TWI444672B - Color filter and liquid crystal display device - Google Patents

Description

Color filter and method of manufacturing liquid crystal display device

The present invention relates to an inkjet ink for color filter used for forming a hardened layer of a pattern such as a pixel (colored layer), a method for producing the ink for inkjet, and a color filter using the ink for inkjet A method of a light sheet, and a method of manufacturing a liquid crystal display device using the color filter.

In recent years, with the development of personal computers, particularly with the development of portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, has increased. However, since the color liquid crystal display is expensive, the cost reduction requirement is high, and the cost reduction of the color filter having a high cost ratio is particularly high.

In such a color filter, for example, on the surface of a transparent substrate formed of glass and plastic, a coloring layer of three primary colors of red (R), green (G), and blue (B) is usually formed, and is viewed from above. It is necessary to form a protective film structure as a general one. The three-color coloring layer is used to form each pixel, and the electrodes corresponding to the respective R, G, and B pixels are turned ON and OFF, so that the liquid crystal operates in a shutter mode, and the respective pixels are color-displayed by appropriate light.

Further, a black matrix composed of a light shielding layer is provided between the pixels. Further, a transparent electrode layer made of an ITO film or the like is provided on the protective film. The protective film is formed by burying the surface step difference in a state in which the colored layer is formed, and preventing heat deterioration of the colored layer or the like in the step of forming the transparent electrode layer.

The method of producing the color filter previously performed may, for example, be a dyeing method. The dyeing method is to form a water-soluble polymer material for dyeing material on a glass substrate first, and to form a pattern of a desired shape by a photolithography step, and then immersing the obtained pattern in a dyeing bath to obtain a coloring pattern. type. This was repeated three times to form color filter layers of R, G, and B.

Further, other methods include a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and the pattern is patterned to obtain a monochrome pattern. Further, this step is repeated three times to form color filter layers of R, G, and B.

Further, other methods include a electrodeposition method, a method of dispersing a pigment in a thermosetting resin, and performing three printing of R, G, and B, followed by a method of thermally curing the resin.

However, any of the methods is to color the R, G, and B3 colors, and the same steps must be repeated three times, which has a problem that the cost becomes high, and the problem that the yield is lowered by repeating the same steps.

As a method of manufacturing a color filter that solves such problems, a method of forming a color layer (pixel portion) by inkjet on a substrate surface has been proposed.

The coloring step in the inkjet method is to discharge any of R, G, or B by the tip end of the nozzle for the inkjet discharge nozzle, and to blow the ink onto the surface of the substrate in accordance with the pattern to form a colored layer. According to the inkjet method, since the coloring steps of R, G, and B can be performed once, the production cost is reduced.

The ink is blown to the correct pattern by the ink jet method to form a pixel, and the ink is required to be straightforward and stable when discharged from the discharge head. However, if the evaporation speed of the ink is too early, the ink viscosity at the tip end of the nozzle of the discharge head sharply increases, and the ink droplets are flying and bent. If the ink is intermittently discharged at intervals, the hole may be clogged and the discharge may not be discharged. . Further, a pigment is often used for the color filter of the color filter, and if the pigment dispersion property of the color filter ink is poor, the pores are clogged at the nozzle portion of the discharge head through the aggregation of the pigment particles. Therefore, in the case of using a pigment as a colorant, the pigment dispersibility also affects the discharge performance of the ink.

In Patent Document 1, it is described that a coloring layer (pixel portion) is formed by blowing a coloring ink by an inkjet method, and a resin having a radiation curable property such as visible light and ultraviolet rays can be used in the method of producing a color filter. A curable resin) is a coloring ink (photocurable ink) of a binder resin. However, when such a conventional photocurable ink is used as it is in the ink jet method, in the blown colored ink, the ink is dried at the tip of the ink jet head and the viscosity is gradually increased, so that the discharge property is deteriorated. . As a result, the discharge amount of the colored ink and the discharge direction are unstable, and the clogging of the holes in the ink jet head may occur. As described above, when an ink containing a coloring agent and a binder component is used, it is fixed in the nozzle via the ink, so that the discharge stability of the inkjet is lowered, and in serious cases, there is a problem that it cannot be discharged immediately.

Patent Document 2 discloses that a resin composition layer having an ink absorbing ability is formed on a transparent substrate, and ink is colored on the resin composition layer along a predetermined color pattern by an inkjet method to form a colored resin composition. The step of layering is repeated two or more times, and a plurality of colored resin composition layers are laminated to form a color filter having a coloring layer. However, in the production method disclosed herein, since the pigment concentration of the colored ink is low, in order to obtain color purity and color reproducibility as a color filter, it is necessary to repeat the complicated steps of the ink filling step, and the yield is lowered.

The color filter constituting the liquid crystal element is required to have high color purity and color reproducibility, that is, a colorant having a high coloring agent concentration in the colored portion, and such a color filter is produced by an inkjet method, and the amount of the ink to be applied is increased. However, if the amount of the ink to be applied is increased, it is difficult to suppress the color mixture which occurs in the ink doping, and the color filter cannot be produced in good yield.

As described above, the method of producing a color filter by the inkjet type colored layer is straightforward when discharged from the nozzle of the ink jet nozzle, and the stability is excellent, and high color purity can be obtained by applying the color component once. The method of color reproducibility has not yet been achieved.

[Patent Document 1] JP-A-11-295520

[Patent Document 2] JP-A-2002-311224

The present invention is excellent in straightness and stability when the nozzle is discharged, and the ink droplets that are springed can be easily wetted to all corners of the entire ink layer forming region, and can be supplied with high color by coating with one color component. Method for producing color filter using inkjet ink for purity and color reproducibility, method for producing color filter using inkjet ink, and method for manufacturing liquid crystal display device using method for producing color filter .

In order to solve the above problems, the inventors of the present invention have found that the above-mentioned problems can be solved by the fact that the pigment of the coloring component and the transparent resin of the binder component are applied in a ratio between the pigment dispersion liquid and the transparent resin solution, respectively. this invention.

That is, the present invention is 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 method of producing a color filter, comprising the step of selectively coating a pigment dispersion liquid by a liquid-jet method in a gap of a spacer portion on a transparent insulating substrate (pigment dispersion coating step), And a step of selectively coating the transparent resin solution by the inkjet method in the gap of the aforementioned spacer after the coating step of the pigment dispersion, and mixing the pigment dispersion and the transparent resin solution in the gap (transparent resin solution coating) And a step of hardening the mixed layer of the pigment dispersion liquid and the transparent resin solution formed by the aforementioned transparent resin solution coating step (hardening step).

(2) The method for producing a color filter according to the first aspect of the invention, wherein the thickness of the coloring liquid layer formed by the pigment dispersion coating step is 0.4 to 2 μm.

(3) The method of producing a color filter according to claim 1 or 2, wherein the mixed liquid layer is formed to have the same film thickness as the spacer.

(4) The method for producing a color filter according to any one of claims 1 to 3, wherein in the pigment dispersion coating step, the coloring liquid layer formed by coating the pigment dispersion liquid is 40 to 160 ° C The temperature is dry.

(5) The method for producing a color filter according to any one of claims 1 to 4, wherein in the step of applying the transparent resin solution, the mixed liquid layer obtained by mixing the pigment dispersion liquid and the transparent resin solution is 80 to 80 Dry at 200 ° C.

(6) The method for producing a color filter according to any one of claims 1 to 5, wherein a solid content ratio of the pigment to the transparent resin in the mixed liquid layer obtained by curing the mixed liquid layer is 1:0.4 ~1.

(7) The method for producing a color filter according to any one of claims 1 to 6, wherein the pigment dispersion liquid 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. .

(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 is composed of a photocurable resin composition.

(9) A liquid crystal display device comprising the color filter manufactured by the manufacturing method according to any one of claims 1 to 8, and a counter substrate, and the color filter and the foregoing A liquid crystal composition sandwiched between the opposing substrates.

According to the present invention, the pigment of the coloring component and the transparent resin composed of the binder component are respectively proportioned in a pigment dispersion liquid of a lower viscosity and a transparent resin solution, and each liquid is applied to the transparent insulating substrate in a separate step. When applied, the following effects can be obtained.

(1) Since the pigment dispersion liquid and the transparent resin solution have an appropriate viscosity, the straightness and stability at the time of discharge from the discharge head are excellent. Therefore, the ink viscosity at the tip end of the nozzle of the discharge head does not increase sharply, and the flying of the ink droplets is sharply bent. When the discharge is intermittently intermittent, the hole is not clogged and the ink can be discharged again, and the workability of forming the colored layer is excellent.

(2) Since a pigment dispersion having a high pigment concentration can be printed at a low viscosity, it is not necessary to apply a plurality of coloring components for color purity and color reproducibility as a color filter, and it is possible to color one time. The component coating step applies a necessary amount of the coloring component, and a liquid crystal element excellent in color display characteristics can be produced in a more favorable yield.

(3) There is no problem such as color mixing, and the ink droplets of the shot can be easily wetted to all corners of the entire ink layer forming region.

Therefore, according to the present invention, it is possible to inexpensively manufacture a color filter having high reliability and high reliability. In particular, a pixel portion having a large penetration density and uniformity and no discoloration can be precisely formed, and a color filter having improved brightness can be manufactured. Moreover, according to the present invention, since a color filter having better performance is used, a liquid crystal display element excellent in color display characteristics can be provided in a good yield, and a high-quality liquid crystal display device can be manufactured.

1. Method of manufacturing color filter

The method for producing a color filter of the present invention is a step of selectively coating a pigment dispersion liquid by a spray on a gap portion of a spacer provided on a transparent insulating substrate (pigment dispersion coating step), and dispersing the pigment in the foregoing After the liquid coating step, a step of selectively coating the transparent resin solution by the inkjet method in the gap of the spacer portion, and mixing the pigment dispersion liquid and the transparent resin solution in the gap (transparent resin solution coating step), and The step of hardening the mixed layer of the pigment dispersion liquid and the transparent resin solution formed by the transparent resin solution coating step (hardening step).

(1) Pigment dispersion

In the production method of the present invention, the pigment dispersion liquid used in the step of coating the pigment dispersion liquid is composed of at least a pigment and a solvent, and other components are blended as needed.

(a) Pigments

The pigment as a coloring agent is a color required for the R, G, B, and the like of the pixel (pixel portion) and the black matrix layer, and any of the organic coloring agent and the inorganic coloring agent is selected and used. As the organic colorant, for example, a dye, an organic pigment, a natural pigment, or the like can be used. Further, as the inorganic colorant, for example, an inorganic pigment, an extender pigment or the like can be used.

Among them, organic pigments are preferably used because of their high color developability and high heat resistance. The organic pigment may, for example, be a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourist Co., Ltd.), specifically, a color index (C.I.) as described below.

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, C. 1. 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 Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Huang 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 Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI 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 violet 32, CI pigment violet 36, CI pigment violet 38;

CI Pigment Red I, 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 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 Pigment Red 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 177, 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 264 , CI 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, CI Pigment Black 7.

Further, specific examples of the inorganic pigment or the extender pigment include titanium oxide, barium sulfate, calcium carbonate, lead white, lead sulfate, yellow lead, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, indigo, Chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, and the like. In the present invention, the pigment may be used alone or in combination of two or more.

In the case of forming a pixel, the pigment is formed in a solid amount relative to the inkjet ink, and is usually blended at a ratio of 1 to 60% by weight, preferably 15 to 40% by weight. If the amount of the pigment is too small, it is feared that the penetration density of the inkjet ink at the time of coating a predetermined film thickness (usually 0.1 to 2.0 μm) is insufficient. In addition, if the amount of the pigment is too large, the coating properties of the inkjet ink on the substrate, such as the adhesion to the substrate, the surface roughness of the cured film, and the hardness of the coating film, may not be sufficient.

(b) Solvent

The solvent of the pigment dispersion used in the present invention is selected in accordance with the printability of the ink jet apparatus. It is preferably selected from solvents having a boiling point of 200 ° C or higher, more preferably 240 ° C or higher. Since the boiling point of the solvent is 200° C., and has moderate drying property and evaporability, it is excellent in straightness and stability when discharged from the head, and can be dried more efficiently, and the ink droplets can be easily wetted by the ink layer. Form all corners of the entire area. As a result, even for a variety of substrates, the ink of the bomb can be widely wetted to the edge of the black matrix, and the discoloration and brightness reduction of the pixels can be prevented. When the boiling point is less than 200 ° C, the drying property in the vicinity of the nozzle is remarkably lowered, and as a result, problems such as clogging of the nozzle may occur.

Further, the solvent is preferably a surface tension of 25 to 35 mN/m, and more preferably 26 to 32 mN/m. If the surface tension is too high, the stability of the dot shape at the time of inkjet discharge is remarkably adversely affected, or the ink does not wet and expand in the gap of the spacer. When the surface tension is too low, there is a significant adverse effect on the stability of the dot shape at the time of inkjet discharge, or a possibility that the ink passes over the spacer and the possibility of diffusing color mixture becomes high.

A solvent satisfying such conditions, specifically, diethylene glycol diethyl ether, diethylene glycol n-butyl ether, diethylene glycol n-butyl ether acetate, diethylene glycol hexyl ether, dipropylene glycol methyl ether acetate, and the like Propylene glycol n-propyl ether, dipropylene glycol n-butyl ether and the like. Further, two or more kinds of solvents may be mixed as described above, and adjusted for use. Among them, a particularly preferred solvent is dipropylene glycol methyl ether acetate or diethylene glycol n-butyl ether acetate.

(c) Other ingredients

In the pigment dispersion liquid of the present invention, a pigment dispersant, a filler, a polymer compound anti-aggregation agent other than the binder polymer, and the like can be blended.

(pigment dispersant)

The pigment dispersant is such that the pigment is well dispersed in the ink and optionally blended. As the pigment dispersant, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, a polyfluorene-based or a fluorine-based surfactant can be used. Among the surfactants, a polymer surfactant (polymer dispersant) exemplified below is also preferred. That is, a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octyl phenyl ether or polyoxyethylene decyl phenyl ether; Alkyl phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate, polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; A polymer surfactant such as an amine-modified polyurethane is preferably used.

(2) Transparent resin solution

The transparent resin solution used in the coating step of the transparent resin solution of the present invention is composed of at least a transparent resin component and a solvent, and other components are blended as needed. Examples of the transparent resin component include a photocurable resin composition, a thermosetting resin composition, and the like.

(a) Photocurable resin composition

The photocurable resin composition is 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 two photopolymerizable functional groups. A functional monomer, a monofunctional monomer having one photopolymerizable functional group, and a photopolymerization initiator via photoactivation. Further, a reactive monomer having a lower viscosity may be blended as a reactive diluent. Examples of the other additives include a filler, a polymer compound other than the binder polymer, a surfactant, an adhesion promoter, an anti-agglomerating agent, an organic acid, a curing agent, and the like. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.

(high molecular weight polymer)

The polymer having a relatively high molecular weight (high molecular weight polymer) means a higher molecular weight than the so-called monomer and oligomer, and the approximate standard is a weight average molecular weight of 5,000 or more. The polymer may be any polymer which is not polymerizable, and may be any polymer having a polymerization reaction system, or two or more kinds thereof may be used in combination.

The solid content of the polymer relative to the transparent resin solution is usually a ratio of 1 to 50% by weight. Here, the solid content of the ink in a specific blending ratio includes all components other than the solvent, and a liquid polymerizable monomer or the like is also contained in the solid component.

In the present invention, a polymer having a relatively high molecular weight is blended in a transparent resin solution for a color filter. Among them, an oligomer having a polymerizable reactive polymer itself is most easily obtained in the market, and examples thereof include ester acrylates, ether acrylates, urethane acrylates, and epoxy acrylates. Amino resin acrylates, acrylic resin acrylates, unsaturated polyesters, and the like.

In order to prevent the viscosity of the ink of the present invention from being excessively high and not adversely affecting the discharge property of the head, the molecular weight of the ethylenic double bond-containing compound which is a polymer having polymerization reactivity itself is used, and the weight average molecular weight is 25,000. The following is better.

(polymer without polymerization)

As the polymer which is not polymerizable by itself, for example, a copolymer composed of two or more kinds of monomers: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid can be used. 2-Hydroxyethyl ester, 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 copolymerization may be used. , acrylic acid / methyl acrylate / polymethyl methacrylate huge monomer copolymer, acrylic acid / benzyl acrylate / polystyrene giant monomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate huge monomer Copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene giant monomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate huge monomer copolymer, Acrylic/benzyl methacrylate copolymer, acrylic acid/methyl methacrylate/styrene copolymer, acrylic acid/benzyl methacrylate/styrene copolymer, acrylic acid/methyl methacrylate/polystyrene giant monomer Copolymer, acrylic acid / methyl methacrylate / polymethyl methacrylate huge monomer copolymer, acrylic acid / benzyl methacrylate / polystyrene giant monomer copolymer, acrylic / methacrylic acid Ester/polymethyl methacrylate huge monomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene giant monomer copolymer, acrylic acid / 2-ethyl methacrylate / Acrylic copolymers such as benzyl methacrylate/polymethyl methacrylate macromonomer copolymer.

If specific examples continue to be listed, 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 giant monomer copolymer, methacrylic acid/benzyl acrylate/polystyrene macromonomer copolymer, Methacrylic acid / benzyl acrylate / polymethyl methacrylate huge monomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene giant monomer copolymer, methacrylic acid / acrylic acid 2 -Hydroxyethyl ester / benzyl acrylate / polymethyl methacrylate huge monomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / methyl acrylate / styrene copolymer, methacrylic / armor Benzyl acrylate/styrene copolymer, methacrylic acid/methyl methacrylate/polystyrene macromonomer copolymer, methacrylic acid/methyl methacrylate/polymethyl methacrylate macromonomer copolymer ,methyl Acrylic acid/benzyl methacrylate/polystyrene macromonomer copolymer, methacrylic acid/benzyl methacrylate/methyl methacrylate huge monomer copolymer, methacrylic acid/2-acrylic acid 2-hydroxyethyl Ester / benzyl methacrylate / polystyrene giant monomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate huge monomer copolymer Acrylic copolymers and the like.

(multifunctional monomer)

In the present invention, a polyfunctional monomer is blended in the aforementioned transparent resin solution. In order to improve the film strength of the hardened layer obtained by curing the photocurable composition and the adhesion to the substrate, a monomer having two or more polymerizable functional groups is added to the photocurable composition (multifunctional single) In order to obtain sufficient film strength and adhesion, a trifunctional or higher polyfunctional monomer is usually used.

However, when a polyfunctional monomer having a large number of polyfunctional groups is blended on the substrate by an inkjet method, the ink is dried and the viscosity is slow at the tip end portion of the ink jet head during the blowing operation. The slowness becomes larger, and the discharge property of the ink deteriorates.

The mixing ratio of the polyfunctional monomer is usually 20 to 70% by weight based on the total amount of the solid content of the transparent resin solution.

Here, in the case where the mixing ratio of the polyfunctional monomer is less than 20% 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 poor, and the film may not be obtained. Fully characterized. Further, in the case where the blending ratio of the polyfunctional monomer exceeds 70% by weight of the total solid content, the ink composition (transparent resin solution) cannot be sufficiently diluted with the monomer, so that the viscosity of the ink becomes higher from the beginning or becomes more volatile after the solvent evaporates. High, it may cause the hole of the inkjet nozzle to be blocked.

(monofunctional monomer)

The monofunctional monomer (monofunctional polymerizable compound) may, for example, be decyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylethyl carbitol acrylate, or acrylic acid 2- Hydroxyethyl ester, N-vinylpyrrolidone, and the like.

(2-functional and 3-functional monomers)

Examples of the polyfunctional monomer having two or more photopolymerizable functional groups include a bifunctional monomer and a trifunctional or higher polyfunctional monomer.

Examples of the bifunctional monomer include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol. Dimethacrylate, 1,10-nonanediol diacrylate, 1,10-nonanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, hydroxypivalic acid Neopentyl glycol diacrylate, hydroxypivalic acid neopentyl glycol dimethacrylate, polybutylene glycol diacrylate, polybutylene glycol dimethacrylate, diethylene glycol diacrylate, diethyl Diol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethyl Glycol dimethacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (400) Dimethacrylate, polyglycol (600) diacrylate, polyethylene glycol (600) dimethacrylate, bisphenol A bis(propylene oxiranyl) ether, 3-methyl pentyl Glycol diacrylate, 3-methyl-pentanediol dimethacrylate, dimethylol - tricyclodecane diacrylate, dimethylol - tricyclodecane dimethacrylate and the like.

Examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide-modified trimethylpropane triacrylate, and ethylene oxide. Modified trimethylpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, tris(2-hydroxyethyl)trimeric isocyanate triacrylate, tris(2-hydroxyethyl)trimeric isocyanate Trimethacrylate, propoxylated glyceryl triacrylate, propoxylated glyceryl trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, bis(trimethylol)propane tetraacrylic acid Ester, bis(trimethylol)propane tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, dipentaerythritol hydroxypentaacrylate, dipentaerythritol hydroxypentamethacrylic acid Ester, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

(reactive diluent)

The "reactive diluent" refers to a monomer having a reactive group having one or more double bonds at the molecular terminal in the molecule. The reactive diluent may, for example, be monofunctional caprolactone acrylate, tridecyl acrylate, isodecyl acrylate, isooctyl acrylate, isomyristyl acrylate, isostearyl acrylate, diethylene glycol acrylic acid. 2-ethylhexyl ester, 2-hydroxybutyl acrylate, 2-propenyl oxiranyl hexahydrophthalic acid, neopentyl glycol acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, Butyloxyethyl acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxy-polyethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxy acrylate Ethyl ester, phenoxy-polyethylene glycol acrylate, nonylphenol ethylene oxide adduct acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy propyl acrylate Ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-propenyloxyethyl succinate, 2-propenyloxyethyl phthalate, 2-propenyl oxiranyl 2-hydroxyethyl phthalate.

(photopolymerization initiator)

The photopolymerization initiator is a reaction form considering a higher molecular weight polymer, a polyfunctional monomer, a bifunctional monomer, and a monofunctional monomer (for example, radical polymerization and cationic polymerization, etc.), and types of materials. Appropriately selected, in order to harden the colored ink, add it as needed.

The photopolymerization initiator may be an active radical generator which generates active radicals via light and heat. Examples of the photopolymerization initiator include an acetophenone-based compound, a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and a triazine-based compound.

Examples of the acetophenone-based compound include diethoxyacetamidine, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-2-. Methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinyl-1-(4- Methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-hydroxy-2-methyl-1 - oligomer of [4-(1-methylvinyl)phenyl]propan-1-one, and the like.

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

Examples of the benzophenone-based compound include benzophenone, methyl ortho-benzoic acid benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldithiobenzene, and 3,3'. 4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone and the like.

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

The triazine-based compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloromethyl). - 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-( 5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl] -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3, 5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

As the active radical generator, for example, 2,4,6-trimethylbenzimidium diphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5 can also be used. '-Tetraphenyl-1,2'-bisimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylethyl Methyl aldehyde, titanium titanate, and the like.

A commercially available substance can also be used as the active radical generator. The commercially available polymerization initiator is, for example, a product name "Irgacure-369" (a phthalic acid photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.).

Examples of the thermal polymerization initiator include an azo compound and a peroxide compound. Examples of the azo compound include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis(4-methyl-2,4- Dimethylvaleronitrile), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 2,2'-azobis(2-methylbutyronitrile), 1,1'-even Nitrogen bis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-2(propenyl)-2-methyl-propanamide], 1-[(cyano-1-methyl) Ethyl)azo]carbamamine, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methyl) Propylamine, a polymeric azo polymerization initiator containing a polydimethylsiloxane subunit (Wako Pure Chemical Industries, VPS series), a polymeric polymerization initiator containing polyethylene glycol units (and Guangchun Pharmaceutical Industry, VPE Series), etc.

Examples of the peroxide compound include peroxyketal, hydrogen peroxide, dialkyl peroxide, dioxane peroxide, peroxydicarbonate, and peroxy ester. Examples of the peroxy ester include a tert-butylperoxylactate (manufactured by Nippon Oil Co., Ltd., trade name "Perbutyl L"), and a tert-butylperoxy-3,5,5-trimethyl group. An acid ester (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perbutyl 355"), a third hexylperoxy-isopropyl-monocarbonate (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perbutyl I"), and the like.

These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator to be used is usually 1 part by mass or more and 30 parts by mass or less, preferably 3 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the total of the binder polymer and the polymerizable compound.

(other additives)

Examples of the other additives include a filler, a polymer compound other than the binder polymer, a surfactant, an adhesion promoter, an anti-agglomerating agent, an organic acid, a curing agent, and the like. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, and N-(2-aminoethyl)-3-amine. Propylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethyl Oxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,1-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy Decane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, and the like.

(b) Thermosetting resin composition

The thermosetting resin composition of the present invention is characterized by comprising at least a thermopolymerizable binder and a bifunctional to trifunctional epoxy group-containing monomer. A coloring agent, a dispersing agent, a hardening accelerator, or other additives may be blended in the thermosetting resin composition as needed. Further, in order to impart suitable fluidity and discharge property to the inkjet method, the thermosetting transparent resin composition may be dissolved or dispersed in a solvent (diluent). Further, a bifunctional to trifunctional epoxy group-containing monomer may be used in combination with a tetrafunctional or higher epoxy group-containing resin.

(adhesive)

As the binder for the thermal polymerization, for example, a monomer or a copolymer obtained by polymerizing an ethylenically unsaturated bond shown below with one or more epoxy group-containing monomers: glycidyl acrylate, methyl group can be used. Glycidyl acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-butyl butyl acrylate, methacrylic acid-3 , 4-epoxybutyl acrylate, methacrylic acid-4,5-epoxypentyl acrylate, acrylate-6,7-epoxyheptyl ester, methacrylic acid-6,7-epoxyheptyl ester, α-ethyl acrylate (meth) acrylates such as -6,7-epoxyheptyl ester; o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, p-vinyl phenyl glycidyl ether, o-vinyl benzyl ether Vinyl glycidyl ethers such as glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.; 2,3-diepoxypropoxystyrene, 3,4-bicyclo Oxypropoxystyrene, 2,4-diepoxypropoxystyrene, 3,5-diepoxypropoxystyrene, 2,6-diepoxypropoxystyrene, 5-vinyl Pyrogallol triple shrinkage Oleic ether, 4-vinylpyrrolol triglycidyl ether, vinyl fluoroglycolamine triglycidyl ether, 2,3-dimethylol styrene diglycidyl ether, 3,4-dimethylol Styrene diglycidyl ether, 2,4-dimethylol styrene diglycidyl ether, 3,5-dimethylol styrene diglycidyl ether, 2,6-dimethylol styrene diglycidyl Ether, 2,3,4-trishydroxymethylstyrene triglycidyl ether, and 1,3,5-trishydroxymethylstyrene triglycidyl ether.

Further, the above-mentioned ethylenically unsaturated bond and one or more epoxy group-containing monomers may be copolymerized with a monomer having no epoxy group as described below, and may be used as a thermopolymerizable bond. Agent: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene Huge monomer, and polymethyl methacrylate huge monomer.

The binder is usually added in an amount of from 1 to 50% by weight based on the total amount of the solid solution of the thermosetting resin composition. Here, the solid content of the thermosetting resin composition having a specific blending ratio is that all the components other than the solvent are contained, and the liquid polymerizable monomer is also contained in the solid component.

When the amount of the binder is less than the above range, the solvent resistance, adhesion, and hardness of the coating film are inferior, and there is a disadvantage that sufficient characteristics cannot be obtained. When it exceeds the above range, the ink composition (transparent resin solution) is not sufficiently diluted by the monomer, and the viscosity of the ink becomes high from the beginning or becomes high after the solvent evaporates, which may cause clogging of the pores of the ink jet head.

(monomer containing epoxy group)

In the thermosetting resin composition, one or a combination of two or more bifunctional to trifunctional epoxy group-containing monomers is used as the thermosetting component. Since the bifunctional to trifunctional epoxy group-containing monomer has a lower viscosity even if it is a thermosetting resin, and the viscosity is less increased by drying, such a bifunctional to trifunctional epoxy group-containing monomer is used. When the ink which is a thermosetting component is used as a monomer, it is difficult to cause the viscosity of the tip of the head to rise in the operation of the ink jet method, and the clogging of the nozzle is not caused, and the discharge property of the ink is stabilized during the operation. Therefore, the discharge amount and the discharge direction of the ink are kept constant, and the ink can be properly formed on the substrate as the specified pattern, and uniformly adhered.

The bifunctional to trifunctional epoxy group-containing monomer can be exemplified by, for example, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like. Hydroxymethylpropane polyglycidyl ether, 2,3-diepoxypropoxystyrene, 3,4-diepoxypropoxystyrene, 2,4-diepoxypropoxystyrene, 3, 5-diepoxypropoxystyrene, 2,6-diepoxypropoxystyrene, 5-vinylpyrrolol triglycidyl ether, 4-vinylcarboxol triglycidyl ether, vinyl Fluoroglycine alcohol triglycidyl ether, 2,3-dimethylol styrene diglycidyl ether, 3,4-dimethylol styrene diglycidyl ether, 2,4-dimethylol styrene Diglycidyl ether, 3,5-dimethylol styrene diglycidyl ether, 2,6-dimethylol styrene diglycidyl ether, 2,3,4-trishydroxymethyl styrene triglycidyl Ether, 1,3,5-trimethylol styrene triglycidyl ether, etc., may be used alone or in combination of two or more.

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 mixing 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 by the monomer, and the ink viscosity is It becomes high from the beginning or becomes high after the solvent evaporates, which may cause clogging of the pores of the ink jet head. Further, when the mixing ratio of the bifunctional to trifunctional epoxy group-containing monomer is more than 70% by weight based on 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 lowered. Poor, I am afraid I can't get enough features.

(other thermosetting ingredients)

Further, in the thermosetting resin composition, the above-mentioned bifunctional to trifunctional epoxy group-containing monomer may be blended with a monofunctional epoxy group-containing monomer, and/or 4, if necessary. A thermosetting component other than the functional group-containing epoxy group-containing resin and/or the epoxy group-containing monomer.

The monofunctional epoxy group-containing monomer may, for example, be methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether or thiol glycated ether. Glycerol ether, stearyl glycidyl ether, allyl glycidyl ether, polypropylene glycol glycidyl ether, butoxy polyethylene glycol monoglycidyl ether.

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

The bifunctional to trifunctional epoxy group-containing monomer is preferably a tetrafunctional or higher epoxy group-containing resin. In the case where all of the epoxy group-containing components contained in the thermosetting resin composition are bifunctional to trifunctional, since the viscosity is hard to be increased due to drying of the ink, the discharge property of the ink jet head is stable, but the reverse side is hardened. The film strength of the hardened layer obtained by the ink layer and the adhesion to the substrate may not be sufficient. Therefore, when the above-mentioned bifunctional to trifunctional epoxy group-containing monomer is blended in an appropriate amount with a tetrafunctional or higher epoxy group-containing resin, sufficient film strength and adhesion can be imparted to the pattern of the hardened layer. .

For the epoxy group-containing resin having four or more functional groups, for example, a novolac resin such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, a tetraglycidyldiamine diphenylmethane or a tetraglycidyl group can be used. A glycidylamine resin such as xylene diamine or a glycidyl ether resin such as tetraphenyl glycidyl ether ethane or triphenyl glycidyl ether methane.

The epoxy group-containing resin having four or more functional groups is preferably added in an amount of from 1 to 30% by weight based on the total solid content of the thermosetting transparent resin composition. Further, in order to stabilize the discharge property due to the bifunctional to trifunctional epoxy group-containing epoxy group, and to improve the strength and adhesion balance of the tetrafunctional or higher epoxy group-containing resin, it is relative to the bifunctional to 3-functional group. 100 parts by weight of the functional monomer, the blending ratio of the epoxy group-containing resin having 4 or more functional groups is usually 1 to 50 parts by weight, preferably the lower limit of the blending ratio is 2 parts by weight or more, and/or the blending ratio The upper limit of the ratio is 35 parts by weight or less.

Here, in the case where the blending ratio of the epoxy group-containing resin having four or more functional groups is less than 1 part by weight based on 100 parts by weight of the above-mentioned bifunctional to trifunctional monomer, there is concern about hardness and solvent resistance after curing of the ink. The characteristics of etc. cannot be fully obtained. When the blending ratio of the epoxy group-containing resin having four or more functional groups is more than 50 parts by weight, there is concern that the curing rate of the ink is slow and the step speed is slow.

(hardener)

In the thermosetting resin composition used in the present invention, a curing agent is usually blended. The hardener is, for example, a polyvalent carboxylic anhydride or a polyvalent carboxylic acid.

Specific examples of the polyvalent carboxylic acid anhydride include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, propylene tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, and dimethyl An aliphatic or alicyclic dicarboxylic anhydride such as tetrahydrofurfuric anhydride, heiming anhydride, benzylidene tetrahydrophthalic anhydride; 1,2,3,4-butanetetracarboxylic dianhydride, An aliphatic polyvalent carboxylic acid dianhydride such as cyclopentane tetracarboxylic dianhydride; an aromatic polyvalent carboxylic acid anhydride such as pyromellitic anhydride, trimellitic anhydride or benzophenone tetracarboxylic anhydride; ethylene glycol bis(p-benzoate) An acid anhydride-containing acid anhydride such as an acid salt or a triglyceride (trimellitic acid salt) is particularly preferably an aromatic polyvalent carboxylic acid anhydride. Further, an epoxy resin curing agent composed of a commercially available carboxylic anhydride is also suitable for use.

Further, 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; An aliphatic polyvalent carboxylic acid such as hydroquinone, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid or cyclopentanetetracarboxylic acid, and citric acid or isophthalic acid The aromatic polyvalent carboxylic acid such as citric acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid or benzophenonetetracarboxylic acid is preferably aromatic. Valence carboxylic acid.

These polyvalent carboxylic anhydrides and polyvalent carboxylic acids may be used alone or in combination of two or more. The amount of the curing agent used in the present invention is usually from 1 to 100 parts by weight, preferably from 5 to 50 parts by weight, per 100 parts by weight of the epoxy group-containing component (monomer and resin). If the amount of the hardener is less than 1 part by weight, the hardening is insufficient and a tough coating film cannot be formed. In addition, when the amount of the curing agent is more than 100 parts by weight, the adhesion of the coating film to the substrate is inferior, and a uniform and smooth coating film cannot be formed.

(other additives)

Examples of the other additives include a filler, a polymer compound other than the binder polymer, a surfactant, an adhesion promoter, an anti-agglomerating agent, an organic acid, a curing agent, and the like. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, and N-(2-aminoethyl)-3-amine. Propylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxypropoxytrimethoxy Baseline, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane , 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, and the like.

(c) solvent

The solvent of the transparent resin solution is selected in the same manner as the solvent of the above-mentioned pigment dispersion liquid, depending on the printing suitability of the ink jet apparatus. It is preferred to use a solvent having a boiling point of 200 ° C or higher. Further, it is preferred to use a solvent having a surface tension in the range of 25 to 35 mN/m. It is particularly preferred to use a solvent having a surface tension of 25 to 35 mN/m and a boiling point of 200 ° C or higher. When the boiling point is less than 200 ° C, the drying property in the vicinity of the nozzle is remarkably high, and as a result, problems such as clogging of the nozzle may occur. Further, when the surface tension exceeds 35 mN/m, there is a fear that the stability of the dot shape at the time of inkjet discharge is remarkably adversely affected, and the transparent resin solution cannot be wetted to the entire corner of the colored layer when applied on the colored layer. .

A solvent satisfying such conditions, specifically, diethylene glycol diethyl ether, diethylene glycol n-butyl ether, diethylene glycol n-butyl ether acetate, diethylene glycol hexyl ether, dipropylene glycol methyl ether acetate, and the like Propylene glycol n-propyl ether, dipropylene glycol n-butyl ether and the like. Further, two or more kinds of solvents may be mixed and adjusted for use in accordance with the above conditions as needed. The most preferred ones are dipropylene glycol methyl ether acetate and diethylene glycol n-butyl ether acetate.

(3) Manufacture of color filters

The method for producing a color filter of the present invention is a step of selectively coating a pigment dispersion liquid by an inkjet method in a gap of a spacer portion on a transparent insulating substrate (pigment dispersion coating step), and a pigment in the foregoing After the dispersion coating step, a step of selectively coating the transparent resin solution by the inkjet method at the gap of the spacer portion, and mixing the pigment dispersion liquid and the transparent resin solution in the gap (transparent resin solution coating step), and The step of hardening the mixed layer of the pigment dispersion liquid and the transparent resin solution formed by the aforementioned transparent resin solution coating step (hardening step).

(a) Pigment dispersion coating step

In the pigment dispersion coating step of the present invention, a spacer (black matrix) is first formed on the transparent insulating substrate of the color filter.

The transparent insulating substrate used for the color filter of the present invention may, for example, be glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide or polyimine. Further, on the transparent insulating substrate, a pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition treatment may be appropriately performed.

The material forming the spacer is a mixed color black containing a resin component and a black pigment (carbon black or the like) and/or a mixture of R (red), G (green), B (blue), Y (yellow), V (purple), and the like. A pigment and a photosensitive resin which decomposes a solvent for dissolving these components. The resin material may be a negative type or a positive type which is generally used as an acrylic resin for a black photosensitive resin. The height of the spacer may be a film thickness of the transparent colored resin film, and when it is used as a color filter of a high chroma region, it is 1.5 μm or more and 5.0 μm or less, and more preferably 2.0 μm or more and 4.0 μm or less. When the width of the spacer is 10 μm or more and 30 μm or less, the light-transmitting region partitioned via the spacer is generally rectangular and curved in a width of 60 μm to 250 μm.

When the photosensitive resin is used to form a spacer on the transparent insulating substrate, a film having a thickness of about 1 to 3 μm is formed by spin coating or the like, and then formed by a photoresist step (exposure and development).

Next, in the gap between the spacers thus obtained, that is, the portion surrounded by the spacer (the portion which becomes the RGB pixel), the pigment dispersion liquid of the desired pigment such as R, G, or B is selected by the ink jet method. Sexual adhesion, coating a pigment dispersion (coloring liquid) on a pixel portion and a light shielding layer to form a coloring liquid layer. The thickness of the coloring liquid layer varies depending on each of the layers of R, G, and B, and is approximately in the range of 0.4 to 2.0 μm. If the thickness of the coloring liquid layer is outside this range, a step difference between the spacer and the coloring layer may occur.

Next, the formed coloring liquid layer is dried as needed (pre-drying step). By performing such pre-drying, the pigment can be reduced only in the solvent dispersion of the pigment dispersion in a state where the pigment is uniformly dispersed in the coloring liquid layer. When the drying of the pigment dispersion liquid (the amount of reduction in the solvent) is insufficient, when the transparent resin solution is applied, the amount of the liquid after the pigment dispersion liquid and the transparent resin solution are mixed becomes large, and the mixed liquid leaks out of the partition portion and is mixed.

It is preferred to carry out drying at a temperature ranging from 40 to 160 °C. When the drying temperature is too low, the volume change of the pigment dispersion liquid becomes small, and the color mixture is feared when the transparent resin solution is applied. Further, when the drying temperature is too high, when the transparent resin solution is applied, the transparent resin solution cannot be uniformly wetted and spread on the coloring liquid layer, and the surface of the cured film may be rough. Although the drying time is not particularly limited, it is preferably from 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 by the inkjet method in the gap of the spacer portion, and the pigment dispersion liquid and the transparent resin solution are mixed in the gap. That is, on the coloring liquid layer formed by the pigment dispersion coating step, a transparent resin solution is applied to form a transparent resin layer, and the two layers are mixed to form a mixed liquid layer composed of a colored liquid layer and a transparent resin layer (colored resin layer). ).

When a transparent resin solution having a low viscosity is applied to the dried pigment dispersion (coloring liquid layer), the pigment is redispersed in the transparent resin solution, so that the pigment dispersion liquid is mixed with the transparent resin solution or the coloring liquid layer Fusion with a transparent resin layer. Therefore, in the above-described pigment dispersion coating step, the formed coloring liquid layer can be sufficiently mixed with the pigment and the transparent resin solution even in a state of being completely dried through the pre-drying step.

The coating amount of the transparent resin solution is different depending on the RGB layers, and the coating amount is appropriately adjusted as the film thickness difference of the colored resin layers of the respective RGB colors is 0.1 μm or less. The coating amount of the transparent resin solution is a ratio of solid content of the pigment dispersion liquid and the transparent resin solution after drying (the ratio of the solid content of the pigment after the mixture layer is hardened to the transparent resin) is pigment: transparent resin = 1: 0.4 to 1 The general adjustment is better.

Moreover, it is desirable that the mixed liquid layer (colored resin layer) has the same film thickness as the above-mentioned spacer, and it is necessary to adjust the coating amount of the transparent resin solution. When the coating amount of the transparent resin solution is small for the pigment dispersion liquid, it may not be wetted and spread to the respective corners of the entire colored resin layer. In addition, when the coating amount of the transparent resin solution is large for the pigment dispersion liquid, the thickness of the colored resin layer becomes large, and the colored resin layer having no difference between the spacer portion and the colored resin layer cannot be formed.

The thickness of the colored resin layer is approximately in the range of 1.0 to 2.5 μm. When the thickness of the colored resin layer exceeds this range, a step is generated between the spacer and the coloring layer, and the flatness of the entire filter is deteriorated.

The step of drying the colored resin layer (prebaking step) is preferably carried out at a temperature of from 80 to 200 °C.

When the drying temperature is too low, the volume change of the colored resin layer becomes small, and the film thickness of the colored resin layer becomes large, so that the colored resin layer having no difference between the spacer and the colored resin layer cannot be formed. In addition, when the drying temperature is too high, the volume change of the colored resin layer becomes large, and the film thickness of the colored resin layer becomes small, so that the colored resin layer having no difference between the spacer and the colored resin layer cannot be formed.

(c) Hardening step

In the present invention, the mixed liquid layer of the pigment dispersion liquid and the transparent resin solution formed by the transparent resin solution coating step is hardened (hardening step).

When a photocurable resin composition is used as the transparent resin, it is cured by irradiation with light. The light to be used is preferably ultraviolet light or visible light, and light having a wavelength of 200 to 500 nm is preferred. Such light sources may, for example, use low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, chemical lamps, black lamps, mercury-xenon lamps, excimer laser lamps, short arc lamps, neo-cadmium lasers, argon lasers, Known conventional light sources such as Nd-YAG laser THG and FHG light lasers. The photohardening condition is not affected by the kind of the light source used and the type and amount of the photopolymerization initiator, but is generally determined to be in the range of 100 to 3000 mJ/m ² . After photohardening, post-hardening (post-baking) treatment is carried out at 200 to 250 ° C for 10 to 30 minutes.

When a thermosetting resin composition is used as the transparent resin, it is cured by heating. The heat curing conditions are such that 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 may be formed thereon as needed. As the protective layer, a photocurable type, a thermosetting type, or a thermo-optic curing type resin composition layer or an inorganic compound layer formed by vapor deposition or sputtering can be usually used.

Next, an ITO (Indium Tin Oxide) film was formed as an electrode on this protective layer. Further, an alignment film (polyimine film) is formed thereon by a known method to produce a color filter.

2. Liquid crystal display device

A liquid crystal display device of the present invention is characterized by comprising a color filter manufactured by the method for producing a color filter of the present invention, an opposite substrate such as a glass substrate, and a color filter sandwiched between the color filter and the color filter. a liquid crystal composition between the opposite counter substrates.

The liquid crystal display device can be formed by combining a substrate on the color filter side and a counter substrate, and enclosing liquid crystal therebetween. On the inner side of the counter substrate, the TFT and the pixel electrode are formed in a rectangular shape. Further, an alignment film is formed on the opposite substrate side so that the liquid crystal molecules are aligned in a certain direction. In the case of the penetrating type, the substrate and the pixel electrode are formed of a transparent material, and the polarizing plate is bonded to the outside of each of the substrates. In the case of the reflective type, the substrate or the pixel electrode is formed of a material having a reflection function or a reflective layer is provided on the substrate, and a polarizing plate is disposed outside the transparent substrate to reflect the light from the side of the color filter. Display.

When the liquid crystal display device of the present invention is configured by using the color filter of the present invention, the prior art can be suitably used for other members.

Further, the present invention is not limited to the above embodiment. The above-described embodiments are exemplified, and have substantially the same configuration as the technical idea described in the patent application scope of the present invention, and the same effects are achieved, and any of them are included in the technical scope of the present invention.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In addition, the evaluation method of each physical property in the following examples is as follows. In addition, in the following examples, "parts" means "parts by weight".

<Manufacturing Example 1; Modulation of Pigment Dispersion for Color Filter> (1) Modulation of color filters with red pigment dispersion

The Red pigment, the pigment dispersant, and the organic solvent were mixed in the following ratio, and 500 parts of zirconia beads having a diameter of 0.3 mm were added, and dispersed using a paint shaker for 4 hours to obtain a pigment dispersion liquid (R).

(composition of pigment dispersion)

Red pigment (C.I. Pigment Red 254): 10 parts

Pigment dispersant (made by AVECIA: Solsperse 24000): 10 parts

DPMA (dipropylene glycol methyl ether acetate; boiling point = 209 ° C, surface tension = 27 mN / m): 80 parts

(2) Modulation of color filter with green pigment dispersion

In the above (1), in addition to using 10 parts of Green Pigment (CI Pigment Green 36) and 10 parts of Yellow Pigment (CI Pigment Yellow 150) instead of 10 parts of Red Pigment (CI Pigment Red 254), the preparation of the pigment dispersion was treated as in Production Example 1. Liquid (G1) and pigment dispersion (Y). 53 parts of the pigment dispersion (G1) and 47 parts of the pigment dispersion (Y) were mixed to prepare a green pigment dispersion (G2).

(3) Modulation of color filter with blue pigment dispersion

In the above (1), the pigment dispersion liquid (B) was prepared in the same manner as in Production Example 1, except that 10 parts of Blue pigment (C.I. Pigment Blue 15:6) was used instead of 10 parts of the Red pigment.

<Production Example 2; Modulation of Pigment Dispersion for Color Filter>

In Production Example 1, except that BCA (diethylene glycol butyl ether acetate; boiling point = 247 ° C, surface tension = 30 mN/m) was used instead of DPMA, it was separately prepared in the same manner as in Production Example 1 (1) to (3). Red, green, and blue pigment dispersions.

<Production Example 3; Preparation of Photocurable Transparent Resin Solution>

15 parts of a polyester acrylic oligomer, 15 parts of dipentaerythritol hexaacrylate (hereinafter referred to as DPHA), 20 parts of 1,6-hexanediol diacrylate, 45.5 parts of dipropylene glycol methyl ether acetate, and 0.5 parts of the photopolymerization initiator "Irgacure 369" manufactured by Ciba Specialty Chemicals Co., Ltd. was mixed, and then filtered using a filter paper having a pore size of 1.0 μm to obtain a transparent resin solution.

<Production Example 4; Preparation of Thermosetting Transparent Resin Solution>

10 parts of a binder (methacrylate glycerol-styrene copolymer), a novolac type epoxy resin (manufactured by Oily Shell Co., Ltd., trade name "Epicoat 154": 10 parts, neopentyl glycol diglycidyl 20 parts by weight of an ether, 5 parts by weight of a curing agent (trimellitic acid), and 55 parts of dipropylene glycol methyl ether acetate were mixed, and then filtered using a filter paper having a pore size of 1.0 μm 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 was formed by a photolithography method using a curable resin composition for a black matrix on a 10 cm × 10 cm glass substrate (manufactured by Asahi Glass Co., Ltd.) having a thickness of 0.7 mm. .

The blue pigment dispersion liquid obtained in Production Example 1 was accurately and uniformly adhered to the blue pigment dispersion portion obtained in the black matrix of the substrate.

Next, the green pigment dispersion liquid of Production Example 1 was accurately and uniformly adhered to the green pigment dispersion portion of the same substrate by an inkjet method. Next, the red pigment dispersion liquid of Production Example 1 was accurately and uniformly adhered to the red pixel dispersion portion of the same substrate by an inkjet method. After the pigment dispersion was applied, it was pre-dried on a hot plate at 100 ° C for 10 minutes.

Thereafter, on the pigment dispersion liquid of each color pixel forming portion in which the black matrix is partitioned, the solid resin solution of the production example 3 was cured in a mixed liquid layer, and the solid content ratio was pigment: transparent resin = 1:0.8 Adjusted and adhered correctly and evenly via the inkjet method. Thereafter, it was prebaked on a hot plate at 180 ° C for 20 minutes, and exposed to light at 200 mJ/cm ² with a high pressure mercury lamp, and then hardened at 230 ° C for 20 minutes.

The substrate of the RGB pixel pattern was formed, immersed in IPA (isopropyl alcohol) for 5 minutes, and then dried by IPA vapor, and then set at a substrate temperature of 200 ° C under a vacuum of 6 × 10 ^-3 Torr at 120 nm. The thickness is formed into an ITO (indium tin oxide) electrode. The substrate on which the ITO film was formed was further immersed in IPA for 5 minutes, and then washed with IPA, and then spin-coated with polyimine, and calcined at 180 ° C for 60 minutes to form an alignment film to obtain color filter. sheet.

<Example 2>

In the first embodiment, a color filter was produced in the same manner as in Example 1 except that the solid content ratio after curing of the mixed liquid layer was a pigment: transparent resin = 1:0.4.

<Example 3>

In the color filter manufacturing step of the second embodiment, the pre-baking after coating the pigment dispersion liquid is performed on a hot plate at 60 ° C for 10 minutes, and the pre-baking after coating the transparent resin solution is at 150 ° C. A color filter was produced in the same manner as in Example 2 except for 20 minutes on a hot plate.

<Example 4>

The same procedure as in Example 2 was carried out except that the thermosetting transparent resin solution of Production Example 4 was used instead of the photocurable transparent resin solution of Production Example 3 in Example 2, and the curing conditions were at 230 ° C for 30 minutes. Color filter.

<Example 5>

In addition to the use of the pigment dispersion liquid of Production Example 2, instead of the pigment dispersion liquid of Production Example 1 used in Example 2 and the solid content ratio after curing of the mixed liquid layer, the pigment: transparent resin = 1:1.2 was coated with a transparent resin solution. A color filter was produced in the same manner as in Example 2.

<Example 6>

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

<Example 7>

Pre-baking after coating the pigment dispersion in Example 5, pre-baking after coating of the transparent resin solution, hot plate at 220 ° C for 20 minutes, and solid solution ratio after hardening of the mixed layer were pigments: A color filter was produced in the same manner as in Example 5 except that a transparent resin solution was applied as a transparent resin = 0.8.

<Example 8>

The same procedure as in Example 7 was carried out except that the thermosetting transparent resin solution of Production Example 4 was used instead of the photocurable transparent resin solution of Production Example 3 in Example 7, and the curing conditions were at 230 ° C for 30 minutes. Color filter.

<Manufacturing Example 5; Modulation of Pigment Inkjet Ink for Color Filter> (1) Modulation of color filters with red inkjet inks

The Red pigment, the pigment dispersant, and the organic solvent were mixed in the following ratio, and 500 parts of zirconia beads having a diameter of 0.3 mm were added, and dispersed using a paint shaker for 4 hours to obtain a pigment dispersion liquid (R). 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 light by Ciba Specialty Chemicals Co., Ltd. After mixing 0.5 parts of the polymerization initiator "Irgacure 369", it was filtered using a filter paper having a pore size of 1.0 μm to obtain a red inkjet ink for a color filter.

(composition of pigment dispersion)

Red pigment (C.I. Pigment Red 254): 20 parts

Pigment dispersant (made by AVECIA: Solsperse 24000): 15 parts

DPMA (dipropylene glycol methyl ether acetate): 65 parts

(2) Modulation of color filter with green inkjet ink

In addition to 20 parts of Green Pigment (CI Pigment Green 36) and 20 parts of Yellow Pigment (CI Pigment Yellow 150), 20 parts of Red Pigment (CI Pigment Red 254) used in the preparation of the inkjet ink of the above Production Example 5 (1) was used. In addition, the green pigment dispersion and the yellow pigment dispersion were also treated in the same manner. 53 parts of the green pigment dispersion liquid and 47 parts of the yellow pigment dispersion liquid were mixed to prepare a green pigment dispersion liquid (G). Using the obtained green pigment dispersion (G), a green inkjet ink was prepared in the same manner as in the above red inkjet ink of (1).

(3) Modulation of color filter with blue inkjet ink

A blue pigment dispersion liquid was prepared in the same manner except that 10 parts of Blue pigment (C.I. Pigment Blue 15:6) was used instead of 20 parts of the Red pigment (C.I. Pigment Red 254) of the above Production Example 5 (1). Using the obtained blue pigment dispersion liquid, a blue inkjet ink was prepared in the same manner as in the above red inkjet ink of (1).

<Manufacturing Example 6; Modulation of Pigment Inkjet Ink for Color Filter> (1) Modulation of color filters with red inkjet inks

The Red pigment, the pigment dispersant, and the organic solvent were mixed in the following ratio, and 500 parts of zirconia beads having a diameter of 0.3 mm were added, and dispersed using a paint shaker for 4 hours to obtain a pigment dispersion liquid. 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 by Cib _a Specialty Chemicals Co., Ltd. After 0.5 parts of the initiator "Irgacure 369" was mixed, it was filtered using a filter paper having a pore size of 1.0 μm to obtain a red inkjet ink for a color filter.

(composition of pigment dispersion)

Red pigment (C.I. Pigment Red 254): 15 parts

Pigment dispersant (made by AVECIA: Solsperse 24000): 15 parts

DPMA (dipropylene glycol methyl ether acetate): 70 parts

(2) Modulation of color filter with green inkjet ink

In addition to using 15 parts of Green Pigment (CI Pigment Green 36) and 15 parts of Yellow Pigment (CI Pigment Yellow 150), instead of 15 parts of Red Pigment (CI Pigment Red 254) of the above Production Example 6 (1), the same treatment was used to prepare the pigment dispersion. Liquid (G1) and pigment dispersion (Y). 53 parts of the pigment dispersion liquid (G1) and 47 parts of the pigment dispersion liquid (Y) were mixed to prepare a green pigment dispersion liquid (G2). Using the obtained green pigment dispersion (G2), a green inkjet ink was prepared in the same manner as the above red inkjet ink.

(3) Modulation of color filter with blue inkjet ink

The pigment dispersion liquid (B) was prepared in the same manner except that 15 parts of Blue pigment (C.I. Pigment Blue 15:6) was used instead of 15 parts of the Red pigment (C.I. Pigment Red 254) of the above Production Example 6 (1). Using the obtained pigment dispersion liquid (B), a blue inkjet ink was prepared in the same manner as the above red inkjet ink.

<Comparative Example 1>

In the blue pixel forming portion partitioned by the black matrix of the same substrate of Example 1, the blue inkjet ink of Production Example 5 was adhered accurately and uniformly via the inkjet method. Next, the green inkjet ink of Production Example 5 was adhered accurately and uniformly to the green pixel forming portion of the same substrate via the inkjet method. Next, the red inkjet ink of Production Example 5 was accurately and uniformly attached via the inkjet method to the red pixel forming portion of the same substrate. Thereafter, it was prebaked on a hot plate at 180 ° C for 20 minutes, and exposed to light at 200 mJ/cm ² using a high-pressure mercury lamp, and then hardened at 230 ° C for 20 minutes.

RGB pixel pattern forming substrate, for 5 minutes, followed by IPA vapor in drying after cleaning in IPA, to set the substrate temperature 200 ℃, at 6 × 10 ^-3 Torr vacuum deposition to a thickness of 120nm ITO (indium tin oxide) electrode. The substrate on which the ITO film was formed was further immersed in IPA for 5 minutes, washed with IPA vapor, and then spin-coated with polyimine, and calcined at 180 ° C for 60 minutes to form an alignment film to obtain a color filter. .

<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 used in the production of Comparative Example 1.

[Evaluation method]

With respect to the pigment dispersion liquid, the transparent resin solution, and the inkjet ink (pigment ink) obtained in the above Production Examples 1 to 6, the viscosity and the discharge stability were evaluated by the following methods. Further, with respect to the color filters produced in the above Examples 1 to 8 and Comparative Examples 1 and 2, the presence or absence of whitening, presence or absence of color mixing, film thickness, and chromaticity were evaluated by the following methods.

(1) Viscosity

The measurement was carried out at 23 ° C using a rotary vibration type viscometer (VM-1G, manufactured by Yamaichi Electric Co., Ltd.).

(2) Spit out stability

The pigment dispersion liquid, the transparent resin solution, and the inkjet ink obtained in the above Examples and Comparative Examples were sprayed once on a photoprinting paper with a droplet size of 15 pL, and then stood for 5 minutes and then sprayed twice, repeatedly. Spray 5 times after 5 minutes of standby. This repetitive process was subjected to four printing inks, and the clogging of the nozzle was evaluated by visual analysis. ○ indicates that there is no change from the initial state, Δ indicates that the portion is not printed, and × indicates that the portion is not completely suppressed.

(3) off white color mixing

With respect to the color filters prepared in the respective steps of the above Examples 1 to 8 and Comparative Examples 1 and 2, the number of defects per 100,000 (whitening, color mixing) was visually counted and evaluated.

(4) Film thickness

The color filter produced was observed with a laser microscope (manufactured by Olympus Co., Ltd.), and the film thickness was measured.

(5) Chroma

The chromaticity of each colored layer of the produced color filter was measured using a microscopic spectroscopic side light device (manufactured by Hamamatsu Hotonix Co., Ltd., trade name "PMA-11").

[Evaluation results] (1) Evaluation of inks, etc.

Table 1 shows the evaluation results of the pigment dispersion liquid, the transparent resin solution (transparent resin composition), the inkjet ink (pigment ink) pigment concentration, the viscosity, and the ink jet discharge stability obtained in the above Production Examples 1 to 6. Compared with the pigment ink, it is understood that the pigment dispersion liquid and the transparent resin solution have a low viscosity and are excellent in inkjet discharge.

(2) Evaluation of color filters

The color filters prepared in the above Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated in Table 2 for the results of whether or not the whitening, the presence or absence of color mixing, the film thickness, and the chromaticity were evaluated. The color filter produced in Comparative Example 1 was observed to have whitening due to lack of ink nozzles, and the color filter produced in Comparative Example 2 was observed to have color mixture due to ink bleeding. The color filters produced in 1 to 8 are known to have no color mixing and whitening.

In the above Table 2, the "drying temperature (A)" indicates the drying temperature in the pre-drying step after the application of the pigment dispersion liquid, and the "drying temperature (B)" indicates the pre-baking step after the application of the transparent resin solution. Drying temperature (heat treatment temperature).

In addition, the "solid content ratio" is a solid content ratio after drying of the pigment dispersion liquid and the transparent resin solution (solid content ratio of the pigment and the transparent resin after the mixed liquid layer is cured = pigment: transparent resin). The "boiling point of the solvent" is the boiling point of the dispersion solvent of the pigment dispersion liquid.

(industrial availability)

According to the present invention, it is possible to produce a color filter having high color purity and color reproducibility by using an inkjet ink which is excellent in straightness and stability when discharged from a head, and therefore has high reliability and high reliability. Color filter. In particular, it is possible to manufacture a color filter in which a pixel portion having a large penetration density and uniformity and no discoloration is precisely formed and brightness is improved. Therefore, by using the color filter excellent in performance obtained by the method of the present invention, a liquid crystal display element excellent in color display characteristics can be provided in a good yield, and a high quality liquid crystal display device can be manufactured.

Claims (12)

A method of producing a color filter, comprising the step of selectively applying a pigment dispersion liquid composed of a pigment, a pigment dispersant, and a solvent by a gap of a spacer included in a transparent insulating substrate (Pigment Dispersion Coating Step), and after the pigment dispersion coating step, selectively applying a transparent resin solution by inkjet in a gap of the aforementioned spacer, and mixing the pigment dispersion and the transparent resin in the gap The step of the solution (the transparent resin solution coating step), and the step of hardening the mixed layer of the pigment dispersion liquid and the transparent resin solution formed by the aforementioned transparent resin solution coating step (hardening step). The method of producing a color filter according to the first aspect of the invention, wherein the thickness of the coloring liquid layer formed by the pigment dispersion coating step is 0.4 to 2 μm. The method of producing a color filter according to the first or second aspect of the invention, wherein the mixed liquid layer is formed to have the same film thickness as the spacer. The method for producing a color filter according to claim 1 or 2, wherein in the step of coating the pigment dispersion, the coloring liquid layer formed by coating the pigment dispersion is dried at a temperature of 40 to 160 ° C. . The method for producing a color filter according to claim 1 or 2, wherein in the coating step of the transparent resin solution, the mixed layer obtained by mixing the pigment dispersion and the transparent resin solution is at 80 to 200 ° C. The temperature is dry. For example, the manufacturer of the color filter of claim 4 In the method of coating the transparent resin solution, the mixed layer obtained by mixing the pigment dispersion and the transparent resin solution is dried at a temperature of 80 to 200 °C. The method for producing a color filter according to the first or second aspect of the invention, wherein the ratio of solid content of the pigment to the transparent resin in the mixed liquid layer obtained by curing the mixed liquid layer is 1:0.4 to 1. The method for producing a color filter according to claim 1 or 2, wherein the solvent in the pigment dispersion is dipropylene glycol methyl ether acetate or diethylene glycol n-butyl ether acetate. The method for producing a color filter according to the fourth aspect of the invention, wherein the solvent in the pigment dispersion is dipropylene glycol methyl ether acetate or diethylene glycol n-butyl ether acetate. The method for producing a color filter according to the first or second aspect of the invention, wherein the transparent resin composition contained in the transparent resin solution is composed of a photocurable resin composition. The method for producing a color filter according to the fifth aspect of the invention, wherein the transparent resin composition contained in the transparent resin solution is composed of a photocurable resin composition. A liquid crystal display device comprising a color filter manufactured according to the manufacturing method of the first or second aspect of the patent application, and a counter substrate, and the color filter and the counter substrate The liquid crystal composition sandwiched between them.