KR100868663B1 - Coloured photosensitive resin compositions - Google Patents

Abstract

The present invention contains 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one as a photopolymerization initiator, and even when heated after development, it is possible to give a coloring pattern with a low amount of sublimation generation. , Colorant (A), binder polymer (B), photopolymerizable compound (C), 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (D) and epoxy compound ( The coloring photosensitive resin composition containing E) is provided. Forming a colored pattern 3 by forming a layer 4 made of such a colored photosensitive resin composition on the substrate 2 (a), exposing the layer (b), then developing and subsequently heating to form a colored pattern 3 (c) ), A color filter is obtained.

Colorant, binder polymer, photopolymerizable compound, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, epoxy compound

Description

Colored photosensitive resin compositions             

1A and 1B are schematic diagrams of a color filter.

2A, 2B and 2C are schematic diagrams showing a step of forming a colored pattern using a colored photosensitive resin composition to produce a color filter.

3A, 3B, and 3C are schematic diagrams showing a step of forming a colored pattern using a colored photosensitive resin composition to produce a color filter.

4A, 4B, and 4C are schematic diagrams showing a step of forming a colored pattern using a colored photosensitive resin composition to produce a color filter.

5A, 5B, and 5C are schematic diagrams showing a step of forming a colored layer in an embodiment.

FIG. 6 is a graph plotting the mass reduction rate (vertical axis) versus the value obtained by dividing the amount of use of the epoxy compound (E) by the total amount of use of the binder polymer (B) and the photopolymerizable compound (C) in the Examples and Comparative Examples. to be.

Explanation of the sign

1: color filter                 

2: substrate

3: coloring pattern

3 ': tinted pattern

3 ": tinted pattern

30: colored layer

    3R: red pixel

    3G: green pixels

    3B: blue pixel

    3BM: Black Matrix

4: coloring photosensitive resin composition layer

4: coloring photosensitive resin composition layer

4 ": colored photosensitive resin composition layer

    41: light non-irradiation area

    42: light irradiation area

5: rays

6: photomask

    61: glass plate

    62: light shielding layer

63: floodlight

The present invention relates to a colored photosensitive resin composition.

A colored photosensitive resin composition (color resist) is a photosensitive resin composition (resist resist) which contains a coloring agent and is colored, for example, it is useful as a raw material for manufacturing a color filter. Here, the color filter 1 is an optical element used for introducing into the color solid-state imaging element which colorizes the display image of a color liquid crystal display device, and obtaining a color image, for example. It is known that the color filter 1 consists of the coloring pattern formed on the same plane on the board | substrate 2 (FIGS. 2A-2C), and the coloring photosensitive resin composition is used for formation of such a coloring pattern. As the colored pattern, for example, red pixels 3R, green pixels 3G, and blue, which are transparent layers colored with respective colors of three colors of light, red, green, and blue, and complementary colors thereof, cyan, magenta, and yellow, respectively. And a black matrix, which is a black layer formed on the boundary of each color pixel such as the pixel 3B and shielding the visible light.

As such colored photosensitive resin composition, what conventionally contains a coloring agent, a binder polymer, a photopolymerizable compound, and a photoinitiator is known. As the photoinitiator, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is known. As a method of manufacturing a color filter using such colored photosensitive resin composition, the layer 4 which consists of colored photosensitive resin composition is formed on the board | substrate 2, for example (FIG. 2A), and the said layer 4 is exposed. After that (FIG. 2B), the method of developing and forming the coloring pattern 3 is mentioned (FIG. 2C). In the colored photosensitive resin composition layer 4 at the time of exposure, although the light non-irradiation area | region 41 with which the light ray 5 was not irradiated, and the light irradiation area 42 with which the light ray is irradiated generate | occur | produce, It is removed upon subsequent development. On the other hand, the light irradiation area 42 remains as it is after image development, and comprises the coloring pattern 3 (FIG. 2C). The coloring pattern 3 after image development heat-processes, and improves mechanical strength, solvent resistance, etc. The formation of such a colored pattern is generally carried out in a clean room in order to prevent the incorporation of foreign matter into the colored pattern.

However, when the coloring pattern 3 formed using the conventional coloring photosensitive resin composition containing 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is heat-processed, it will coloring. There exists a problem that a sublimation arises from a pattern. Sublimates generated during the heat treatment may become contaminants in the clean room and may be mixed as foreign matter in the coloring pattern.

Therefore, the present inventors can give a coloring pattern with a small amount of sublimation generated upon heating after development even if 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is contained as a photopolymerization initiator. It earnestly examined to develop the coloring photosensitive resin composition which can be. As a result, when the coloring photosensitive resin composition containing 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one further contains an epoxy compound, the said coloring photosensitive resin composition is used. By heating the formed coloring pattern, it was revealed that no sublimation was generated, and the present invention was reached.

That is, this invention is a coloring agent (A), a binder polymer (B), a photopolymerizable compound (C), and 2-methyl- 2-morpholino- 1- (4-methylthiophenyl) propane- 1-one (D) And an epoxy compound (E). A colored photosensitive resin composition is provided.

The coloring agent (A) contained in the coloring photosensitive resin composition of this invention may be an organic coloring agent which is an organic substance, and may be an inorganic coloring agent which is an inorganic substance. The organic colorant may be an organic pigment and may be an organic dye. In addition, it may be a synthetic dye, and may be a natural dye. The inorganic colorant may be an inorganic pigment such as a metal oxide, a metal complex salt, or an inorganic salt (barium pigment) of barium sulfate. Among these colorants, organic colorants, particularly organic pigments, are preferably used.

As an organic pigment, the compound classified as pigment in the color index (The Society of Dyers and Colourists) is mentioned, for example. Specifically, C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow l3, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow l6, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 125, C.I. Pigment Yellow 128, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment 173;

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

C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red l05, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red l44, C.I. Pigment Red 149, C.I. Pigment Red l66, C.I. Pigment Red 168, C.I. Pigment Red l76, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment red 265;

C.I Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment blue 60;

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Pigment violet 38;

C.I. Pigment Green 7, C.I. Pigment green 36;

C.I. Pigment Brown 23, C.I. Pigment brown 25;

C.I. Pigment Black 1, C.I. Pigment black 7 and the like. These organic pigments may be used alone or in combination of two or more thereof.

Organic pigments include rosin treatments, surface treatments using pigment derivatives in which acidic groups or basic groups are introduced, graft treatments on pigment surfaces with polymer compounds, atomization treatments such as sulfuric acid atomization, or the like, as necessary. Washing | cleaning process by an organic solvent, water, etc. can be performed.

The content range of the colorant is a mass fraction with respect to the solid content after the volatile component of the colored photosensitive resin composition is volatilized, and is usually 5% or more, preferably 10% or more, more preferably 20% or more, usually 60% Below, Preferably it is 50% or less. In addition, when using an organic pigment as a coloring agent, the usage-amount of the said organic pigment is 50% or more normally, Preferably it is 55% or more by mass fraction with respect to the coloring agent whole quantity.

Binder polymer (B) can disperse a coloring agent, and also gives the coloring photosensitive resin composition layer 4 the function which the light non-irradiation area | region 41 is removed in image development, and the light irradiation area | region 42 remains. Capable polymers are used. As such a binder polymer, the polymer which consists of a monomeric unit containing a carboxyl group is mentioned, for example.

As a monomer containing a carboxyl group, the unsaturated carboxylic acid containing one or more carboxyl groups in a molecule | numerator, such as unsaturated carboxylic acid, unsaturated dicarboxylic acid, etc. is mentioned, For example, acrylic acid, methacrylic acid, crotonic acid, ita Cholic acid, maleic acid, fumaric acid, etc. are mentioned. These monomers are compounds having a carbon-carbon unsaturated bond, and may be used alone or in combination of two or more.

The binder polymer may be a homopolymer of a monomer having such a carboxyl group and may also be a copolymer of a monomer having a carboxyl group with another monomer. Other monomers are, for example, monomers having a carbon-carbon unsaturated bond and copolymerizable with monomers having a carboxyl group, and for example, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and methyl acrylate. Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, etc. Unsaturated carboxylic acid aminoalkyl ester compounds such as unsaturated carboxylic acid ester compounds and aminoethyl acrylate, unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate, vinyl acetate and vinyl propionate Carboxylic Acid Vinyl Ester Compound, Acrylonitrile, Meta Vinyl cyanide compounds, such as chloronitrile and the (alpha)-chloro acrylonitrile, 3-methyl- 3-acryloxy methyl oxetane, 3-methyl- 3-methacryloxy methyl oxetane, 3-ethyl-3- acryloxy methyl Oxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl And unsaturated carboxylic acid oxetane ester compounds such as oxetane and 3-methyl-3-methacryloxyethyl oxetane. These monomers are each used alone or in combination of two or more.

As such a copolymer, for example, 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / Methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / methyl methacrylate / Methacrylic acid / styrene copolymer, etc. are mentioned. The content of the monomer unit having a carboxyl group in such a copolymer is 5% or more and 50% or less, preferably 10% or more and 40% or less in terms of mass fraction.

As such a binder polymer, the weight average molecular weight (Mw) range required by gel permeation chromatography (GPC) based on polystyrene is preferably 5,000 to 400,000 and more preferably 10,000 to 300,000.

The content range of the binder polymer in the colored photosensitive resin composition of the present invention is a mass fraction with respect to the solid content of the colored photosensitive composition, and is usually 5% or more, preferably 20% or more, usually 90% or less, preferably 70% It is about the following.

The photopolymerizable compound (C) is a compound capable of initiating polymerization by active radicals generated from 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one by irradiation with light. For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned. Such a compound may be a monofunctional photopolymerizable compound, and may be a bifunctional or trifunctional or higher polyfunctional photopolymerizable compound.

Examples of the monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N. -Vinylpyrrolidone, etc. are mentioned.

As a bifunctional photopolymerizable compound, for example, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol di Acrylate, neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3- Methylpentanediol dimethacrylate etc. are mentioned.

As a trifunctional or more than polyfunctional photopolymerizable compound, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylic The rate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned.

These photopolymerizable compounds are used individually or in combination of two or more, respectively. Among these photopolymerizable compounds, bifunctional or higher polyfunctional photopolymerizable compounds are preferably used, and when two or more photopolymerizable compounds are used, at least one of them is preferably a polyfunctional photopolymerizable compound.

In the colored photosensitive resin composition of this invention, content of a photopolymerizable compound is 0.1-1 mass part or more and 70 mass parts or less normally per 100 mass parts of total amounts of a binder polymer and a photopolymerizable compound, Preferably they are 10 mass parts or more and 60 mass parts It is as follows.

The photoinitiator contained in the coloring photosensitive resin composition of this invention is 2-methyl- 2-morpholino-1- (4-methylthio phenyl) propane- 1-one (D). Such compounds are active radical generators that generate active radicals by irradiation with light. The content of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one in the colored photosensitive resin composition of the present invention is usually per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. It is 2 mass parts or more, Preferably it is 4 mass parts or more, Usually, it is 36 mass parts or less, Preferably it is 24 mass parts or less.

Although the coloring photosensitive resin composition of this invention contains 2-methyl- 2-morpholino-1- (4-methylthiophenyl) propane- 1-one as a photoinitiator, it can contain another photoinitiator. As such a photoinitiator, an active radical generator, an acid generator, etc. are mentioned, for example. As an active radical generating agent, an acetophenone type photoinitiator, a benzoin type photoinitiator, a benzophenone type photoinitiator, a thioxanthone type photoinitiator, a triazine type photoinitiator, etc. are mentioned, for example.

As an acetophenone type photoinitiator, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1- Oligomers of on, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

As a benzoin type photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a benzophenone type photoinitiator, a benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra- (Tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As a thioxanthone type photoinitiator, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro, for example 4-propoxy thioxanthone etc. are mentioned.

As a triazine photoinitiator, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example. -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-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 (trichloro Romethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

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, phenylglyoxylate, titanocene compound, etc. Can be used.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate and 4-acetoxyphenyldimethylsulfonium p-toluenesulfo Nate, 4-acetoxyphenylmethyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfo Onium salts such as nate and diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzointosylates and the like.

In addition, there are some compounds which generate an acid simultaneously with the active radicals in the compound as an active radical generator, for example, a triazine photopolymerization initiator is used as an acid generator.

These photopolymerization initiators are used alone or in combination with 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, respectively.

The coloring photosensitive resin composition of this invention can contain a photoinitiation start adjuvant. A photoinitiator adjuvant is a compound used in combination with a photoinitiator, and is used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started by a photoinitiator. As photopolymerization start adjuvant, an amine photoinitiation start adjuvant, an alkoxy anthracene type photoinitiation start adjuvant, etc. are mentioned, for example.

Examples of the amine photopolymerization initiation aid include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoic acid. Aminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's Ketone), 4,4'-bis (di Ethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, and the like.

As an alkoxy anthracene type photoinitiator, it is 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy, for example. Anthracene and the like.

Commercially available ones can be used as the photopolymerization initiation assistant, and commercially available photopolymerization initiation assistants include, for example, the trade name "EAB-F" (manufacturer: Hodogaya Chemical Co., Ltd.).

When using such a photoinitiator, the usage-amount thereof is 10 mol or less normally, Preferably it is 0.01 mol or more and 5 mol or less per mole of a photoinitiator. As for the usage-amount of a photoinitiator and a photoinitiator, the amount whose total amount is 3 mass parts or more and 30 mass parts or less normally with respect to 100 mass parts of total amounts of a binder polymer and a photopolymerizable compound, Preferably it is 5 mass parts or more and 25 mass parts or less to be.

As an epoxy compound (E), the epoxy compound which can crosslink a binder polymer at the time of heat processing of the coloring pattern after image development is mentioned, for example. Moreover, the epoxy compound which can superpose | polymerize independently by heating is good. The epoxy compound cures the coloring pattern by crosslinking the binder polymer or polymerizing itself. As a result, a sublimation does not generate | occur | produce from a coloring pattern at the time of the heat processing after image development.

As such an epoxy compound, For example, aromatic epoxy resins, such as a bisphenol-A epoxy resin, a hydrogenated bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a hydrogenated bisphenol F-type epoxy resin, a novolak-type epoxy resin;

Epoxy resins such as alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxidation;

Brominated derivatives of the epoxy resins;

Epoxides of aliphatic compounds, Epoxides of alicyclic compounds, Epoxy compounds of aromatic compounds, Epoxides of (co) polymers of butadiene, Epoxides of (co) polymers of isoprene, Glycidyl (meth) acrylates ) Polymer and triglycidyl isocyanurate.

In the coloring photosensitive resin composition of this invention, content of an epoxy compound is 2 mass parts or more normally, Preferably it is 4 mass parts or more, More preferably, 7 mass parts with respect to 100 mass parts of total amounts of a binder polymer and a photopolymerizable compound. Or more, particularly preferably 15 parts by mass or more. Moreover, such content is 30 mass parts or less normally, Preferably it is 25 mass parts or less with respect to 100 mass parts of total amounts of a binder polymer and a photopolymerizable compound. When it exceeds 30 mass parts, when heating the coloring pattern after image development, its shape may collapse.

The coloring photosensitive resin composition of this invention can contain an additive. As an additive, a pigment dispersant is mentioned, for example. By containing a pigment dispersant, even when using a pigment as a coloring agent, it becomes easy to disperse | distribute the said pigment uniformly to a coloring photosensitive resin composition. Examples of such pigment dispersants include surfactants such as nonionic surfactants, cationic surfactants and anionic surfactants, polyester polymer dispersants, acrylic polymer dispersants, polyurethane polymer dispersants, and the like. Each may be used alone or in combination of two or more. When using a pigment dispersant, its usage-amount is normally 0.01 mass part or more, Preferably it is 0.05 mass part or more, and normally 1 mass part or less, Preferably it is 0.5 mass part or less per 1 mass part of colorants.

As an additive contained in the coloring photosensitive resin composition of this invention, a filler, a high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, an anticoagulant, an organic acid, an organic amino compound, a curable compound, etc. are mentioned.

As a filler, glass, alumina, etc. are mentioned, for example.

As a high molecular compound, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate is mentioned, for example.

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

As antioxidant, 2, 2- thiobis (4-methyl-6-t-butylphenol), 2, 6- di-t- butylphenol, etc. are mentioned, for example.

As a ultraviolet absorber, 2- (3-t- butyl- 5-methyl-2-hydroxyphenyl) -5-chloro benzotriazole, alkoxy benzophenone, etc. are mentioned, for example.

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

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, diether acetic acid, enanthic acid and caprylic acid, oxalic acid, malonic acid, succinic acid, and gluconic acid. Tartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, ita Aliphatic dicarboxylic acids such as cholic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid, aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid, benzoic acid, toluic acid, cuminic acid, melitric acid and mesityl Aromatic polycarboxylic acids such as aromatic monocarboxylic acids such as lenic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, trimellitic acid, trimesic acid, melanoic acid, pyromellitic acid, and the like. .

Examples of the organic amino compound include n-propylamine, i-propylamine, n-butylamine, i-butylamine, secondary-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, Mono (cyclo) alkylamines such as 4-methylcyclohexylamine;                     

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di n-propylamine, di i-propylamine, di n-butylamine, di i-butylamine, di-butyl-butyl Di (cyclo) alkylamines such as amine, dit-butylamine, di n-pentylamine, di n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexylamine, dimethylethylamine, methyldiethyl Amine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi n-propylamine, ethyldi n-propylamine, tri n-propylamine, tri i-propylamine, tri n-butylamine , Tri i-butylamine, tri-butylamine, tri t-butylamine, tri n-pentylamine, tri n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, Tri (cyclo) alkylamines, such as ethyldicyclohexylamine and tricyclohexylamine, 2-aminoethane , 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-cyclo Mono (cyclo) alkanolamines such as hexanol, diethanolamine, di n-propanolamine, di i-propanolamine, di n-butanolamine, di i-butanolamine, di n-pentanolamine, di n- Di (cyclo) alkanolamines such as hexanolamine and di (4-cyclohexanol) amine, triethanolamine, tri n-propanolamine, tri i-propanolamine, tri n-butanolamine, tri i-butanolamine, Tri (cyclo) alkanolamines such as tri n-pentanolamine, tri n-hexanolamine, tri (4-cyclohexanol) amine, 3-amino-1,2-propanediol, 2-amino-1, 3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3 -Dimethylamino-1,2-propanediol, 3-diethylami 1,2-propanediol, 2-dimethylamino-1,3-propanediol, amino (cyclopropyl), 2-diethylamino-1,3-propanediol alkane diols;

1-aminocyclopentanonemethanol, 4-aminocyclopentanonemethanol, 1-aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4 Amino group-containing cycloalkanethanols such as dimethylaminocyclohexanemethanol and 4-diethylaminocyclohexanemethanol, β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, Aminocarboxylic acids such as 3-aminoisoacetic acid, 2-amino valeric acid, 5-amino valeric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid, Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, pn-butylaniline, pt-butylaniline, 1- Aromatic amines such as propylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline, o-aminobenzyl alcohol, m-aminobenzyl alcohol aminobenzyl alcohols such as p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol, o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p- Aminophenols such as aminophenols such as diethylaminophenol, m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

Examples of the curable compound include oxetane compounds such as carbonate bis oxetane, xylylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexanedicarboxylic acid bis oxetane.                     

The coloring photosensitive composition of this invention can contain the compound which can ring-open-polymerize an epoxy compound. Such a compound ring-opens-polymerizes an epoxy compound by ring-opening the epoxy group of an epoxy compound. In addition, such a compound is a compound which can ring-open-polymerize an oxetane compound, and when a coloring photosensitive resin composition contains an oxetane compound, the said oxetane compound is ring-opened-polymerized. As a compound which can ring-open-polymerize an epoxy compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

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, 3,3 ', 4, Aromatic polyhydric carboxylic acids such as 4'-benzophenone tetracarboxylic acid;

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

Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1 Alicyclic polyhydric carboxylic acids, such as a 2,4, 5- cyclohexane tetracarboxylic acid, etc. are mentioned.

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

Aliphatic polyvalent carboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbaric acid, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride;

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

Ester group containing carboxylic anhydrides, such as ethylene glycol bistrimellitate acid and glycerin tristrimellitate anhydride, etc. are mentioned.

As polyhydric carboxylic acid anhydride, what is marketed as an epoxy resin hardener can be used. As such an epoxy resin hardening | curing agent, For example, brand name "adekaha donor EH-700" [manufacturer: Asahi Denka Kogyo Co., Ltd.], a brand name "Lika seed HH" [manufacturer: Shin-Nipponika Kabushiki Kaisha], A brand name "MH-700" [manufacturer: Shin-Nippon Chemical Co., Ltd.] etc. are mentioned.

Compounds capable of ring-opening polymerization of such epoxy compounds may be used alone or in combination of two or more.

The coloring photosensitive resin composition of this invention is manufactured and preserve | saved normally in the state diluted with the solvent (F). As a solvent, the same solvent used for a normal colored photosensitive resin composition can be used. As a solvent, For example, Ethylene glycol monoalkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;

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

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

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;

Aromatic hydrocarbons such as benzene, toluene and xylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;

Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. These solvents may be used alone or in combination of two or more kinds.

The amount of the solvent used is such that the content of the solvent is usually 50% or more and 90% or less, preferably 60% or more and 85% or less by mass fraction in the colored photosensitive composition in the state diluted with the solvent.

The coloring photosensitive resin composition of this invention is a coloring agent (A), a binder polymer (B), a photopolymerizable compound (C), 2-methyl-2- morpholino-1- (4-methylthiophenyl), for example. It can be manufactured by the method of mixing a propane-1-one (D), an epoxy compound (E), and a solvent (F). When mixing, the colorant is usually used as a mixture previously mixed with a solvent. The content of the colorant in such a mixture is usually 5 parts by mass or more, preferably 10 parts by mass or more, and usually 60 parts by mass or less, preferably 30 parts by mass or less per 100 parts by mass of the total amount of the colorant and the solvent. When using a pigment as a coloring agent, a mixture with a pigment, a pigment dispersant, and a solvent is used normally. The content of the pigment dispersant in the mixture is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less per 1 part by mass of the colorant. The mixture of colorant and solvent may contain a binder polymer.

This mixture was prepared with a binder polymer (B), a photopolymerizable compound (C), 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (D) and an epoxy compound (E). The coloring photosensitive resin composition of this invention can be obtained by mixing.

When the colored photosensitive resin composition contains other photopolymerization initiators or additives, these photopolymerization initiators or additives may be added to the mixture of the pigment and the solvent in advance, and the mixture of the pigment and the solvent may be added to the binder polymer, the photopolymerizable property. Compound, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and an epoxy compound.

In order to form a coloring pattern using the coloring photosensitive resin composition of this invention obtained in this way, the layer 4 which consists of a coloring photosensitive resin composition of this invention is formed on the board | substrate 2 (FIG. 2A), and the said layer ( After exposing 4) (FIG. 2B), it is good to develop and then heat-process (FIG. 2C).

As the board | substrate 2, a glass plate, a silicon wafer, a plastic board, etc. are mentioned, for example. When a silicon wafer or the like is used as the substrate, a charge coupled device (CCD) or the like may be formed on the surface of the silicon wafer.

In order to form the layer 4 made of the colored photosensitive resin composition on the substrate 2, for example, the colored photosensitive resin composition in a diluted state with a solvent may be formed by a method such as a spin coating method (spin coating method). It is good to apply | coat on the) and to volatilize volatile components, such as a solvent. In order to volatilize a volatile component, it is good to heat-dry after application | coating. The temperature range at the time of heat drying is 40 degreeC or more and 130 degrees C or less normally. The coloring photosensitive resin composition layer 4 formed in this way is a layer which consists of solid content of a coloring photosensitive resin composition, and contains little volatile component.

Next, the coloring photosensitive resin composition layer 4 is exposed. In order to expose, it is good to irradiate the light ray 5 through the photomask 6, for example. As the light ray 5, ultraviolet rays, such as g line | wire (wavelength 436nm) and i line | wire (wavelength 365nm), are used normally. As for the photomask 6, the light shielding layer 62 which shields a light ray is provided in the surface of the glass plate 61, etc., for example, and the light ray 5 is shielded by the said light shielding layer 62. As shown in FIG. The part in which the light shielding layer 62 is not provided in the glass plate 61 is the light transmission part 63 which the light ray 5 permeate | transmits, and the coloring photosensitive resin composition layer 4 according to the pattern of this light transmission part 63 is carried out. This is exposed. The irradiation amount of the light ray 5 is the type and content of the colorant, the binder polymer, the photopolymerizable compound, and the epoxy compound used, and 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one. It is suitably selected according to content etc.

After exposure, it develops. In order to develop, it is good to immerse the coloring photosensitive resin composition layer 4 after exposure in a developing solution, for example. As a developing solution, the aqueous solution of alkaline compounds, such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, is used, for example. By the image development, the light non-irradiation area | region 41 in the coloring photosensitive resin composition layer 4 is removed. On one side thereof, the light irradiation region 42 remains to form the colored pattern 3. After image development, water washing and drying are normally performed.

Develop and dry, then heat treatment. By heat-processing, the coloring pattern 5 is hardened and its mechanical strength improves. The heating temperature at the time of heat processing is 180 degreeC or more normally, Preferably it is 200 degreeC or more, and is 250 degrees C or less normally. Since the coloring photosensitive resin composition of this invention generate | occur | produces sublimation at the time of such heat processing, a clean room hardly becomes contaminated by a sublimation.

Thus, although the desired coloring pattern 3 is formed, the coloring photosensitive resin composition layer 4 'is again formed on the board | substrate 2 by changing the color of the coloring agent (A) contained in a coloring photosensitive resin composition, and making it the same as the above. 3A, the layer 4 'is exposed (FIG. 3B), and then developed and then heat treated to form a colored pattern 3' (FIG. 3C). By repeating the above operation while changing the color of the colorant contained in the colored photosensitive resin composition, the colored pattern 3 ″ can also be formed (FIG. 4), and the desired color filter 1 can be produced.

The color filter 1 thus obtained consists of colored patterns 3, 3 'and 3 ".

When the coloring photosensitive resin composition of this invention forms a coloring pattern using this, even if it heats the coloring pattern after image development, there is little generation | occurrence | production of a sublimation, and therefore, it does not pollute a clean room etc ..

Example

Next, although an Example demonstrates this invention in detail, this invention is not limited by this Example.

Example 1

[Production of Colored Photosensitive Resin Composition]

(A) C.I. Pigment Blue 15: 6 (1.030 parts by mass),

(A) C.I. Pigment violet 23 (0.016 parts by mass),

(B) Copolymer of methacrylic acid and benzyl methacrylate [The composition ratio of the methacrylic acid unit and the benzyl methacrylate unit is 3: 7 by mass mass ratio (molar ratio), and the weight average molecular weight (Mw) is 25000] (0.757 mass part),                     

(C) dipentaerythritol hexaacrylate (`` KAYARAD DPHA '', manufactured by Nihon Kayaku Co., Ltd.) (0.757 parts by mass),

(D) 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (0.182 parts by mass),

(D2) 2,4-diethyl thioxanthone (`` KAYACURE DETX '', Nippon Kayaku Co., Ltd.) (0.091 parts by mass),

(E) Epoxy compound [ortho cresol novolak-type epoxy resin, "Sumiepoxy ESCN-195 XL-80" (manufacturer: Sumitomo Kagaku Kogyo Kushiki Kaisha)] (0.151 mass part)

Nonionic surfactant (0.314 parts by mass) and

(F) Propylene glycol monomethyl ether acetate (about 11.7 parts by mass) is mixed to obtain a colored photosensitive resin composition (blue).

[Formation of colored layer]

After apply | coating the coloring photosensitive resin composition obtained above to the surface of a glass substrate (manufacturer: Corning Corporation, "# 7059") (2) by a spin coating method, volatilizing a volatile component for 3 minutes at 100 degreeC, and coloring coloring photosensitive resin composition. Layer 4 is formed (FIG. 5A). After cooling, this colored photosensitive resin composition layer 4 is irradiated with i-line (wavelength 365nm) over the whole surface without interposing a photomask (FIG. 5B). An ultrahigh pressure mercury lamp is used for the light source of i line | wire, and an irradiation light source shall be 15OmJ / cm <^2> . Subsequently, the solution was immersed in a developing solution (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate in mass fractions), developed, washed with pure water, and then a blue colored layer formed over the entire surface of the glass substrate. 30 is obtained (FIG. 5C).

[evaluation]

Taken cut of the colored layer 30 is formed on the glass substrate (2), measures the counter mass (M ₀₎ in 23 ℃. It is then heated at 220 ° C. for 85 minutes and then cooled at 23 ° C. to determine its mass (M ₁ ). It was 0.08 when the mass reduction rate ((DELTA) M) was computed by following Formula (1).

The smaller the mass reduction rate, the less generation of the sublimate upon heating after development.

[Formation of colored pattern]

Except for irradiating i-line through the photomask 6, the coloring pattern 3 formed by operation similar to the above (FIG. 2) has a small mass reduction rate even after heat-processing at 220 degreeC after image development. Less sublimation

Example 2

(B) the amount of copolymer of methacrylic acid and benzyl methacrylate is 0.702 parts by mass,

(C) the use amount of dipentaerythritol hexaacrylate is 0.702 parts by mass,

(D) The amount of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is 0.169 parts by mass,

(D2) The amount of 2,4-diethyl thioxanthone is made 0.084 parts by mass,

(E) A colored photosensitive resin composition (blue) was obtained in the same manner as in Example 1 except that the amount of the epoxy compound used was 0.281 parts by mass to form a colored layer. The mass reduction rate of this colored layer is 0.06.

[Formation of colored pattern]

Except for irradiating i-line through the photomask 6, the coloring pattern 3 formed by operation similar to the above (FIG. 2) has a small mass reduction rate even after heat-processing at 220 degreeC after image development. Less sublimation

Example 3

(B) The amount of the copolymer of methacrylic acid and benzyl methacrylate is 0.788 parts by mass,

(C) the amount of dipentaerythritol hexaacrylate is 0.788 parts by mass,

(D) The amount of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is 0.189 parts by mass,                     

(D2) The amount of 2,4-diethyl thioxanthone is made 0.095 parts by mass,

(E) A colored photosensitive resin composition (blue) was obtained in the same manner as in Example 1 except that the amount of the epoxy compound used was 0.076 parts by mass to form a colored layer. The mass reduction rate of this colored layer is 0.09.

[Formation of colored pattern]

Except for irradiating i-line through the photomask 6, the coloring pattern 3 formed by operation similar to the above (FIG. 2) has a small mass reduction rate even after heat-processing at 220 degreeC after image development. Less sublimation

Example 4

(B) the amount of copolymer of methacrylic acid and benzyl methacrylate is 0.801 parts by mass,

(C) the amount of dipentaerythritol hexaacrylate is 0.801 parts by mass,

(D) The amount of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is 0.192 parts by mass,

(D2) The amount of 2,4-diethyl thioxanthone is used as 0.196 parts by mass,

(E) A colored photosensitive resin composition (blue) was obtained in the same manner as in Example 1 except that the amount of the epoxy compound used was 0.048 parts by mass to form a colored layer. The mass reduction rate of this colored layer is 0.10.

[Formation of colored pattern]

Except for irradiating i-line through the photomask 6, the coloring pattern 3 formed by operation similar to the above (FIG. 2) has a small mass reduction rate even after heat-processing at 220 degreeC after image development. Less sublimation

The results of Examples 1 to 4 are summarized in Table 1.

(A) (B) (C) (D) (D2) (E) (E) / [(B) + (C)] ^{* 1} Mass reduction rate Example 1 1.046 0.757 0.757 0.182 0.091 0.151 0.10 0.08 Example 2 1.046 0.702 0.702 0.169 0.084 0.281 0.20 0.06 Example 3 1.046 0.788 0.788 0.189 0.095 0.076 0.048 0.09 Example 4 1.046 0.801 0.801 0.192 0.096 0.048 0.030 0.10 (A) Pigment [C.I. Pigment Blue 15: 6 and C.I. Total with pigment violet 23] (mass part) (B) Binder polymer [copolymer of methacrylic acid and benzyl methacrylate] (mass part) (C) photopolymerizable compound [dipentaerythritol hexaacrylate] ( Mass parts) (D) 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-ol (mass parts) (D2) photoinitiator [2,4-diethyl thioxanthone] (Mass part) (E) Epoxy compound (mass part) * 1: It is the value which divided | diluted the usage-amount (E) of an epoxy compound by the total usage-amount of a binder polymer and a photopolymerizable compound.

Example 5

[Production of Colored Photosensitive Resin Composition]

(A) C.I. Pigment green 36 (2.295 mass parts),

(A) C.I. Pigment Yellow 150 (1.055 parts by mass),

(B) Copolymer of methacrylic acid and benzyl methacrylate [The composition ratio of the methacrylic acid unit and the benzyl methacrylate unit is 35:65 by mass mass ratio (molar ratio), and the weight average molecular weight (Mw) is 35,000] (2.441 mass part),

(C) dipentaerythritol hexaacrylate (`` KAYARAD DPHA '', manufactured by Nihonka Yakusa) (1.464 parts by mass),

(D) 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (0.586 parts by mass),

(D2) 4,4'-bis (diethylamino) benzophenone ("EAB-F", a make: Hodoka Chemical Co., Ltd.) (0.195 mass part),

(E) Epoxy compound [orthocresol novolak-type epoxy resin, "Sumi epoxy ESCN-195 XL-80" (manufactured by Sumitomo Chemical Co., Ltd.)] (0.976 mass parts)

Nonionic surfactant (0.988 parts by mass) and

(F) Propylene glycol monomethyl ether acetate (about 36.5 parts by mass) is mixed to obtain a colored photosensitive resin composition (green).

[Formation and Evaluation of Colored Layer]

Instead of the colored photosensitive resin composition (blue) obtained in Example 1, except that the colored photosensitive resin composition obtained above was used, it carried out similarly to Example 1, and the colored layer 30 on the board | substrate 2 was carried out. Form. The mass reduction rate of this colored layer is 0.06.

[Formation of colored pattern]

Except for irradiating i-line through the photomask 6, the coloring pattern 3 formed by the same operation as above (FIG. 2) has a small mass reduction rate even after heat treatment at 220 캜 after development. Less sublimation

Comparative Example 1

Except not using an epoxy compound, it operated like Example 5 and obtained colored photosensitive resin composition (green) and formed a colored layer. The mass reduction rate of this colored layer is 0.14.

The results of Example 5 and Comparative Example 1 are summarized in Table 2.

(A) (B) (C) (D) (D3) (E) (E) / [(B) + (C)] ^{* 1} Mass reduction rate Example 5 3.350 2.441 1.464 0.586 0.195 0.976 0.25 0.06 Comparative Example 1 3.350 2.441 1.464 0.586 0.195 0.000 0.0 0.14 (A) Pigment [C.I. Pigment Green 36 and C.I. Total with pigment yellow 150] (mass part) (B) Binder polymer [copolymer of methacrylic acid and benzyl methacrylate] (mass part) (C) photopolymerizable compound [dipentaerythritol hexaacrylate] ( Parts by mass) (D) 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-ol (parts by mass) (D3) photoinitiator [4,4'-bis (diethylamino ) Benzophenone] (mass part) (E) Epoxy compound (mass part) * 1: It is the value which divided | diluted the usage-amount (E) of an epoxy compound by the total usage-amount of a binder polymer and a photopolymerizable compound.

The relationship between the mass reduction rate in Examples 1 to 5 and Comparative Example 1 and the amount (mass) of epoxy compound (E) to the total amount (mass) of binder polymer (B) and photopolymerizable compound (C) 6 is shown.

The coloring photosensitive resin composition which concerns on this invention contains 2-methyl- 2-morpholino- 1- (4-methylthiophenyl) propane- 1-one as a photoinitiator, and coloring with little generation | occurrence | production amount of a sublimation even if it heats after image development You can give a pattern.

Claims (5)

Colorant (A), binder polymer (B), photopolymerizable compound (C), 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (D) and epoxy compound (E ), A colored photosensitive resin composition. The colored photosensitive resin composition of Claim 1 whose content of an epoxy compound (E) is 3 mass parts or more and 30 mass parts or less with respect to 100 mass parts of total amounts of a binder polymer (B) and a photopolymerizable compound (C). A method of forming a colored pattern, wherein a layer made of the colored photosensitive resin composition according to claim 1 is formed on a substrate, the layer is exposed, then developed, and subsequently heat treated. The formation method of a coloring pattern of Claim 3 which heat-processes at the temperature of 180 degreeC or more and 250 degrees C or less. A method of producing a color filter, characterized in that the coloring pattern is formed by the method according to claim 3.

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