KR20090110787A - Colored photosensitive resin composition - Google Patents

Abstract

PURPOSE: A coloring photosensitive resin is provided to easily re-dissolve the composition. CONSTITUTION: A coloring photosensitive resin composition contains coloring agent, binder resin, photo polymerizable compound, photopolymerization initiator and solvent. The solvent comprises a solvent selected from dipropylene glycol monoalkylether ester of C1-C4 alkyl group and dipropylene glycol monoalkylether of C1-C4 alkyl group and other solvent. The content of the solvent is more than 5 mass% and less than 40 mass% based on total solvent amount.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a colored photosensitive resin composition and a pattern and a color filter formed using the same.

In recent years, a liquid saving coater typified by a slit-and-spin method or a spinless method has been used as a coating apparatus used for the production of color filters (Patent Document 1). This liquid-saving coater is excellent in cost because it can be applied to a substrate with a small amount of colored photosensitive resin composition as compared with a conventional spin coater.

However, in this liquid-saving coater, the colored photosensitive resin composition may dry and become a foreign material at the slit periphery portion where the colored photosensitive resin composition is brought into contact with the substrate, and may fall onto the substrate, causing a decrease in the yield of the color filter. In order to avoid this, a washing operation around the slit is required, and improvement in productivity has been desired.

On the other hand, it is generally conceivable to prevent drying by using a solvent having a high boiling point in the colored photosensitive resin composition. However, when the solvent with a high boiling point is used excessively, there exists a problem that the workability of the prebaking process which volatilizes and removes a solvent before an exposure process falls.

[Patent Document 1]

Japanese Patent Laid-Open No. 2002-23352, page 2, right column 11th to 22nd row

An object of the present invention is to provide a colored photosensitive resin composition which is not easily dried and can be easily redissolved even when dried.

The present inventors found that the above problems can be solved by using any kind of solvent in a certain range.

That is, this invention provides the following [7].

[One]. In the coloring photosensitive resin composition containing a coloring agent, binder resin, a photopolymerizable compound, a photoinitiator, and a solvent,

The solvent is different from at least one solvent (A) and (A) selected from the group consisting of dipropylene glycol monoalkyl ethers having 1 to 4 carbon atoms of an alkyl group and dipropylene glycol monoalkyl ether esters having 1 to 4 carbon atoms of an alkyl group. Consisting of different solvents (B),

Content of solvent (A) is 5 mass% or more and 40 mass% or less with respect to all solvent amounts,

The coloring photosensitive resin composition whose content of a solvent (B) is 60 mass% or more and 95 mass% or less with respect to all solvent amounts.

[2]. The coloring photosensitive resin composition as described in [1] whose solvent (B) is a solvent which has a boiling point of 121 degreeC or more and 171 degrees C or less.

[3]. The colored photosensitive resin composition as described in [1] or [2] whose solvent (A) is a C1-C4 dipropylene glycol monoalkyl ether of an alkyl group.

[4]. The coloring photosensitive resin composition in any one of [1]-[3] whose solvent (A) is dipropylene glycol monomethyl ether.

[5]. The coloring photosensitive resin composition in any one of [1]-[4] whose solvent (B) is propylene glycol methyl ether acetate.

[6]. The pattern formed using the coloring photosensitive resin composition in any one of [1]-[5].

[7]. The color filter containing the pattern of [6].

The coloring photosensitive resin composition of this invention mainly contains a coloring agent, binder resin, a photopolymerizable compound, a photoinitiator, and a solvent.

The colorant used in the present invention may be an organic pigment or an inorganic pigment. Moreover, dye may be sufficient. Especially, since it is excellent in heat resistance and color development, an organic pigment is used preferably.

Examples of the organic and inorganic pigments described above include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

Specifically, CI Pigment Yellow 1 (hereinafter, CI Pigment Yellow is omitted and only numbers are described. Other colors are also described in the same manner.), 3, 12, 13, 14, 15, 16, 17, 20, Yellow such as 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 Pigments;

C. I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 264, 265 and the like;

C. I. Blue pigments, such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; C. I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38;

C. I. Green pigment, such as Pigment Green 7, 36;

C. I. Brown pigments, such as Pigment Brown 23 and 25;

C. I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

These organic pigments and inorganic pigments may be used alone, or two or more thereof may be mixed and used. For example, it is preferable to contain CI pigment red 254 and CI pigment red 177 or CI pigment yellow 139 in order to form a red pixel, and CI pigment green 36 and CI pigment to form a green pixel. It is preferable to contain at least 1 sort (s) chosen from the group which consists of yellow 150 and CI pigment yellow 138, and in order to form a blue pixel, it contains CI pigment blue 15: 6 and CI pigment violet 23. desirable.

As said dye, if it is a dye soluble in the organic solvent, it can use without a restriction | limiting in particular. From the viewpoint of the chemical structure, the organic solvent soluble dyes include triphenyl methane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, Dye, such as benzopyran system and indigo system, can be used. Preferably, they are dyes of a pyrazole azo system, an anilino azo system, a pyrazolotriazole azo system, a pyridone azo system, an anthraquinone system, and an anthrapyridone system.

Among the above dyes, examples of the acid dyes and direct dyes include the following.

Acid alizarin violet N;

Acid blacks 1, 2, 24, 48;

Acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

Acid chrome violet K;

Acid Fuchsin;

Acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109;

Acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

Acid violet 6B, 7, 9, 17, 19;

Acid yellow (1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251

Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

Direct Orenge 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;

Mortant Orenge 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 ;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38 , 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

Mortant Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41 , 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

Mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;

Food Yellow 3;

And derivatives of these dyes. As a derivative, what amidated the sulfonic acid group with the amine is used suitably.

As for content of a coloring agent, 25 mass% or more and 60 mass% or less are preferable by mass fraction with respect to solid content of the photosensitive resin composition, More preferably, they are 27 mass% or more and 55 mass% or less, More preferably, it is 30 mass% or more It is 50 mass% or less. When content of a coloring agent exists in the said range, since the color concentration at the time of using a color filter can be sufficient, and a binder resin can be contained in a composition in a required amount, the pattern excellent in mechanical strength can be formed.

The pigment may be optionally treated with rosin treatment, surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound, atomization treatment by a sulfur atomization method, or impurities. A washing treatment with an organic solvent, water, or the like for removal, or a treatment for removing ionic impurities by an ion exchange method or the like may be performed.

It is preferable that the pigment | dye is uniform particle diameter of the colored photosensitive resin composition obtained by this invention.

In order to make the pigment a uniform particle diameter, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution by containing a surfactant and performing a dispersion treatment.

As said surfactant, surfactant, such as cationic, anionic, nonionic, and amphoteric, etc. are mentioned, for example, It is used individually or in combination of 2 or more types, respectively.

When surfactant is used at the time of preparation of a pigment dispersion, the usage-amount is 1 mass part or less normally per 1 mass part of pigment, Preferably it is 0.05 mass part or more and 0.5 mass part or less. When the usage-amount of surfactant exists in the said range, there exists a tendency for the pigment of a uniform particle diameter to be obtained.

The coloring photosensitive resin composition of this invention contains a binder resin. As said binder resin, an acryl-type copolymer can be used. As an acryl-type copolymer, the copolymer etc. of carboxyl group-containing monomers, such as (meth) acrylic acid, and the other monomer copolymerizable with this monomer are mentioned, for example. In this specification, (meth) acrylic acid represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. The same applies to (meth) acrylate.

As said carboxyl group-containing monomer, unsaturated carboxylic acid which has at least 1 carboxyl group in a molecule | numerator, such as unsaturated monocarboxylic acid, unsaturated polycarboxylic acid, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, is mentioned, for example.

Here, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example.

The unsaturated polyhydric carboxylic acid may be an acid anhydride, specifically maleic anhydride, itaconic anhydride, citraconic anhydride, or the like. Moreover, the mono (2-methacryloyloxyalkyl) ester may be sufficient as unsaturated polyhydric carboxylic acid, For example, succinic acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyloxy). Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, or the like. Unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the both terminal dicarboxy polymers, for example, (omega) -carboxypolycaprolactone monoacrylate, (omega) -carboxypolycaprolactone monomethacrylate, etc. may be sufficient as it. These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

As another monomer copolymerizable with said carboxyl group-containing monomer, the monomer which has an ethylenically unsaturated bond, and / or the monomer which can be addition-polymerized, etc. are mentioned, For example, styrene, (alpha) -methylstyrene, o-vinyltoluene, m- Vinyltoluene, p-vinyltoluene, p-chlorstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl Aromatic vinyl compounds such as ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and indene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy Tyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate , 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, Methoxy triethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, Dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate Unsaturated carboxylic acid esters such as yate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxylates such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Main acid aminoalkyl esters;

Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide;

Unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane Macromonomers; and the like.

These monomers can be used individually or in mixture of 2 or more types, respectively.

The content of the carboxyl group-containing monomer unit in the copolymer described above is preferably 5% to 45%, more preferably 10% to 40%, and more preferably to the total moles of the precursor units of the copolymer. Is 15% to 35%. When content of a carboxyl group-containing monomeric unit exists in the said range, solubility to a developing solution is favorable and it exists in the tendency for a pattern to be formed correctly at the time of image development.

As said acrylic polymer, it is (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth), for example. ) Acrylic / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylic Late macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth ) Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) a Relate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monoacid mono (2-acryloyl) Oxyethyl) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monoacid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenyl Maleimide copolymer (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer and the like.

Above all, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / Methyl (meth) acrylate / styrene copolymer, etc. are preferable.

These can be used individually or in mixture of 2 or more types, respectively.

The polystyrene reduced weight average molecular weight of the binder resin is preferably 5,00O to 50,000, more preferably 7,000 to 40,000, and particularly preferably 8,000 to 35,000. When the molecular weight of the binder resin is in the above-described range, the coating film hardness is improved, the residual film ratio is also high, the solubility in the developer of the unexposed part is good, and the resolution tends to be improved.

The acid value of binder resin becomes like this. Preferably it is 50-150, More preferably, it is 60-140, More preferably, it is 70-130. When the acid value is in the above-described range, the solubility in the developer is improved, the unexposed portion is easily dissolved, and the sensitivity is increased, and the pattern of the exposed portion remains at the time of development, and the residual film ratio tends to be improved.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of a resin having a group such as carboxylic acid, and can usually be obtained by titration using a conventional aqueous potassium hydroxide solution.

Content of binder resin is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 5 mass% or more and 30 mass% or less, More preferably, it is 10 mass% or more and 28 mass% or less, More preferably, 15 mass% It is more than 26 mass%. When content of a binder resin exists in the said range, a pattern can be formed and there exists a tendency for the resolution and residual film rate to improve.

The coloring photosensitive resin composition of this invention contains a photopolymerizable compound. A photopolymerizable compound is a compound which can superpose | polymerize with active radicals, an acid, etc. which generate | occur | produced by irradiating light, and a compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned, for example.

It is preferable that said photopolymerizable compound is a trifunctional or more than polyfunctional photopolymerizable compound.

As a trifunctional or more than polyfunctional photopolymerizable compound, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Pentaerythritol hexamethacrylate etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

The content is the mass fraction of the coloring photosensitive resin composition, Preferably it is 5 mass% or more and 90 mass% or less, More preferably, it is 10 mass% or more and 80 mass% or less, More preferably, it is 20 mass% or more and 70 mass% or less to be. When content of the said photopolymerizable compound is 5 mass% or more and 90 mass% or less, hardening will fully arise and a residual film ratio will improve and it will become difficult to undercut into a pattern, and adhesiveness tends to become favorable.

The coloring photosensitive resin composition of this invention contains a photoinitiator.

As said photoinitiator, an acetophenone type compound, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, a triazine type compound, an oxime type compound, an active radical generator, an acid generator, etc. are mentioned.

As said acetophenone type compound, diethoxy acetophenone, 2-methyl- 2-morpholino-1- (4-methylthio phenyl) propane- 1-one, 2-hydroxy-2- methyl-, 1-phenylpropane-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketones, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, and the like, and preferably 2-methyl-2-morpholino-. 1- (4-methylthiophenyl) propan-1-one etc. are mentioned.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- Tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro- 4-propoxy city oxanthone etc. are mentioned.

As said triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tri Azine, 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) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3, 5-triazine etc. are mentioned.

As said oxime type compound, an O-acyl oxime type compound is mentioned, for example, As a specific example, 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O- Benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O- Acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime-0-acetate, and the like.

As the above-mentioned active radical generator, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenansrenquinone, camphorquinone, phenylglyoxylate, titanocene compound, etc. You can also use

As said acid generator, 4-hydroxyphenyl dimethyl sulfonium p-toluene sulfonite, 4-hydroxyphenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl sulfonium p-toluene, for example Sulfonate, 4-acetoxyphenylmethyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfo Onium salts, such as a nitrate and diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzoin tosylate, etc. are mentioned.

These can be used individually or in combination of 2 types or more, respectively.

The content of the photopolymerization initiator is a mass fraction with respect to the total amount of the binder resin and the photopolymerizable compound, preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less. When content of a photoinitiator exists in the said range, it becomes high sensitivity and shortens an exposure time, and productivity improves, on the other hand, there exists a tendency for the high sensitivity to be excessive and a resolution not to become bad.

In the coloring photosensitive resin composition of this invention, you may use a photoinitiator. A photoinitiator is a compound which may be used in combination with a photoinitiator, and is used in order to further accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started by a photoinitiator.

As a photoinitiator, an amine compound, an alkoxy anthracene type compound, a thioxanthone type compound, etc. are mentioned.

As said amine type compound, for example, triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, and benzoic acid 2-dimethylamino Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name mihiraketone), 4,4'-bis (diethylamino) Benzophenone, 4, 4'-bis (ethylmethylamino) benzophenone, etc. are mentioned. Especially, 4, 4'-bis (diethylamino) benzophenone is preferable.

As said alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, for example Etc. can be mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro- 4-propoxy city oxanthone etc. are mentioned.

Moreover, a commercial thing can also be used as a photoinitiator, As a commercial photoinitiator, a brand name "EAB-F" (made by Hodogaya Chemical Co., Ltd.) etc. is mentioned, for example.

A photoinitiator can be used individually or in combination of 2 types or more, respectively.

As a combination of the photoinitiator and the photoinitiator in the coloring photosensitive resin composition of this invention, diethoxy acetophenone / 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-hydroxycyclohexylphenylketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2 Oligomer / 4,4'-bis (diethylamino) benzophenone of 2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2-benzyl-2-dimethylamino-1- ( And combinations of 4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone. Among them, a combination of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one / 4,4'-bis (diethylamino) benzophenone is preferable.

When using these photoinitiators, the usage-amount is per mol of photoinitiators, Preferably it is 10 mol or less, More preferably, it is 0.01 mol or more and 5 mol or less.

The solvent used for the coloring photosensitive resin composition of this invention is at least selected from the group which consists of a dipropylene glycol monoalkyl ether of C1-C4 of an alkyl group, and the dipropylene glycol monoalkyl ether ester of C1-C4 of an alkyl group. It contains 1 type of solvent (A) (Hereinafter, it may be called "solvent (A).").

Here, dipropylene glycol monoalkyl ether ester means the compound in which one hydroxyl group of dipropylene glycol forms an ether bond, and another hydroxyl group acylates and becomes ester.

As an alkyl group, a methyl group, an ethyl group, a propyl group, n butyl group, t butyl group, i butyl group is mentioned, for example. Especially, a methyl group and an ethyl group are preferable and a methyl group is more preferable.

Specifically, as a C1-C4 dipropylene glycol monoalkyl ether of an alkyl group, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether is mentioned. have. Preferably, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether are mentioned, More preferably, dipropylene glycol monomethyl ether is mentioned.

Dipropylene glycol monomethyl ether acetate is mentioned as a C1-C4 dipropylene glycol monoalkyl ether ester of an alkyl group.

Among these, the solvent (A) is preferably a dipropylene glycol monoalkyl ether having 1 to 4 carbon atoms of an alkyl group, and more preferably dipropylene glycol monomethyl ether.

Content of solvent (A) is 5 mass% or more and 40 mass% or less with respect to the total amount of solvent, It is preferable that they are 10% or more and 40% or less, It is more preferable that they are 10% or more and 30% or less. Thereby, a coloring photosensitive resin composition solidifies in the slit part of a slit coater, and it can prevent that a foreign material arises on a color filter. Moreover, the prebaking time before exposure can be shortened and productivity can be improved. In some cases, the solvent condenses in the prebaking furnace, and the condensed solvent falls on the substrate, causing staining to occur at the site where the solvent has fallen on the substrate obtained after development, resulting in a yield. Although it may reduce, it can prevent this effectively by making it into the said range.

Moreover, it is preferable that the solvent of this invention has an appropriate boiling point in addition to the property, such as the chemical structure of a specific solvent as mentioned above from another viewpoint. For example, about 172 degreeC or more is preferable, about 180 degreeC or more is more preferable, about 230 degreeC or less is preferable, and, as for the range of a boiling point, about 220 degreeC or less is more preferable. By using a solvent having a boiling point in such a range, the coloring photosensitive resin composition can be prevented from drying and the volatilization of the solvent can be achieved by combination with other kinds and amounts of other solvents and other components.

Moreover, in addition to the solvent (A) mentioned above, the solvent contains a solvent (B) different from the solvent (A). Examples of the solvent (B) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like excluding dipropylene glycol ethers and dipropylene glycol ether esters.

As said ether, for example,

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and diethylene glycol dibutyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monobutyl ether;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol dimethyl ether acetate, methoxy butyl acetate and methoxy pentyl acetate;

Alkyl ether acetates such as methoxy butyl acetate and methoxy pentyl acetate;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

In addition, ethyl carbitol acetate, butyl carbitol acetate, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, phentol, methyl anisole, etc. are mentioned.

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and the like. have.

Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, diacetone alcohol, 3-methyl-3-methoxy-1-butanol, and the like.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam acetate, isobutyl acetate, butyl propionate, isopropyl acetate, ethyl butyrate, butyl butyrate and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl acetate, ethoxyacetic acid, ethyl ethoxyacetate, methyl 3-oxypropionate, Ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropionic acid In propyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid , Methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl fibrate, ethyl fibrate Propyl fibrate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone Etc. can be mentioned.

In particular, solvents of ethers are preferable, and alkylene glycol alkyl ether acetates are preferred, and propylene glycol methyl ether acetate is more preferable.

As said amides, N, N- dimethylformamide, N, N- dimethylacetoamide, etc. are mentioned, for example.

As another solvent, N-methylpyrrolidone, dimethyl sulfoxide, etc. are mentioned, for example.

These can be used individually or in combination of 2 types or more, respectively.

Content of a solvent (B) is 60 mass% or more and 95 mass% or less with respect to the total amount of solvent, 60% or more and 90% or less are preferable, and 70% or more and 90% or less are more preferable. Thereby, a coloring photosensitive resin composition solidifies in the slit part of a slit coater, and it can prevent that a foreign material arises on a color filter. Moreover, the prebaking time before exposure can be shortened and productivity can be improved. In some cases, the solvent condenses in the prebaking furnace, and the condensed solvent falls on the substrate, leading to the occurrence of spots on the site where the solvent has fallen on the substrate obtained after development, thereby improving the yield. Although it may reduce, by setting it as said range, this can be effectively prevented.

Moreover, it is preferable that the solvent (B) of this invention has a suitable boiling point in addition to the property, such as chemical structure of specific solvent (A), as mentioned above from another viewpoint. For example, it is preferable that the ranges of a boiling point are 171 degreeC or less and 121 degreeC or more. By using the solvent which has a boiling point of such a range, in the coloring photosensitive resin composition, the balance of the prevention of drying and the volatilization of a solvent can be aimed at by the kind and quantity of another solvent, and the combination with another component, While improving the yield, it is confirmed that the occurrence of spots on the surface after development is suppressed.

As a combination of a solvent (A) and a solvent (B), Preferably, the combination of the said solvent (A) and alkylene glycol alkyl ether acetates [solvent (B)], the said solvent (A) and propylene glycol monomethyl ether acetate Combination with [Solvent (B)], a combination of a solvent [solvent (A)] and propylene glycol monomethyl ether acetate [solvent (B)] selected from one or more types of dipropylene glycol monoalkyl ethers having 1 to 4 carbon atoms Can be mentioned.

The coloring photosensitive resin composition of this invention may contain surfactant. As said surfactant, silicone type surfactant which has a silicone type surfactant, a fluorine type surfactant, and a fluorine atom is mentioned.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned. Specifically, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone 29SHPA, Toray silicone SH30PA, Polyether modified silicone oil SH8400 (Toray silicone ( KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (GE Toshiba Silicone Co., Ltd.) 1) etc. can be mentioned.

As a fluorine-type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned.

Specifically, Florinat FC430, Florinat FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (brand name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Mega pack R30 (made by Dainippon Ink and Chemicals Co., Ltd.), F top (brand name) EF301, F top EF303, F top EF351, F top EF352 (manufactured by Shin-Aki Kasei Co., Ltd.), saffron (brand name) S381, Saffron S382, Saffron SC101, Saffron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute), BM-1000, BM-1100 (all manufactured by BM Chemie Corporation), etc. Can be mentioned.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, mega pack (brand name) R08, mega pack BL20, mega pack F475, mega pack F477, mega pack F 443 (made by Dainippon Ink and Chemicals, Inc.), etc. are mentioned.

These surfactant can be used individually or in combination of 2 or more types.

When using these surfactant, the content is 0.0005 mass% or more and 0.6 mass% or less in mass fraction with respect to a coloring photosensitive resin composition, Preferably it is 0.001 mass% or more and 0.5 mass% or less. When content of surfactant exists in the said range, there exists a tendency for the flatness of the coating film obtained to improve.

The coloring photosensitive resin composition of this invention may contain additives, such as a high molecular compound other than a filler and binder resin, an adhesion promoter, antioxidant, an ultraviolet absorber, an aggregation agent, an organic acid, an organic amine compound, and a hardening | curing agent.

As a filler, microparticles | fine-particles, such as glass and alumina, are mentioned, for example.

Examples of the polymer compound other than the binder resin include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.

Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N. -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Oxysilane, etc. are mentioned.

As antioxidant, 4,4'- thiobis (6-t- butyl- 3-methyl phenol), 2, 6- di- t- butyl- 4-methyl phenol, etc. are mentioned, for example.

As a ultraviolet absorber, benzotriazole type, such as 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-octyloxybenzophenone, etc., for example Benzoate, such as benzophenone series, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1, Triazines such as 3,5-triazin-2-yl) -5-hexyloxyphenol; and the like.

As an aggregation inhibitor, sodium polyacrylate etc. are mentioned, for example.

As an organic acid, For example, aliphatic monocarboxylic acids, such as formic acid, an acetic acid, propionic acid, butyric acid, a citric acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid, caprylic acid;

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, sublinic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl amber acid, tetramethyl amber acid, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;

Aliphatic tricarboxylic acids such as tricarvalic acid, aconitic acid and camphoronic acid;

Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;

Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid.

As an organic amine compound, n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n, for example Monoalkylamines such as -heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine and n-dodecylamine;

Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, and 4-methylcyclohexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, din-propylamine, dii-propylamine, din-butylamine, dii-butylamine, disec-butylamine, Dialkyl amines such as dit-butyl amine, din-pentylamine and din-hexylamine;

Monoalkyl monocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;

Dicycloalkylamines such as dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldin-propylamine, ethyldin-propylamine, trin-propylamine, trii-propyl Trialkylamines such as amine, trin-butylamine, trii-butylamine, trisec-butylamine, trit-butylamine, trin-pentylamine and trin-hexylamine;

Dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;

Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

Monoalkanes such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol Olamines;

Monocycloalkanolamines such as 4-amino-1-cyclohexanol;

Dialkanolamines such as diethanolamine, din-propanolamine, dii-propanolamine, din-butanolamine, dii-butanolamine, din-pentanolamine, and din-hexanolamine;

Dicycloalkanolamines such as di (4-cyclohexanol) amine;

Trialkanolamines such as triethanolamine, trin-propanolamine, trii-propanolamine, trin-butanolamine, trii-butanolamine, trin-pentanolamine, and trin-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-1,2 Aminoalkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol and 2-diethylamino-1,3-propanediol;

Amino cycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;

Amino group-containing cycloalkanol methanols such as 1-amino cyclopentanone methanol and 4-aminocyclopentanone methanol;

1-aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol Amino group-containing cycloalkanethanols;

β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminogilic acid, 5-aminogilic acid, 6-aminocaproic acid, Aminocarboxylic acids such as 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid;

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, pn-butylaniline, pt-butylaniline, 1-naphthylamine, 2- Aromatic amines such as naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and p-methyl-N, N-dimethylaniline;

aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol;

aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;

and aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

As a hardening | curing agent, the compound which can crosslink a binder polymer by reacting with the carboxyl group in a binder polymer by heating, for example is mentioned. Moreover, the compound which can superpose | polymerize independently and harden a coloring pattern is mentioned. As said compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example.

Examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolak epoxy resins, other aromatic epoxy resins, cycloaliphatic epoxy resins, Epoxy resins such as heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxidized oils, and aliphatic, alicyclic or aromatic groups other than brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins. Epoxide compounds, epoxides of (co) polymers of butadiene, epoxides of (co) polymers of isoprene, (co) polymers of glycidyl (meth) acrylate, triglycidyl isocyanurate, and the like. have.

Examples of the oxetane compound include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane.

When the coloring photosensitive composition of this invention contains an epoxy compound, an oxetane compound, etc. as a hardening | curing agent, even if it contains the compound which can ring-open-polymerize the epoxy group of an epoxy compound, the oxetane skeleton of an oxetane compound, do. As said compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

Examples of the polycarboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ', 4 Aromatic polyhydric carboxylic acids such as, 4'-benzophenone tetracarboxylic acid;

Aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid and itaconic acid;

Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, cyclopentanetetracar Alicyclic polyhydric carboxylic acids, such as this acid and 1,2,4,5-cyclohexane tetracarboxylic acid, etc. are mentioned.

As polyhydric carboxylic anhydride, For example, Aromatic polyhydric carboxylic anhydrides, such as a phthalic anhydride, a pyromellitic anhydride, trimellitic anhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride;

Aliphatic polyhydric carboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodechenyl anhydride, tricarvallylic acid, maleic anhydride, and 1,2,3,4-butanetetracarboxylic dianhydride;

Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic acid anhydride, 1,2,4-cyclohexanetricarboxylic acid anhydride, cyclopentanetetracarboxylic acid dianhydride, 1 Alicyclic polyhydric carboxylic acid anhydrides such as 2,4,5-cyclohexanetetracarboxylic acid dianhydride, hymic acid anhydride and nadic anhydride;

And ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitate acid and glycerin tristrimellitate anhydride.

As carboxylic anhydrides, those commercially available as epoxy resin curing agents may be used. As said epoxy resin hardening | curing agent, for example, brand name "adekahardner EH-700" (made by Asahi Denka Kogyo Co., Ltd.), brand name "Licashid HH" (made by Shin-Nihon Rika Co., Ltd.), brand name "MH- 700 "(made by Shin-Nihon Rika Co., Ltd.), etc. are mentioned.

Said hardening | curing agent can be used individually or in combination of 2 or more types, respectively.

Specifically as a method of forming a pattern using the colored photosensitive resin composition of this invention, the solid colored photosensitive resin composition layer (henceforth a board | substrate etc.) which formed the coloring photosensitive resin composition of this invention on a board | substrate or a board | substrate is mentioned specifically, And a volatile component such as a solvent is removed from the applied colored photosensitive resin composition layer and exposed to a layer from which the volatile component has been removed via a photomask, followed by development.

Examples of the substrate include flat substrates such as glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamideimide substrates, polyimide substrates, Al substrates, and GaAs substrates. 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, vapor phase reaction treatment, vacuum deposition treatment, or the like. When a silicon substrate or the like is used as the substrate, a charge coupling element (CCD), a thin film transistor (TFT), or the like may be formed on the surface of the silicon substrate or the like.

In order to apply | coat a coloring photosensitive resin composition on the said board | substrate, it apply | coats on a board | substrate etc. using a spin coater, a liquid saving coater, especially a slit coater, and then volatile matters, such as a solvent, may be volatilized by heating. In this way, the layer which consists of solid content of a coloring photosensitive resin composition on a board | substrate etc. is formed flat. Thus, the coating film obtained is irradiated with an ultraviolet-ray through the mask for forming a desired image. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate may be performed. Moreover, the target image is obtained by then contacting the aqueous alkali solution with the aqueous alkali solution, dissolving and developing the non-exposed portion. After image development, you may perform a post-baking about 10 to 60 minutes at 150-230 degreeC as needed.

The developing solution used for image development after patterning exposure is the aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound described above may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compounds described above include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium hydrogen diphosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate. And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

Specific examples of the organic alkaline compound described above include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned.

These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.

Preferable concentration of the alkaline compound in the alkaline developer is 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Moreover, any of nonionic surfactant, anionic surfactant, or cationic surfactant may be sufficient as surfactant in alkaline developing solution.

Specific examples of the above nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters. , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the aforementioned anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

As an example of said cationic surfactant, amine salt, quaternary ammonium salt, etc., such as stearyl amine hydrochloride and lauryl trimethylammonium chloride, etc. are mentioned.

These surfactants may be used alone, or may be used in combination of two or more thereof.

The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

The pixel corresponding to the color of the coloring material in a colored photosensitive resin composition is obtained through each operation of application | coating, drying of the above-mentioned colored photosensitive resin composition, and patterning exposure to the dry coating film obtained, and image development, and these operations By repeating as many times as the number of colors required for a color filter, a color filter is obtained. In addition, the thickness of a color filter is not specifically limited, According to the kind and quantity of the used coloring agent, the kind and quantity of the used binder resin, a solvent, etc., it can adjust suitably.

According to the present invention, the colored photosensitive resin composition is hardly solidified around the slit, and even if partially solidified, the colored photosensitive resin composition is easily re-dissolved by the solvent in the colored photosensitive resin composition, so that generation of foreign matter on the color filter can be suppressed. Moreover, productivity can be improved by reducing the frequency of slit cleaning or ensuring productivity of a prebaking process.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples,% and parts indicating content to amount of use are based on mass unless otherwise specified.

<Synthesis of Binder Resin>

150 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a gas introduction tube. Thereafter, nitrogen gas is introduced into the flask through a gas introduction pipe, and the atmosphere in the flask is replaced with nitrogen gas. Subsequently, the solution in the flask was heated to 100 ° C., benzyl methacrylate 130.4 g (0.74 mol), methacrylic acid 31.0 g (0.26 mol), azobisisobutylonitrile 2.6 g and propylene glycol monomethyl ether acetate 163 The mixture consisting of g was added dropwise to the flask over 2 hours using the dropping lot. After completion of the dropwise addition, stirring was continued at 100 ° C for 5 hours. Solid content 34 mass% and the acid value 100 mgKOH / g resin were obtained.

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of a polymer having an acid group such as carboxylic acid, and is usually titrated using an aqueous solution of potassium hydroxide at a conventional concentration. It is calculated | required by setting.

The weight average molecular weight of polystyrene conversion measured by the GPC method of the following conditions of the obtained binder resin was 25,000.

Device ; HLC-8120 GPC (manufactured by Tosoh Corporation)

column ; TSK- GEL G2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Test liquid solids concentration; 0.001 to 0.01 mass%

Injection volume; 50 μL

Detector; RI

Calibration standard; TSK STANDARD POLYASTYRENE F-40, F-4, F-1, A-2500, A-500 (made by Tosoh Corporation)

<Example 1>

14.6 parts of binder resin (methacrylic acid / benzyl methacrylate copolymer) obtained by making it above, 3.3 parts of photopolymerizable compounds (dipentaerythritol hexaacrylate), 0.5 part of photoinitiators (ircacure-907), photopolymerization 0.5 part of the initiator (2,4-diethyl thioxanthone), 10 parts of propylene glycol monomethyl ether acetate, and 35.4 parts of dipropylene glycol monomethyl ether were mixed as a solvent. In addition, 10.2 parts of a coloring agent (CI pigment red 254), a dispersing agent (Azispa PB821; acid value 17 mg (KOH) / g; 3 parts of Ajinomoto Pinetechno Co., Ltd.), and 63 parts of propylene glycol monomethyl ether acetate beforehand The thing which mixed-dispersed was added and stirred, and the coloring photosensitive resin composition was obtained.

Next, the chromium film patterned on the glass substrate (# 1737 (manufactured by Corning Japan Co., Ltd.) in a lattice shape) was washed with a neutral detergent, water, and alcohol in that order and dried.

On this glass substrate, the obtained colored photosensitive resin composition was apply | coated with the coater provided with the slit nozzle so that it might become chromaticity x = O.655 (CIE1931 colorimetric system) after post-baking, and it is 1 torr, 70 degreeC, 60 in a pressure reduction drying apparatus. Hold for a second to distill off the solvent. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask having a stripe pattern was set to 150 µm, and an exposure amount of 100 mJ / cm 2 under an atmospheric atmosphere using an ultrahigh pressure mercury lamp (365 nm standard). ) Was irradiated with light.

Then, image development was performed by spraying the developing solution which is the aqueous solution containing 0.12% of nonionic surfactant and 0.06% of potassium hydroxide at 23 degreeC for 80 second through the shower nozzle. After washing with water, post-baking was performed at 220 ° C. for 20 minutes to form a pattern.

<Evaluation>

On the obtained patterned substrate, staining was observed under a sodium lamp. Although the pin which supports a board | substrate is arrange | positioned in a fixed position in the used pressure reduction drying apparatus, when a spot can be confirmed in the position on the board | substrate corresponding to the position of this pin, it is judged that the said board | substrate is a defect by pin spot. When more than 30% of such pin spots were observed, the pin spots in Table 1 were described as x. In the case of 30% or less, it described as (circle).

In addition, when a stain was observed in the part which does not correspond to the position of a pin, the part was observed with the optical microscope, and the red foreign material was confirmed when the same color as the colored photosensitive resin composition, ie, the red colored photosensitive resin composition, was used. In this case, the number of substrates was recorded as a defective substrate due to foreign matter.

When the difference between the total number of the board | substrates thrown in and the cumulative total of the defective board | substrate by a foreign material is 95% or more of the total number of the board | substrates put, it described in the yield column of Table 1 as (circle). When less than 95%, it described by x.

<Examples 2-7, Comparative Examples 1-5>

The solvent of Example 1 was changed to the thing of Table 1, the coloring photosensitive resin composition was similarly produced, apply | coated, exposed, and developed, and the pattern substrate was obtained.

The above evaluation results are shown in Table 1.

The number next to a solvent name shows the mass fraction of each solvent with respect to the whole solvent.

PGMEA; Propylene glycol monomethyl ether acetate (boiling point 146 degrees Celsius)

PGME; Propylene glycol monomethyl ether (boiling point l21 degrees Celsius)

EEP; Ethoxyethyl propionate (boiling point of 165 ° C)

MFDG; Dipropylene glycol monomethyl ether (boiling point 190 degrees Celsius)

MBA; Methoxybutyl acetate (boiling point 171 ° C)

CHN; Cyclohexanone (boiling point 156 degrees Celsius)

According to Table 1, in this Example, the yield was good in all of them, and pin unevenness was hardly observed.

Creation of Green Pixels

A green-colored photosensitive composition was prepared in the same manner except that the colorant described in Example 1 was changed to CI Pigment Green 36 (7.1 parts) and CI Pigment Yellow 150 (3.1 parts), and the above-described red pixel was prepared on a substrate. Similarly, application | coating, exposure, image development, and post-baking were performed, and the green pixel was created. However, application | coating was performed so that it might become chromaticity y = 0.590 (CIE1931 colorimetric system) after green post-baking.

Creating Blue Pixels

A blue-colored photosensitive composition was prepared in the same manner as in Example 1 except that the colorant was changed to CI Pigment Blue 15: 6 (7 parts) and CI Pigment Violet 23 (0.5 parts). In the same manner, coating, exposure, development, and post-baking were performed, blue pixels were created, and a color filter having an RGB pattern was created. However, application | coating was performed so that it might become chromaticity y = 0.100 (CIE1931 colorimetric system) after blue post-baking.

Example 8 Preparation of Black Matrix

[Preparation of Binder Resin]

In a four-necked flask with a volume of 300 mL, 46.3 g of bisphenol fluorenediglycidyl ether, 8.7 g of itaconic acid, 0.09 g of triethylbenzylammonium chloride, 0.18 g of tetraethylammonium bromide, 0.02 g of methquinone, and propylene glycol mono 55 g of methyl ether acetates were prepared and reacted at 120 degreeC for 4 hours, under heating and stirring, and the transparent pale yellow viscous liquid was obtained. To the obtained viscous liquid, 4.8 g of propylene glycol monomethyl ether acetate and 4.8 g of acrylic acid were further added, and the mixture was allowed to react at 120 ° C for 8 hours. This is called Compound A.

Next, 55 g of Compound A, 10.2 g of tetrahydrophthalic anhydride, and 10.2 g of propylene glycol monomethyl ether acetate were prepared, and reacted at 120 ° C. under heating and stirring for 2 hours to give a pale yellow transparent unsaturated group-containing carboxylic acid compound solution A1. Got.

[Production of Colored Photosensitive Resin Composition]

52 parts by mass of a coloring agent [40 parts by mass of a black pigment (C. I. pigment black 7) having an average particle diameter of 0.03 μm and 12 parts by mass of a dispersant);

Binder resin (resin solution A1 obtained above) 33 mass parts (solid content conversion),

10 parts by mass of an addition polymerizable compound [dipentaerythritol hexaacrylate] having an ethylenically unsaturated bond,

5.0 parts by mass of a photopolymerization initiator [2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine] and

252 parts by mass of the solvent [propylene glycol monomethyl ether acetate] and 122 parts by mass of [dipropylene glycol monomethyl ether] were mixed to obtain a colored photosensitive resin composition (black).

[Formation of black pattern]

The black photosensitive resin composition obtained on the glass substrate (# 1737; Corning Japan Co., Ltd. product) which was wash | cleaned in order with neutral detergent, water, and alcohol then, was made into the coater provided with the slit nozzle so that the optical density after post-baking might be 3.1. Applied.

Next, the solvent was distilled off by holding for 1 torr, 70 degreeC, and 60 second with a vacuum drying apparatus. After cooling, the space | interval of the board | substrate which apply | coated this coloring photosensitive resin composition and a quartz glass photomask (it has a 30 micrometers wide light transmission part, and a light shielding part has a rectangular grid pattern which has 80 micrometers and 40 micrometers sides). It was set to 150 micrometers, and it irradiated with the exposure amount (365 nm reference | standard) of 200 mJ / cm <2> under atmospheric conditions using the ultrahigh pressure mercury lamp.

Then, image development was performed by spraying the developing solution which is an aqueous solution containing 0.12% of nonionic surfactant and 0.06% of potassium hydroxide for 80 second at 23 degreeC through the shower nozzle. After washing with water, post-baking was carried out at 220 ° C. for 20 minutes to form a black matrix.

Similarly, black matrix substrates prepared in total of 451 sheets were observed under a sodium lamp and under an optical microscope, and the presence or absence of black foreign matter was observed and the number was accumulated. The result was divided by the total number of sheets 451 to calculate the number of black foreign matters observed per sheet. The results are shown in Table 2.

Comparative Example 6

Instead of 252 parts by mass of solvent [propylene glycol monomethyl ether acetate] and 122 parts by mass of [dipropylene glycol monomethyl ether] used in [production of colored photosensitive resin composition] of Example 6, solvent [propylene glycol monomethyl ether acetate] Except having prepared the coloring photosensitive resin composition (black) using 377 mass parts, it operated similarly and created 235 black-matrix board | substrates.

The obtained board | substrate was observed under the sodium lamp further by the optical microscope, the presence or absence of the black foreign material was observed, and the number accumulate | stored. The result was divided by the total number of sheets 235 to calculate the number of black foreign matters observed per sheet (370 mm x 470 mm). The results are shown in Table 2.

As described above, in Comparative Examples 1 to 3 and 5, while the yield is less than 95%, in Examples 1 to 7 using the colored photosensitive resin composition of the present invention, it can be seen that the yield is high at 95% or more and excellent in productivity. . Since the comparative example 4 has many defects by pin spots, productivity is inferior.

Moreover, when Example 8 and Comparative Example 6 were compared, the rate of the occurrence of the board | substrate to which Example 8 which used the coloring photosensitive resin composition of this invention uses few foreign substances per sheet, ie, a defect is low is low. It turns out that productivity is excellent.

<Examples 9-12>

The solvent of Example 1 is changed to the thing of Table 3, the coloring photosensitive resin composition is produced similarly, and it apply | coats, exposes, and develops, and a pattern substrate is obtained. Either way, as in Example 1, good results are obtained.

The number next to a solvent name shows the mass fraction of each solvent with respect to the whole solvent.

PGMEA; Propylene glycol monomethyl ether acetate (boiling point 146 degrees Celsius)

MFDG; Dipropylene glycol monomethyl ether (boiling point 190 degrees Celsius)

DPMA; Dipropylene glycol monomethyl ether acetate (boiling point of 209 degreeC)

The coloring photosensitive resin composition of this invention can be used in order to improve productivity in manufacture of a color filter, and also various filters, a film | membrane, a layer, such as adding various optical characteristics or adding light shielding etc. It can be used suitably for formation of the back.

Claims (7)

In the coloring photosensitive resin composition containing a coloring agent, binder resin, a photopolymerizable compound, a photoinitiator, and a solvent, The solvent is different from at least one solvent (A) and (A) selected from the group consisting of dipropylene glycol monoalkyl ethers having 1 to 4 carbon atoms of an alkyl group and dipropylene glycol monoalkyl ether esters having 1 to 4 carbon atoms of an alkyl group. Consisting of different solvents (B), Content of solvent (A) is 5 mass% or more and 40 mass% or less with respect to all solvent amounts, Content of solvent (B) is 60 mass% or more and 95 mass% or less with respect to the total amount of solvent, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1, A solvent (B) is a solvent which has a boiling point of 121 degreeC or more and 171 degrees C or less, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1 or 2, The solvent (A) is C1-C4 dipropylene glycol monoalkyl ether of an alkyl group, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 3, The solvent (A) is dipropylene glycol monomethyl ether, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 4, The solvent (B) is propylene glycol methyl ether acetate, The coloring photosensitive resin composition characterized by the above-mentioned. It is formed using the coloring photosensitive resin composition of any one of Claims 1-5, The pattern characterized by the above-mentioned. The color filter containing the pattern of Claim 6.