JP2011102991A - Colored photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition with which a film with good flatness is formed by using a liquid-saving coater. <P>SOLUTION: The colored photosensitive resin composition contains: a coloring agent (A); a binder resin (B); a photopolymerizable compound (C); a photopolymerization initiator (D); a solvent (E); and a surfactant (F), and is characterized in that the composition has a viscosity of 2.0-5.0 mPa s and a contact angle of 10-20°, the contact angle being formed by dropping 2 μL of the composition on a glass substrate and measured after a lapse of 0.2 s, and that the solvent (E) contains propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate, and the surfactant (F) is at least one selected from the group composed of a silicone based surfactant and a silicone based surfactant composed of a compound having fluorine atoms. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition.

  The 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.

  Conventionally, as a method of forming a film using a colored photosensitive resin composition on a substrate to be coated such as a wafer, a method using a spin coater is known (see, for example, Patent Document 1). However, in the method using a spin coater, since it is difficult to rotate a substrate such as a glass having a large area such as 1 m square, a liquid-saving coater such as a slit coater that does not rotate the substrate has been developed.

  As a colored photosensitive resin composition that can be used for forming a film by a liquid-saving coater such as a slit coater, conventionally, a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, propylene glycol monomethyl ether acetate, and an interface are used. Colored photosensitive resin composition containing an activator (viscosity is about 7 mPa · s, 2 μL of the composition is dropped on a glass substrate, and the contact angle after 0.2 seconds is about 22 °) Is known (for example, see Patent Document 2), but when the composition is applied to a liquid-saving coater such as a slit coater, streaks occur during application, and the flatness of the formed film is not sufficient. There was a problem.

JP 2002-88136 A JP 2004-318111 A

  An object of the present invention is to provide a colored photosensitive resin composition capable of forming a film having good flatness by a liquid-saving coater.

  As a result of intensive investigations on a colored photosensitive resin composition that can form a film with good flatness when applied to a liquid-saving coater, the present inventors found that the viscosity is within a certain range and contains certain compounds. When a colored photosensitive resin composition containing a certain amount of a solvent and containing a certain amount of a surfactant is applied to a liquid-saving coater, a film with good flatness can be formed. I found out.

That is, the present invention is a colored photosensitivity containing a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F). A resin composition having a viscosity at 23 ° C. of 2.0 mPa · s or more and 5.0 mPa · s or less, and 0.2 μl after 2 μL of the composition was dropped on a glass substrate. And the solvent (E) contains propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate, and the content of the solvent (E) in the composition Is a silicone-based interface consisting of 80% by mass to 95% by mass with respect to the composition, and the surfactant (F) is composed of a silicone-based surfactant and a compound having a fluorine atom. Is it a group of active agents? It is at least one selected, and the content of the surfactant is 0.01% by mass or more and 0.15% by mass or less in terms of mass fraction with respect to the solid content of the composition. A colored photosensitive resin composition is provided.
In addition, the present invention provides a colored photosensitive resin composition in which the colored photosensitive resin composition according to any one of the above is applied on a substrate or a layer made of a solid content of the previously formed colored photosensitive resin composition. There is provided a pattern forming method comprising removing a volatile component from a product to form a film made of a colored photosensitive resin composition, exposing the film through a photomask, and developing the film.
The present invention also provides the method described above, wherein the colored photosensitive resin composition is applied using a spinless coater.
The present invention also provides a color filter having a pattern formed by the method described above.
Furthermore, the present invention provides a liquid crystal display device comprising the color filter described above.

  According to the composition of the present invention, when applied to a liquid-saving coater such as a slit coater, a film with good flatness can be formed, and a colored pattern constituting a color filter can be formed with high accuracy. Therefore, it is extremely useful industrially.

The colored photosensitive resin composition of the present invention comprises a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E), and a surfactant (F). The solvent (E) contains propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate, and the content of the solvent (E) in the composition is Silicone surfactant having a mass fraction of 80% by mass to 95% by mass with respect to the composition, and wherein the surfactant (F) comprises a silicone surfactant and a compound having a fluorine atom. At least one selected from the group consisting of, and the content of the surfactant is 0.01% by mass or more and 0.15% by mass or less in terms of mass fraction with respect to the solid content of the composition, And the group at 23 ° C. The viscosity of the product is 2.0 mPa · s or more and 5.0 mPa · s or less, and 2 μL of the composition is dropped on a glass substrate, and the contact angle 0.2 seconds later is 10 ° or more and 20 ° or less. .
In addition, the composition is prepared by inclining a glass substrate patterned with a 100 μm line and space pattern (film thickness: a) by 30 degrees with respect to a horizontal plane and dropping one drop of the composition on the glass substrate. When the film step on the 100 μm line and the space after baking for 3 minutes at 100 ° C. is b, the flattening ratio represented by the formula (1) is It is preferable that it is 0.20 or more and 1 or less.
Flattening rate: (ab) / a (1)

  The viscosity of the colored photosensitive resin composition of the present invention is determined by using a viscometer (for example, VISCOMETER RE120L SYSTEM; manufactured by Toki Sangyo Co., Ltd.) at a liquid temperature of 23 ° C. It can be measured by keeping it constant (usually 50 rpm). The viscosity of the colored photosensitive resin composition of the present invention is 2.0 mPa · s or more when measured at a liquid temperature of 23 ° C. and a rotation speed of 50 rpm using a viscometer (VISCOMETER RE120L SYSTEM; manufactured by Toki Sangyo Co., Ltd.). It is 5.0 mPa · s or less, preferably 2.1 mPa · s or more and 4.5 mPa · s or less, and more preferably 2.2 mPa · s or more and 4.0 mPa · s or less. When the viscosity of the composition is 2.0 mPa · s or more and 5.0 mPa · s or less, a film with good flatness can be obtained by a liquid-saving coater.

  The flattening rate (calculated by (ab) / a) is prepared by preparing a glass substrate patterned (film thickness: a) with a 100 μm line and space pattern, and a plane including the glass substrate and a horizontal plane. Tilt the glass substrate 30 degrees so that the straight line generated by crossing and the straight line indicating the pattern direction of the line and space pattern are perpendicular to each other, and drop one drop of the composition onto the upper part (the higher side of the tilted glass substrate) Then, a drop of the composition is allowed to flow in a direction parallel to the line and space pattern, and then baked at 100 ° C. for 3 minutes. The value is 0.20 or more, preferably 0.22 or more, more preferably 0.24 or more, and further preferably 0.26 or more. When the flattening rate is 0.20 or more, a good film can be obtained by a liquid-saving coater.

  As for the contact angle described above, 2 μL of the colored photosensitive resin composition is dropped on a glass substrate (preferably a clean glass substrate), and the contact angle 0.2 seconds after dropping is determined by a contact angle measuring device (for example, DGD Fast / 60). Measured using Contact Angle Meter (manufactured by GBX). The contact angle is 10 ° to 20 °, preferably 10 ° to 15 °. When the contact angle is 10 ° or more or 20 ° or less, a good film can be obtained by a liquid-saving coater.

  Examples of the substrate used for measuring the contact angle include a clean glass substrate used for forming a color filter. As the glass substrate, for example, # 1737 (trade name) manufactured by Dow Corning can be used. In order to clean the glass substrate, for example, there is a method of removing foreign substances on the substrate by ultrasonically cleaning the glass substrate in a solvent such as acetone.

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

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

Specifically, for example, C.I. I. Pigment Yellow 1, the same (hereinafter “the same” is omitted) 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117 , 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc .;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Among these, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. 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. At least one pigment selected from CI Pigment Green 36 is preferred.

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

  For the above pigments, rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, sulfuric acid atomization method, etc., if necessary May be subjected to atomization treatment by, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method or the like.

  Content of a coloring agent (A) is a mass fraction with respect to solid content of this composition, Preferably it is 25 to 60 mass%, More preferably, it is 27 to 55 mass%. Particularly preferably, the content is 30% by mass or more and 50% by mass or less. It is preferable that the content of the colorant (A) is in the above range because the color density when the color filter is obtained is sufficient.

  The pigment used as the colorant (A) preferably has a uniform particle size. Examples of the method for uniformizing the particle size of the pigment include a method of performing a dispersion treatment by containing a surfactant other than the component (F) described later as a pigment dispersant. A pigment dispersion 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 are used alone or in combination of two or more.
When using the pigment dispersant, the amount used is preferably 0.01 parts by mass or more and 1 part by mass or less, more preferably 0.05 parts by mass or more and 0.5 parts by mass or less per 1 part by mass of the colorant. When the amount of the pigment dispersant used is in the above range, it is preferable because a pigment having a uniform particle diameter tends to be obtained.

  As binder resin (B) used in this invention, an alkali-soluble copolymer is mentioned, for example. Examples of the alkali-soluble copolymer include a copolymer of another monomer copolymerizable with a carboxyl group-containing monomer and a carboxyl group-containing monomer.

  Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated polyvalent carboxylic acid.

Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

  The unsaturated polyvalent carboxylic acid may be its acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxy). Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxyl group-containing monomers may be used alone or in admixture of two or more.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, and o-methoxystyrene. , M-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl Aromatic vinyl compounds such as glycidyl ether and indene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec -Butyl methacrylate, tert-butyl acrylate, tert-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, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate Relate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2- Unsaturated carboxylic esters such as hydroxy-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 Unsaturated alkylaminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane. Can do.
These monomers may be used alone or in combination of two or more.

  The content of the carboxyl group-containing monomer unit in the copolymer is a mass fraction, preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and particularly preferably 20 to 40% by mass. It is preferable that the content of the carboxyl group-containing monomer unit is in the above-mentioned range since the solubility in a developer is good and the pattern tends to be formed accurately during development.

The alkali-soluble copolymer is preferably a (meth) acrylic acid / benzyl (meth) acrylate copolymer (weight average molecular weight in terms of polystyrene of the copolymer; 15,000 to 35,000, acid value; 80-135) and a reaction product of a glycidyl methacrylate / tricyclodecane skeleton monomethacrylate / benzyl (meth) acrylate copolymer and (meth) acrylic acid (polystyrene equivalent weight average molecular weight of the reaction product; 8,000-20, 000, acid value; 50 to 120), at least one polymer compound selected from the group consisting of.
Furthermore, other alkali-soluble copolymers may be used in combination as long as the effects of the present invention are not impaired.
Examples of the alkali-soluble copolymer that may be used in combination include (meth) acrylic acid / methyl (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, (meta ) 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 (me ) 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, (meta ) Acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / Glycerol mono (meta Examples thereof include acrylate copolymers, (meth) acrylic acid / glycidyl methacrylate / monocyclomethacrylate / benzyl (meth) acrylate copolymer of tricyclodecane skeleton, preferably (meth) acrylic acid / benzyl (meth) acrylate / styrene Examples include copolymers, (meth) acrylic acid / methyl (meth) acrylate copolymers, and (meth) acrylic acid / methyl (meth) acrylate / styrene copolymers.
In the present specification, (meth) acrylate is at least one selected from the group consisting of acrylate and methacrylate, and (meth) acrylic acid is at least selected from the group consisting of acrylic acid and methacrylic acid. Each means one kind.

  In the alkali-soluble copolymer that may be used in combination, the polystyrene-equivalent weight average molecular weight is preferably 5,000 to 50,000, more preferably 6,000 to 45,000, and particularly preferably. It is 7,000 to 40,000, more preferably 8,000 to 35,000. When the weight average molecular weight is within the above range, the coating film hardness is improved, the remaining film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved.

  In the alkali-soluble copolymer that may be used in combination, the acid value is preferably 50 to 150, more preferably 50 to 145, even more preferably 50 to 140, and even more preferably 50 to 135. . When the acid value is in the above range, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio tends to be improved. This is preferable.

  Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g, and can usually be determined by titration using an aqueous potassium hydroxide solution.

  Content of binder resin (B) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 5 mass% or more and 26 mass% or less, More preferably, 10 mass% or more and 26 mass% or less, More preferably, it is 15 mass% or more and 26 mass% or less. It is preferable that the content of the binder resin (B) is in the above range because a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

  The photopolymerizable compound (C) used in the present invention is a compound that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator when irradiated with light, and is, for example, a polymerizable carbon-carbon. Examples thereof include compounds having an unsaturated bond.

  The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned. The photopolymerizable compounds (C) may be used alone or in combination of two or more.

  Content of a photopolymerizable compound (C) is a mass fraction with respect to the total amount of binder resin (B) and a photopolymerizable compound (C), Preferably it is 35 mass% or more and 60 mass% or less, More preferably Is 37% to 58% by mass, particularly preferably 39% to 56% by mass, and more preferably 40% to 55% by mass. When the content of the photopolymerizable compound (C) is in the above range, curing is sufficiently performed and the remaining film ratio is improved, and the pattern is less likely to be undercut and the adhesion tends to be favorable. .

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). The photopolymerization initiator (D) preferably contains at least one acetophenone compound.
Examples of the photopolymerization initiator (D) include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds, acid generators, and active radical generators.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 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] propan-1-one oligomer and the like. Among these, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is preferably used.

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

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

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (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) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate and the like.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Examples of the active radical generator include 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 compound and the like can also be used.

  Among the above-mentioned compounds that are active radical generators, there are compounds that generate an acid simultaneously with an active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

Content of a photoinitiator (D) is a mass fraction with respect to the total amount of binder resin (B) and a photopolymerizable compound (C), Preferably it is 0.1 to 20 mass%, From more Preferably they are 1 mass% or more and 15 mass% or less.
When the content of the photopolymerization initiator (D) is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation assistant (G).
When using the photopolymerization initiation assistant (G), it is usually used in combination with the photopolymerization initiator (D), and the photopolymerizable compound (C) whose polymerization has been initiated by the photopolymerization initiator (D). Used to further accelerate the polymerization. Examples of the photopolymerization initiation aid (G) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, among which 4,4′-bis (diethylamino) benzophenone is preferably used.

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

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

  The photopolymerization initiator (D) may be used alone or in combination. Commercially available photopolymerization initiation assistant (G) can also be used. Examples of commercially available photopolymerization initiation assistant (G) include, for example, trade name “EAB-F” (Hodogaya Chemical Co., Ltd.). Manufactured).

  In the colored photosensitive resin composition of the present invention, when the photopolymerization initiation assistant (G) is used, as a combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (G), for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one / 4,4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-Hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzopheno 1-hydroxycyclohexyl phenyl ketone / 4,4′-bis (diethylamino) benzophenone, oligomer of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one / 4 4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, and the like are preferable. -Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone.

  When using the photopolymerization initiation assistant (G), the amount used is preferably 0.01 mol or more and 10 mol or less, preferably 0.01 mol or more and 5 mol or less, per mol of the photopolymerization initiator (D). is there.

The colored photosensitive resin composition of the present invention contains a solvent (E).
As the solvent, a solvent containing ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate is preferably used. Content of ethyl 3-ethoxypropionate in this solvent is a mass fraction with respect to the total amount of a solvent, Preferably it is 3-50 mass%, More preferably, it is 5-45 mass%, Most preferably, it is 7 It is -40 mass%, More preferably, it is 9-35 mass%. The content of propylene glycol monomethyl ether acetate in the solvent is preferably 50 to 97% by mass, more preferably 55 to 95% by mass, particularly preferably 60 to 93% by mass, and further preferably 65 to 91%. % By mass.
The solvent (E) may contain a solvent other than ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate. For example, ethers, aromatic hydrocarbons, ketones, alcohols, esters, Examples include amides.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, pro Lenglycol monoethyl ether, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, anisole, phenetole, methyl Anisole etc. are mentioned.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.
These solvents may be used alone or in combination of two or more.

  Content of the solvent (E) in the colored photosensitive resin composition of this invention is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 80 to 95 mass%, More preferably, it is 85 mass. % To 90% by mass. When the content of the solvent (E) is in the above range, it is preferable because the flatness at the time of coating is good and the color density when the color filter is formed is sufficient and the display characteristics are good.

  Examples of the surfactant (F) used in the present invention include at least one surfactant selected from the group consisting of a silicone surfactant and a silicone surfactant having a fluorine atom.

  Examples of silicone surfactants include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA (trade name), Torre Silicone SH7PA (trade name), Torre Silicone DC11PA (trade name), Torre Silicone SH21PA (trade name), Torre Silicone SH28PA (trade name), Torre Silicone 29SHPA (Product) Name), Torre Silicone SH30PA (trade name), polyether-modified silicone oil SH8400 (trade name) (manufactured by Torre Silicone Co., Ltd.), KP321 (trade name), KP322 (trade name), KP323 (trade name), KP324 ( Product Name), KP326 (Product Name), KP340 (Product Name), KP341 (Product Name) (Shin-Etsu Silicone), TSF400 (Product Name), TSF401 (Product Name), TSF410 (Product Name), TSF4300 (Product Name) , TSF4440 (trade name) TSF4445 (trade name), TSF-4446 (trade name), TSF4452 (trade name), TSF4460 (trade name) (manufactured by GE Toshiba Silicones Co., Ltd.), and the like.

  Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Mega Fuck R08 (trade name), Mega Fuck BL20 (trade name), Mega Fuck F475 (trade name), Mega Fuck F477 (trade name), Mega Fuck F 443 (trade name) (Dainippon Ink and Chemicals, Inc.) Etc.).

These surfactants may be used alone or in combination of two or more.
Among these, polyether-modified silicone oil SH8400 (trade name) (manufactured by Torre Silicone Co., Ltd.) and MegaFac F475 (trade name) are preferably used.

  Content of surfactant (F) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 0.01 mass% or more and 0.15 mass% or less, More preferably, it is 0.015 mass. % Or more and 0.13% by mass or less, particularly preferably 0.02% by mass or more and 0.12% by mass or less. It is preferable that the content of the surfactant is in the above range because the flatness of the obtained coating film tends to be further improved.

  As a method for preparing the colored photosensitive resin composition of the present invention, for example, after mixing the components excluding the surfactant, the surfactant is added so that the contact angle and the flattening rate are within a predetermined range. And a method of preliminarily determining the relationship between the addition amount of the surfactant, the contact angle, and the flattening ratio, and mixing the components all together based on the addition amount. .

  The colored photosensitive resin composition of the present invention further includes a filler, a polymer compound other than the binder resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amine compound, and a curing agent. Such additives may be contained.

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

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

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

  Examples of the antioxidant include 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

  Examples of the ultraviolet absorber include benzotriazole compounds such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, and 2-hydroxy-4-octyloxybenzophenone. Benzophenone compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5 -Triazine-based compounds such as -triazin-2-yl) -5-hexyloxyphenol.

  Examples of the aggregation preventing agent include sodium polyacrylate.

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, diethyl acetic acid, enanthic acid, and caprylic acid; oxalic acid, malonic acid, and succinic acid. 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, itaconic acid , Aliphatic dicarboxylic acids such as citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid are listed.

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

  Examples of the curing agent include a compound capable of reacting with a carboxyl group in the binder resin by being heated to crosslink the binder resin, a compound capable of curing the colored pattern by polymerizing the curing agent alone, and the like. Can be mentioned. Examples of the compound capable of crosslinking the binder resin include an epoxy compound and an oxetane compound.

  Examples of the epoxy compound include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, novolac type epoxy resins, other aromatic type epoxy resins, Aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oils, brominated derivatives of these epoxy resins, fats other than epoxy resins and brominated derivatives thereof Aliphatic, alicyclic or aromatic epoxy compounds, epoxidized butadiene (co) polymers, epoxidized isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate Etc.

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

  When an epoxy compound, an oxetane compound or the like is contained as a curing agent, a compound capable of ring-opening polymerization of an epoxy group of the epoxy compound or an oxetane skeleton of the oxetane compound may be included. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

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

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

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

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

  As a method for forming a pattern on a substrate using the colored photosensitive resin composition of the present invention and producing a color filter having the pattern, for example, the colored photosensitive resin composition of the present invention is applied to the substrate. Alternatively, a solid colored photosensitive resin composition film (hereinafter referred to as a substrate or the like) previously formed on a substrate is coated on the coated colored photosensitive resin composition, a solvent or the like. Examples include a method in which a volatile component is removed by heating to form a colored photosensitive resin composition film, the film is exposed through a photomask, and then developed.

  Examples of the substrate include flat substrates such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, and a GaAs substrate. These substrates may be subjected to pretreatment such as chemical treatment with chemicals such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum deposition treatment. When a silicon substrate 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.

  Examples of the method for applying the colored photosensitive resin composition on the substrate include a method using a conventional spin coater and a method using a spinless coater. Among the spinless coaters, liquid-saving such as a slit coater. A method using a coater is preferable, and a method using a slit coater is particularly preferable.

As a preferred method of forming a pattern using the colored photosensitive resin composition of the present invention, the colored photosensitive resin composition of the present invention is applied onto a substrate or the like using a liquid-saving coater such as a slit coater, Next, a method of volatilizing a volatile component such as a solvent by heating can be mentioned. In this way, a film made of a solid content of the colored photosensitive resin composition is formed on the substrate or the like with good flatness.
Here, regarding “flatness”, a substrate having a pre-baked colored photosensitive resin composition layer is irradiated with a Na lamp, and the surface state of the layer is observed from various angles, resulting in unevenness. Is determined based on the following criteria: When the streaks and the coating film appear to be uneven by visual observation, it is determined that unevenness has occurred.

  According to the present invention, it is possible to provide a colored photosensitive resin composition capable of forming a film having good flatness.

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

  Since the pattern formed using the composition has good flatness, it can be suitably used as a material for forming a colored pattern constituting a color filter.

  Next, an example of a method for manufacturing a liquid crystal display device using the color filter will be described. A transparent protective film is formed on the color filter obtained as described above, and a transparent electrode such as an ITO film is further formed thereon. Next, this color filter substrate and a reflective electrode substrate on which a reflective electrode such as a metal vapor deposition film is formed, and a liquid crystal alignment film further subjected to a rubbing treatment for liquid crystal alignment provided on those substrates, and It is bonded to face each other through a spacer for maintaining the cell gap. In addition to the reflective electrode, a projection for light diffusion, a thin film transistor (TFT) element or a thin film diode (TFD) element, a scanning line, a signal line, etc. are provided on the reflective electrode substrate, and a TFT liquid crystal display device, A TFD liquid crystal display device can be produced. If it has a backlight, it is placed on the back of the liquid crystal display. The edge-light type uses acrylic resin with excellent light transmittance as the light guide plate, LED light sources are installed on its two sides or one side, the reflective part is processed on the back side of the light guide plate, and the reverse plate is processed A prism sheet, a diffusion plate, or the like can be disposed on the side. If it has a front light, it is placed in front of the liquid crystal display. A reflector and an LED light source can be disposed on the upper part of the light guide plate made of transparent resin or the like. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. Finally, a liquid crystal display device can be manufactured by mounting an IC driver or the like.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it cannot be overemphasized that this invention is not limited by these Examples.

<Synthesis of Resin B>
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And propylene glycol monomethyl ether acetate (136 g) in a solution obtained by adding 3.6 g of azobisisobutyronitrile to the flask from the dropping funnel over 2 hours, and further stirring at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain Resin B having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC method was 13,000, and the molecular weight distribution (Mw / Mn) was 2.1.

About the measurement of the polystyrene conversion weight average molecular weight of said binder resin, it carried out on condition of the following using GPC method.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

A glass substrate patterned with a line and space pattern for the flatness test of the example was produced as follows.
[Production of colored photosensitive resin composition]
(A) C.I. I. Pigment green 36 (2.295 parts by mass),
(A) C.I. I. Pigment yellow 150 (1.055 parts by mass),
(B) Copolymer of methacrylic acid and benzyl methacrylate [composition ratio of methacrylic acid unit and benzyl methacrylate unit is 35:65 by weight ratio (molar ratio), weight average molecular weight (Mw) is 35,000] ( 2.441 parts by mass)
(C) Dipentaerythritol hexaacrylate (KAYARAD DPHA (trade name); manufactured by Nippon Kayaku Co., Ltd.) (1.464 parts by mass),
(D) 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (0.586 parts by mass),
(G) 4,4′-bis (diethylamino) benzophenone (EAB-F (trade name); manufactured by Hodogaya Chemical Co., Ltd.) (0.195 parts by mass),
(H) Epoxy compound (Sumiepoxy ESCN-195XL-80 (trade name); manufactured by Sumitomo Chemical Co., Ltd.) (0.976 parts by mass)
Polyester dispersant (0.988 parts by mass) and (E) propylene glycol monomethyl ether acetate (36.5 parts by mass)
Were mixed to obtain a colored photosensitive resin composition (green).

(Formation of colored film)
The colored photosensitive resin composition (green) obtained above is applied on the surface of a glass substrate (# 1737 (trade name); manufactured by Corning) by spin coating, and then the volatile components are volatilized at 100 ° C. for 3 minutes. Thus, a colored photosensitive resin composition layer was formed. After cooling, the colored photosensitive resin composition layer was exposed by irradiating with i-line [wavelength 365 nm] through a photomask. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 150 mJ / cm ² .
As the photomask, a photomask for forming linear color pixels having a line width of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, and 100 μm was used. Next, a glass substrate after exposure [a colored photosensitive resin composition layer is formed on the surface. ] At 25 ° C. [Aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction, respectively. ] For 120 seconds, developed, washed with pure water, and then heated at 220 ° C. for 20 minutes to form a green pixel (film thickness: 1.65 μm). Thus, a glass substrate patterned with a green line and space pattern was obtained.

The components used in this example are as follows, and may be omitted below.
(A-1) Colorant: C.I. I. Pigment Blue 15: 6
(A-2) Colorant: C.I. I. Pigment Violet 23
(A-3) Colorant: C.I. I. Pigment Red 254
(A-4) Colorant: C.I. I. Pigment Yellow 139
(B-1) Binder resin: Copolymer of methacrylic acid and benzyl methacrylate [ratio of methacrylic acid unit and benzyl methacrylate unit is 27:73 by mass ratio (molar ratio), acid value is 102, polystyrene equivalent weight The average molecular weight is 24,000
(B-2) Binder resin: Copolymer of methacrylic acid and benzyl methacrylate [ratio of methacrylic acid unit and benzyl methacrylate unit is 30:70 by mass ratio (molar ratio), acid value is 113, polystyrene equivalent weight The average molecular weight is 24,000
(B-3) Resin B
(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (D-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (D-2) Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (D-3) photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl- 1,3,5-triazine (G-1) photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (G-2) photopolymerization initiation assistant: 2,4-diethylthioxanthone (E-1) Solvent: Propylene glycol monomethyl ether acetate (E-2) Solvent: Ethyl 3-ethoxypropionate (F-1) Surfactant: F475 (trade name) (Dainippon Ink Chemical Co., Ltd.) Made)
(F-2) Surfactant: SH8400 (trade name) (manufactured by Torre Silicone Co., Ltd.)
(F-3) Surfactant: E5844 (manufactured by Daikin Fine Chemical Laboratory)
(H) Epoxy compound; Sumiepoxy ESCN-195XL-80 (trade name) (manufactured by Sumitomo Chemical Co., Ltd.)

Example 1-6, Comparative Example 1-5
[Preparation of colored photosensitive resin pre-composition 1]
(A-1) 3.888 parts by mass (A-2) 0.432 parts by mass Polyester dispersant 2.014 parts by mass (B-2) 4.127 parts by mass (C) 2.751 parts by mass (D- 1) 0.825 parts by mass (G-1) 0.275 parts by mass (E-1) 51.000 parts by mass (E-2) 34.000 parts by mass (H) 0.688 parts by mass are mixed and colored. The photosensitive resin pre-composition 1 was obtained.

To the colored photosensitive resin pre-composition 1, 0.0008 part by mass of (F-2) is mixed, and the colored photosensitive resin composition 1-1 is mixed.
(F-2) 0.0015 part by mass is mixed, and the colored photosensitive resin composition 1-2 is
(F-2) 0.0030 parts by mass are mixed, and the colored photosensitive resin composition 1-3 is mixed.
(F-2) 0.0060 parts by mass are mixed, and the colored photosensitive resin composition 1-4 is mixed.
(F-2) 0.0090 parts by mass are mixed, and the colored photosensitive resin composition 1-5 is mixed.
(F-2) 0.0120 parts by mass are mixed, and the colored photosensitive resin composition 1-6 is
(F-1) 0.0030 part by mass is mixed, and the colored photosensitive resin composition 1-7 is
(F-3) 0.0030 part by mass is mixed, and the colored photosensitive resin composition 1-8 is mixed.
(F-2) 0.0060 parts by mass and (F-3) 0.0030 parts by mass are mixed, and the colored photosensitive resin composition 1-9 is mixed.
(F-1) 0.0120 parts by mass are mixed, and the colored photosensitive resin composition 1-10 is
I got each.

[Contact angle evaluation]
Using a contact angle measurement device (DGD Fast / 60-type Contact Angle Meter; manufactured by GBX) and on glass (# 1737 (trade name); manufactured by Corning) after washing with acetone, the colored photosensitive resin composition 1 2 μL of ˜1-9 was dropped, and after dropping, the contact angle after 0.2 seconds and the contact angle after 1 second after saturation were as follows.

[Viscosity evaluation]
Using a viscosity measuring device (VISCOMETER RE120L SYSTEM type (manufactured by Toki Sangyo Co., Ltd.)) and measuring the viscosity of the colored photosensitive resin compositions 1 to 1-10 at 23 ° C., the viscosity at 50 rpm is All were 4.1 mPa · s.

[Evaluation of flatness]
After tilting the glass substrate obtained by patterning (film thickness: a) 100 μm line-and-space pattern in the previously created green pixel by 30 degrees, each of the colored photosensitive resin compositions 1 to 1-10 is formed thereon. Drops were dropped and the drops were allowed to flow parallel to the line-and-space pattern, held for 5 minutes, and then baked at 100 ° C. for 3 minutes, and the film step on the 100 μm line and space was defined as b. At that time, the flattening rate: (ab) / a was as follows.

[Evaluation with slit coater]
When the obtained colored photosensitive resin compositions 1 to 1-10 were formed using a slit coater in which pigment aggregates partially adhered, the following results were obtained.
In addition, unevenness indicates that when the substrate applied in the dark room is irradiated with a sodium lamp and a green lamp and the substrate is observed from various angles, the streaks and the coating film that are visually observed look uneven. Those with no unevenness were judged to have good flatness.

Examples 7-10, Comparative Example 6
[Preparation of colored photosensitive resin composition 2]
In the colored photosensitive resin compositions 1 and 1-3 to 1-6 used in Comparative Example 1 and Examples 1 to 6, the content of the component (B-2) is 3.164 parts by mass, the component (C) Colored photosensitive resin compositions 2 and 2-3 to 2-6 were obtained in the same manner except that the content of was changed to 3.714 parts by mass.
[Contact angle evaluation]

  When the contact angles of the colored photosensitive resin compositions 2 and 2-3 to 2-6 were measured in the same manner as in Examples 1 to 6, it was as follows.

[Viscosity evaluation]
When the viscosity of the colored photosensitive resin composition 2 and 2-3 to 2-6 at 23 ° C. was measured in the same manner as in Examples 1 to 6, the viscosity at 50 rpm was 3.8 mPa · s. there were.

[Evaluation of flatness]
When the flattening rate was obtained in the same manner as in Example 1, it was as follows.

[Evaluation with slit coater]
When the coating film was formed using the slit coater in which the pigment agglomerates adhered to the obtained colored photosensitive resin compositions 2 to 2-4, the following results were obtained.

Comparative Example 7
[Preparation of colored photosensitive resin composition 3]
(A-3) 5.293 parts by mass (A-4) 1.407 parts by mass Polyester dispersant 2.540 parts by mass (B-1) 5.466 parts by mass (C) 3.644 parts by mass (D- 2) 0.547 parts by mass (D-3) 0.547 parts by mass (G-2) 0.547 parts by mass (E-1) 79.910 parts by mass (F-2) 0.010 parts by mass were mixed. Thus, a colored photosensitive resin composition 3 was obtained.

[Contact angle evaluation]
When the contact angle of the colored photosensitive resin composition 3 was measured in the same manner as in Example 1, the contact angle after 0.2 seconds was 21.5 °. The contact angle after 1 second of saturation was 19.2 °.

[Viscosity evaluation]
When the viscosity of the colored photosensitive resin composition 3 was measured in the same manner as in Examples 1 to 6, it was 6.8 mPa · s.

[Evaluation of flatness]
When the flattening rate was obtained in the same manner as in Examples 1 to 6, it was as follows.

[Evaluation with slit coater]
When the obtained colored photosensitive resin composition was formed into a coating film using a slit coater, an uneven coating film was obtained. Even when a coating film is formed using a slit coater with pigment agglomerates partially adhered to it, there are streaky irregularities in the part where the pigment agglomerate adhering part of the slit coater has passed, and coating with poor flatness. A membrane was obtained.

Examples 11-14, Comparative Example 8
[Preparation of colored photosensitive resin composition 4]
In the same manner as in Examples 1 to 6, except that (B-2) 4.127 parts by mass were changed to (B-3) 3.439 parts by mass, and (C) was changed to 3.439 parts by mass. Resin compositions 4 and 4-3 to 4-6 were obtained.

[Contact angle evaluation]
When the contact angles of the colored photosensitive resin compositions 4 and 4-3 to 4-6 were measured in the same manner as in Examples 1 to 6, it was as follows.

[Viscosity evaluation]
When the viscosity of the colored photosensitive resin compositions 4 and 4-1 to 4 at 23 ° C. was measured in the same manner as in Examples 1 to 6, the viscosity at 50 rpm was 3.3 mPa · s.

[Evaluation of flatness]
When the flattening rate was obtained in the same manner as in Example 1, it was as follows.

[Evaluation with slit coater]
A coating film was formed on the obtained colored photosensitive resin compositions 4, 4-3 to 6 using a slit coater in which a pigment aggregate was partially adhered, and the following results were obtained.

Claims (6)

  A colored photosensitive resin composition containing a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F). The viscosity of the composition at 23 ° C. is 2.0 mPa · s or more and 5.0 mPa · s or less, and 2 μL of the composition is dropped on a glass substrate and the contact angle after 0.2 seconds is 10 And the solvent (E) contains propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate, and the content of the solvent (E) in the composition is the composition. The mass fraction is 80% by mass to 95% by mass with respect to the surfactant, and the surfactant (F) is a group consisting of a silicone surfactant and a silicone surfactant and a compound having a fluorine atom. At least selected from 1 type, The content of this surfactant is 0.01 mass% or more and 0.15 mass% or less by mass fraction with respect to solid content of this composition, The coloring photosensitivity characterized by the above-mentioned. Resin composition.   The binder resin (B) is a reaction product of a glycidyl methacrylate / tricyclodecane skeleton monomethacrylate / benzyl (meth) acrylate copolymer and (meth) acrylic acid (weight average molecular weight in terms of polystyrene of the reaction product; 8,000 to 20,000, acid value; 50 to 120), and the content of the photopolymerizable compound (C) is a mass fraction with respect to the total amount of the binder resin (B) and the photopolymerizable compound (C). The colored photosensitive resin composition according to claim 1, wherein the content is 35% by mass to 60% by mass.   The colored photosensitive resin composition according to claim 1 or 2 is applied onto a substrate or a layer made of a solid content of the colored photosensitive resin composition previously formed, and the applied colored photosensitive resin composition is applied. A method for forming a pattern comprising removing a volatile component to form a colored photosensitive resin composition film, exposing the film through a photomask, and developing the film.   4. The method according to claim 3, wherein the colored photosensitive resin composition is applied using a spinless coater.   A color filter comprising a pattern formed by the method according to claim 3.   A liquid crystal display device comprising the color filter according to claim 5.