JP2000035670A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin compsn. hardly to cause the chipping of an image in development by incorporating a pigment, a carboxyl group-contg. copolymer, a photopolymerizable monomer, a photopolymn. initiator, an amine type silane coupling agent and a solvent. SOLUTION: A pigment is dispersed in a solvent and a carboxyl-contg. copolymer as a resin binder, a photopolymerizable monomer and a photopolymn. initiator are further incorporated. Other additives are optionally dissolved or dispersed and a small amt. of an amine type silane coupling agent is further added. The pigment is an org. pigment or an inorg. pigment such as iron. The carboxyl-contg. polymer is obtd. by copolymerizing a carboxyl-contg. monomer with other monomer copolymerizable with the carboxyl-contg. monomer. The photopolymerizable monomer is a compd. having a polymerizable carbon-carbon unsatd. bond. e.g. nonyl phenyl carbitol acrylate. The photopolymn. initiator is an acetophenone initiator such as diethoxyacetophenone or a benzoin initiator such as benzoin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a photosensitive resin composition which is widely used in ultraviolet curable inks and photoresists, and more particularly to an improvement in a color liquid crystal display device and an image pickup device. The present invention relates to a colored photosensitive resin composition suitable for a resist composition for forming a colored image (also referred to as a pixel).

[0002]

2. Description of the Related Art A color filter in a color liquid crystal display or an image pickup device is usually manufactured by forming three primary color pixels of red, green and blue on a substrate such as glass or a silicon wafer. In addition, a black matrix is usually provided to shield light between these pixels. Then, in order to form pixels of these colors, a resist solution containing a pigment corresponding to each color is uniformly applied on a substrate on which a light-shielding layer is formed by a spin coater, and then heated and dried (prebaked). A method of exposing and developing the coating film is adopted, and an image of each color is obtained by repeating these operations for each color required for the color filter. As such a resist, a composition containing a photopolymerizable monomer and a photopolymerization initiator together with a pigment and a binder resin is often used. In addition, a resist containing a black pigment may be used for forming a black matrix.

[0003] In order to secure the reliability of the color filter, a glass portion and a black matrix portion on a substrate to be coated are formed on a coating film formed from a resist containing a pigment corresponding to three primary color pixels of red, green or blue. And high adhesion to the film. In particular, since the contact area of the coating film is large with respect to the glass portion serving as the opening of the color filter, it is very important to ensure that the resist coating film has sufficient adhesion. The adhesion between the resist coating film and the glass largely depends on the properties of resin components other than pigments present in the resist coating film and the curability of the coating film. Under these circumstances, Japanese Patent Application Laid-Open No. 8-106163 proposes to use at least two kinds of specific silane coupling agents in combination in order to improve the adhesion between a resist coating film and a glass substrate.

On the other hand, as a recent trend of the liquid crystal display, in addition to a conventional notebook personal computer, a range of use for a monitor has been expanded as a substitute for a cathode ray tube (CRT) display. Accordingly, the required characteristics of the color filters used have been changing. In other words, in laptop applications, high transmittance was demanded in order to reduce power consumption. However, monitors can usually secure power from the power outlet at all times, so the image density and vividness are lower than the transmittance. Is often required. To cope with such darkness and vividness of an image, the blending ratio of the pigment component in the resin composition is increased to cope with the problem. However, when the mixing ratio of the pigment component is increased, a component that contributes to the curability of the coating film,
For example, the amount of the polyfunctional acrylate component or the like is relatively reduced, and the coating film is hardly sufficiently cured. as a result,
The problem that the adhesion between the coating film and the glass substrate is reduced and the chipping or peeling of the pixel easily occurs during the development has become apparent.

[0005] In the case of a black resin composition containing a black pigment used for forming a black matrix, the demand for further increasing the light-shielding ratio tends to increase, and the content of the black pigment in the resin composition is increased. The situation has been forced to increase the amount. As a result, similarly to the resist composition containing the pigment corresponding to the three primary color pixels, the compounding ratio of the polyfunctional acrylate component and the like contributing to the curability becomes relatively small, and the coating film becomes hard to sufficiently cure, and The problem that the adhesion between the film and the glass substrate is reduced and the chipping or peeling of the pixel is likely to occur during the development has become apparent.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to increase the pigment concentration in a resin composition and to relatively reduce the amount of a polyfunctional acrylate component or the like contributing to curing, so that a sufficient coating film can be obtained. Even when curability becomes difficult to obtain, it is an object of the present invention to provide a colored photosensitive resin composition that maintains sufficient adhesion between a coating film and a glass substrate and is less likely to cause chipping or peeling of pixels during development. .

The inventors of the present invention have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, together with a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, a silane coupling agent having a specific structure has been developed. It has been found that excellent results can be obtained by adding a small amount of, and the present invention has been completed.

[0008]

That is, the present invention provides:
(A) a pigment, (B) a carboxyl group-containing copolymer,
(C) a photopolymerizable monomer, (D) a photopolymerization initiator, (E)
An object of the present invention is to provide a colored photosensitive resin composition containing an amine silane coupling agent and (G) a solvent. This composition usually does not need to contain a silane coupling agent other than component (E).

Generally, in order to improve the adhesion to the substrate,
Adding a silane coupling agent to the resin composition,
It is also described in catalogs of silane coupling agent manufacturers. On the other hand, the present invention, among a wide variety of silane coupling agents, an amine-based silane coupling agent is particularly excellent in improving the adhesion of a coating film obtained from a colored photosensitive resin composition to a glass substrate. There is a great feature in that the present invention has been found to exhibit such an effect.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The colored photosensitive resin composition of the present invention is mainly used as a pigment-dispersed resist, in which a pigment (A) is dispersed in a solvent, and a carboxyl group-containing copolymer (B) called a binder resin, The polymerizable monomer (C) and the photopolymerization initiator (D), and optionally other additives, are dissolved or dispersed, and a small amount of the amine-based silane coupling agent (E) is blended therein. .

The pigment (A) can be an organic pigment or an inorganic pigment usually used for a pigment-dispersed resist. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts.Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony Oxides or composite metal oxides are mentioned. As the organic pigment, specifically, a color index (Color Index) (The Societ
y of Dyers and Colorists published)
gment). These pigments can be used alone or in combination of two or more. More specifically, compounds having the following color index (C.I.) numbers are included, but are not limited thereto.

CI Pigment Yellow 20, 24, 31, 5
3, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 13
9, 147, 148, 153, 154, 166 and 173; CI Pigment Orange 13, 31, 36, 38, 40, 42, 4
3, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122, 123, 144,
149, 166, 168, 176,177, 180, 192, 215, 216, 224, 2
42 and 254; CI Pigment Violet 14, 19, 23, 29, 32, 3
3, 36, 37 and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6 etc.), 21, 22, 28, 60 and 64; CI Pigment Green 7, 10, 15, 25, 36 and 4
7; CI Pigment Brown 28; CI Pigment Black 1 and 7, and the like.

The pigment (A) is used in an amount of generally 15 to 60% by weight, preferably 20 to 55% by weight, based on the total solid content in the colored photosensitive resin composition. In particular, the composition of the present invention can be used in a high pigment concentration range, specifically, a pigment having an amount of more than 30% by weight based on the total solid content in the colored photosensitive resin composition, and a pigment having an amount of 35% by weight or more. High effect is exhibited for the composition containing

The binder resin imparts alkali developability to the unexposed coating film and acts as a dispersion medium for the pigment. In the present invention, the carboxyl group-containing copolymer (B) is used as the binder resin. Used. The carboxyl group-containing copolymer can be obtained, for example, by copolymerizing a carboxyl group-containing monomer with another monomer copolymerizable therewith.

The carboxyl group-containing monomer is, for example,
It can be an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid or unsaturated dicarboxylic acid, and specifically, acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid,
Fumaric acid and the like. These can be used alone or in combination of two or more. Further, a monomer copolymerizable with these carboxyl group-containing monomers is a compound having a polymerizable unsaturated bond. Specifically, aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and benzyl Unsaturated carboxylic acid esters such as (meth) acrylate, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate, vinyl acetate and vinyl propionate Carboxylic acid vinyl ester, (meth)
And vinyl cyanide compounds such as acrylonitrile and α-chloroacrylonitrile. These monomers can also be used alone or in combination of two or more.

Further, a copolymer obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated carboxylic acid glycidyl ester, in which an unsaturated carboxylic acid is added to a glycidyl group, is obtained by copolymerizing styrene with maleic anhydride. Polymers having a photopolymerizable unsaturated group on the side chain of the polymer, such as a copolymer obtained by adding 2-hydroxyethyl acrylate to a portion derived from maleic anhydride of a copolymer obtained by the above method, can also be used as a carboxyl group-containing copolymer (B ) Can be used.

In the carboxyl group-containing copolymer (B), the carboxyl group-containing monomer unit is
It is preferably present in the range of 10 to 50% by weight, more preferably 15 to 40% by weight, based on the whole monomer. The amount of the carboxyl group-containing monomer unit referred to herein means, when the carboxyl group-containing copolymer is a copolymer of a carboxyl group-containing monomer and another monomer, the amount of the carboxyl group-containing monomer among them. When the copolymer has a photopolymerizable unsaturated group in the side chain of the polymer, it means a monomer unit that finally remains as a carboxyl group. To explain the latter more specifically, for example, a copolymer obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated carboxylic acid glycidyl ester with an unsaturated carboxylic acid added to a glycidyl group of a copolymer obtained,
Finally, the unsaturated carboxylic acid to be reacted with the glycidyl group is
Only units of unsaturated carboxylic acids that are first copolymerized with the unsaturated carboxylic acid glycidyl ester correspond to carboxyl group-containing monomer units because they are attached to the polymer backbone in the form of esters. Further, in a copolymer obtained by copolymerizing styrene and maleic anhydride with 2-hydroxyethyl acrylate added to a maleic anhydride-derived portion, the maleic anhydride-derived portion opens a ring to form a carboxyl group. Therefore, the unit derived from maleic anhydride corresponds to the carboxyl group-containing monomer unit.

Preferred examples of the carboxyl group-containing copolymer (B) include benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid /
Styrene copolymers, methyl methacrylate / methacrylic acid copolymers, methyl methacrylate / methacrylic acid / styrene copolymers and the like can be mentioned. These carboxyl group-containing copolymers preferably have a polystyrene equivalent weight average molecular weight in the range of 5,000 to 400,000, and more preferably have a weight average molecular weight in the range of 20,000 to 300,000. The carboxyl group-containing copolymer (B) is generally 5 to 9 based on the total solid content in the colored photosensitive resin composition.
0% by weight, preferably in the range of 20 to 70% by weight.

The photopolymerizable monomer (C) is a compound that causes a chain polymerization typified by radical polymerization by the action of light and a photopolymerization initiator, and generally a compound having a polymerizable carbon-carbon unsaturated bond. Corresponds to. This monomer (C) can be a monofunctional monomer, or a difunctional or other polyfunctional monomer. Specific examples of the radical polymerizable monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate,
N-vinylpyrrolidone and the like can be mentioned. Further, specifically, as a radical polymerizable bifunctional monomer, 1,6-
Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentane Diol di (meth) acrylate and the like. Specific examples of other radically polymerizable polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Above all, a polyfunctional monomer having two or more functional groups is preferably used, and in some cases, a monofunctional monomer may be used in combination.

A photopolymerizable monomer having a cationically polymerizable functional group represented by a vinyl ether group or a propenyl ether group can also be used. Specific examples of the cationic polymerizable monomer include triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, and 4- (1-propenyloxymethyl) -1,3-dioxolane. -2-one (manufactured chemical name is "propenyl ether propylene carbonate"; ISP Investment's "RAPI
-CURE PEPC ”).

These photopolymerizable monomers (C) can be used alone or in combination of two or more. The amount thereof is generally in the range of 0.1 to 80 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the total of the carboxyl group-containing copolymer (B) and the photopolymerizable monomer (C). Range.

Next, the photopolymerization initiator (D) will be described. An appropriate one is selected from a photoradical polymerization initiator and a photocationic polymerization initiator according to the type of the photopolymerizable monomer (C). The species may be used alone or in combination of two or more. For example, when the photo-radical polymerizable monomer is the component (C), an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, or other initiator can be used as the photopolymerization initiator (D).
More specifically, the following compounds can be mentioned.

(A) Acetophenone initiator diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) Phenyl] -2-methylpropane-1-
On, 1-hydroxycyclohexyl phenyl ketone,
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-
1-one, 2-hydroxy-2-methyl-1- [4-
(1-methylvinyl) phenyl] oligomers of propan-1-one and the like.

(B) Benzoin initiators Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.

(C) Benzophenone initiator Benzophenone, methyl o-benzoylbenzoate,
Phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

(D) Thioxanthone initiator 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone,
4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

(E) Other initiators 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.

Furthermore, the s-triazine-based photopolymerization initiator can initiate both photoradical polymerization and photocationic polymerization. Therefore, when both the photo-radical polymerizable monomer and the photo-cation polymerizable monomer are used as the component (C), not only can such an s-triazine photopolymerization initiator be used, but also the photo-radical polymerizable monomer can be used. Even when only one of the monomer and the cationic photopolymerizable monomer is used as the component (C), an s-triazine-based photopolymerization initiator can be used. The s-triazine photopolymerization initiator usually has a halomethyl group, and advantageously has, for example, a chloromethyl group, especially a trichloromethyl group. Specifically, the following compounds can be mentioned.

2,4-bis (trichloromethyl) -6
(4-methoxyphenyl) -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-
Triazine, 2,4-bis (trichloromethyl) -6
(4-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-dimethoxyphenyl) ethenyl]- 1,3,5-triazine and the like.

When the cationic photopolymerizable monomer is used as the component (C), a photoinitiator that initiates cationic photopolymerization may be used alone or in combination with an initiator that initiates photoradical polymerization. I do. The cationic photopolymerization initiator includes onium salts such as aromatic sulfonium salts and aromatic iodonium salts, iron arene complex compounds, and the like, in addition to the above-mentioned s-triazine compounds.

Further, a photopolymerization initiator may be used in combination with a photoinitiator. Specific examples of the photoinitiating aid include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine,
4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene,
9,10-diethoxyanthracene, 2-ethyl-9,
10-diethoxyanthracene and the like. These photoinitiating aids can be used alone or in combination of two or more.

The photopolymerization initiator (D) is generally used in an amount of 0.1 parts by weight based on 100 parts by weight of the total of the carboxyl group-containing copolymer (B) and the photopolymerizable monomer (C) in the photosensitive resin composition. It is contained in an amount of from 50 to 50 parts by weight, preferably from 1 to 30 parts by weight. When a photoinitiator is used in addition to the photoinitiator (D), the total amount of the photoinitiator (D) and the photoinitiator is preferably in the above range.

In the present invention, in addition to the pigment (A), the carboxyl group-containing copolymer (B), the photopolymerizable monomer (C) and the photopolymerization initiator (D), an amine silane coupling is used. A small amount of the agent (E) is blended. The amine-based silane coupling agent used herein means that one of the hydrogens of the silane SiH ₄ is an organic functional group, the remaining two or three are hydrolyzable groups, and if another is left, it is not. Is substituted with a non-functional organic group, and the compound having an amino group in the molecule, generally, the above-mentioned organic functional group. This amino group is usually primary or secondary. Typical examples of such an amine-based silane coupling agent include those represented by the following formula.

[0034]

In the formula, A represents an alkylene optionally having an imino (—NH—) interposed therebetween, R ¹ represents hydrogen or a monovalent hydrocarbon residue, and R ² and R ³ independently of each other Represents lower alkoxy, and R ⁴ represents lower alkyl or lower alkoxy. The alkylene represented by A can have a total of about 2 to 8 carbon atoms, including when an imino is interposed in the middle, and the monovalent hydrocarbon residue represented by R ¹ is a lower alkyl, It can be cycloalkyl, phenyl and the like. The lower alkyl and the lower alkoxy may each have about 1 to 4 carbon atoms.

Specific examples of the amine silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3.
-Aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and the like. These amine silane silane coupling agents are generally used in an amount of 10 to 10% based on the total weight of the colored photosensitive resin composition containing the solvent (G).
It is blended in the range of 5,000 ppm, preferably in the range of 30 to 3,000 ppm.

The solvent (G) can be any of those used in this field. Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dipropyl ether. Diethylene glycol dialkyl ethers such as butyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Propylene glycol alkyl ether acetates such as luacetate; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol and butanol , Hexanol, cyclohexanol,
Alcohols such as ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more. The amount of the solvent used is preferably 60 to 9 based on the total amount of the colored photosensitive resin composition containing the solvent.
0% by weight, more preferably 70 to 85% by weight.

The colored photosensitive resin composition of the present invention may also contain, if necessary, a filler, another polymer compound, a surfactant (pigment dispersant), an antioxidant, an ultraviolet absorber, an agglomeration inhibitor and the like. May be contained. Specific examples of the filler include glass, silica, and alumina, and specific examples of the other polymer compound include polyvinyl alcohol,
Polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like, respectively, and as a surfactant (pigment dispersant),
Various types such as nonionic, cationic, and anionic are used, and specific examples of the antioxidant include 2,2'-
Thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol and the like are specifically mentioned as 2- (3-
tert-butyl-2-hydroxy-5-methylphenyl)
-5-chlorobenzotriazole, alkoxybenzophenone and the like, and specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The colored photosensitive resin composition of the present invention can be prepared, for example, as follows. That is, the pigment (A) is mixed with the solvent (G) in advance, and the average particle diameter of the pigment is 0.2 μm.
Disperse the mixture using a bead mill or the like until the dispersion becomes about the following. At this time, a dispersant is used as needed, and a part or all of the carboxyl group-containing copolymer (B) may be blended. Pigment dispersion obtained (mill base)
In addition, the remaining of the carboxyl group-containing copolymer (B), the photopolymerizable monomer (C) and the photopolymerization initiator (D), other components used as needed, and, if necessary, an additional solvent, Add to a predetermined concentration. The amine-based silane coupling agent (E) may be added together with the photopolymerizable monomer (C), or may be added after all other components have been mixed. Thus, the desired colored photosensitive resin composition is obtained.

The photosensitive resin composition thus prepared is
For example, a colored image can be formed by applying the composition on a substrate, photocuring and developing as described below. First, this composition is spin-coated on a substrate (usually glass), and dried by heating (prebaking) to remove the solvent to obtain a smooth coating film. At this time, the thickness of the coating film is about 1-2.
It is about μm. The obtained coating film is irradiated with ultraviolet rays through a negative mask for forming a target image. At this time, it is preferable to use a device such as a mask aligner so that the entire exposed portion is uniformly irradiated with parallel rays and the mask and the substrate are accurately aligned. Thereafter, the cured coating film is brought into contact with a dilute aqueous alkaline solution to dissolve the unexposed portion and develop it, thereby obtaining an intended image. After development, if necessary,
Post-curing (post-baking) at 30 ° C. for about 10 to 60 minutes can also be performed.

The developer used for the development after the patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide,
Disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate , Potassium borate, ammonia and the like. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine,
Triethylamine, monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferred concentration of the alkaline compound in the alkaline developer is
0.01 to 10% by weight, more preferably 0.0 to 10% by weight.
It is 3 to 5% by weight.

The surfactant may be any of a nonionic surfactant, a cationic surfactant and an anionic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene alkyl ether. Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned. Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzene sulfonate; Alkyl aryl sulfonates such as sodium dodecylnaphthalene sulfonate, and the like. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more. The concentration of the surfactant in the alkali developer is usually 0.0
1 to 10% by weight, preferably 0.05 to 8% by weight,
More preferably, the content is 0.1 to 5% by weight.

The application and drying of the photosensitive resin liquid as described above
Through each operation of patterning exposure to the obtained dried coating film and development, a pixel corresponding to the color of the pigment in the photosensitive resin composition is obtained, and these operations are further performed by the color required for the color filter. By repeating the same number of times, a color filter is obtained. That is, the color filter is usually one in which red, green and blue pixels are arranged on a substrate, and the above operation is performed using the colored photosensitive resin composition of the present invention containing a pigment corresponding to a certain color. By doing so, a pixel of that color is obtained, and the same operation is performed using the colored photosensitive resin composition of the present invention containing a pigment corresponding to a desired color also for the other colors, and the three-color pixels are formed on the substrate. Can be arranged. Of course, the colored photosensitive resin composition of the present invention can be applied to only one or two of the three colors. Further, the colored photosensitive resin composition of the present invention containing a black pigment can be used for forming a black matrix which is a light shielding layer.

[0044]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the used amount are based on weight unless otherwise specified.

Examples 1 to 3 and Comparative Examples 1 to 8 As representative examples, examples and comparative examples in which a green photosensitive resin composition was prepared and evaluated are shown. The composition of the photosensitive resin composition used here is as shown in Table 1.

[0046]

Table 1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ (A) Pigment: CI Pigment Green 36 4.95 parts C.I. Polymerizable monomer: 2.83 parts of dipentaerythritol hexaacrylate (D) Photopolymerization initiator: 1.48 parts of 2-pentasil-2-dimethylamino-1- (4-morpholinophenyl) phthal-1-one 2,4-bis (trichloro) (Methyl) -6-hydroxyperonyl-1,3,5-triazine 0.21 part (F) Other components: Nonionic pigment dispersant 2.25 parts (G) Solvent: Propylene glycol monomethyl ether acetate 80.00 parts ━━━━━━━━━━━━━━━━ ━━━━━━━━━━━

Among the above components, the total amount of each of the pigment and the pigment dispersant is mixed in advance with a partial amount of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed using a bead mill and finely divided. The remaining components including the remaining amount of propylene glycol monomethyl ether acetate were added and mixed. To this photosensitive resin solution, 1,000 ppm of the silane coupling agents shown in Table 2 were added to obtain a resin solution for evaluation.

A 2-inch square quartz glass substrate was washed sequentially with a neutral detergent, water and alcohol, and then dried. Each of the photosensitive resin solutions prepared above was spin-coated on the glass substrate so as to have a predetermined thickness, and then prebaked in a clean oven at 100 ° C. for 3 minutes. Then, using a Gardner cross cut tester, cut into the coating on the glass substrate so that 100 squares of 1 mm x 1 mm were formed, and a cellophane tape was placed on the square. A tape peeling test was conducted in which the tape was peeled off after being stuck. Of the 100 squares, the number of squares remaining without peeling after the tape peeling test was visually counted, and 100/100 was set for all remaining and 0/100 was set for all peeled. Table 2 summarizes the results.

[0049]

[Table 2] 例 Example No. Silane coupling agent Tape peeling test result ━━━ Example 1 N- (2-aminoethyl) -3-aminofluoromethyldimethylmethoxysilane 100 / 100 2 N-phenyl-3-aminofluorotrimethoxysilane 100/100 3 3-aminofluorotrimethoxysilane 100/100比較 Comparative Example 1 phenyltriethoxysilane 0/100 〃2 phenyltrimethoxysilane 0/100 〃3 3-methacryloyloxyfluorotrimethoxysilane 0/100 ４42- (3 , 4-Ethoxycyclohexyl) ethyltrimethoxysilane 0/100 ５53-polycitoxyfluoro O-Trimethoxysilane 0/100 〃 6 3-Cryoxypropylmethylmethylethoxysilane 0/100 ７ 7 3-Mercaptofluoropropyltrimethoxysilane 0/100 〃 8 None 0/100 ━━━━━━━━━━━━━━━━━━━━━━

In all of Examples 1 to 3 to which an amine silane coupling agent was added, the adhesion of the coating film to the glass substrate was good, and no peeling of the coating film was observed after the tape peeling test. On the other hand, in Comparative Examples 1 to 7 in which a silane coupling agent other than an amine type was added and Comparative Example 8 in which no silane coupling agent was added, the adhesion of the coating film to the glass substrate was insufficient, and the tape peeling test was performed. Later, all 100 squares were peeled off. Further, the coating films obtained in Examples 1 to 3 were immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at room temperature for 2 minutes and then washed with water. No development residue was observed.

[0051]

The colored photosensitive resin composition of the present invention shows good adhesion when applied to a glass substrate, and does not sacrifice development characteristics such as development residues. Therefore, if this composition is used as a pigment-dispersed resist,
When producing a high-saturation color filter in which the resin component is relatively reduced by increasing the pigment concentration in a coating film containing a red, green or blue pigment, or the pigment concentration in a coating film containing a black pigment In the case of producing a black matrix having a high light blocking ratio such that the resin component is relatively reduced by increasing the resin component, the peeling of the coating film from the glass substrate is reduced, and high productivity (yield) and reliability can be secured. .

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03F 7/028 G03F 7/028 7/033 7/033 F term (Reference) 2H025 AA04 AA14 AB13 AC01 AD01 BC12 BC14 BC31 BC34 BC43 BC52 BC53 CB43 CC03 CC06 CC12 2H048 BA02 BA45 BA48 BB02

Claims (5)

[Claims] 1. A pigment (A), a carboxyl group-containing copolymer (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an amine silane coupling agent (E), and (G)
A colored photosensitive resin composition comprising a solvent. 2. The composition according to claim 1, wherein the pigment (A) is present in the range of 15 to 60% by weight based on the total solid content in the composition. 3. A composition according to claim 2, wherein the pigment (A) is present in a proportion exceeding 30% by weight, based on the total solids in the composition. 4. An amine-based silane coupling agent (E) comprising:
Lower formula (In the formula, A represents alkylene optionally having -NH- in the middle, R ¹ represents hydrogen or a monovalent hydrocarbon residue,
R ² and R ³ independently represent lower alkoxy;
⁴ represents a lower alkyl or lower alkoxy), the composition according to any one of claims 1 to 3. 5. An amine-based silane coupling agent (E) comprising:
The composition according to any one of claims 1 to 4, which is present in the range of 10 to 5,000 ppm based on the whole composition.