JP2003330187A - Colored photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition having good suitability to coating when a liquid-saving coater such as a spin coater is used. <P>SOLUTION: In the colored photosensitive resin composition comprising (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, the acid value of the binder polymer (B) is 50-150, the weight average molecular weight of the polymer (expressed in terms of polystyrene) is 5,000-50,000, the polymer content is 15-26 mass% based on the solid content of the colored photosensitive resin composition, the solvent (E) is at least one selected from the group comprising propylene glycol monomethyl ether acetates and ethyl 3-ethoxypropionates and the amount of the solvent is 70-95 parts by mass based on 100 parts by mass of the colored photosensitive resin composition. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored photosensitive resin composition.

[0002]

2. Description of the Related Art A colored photosensitive resin composition is a photosensitive resin composition containing a colorant and is useful as a material for forming a colored pattern constituting a color filter. Here, the color filter is an optical element used for colorizing a display image of a liquid crystal display device or for colorizing an image captured by a solid-state image sensor. The coloring pattern is, for example,
It is a color pixel of red, green, blue, etc., a black matrix, etc., and has a line shape or a mosaic shape.

Conventionally, in order to form a film using a colored photosensitive resin composition on a substrate to be coated such as a wafer, the colored photosensitive resin composition is dropped from a nozzle near the center of the substrate to be coated, After dropping the colored photosensitive resin composition on the substrate to be coated from a slit-shaped nozzle, the substrate is rotated at a speed of several hundreds to several thousand rpm, and the solvent and excessively dropped colored photosensitive resin on the substrate. A flat coating film was obtained using a spin coater that repels the volatile resin composition. However, by using a spin coater, the colored photosensitive resin composition dropped excessively on the substrate is thrown away and discarded without forming the colored photosensitive resin layer, so that it is wasted and prevented, and Since it has been difficult to apply a conventional spin coater on a substrate such as glass having a large area of 1 m square, a liquid-saving coater such as a spinless coater that does not spin has been developed. Among the liquid-saving coaters, the spinless coater is disclosed in
No. 001-62370. On the other hand, even if a colored photosensitive resin composition optimized for a conventional spin coater is applied to a spinless coater, which is one type of liquid-saving coater, flatness tends to be difficult to obtain. This is because in a spin coater, the flatness in the coated state is not so important and the spin provides some flatness, and most of the solvent is removed by the spin, so the process of removing the solvent by heating or the like. This is because the flatness is not significantly impaired because the amount of solvent removed from the inside of the formed layer is small. On the other hand, the spinless coater does not remove the solvent by spinning,
Most of the flatness is determined by the coating state, and the amount of solvent removed by heating etc. is significantly larger than that of the spin coater, so the solvent is also removed from the inside of the formed layer, resulting in poor flatness. There is. Then, conventionally, in order to improve the coating property of the colored photosensitive resin composition, a method of adding a polymer additive such as a leveling agent has been used. However, when a polymer additive such as a leveling agent is added, the undried coating film obtained by applying the colored photosensitive resin composition is a frame portion (undried coating film) formed along the peripheral portion of the substrate immediately after the application. The thick film portion) moves to the center of the substrate, impairing the in-plane uniformity. Moreover, since the binder polymer generally used in the colored photosensitive resin composition is a polymer and has a polar group such as carboxylic acid, the viscosity of the colored photosensitive resin composition tends to be high. . If the viscosity is too high, there is a problem that the spread of the colored photosensitive resin composition on the substrate is poor, and further, unevenness is likely to occur during coating. By the way, Japanese Patent Application 20
No. 01-176766, the content of the binder polymer is 5 per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound in the colored photosensitive resin composition.
It is described that when it is 5 parts by mass or more, a colored pattern having a forward tapered cross section can be stably formed. However, even in the case of the colored photosensitive resin composition described above, when the content of the binder polymer in the solid content of the colored photosensitive resin composition is high, when used in a liquid-saving coater such as a spinless coater, the coating property is low. There was a problem of being bad.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a colored photosensitive resin composition having good coatability when a liquid-saving coater such as a spinless coater is used.

[0005]

Therefore, as a result of intensive studies to solve the above problems, the present inventor has determined that the acid value of the binder polymer, the polystyrene-converted weight average molecular weight, and the content in the colored photosensitive resin composition are specified. It was found that a colored photosensitive resin composition containing a specific solvent in a specific amount within the above range can solve the above-mentioned problems, and has reached the present invention. That is, the present invention provides a colored photosensitive resin composition containing (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. Acid value of binder polymer is 50 or more 150
Below, the polystyrene-converted weight average molecular weight is 5,000.
To 50,000, the content thereof is 15% to 26% by mass fraction in the solid content of the colored photosensitive resin composition, and (E) the solvent is propylene glycol monomethyl ether acetate and 3-ethoxypropionic acid. A colored photosensitive resin composition for a liquid-saving coater, which is at least one selected from the group consisting of ethyl, and contains the solvent in an amount of 70 parts by mass or more and 95 parts by mass or less in 100 parts by mass of the colored photosensitive resin composition. The colored photosensitive resin composition is applied onto a substrate or a layer formed of the solid content of the colored photosensitive resin composition previously formed, and volatile components are removed from the applied colored photosensitive resin composition layer. A method for forming a pattern by exposing and developing the layer through a photomask, a color filter including the pattern formed by the method, and the color filter To provide a liquid crystal display device.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) colorant used in the colored photosensitive resin composition of the present invention may be an organic pigment which is an organic substance, or an inorganic pigment which is an inorganic substance.
Among them, organic pigments are preferably used because they are excellent in heat resistance and color development.

Specific examples of organic pigments and inorganic pigments include color indexes (The Society of Dyers and C
Published by olourists) include compounds that are classified as Pigment. Specifically, for example, C.I. I.
Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14,
C. I. Pigment Yellow 15, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I.
I. Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 31, C.I. I.
Pigment Yellow 53, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 9
4, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 1
17, C.I. I. Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I.
Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I.
I. Pigment Yellow 150, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154,
C. I. Pigment Yellow 166, C.I. I. Pigment Yellow 173, C.I. I. Pigment Yellow 19
4, C.I. I. Pigment Yellow 214, a yellow pigment such as C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 36,
C. I. Pigment Orange 38, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 42, C.I.
I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I.
Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 65, C.I. I. Pigment Orange 7
1, C.I. I. Pigment Orange 73, an orange pigment such as C.I. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 105,
C. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 144, C.I.
I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I.
Pigment Red 176, C.I. I. Pigment Red 1
77, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 20
9, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 224,
C. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264, C.I.
I. Pigment Red 265 and other red pigments, C.I. I.
Pigment Blue 15, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Blue 15: 4, C.I. I.
Pigment Blue 15: 6, C.I. I. Pigment Blue 60, a blue pigment such as C.I. I. Pigment Violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 32,
C. I. Pigment Violet 36, C.I. I. Pigment Violet 38, violet color pigments such as C.I.
I. Pigment Green 7, C.I. I. Pigment Green 36, a green pigment such as C.I. I. Pigment Brown 2
3, C.I. I. Pigment Brown 25 and the like, C.I. I. Pigment Black 1, C.I. I. Pigment Black 7 and the like, and black pigments such as C.I.
I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150,
C. I. Pigment Red 177, C.I. I. Pigment Red 209, C.I. I. Pigment Red 254, C.I.
I. Pigment Red Violet 23, C.I. I. Pigment Blue 15: 6 and C.I. I. Pigment Green 36 preferably contains at least one pigment.

These organic pigments and inorganic pigments may be used alone or in admixture of two or more. For example, in order to form a red pixel, C.I. I. Pigment Red 209 and C.I. I. Pigment Yellow 139 is contained in C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 150 and C.I. I. Pigment Yellow 138 contains at least one selected from the group consisting of C.I. I. Pigment Blue 15: 6 is preferably contained.

Of the above pigments, the organic pigments are, if necessary, rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced, graft treatment on the pigment surface with a polymer compound, etc. Atomization treatment by a sulfuric acid atomization method or the like, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.

The amount of the pigment used is usually 25 parts by mass or more and 60 parts by mass or less, preferably 27 parts by mass or more and 55 parts by mass or less, when the solid content in the colored photosensitive resin composition is 100 parts by mass. And more preferably 30 parts by mass or more and 50 parts by mass or less. When the content of the pigment is 25 parts by mass or more and 60 parts by mass or less, the color density when used as a color filter is sufficient, and a necessary amount of a binder polymer can be contained in the composition, so that the mechanical strength is improved. Is preferable because it can form a sufficient pattern.

In the colored photosensitive resin composition obtained in the present invention, it is preferable that the pigment as a colorant has a uniform particle size. In order to make the pigment have a uniform particle diameter, a surfactant is added as a pigment dispersant and the dispersion treatment is performed, whereby a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained. Examples of the pigment dispersant include cationic, anionic, nonionic and amphoteric surfactants, which may be used alone or in combination of two or more. The amount of the pigment dispersant used is usually 1 part by mass or less, preferably 0.05 part by mass or more and 0.5 part by mass or less, per 1 part by mass of the colorant. When the amount of the pigment dispersant used is usually 1 part by mass or less per 1 part by mass of the colorant, a pigment having a uniform particle size tends to be obtained, which is preferable.

The binder polymer (B) used in the present invention has an acid value of 50 or more and 150 or less and a polystyrene-equivalent weight average molecular weight of 5,000 to 50,0.
The content is 15% to 26% in terms of mass fraction in the solid content of the colored photosensitive resin composition.

As the binder polymer (B) used in the present invention, an acrylic copolymer can be used,
Examples thereof include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable therewith.

As the carboxyl group-containing monomer, for example, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid,
Unsaturated carboxylic acids having at least one carboxyl group in the molecule such as unsaturated polycarboxylic acids such as unsaturated tricarboxylic acids can be mentioned. Here, as the unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid,
Examples thereof include crotonic acid, α-chloroacrylic acid, cinnamic acid and the like. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. The unsaturated polycarboxylic acid may be an acid anhydride thereof, specifically maleic anhydride, itaconic anhydride, citraconic anhydride, or the like. Further, the unsaturated polyvalent carboxylic acid may be its mono (2-methacryloyloxyalkyl) ester, and examples thereof include succinic acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyloxy). Ethyl), mono phthalate (2
-Acryloyloxyethyl), mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of its both-end dicarboxy polymer, for example, ω-
Carboxypolycaprolactone monoacrylate, ω-
It may be carboxypolycaprolactone monomethacrylate or the like. These carboxyl group-containing monomers can be used alone or in admixture of two or more.

Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene and α-
Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-
Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-
Aromatic vinyl compounds such as vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 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-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-
Hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl 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, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxy Triethylene glycol acrylate, methoxy triethylene glycol dimethacrylate,
Methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy- Unsaturated carboxylic acid esters such as 3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate , 2-dimethylaminoethyl methacrylate, 2-
Aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-
Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, acetic acid Carboxylic acid vinyl esters such as vinyl, vinyl propionate, vinyl butyrate and vinyl benzoate, unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, cyan Vinyl cyanide compounds such as vinylidene chloride, acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylate Lamide, unsaturated amides such as N-2-hydroxyethylmethacrylamide, maleimide, N-phenylmaleimide, unsaturated imides such as N-cyclohexylmaleimide, and aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Class, polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n
Examples include macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of -butyl methacrylate and polysiloxane. These monomers can be used alone or in admixture of two or more.

The content of the carboxyl group-containing monomer unit in the above copolymer is usually 10 to 50% by mass, preferably 15 to 40% by mass, particularly preferably 25 to 40% by mass. When the content of the carboxyl group-containing monomer unit is 10 to 50% by mass, the solubility in the developing solution is good and the pattern tends to be accurately formed during development, which is preferable. The acid value of the (B) binder polymer used in the present invention is usually 50 to 150, preferably 60 to 140, and particularly preferably 80 to 135. The acid value is 5
When it is from 0 to 150, the solubility in a developing solution is improved and the unexposed area is more likely to be dissolved, and the pattern of the exposed area remains during development due to higher sensitivity, and the residual film rate tends to be improved, which is preferable. . Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and can be usually obtained by titration with an aqueous potassium hydroxide solution. . Examples of the acrylic polymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl. (Meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate 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) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl)
/ Styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono (2-acryloyloxyethyl) succinate / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer Examples thereof include (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer. In addition, (meth) acrylate shows that it is an acrylate or a methacrylate.

Among them, (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 and the like are preferable.

The polystyrene-based weight average molecular weight of the acrylic polymer is usually 5,000 to 50,000.
0, preferably in the range of 8,000 to 4,000, particularly preferably 10,000 to 35,000.
Is. When the molecular weight is 5,000 to 50,000,
The coating film hardness is improved, the residual film ratio is also high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved.
preferable. The binder polymer is usually 5% by mass or more and 2% by mass based on the solid content of the colored photosensitive resin composition.
It is used in an amount of 6 mass% or less, preferably 10 mass% or more and 26 mass% or less, and particularly preferably 15 mass% or more and 26 mass% or less. When the content of the binder polymer is 5% by mass or more and 26% by mass or less, a pattern can be formed, and the resolution and the residual film rate tend to be improved, which is preferable.

The (C) photopolymerizable compound used in the present invention is a compound which can be polymerized by an active radical generated from a photopolymerization initiator upon irradiation with light, an acid or the like. The compound etc. which have a carbon-carbon unsaturated bond are mentioned.

The photopolymerizable compound is preferably a trifunctional or higher-functional polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and dipentaerythritol. Examples thereof include erythritol hexaacrylate and dipentaerythritol hexamethacrylate. The photopolymerizable compounds are used alone or in combination of two or more, and the content thereof is usually 5% by mass or more and 90% by mass or less, preferably 10% by mass in mass fraction of the colored photosensitive resin composition. It is used in the range of not less than 80% by mass and particularly preferably not less than 20% by mass and not more than 70% by mass. The content of the photopolymerizable compound described above is 5% by mass or more and 90%.
When the content is at most% by mass, curing will occur sufficiently and the residual film rate will be improved, which is preferable.

The photopolymerization initiator (D) used in the present invention contains at least one of an acetophenone compound, a triazine compound and an imidazole compound. Examples of the acetophenone-based compound include diethoxyacetophenone and 2-methyl-2-morpholino-1- (4
-Methylthiophenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-
Methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-
[4- (1-methylvinyl) phenyl] propane-1-
Examples thereof include on-oligomers, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl).
Propan-1-one and the like can be mentioned. Also, a plurality of acetophenone-based and other photopolymerization initiators may be used in combination. Examples of the photopolymerization initiator other than the acetophenone-based initiator include active radical generators and sensitizers that generate active radicals when irradiated with light.
As the biimidazole compound, 2,2'-bis (o-
Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-carboethoxyphenyl) biimidazole , 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-bromophenyl) biimidazole, 2,2'-bis (o-
Chlorophenyl) -4,4 ', 5,5'-tetra (o,
p-dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-
Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-
Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 ' -Bis (o-methylphenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole and the like can be mentioned. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and triazine compounds.

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

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate,
4-phenylbenzophenone, 4-benzoyl-4'-
Methyldiphenyl sulfide, 3,3 ', 4,4'-
Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone,
2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like can be mentioned.

Examples of triazine compounds include:
2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl)
-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5
-Triazine, 2,4-bis (trichloromethyl) -6
-[2- (5-methylfuran-2-yl) ethenyl]-
1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl]-
1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,
4-bis (trichloromethyl) -6- [2- (3,4-
And dimethoxyphenyl) ethenyl] -1,3,5-triazine.

As the 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-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can also be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate and 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate.
Onium salts such as acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitro. Benzyl tosylate, benzoin tosylate, etc. can be mentioned.

Further, among the above-mentioned compounds as the active radical generator, there are also compounds which generate an acid at the same time as the active radical. For example, a triazine photopolymerization initiator is also used as the acid generator.

The content of the (D) photopolymerization initiator is usually 0.1 part by mass or more and 20 parts by mass or less, preferably 100 parts by mass of the total amount of the (B) binder polymer and (C) photopolymerizable compound. Is 1 part by mass or more and 15 parts by mass or less.
When the content of the photopolymerization initiator is 0.1 part by mass or more and 20 parts by mass or less, the sensitivity is increased, the exposure time is shortened, the productivity is improved, and the sensitivity is too high, and the resolution tends not to be poor. ,preferable.

In the present invention, a photopolymerization initiation auxiliary agent may be used. The photopolymerization initiation aid is a compound that is sometimes used in combination with the photopolymerization initiator and is used for promoting the polymerization of the photopolymerizable compound whose polymerization is initiated by the photopolymerization initiator. Examples of the photopolymerization initiation aid include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly called Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 ′ -Bis (ethylmethylamino) benzophenone and the like can be mentioned, and among them, 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene and 2-
Ethyl-9,10-dimethoxyanthracene, 9,10
-Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like can be mentioned.

Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone,
2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like can be mentioned.

The photopolymerization initiation aid may be used alone or in combination of two or more. Further, a commercially available photopolymerization initiation aid can be used, and examples of the commercially available photopolymerization initiation aid include trade name "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.). .

As the combination of the photopolymerization initiator and the photopolymerization initiation assistant in the colored photosensitive resin composition of the present invention, diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone and 2-methyl-2-morpholino are used. -1- (4-methylthiophenyl) propane-1-
On / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4'-bis (diethylamino) benzophenone, benzyldimethylketal / 4,4'- Bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy)
Phenyl] propan-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1
-[4- (1-Methylvinyl) phenyl] propane-1
-One oligomer / 4,4'-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone And the like, and preferably 2-methyl-2
A combination of -morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone.

When these photopolymerization initiation aids are used, the amount used is usually 10 mol or less, preferably 0.01 mol or more and 5 mol or less, per mol of the photopolymerization initiator.

As the solvent (E) used in the present invention,
It is at least one kind selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate, and contains the solvent in an amount of 70 parts by mass or more and 95 parts by mass or less in 100 parts by mass of the colored photosensitive resin composition. To do.

As the solvent, the above-mentioned solvent may be mixed with another solvent. When the above-mentioned solvent and other solvent are used in combination, the mixing ratio thereof is selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate with respect to the amount of all the solvents used in mass fraction. At least one is usually 5
It is from 0 to 100 mass, preferably from 60 to 100%. When at least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate has a mass fraction of 50 to 100 mass% with respect to all the solvents, the flatness is improved. It tends to be preferable. Examples of the other solvent include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

Examples of ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl Examples thereof include ether acetate, methoxybutyl acetate, methoxypentyl acetate, anisole, phenetole, and methylanisole. Examples of aromatic hydrocarbons include benzene and
Toluene, xylene, mesitylene, etc. may be mentioned. Examples of ketones include acetone, 2-butanone, and 2
-Heptanone, 3-heptanone, 4-heptanone, 4-
Methyl-2-pentanone, cyclopentanone, cyclohexanone and the like can be mentioned. Examples of alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin. Examples of the esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate,
Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-
Ethyl oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxy Propyl propionate, 2-
Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate,
Ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-
Ethyl 2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2
-Ethyl oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-
Examples include butyrolactone. As amides,
For example, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be mentioned. Examples of the other solvent include N-methylpyrrolidone and dimethyl sulfoxide. Among the above solvents, 3
-Ethyl ethoxypropionate and propylene glycol monomethyl ether acetate are preferably used.
The above-mentioned solvents may be used alone or in combination of two or more, and the content thereof in the colored photosensitive resin composition is usually 70% by mass or more and 9% by mass or more.
It is 5 mass% or less, preferably 75 mass% or more and 90 mass% or less. When the content of the solvent is lower than 70% by mass, the solid content is high, so that the flatness during coating tends to be poor. On the other hand, when it is higher than 90% by mass, the color density is insufficient when a color filter is formed. Then, the display characteristics tend to deteriorate, which is not preferable.

The colored photosensitive resin composition of the present invention comprises a surfactant, a filler, a polymer compound other than a binder polymer, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, an organic acid and an organic amino acid. It may contain additives such as compounds and curing agents.

As the surfactant, at least one selected from the group consisting of silicone-based surfactants, fluorine-based surfactants and silicone-based surfactants having a fluorine atom can be used. Silicone-based surfactants include Toray Silicone DC3PA and SH7P
A, same DC11PA, same SH21PA, same SH28P
A, 29SHPA, SH30PA, polyether modified silicone oil SH8400 (trade name: manufactured by Toray Silicone Co., Ltd.), KP321, KP322, KP32.
3, KP324, KP326, KP340, KP341
(Made by Shin-Etsu Silicone), TSF400, TSF401,
TSF410, TSF4300, TSF4440, TS
F4445, TSF-4446, TSF4452, TS
F4460 (manufactured by GE Toshiba Silicones Co., Ltd.) and the like. As the fluorine-based surfactant, Fluorinert (registered trademark) FC430, FC431 (Sumitomo 3M Limited), Megafac (registered trademark) F142D,
F171, F172, F173, F177, F183, R30 (Dainippon Ink and Chemicals, Inc.)
Manufactured), F-top (registered trademark) EF301, EF30
3, EF351, EF352 (Shin-Akita Kasei Co., Ltd.)
Manufactured), Surflon (registered trademark) S381, S382,
SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5
844 (manufactured by Daikin Fine Chemicals Co., Ltd.),
BM-1000, BM-1100 (Both are brand names: B
M Chemie) and the like. Examples of silicone-based surfactants having a fluorine atom include Megafac (registered trademark) R08, BL20, F475 and F475.
477, F443 (manufactured by Dainippon Ink and Chemicals, Inc.)
And so on. These surfactants can be used alone or in combination of two or more kinds. These surfactants are 0.6 parts by mass or less with respect to 100 parts by mass of the colored photosensitive resin composition excluding the surfactant (F),
It is preferably used in the range of 0.001 part by mass or more and 0.5 part by mass or more. When the content of the surfactant is 0.6 part by mass or less, flatness tends to be improved, which is preferable.

Examples of the filler include fine particles such as glass and alumina.

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

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
3-glycidoxymethyldimethoxysilane, 2- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-
Examples thereof include chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

Examples of the antioxidant include 4,4'-
Thiobis (6-t-butyl-3-methylphenol),
2,6-di-t-butyl-4-methylphenol and the like can be mentioned.

Examples of the ultraviolet absorber include 2- (2
-Hydroxy-3-t-butyl-5-methylphenyl)
Benzotriazoles such as -5-chlorobenzotriazole, benzophenones such as 2-hydroxy-4-octyloxybenzophenone, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxy Benzoate-based such as benzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-
Examples include triazine compounds such as hexyloxyphenol.

Examples of the anticoagulant include sodium polyacrylate and the like.

Examples of the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and caprylic acid, oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itacone Acids, citraconic acid, maleic acid, fumaric acid, aliphatic dicarboxylic acids such as mesaconic acid, tricarballylic acid,
Aliphatic tricarboxylic acids such as aconitic acid, camphoronic acid, benzoic acid, toluic acid, cuminic acid, hemelitic acid,
Examples thereof include aromatic monocarboxylic acids such as mesitylene acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanoic acid and pyromellitic acid.

As the organic amino compound, for example, n-
Propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n- Monoalkylamines such as decylamine, n-undecylamine and n-dodecylamine,
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine and 4-methylcyclohexylamine,
Methyl ethyl amine, diethyl amine, methyl n-propyl amine, ethyl n-propyl amine, di n-propyl amine, di i-propyl amine, di n-butyl amine, di i-butyl amine, di sec-butyl amine, di t-butyl amine, di Dialkylamines such as n-pentylamine and di-n-hexylamine, monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine, dicycloalkylamines such as dicyclohexylamine, dimethylethylamine, methyldiethylamine and triethylamine , Dimethyl n-propylamine, diethyl n-propylamine, methyldi n-propylamine, ethyldi n-
Trialkyls such as propylamine, tri-n-propylamine, tri-i-propylamine, tri-n-butylamine, tri-i-butylamine, trisec-butylamine, trit-butylamine, tri-n-pentylamine, tri-n-hexylamine and the like. Dialkylmonocycloalkylamines such as amines, dimethylcyclohexylamine and diethylcyclohexylamine, monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine, 2-aminoethanol, 3-amino-1 -Propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol,
Monoalkanolamines such as 6-amino-1-hexanol, monocycloalkanolamines such as 4-amino-1-cyclohexanol, diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, Dialkanolamines such as di-butanolamine, di-n-pentanolamine and di-n-hexanolamine, dicycloalkanolamines such as di (4-cyclohexanol) amine, triethanolamine, tri-n-propanolamine , Tri i-propanolamine, tri n-butanol amine, tri i-butanol amine, tri n-pentanol amine, tri n-hexanol amine and other trialkanol amines, tri (4-cyclohexanol)
Tricycloalkanolamines such as amines, 3-amino-1,2-propanediol, 2-amino-1,3
-Propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2 -Dimethylamino-1,3-propanediol, 2-diethylamino-
Aminoalkanediols such as 1,3-propanediol, 4-amino-1,2-cyclohexanediol,
Aminocycloalkane diols such as 4-amino-1,3-cyclohexanediol, 1-aminocyclopentanone methanol, amino group-containing cycloalkanone methanols such as 4-aminocyclopentanone methanol, 1-aminocyclohexanone methanol, Amino group-containing cycloalkanemethanols such as 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol and 4-diethylaminocyclohexanemethanol,
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-
Aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1
-Aminocarboxylic acids such as 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-naphthylamine, N, N-dimethylaniline,
Aromatic amines such as N, N-diethylaniline, p-methyl-N, N-dimethylaniline, o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p -Aminobenzyl alcohols such as diethylaminobenzyl alcohol, o-aminophenol, m-aminophenol, p-aminophenol, p
-Aminophenols such as dimethylaminophenol and p-diethylaminophenol, and aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

Examples of the curing agent include compounds capable of reacting with the carboxyl groups in the binder polymer to crosslink the binder polymer when heated. Moreover, the compound which can be polymerized by itself and can harden a coloring pattern is also mentioned. Examples of the compound include epoxy compounds and oxetane compounds.

Examples of the epoxy compound include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, and other aromatic type epoxy resins. , Alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester resin, glycidyl amine resin, epoxy resin such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resin and other than brominated derivatives thereof Of aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co)
Polymer epoxide, isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co)
Examples thereof include polymers and triglycidyl isocyanurate.

Examples of the oxetane compound include carbonate bisoxetane, xylylenebisoxetane,
Examples thereof include adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

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

Examples of polycarboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,4.
5,8-naphthalenetetracarboxylic acid, 3,3 ′, 4
Aromatic polycarboxylic acids such as 4′-benzophenonetetracarboxylic acid, succinic acid, glutaric acid, adipic acid,
Aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid and itaconic acid, hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexa Hydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid,
Examples thereof include alicyclic polycarboxylic acids such as cyclopentane tetracarboxylic acid and 1,2,4,5-cyclohexane tetracarboxylic acid.

Examples of the polycarboxylic acid anhydrides include aromatic compounds such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride. Polycarboxylic acid anhydrides, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride,
Aliphatic polycarboxylic acid anhydrides such as maleic anhydride, 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, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, Hymic anhydride Examples thereof include alicyclic polyvalent carboxylic acid anhydrides such as acids and nadic anhydride, ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitate acid, and glycerin tris trimellitate anhydride.

As the carboxylic acid anhydride, those commercially available as an epoxy resin curing agent may be used. Examples of the epoxy resin curing agent include a trade name “ADEKA HARDNER EH-700” (manufactured by Asahi Denka Kogyo Co., Ltd.), a trade name “RIKACID HH” (manufactured by Shin Nippon Rika Co., Ltd.), and a trade name “MH- 700 ”(manufactured by Shin Nippon Rika Co., Ltd.) and the like.

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

As a method for forming a pattern using the colored photosensitive resin composition of the present invention, specifically, the colored photosensitive resin composition of the present invention is a substrate or a solid formed on the substrate in advance. Is coated on the colored photosensitive resin composition layer (hereinafter, this may be referred to as a substrate, etc.) to remove volatile components such as a solvent from the coated colored photosensitive resin composition layer,
A method in which the layer from which the volatile components have been removed is exposed through a photomask and then developed is mentioned.

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

In order to apply the colored photosensitive resin composition onto the substrate, it is applied onto the substrate or the like using a conventional spin coater or a liquid-saving coater, especially a spinless coater,
Then, a volatile component such as a solvent may be volatilized by heating. In this way, a layer made of the solid content of the colored photosensitive resin composition is formed on the substrate or the like with good flatness. As a method for easily confirming the flatness of a coating film formed by using a liquid-saving coater such as a spinless coater, the following method can be mentioned. A substrate such as glass is placed horizontally, one drop of the colored photosensitive resin composition is dropped on the substrate, and then the substrate is tilted at 45 degrees to flow down to form a coating film.
Volatile components are removed by drying at 3 ° C. for 3 minutes to form a colored photosensitive resin composition layer. In the layer formed of the solid content of the colored photosensitive resin composition formed by the above method, when the haze value of 1 μm is 2 or more, streak unevenness in the advancing direction and adsorption unevenness in the area where the substrate is adsorbed are observed. However, if the haze value is 2 or less, no adsorption unevenness is observed and no stripe unevenness is observed, or the haze value is improved to a level that does not cause a problem in a subsequent step, and a film is formed using a spinless coater. However, it can be expected that a film having good flatness can be formed.

The film thickness is measured using a stylus type surface profiler. Preferably, it can be measured using Dektak3; manufactured by ULVAC, Inc. The haze value can be measured by the following method. The haze value of the transmission of the substrate such as glass in the blank before applying the colored photosensitive resin composition was measured, and then the colored photosensitive resin composition was applied to measure the haze value after film formation, It can be obtained by subtracting the haze value in the blank from the haze value after film formation. Preferably, it can be measured using a direct reading haze computer (HGM-2DP; manufactured by Suga Test Instruments Co., Ltd.). The haze value is converted into a haze value per 1 μm so that different film thicknesses can be compared.

[0061]

Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. Not limited. The scope of the present invention is defined by the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The components used in this example are as follows, and may be omitted in the following description. (A-1) Colorant: C.I. I. Pigment Red 254 (A-2) Colorant: C.I. I. Pigment Yellow 139 (B) Binder polymer: copolymer of methacrylic acid and benzyl methacrylate [The ratio of the methacrylic acid unit to the benzyl methacrylate unit is 3 in terms of a substance amount ratio (molar ratio).
0:70, acid value 113, polystyrene equivalent weight average molecular weight 15,000 (C) Photopolymerizable compound: dipentaerythritol hexaacrylate (D-1) Photopolymerization initiator: 2-methyl-2-morpholino-1 -(4-Methylthiophenyl) propan-1-one (D-2) photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (G-1) photopolymerization Starting aid: 2,4-diethylthioxanthone (E-1) solvent: propylene glycol monomethyl ether acetate (E-2) solvent: ethyl 3-ethoxypropionate

Example 1 [Production of colored photosensitive resin composition] (A-1) 4.069 parts by mass (A-2) 0.956 parts by mass Dispersant 1.507 parts by mass (B) 3.546 parts by mass (C) 3.546 parts by mass (D-1) 0.425 parts by mass (D-2) 0.425 parts by mass (G-1) 0.425 parts by mass (E-1) 75.598 parts by mass (E-2) 8.500 parts by mass To obtain a colored photosensitive resin composition 1.

[Formation of Coating Film] A glass substrate [50 mm × 50 mm] washed with acetone is placed horizontally, and the colored photosensitive resin composition 1 obtained above is placed on the glass substrate 1
After dropping and dropping, the substrate was tilted at 45 degrees to form a coating film. Volatile components were removed by drying at 100 ° C. for 3 minutes to form a colored photosensitive resin composition layer. [Evaluation] The thickness of the obtained layer was 3.8 μm, and there was no unevenness, and the haze value in terms of 1 μm was 2 or less (1.2), which was good. Film thickness: 3.8 μm Haze value: 4.6 1 μm equivalent haze value: 1.2 [Evaluation with spinless coater] A coating film was formed from the obtained colored photosensitive resin composition using a spinless coater. However, a coating film having good flatness and no unevenness was obtained.

Example 2 (191) (B) 3.191 parts by mass, (C) 3.90
A coating film was formed in the same manner as in Example 1 except that the amount was changed to 0 part by mass. [Evaluation] When evaluated in the same manner as in Example 1, the thickness of the obtained layer was 3.5 μm, there was no unevenness, and the haze value in terms of 1 μm was 2 or less (0.5), which was good. Film thickness: 3.5 μm Haze value: 1.8 1 μm equivalent haze value: 0.5 [Evaluation with spinless coater] A coating film was formed from the obtained colored photosensitive resin composition using a spinless coater. However, a coating film having good flatness and no unevenness was obtained.

Comparative Example 1 (B) of Example 1 4.255 parts by mass, (C) 2.83
A coating film was formed in the same manner as in Example 1 except that the amount was changed to 7 parts by mass. [Evaluation] When evaluated in the same manner as in Example 1, the thickness of the obtained layer was 3.8 μm, unevenness was observed, and the 1 μm-converted haze value was 2 or more (20.4). Film thickness: 3.8 μm Haze value: 77.5 1 μm equivalent haze value: 20.4 [Evaluation with spinless coater] A coating film was formed from the obtained colored photosensitive resin composition using a spinless coater. However, a coating film having poor flatness and unevenness was obtained.

Comparative Example 2 (B) 3.900 parts by mass of Example 1, (C) 3.19
A coating film was formed in the same manner as in Example 1 except that the amount was changed to 1 part by mass. [Evaluation] When evaluated in the same manner as in Example 1, the film thickness of the obtained layer was 3.5 μm, unevenness was observed, and the 1 μm-converted haze value was 2 or more (8.4). Film thickness: 3.5 μm Haze value: 29.5 1 μm equivalent haze value: 8.4 [Evaluation with spinless coater] A coating film was formed from the obtained colored photosensitive resin composition using a spinless coater. However, a coating film having poor flatness and unevenness was obtained.

[0068]

According to the colored photosensitive resin composition of the present invention, even if the colored photosensitive resin composition is applied onto a substrate by using a liquid-saving coater such as a spinless coater, the film thickness within the plane is obtained. It is possible to form a color filter having good uniformity and no unevenness.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/20 101 G02B 5/20 101 G03F 7/004 501 G03F 7/004 501 505 505 F term (reference) 2H025 AB13 AC01 AD01 BC14 BC42 CA01 CA02 CA28 CB13 CB14 CB43 CB51 CB55 CC03 CC11 FA03 FA17 2H048 BA02 BA45 BA48 BB02 BB42 4J011 AA05 PA24 PA47 PA69 PA70 PB24 AC30 BA23 AC08 BA23 ABB36 A02 A08 AA4A45A23 DB28 DB36 FA05 GA07 GA10

Claims (4)

[Claims] 1. A colored photosensitive resin composition comprising (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent.
(B) The binder polymer has an acid value of 50 or more and 150 or less and a polystyrene-equivalent weight average molecular weight of 5,000 to 5
And the content thereof is 15% to 26% by mass fraction in the solid content of the colored photosensitive resin composition, and (E) the solvent is propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate. A colored photosensitive resin composition for a liquid-saving coater, which is at least one selected from the group consisting of, and contains the solvent in an amount of 70 parts by mass or more and 95 parts by mass or less in 100 parts by mass of the colored photosensitive resin composition. 2. The colored photosensitive resin composition according to claim 1, which is applied onto a substrate or a layer formed of a solid content of the colored photosensitive resin composition previously formed, and the applied colored photosensitive resin. A method for forming a pattern, wherein a volatile component is removed from a composition layer, the layer is exposed through a photomask, and developed. 3. A color filter including a pattern formed by the method according to claim 2. 4. A liquid crystal display device using the color filter according to claim 3.