JP4675693B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a pattern using the photosensitive resin composition, and a color filter provided with the pattern.

For example, in a color filter used in a color display device, pixels (colored layers) each having a color of red (R), green (G), and blue (B) are generally formed in a lattice-shaped light shielding layer called a black matrix. It has the structure enclosed by.
A method for forming a colored layer and a black matrix of such a color filter by a photolithography method using a photosensitive resin composition containing a pigment is known.

  However, in the photosensitive resin composition containing a pigment, there exists a difficulty that the dispersibility of a pigment is bad. A photosensitive resin composition with poor pigment dispersibility is prone to reaggregation of the pigment during storage, and thus has a problem of thickening due to aging or precipitation of the pigment component in extreme cases. And a foreign material tends to generate | occur | produce in the film | membrane formed using such a photosensitive resin composition, and will cause the quality deterioration of a color filter.

Patent Document 1 below proposes a method for improving the storage stability of a polymerizable composition for a color filter by using a solvent mixture having a specific solubility parameter (SP value).
The following Patent Document 2 proposes a method for improving the solubility of the resin solids and the dispersibility of the pigment in the photosensitive resin composition for the color filter by using a solvent containing alkoxybutyl acetate and / or alkoxypentyl acetate. Has been.
JP-A-8-220328 JP-A-6-289601

However, in the conventional photosensitive resin composition for color filters, reaggregation of the pigment during storage cannot be sufficiently suppressed, and improvement in storage stability is required.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition containing a pigment and having excellent storage stability, and a pattern and a color filter using the same.

To achieve the above object, the photosensitive resin composition of the present invention, (A) a pigment, (B) an alkali-soluble resin, (C) photopolymerizable compound, (D) a photopolymerization initiator, and (E ) A photosensitive resin composition containing a solvent, wherein (E) the solvent contains (E1) an alkyl group-containing aromatic solvent , and (E1) the alkyl group-containing aromatic solvent contains a monoalkylbenzene. And dialkylbenzene and trialkylbenzene .

According to the present invention, a photosensitive resin composition having excellent storage stability can be obtained despite containing a pigment.
By using the photosensitive resin composition of the present invention, a high quality pattern can be formed, and a high quality color filter can be obtained.

<(A) Pigment>
As the pigment in the present invention, an organic pigment or an inorganic pigment is used. Further, an inorganic salt such as barium sulfate called extender may be used in combination.
The color tone of the pigment is not particularly limited, and can be appropriately selected according to the color tone of the colored layer of the color filter to be obtained or the color tone of the black matrix. For example, for use in a colored layer of a color filter, it is preferable to use one or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, a yellow pigment, and a purple pigment. For black matrix applications, black pigments are preferably used.
The pigment used in the color filter is preferably a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance, and an organic pigment is preferable.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically the following color index (C.I. I.) Numbers can be mentioned.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

Examples of the orange pigment include C.I. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;
Examples of purple pigments include C.I. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

  Examples of red pigments include C.I. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 79, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

Examples of blue pigments include C.I. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;
Examples of green pigments include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
Examples of brown pigments include C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment Brown 28.

  Examples of black pigments include C.I. I. In addition to Pigment Black 1 and Pigment Black 7, carbon black, titanium black, chromium oxide, iron oxide, aniline black, perylene pigments and the like can be used. Carbon black is particularly preferable.

(A) Any one type of pigment may be used alone, or two or more types may be mixed. The organic pigment can be purified and used by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination of these.
(A) The addition amount of the pigment is appropriately changed according to the target color tone, but generally in the case of an organic pigment, it is 5 to 300 with respect to 100 parts by mass of (B) the alkali-soluble resin. It is preferable to add in the range of parts by mass, and a more preferable range is about 10 to 250 parts by mass.

<(B) Alkali-soluble resin>
(BI) Alkali-soluble resin As the alkali-soluble resin in the present invention, one or more selected from monomers having a carboxy group such as acrylic acid and methacrylic acid,
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, A copolymer with at least one selected from benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, cardo epoxy diacrylate, styrene, acrylamide, acrylonitrile, and the like;
Resins such as phenol novolac type epoxy acrylate polymer, phenol novolac type epoxy methacrylate polymer, cresol novolac type epoxy acrylate polymer, cresol novolac type epoxy methacrylate polymer, bisphenol A type epoxy acrylate polymer, bisphenol S type epoxy acrylate polymer Is mentioned.
Since these resins have an acryloyl group or a methacryloyl group introduced, the crosslinking efficiency is improved and the light resistance and chemical resistance of the coating film are excellent.
Of the monomer components constituting the alkali-soluble resin, the content of monomer components having a carboxy group such as acrylic acid and methacrylic acid is preferably in the range of 5 to 40% by mass.

(B-II) Alkali-soluble resin having photocurability Further, as the alkali-soluble resin in the present invention, a polymer represented by the following general formula (I) is also applicable. The compound represented by the general formula (I) itself has photopolymerizability (photocurability).

(Wherein X is a group represented by the following chemical formula (II), Y is a residue obtained by removing a carboxylic anhydride group (—CO—O—CO—) from dicarboxylic anhydride, and Z is a tetra (This is a residue obtained by removing two carboxylic anhydride groups from carboxylic dianhydride, where n represents the number of repeating units in [].)

Specific examples of the dicarboxylic acid anhydride (the dicarboxylic acid anhydride before removing the carboxylic acid anhydride group) for deriving Y include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, and glutaric anhydride.
Specific examples of the tetracarboxylic dianhydride for deriving Z (tetracarboxylic dianhydride before removing two carboxylic anhydride groups) include, for example, pyromellitic anhydride, benzophenone tetracarboxylic acid bis Examples thereof include tetracarboxylic dianhydrides such as anhydrides, biphenyl tetracarboxylic dianhydrides, and biphenyl ether tetracarboxylic dianhydrides.

(B) The alkali-soluble resin may be used alone or in combination of two or more. Further, only the alkali-soluble resin (BI) may be used, or only the alkali-soluble resin (B-II) having photocurability may be used, or both may be used in combination.
The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of (B) alkali-soluble resin in the present invention is not particularly limited, but is preferably 1000 to 100,000, more preferably 3000 to 50000, Most preferred is 5000-15000. If it is smaller than the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist. If it is larger than the lower limit of this range, the resist pattern cross-sectional shape is good.

<(C) Photopolymerizable compound>
Examples of the photopolymerizable compound in the present invention include methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, Triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetra Methacrylate, pe Taerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol Examples include, but are not limited to, diacrylate, benzyl acrylate, benzyl methacrylate, cardo epoxy diacrylate, acrylic acid, methacrylic acid, and the like.
A photopolymerizable compound may be used individually by 1 type, and may use 2 or more types together.
In the present invention, the photopolymerizable polymer is included in the (B) alkali-soluble resin (B-II), and the photopolymerizable monomer is included in the (C) photopolymerizable compound. To do.

(C) The compounding quantity of a photopolymerizable compound has the preferable range of 5-200 mass parts with respect to 100 mass parts of (B) alkali-soluble resin.
(C) The compounding quantity of a photopolymerizable compound is 5-500 mass with respect to 100 mass parts of this resin (BI), when (B) alkali-soluble resin contains the said alkali-soluble resin (BI). The range of parts is preferable, and the more preferable range is 20 to 300 parts by mass.
Moreover, when (B) alkali-soluble resin contains the said alkali-soluble resin (B-II), the compounding quantity of (C) photopolymerizable compound is 0.00 with respect to 100 mass parts of this resin (B-II). The range of 05-300 mass parts is preferable, and a more preferable range is 1-100 mass parts.
(C) By making the compounding quantity of a photopolymerizable compound more than the lower limit of the said range, it is hard to produce the hardening defect at the time of exposure, and sufficient heat resistance and chemical-resistance can be obtained. Moreover, when obtaining favorable film formation ability, it is preferable to set it as the upper limit or less of the said range.

<(D) Photopolymerization initiator>
As the photopolymerization initiator (D) in the present invention, a compound represented by the following general formula (III) is preferable.

(In the formula, X ′ is a group represented by the general formula (IV) or the general formula (V), and R ¹¹ is a phenyl group, an alkyl group having 1 to 20 carbon atoms, CN, NO _2, or 1 carbon atom. -4 halogenated alkyl group, and R ¹² is an acyl group having 2 to 12 carbon atoms or an alkenoyl group having 4 to 6 carbon atoms.)

^(Wherein the R 13 ^{to R 17} each independently represent a hydrogen atom, a halogen atom, an alkyl group, phenyl group having 1 to 12 carbon atoms is a phenylsulfanyl group _{(C 6 H 5 S-).} )

(Wherein R ^{18 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group.)

  The compound represented by the above general formula (III) is a compound obtained by the method described in JP-A No. 2000-80068. The compound is extremely sensitive to light compared to other known photopolymerization initiators, and can be efficiently activated by a small amount of light to cure the photopolymerizable compound.

Moreover, photoinitiators other than the compound shown by the said general formula (III) can also be used.
Specific examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl. -1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1 -One, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,4,6-trimethyl Nzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4- Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) ) Oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4 -Jie Ruthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumeneper Oxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2- Chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, ben In, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, Dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2- Methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylamino Benzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(4-Diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) eth L] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- ( 3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6 -(3-Bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-to Examples include lyazine.

  Among these, triazines such as p-methoxytriazine; 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis ( Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4- Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 Halomethyl groups such as (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Triazine compounds such as: Triazine compounds such as 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer; Imidazolyl compounds such as 2-benzyl-2-dimethylamino-1 An amino ketone compound such as-(4-morpholinophenyl) -butan-1-one; is preferably used.

In the present invention, it is preferable to use a compound represented by the general formula (III) in combination with at least one other compound as a photopolymerization initiator. Use of at least two kinds of compounds (photopolymerization initiators) in this way is preferable in that they can be efficiently activated by a small amount of light to further increase sensitivity and development margin. This is because a compound having a different electronic band spectrum (photopolymerization initiator) coexists in the photosensitive resin composition, so that the entire photopolymerization initiator broadens the net wavelength range of light having high sensitivity, or at least two. This is thought to be due to the interaction of certain compounds.
Preferred examples (1) to (3) of the combination of the compound represented by the general formula (III) and at least one other compound are shown below.

(1) At least one photopolymerization initiator of the O-acyloxime compound represented by the general formula (III) and a compound other than the O-acyloxime compound (light other than the compound represented by the general formula (III) A combination with a polymerization initiator) is preferred.
Among the above O- acyl oxime compound, in the general formula ^{(III), R 11} is n- hexyl _{(C 6 H 13} ^-), in ^{R 12} is a benzoyl group, X 'is represented by the general formula (IV) And R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ are hydrogen atoms and R ¹⁵ is a phenylsulfanyl group (C ₆ H ₅ S—), that is, 1,2-octanedione represented by the following formula (VI) -1- [4- (Phenylthio) phenyl] -2- (O-benzoyloxime) is preferable in terms of sensitivity to light and availability.

Further, among the O-acyloxime compounds, in general formula (III), R ¹¹ is methyl, R ¹² is an acetyl group, X ′ is represented by general formula (V), and R ¹⁸ is ethyl. R ¹⁹ is a methyl group, that is, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- represented by the following formula (VII) (O-acetyloxime) is more preferable because it has higher sensitivity to light.

(2) A combination of a photopolymerization initiator represented by the above general formula (III) and X ′ represented by the general formula (IV) and a triazine compound is also preferable.
In particular, as the triazine compound, a triazine compound represented by the following formula (VIII), the following formula (IX), or the following formula (X) (wherein R ²¹ and R ²² represent an alkyl group having 1 to 3 carbon atoms). Is particularly preferred. 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one can also be used in the same manner as the triazine compound.

(3) a photopolymerization initiator represented by the above general formula (III) and X ′ represented by the general formula (V), and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane A combination with -1-one is also preferred. Moreover, the above-mentioned triazine compound can be similarly combined instead of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

  The compounding ratio of the compound represented by the general formula (III) and other compounds other than the compound represented by the general formula (III) (especially triazine compound, imidazolyl compound and aminoketone compound) is 10:90 to mass ratio. 90:10 is preferable, and 20:80 to 80:20 is particularly preferable. Since the compounding ratio of the compound represented by the general formula (III) and the other compound other than the compound represented by the general formula (III) is within the above-mentioned range, both compounds effectively interact with each other. Further, the sensitivity of the photosensitive resin composition and the development margin can be further improved.

  The blending amount of the photopolymerization initiator (D) in the photosensitive resin composition of the present invention is preferably in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the (B) alkali-soluble resin.

<(E) Solvent>
The photosensitive resin composition of the present invention contains (E) a solvent, and the (E) solvent contains at least (E1) an alkyl group-containing aromatic solvent.

(E1) Alkyl group-containing aromatic solvent (E1) The component is a solvent mainly composed of an aromatic compound having an alkyl group. 90% by mass or more of the component (E1) is preferably an aromatic compound having an alkyl group, more preferably 98% by mass or more, and still more preferably 100% by mass.

Examples of the aromatic compound having an alkyl group include monoalkylbenzene, dialkylbenzene, and trialkylbenzene.
Specific examples of monoalkylbenzene include toluene, ethylbenzene, propylbenzene, 1-methylethylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene and the like.
Specific examples of the dialkylbenzene include xylene, dimethylbenzene, diethylbenzene, ethylmethylbenzene and the like.
Specific examples of the trialkylbenzene include trimethylbenzene and ethyldimethylbenzene.
Moreover, what has a condensed ring with benzene rings, such as indane, is also mentioned.
The aromatic compound having an alkyl group contained in the component (E1) may be any one of the above, or may be two or more. In particular, dialkylbenzene and trialkylbenzene are preferably contained, and monoalkylbenzene, dialkylbenzene and trialkylbenzene are more preferably contained.

A preferable composition in the component (E1) containing monoalkylbenzene, dialkylbenzene and trialkylbenzene is about 25 to 45% by mass of monoalkylbenzene, 10 to 30% by mass of dialkylbenzene, and about 35 to 55% by mass of trialkylbenzene.
As the alkyl group-containing aromatic solvent having such a composition, commercially available Solvesso 100 (trade name, manufactured by Exxon Chemical Co., Ltd.), Swazol 1000 (trade name: manufactured by Maruzen Petrochemical Co., Ltd.) and the like can be used.

(E1) The alkyl group-containing aromatic solvent preferably has a boiling point in the range of 110 to 180 ° C. When (E1) component is a mixture of a plurality of components, all components of (E1) component The boiling point of is preferably within the above range. (E1) When the boiling point of the alkyl group-containing aromatic solvent is within the above range, it is possible to improve the applicability of the photosensitive resin composition and to provide preferable drying properties. .
As the alkyl group-containing aromatic solvent having such a boiling point, commercially available Solvesso 100 (trade name, manufactured by Exxon Chemical Co., Ltd.), Swazol 1000 (trade name: manufactured by Maruzen Petrochemical Co., Ltd.), or the like can be used.

(E) As a solvent, it is preferable to use a mixture of (E1) an alkyl group-containing aromatic solvent and other (E2) other solvent.
(E2) Other solvents include benzene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether Acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate and carbonate butyl.
Among these, propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, and 3-methoxybutyl acetate are preferable.
In particular, 3-methoxybutyl acetate exhibits excellent solubility in soluble components in the photosensitive resin composition and can contribute to improving the dispersibility of insoluble components such as pigments. It is preferable to contain methoxybutyl acetate.
As the component (E2), any one type may be used alone, or two or more types may be used in combination.

(E) The content ratio of the (E1) alkyl group-containing aromatic solvent in the solvent is preferably 1 to 50 mass%, more preferably 2 to 40 mass%. By making the content rate of this (E1) component into the said range, the effect of improving the compatibility and dispersibility of each component of the photosensitive resin composition can fully be acquired.
The content of the solvent (E) in the photosensitive resin composition of the present invention is not particularly limited, but is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness.
5-100 mass% is preferable and, as for the solid content density | concentration of the photosensitive resin composition, 10-50 mass% is more preferable.

<Other ingredients>
Moreover, you may add a thermal-polymerization inhibitor, an antifoamer, surfactant, etc. to the photosensitive resin composition of this invention.
The thermal polymerization inhibitor may be a conventionally known one, and examples thereof include hydroquinone and hydroquinone monoethyl ether.
As said antifoamer, a conventionally well-known thing may be used and a silicone type and a fluorine-type compound are mentioned.
The surfactant may be a conventionally known surfactant, and examples thereof include anionic, cationic and nonionic compounds.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition of the present invention can be prepared, for example, by the following method.
(A) Pigment, (B) Alkali-soluble resin, (C) Photopolymerizable compound, (D) Photopolymerization initiator, organic additives as required, and (E) solvent, three roll mill, ball mill, A photosensitive resin composition is prepared by mixing (dispersing and kneading) with a stirrer such as a sand mill and filtering with a 5 μm membrane filter.

  The photosensitive resin composition of this invention can be used suitably for forming a pattern by the photolithographic method. In particular, it can be suitably used for the purpose of forming a pattern forming a black matrix and / or a colored layer constituting a color filter.

<Pattern formation method>
Hereinafter, a method for forming a pattern using the photosensitive resin composition of the present invention will be described by taking a pattern (black matrix and colored layer) used for a color filter as an example.

1. Formation of black matrix (black colored layer) First, a photosensitive resin composition (including a black pigment) is applied onto a substrate by a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or spinner (rotary coating device). Coating is performed using a non-contact type coating apparatus such as a curtain flow coater. As the substrate, a light-transmitting substrate is used, for example, a glass substrate having a thickness of 0.5 to 1.1 mm.
In order to improve the adhesion between the glass substrate and the photosensitive resin composition, a silane coupling agent may be applied on the glass substrate in advance. Alternatively, a silane coupling agent may be added during the preparation of the photosensitive resin composition.
After the application, the solvent is removed by drying. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds to 120 seconds, (2) several hours at room temperature Any one of a method of leaving for several days, and a method of removing the solvent by putting in a warm air heater or an infrared heater for several tens of minutes to several hours may be used.

Next, exposure is performed partially by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably about 30 to 2000 mJ / cm ² , for example.
The exposed film is developed with a developer to be patterned into a desired shape.
The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, and quaternary ammonium salts. Can be mentioned.
After development, post-baking is performed at about 200 ° C. Further, it is preferable to expose the entire surface of the formed pattern.

2. Formation of other colored layers The photosensitive resin composition is applied to the glass substrate having the pattern (black matrix) formed as described above, dried, exposed and developed in the same manner as described above to form a colored layer of a predetermined color. A pattern (stripe or dot) is formed at a predetermined position (opening) of the matrix.
For example, when an RGB color filter is manufactured, the above process is repeated using photosensitive resin compositions of R, G, and B colors to form a three-color pattern (colored layer).
As described above, a color filter can be formed.

According to the photosensitive resin composition of the present invention, the compatibility and dispersibility of each component in the composition are improved by including the (E1) alkyl group-containing aromatic solvent in the (E) solvent, As a result, reaggregation of the pigment is suppressed, and the generation of foreign matters during storage and the increase in viscosity are improved. Thereby, the temporal stability of the photosensitive resin composition is improved, and the yield is improved.
Therefore, by using the photosensitive resin composition of the present invention, a good pattern can be stably formed, and a high-quality color filter can be formed.
In particular, in the photosensitive resin composition in which carbon is dispersed, the effect of improving the pigment aggregation phenomenon by using the component (E1) is high.

Example 1
The photosensitive resin composition (a1) was prepared by mixing each component with the following composition.
(A) As a black pigment, 175 parts by mass of a 20% solution of 3-methoxybutyl acetate in which carbon black was dispersed with an acrylic resin was used.
(B) As an alkali-soluble resin, 100 parts by mass of cardo epoxy diacrylate, acrylic acid, and methacrylic acid copolymer were used.
(C) As a photopolymerizable compound, 35 parts by mass of dipentaerythritol hexaacrylate was used.
(D) 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,4-trichloromethyl as a photopolymerization initiator (4'-methoxystyryl) -6-triazine and 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-bisimidazole were blended in an equal ratio. 40 parts by mass were used.
(E) As a solvent, a mixed solvent in which 95 parts by mass of a 3-component mixture having a mass ratio of 3-methoxybutyl acetate: PGMEA: cyclohexanone of 6: 2: 2 and 5 parts by mass of Solvesso 100 (trade name) is used. It was. (E) The usage-amount of the solvent was adjusted so that solid content concentration might be 30 mass%.

(Comparative Example 1)
In Example 1, the photosensitive resin composition (b1) was prepared in the same manner as in Example 1 except that the Solvesso 100 was not used and the three-component mixture was used as a solvent.

(Comparative Example 2)
In Example 1, a photosensitive resin composition (b2) was prepared in the same manner as in Example 1 except that 5 parts by mass of water was used instead of Solvesso 100.
(Comparative Example 3)
In Example 1, a photosensitive resin composition (b3) was prepared in the same manner as in Example 1 except that 5 parts by mass of N, N-dimethylacetamide was used instead of Solvesso 100.
(Comparative Example 4)
In Example 1, a photosensitive resin composition (b4) was prepared in the same manner as in Example 1 except that 5 parts by mass of acetone was used instead of Solvesso 100.
(Comparative Example 5)
In Example 1, a photosensitive resin composition (b5) was prepared in the same manner as in Example 1 except that 5 parts by mass of 3-methoxybutyl acetate was used instead of Solvesso 100.

[Evaluation of storage stability]
Each photosensitive resin composition (a1) and (b1) to (b5) prepared above was stored in a dark place at room temperature for 3 weeks. Viscosity was measured before and after storage, and changes in viscosity were evaluated according to the following criteria. The results are shown in Table 1 below.
○: Viscosity hardly changed before and after storage.
X: Viscosity increased after storage compared to before storage.

[Evaluation of foreign matter generation]
After the preparation, using each photosensitive resin composition (a1) and (b1) to (b5) stored in a dark place at room temperature for 3 weeks, a spin coater (1H-360s: Micasa Co., Ltd.) and dried on a hot plate at 90 ° C. for 2 minutes to form a coating film.
The obtained film was visually observed, and the presence or absence of foreign matter was evaluated according to the following criteria. The results are shown in Table 1 below.
○: Almost no foreign matter is generated.
X: Foreign matter was generated.

As shown in the results of Table 1, in Example 1, the viscosity did not increase during storage, the generation of foreign matter after storage was reduced, and excellent storage stability was obtained.

Claims (7)

A photosensitive resin composition comprising (A) a pigment, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent,
The (E) solvent contains an (E1) alkyl group-containing aromatic solvent,
The (E1) alkyl group-containing aromatic solvent contains monoalkylbenzene, dialkylbenzene, and trialkylbenzene.   The photosensitive resin composition according to claim 1, wherein the (E1) alkyl group-containing aromatic solvent has a boiling point of 110 to 180 ° C.   The photosensitive resin composition according to claim 1 or 2, wherein a content ratio of the (E1) alkyl group-containing aromatic solvent in the (E) solvent is 1 to 50% by mass.   The photosensitive resin composition according to claim 1, wherein the solvent (E) further contains 3-methoxybutyl acetate.   The photosensitive resin composition as described in any one of Claims 1-4 in which the said (A) pigment contains a black pigment.   The photosensitive resin composition according to claim 5, wherein the black pigment is carbon black.   The photosensitive resin composition as described in any one of Claims 1-6 in which the said (A) pigment contains at least 1 sort (s) chosen from the group which consists of a red pigment, a green pigment, a blue pigment, a yellow pigment, and a purple pigment. object.