JP2016085323A - Method for manufacturing color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a color filter directly on a substrate having a heatproof temperature of 150°C or lower.SOLUTION: A color filter is manufactured by using the following photosensitive resin composition and by applying and curing the composition at an ambient temperature not exceeding the heatproof temperature of the substrate. The photosensitive resin composition comprises: (A) a compound obtained by reacting a cyclic acid anhydride with a hydroxy group-containing compound that is obtained by the reaction of a bisphenol fluorene type epoxy compound with an ethylenically unsaturated bond group-containing carboxylic acid; (B) a polymerizable monomer having at least one ethylenically unsaturated bond; and (C) a photopolymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to a color filter manufacturing method and a color filter. In particular, the present invention relates to a method for producing a color filter on a substrate having a heat-resistant temperature of 150 ° C. or lower and a color filter produced by such a production method.

  Currently, color filters are widely used for colorization of liquid crystal display devices, white organic EL devices, solid-state imaging devices, and the like. As a method for forming a color filter on a substrate, photolithography using a photosensitive resin composition has been the mainstream, and until now, a relatively high heat-resistant substrate such as glass or silicon wafer has been used for photosensitivity. It has been performed that the resin composition is treated at a high temperature of 200 ° C. or higher (also referred to as post-baking) and finally cured.

  Recently, for the purpose of making a device flexible or one-chip, it is required to form a color filter directly on a plastic substrate or a white organic EL device. However, these base materials have poor heat resistance and may have a heat resistance temperature of about 150 ° C. at most. When a color filter is manufactured for a substrate having such a low heat resistant temperature, the first color filter is formed by forming the color filter portion of the first color at 150 ° C. or less (below the heat resistant temperature of the substrate). The portion had a problem that the strength of the cured film was insufficient and color bleeding occurred when the second color was applied.

  In order to avoid the restriction of the heat-resistant temperature of the substrate, there is a proposal for a special manufacturing method. For example, Patent Document 1 discloses a method of manufacturing a color filter by flexographic printing of UV curable ink, and Patent Document 2 discloses a method of manufacturing a color filter by irradiating a pattern with an electron beam.

  On the other hand, Patent Documents 3 and 4 disclose a method of manufacturing a color filter that performs post-exposure.

JP 2003-107226 A JP 2010-107928 A JP-A-11-174221 JP 2008-65150 A

  However, in the special methods as described in Patent Documents 1 and 2, the quality and yield of the color filter are likely to be problems as compared with the conventional methods. Considering productivity, it is most advantageous that a color filter can be formed without using a special manufacturing method, and a photosensitive resin composition that can be used suitably for such purposes has been strongly desired.

  Patent Documents 3 and 4 do not mention any color filter formation on a substrate having a low heat-resistant temperature.

  The present invention has been made in view of the problems of the prior art, and provides a method for producing a color filter that can directly form a color filter on a substrate having a low heat-resistant temperature, such as a plastic substrate or a white organic EL device. The purpose is to provide.

  As a result of studies to solve the above problems, the present inventors have found that a photosensitive resin composition using a compound having a specific structure is suitable for this purpose, and completed the present invention.

  That is, the present invention provides photosensitivity for a color filter of a second color different from the first color on a base material on which a color filter portion of the first color obtained by curing the photosensitive resin composition is formed. A method for producing a color filter comprising a step of applying and curing a resin composition, wherein the photosensitive resin composition comprises (A) a bisphenolfluorene type epoxy compound and an ethylenically unsaturated bond group-containing carboxylic acid. A compound obtained by reacting a cyclic acid anhydride with the reacted hydroxy group-containing compound, (B) a polymerizable monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator. And the heat resistance temperature of the base material is 150 ° C. or less, and the process is performed at an environmental temperature not exceeding the heat resistance temperature of the base material.

  Here, the manufacturing method includes (a) a step of applying a photosensitive resin composition to a substrate, (b) a step of drying the photosensitive resin composition, and (c) a step of exposing the photosensitive resin composition to an image. (D) preferably includes a step of developing the photosensitive resin composition, and (e) a step of post-exposure of the photosensitive resin composition, and each of the red, green and blue photosensitive resin compositions is included. It is preferably used to form a color filter. Furthermore, the present invention is a color filter manufactured by any one of the methods described above.

Hereinafter, the present invention will be described in detail.
In the production method of the present invention, a photosensitive material for a color filter of a second color different from the first color is formed on a substrate on which a color filter portion of the first color obtained by curing the photosensitive resin composition is formed. The process of apply | coating an adhesive resin composition is included. Forming a color filter using a plurality of photosensitive resin compositions having different hues is widely performed. Typically, a pixel is formed using three types of photosensitive resin compositions of red, green, and blue. It is formed. In addition, yellow, orange, purple, cyan, magenta, and the like are used as necessary, and transparent pixels are added to improve screen brightness. Furthermore, it is also common to form a structure (also referred to as a black matrix) for shielding light between the peripheral portion of the screen and between pixels using a black or light-shielding photosensitive resin composition. The hue of the photosensitive resin composition used in the present invention is not particularly limited, and may be other than the hue described above.

  The production method of the present invention is characterized in that a substrate having a heat resistant temperature of 150 ° C. or lower is used at an environmental temperature not exceeding the heat resistant temperature of the substrate. The heat-resistant temperature of a base material means the upper limit of the temperature at which no dimensional change or characteristic change occurs that affects the function of the device in manufacturing a device using the base material. An example of a plastic substrate is a PET film. Generally, the temperature is about 100 ° C., and the PEN film is about 150 ° C. When a white organic EL device is used as a base material, since the organic EL element is vulnerable to heat, about 100 ° C. is often the heat resistant temperature as in the case of a PET film. In addition, the fact that the color filter is manufactured at an environmental temperature that does not exceed the heat resistance temperature of the base material does not simply mean the temperature set on the equipment, but the base material and the base material in all steps of the process. It means that the upper photosensitive resin composition does not reach a temperature exceeding the heat resistance temperature of the substrate.

  The photosensitive resin composition used in the production method of the present invention reacts a cyclic acid anhydride with a hydroxy group-containing compound obtained by reacting (A) a bisphenolfluorene type epoxy compound and an ethylenically unsaturated bond group-containing carboxylic acid. And (B) a polymerizable monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator. The component A is a compound obtained by reacting a cyclic acid anhydride with a hydroxy group-containing compound obtained by reacting a bisphenolfluorene type epoxy compound and an ethylenically unsaturated bond group-containing carboxylic acid. Such a compound is known as a photosensitive resin, and examples thereof include compounds described in JP-A-5-339356. As a preferable range of the physical property of A component, a weight average molecular weight is 1,000-20,000, More preferably, it is 2,000-10,000, An acid value is 50-150 mgKOH / g, More preferably, 70-120 mgKOH / g can be illustrated. As the component A, only one type of compound may be used, or a plurality may be used in combination.

  In the present invention, the weight average molecular weight of the component A is obtained by dissolving the sampled solution in tetrahydrofuran, measuring the molecular weight distribution with HLC-8220GPC manufactured by Tosoh Corporation, and calculating the weight average molecular weight in terms of standard polystyrene. The acid value of component A is determined by dissolving the sampled solution in a mixed solution of tetrahydrofuran and water and neutralizing with a 0.1N aqueous potassium hydroxide solution, and calculating the acid value in terms of solid content of the sample solution from the equivalence point. Use the calculated value.

  The bisphenol fluorene type epoxy compound used as a raw material for the synthesis of the component A refers to a compound represented by the following general formula (1), and particularly refers to a compound having a value of n in the range of 0-20. Practically, the average value of n is preferably 0 to 2, and more preferably 0.1 to 1.0.

（ただし、Ｒはそれぞれ独立に炭素数１〜２０の飽和又は不飽和の炭化水素基を表し、ｍはＲの数を表し、ｍはそれぞれ独立に０〜４の数を表す。上記炭化水素基は、好ましくは炭素数１〜６のアルキル基又はフェニル基である。）

(However, R represents a C1-C20 saturated or unsaturated hydrocarbon group each independently, m represents the number of R, m represents the number of 0-4 each independently. The said hydrocarbon group. Is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

  The method for synthesizing the bisphenolfluorene type epoxy compound is not particularly limited, but the method described in JP-A-9-328534, that is, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are condensed in the presence of an alkali. The most common and preferred method. 9,9-bis (4-hydroxyphenyl) fluorene may be substituted with m R as shown in the general formula (1). The value of n is the degree of polymerization of the epoxy compound, and can be set to a desired value by adjusting the molar ratio of the raw material compounds and reaction conditions during synthesis.

  When a bisphenolfluorene type epoxy compound is reacted with an ethylenically unsaturated bond group-containing carboxylic acid, a hydroxy group-containing compound, which is a synthetic intermediate of component A, is obtained. Specific examples of the ethylenically unsaturated bond group-containing carboxylic acid include (meth) acrylic acid, (meth) acrylic acid dimer, 2-hydroxyethyl (meth) acrylate and succinic anhydride half ester, 2-hydroxyethyl (Meth) acrylate and phthalic anhydride half ester, 2-hydroxyethyl (meth) acrylate and cyclohexane-1,2-dicarboxylic anhydride half ester, 4-vinylbenzoic acid, etc. Acid is most preferred. Here, (meth) acrylic acid refers to acrylic acid or methacrylic acid, and (meth) acrylate refers to acrylate or methacrylate (and so on).

  The method of reacting the bisphenolfluorene type epoxy compound with the ethylenically unsaturated bond group-containing carboxylic acid is not particularly limited, but the method described in JP-A-3-205417, that is, the method of reacting by heating in the presence of a catalyst, The most common and preferred. As the catalyst, tertiary amine, quaternary ammonium salt, tertiary phosphine, quaternary phosphonium salt and the like can be used. Ideally, it is desirable that the epoxy group of the bisphenolfluorene type epoxy compound and the carboxy group of the carboxylic acid containing the ethylenically unsaturated bond group are reacted one-to-one to completely convert the functional group into an ester bond and a hydroxy group. However, the reaction may be terminated when the necessary and sufficient reaction rate is reached due to the restriction of the time required for the reaction and the concern about the progress of the side reaction. The reaction rate can be calculated by measuring the epoxy equivalent and the acid value. Generally, it is sufficient that the reaction rate reaches 98 mol% or more.

  The compound of component A is obtained by reacting the thus obtained hydroxy group-containing compound with a cyclic acid anhydride. Here, the cyclic acid anhydride refers to an intramolecular acid anhydride of a polyvalent carboxylic acid, such as succinic anhydride, maleic anhydride, cyclohexane-1,2-dicarboxylic anhydride, cyclohexene-1,2-dicarboxylic anhydride. , Cyclohexene-4,5-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, phthalic anhydride, benzene-1,2,4-tricarboxylic acid-1,2-anhydride, cyclohexane-1, 2,4-tricarboxylic acid-1,2-anhydride, benzene-1,2,4,5-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, butane 1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic Dianhydride, diphenylsulfone-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-[1,1,1,3,3 , 3-hexafluoropropane-2,2-diyl] diphthalic dianhydride and the like. A 6-membered acid anhydride such as glutaric acid anhydride can also be used.

  The method of reacting the cyclic acid anhydride with the hydroxy group-containing compound is not particularly limited, but the method described in JP-A-5-339356, that is, the method of heating and reacting in the presence of a catalyst is the most common and preferred. As the catalyst, tertiary amine, quaternary ammonium salt, tertiary phosphine, quaternary phosphonium salt and the like can be used. Cyclic acid anhydrides have the effect of imparting an acid value to the compound by half-esterifying the hydroxy group and converting it to a carboxy group, but if acid dianhydride is selected, it becomes a crosslinking point and simultaneously increases the molecular weight It is useful because it can. Among them, the method of controlling both the acid value and the molecular weight by using both acid dianhydride and acid monoanhydride is particularly advantageous, and 0.01 to 10 mol of acid monoanhydride is used per 1 mol of acid dianhydride. It is preferable to use a combination in the range. The addition amount of the cyclic acid anhydride with respect to the hydroxy group may be set according to the target acid value, but is preferably 0.5 to 1.0 mol with respect to 1 mol of the hydroxy group. The progress of the reaction can be confirmed by observing the characteristic absorption spectrum of the acid anhydride group by infrared spectroscopy.

  Component A is derived from heat resistance and optical properties derived from the bisphenolfluorene skeleton (high transparency, high refractive index, low birefringence), polymerizability derived from ethylenically unsaturated bond group-containing carboxylic acid, and cyclic acid anhydride. Since it has alkali solubility, it is a compound that can be suitably used for a photosensitive resin composition for color filters. When a color filter is directly formed on a substrate having a low heat-resistant temperature, final curing by post-baking is limited, so that the degree of curing of the photosensitive resin composition is lower than that of the conventional manufacturing method. Has the advantage that a high cured film physical property can be obtained even at a low degree of curing because of the uniqueness of the structure that a rigid bisphenolfluorene skeleton is incorporated into the curing system. Therefore, the photosensitive resin composition using the component A can be suitably used for forming a direct color filter on a substrate having a low heat resistance temperature. On the other hand, if the component A is not used, it will be difficult to impart sufficient physical properties to the cured film. For example, the three color pixels of the color filter will be formed sequentially. This causes a problem that the photosensitive resin composition is attacked.

  Component B is a polymerizable monomer having at least one ethylenically unsaturated bond, and any known compound conventionally used in photosensitive materials can be used without particular limitation. Specifically, (meta) such as diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. ) Acrylic acid ester derivatives, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenolfluorene type epoxy di (meth) acrylate, phenol novolac type epoxy poly (meth) acrylate, cresol novolac type epoxy poly ( Examples include (meth) acrylic acid epoxy ester derivatives such as (meth) acrylate. In addition, a reaction product of the above (meth) acrylic acid derivative and a compound having an (preferably plural) isocyanate group or an acid anhydride group in the structure is also suitable (however, a compound corresponding to the component A is except). In addition to (meth) acrylic acid derivatives, maleic acid derivatives, maleimide derivatives, crotonic acid derivatives, itaconic acid derivatives, cinnamic acid derivatives, vinyl derivatives, vinyl alcohol derivatives, vinyl ketone derivatives, vinyl aromatic derivatives, etc. it can. These compounds having an ethylenically unsaturated bond may further have a thermal functional group such as an epoxy group, an alkali-soluble functional group such as a carboxy group, etc. Good. As the component B, only one type of compound may be used, or a plurality may be used in combination.

Component C is a photopolymerization initiator, and known compounds conventionally used in photosensitive materials can be used without particular limitation. Specifically, acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, benzophenone, 2,4,6-trimethylbenzophenone, 4,4′-bis ( Benzophenone compounds such as N, N-diethylamino) benzophenone, benzoin ether compounds such as benzoin ethyl ether and benzoin-tert-butyl ether, 2-methyl-1- [4- (methylsulfanyl) phenyl] -2-morpholinopropane-1- Thioxanthone such as ON, α-aminoalkylphenone compounds such as 2-benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one, thioxanthone and 2,4-diethylthioxanthone Compound, 3,3 ′, , 4'-tetrakis (tert-butylperoxycarbonyl) benzophenone and other organic peroxides, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2-bi Biimidazole compounds such as imidazole, titanocene compounds such as bis (η ⁵ -cyclopentadienyl) bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] titanium, 2,4,6-tris (trichloromethyl) ) -1,3,5-triazine, triazine compounds such as 2- [3,4- (methylenedioxy) phenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, (2, Acyl phosphines such as 4,6-trimethylbenzoyl) diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Quinone compounds such as tin oxide compounds, camphorquinone, 1- [4- (phenylsulfanyl) phenyl] octane-1,2-dione = 2-O-benzoyloxime, 1- [9-ethyl-6- (2-methylbenzoyl) ) Carbazol-3-yl] ethanone = O-acetyloxime, (9-ethyl-6-nitrocarbazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone = O -Although oxime ester compounds, such as acetyl oxime, can be mentioned, an oxime ester compound is especially preferable. As the component C, only one type of compound may be used, or a plurality of components may be used in combination.

  In addition, as the oxime ester compound of component C, a compound represented by the following general formula (2) is also suitable, which is very sensitive and has little discoloration (yellowing) due to exposure. Suitable for

（ただし、Ｒ^１〜Ｒ^１１はそれぞれ独立に水素原子又は１価の有機基を表す。上記１価の有機基は、好ましくは炭素数１〜２０の飽和又は不飽和の炭化水素基であり、より好ましくは炭素数１〜１０のアルキル基（メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、デシル基、イソプロピル基、２−エチルヘキシル基、シクロヘキシル基等）、炭素数６〜１０のアリール基（フェニル基、ナフチル基等）、炭素数６〜１０のアリール基で置換された炭素数１〜４のアルキル基（フェニルメチル基、２−フェニルエチル基、ナフタレン−１−イルメチル基等）、及び炭素数１〜４のアルキル基で置換された炭素数６〜１０のアリール基（２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２，４−ジメチルフェニル基、２，４，６−トリメチルフェニル基、２−エチルフェニル基、４−メチルナフタレン−１−イル基等）である。上記のアルキル基は分岐構造や環構造を有していてもよい。）

(However, R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, More preferably, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, isopropyl group, 2-ethylhexyl group, cyclohexyl group, etc.) 10 aryl groups (phenyl group, naphthyl group, etc.), alkyl groups having 1 to 4 carbon atoms substituted with aryl groups having 6 to 10 carbon atoms (phenylmethyl group, 2-phenylethyl group, naphthalen-1-ylmethyl group) Etc.), and an aryl group having 6 to 10 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms (2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4- Methylphenyl group, 2,4,6-trimethylphenyl group, 2-ethylphenyl group, 4-methylnaphthalen-1-yl group, etc.) The alkyl group may have a branched structure or a ring structure. Good.)

  The photosensitive resin composition used in the present invention preferably contains (D) a pigment, (E) a dispersant, and (Z) a solvent as components other than the components A to C.

  The component D is a pigment, and known compounds (organic pigments, inorganic pigments, carbon black, titanium black, etc.) known as colorants for color filters can be used without particular limitation. The photosensitive resin composition for forming the color filter pixels (red, green, blue, etc.) preferably contains an organic pigment as component D, and more specifically, an azo pigment, a condensed azo pigment, or an azomethine pigment. Phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, dioxazine pigment, selenium pigment, perylene pigment, perinone pigment, quinophthalone pigment, diketopyrrolopyrrole pigment, thioindigo pigment and the like. Color index names of organic pigments include Pigment Red 2, 3, 3, 4, 9, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202 207, 208, 209, 210, 213, 214, 220, 221, 222, 247, 253, 254, 255, 256, 257, 262, H.264, 266, 272, 279, Pigment Orange 5, 13, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74 81, Pigment Yellow 1, 3, 12, 12, 13, 16, 17, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154 155, 173, 174, 175, 176, 176, 180, 181, 183, 185, 191, 191, 194, 199, 213, 214, Pigment Green 7, 36 58, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, 80, Pigment Violet 19, 23 And 37 etc. That. As the component D, only one kind of compound may be used, or a plurality thereof may be used in combination. In order to control the color characteristics of the color filter, it is common to select and use a plurality of organic pigments at a predetermined ratio.

The organic pigment is preferably subjected to atomization and has a specific surface area of 50 m ² / g or more by the BET method. As the method for atomizing the organic pigment, known methods can be used, and examples thereof include a dry milling method, a solvent milling method, a salt milling method, a solvent salt milling method, an acid pasting method, and an acid slurry method. In atomization, it is important to make the particle size uniform and at the same time make the particle size uniform.

  The component E is a dispersant, and known compounds conventionally used for dispersing pigments and the like, for example, compounds commercially available under the names of dispersants, dispersion stabilizers, dispersion wetting agents, dispersion accelerators, etc. As long as the above effect can be obtained, it can be used without particular limitation. Examples of the dispersant effective for stabilizing the dispersion of the pigment include a cationic polymer dispersant, an anionic polymer dispersant, a nonionic polymer dispersant, and a pigment derivative type dispersant (dispersion aid). In particular, it has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to the pigment, and an amine value of 1 to 100 mgKOH / g, number A cationic polymer dispersant having an average molecular weight in the range of 1,000 to 100,000 is preferred. Examples of such cationic polymer dispersants are disclosed in JP-A-9-169821. As the E component, only one kind of compound may be used, or a plurality thereof may be used in combination. Examples of commercially available E ingredients include “BYK (registered trademark)” series manufactured by BYK Chemie, “Efka (registered trademark)” series manufactured by BASF, “Solspers (registered trademark)” series manufactured by Lubrizol, and Ajinomoto Fine Techno. “Ajisper” (registered trademark of Ajinomoto Co., Inc.) series manufactured by the company. High viscosity substances such as resins generally have an action of stabilizing the dispersion, but those not having the ability to promote dispersion are not treated as dispersants. However, the present invention does not limit the use of high viscosity materials such as resins for the purpose of stabilizing dispersion.

  Z component is a solvent, for example, ester solvents (butyl acetate, cyclohexyl acetate, etc.), ketone solvents (methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, etc.), alcohol solvents ( 3-methoxybutanol, ethylene glycol mono-t-butyl ether, etc.), aromatic solvents (toluene, xylene, etc.), aliphatic solvents, amine solvents, amide solvents, and other known solvents are used without particular limitation. Can do. From the viewpoint of safety, ester or ether solvents having a propylene glycol skeleton, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl. Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate and the like are preferably used. Further, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 1,3-butylene glycol diacetate and the like having a similar structure are also preferable. As the Z component, only one kind of compound may be used, or a plurality of compounds may be used in combination. However, in the present invention, a solvent having a boiling point of less than 150 ° C. at normal pressure is used to reduce the amount of the solvent remaining in the cured film. As a main component, it is advantageous to use a solvent having a boiling point of 150 ° C. or higher at normal pressure within 20% by weight of the total solvent. In addition, although there is no restriction | limiting in particular about the solid content density | concentration of the photosensitive resin composition used by this invention, It is common to adjust to the range of 10 to 30 weight%.

  The weight ratio of each component in the photosensitive resin composition of the present invention is as follows: A: B: C: D: E = (1-80) :( 1-50) : (0.1-10) :( 0-80) :( 0-40) are preferable, (5-60) :( 5-40) :( 0.5-5) :( 10-70) :( 2-30) is more preferable, and (10-40) :( 10-30) :( 1-3) :( 20-60) :( 4-20) is the most preferable. In order to improve the color purity by reducing the thickness of the color filter, it is important to increase the content of the D component. However, according to the production method of the present invention, the substrate having a low heat resistance temperature even under such high pigment concentration conditions. It is possible to form a color filter. Furthermore, you may add another preferable component within 30 weight% with respect to the sum total of AE component.

  Examples of other preferable components include resins such as epoxy resins, vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, melamine resins, crosslinking agents, surfactants, and silane cups. Known compounds applied to color filter photosensitive resin compositions, such as ring agents, viscosity modifiers, wetting agents, antifoaming agents, antioxidants, ultraviolet absorbers, chain transfer agents, etc. As long as the above effect can be obtained, it can be used without particular limitation. More specifically, epoxy resins (bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, tetramethylbiphenyl type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, many Glycidyl ether of polyhydric alcohol, glycidyl ester of polyvalent carboxylic acid, polymer containing glycidyl (meth) acrylate as a unit, alicyclic typified by 3,4-epoxycyclohexanecarboxylic acid (3,4-epoxycyclohexyl) methyl 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of a formula epoxy compound, 2,2-bis (hydroxymethyl) -1-butanol (for example, “EHPE3150” manufactured by Daicel), Poxylated polybutadiene (for example, “Nisso-PB / JP-100” manufactured by Nippon Soda Co., Ltd.), epoxy compounds having a silicone skeleton, etc., surfactants (fluorinated surfactants (for example, “Megafuck” manufactured by DIC) ”Series), silicone surfactants (for example,“ FZ ”series manufactured by Toray Dow Corning), etc., and silane coupling agents (3- (glycidyloxy) propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane) , 3-ureidopropyltriethoxysilane, etc.). Moreover, colorants other than pigments, such as fillers, such as a silica and a talc, and organic dyes, can also be used.

  In addition, you may use a thermal-polymerization initiator as another preferable component. As the thermal polymerization initiator, known azo compounds and peroxide compounds can be used, but 1,1′-azobis (1-acetoxy-1-phenylethane) having high compatibility with the photosensitive resin composition, 2,2'-azobis (2-methylpropionic acid) dimethyl, benzoyl peroxide and the like are preferable. The 10-hour half-life temperature of the thermal polymerization initiator is advantageously 50 to 80 ° C., and such a thermal polymerization initiator cures the photosensitive resin composition even at an environmental temperature not exceeding the heat resistance temperature of the substrate. Can be promoted. On the other hand, a thermal polymerization initiator having a 10-hour half-life temperature of less than 50 ° C. is too reactive and may reduce the storage stability of the photosensitive resin composition.

  The photosensitive resin composition of the present invention can be preferably used as a negative photolithography material due to the above-described configuration. In negative photolithography, a portion selectively irradiated with light by image exposure (also referred to as an exposure portion) is patterned as a cured film. On the other hand, a portion that is not irradiated with light (also referred to as an unexposed portion) is removed in the development process.

  In the production method of the present invention, the step of forming each color filter includes (a) a step of applying a photosensitive resin composition to a substrate, (b) a step of drying the photosensitive resin composition, and (c) photosensitivity. It is preferable to sequentially include a step of image-exposing the photosensitive resin composition, (d) a step of developing the photosensitive resin composition, and (e) a step of post-exposing the photosensitive resin composition. Here, including in order means that the steps (a) to (e) are performed without changing the order, but the steps (a) to (e) are not necessarily performed continuously. Another process (for example, a transport process etc.) may be included in the meantime.

  (A) In the step of applying the photosensitive resin composition to the substrate, the photosensitive resin composition is applied to the substrate using a known coating apparatus. Examples of the coating apparatus include a spin coater, a slit coater, a bar coater, a curtain coater, and a spray coater, and a spin coater and a slit coater are preferable. The coating conditions are affected by the solid content concentration and viscosity of the photosensitive resin composition, but may be adjusted so that a desired film thickness is obtained in the coating apparatus to be used.

  (A) In the step of drying the photosensitive resin composition, the photosensitive resin composition on the substrate is dried using a known drying apparatus. Examples of the drying device include a vacuum dryer, a hot plate, and an oven. A vacuum dryer and a hot plate are preferable. After drying, the solvent in the photosensitive resin composition must be removed to form a smooth coating film. The solid content concentration of the photosensitive resin composition, the film thickness to be formed, the boiling point of the solvent used, etc. Adjust the conditions in consideration of Examples of the drying conditions include 1 to 100 Pa as the ultimate pressure for drying under reduced pressure, and 50 to 100 ° C. for 1 to 10 minutes as heat drying. In the case of heat drying, attention should be paid to the upper limit of the temperature so that the heat resistant temperature of the substrate is not exceeded.

(C) In the step of exposing the photosensitive resin composition to an image, the photosensitive resin composition on the substrate is selectively irradiated with light using a known photolithography exposure machine and photomask. Examples of the light source for exposure include a xenon lamp, a halogen lamp, a tungsten lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, and an LED lamp. A light source (such as an ultra-high pressure mercury lamp) containing ultraviolet light is preferred. Examples of the light irradiation condition include a reference of 365 nm, an illuminance of 1 to 100 mW / cm ² , and an exposure amount of 10 to 1000 mJ / cm ² . Further, a method (direct imaging) in which an image is directly drawn using a laser or the like as a light source without using a photomask can be applied.

  (D) In the step of developing the photosensitive resin composition, the photosensitive resin composition in the unexposed area is removed using a known developer. The developer is not particularly limited as long as it is a developer that dissolves unexposed portions and does not dissolve exposed portions, but is preferably an alkaline aqueous solution containing various additives. Examples of the alkali component of the developer include alkali metal carbonates, alkali metal hydroxides, and quaternary ammonium hydroxides. The concentration of the alkali component is preferably 0.001 to 5% by weight in the developer, and more preferably 0.01 to 0.5% by weight. Further, as the additive, for example, a surfactant, an antifoaming agent, an antifungal agent and the like can be applied, but it is particularly preferable to use 0.001 to 5% by weight of a nonionic surfactant in the developer. . From the viewpoint of environmental load, the alkali development method is advantageous, and the constitution of the photosensitive resin composition shown in the present invention corresponds to that, but a solvent development method using an organic solvent can also be applied. As a developing method, a known method can be used, and examples thereof include immersion development, paddle development, shower development, spray development, brush development, and ultrasonic development. Although the development conditions are affected by the dissolution rate of the photosensitive resin composition and the film thickness thereof, the temperature of the developer can be 10 to 30 ° C., and the processing time can be 10 to 120 seconds. After development, it is preferable to thoroughly drain with pure water to wash away the developer components, and then drain and dry.

(E) In the step of post-exposure of the photosensitive resin composition, exposure is performed again after development in order to increase the strength of the cured film formed with an image. The post-exposure may use the same light source as that of the image exposure, but it is preferable to use a light source having a shorter wavelength. For example, light irradiation with a low-pressure mercury lamp is effective. Since the post-exposure is not intended for image formation, irradiation with scattered light may be performed, and irradiation may be performed from both sides of the substrate if possible. Conditions of light irradiation, for example at 254nm reference, 1 to 100 mW / cm ² as illuminance, the exposure can be mentioned 100~10000mJ / cm ^2.

  In addition, you may perform thermosetting at the temperature which does not exceed the heat-resistant temperature of a base material before or after a process (e), or simultaneously with a process (e). For example, heat baking can be performed at 100 to 150 ° C. for 1 to 60 minutes using a hot plate or an oven.

  The production method of the present invention is most suitable when a color filter is formed using each of the red, green and blue photosensitive resin compositions, and the first color photosensitive resin composition with the solvent of the second color photosensitive resin composition. The process can proceed without causing the problem that the cured film of the conductive resin composition is eroded. In addition, as a specific color filter design and a method for producing the same, a known method can be used.

  The production method of the present invention is extremely useful because a color filter can be directly formed on a substrate having a low heat-resistant temperature, such as a plastic substrate or a white organic EL device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. The number of parts and percentage (%) represent parts by weight and percentage by weight (% by weight) unless otherwise specified.

The components used in Examples and Comparative Examples are shown below.
A-1 to 3: Components synthesized in Synthesis Examples 1 to 3 (solid content of 50% solution)
AX-1: component synthesized in Synthesis Example 4 (solid content of 50% solution)
B-1: Dipentaerythritol hexaacrylate B-2: Pentaerythritol tetraacrylate C-1: 1- [4- (phenylsulfanyl) phenyl] octane-1,2-dione = 2-O-benzoyloxime C-2: 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] ethanone = O-acetyloxime C-3: 1- [7- (2-methylbenzoyl) -9,9-dipropyl-9H -Fluoren-2-yl] ethanone = O-acetyloxime (In the general formula (2), R ¹ · R ³ · R ⁴ · R ⁵ · R ⁶ · R ⁸ = hydrogen atom, R ² · R ¹¹ = methyl group , R ⁷ = 2-methylphenyl group, R ⁹ · R ¹⁰ = propyl group)
D-1: Atomized Pigment Red 177 (specific surface area of 70 m ² / g by BET method)
D-2: Atomized Pigment Red 254 (specific surface area 85 m ² / g by BET method)
D-3: Atomized pigment green 36 (specific surface area 65 m ² / g by BET method)
D-4: Atomized pigment green 58 (specific surface area 75 m ² / g by BET method)
D-5: Atomized Pigment Yellow 138 (specific surface area by BET method 70 m ² / g)
D-6: Atomized pigment blue 15: 6 (specific surface area by BET method 90 m ² / g)
D-7: Atomized pigment violet 23 (specific surface area of 50 m ² / g by BET method)
E-1: “Ajisper PB822” manufactured by Ajinomoto Fine Techno Co., Ltd.
S-1: Random copolymer of methacrylic acid and benzyl methacrylate (solid content of an acid value of 100 mg KOH / g, weight average molecular weight 10,000, synthesized as a 35% solution of propylene glycol monomethyl ether acetate)
S-2: “EHPE3150” manufactured by Daicel Corporation
S-3: “FZ-2122” manufactured by Toray Dow Corning
Z-1: Propylene glycol monomethyl ether acetate Z-2: Propylene glycol diacetate Here, "A-", "B-", "C-", "D-", "E-", and "Z-" are A in the present invention. , B, C, D, E, and Z components, and “S-” indicates other components used as necessary. “AX-” indicates that it does not have the structure of the component A of the present invention.

[Synthesis example 1 of component A-1]
510 g of a bisphenolfluorene type epoxy compound (epoxy equivalent 255) represented by the general formula (1), 2.0 mol of acrylic acid (ethylenically unsaturated bond group-containing carboxylic acid), 0.10 mol of triphenylphosphine (catalyst), 0.05 mol of BHT (polymerization inhibitor) was dissolved in 255 g of propylene glycol monomethyl ether acetate and reacted at 100 ° C. while bubbling dry air. When the reaction rate of epoxy group and carboxy group reached 99 mol%, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride (cyclic acid anhydride) 0.50 mol and cyclohexene-4,5 -Dicarboxylic acid anhydride (cyclic acid anhydride) 0.50 mol was added, and it was made to react further. After confirming the consumption of the acid anhydride group by infrared spectroscopy, the solution was diluted with propylene glycol monomethyl ether acetate and cooled to room temperature to obtain a 50% solid content concentration solution of the A-1 component. The acid value of component A-1 was 96 mgKOH / g, and the weight average molecular weight was 4,000.

[Synthesis example 2 of component A-2]
630 g of a bisphenolfluorene type epoxy compound represented by the general formula (1) (epoxy equivalent 315), 2.0 mol of acrylic acid (ethylenically unsaturated bond group-containing carboxylic acid), 0.10 mol of triphenylphosphine (catalyst), 0.05 mol of BHT (polymerization inhibitor) was dissolved in 315 g of propylene glycol monomethyl ether acetate and reacted at 100 ° C. while bubbling dry air. When the reaction rate of epoxy group and carboxy group reached 99 mol%, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride (cyclic acid anhydride) 0.50 mol and cyclohexene-4,5 -Dicarboxylic acid anhydride (cyclic acid anhydride) 0.50 mol was added, and it was made to react further. After confirming consumption of the acid anhydride group by infrared spectroscopy, the solution was diluted with propylene glycol monomethyl ether acetate and cooled to room temperature to obtain a 50% solid content concentration solution of the A-2 component. The acid value of component A-2 was 84 mgKOH / g, and the weight average molecular weight was 6,000.

[Synthesis Example 3 of A-3 Component]
510 g of a bisphenolfluorene type epoxy compound (epoxy equivalent 255) represented by the general formula (1), 2.0 mol of acrylic acid (ethylenically unsaturated bond group-containing carboxylic acid), 0.10 mol of triphenylphosphine (catalyst), 0.05 mol of BHT (polymerization inhibitor) was dissolved in 255 g of propylene glycol monomethyl ether acetate and reacted at 100 ° C. while bubbling dry air. When the reaction rate of epoxy group and carboxy group reached 99 mol%, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride (cyclic acid anhydride) 0.65 mol and cyclohexene-4,5 -0.02 mol of dicarboxylic acid anhydride (cyclic acid anhydride) was added and further reacted. After confirming the consumption of the acid anhydride group by infrared spectroscopy, it was diluted with propylene glycol monomethyl ether acetate and cooled to room temperature to obtain a 50% solid content concentration solution of the A-3 component. The acid value of A-3 component was 87 mgKOH / g, and the weight average molecular weight was 9,000.

[Synthesis Example 4 of AX-1 Component]
370 g of bisphenol A type epoxy compound (epoxy equivalent 185), 2.0 mol of acrylic acid (ethylenically unsaturated bond group-containing carboxylic acid), 0.10 mol of triphenylphosphine (catalyst), 0.05 BHT (polymerization inhibitor) Mole was dissolved in 185 g of propylene glycol monomethyl ether acetate and reacted at 100 ° C. while bubbling dry air. When the reaction rate of epoxy group and carboxy group reached 99 mol%, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride (cyclic acid anhydride) 0.50 mol and cyclohexene-4,5 -Dicarboxylic acid anhydride (cyclic acid anhydride) 0.50 mol was added, and it was made to react further. After confirming the consumption of the acid anhydride group by infrared spectroscopy, it was diluted with propylene glycol monomethyl ether acetate and cooled to room temperature to obtain a 50% solid concentration solution of the AX-1 component. The acid value of the AX-1 component was 114 mgKOH / g, and the weight average molecular weight was 3,000.

[Preparation of photosensitive resin composition for color filter]
(Preparation Example 1 of photosensitive resin composition for color filter)
A part 50% solid content solution of A-1 (solution obtained in Synthesis Example 1) 10.0 parts, D-1 ingredient 6.0 parts, D-2 ingredient 6.0 parts, E-1 ingredient 3.0 And 75.0 parts of the Z-1 component are mixed and kept at a temperature of 30 ° C. or lower with cooling water until a stable state is achieved with a bead mill having an internal volume of 600 mL filled with 80% of zirconia beads having a diameter of 0.3 mm. A dispersion was obtained by dispersing at a peripheral speed of 8.5 m / s. Next, A-1 component 10.0 parts, B-1 component 2.0 parts, B-2 component 2.0 parts, C-1 component 0.4 parts, S-2 component 0.5 parts, S-3 0.1 part of a component, 20.0 parts of a Z-1 component, and 15.0 parts of a Z-2 component were mixed in the dispersion, and the mixture was stirred and mixed at room temperature for 3 hours using a mixer. Finally, pressure filtration was performed at a pressure of 0.05 MPa using a membrane filter having a filtration accuracy of 0.6 μm to obtain a red photosensitive resin composition for a color filter.

  Table 1 shows the production conditions of the photosensitive resin composition for a color filter of Preparation Example 1. In this table, only the solid content is described as the A-1 component, and the solvent content of the 50% solution is included in the Z-1 component (hereinafter referred to as A-2, A-3, AX-1, S-1). The same applies to the ingredients).

[Preparation Examples 2 to 9 of photosensitive resin composition for color filter]
The production conditions of Preparation Example 1 were changed as shown in Table 1, and the others were made in the same manner as Preparation Example 1, and Photosensitive Resin Compositions for Color Filters of Preparation Examples 2 to 9 were prepared.

[Example 1]
(Production of color filter)
On the PEN film held on the glass substrate, the photosensitive resin composition for color filter of Preparation Example 1 was spin-coated at a rotation speed such that the film thickness after curing was 1.0 μm (step (A)), 90 The specimen was dried for 2 minutes on a hot plate at 0 ° C. (step (i)). Next, image exposure is performed by irradiating 150 mJ / cm ² of ultraviolet rays (numerical values are based on i-line) with an ultrahigh pressure mercury lamp having an illuminance of 30 mW / cm ² through a photomask having a test pattern shape of the color filter pixels. (Step (c)). Thereafter, the test piece was treated for 1 minute with a 25 ° C. potassium hydroxide alkaline developer (“NSID” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image (step (D)). ). Finally, the test piece was irradiated with 1500 mJ / cm ² of ultraviolet rays (numerical value is 254 nm standard) with a low-pressure mercury lamp having an illuminance of 10 mW / cm ² to perform post-exposure (step (e)). Thus, a cured film (first color pixel) of the photosensitive resin composition for a color filter having a red hue was obtained.

  Next, the above procedure was repeated on the same PEN film using the photosensitive resin composition for color filter of Preparation Example 2, and the cured film of the photosensitive resin composition for color filter of green hue (2 Color pixel). Furthermore, the above procedure was repeated on the same PEN film using the color filter photosensitive resin composition of Preparation Example 3, and a cured film of the blue hue color photosensitive resin composition (third color) Obtained). In this way, a color filter having clear three-color pixels of red, green, and blue was produced.

[Example 2]
The composition of Preparation Example 1 used in Example 1 was changed to Preparation Example 4, the composition of Preparation Example 2 was changed to Preparation Example 5, the composition of Preparation Example 3 was changed to Preparation Example 6, and the others were changed to Example 1. In the same manner as described above, a color filter having clear three-color pixels of red, green, and blue was produced.

[Comparative Example 1]
The composition of Preparation Example 1 used in Example 1 was changed to Preparation Example 7, the composition of Preparation Example 2 was changed to Preparation Example 8, the composition of Preparation Example 3 was changed to Preparation Example 9, and the others were changed to Example 1. A color filter was prepared in the same manner as described above. If an attempt is made to form a pixel of the second color, the pixel of the first color (the cured film of the composition of Preparation Example 7) is eroded by the solvent of the composition of Preparation Example 8, and the color oozes out to obtain a clear pixel. I can't. Even if the order of forming the hues of the pixels is changed and the first color pixel is formed from the composition of Preparation Example 8 or Preparation Example 9, color bleeding is observed in the same manner when the second color pixel is formed. It was not possible to obtain clear pixels.

  By applying the manufacturing method of the present invention, it is possible to directly form a color filter on a plastic substrate or a white organic EL device, and the device can be easily made flexible or made into one chip. The photosensitive resin composition used in the present invention can be used not only for the production of color filters but also for coloring components such as paints, printing inks, writing instrument inks, and plastics.

Claims (4)

  A photosensitive resin composition for a color filter of a second color different from the first color is applied to a substrate on which a color filter portion of the first color obtained by curing the photosensitive resin composition is formed. A method for producing a color filter including a curing step, wherein the photosensitive resin composition comprises (A) a hydroxy group obtained by reacting a bisphenolfluorene type epoxy compound with an ethylenically unsaturated bond group-containing carboxylic acid. A compound obtained by reacting a cyclic acid anhydride with a compound, (B) a polymerizable monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator, The heat resistance temperature of the color filter is 150 ° C. or less, and the process is performed at an environmental temperature not exceeding the heat resistance temperature of the substrate.   (A) a step of applying a photosensitive resin composition to a substrate, (b) a step of drying the photosensitive resin composition, (c) a step of image-exposing the photosensitive resin composition, and (d) a photosensitive resin composition. The method for producing a color filter according to claim 1, comprising a step of developing the product and (e) a step of post-exposure of the photosensitive resin composition.   The manufacturing method of the color filter of Claim 1 or 2 which uses the photosensitive resin composition of red, green, and blue, respectively.   The color filter manufactured by the method of any one of Claims 1-3.