having a thickness of about 1 to 3 μm is formed on the entire surface by spin coating, for example, and then a photoresist process (exposure and development). Can be formed.

  Next, the above-described pigment dispersion in which a desired pigment such as R, G, B, etc. is blended in the gap between the partition portions thus obtained, that is, the portion surrounded by the partition portion (the portion that becomes the RGB pixel) is inkjetted. By selectively attaching by a method, a pigment dispersion liquid (colored liquid) is applied to the pixel portion, the light shielding layer, and the like to form a colored liquid layer. The thickness of the colored liquid layer varies depending on the R, G, and B layers, but is generally in the range of 0.4 to 2.0 · m. If the thickness of the colored liquid layer is outside this range, a step between the partition portion and the colored layer may occur.

Next, the formed colored liquid layer is dried as necessary (preliminary drying step). By performing such preliminary drying, only the solvent component of the pigment dispersion can be reduced in a state where the pigment is uniformly dispersed in the colored liquid layer. If the pigment dispersion is not sufficiently dried (reduced amount of solvent), when the transparent resin solution is applied, the amount of liquid after mixing the pigment dispersion and the transparent resin solution increases, and the mixed solution protrudes from the partition. There is a risk of color mixing.
Drying is preferably performed in a temperature range of 40 to 160 ° C. If the drying temperature is too low, the volume change of the pigment dispersion liquid becomes small, and there is a risk of color mixing when the transparent resin solution is applied. On the other hand, if the drying temperature is too high, when the transparent resin solution is applied, the transparent resin solution may not be uniformly spread on the colored liquid layer and the cured film surface may be roughened. The drying time is not particularly limited, but is preferably 1 to 20 minutes.

(B) Transparent resin solution coating step In the transparent resin solution coating step of the present invention, the transparent resin solution is selectively applied to the gaps of the partition portions by an ink jet method, and the pigment dispersion and the transparent resin solution are placed in the gaps. Mix. That is, on the colored liquid layer formed in the pigment dispersion application step, a transparent resin solution is applied to form a transparent resin layer, and both layers are mixed to form a mixed liquid composed of the colored liquid layer and the transparent resin layer. A layer (colored resin layer) is formed.
When a transparent resin solution having a low viscosity is applied on the dried pigment dispersion (colored liquid layer), the pigment is re-dispersed in the transparent resin solution, thereby mixing the pigment dispersion and the transparent resin solution. Alternatively, the colored liquid layer and the transparent resin layer are fused. Therefore, in the pigment dispersion application step, the pigment and the transparent resin solution are sufficiently mixed even if the formed colored liquid layer is completely dried by the preliminary drying step.

The coating amount of the transparent resin solution varies depending on the RGB layers, but the coating amount can be appropriately adjusted so that the difference in film thickness between the colored resin layers of RGB colors is 0.1 μm or less. The coating amount of the transparent resin solution is the ratio of the solid content after drying the pigment dispersion and the transparent resin solution (ratio of the solid content of the pigment and the transparent resin after curing the mixed liquid layer): pigment: transparent resin = 1 : It is preferable to adjust so that it may become 0.4-1.
The mixed liquid layer (colored resin layer) is preferably formed to have the same film thickness as the partition part, and it is necessary to adjust the coating amount of the transparent resin solution as such. When the coating amount of the transparent resin solution is small relative to the pigment dispersion, there is a possibility that the entire colored resin layer may not be wetted and spread. Moreover, when the coating amount of the transparent resin solution is large relative to the pigment dispersion, the thickness of the colored resin layer increases, and a colored resin layer having no step between the partition portion and the colored resin layer is formed. Will not be able to.

  The thickness of the colored resin layer is generally in the range of 1.0 to 2.5 · m. When the thickness of the colored resin layer is out of this range, a step may be generated between the partitioning portion and the colored layer, which may cause a drawback that the flatness of the entire filter is deteriorated.

The step of drying the colored resin layer (pre-baking step) is preferably performed in a temperature range of 80 to 200 ° C.
If the drying temperature is too low, the volume change of the colored resin layer is reduced, and the thickness of the colored resin layer is increased, making it impossible to form a colored resin layer having no step between the partition portion and the colored resin layer. There is a risk that. Also, if the drying temperature is too high, the volume change of the colored resin layer becomes large, the thickness of the colored resin layer becomes small, and a colored resin layer having no step between the partition portion and the colored resin layer can be formed. You might not be able to do it.

(C) Curing Step In the present invention, the mixed liquid layer of the pigment dispersion and the transparent resin solution formed in the transparent resin solution coating step is cured (curing step).
When using a photocurable resin composition as the transparent resin, curing is performed by irradiating light. The light to be used is preferably ultraviolet light or visible light, and light having a wavelength of 200 to 500 nm is particularly preferable. As these light sources, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, a short arc lamp, a helium / cadmium laser, an argon laser, A publicly known and commonly used light source such as THG or FHG laser using Nd-YAG laser can be used. Light curing conditions, the type of light source used, the influence of type and amount of the photopolymerization initiator is not determined unequivocally, it is generally preferably in the range of 100~3000mJ / m ^2. After photocuring, a post-curing treatment is performed at 200 to 250 ° C. for 10 to 30 minutes.
When a thermosetting resin composition is used as the transparent resin, curing is performed by heating. As curing conditions by heating, the heating temperature is about 200 to 250 ° C., and the heating time is about 20 to 60 minutes.

  In the method for producing a color filter of the present invention, after the mixed liquid layer (colored resin layer) is cured, a protective layer can be formed thereon if necessary. As the protective layer, a photocurable, thermosetting, or combined heat / light curable resin composition layer, or an inorganic compound layer formed by vapor deposition or sputtering can be used.

  Next, an ITO (indium tin oxide) film is formed as an electrode on the protective layer. Furthermore, a color filter is manufactured by forming an alignment film (polyimide film) thereon by a known method.

2. Liquid crystal display device The liquid crystal display device of the present invention is sandwiched between a color filter manufactured by the above-described method for manufacturing a color filter of the present invention, a counter substrate such as a glass substrate, and the color filter and the counter substrate. And a liquid crystal composition prepared.
A liquid crystal display device is formed by combining a substrate on the color filter side and a counter substrate, and enclosing a liquid crystal therebetween. Inside the counter substrate, TFTs and pixel electrodes are formed in a matrix. An alignment film is also formed on the counter substrate side, and liquid crystal molecules are arranged in a certain direction. In the case of the transmissive type, the substrate and the pixel electrode are formed of a transparent material, and a polarizing plate is bonded to the outside of each substrate. In the case of the reflective type, the substrate or pixel electrode is formed of a material having a reflection function, or a reflective layer is provided on the substrate, a polarizing plate is provided outside the transparent substrate, and light incident from the color filter side is reflected. To display.
As long as the liquid crystal display device of the present invention is configured using the color filter of the present invention, conventional techniques can be appropriately used for other members.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the evaluation method of each physical property in the following examples is as follows. In the following examples, “part” means “part by weight”.

<Production Example 1: Preparation of pigment dispersion for color filter>
(1) Preparation of red pigment dispersion for color filter Red pigment, pigment dispersant, and organic solvent are mixed in the following ratio, 500 parts of zirconia beads having a diameter of 0.3 mm are added, and dispersed for 4 hours using a paint shaker. Thus, a pigment dispersion (R) was obtained.
(Composition of pigment dispersion)
Red pigment (CI Pigment Red 254): 10 parts pigment dispersant (manufactured by AVECIA: Solsperse 24000): 10 parts DPMA (dipropylene glycol methyl ether acetate; boiling point = 209 ° C., surface tension = 27 mN / m): 80 copies

(2) Preparation of Green Pigment Dispersion for Color Filter Instead of 10 parts of Red pigment (CI Pigment Red 254) in (1) above, 10 parts of Green Pigment (CI Pigment Green 36), Yellow Pigment A pigment dispersion (G1) and a pigment dispersion (Y) were prepared in the same manner as in Production Example 1 except that 10 parts of (CI Pigment Yellow 150) were used. A green pigment dispersion (G2) was prepared by mixing 53 parts of the pigment dispersion (G1) and 47 parts of the pigment dispersion (Y).

(3) Preparation of Blue Pigment Dispersion for Color Filter Production Example 1 except that 10 parts of Blue pigment (CI Pigment Blue 15: 6) were used instead of 10 parts of Red pigment in (1) above. Similarly, a pigment dispersion (B) was prepared.

<Production Example 2: Preparation of pigment dispersion for color filter>
Red in the same manner as in Production Examples 1 (1) to (3) except that BCA (diethylene glycol butyl ether acetate; boiling point = 247 ° C., surface tension = 30 mN / m) was used as the solvent in Production Example 1 instead of DPMA. , Green and blue pigment dispersions were prepared respectively.

<Production Example 3; Preparation of photocurable transparent resin solution>
15 parts of polyester acrylic oligomer, 15 parts of dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA), 20 parts of 1,6-hexanediol diacrylate, 45.5 parts of dipropylene glycol methyl ether acetate, and Ciba Specialty Chemicals After mixing 0.5 part of a photopolymerization initiator “Irgacure 369” manufactured by the company, the mixture was filtered using a filter having a pore size of 1.0 · m to obtain a transparent resin solution.

<Production Example 4; Preparation of thermosetting transparent resin solution>
Binder (glycidyl methacrylate-styrene copolymer) 10 parts, novolak type epoxy resin (manufactured by Yuka Shell, trade name “Epicoat 154”): 10 parts, neopentyl glycol diglycidyl ether 20 parts by weight, curing agent (trimerit Acid) 5 parts by weight and 55 parts of dipropylene glycol methyl ether acetate were mixed, followed by filtration using a filter having a pore size of 1.0 m to obtain a thermosetting transparent resin solution.

<Example 1; Production of color filter>
A black matrix pattern having a line width of 20 μm and a film thickness of 1.6 μm is formed on a glass substrate (manufactured by Asahi Glass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 10 cm by a photolithographic method using a curable resin composition for black matrix. Formed.
The blue pigment dispersion obtained in Production Example 1 was adhered accurately and uniformly to the blue pixel forming portion partitioned by the black matrix of the substrate by an inkjet method.

  Next, the green pigment dispersion liquid of Production Example 1 was adhered accurately and uniformly to the green pixel forming portion of the same substrate by the inkjet method. Next, the red pigment dispersion liquid of Production Example 1 was adhered accurately and uniformly to the red pixel forming portion of the same substrate by an inkjet method. After applying the pigment dispersion, preliminary drying was performed on a hot plate at 100 ° C. for 10 minutes.

Thereafter, the transparent resin solution of Production Example 3 is applied on the pigment dispersion of each color pixel forming section partitioned by the black matrix, and the solid content ratio after curing of the mixed liquid layer is pigment: transparent resin = 1: 0.8. It adjusted so that it might become and it was made to adhere correctly and uniformly by the inkjet system. Thereafter, prebaking was performed on a hot plate at 180 ° C. for 20 minutes, exposure was performed at 200 mJ / cm ² with a high-pressure mercury lamp, and photocuring was performed, followed by further curing at 230 ° C. for 20 minutes.

The substrate on which the RGB pixel pattern is formed is immersed in IPA (isopropyl alcohol) for 5 minutes, then dried and washed with IPA vapor, and then at a substrate set temperature of 200 ° C. under a vacuum of 6 × 10 ⁻³ Torr. An ITO (indium tin oxide) electrode was formed to a thickness of 120 nm. The substrate on which this ITO film was formed was further immersed in IPA for 5 minutes, steam-washed with IPA, spin-coated with polyimide, and baked at 180 ° C. for 60 minutes to form an alignment film. Got.

<Example 2>
In Example 1, a color filter was prepared in the same manner as in Example 1 except that the transparent resin solution was applied so that the solid content ratio of the mixed liquid layer after curing was pigment: transparent resin = 1: 0.4. Was made.

<Example 3>
In the color filter production process of Example 2, the preliminary drying after applying the pigment dispersion is 10 minutes on a hot plate at 60 ° C., and the pre-baking after applying the transparent resin solution is 20 minutes on a hot plate at 150 ° C. A color filter was produced in the same manner as in Example 2 except that.

<Example 4>
Instead of using the photocurable transparent resin solution of Production Example 3 in Example 2, the thermosetting transparent resin solution of Production Example 4 was used, except that it was heated at 230 ° C. for 30 minutes as the curing conditions. A color filter was produced in the same manner as in No. 2.

<Example 5>
Instead of using the pigment dispersion liquid of Production Example 1 in Example 2, the pigment dispersion liquid of Production Example 2 was used, and the solid content ratio after curing of the mixed liquid layer was pigment: transparent resin = 1: 1. A color filter was produced in the same manner as in Example 2 except that the transparent resin solution was applied so as to be 2.

<Example 6>
In Example 5, a color filter was produced in the same manner except that the transparent resin solution was applied so that the solid content ratio of the mixed liquid layer after curing was pigment: transparent resin = 1: 0.2.

<Example 7>
In Example 5, the preliminary drying after the pigment dispersion application was not performed, the pre-baking after the application of the transparent resin solution was performed for 20 minutes on a 220 ° C. hot plate, and the solid content ratio after curing of the mixed liquid layer was A color filter was produced in the same manner as in Example 5 except that the transparent resin solution was applied so that pigment: transparent resin = 1: 0.8.

<Example 8>
Instead of using the photocurable transparent resin solution of Production Example 3 in Example 7, except that the thermosetting transparent resin solution of Production Example 4 was used and that the curing conditions were heated at 230 ° C. for 30 minutes, A color filter was produced in the same manner as in Example 7.

<Production Example 5: Preparation of pigment inkjet ink for color filter>
(1) Preparation of red inkjet ink for color filter Red pigment, pigment dispersant, and organic solvent are mixed in the following proportions, 500 parts of 0.3 mm diameter zirconia beads are added, and dispersed for 4 hours using a paint shaker. A pigment dispersion (R) was obtained. 50 parts of the obtained pigment dispersion (R), 10 parts of polyester acrylic oligomer, 10 parts of DPHA, 20 parts of 1,6-hexanediol diacrylate, 9.5 parts of DPMA, and photopolymerization initiator “Irga” manufactured by Ciba Specialty Chemicals After 0.5 parts of Cure 369 ”was mixed, the mixture was filtered using a filter having a pore size of 1.0 μm to obtain a red inkjet ink for a color filter.
(Composition of pigment dispersion)
Red pigment (CI Pigment Red 254): 20 parts Pigment dispersant (manufactured by AVECIA: Solsperse 24000): 15 parts DPMA (dipropylene glycol methyl ether acetate: 65 parts)

(2) Preparation of Green Inkjet Ink for Color Filter Instead of 20 parts of Red pigment (CI Pigment Red 254) used for preparing the inkjet ink of Production Example 5 (1), Green pigment (CI Pigment) A green pigment dispersion and a yellow pigment dispersion were prepared in the same manner except that 20 parts of Green 36) and 20 parts of Yellow pigment (CI Pigment Yellow 150) were used. A green pigment dispersion (G) was prepared by mixing 53 parts of the green pigment dispersion and 47 parts of the yellow pigment dispersion. Using the obtained green pigment dispersion (G), a green inkjet ink was prepared in the same manner as the red inkjet ink of (1) above.

(3) Preparation of Blue Inkjet Ink for Color Filter Instead of 20 parts of Red Pigment (CI Pigment Red 254) in Production Example 5 (1), Blue Pigment (CI Pigment Blue 15: 6) 10 A blue pigment dispersion was prepared in the same manner except that the parts were used. Using the obtained blue pigment dispersion, a blue inkjet ink was prepared in the same manner as the red inkjet ink of (1) above.

<Production Example 6; Preparation of pigment inkjet ink for color filter>
(1) Preparation of red inkjet ink for color filter Red pigment, pigment dispersant, and organic solvent are mixed in the following ratio, 500 parts of 0.3 mm diameter zirconia beads are added, and dispersed for 4 hours using a paint shaker. A pigment dispersion was obtained. 50 parts of the obtained pigment dispersion, 10 parts of polyester acrylic oligomer, 10 parts of DPHA, 20 parts of 1,6-hexanediol diacrylate, 9.5 parts of DPMA, and photopolymerization initiator “Irgacure 369” manufactured by Ciba Specialty Chemicals After mixing 0.5 part, it filtered using the filter with a hole diameter of 1.0 micrometer, and obtained the red inkjet ink for color filters.
(Composition of pigment dispersion)
Red pigment (CI Pigment Red 254): 15 parts Pigment dispersant (manufactured by AVECIA: Solsperse 24000): 15 parts DPMA (dipropylene glycol methyl ether acetate: 70 parts

(2) Preparation of Green Inkjet Ink for Color Filter Instead of 15 parts of Red Pigment (CI Pigment Red 254) in Production Example 6 (1), 15 parts of Green Pigment (CI Pigment Green 36), A pigment dispersion (G1) and a pigment dispersion (Y) were prepared in the same manner except that 15 parts of a yellow pigment (CI Pigment Yellow 150) was used. A pigment dispersion (G2) was prepared by mixing 53 parts of the pigment dispersion (G1) and 47 parts of the pigment dispersion (Y). A green inkjet ink was prepared in the same manner as the red inkjet ink using the obtained pigment dispersion (G2).

(3) Preparation of Blue Inkjet Ink for Color Filter Instead of 15 parts of Red Pigment (CI Pigment Red 254) in Production Example 6 (1), Blue Pigment (CI Pigment Blue 15: 6) 15 A pigment dispersion (B) was prepared in the same manner except that the parts were used. A blue inkjet ink was prepared by the same method as the red inkjet ink using the obtained pigment dispersion.

<Comparative Example 1>
The blue ink-jet ink of Production Example 5 was adhered accurately and uniformly to the blue pixel forming portion partitioned by the black matrix of the same substrate as in Example 1 by the ink-jet method. Next, the green inkjet ink of Production Example 5 was accurately and uniformly attached to the green pixel forming portion of the same substrate by the inkjet method. Next, the red ink-jet ink of Production Example 5 was accurately and uniformly attached to the red pixel forming portion of the same substrate by the ink-jet method. Thereafter, prebaking was performed on a 180 ° C. hot plate for 20 minutes, exposure was performed at 200 mJ / cm ² using a high-pressure mercury lamp, and photocuring was performed, followed by further curing at 230 ° C. for 20 minutes.

The substrate on which the RGB pixel pattern is formed is immersed in IPA for 5 minutes, then dried with IPA vapor, washed, and then ITO (indium oxide) at a substrate set temperature of 200 ° C. under a vacuum of 6 × 10 ⁻³ Torr. A tin) electrode was deposited to a thickness of 120 nm. The substrate on which this ITO film was formed was further immersed in IPA for 5 minutes, steam-washed with IPA, spin-coated with polyimide, and baked at 180 ° C. for 60 minutes to form an alignment film. Got.

<Comparative example 2>
A color filter was produced in the same manner as in Comparative Example 1 except that the inkjet ink of Production Example 6 was used instead of the inkjet ink of Production Example 5 in the production of Comparative Example 1.

[Evaluation methods]
The viscosity and ejection stability of the pigment dispersions, transparent resin solutions, and inkjet inks (pigment inks) obtained in Production Examples 1 to 6 were evaluated by the following methods. Moreover, about the color filter produced in the said Examples 1-8 and Comparative Examples 1-2, the presence or absence of a white spot, the presence or absence of color mixing, a film thickness, and chromaticity were evaluated with the following method.

(1) Viscosity The viscosity was measured at 23 ° C. using a rotational vibration viscometer (VM-1G, manufactured by Yamaichi Electronics Co., Ltd.).
(2) Discharge stability After jetting the pigment dispersion liquid, the transparent resin solution, and the inkjet ink obtained from the examples and comparative examples once onto a photographic printing paper so that the droplet size is 15 pL, After waiting for 5 minutes and spraying twice again, after waiting repeatedly for 5 minutes and spraying again 3 times. The ink printed after four iterations was analyzed with the naked eye to evaluate nozzle clogging. ○ indicates that there is no change compared to the initial state, Δ indicates that partial printing was not performed, and x indicates that printing was not performed at all.

(3) White spots and mixed colors For the color filters prepared in the steps of Examples 1 to 8 and Comparative Examples 1 and 2, the number of defective spots (white spots, mixed colors) per 100,000 locations was visually counted and evaluated.
(4) Film thickness The produced color filter was observed with a laser microscope (manufactured by Olympus), and the film thickness was measured.
(5) Chromaticity The chromaticity of each colored layer of the produced color filter was measured using a microspectroscopic light device (trade name “PMA-11” manufactured by Hamamatsu Photonics).

[Evaluation results]
(1) Evaluation of ink, etc. Evaluation of pigment dispersion, transparent resin solution (transparent resin composition), pigment concentration and viscosity of inkjet ink (pigment ink), and inkjet discharge stability obtained in Production Examples 1 to 6 The results are shown in Table 1. It can be seen that the pigment dispersion and the transparent resin solution have a lower viscosity and better ejection by inkjet as compared with the pigment ink.

(2) Evaluation of color filter Table 2 shows the results of evaluating the presence or absence of white spots, the presence or absence of color mixing, the film thickness, and the chromaticity of the color filters produced in Examples 1 to 8 and Comparative Examples 1 and 2. . The color filter produced in Comparative Example 1 shows white spots due to lack of ink nozzles, and the color filter produced in Comparative Example 2 produced mixed colors due to the protrusion of ink, whereas it was produced in Examples 1-8. It can be seen that the mixed color filter does not have mixed colors or white spots.

In Table 2 above, “drying temperature (A)” is the drying temperature in the preliminary drying step after application of the pigment dispersion, and “drying temperature (B)” is the drying temperature (heat treatment temperature) in the prebaking step after application of the transparent resin solution. Represents.
The “solid content ratio” represents the solid content ratio after drying of the pigment dispersion and the transparent resin solution (solid content ratio of the pigment and the transparent resin after curing the mixed liquid layer = pigment: transparent resin). The “boiling point of the solvent” represents the boiling point of the dispersion solvent of the pigment dispersion.

  According to the present invention, a color filter having high color purity and color reproducibility can be produced using an inkjet ink that is excellent in straightness and stability when ejected from a head, and therefore has higher performance. A highly reliable color filter can be manufactured at low cost. In particular, it is possible to manufacture a color filter that has a high transmission density, a uniform pixel portion, and a pixel portion that has no color loss and is improved in brightness. And by using the color filter of the outstanding performance obtained by such a method of this invention, the liquid crystal display element excellent in the color display characteristic can be provided with a sufficient yield, and a high quality liquid crystal display device is manufactured. be able to.

Claims (9)

  A step of selectively applying the pigment dispersion liquid to the gap of the partitioning portion on the transparent insulating substrate by an inkjet method (pigment dispersion liquid coating step), and a transparent resin in the gap of the partitioning portion after the pigment dispersion liquid coating step A step of selectively applying the solution by an ink jet method and mixing the pigment dispersion and the transparent resin solution in the gap (transparent resin solution application step), and the pigment dispersion formed in the transparent resin solution application step and the transparent The manufacturing method of a color filter including the process (curing process) of hardening a liquid mixture layer with a resin solution.   The method for producing a color filter according to claim 1, wherein the color liquid layer formed in the pigment dispersion application step has a thickness of 0.4 to 2 μm.   The method for producing a color filter according to claim 1, wherein the mixed liquid layer is formed to have the same film thickness as the partitioning portion.   The color filter according to any one of claims 1 to 3, wherein in the pigment dispersion application step, a colored liquid layer formed by applying the pigment dispersion is dried at a temperature of 40 to 160 ° C. Manufacturing method.   In the said transparent resin solution application | coating process, the liquid mixture layer obtained by mixing a pigment dispersion liquid and a transparent resin solution is dried at the temperature of 80-200 degreeC, The any one of Claims 1-4 characterized by the above-mentioned. Manufacturing method of color filter.   6. The solid content ratio of the pigment and the transparent resin in the mixed liquid layer after the mixed liquid layer is cured is 1: 0.4 to 1, 6. Manufacturing method of color filter.   The method for producing a color filter according to claim 1, wherein the pigment dispersion comprises at least a pigment, a pigment dispersant, and a solvent, and the solvent has a boiling point of 200 ° C. or higher. .   The method for producing a color filter according to claim 1, wherein the transparent resin composition contained in the transparent resin solution comprises a photocurable resin composition.   A color filter manufactured by the manufacturing method according to claim 1, a counter substrate, and a liquid crystal composition sandwiched between the color filter and the counter substrate. A liquid crystal display device.