JP2007333847A - Colored photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which ensures a small viscosity change during storage and enables a pattern and a coating film excellent in solvent resistance to be formed. <P>SOLUTION: The colored photosensitive resin composition comprises a binder resin (A), a colorant (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the binder resin (A) comprises a constitutional unit derived from a monomer (A1) having a carbon-carbon double bond and an aliphatic polycyclic epoxy group and a constitutional unit derived from at least one monomer (A2) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition used for forming a color filter.

  A pixel of a color filter used in a liquid crystal display device is formed using a colored photosensitive resin composition.

In the formation of each pixel, in detail, a colored photosensitive resin composition containing any one of the three colors R, G, and B is applied on a substrate using a coating apparatus, and a volatile component is formed. Is removed by heating or the like, and then exposed through a mask. Then, in the case of a negative type, the unexposed part is developed, and in the case of a positive type, the exposed part is developed and removed with a developer such as an alkaline aqueous solution. A pattern is formed, and the obtained pattern is subjected to heat treatment (hereinafter sometimes referred to as post-baking) to form a pixel. Then, the same operation is performed using the remaining two colored photosensitive resin compositions of the three RGB colors, and a color pattern is formed by the same operation, and finally the color filter having the three RGB colors Form.
Examples of the colored photosensitive composition include those containing a binder resin (A), a colorant (B), a photopolymerizable compound (C) and a photopolymerization initiator (D). As A), an alkali-soluble resin is usually used, and specifically, a copolymer of methacrylic acid and benzyl methacrylate is known (for example, see Patent Document 1).
The colored pattern formed using the colored photosensitive composition is preferably thin. In order to obtain a sufficiently colored pattern even if the thickness is small, a colored photosensitive composition containing a colorant (B) at a high concentration may be used. However, when the content of the colorant is increased, the content of other components must be decreased. When such a composition is used, for example, the solvent resistance of the pattern to be formed tends to decrease. .

Japanese Patent Laid-Open No. 9-134004, page 3, right column, line 6 to page 3, right column, line 11

For example, according to the study of the present inventor, a colored photosensitive resin composition containing a copolymer of methacrylic acid and benzyl methacrylate as the binder resin (A) and having a concentration of the colorant (B) in the solid content of 39% The product was found to have very poor solvent resistance.
Also, depending on the colored photosensitive resin composition, although the solvent resistance of the colored pattern is good, when the composition is stored, the composition may thicken or gelate. . For example, according to the study of the present inventors, it was found that a colored photosensitive resin composition containing a glycidyl group has insufficient storage stability when stored at 23 ° C.

  Therefore, an object of the present invention is to provide a colored photosensitive resin composition that can form a pattern or a coating film that has a small viscosity change during storage and that has excellent solvent resistance.

As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventors have found that the colored photosensitive resin composition of the present invention can solve the above-mentioned problems, and have reached the present invention.
That is, the present invention relates to a colored photosensitive resin composition containing a binder resin (A), a colorant (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E). Resin (A) is a structural unit derived from a monomer (A1) having a carbon-carbon double bond and an aliphatic polycyclic epoxy group, and a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Provided is a colored photosensitive resin composition containing a structural unit derived from at least one monomer (A2) selected.
The present invention also provides a color filter formed using the colored photosensitive resin composition and a liquid crystal display device including the color filter.

  The colored photosensitive resin composition of the present invention has a small viscosity change during storage and can form a coating film excellent in solvent resistance.

  Hereinafter, the present invention will be described in detail.

  The colored photosensitive resin composition of the present invention is mainly used as a colored pattern forming material, and includes a binder resin (A), a colorant (B), a photopolymerizable compound (C), and a photopolymerization initiator. (D) and, optionally, other additives (F) are dissolved or dispersed in the solvent (E).

  The binder resin (A) used in the colored photosensitive resin composition of the present invention has alkali solubility and is a monomer (A1) having a carbon-carbon double bond and an aliphatic polycyclic epoxy group. ), A copolymer containing structural units derived from at least one monomer (A2) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

The monomer (A1) having a carbon-carbon double bond and an aliphatic polycyclic epoxy group refers to a compound having an epoxy group in the ring of the aliphatic polycyclic compound and having an unsaturated bond. Examples of the aliphatic polycyclic compound include dicyclopentane and tricyclodecane.
The monomer having a carbon-carbon double bond and an aliphatic polycyclic epoxy group is preferably at least selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II). One compound is mentioned.

[In formula (I) and formula (II), R represents a C1-C4 alkyl group which may be substituted by the hydrogen atom or the hydroxyl group each independently.
X represents each independently a C1-C6 alkylene group which may contain a single bond or a hetero atom. ]

Specific examples of the alkyl group having 1 to 4 carbon atoms that may be substituted with a hydroxyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. Tert-butyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1 -Hydroxy-isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, etc. Preferably a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, more preferably a methyl group. Group, and the like.
R is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

  As a hetero atom in a C1-C6 alkylene group which may contain a hetero atom, an oxygen atom, a sulfur atom, and -NH- are said. In addition, a hetero atom is not contained in C1-C6.

Examples of the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include a methylene group, an ethylene group, a propylene group, an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, and an aminomethylene group. Group, aminoethylene group, aminopropylene group and the like, preferably methylene group, ethylene group, oxymethylene group and oxyethylene group, more preferably oxyethylene group.
X is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15), preferably the formula (I-1) and the formula (I-3). , Formula (I-5), formula (I-7), formula (I-9), compounds represented by formula (I-11) to formula (I-15), and more preferably formula (I -1), formula (I-7), formula (I-9), and compounds represented by formula (I-15).

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15), preferably the formula (II-1) and the formula (II-3). , Formula (II-5), formula (II-7), formula (II-9), compounds represented by formula (II-11) to formula (II-15), and more preferably formula (II) -1), formula (II-7), formula (II-9), and a compound represented by formula (II-15).

  At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) can be used alone. They can also be mixed in any ratio. In the case of mixing, the mixing ratio is a molar ratio of formula (I): formula (II), preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and particularly preferably 20:80 to 80:20.

Examples of the at least one compound (A2) selected from the group consisting of the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
Anhydrides of the aforementioned unsaturated dicarboxylic acids;
Unsaturated mono [(meth) acryloyloxy of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Alkyl] esters;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferably used from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution. These may be used alone or in combination.

The binder resin (A) used in the present invention is a copolymer containing a structural unit derived from the monomer (A1) and a structural unit derived from (A2), and the ratio of the structural units derived from each of them. However, when the molar fraction is in the following range with respect to the total number of moles of the constituent units constituting the copolymer, the storage stability, heat resistance and mechanical strength tend to be good, which is preferable.
Structural units derived from (A1); 2 to 98 mol%
Structural units derived from (A2); 2-98 mol%

Moreover, it is more preferable in the point of developability and solvent resistance that the ratio of the said structural unit is the following ranges.
Structural units derived from (A1); 40 to 85 mol%
Structural unit derived from (A2); 15 to 60 mol%

The binder resin (A) is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972). And it can manufacture with reference to the cited reference described in the said literature.
Specifically, a predetermined amount of monomers (A1) and (A2) leading to the copolymer, a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is substituted with nitrogen, so that oxygen is not present. Thus, a polymer is obtained by stirring, heating, and heat-retaining. In addition, the obtained copolymer may use the solution after the reaction as it is, may use a concentrated or diluted solution, and was taken out as a solid (powder) by a method such as reprecipitation. Things may be used.

  The binder resin (A) is composed of a structural unit derived from a monomer (A1) having a carbon-carbon double bond and an aliphatic polycyclic epoxy group, and an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. In addition to the structural unit derived from at least one monomer (A2) selected from the group consisting of the monomers (A1) and a monomer copolymerizable with the monomer (A2) (however, ( A1) and (A2) are excluded.) A structural unit derived from (A3) can be contained. By containing the structural unit derived from (A3), the balance of developability, adhesion, pattern shape, and the like is improved, which is preferable.

As the monomer (A3) (excluding (A1) and (A2)) copolymerizable with the monomer (A1) and the monomer (A2), methyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate;
Alkyl acrylates such as methyl acrylate and isopropyl acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isoboronyl (meth) acrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (commonly referred to in the art as dicyclopentanyl acrylate), dicyclo Acrylic acid cyclic alkyl esters such as pentaoxyethyl acrylate and isobornyl acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1 ] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6- Di (hydroxymethyl) bicyclo [2.2.1] hept-2-e 5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6 -Diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2 .1] Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Ethylbicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxy Carbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2. 1] Bicyclo unsaturated compounds such as hept-2-ene and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl , O-Vinylbenzylglycidyl A Le, m- vinylbenzyl glycidyl ether, p- vinylbenzyl glycidyl ether. Here, in the present specification, (meth) acrylate represents at least one selected from the group consisting of acrylate and methacrylate. (Meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid.
Among these, benzyl acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are copolymerizable and soluble in an aqueous alkali solution. It is preferable from the point.
Said (A3) component is used individually or in combination.

When the ratio of the structural units derived from (A1) to (A3) is a mole fraction with respect to the total number of moles of the structural units constituting the copolymer, and is in the following range, storage stability and development , Adhesion, pattern shape, solvent resistance, heat resistance, mechanical strength and balance thereof are preferable.
Structural units derived from (A1); 2 to 97 mol%
Structural units derived from (A2); 2 to 97 mol%
Structural units derived from (A3); 1 to 96 mol%

  The binder resin (A) containing the above (A1) to (A3) can be produced in the same manner as described above.

  Moreover, as a structural unit in the said binder resin (A), the macromonomer which has a monoacryloyl group or a monomethacryloyl group at the terminal, the unit represented by Formula (III), the unit represented by Formula (IV), etc. When it contains, it is more preferable at the point of pattern adhesiveness and solvent resistance.

(In Formula (III) and Formula (IV), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

  The binder resin having the structural unit represented by the formula (III) is obtained by polymerizing the monomer (A1), the monomer (A2) and the monomer (A3) to obtain a three-component polymer. The obtained three-component polymer and the compound represented by the formula (V) can be obtained by reacting at the carboxyl group moiety or acid anhydride group moiety derived from the component (A2).

  A binder resin having a constituent represented by the formula (IV) is obtained by polymerizing (A1), (A2) and (A3) to obtain a three-component polymer, and the obtained three-component polymer and glycidyl methacrylate. Can be obtained in the same manner as in the method described in JP-A-2005-189574, for example.

The polystyrene-reduced weight average molecular weight of the binder resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the above range, the coating property tends to be good, the film is not easily reduced during development, and the non-pixel portion is easily removed during development. It tends to be preferable.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. The molecular weight distribution in the above range is preferable because it tends to be excellent in developability.
Content of binder resin (A) used for the colored photosensitive resin composition of this invention is a mass fraction with respect to solid content in a colored photosensitive resin composition, Preferably it is 10-35 mass%, More preferably Is 15-30 mass%. When the content of the binder resin (A) is in the above range, the solubility in the developer is sufficient, and a development residue is hardly generated on the non-pixel portion of the substrate. This is preferable because the film loss is less likely to occur, and the non-pixel portion is liable to be removed.

  The colorant (B) used in the colored photosensitive resin composition of the present invention may be an organic pigment or an inorganic pigment. Of these, organic pigments are preferably used because of their excellent heat resistance and color developability.

Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment by Color Index (published by The Society of Dyers and Colorists). Specifically, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7. Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 6 and C.I. I. It is preferable that at least one pigment selected from CI Pigment Green 36 is contained.

These pigments may be used alone or in combination of two or more.
For example, in order to form a red pixel, C.I. I. Pigment red 209 and C.I. I. Pigment Yellow 139 contains C.I. to form a green pixel. I. Pigment green 36 and C.I. I. Pigment yellow 150 and C.I. I. In order to form a blue pixel by containing at least one selected from the group consisting of CI Pigment Yellow 138, C.I. I. Each of them preferably contains CI Pigment Blue 15: 6.

  Among the above pigments, organic pigments are optionally treated with rosin, surface treatment with a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid fine particles, etc. A pulverization process such as an atomization method, a cleaning process using an organic solvent or water for removing impurities, a removal process using an ion exchange method for ionic impurities, or the like may be performed.

Content of a coloring agent (B) is a mass fraction with respect to the solid part in a colored photosensitive resin composition, Preferably it is 10 mass%-60 mass%, More preferably, it is 15-50 mass%. .
When the content of the colorant (B) is in the above range, the color density when it is used as a color filter is sufficient, and the binder polymer can be contained in the composition in a necessary amount, so that the mechanical strength is high. It is preferable because a sufficient pattern can be formed.

The colorant (B) preferably has a uniform particle size. When the colorant (B) is a face amount, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained by adding a pigment dispersant and performing a dispersion treatment.
Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and may be used alone or in combination of two or more.
When using a pigment dispersant, the amount used is preferably 1 part by mass or less, more preferably 0.05 to 0.5 part by mass, per 1 part by mass of the colorant. It is preferable that the amount of the pigment dispersant used is in the above range because a pigment in a uniform dispersion state tends to be obtained.

The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention can be a monofunctional monomer, a bifunctional monomer, or another polyfunctional monomer having three or more functions.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Bis (acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, and the like.
Specific examples of other trifunctional or higher polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like. Of these, polyfunctional monomers having two or more functions are preferably used. These photopolymerizable compounds (C) can be used alone or in combination of two or more.
Content of a photopolymerizable compound (C) is a mass fraction when content of binder resin (A) is 100 mass%, Preferably it is 10-90 mass%, More preferably, it is 20-80 mass. %, And more preferably 30 to 70% by mass. When the content of the photopolymerizable compound (C) is in the above range, curing is sufficiently performed, the film thickness ratio before and after the development is improved, and the undercut is difficult to enter into the pattern and the adhesion is good. It is preferable because it tends to become.

  The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention is preferably an acetophenone-based, biimidazole-based, oxime-based, triazine-based, or acylphosphine oxide-based initiator. By using the photopolymerization initiator (G) in combination with the photopolymerization initiator (D), the resulting colored photosensitive resin composition has a higher sensitivity, so when using this to form a pattern, This is preferable because the productivity of the pattern is improved.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]. 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methylbenzyl) -2-dimethylamino -1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-moly Holinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholino Phenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholino) Phenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholino) Phenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 -(2-Methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propan-1-one oligomer and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913) and the like, preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole may be mentioned. In addition

  Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, a compound represented by formula (3), a compound represented by formula (4), and the like.

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

  Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Moreover, as long as the effects of the present invention are not impaired, a photopolymerization initiator or the like usually used in this field can be further used together. Examples of the photopolymerization initiator include benzoin compounds and benzophenones. Compounds, thioxanthone compounds, anthracene compounds, and the like.
More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.

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

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

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

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done.

  Other examples of the photopolymerization initiator include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds. .

Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 can be used.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the photoinitiator of following formula (5)-(10) is mentioned, for example.

  The photopolymerization initiator having a group capable of causing chain transfer can also be used as the constituent component (A3) of the copolymer. And the obtained copolymer can be used for the binder resin used as a binder resin of the colored photosensitive resin composition of this invention, and can also be used together.

Further, the photopolymerization initiator may be used in combination with the photopolymerization initiator auxiliary agent (G). Examples of the photopolymerization initiation aid (G) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. Can be mentioned.

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

  The photopolymerization initiation assistant (G) may be used alone or in combination of two or more. Moreover, as a photoinitiation adjuvant (G), a commercially available thing can also be used, and as a commercially available photoinitiation assistant (G), brand name "EAB-F" (Hodogaya Chemical Industry ( Etc.).

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (G) in the colored photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4 4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl fe Luketone / 4,4′-bis (diethylamino) benzophenone, oligomer of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one / 4,4′-bis (diethylamino) ) Benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, etc., preferably 2-methyl-2-morpholino Examples include -1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

Content of a photoinitiator (D) is a mass fraction with respect to the total amount of binder resin (A) and a photopolymerizable compound (C), Preferably it is 0.1-40 mass%, More preferably, it is 1 -30 mass%.
Moreover, when using photoinitiator adjuvant (G), the usage-amount is with respect to 1 mol of photoinitiators (D), Preferably it is 0.01 mol or more and 10 mol or less, More preferably, it is 0.01 mol or more and 5 mol. It is below the mole.
When the total amount of the photopolymerization initiator (D) is in the above range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the colored photosensitive resin composition, The smoothness on the surface of the pixel tends to be good, which is preferable. In addition to the above, when the amount of the photopolymerization initiation auxiliary agent (G) is in the above range, the sensitivity of the obtained colored photosensitive resin composition is further increased, and formed using the colored photosensitive resin composition. This is preferable because the productivity of the patterned substrate tends to be improved.

  The colored photosensitive resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, N-methylpyrrolidone, dimethylsulfoxide, and the like.

Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Over DOO, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.
Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Among these, propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate are preferable, and it is more preferable to use these in combination.
Furthermore, the said solvent may be used individually or in combination of 2 or more types.
Content of the solvent (D) in the colored photosensitive resin composition of this invention is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 60-95 mass%, More preferably, it is 75-90 mass%. is there. When the content of the solvent (D) is within the above range, when applied by a spin coater, slit & spin coater, slit coater (sometimes called a die coater or curtain flow coater), an ink jet or the like. The coating property is expected to be good, and is preferable.

  In the colored photosensitive resin composition of the present invention, a surfactant, a filler, a polymer compound other than the binder resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic acid, if necessary. In addition, additives (F) such as organic amino compounds and curing agents may be used in combination.

Examples of the surfactant include at least one selected from the group consisting of a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom.
Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).
Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck (trade name) F142D, F171, F172, F173, F177, F183, R183 (large) Nippon Ink Chemical Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352, EF352 (manufactured by Shin-Akita Kasei), Surflon (tradename) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie) and the like.
Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.
Content of surfactant is a mass fraction with respect to a coloring photosensitive resin composition, Preferably it is 0.0005 mass% or more and 0.6 mass% or less, More preferably, it is 0.001 mass% or more and 0.5 or less. % By mass. When the content of the surfactant is in the above range, the flatness tends to be good, which is preferable.

  Specific examples of the filler include glass, silica, and alumina.

  Examples of the polymer compound other than the binder resin (A) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and a dispersant.

  Examples of the dispersant include Disperbyk-115, Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-167, DisperDik69, Disperbyk69 -171, Disperbyk-174, Disperbyk-182 (all manufactured by BYKChemie).

  Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

  Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

Examples of the ultraviolet absorber include benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole;
Benzophenone series such as 2-hydroxy-4-octyloxybenzophenone;
Benzoate systems such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate;
And triazines such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Specific examples of the flocculant include sodium polyacrylate.

The organic acid is used for adjustment of developability. Specifically, for example, aliphatic monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and caprylic acid are used. Carboxylic acids;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid are listed.

Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n- Monoalkylamines such as octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di- dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Kind;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkanediols such as 1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanols such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

  Examples of the curing agent include a compound that can react with a carboxyl group in the binder resin by being heated to crosslink the binder resin, and a compound that can be polymerized alone to cure the colored pattern. . Examples of the compound include an epoxy compound and an oxetane compound.

Here, as the epoxy compound, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic epoxy resins , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, cycloaliphatic or aromatic epoxy compounds, epoxidized butadiene (co) polymers, epoxidized isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, triglycidyl Examples include isocyanurate.
Examples of commercially available epoxy resins include orthocresol novolac type epoxy resins, “SUMI Epoxy ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored photosensitive composition of the present invention contains an epoxy compound, an oxetane compound or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. . Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3 Aromatic polycarboxylic acids such as 3,3 ', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic acid anhydrides include aromatic phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. Carboxylic anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;
Examples include ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic anhydride.

  As said carboxylic acid anhydride, you may use what is marketed as an epoxy resin hardening | curing agent. Examples of the epoxy resin curing agent include a trade name “Adeka Hardener EH-700” (manufactured by Asahi Denka Kogyo Co., Ltd.), a trade name “Licacid HH” (manufactured by Shin Nippon Rika Co., Ltd.), and a trade name “MH”. -700 "(manufactured by Shin Nippon Rika Co., Ltd.).

  The above curing agents may be used alone or in combination of two or more species.

  As a method for preparing the colored photosensitive resin composition of the present invention, for example, a pigment dispersant is coexisted in the solvent (E) to disperse the colorant (B) such as a pigment, and the colorant (B) dispersion liquid. Further, the binder polymer (A), photopolymerizable compound (C), photopolymerization initiator (D), and other additives as necessary dissolved in a solvent are dissolved, and the colorant (B ) A method of mixing with a dispersion and adding a solvent if necessary.

  In addition, the colored photosensitive resin composition of the present invention is usually enclosed in a container and distributed and stored.

  As a method for forming a color filter pattern using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, on the substrate first). To another colored photosensitive resin composition layer, etc. formed on the substrate, remove volatile components such as a solvent to form a colored layer, expose the colored layer through a photomask, and develop The method etc. are mentioned.

  Here, examples of the substrate include a substrate having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, and a GaAs substrate. These substrates may be subjected to pretreatment such as chemical treatment with a chemical such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum deposition treatment. When a silicon substrate is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT), or the like may be formed on the surface of the silicon substrate.

  In order to apply the colored photosensitive resin composition on the substrate or another resin layer, it is applied on the substrate using a spin coater, a liquid-saving coater, or a spinless coater, and then a volatile component such as a solvent. Is preferably volatilized by heating. In this way, a colored layer made of a solid content of the colored photosensitive resin composition is formed on the substrate or another resin layer with good flatness.

In order to form a pattern from the colored layer, the following method is exemplified. A colored photosensitive resin composition is applied on the surface of a glass substrate (# 1737; manufactured by Corning) by spin coating, and then heated at 100 ° C. for 3 minutes to volatilize volatile components, thereby coloring the photosensitive resin composition. Form a layer. After cooling, the colored photosensitive resin composition layer is irradiated with i-line [wavelength 365 nm] using a photomask. For example, an ultra-high pressure mercury lamp (HB-75105AA OP1; manufactured by Ushio Electric Co., Ltd.) is used as the i-line light source, and the irradiation light amount is usually about 150 mJ / cm ² . Next, the film was developed by immersing it in a developer (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction), washed with pure water, and then colored the glass substrate. A layer is obtained. Thereafter, heat treatment may be performed to increase the durability of the colored layer. Thus, a pattern can be formed from the colored layer.

Next, in order to manufacture a color filter, the following method is illustrated. A colored photosensitive resin composition (for example, a red composition) is applied on the surface of a glass substrate (# 1737; manufactured by Corning) by spin coating, and then heated at 100 ° C. for 3 minutes to volatilize volatile components. A colored photosensitive resin composition layer is formed. After cooling, the colored photosensitive resin composition layer is irradiated with i-line (wavelength 365 nm) over a glass 1/3 through a photomask. As an i-line light source, for example, an ultra-high pressure mercury lamp (for example, HB-75105AA OP1; manufactured by Ushio Electric Co., Ltd.) is used, and the irradiation light amount is usually about 150 mJ / cm ² . Next, the film was immersed in a developer (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalene sulfonate by mass), developed, and washed with pure water. / 3 A colored layer formed over the 3rd surface is obtained. If necessary, heat treatment is performed at 180 to 220 ° C. for 20 minutes. Next, each of the above steps can be repeated using a colored photosensitive resin composition having a different hue to obtain a color filter.

Next, in order to manufacture the liquid crystal display device, the following method is exemplified.
A liquid crystal display device can be manufactured by bonding ITO, an alignment film, a rubbing process substrate and a TFT substrate through a spacer on the color filter obtained above, and injecting liquid crystal.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

Synthesis example 1
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 100 parts by mass of 3-methoxybutyl acetate were added. And heated to 70 ° C. with stirring. Next, 54 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound to be mixed is mixed at a molar ratio of 50:50.) 180 parts by mass and 67 parts by mass of N-cyclohexylmaleimide are dissolved in 140 parts by mass of 3-methoxy-1-butanol to prepare a solution. The liquid was dripped in the flask kept at 70 degreeC over 4 hours using the dripping pump. On the other hand, a solution obtained by dissolving 20 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping pump. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and a copolymer having a solid content of 32.6% by mass and an acid value of 34.3 mg-KOH / g ( A solution of Resin A-1) was obtained. The obtained resin A-1 had a weight average molecular weight Mw of 9000 and a dispersity of 1.9.

Synthesis example 2
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 100 parts by mass of 3-methoxybutyl acetate were added. And heated to 70 ° C. with stirring. Next, 68 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound to be mixed is mixed at a molar ratio of 50:50.) 150 parts by mass and 82 parts by mass of styrene are dissolved in 140 parts by mass of 3-methoxy-1-butanol to prepare a solution. It was dripped in the flask kept at 70 degreeC over 4 hours using the dripping pump. On the other hand, a solution obtained by dissolving 20 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping pump. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and a copolymer having a solid content of 27.1% by mass and an acid value of 44.2 mg-KOH / g ( A solution of Resin A-2) was obtained. The obtained resin A-2 had a weight average molecular weight Mw of 7000 and a dispersity of 1.7.

Synthesis example 3
Nitrogen was flowed at 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, 300 parts by mass of diethylene glycol methyl ethyl ether was added, and the mixture was heated to 70 ° C. with stirring. Next, 46 parts by mass of methacrylic acid, 95 parts by mass of glycidyl methacrylate, 84 parts by mass of N-cyclohexylmaleimide and 37 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) were added to 225 of diethylene glycol methyl ethyl ether. A solution was prepared by dissolving in parts by mass, and the solution was dropped into a flask kept at 70 ° C. over 1 hour. After completion of the dropwise addition, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin A-3) having a solid content of 30.0% by mass and an acid value of 39.0 mg-KOH / g. A solution was obtained. The obtained resin A-3 had a weight average molecular weight Mw of 10,700 and a dispersity of 2.74.

About the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the said binder polymer, it carried out on condition of the following using GPC method.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Test solution concentration: 25 mg / mL (solvent: THF)
Flow rate: 1.0 mL / min
Detector; RI
The ratio of the weight average molecular weight and the number average molecular weight obtained in the above-mentioned manner as polystyrene was defined as the dispersity (Mw / Mn).

The components used in this example are as follows, and may be omitted below.
(Resin A-4) Binder resin: Copolymer of methacrylic acid and benzyl methacrylate [ratio of methacrylic acid unit and benzyl methacrylate unit is 30:70 by mass ratio (molar ratio), acid value is 113, polystyrene conversion Weight average molecular weight 25,000] solid content 34%, solvent is propylene glycol monomethyl ether acetate)
(B-1) Colorant: C.I. I. Pigment Red 254
(B-2) Colorant: C.I. I. Pigment Red 177
(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (D-1) photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (D-2) light Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (D-3) photopolymerization initiator auxiliary agent: 4,4′-bis (diethylamino) benzophenone (E-1) ) Solvent: Propylene glycol monomethyl ether acetate (E-2) Solvent: 3-methoxy-1-butanol (E-3) Solvent: 3-methoxybutyl acetate (E-4) Solvent: Diethylene glycol methyl ethyl ether (E-5) Solvent: ethyl 3-ethoxypropionate

Example 1
Each component is mixed with the resin solution part (solid content conversion: 5.172 parts) containing (Resin A-1) obtained in Synthesis Example 1 so as to have the composition shown in Table 1, and the colored photosensitive resin composition. 1 was obtained. The photosensitive resin composition 1 was evaluated for storage stability, and the results are shown in Table 2.

<Storage stability>
The colored photosensitive resin composition was stored at 23 ° C. and 40 ° C. for 4 days, and the value obtained by dividing the viscosity of the colored photosensitive resin composition after storage by the viscosity of the composition before storage was shown in%. The smaller the change in viscosity, the better, for example, at 23 ° C. in the range of 98 to 102%.

Viscosity: Measured at 23 ° C. and 40 ° C. using a viscometer (VISCOMETER TV-30; manufactured by Toki Sangyo Co., Ltd.).

<Pattern formation>
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. The colored photosensitive resin composition 1 was spin-coated on this glass substrate, and then pre-baked at 100 ° C. for 3 minutes in a clean oven.
After cooling, the colored photosensitive composition layer formed is passed through a photomask (100 μm, 50 μm, 40 μm line and space pattern) and exposed to the atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Under the irradiation, light was irradiated with an exposure amount (365 nm) of 150 mJ / cm ² . Next, the film was developed by immersing it in a developer (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction), washed with pure water, and then washed at 230 ° C. for 20 hours. Heated for a minute to form a colored pattern. The resulting colored pattern was as intended.
Further, a colored layer was formed over the entire surface of the glass plate by operating in the same manner as described above except that the light was irradiated without passing through a photomask. When the chromaticity x1 of the obtained colored layer was measured using a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS), x = 0.654. The obtained colored layer was evaluated for solvent resistance, and the results are shown in Table 2.

<Solvent resistance>
The chromaticity x1 of the produced colored layer was measured using a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS). Then, it was immersed in N-methylpyrrolidone at 23 ° C. for 30 minutes, and the chromaticity x2 after the immersion was measured to determine the difference between x2 and x1. As the difference is smaller, for example, 0.005 or less, the color change is small and the solvent resistance is excellent and good.

Example 2
A colored photosensitive resin composition 2 was obtained in the same manner as in Example 1 so as to obtain the composition shown in Table 1. The results of evaluation in the same manner as in Example 1 are shown in Table 2.

Comparative Example 1
A colored photosensitive resin composition 3 was obtained in the same manner as in Example 1 so as to obtain the composition shown in Table 1. When the storage stability was measured in the same manner as in Example 1, the viscosity was increased and the evaluation was stopped.

Comparative Example 2
A colored photosensitive resin composition 4 was obtained in the same manner as in Example 1 so that the composition shown in Table 1 was obtained. The results of evaluation in the same manner as in Example 1 are shown in Table 2.

From the results of Examples 1 and 2 shown in Table 2, the colored photosensitive resin composition of the present invention containing a binder resin having an epoxy group having a specific structure is excellent in storage stability, and the colored photosensitive resin of the present invention. It turns out that the pattern and coating film excellent in solvent resistance are obtained when a composition is used.
On the other hand, the colored photosensitive resin composition which does not contain the specific binder resin according to the present invention described in Comparative Example 1 is only inferior in storage stability, and the present invention described in Comparative Example 2 In the colored photosensitive resin composition not containing the specific binder resin, only a coating film having poor solvent resistance was obtained.

Claims (5)

  In the colored photosensitive resin composition containing the binder resin (A), the colorant (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and the solvent (E), the binder resin (A) is , At least one selected from the group consisting of a structural unit derived from a monomer (A1) having a carbon-carbon double bond and an aliphatic polycyclic epoxy group, and an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. A colored photosensitive resin composition containing a structural unit derived from the monomer (A2).   Claim that the binder resin (A) further contains a structural unit derived from a monomer copolymerizable with (A1) and (A2) (excluding (A1) and (A2)) (A3) Item 2. The colored photosensitive resin composition according to Item 1. The monomer (A1) having a carbon-carbon double bond and an aliphatic polycyclic epoxy group is selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II). The colored photosensitive resin composition according to claim 1, which is at least one compound.

[In formula (I) and formula (II), R represents a C1-C4 alkyl group which may be each independently substituted with a hydrogen atom or a hydroxyl group.
X represents each independently a C1-C6 alkylene group which may contain a single bond or a hetero atom. ]   A color filter formed using the colored photosensitive resin composition according to claim 1. A liquid crystal display device comprising the color filter according to claim 4.