KR20040100965A - Colored photosensitive resin composition - Google Patents

Abstract

PURPOSE: A coloring photosensitive resin composition, a method for forming a colored pattern by using the composition and a color pattern containing the colored pattern formed by the method are provided, to improve development and to form a cured resin layer having high surface hardness. CONSTITUTION: The coloring photosensitive resin composition comprises a colorant; a binder resin; a photopolymerizable compound; a photopolymerization initiator; a pigment dispersant; and a solvent, wherein a cured resin layer obtained by coating the composition on a glass substrate to form a resin layer and prebaking, exposing, developing and postbaking the resin layer, has the hardness of 3H to 9H by pencil hardness; and the part where the unexposed part of a photosensitive resin layer is dissolved, shows transmittance of 98-100 % (average of 400-780 nm) when the photosensitive layer obtained by prebaking the resin layer and exposing it with a mask is dipped in an alkali aqueous solution of 25 deg.C with stirring with 100 rpm and 120 sec has passed. Preferably the binder resin is a resin comprising a structural unit derived from a (meth)acrylic acid; and the pigment dispersant is at least one kind of surfactant selected from the group consisting of polyester-based, polyethyleneimine-based, polyurethane-based and acrylic acid-based compounds.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a colored photosensitive resin composition.

The color filter used for a color liquid crystal display device, an imaging element, etc. is manufactured by forming the colored layer corresponded to three primary colors of red, green, and blue on the board | substrate with which the black matrix was patterned.

The colored layer (colored pixel) formed in the conventional pattern shape is insufficient in hardness, and the colored layer is damaged in a later step such as an alignment film rubbing treatment after producing a color filter, or interposed between two substrates during assembly of the liquid crystal panel. Since the colored layer tends to be deformed due to the pressure from the spacer material, there is a problem that the cell cap is locally deformed to easily cause display defects.

The colored layer is formed from a colored resin composition. As the colored resin composition, a colored photosensitive resin composition containing a colorant, a binder resin, a dispersant, a solvent, and ceramic particles is known (see Japanese Patent Laid-Open No. 10-186126), but the composition is prebaked and exposed through a mask. Thereafter, when the photosensitive resin layer of the non-exposed part was immersed in an aqueous alkali solution to dissolve the photosensitive resin layer, since the ceramic particles were contained, residues were generated and the transmittance (average of 400 to 780 nm) of the dissolved portion was low and developability. There was a problem that this was not enough.

The objective of this invention is providing the coloring photosensitive resin composition which is excellent in developability and can form the cured resin layer with high surface hardness.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered the coloring photosensitive resin composition which can form the cured resin layer excellent in developability and high surface hardness.

That is, the present invention provides the following [1] to [11].

[1] In the coloring photosensitive resin composition containing a coloring agent (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), a pigment dispersant (E), and a solvent (F), said coloring When the photosensitive resin composition is applied onto a glass substrate to form a resin layer, and when the resin layer is prebaked, exposed through a mask, developed, or postbaked, the hardness of the cured resin layer obtained after the postbaking is 3H in pencil hardness. The transmittance (400) of the portion in which the non-exposed portion of the photosensitive resin layer dissolved after dipping the photosensitive resin layer obtained after exposure through 9 h or less and prebaking and a mask at 25 rpm in an aqueous alkali solution at 100 rpm was dissolved. Colored photosensitive resin composition whose average of -780 nm) is 98% or more and 100% or less.

[2] The colored photosensitive resin composition according to [1], wherein the binder resin (B) is a resin containing a structural unit derived from (meth) acrylic acid.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the content of the structural unit derived from (meth) acrylic acid is 16 mol% or more and 40 mol% or less in all the structural units constituting the binder resin (B).

[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the binder resin (B) further comprises a structural unit derived from benzyl (meth) acrylate.

[5] The colored photosensitive resin composition according to any one of [1] to [4], wherein the binder resin (B) is a resin further comprising a structural unit represented by formula (I).

(I)

(In formula (I), R^OneAnd R²Each independently represents a hydrogen atom or a methyl group.)

[6] The colored photosensitive resin composition according to any one of [1] to [5], wherein the polystyrene reduced weight average molecular weight of the binder resin (B) is 5,000 or more and 35,000 or less.

[7] The colored photosensitive resin composition according to any one of [1] to [6], wherein the pigment dispersant (E) is at least one surfactant selected from the group consisting of polyesters, polyethyleneimines, polyurethanes, and acrylic acids.

[8] The colored photosensitive resin composition according to any one of [1] to [7], wherein the pigment dispersant (E) is an acrylic acid surfactant.

[9] A resin layer made of the colored photosensitive resin composition according to any one of [1] to [8] is formed on a substrate, and the resin layer is exposed through a mask, followed by development and post-baking. The formation method of the coloring pattern to make.

[10] The method of forming a colored pattern of [9], wherein the temperature of the post bake treatment is 180 ° C or more and 250 ° C or less.

[11] A color filter containing a coloring pattern formed by the method of [9] or [10].

Mode for carrying out the invention

The coloring photosensitive resin composition of this invention is a coloring photosensitive resin composition containing a coloring agent (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), a pigment dispersant (E), and a solvent (F). When the said colored photosensitive resin composition is apply | coated on a glass substrate, and a resin layer is formed, when the said resin layer is prebaked, exposure through a mask, image development, and postbaking, the hardness of the cured resin layer obtained after postbaking is The hardness of the pencil was 3H or more and 9H or less, and the photosensitive resin layer obtained after prebaking and exposure through a mask was immersed in an aqueous alkali solution at 25 ° C. stirred at 100 rpm to dissolve the non-exposed portion of the photosensitive resin layer after 120 seconds. The transmittance | permeability (average of 400-780 nm) of a part is 98% or more and 100% or less.

The hardness of cured resin layer (coating film) needs to be 3H or more and 9H or less by pencil hardness, Preferably they are 4H or more and 9H or less, More preferably, they are 5H or more and 9H or less. The cured resin layer (coating film) is a portion that becomes the pixel portion, and if the pencil hardness is 3H or more and 9H or less, damage is unlikely to occur in the cured resin layer (coating film) in a process such as production of a liquid crystal alignment film performed after pixel formation. desirable. Pencil hardness is measured according to the method of JISK5400.

It is preferable to apply | coat said coloring photosensitive resin composition on a glass substrate, and said prebaking is performed at about 100 degreeC for about 3 minutes.

The photosensitive resin layer obtained after prebaking and exposure through a mask is immersed in 25 degreeC alkali aqueous solution stirred at 100 rpm. Here, the aqueous alkali solution usually uses the aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalene sulfonates by mass fraction.

When the non-exposed part of the said photosensitive resin layer is immersed in the 25 degreeC alkali aqueous solution stirred at 100 rpm, it is preferable to melt | dissolve within 120 second, More preferably, it is 1 second or more and 100 second or less, More preferably, it is 1 second or more 80 seconds or less, More preferably, it is 1 second or more and 60 seconds or less. When the time required for dissolution is in the above range, the decrease in productivity of the color filter can be suppressed, which is preferable.

The non-exposure part of the said photosensitive resin layer was immersed in the 25 degreeC alkali aqueous solution which is stirred at 100 rpm, and the transmittance | permeability (average value of the range whose transmission wavelength is 400 nm-780 nm) of the part in which the photosensitive resin layer melt | dissolved after 120 second is 98. It is necessary to be% or more and 100% or less, preferably 99% or more and 100% or less, more preferably 99.5% or more and 100.0% or less. If the transmittance is 98% or more and 100% or less, since the influence on the brightness of the colored layer is small, it is preferable.

The colorant (A) used in the present invention may be either an organic colorant or an inorganic colorant. The organic colorant may be an organic pigment or an organic dye. The organic colorant may be a synthetic colorant or a natural colorant. The inorganic colorant may be an inorganic pigment such as a metal oxide, a metal complex salt, or an inorganic salt (constitution pigment) of barium sulfate. Among these colorants, an organic colorant is particularly preferably used as an organic colorant.

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

Specifically, CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 125, CI Pigment Yellow 128, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow 173, C.I. Pigment Yellow 194, C.I. Yellow pigments such as pigment yellow 214;

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. Orange pigments such as pigment orange 73;

C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 209, 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. Red pigments such as 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. Blue pigments such as 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. Violet pigments such as pigment violet 38;

C.I. Pigment Green 7, C.I. Green pigments such as pigment green 36;

C.I. Pigment Brown 23, C.I. Brown pigments such as pigment brown 25;

C.I. Pigment Black 1, C.I. Black pigments, such as pigment black 7, etc. are mentioned.

Among them, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 6 and C.I. It is preferable that at least one pigment selected from pigment green 36 is contained.

These organic pigments and inorganic pigments can be used individually or in mixture of 2 or more types, respectively.

For example, to form a red pixel, C.I. Pigment Red 254 and C.I. It is preferable to contain Pigment Yellow 139.

To form green pixels, C.I. Pigment Yellow 150 and C.I. Pigment yellow 138 and at least one selected from the group consisting of C.I. It is preferable that Pigment Green 36 is contained.

To form blue pixels, C.I. Pigment Blue 15: 6 and C.I. It is preferable that it contains pigment violet 23, respectively.

Among the pigments, organic pigments may be prepared by rosin treatment, surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, grafting treatment on the pigment surface by a polymer compound, sulfuric acid atomization, or the like. The atomization treatment, the washing treatment with an organic solvent or water for removing impurities, the removal treatment by an ion exchange method of ionic impurities, or the like may be performed. Moreover, after preparing a coloring photosensitive resin composition, the removal process, such as an ion exchange method, may be performed, for example.

When content of a coloring agent (A) makes solid content in a coloring photosensitive resin composition 100 mass parts, it is 25 mass parts or more and 60 mass parts or less normally, Preferably they are 27 mass parts or more and 55 mass parts or less, More preferably, it is 30 mass parts It is more than 50 parts by mass. When content of a coloring agent (A) is 25 mass parts or more and 60 mass parts or less, since the color concentration at the time of setting it as a color filter is sufficient, and a binder resin can be contained in a composition in a required amount, and a pattern with sufficient mechanical strength can be formed. desirable.

Here, solid content in a coloring photosensitive resin composition means the remainder part except a solvent (F) in a coloring photosensitive resin composition.

In the coloring photosensitive resin composition of this invention, when using a pigment as a coloring agent (A), it is preferable that the particle diameter is uniform. In order to make a pigment into a uniform particle size, the method of containing a surfactant as a pigment dispersant (E) and performing a dispersion process is mentioned.

As said pigment dispersant (E), surfactant, such as a polyoxy ethylene alkyl ether type, a polyoxy ethylene alkyl phenyl ether type, polyester type, acrylic acid type, polyurethane type, polyethylene imine type, etc. are mentioned, for example, It can also be used individually or in combination of 2 or more types, respectively.

Examples of the polyoxyethylene alkyl ether-based surfactants include those having a structure of the following formula (1286 pages of 14102 chemical products (published on January 29, 2002).

RO (CH ₂ CH ₂ O) _n H

In the formula, R represents an alkyl group having 12 to 22 carbon atoms, and n represents a number having 2 to 60 carbon atoms.

As surfactant of a polyoxyethylene alkyl ether system, for example, polyoxy ethylene decyl ether, polyoxy ethylene lauryl ether, polyoxy ethylene cetyl ether, polyoxy ethylene stearyl ether, polyoxy ethylene oleyl ether, polyoxy ethylene 2-ethylhexyl ether, etc. are mentioned.

Commercially available polyoxyethylene alkyl ether surfactants include BLAUNON-EL series, BLAUNON-CH series, BLAUNON-SR series, BLAUNON-EN series, BLAUNON-EH series, BLAUNON-DAL series, BLAUNON-DAI series, and BLAUNON-DAH series. And BLAUNON-OX series (all of which are manufactured by Aoki Yuji Co., Ltd.).

Examples of the polyoxyethylene alkyl phenyl ether-based surfactant include those having a structure of the following formula (1287 pages of chemical products of 14102 (chemical industry daily report, issued on January 29, 2002)).

In the formula, m represents an integer of 1 to 5, n represents a number of 2 to 60, and R represents an alkyl group having 12 to 22 carbon atoms or a phenyl group which may be substituted. However, when m is 2-5, R may be same or different.

Commercially available surfactants of polyoxyethylene alkyl phenyl ether-based BLAUNON-NK series, BLAUNON-N series, BLAUNON-DP series, BLAUNON-DNP series, BLAUNON-DSP series, BLAUNON-TSP series, BLAUNON-PH series, BLAUNON- BA series etc. are illustrated, and the equivalent products of other companies can also be used similarly.

The polyester-based interfacial agent has a polyester structure. Examples of the polyester-based surfactants include Disperbyk-161, Copper 170 (manufactured by BYK Chemie), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

Polyethylenimine-based surfactants have an ethyleneimine structure. Examples of polyethyleneimine-based surfactants include Solsperpers 24000GR (manufactured by Geneca Co., Ltd.) and the like, and equivalent products of other companies can be used in the same manner.

The acrylic acid surfactant has an acrylic copolymer structure. Examples of the acrylic acid-based surfactants include Disperbyk-352, Copper 354, Copper 2000, Copper 2001 (manufactured by BYK Chemie), EFKA-Polymer-401 (manufactured by EFKA CHEMICALS), and the like. have.

The polyurethane-based surfactant has a polyurethane structure. Examples of the polyurethane-based surfactants include EFKA-Polymer-452 and EFKA-47 (manufactured by EFKA CHEMICALS Co., Ltd.), and the like.

Moreover, as surfactant other than the above, KP (made by Shin-Etsu Chemical Co., Ltd.), polyflow (made by Kyei Chemical Co., Ltd.), F-top (made by Tochem Products Co., Ltd.), and MegaFax (Tokyo Ink Chemical Industry Co., Ltd.) are brand names. Co., Ltd., Florad (Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, Asahi Glass Co., Ltd.), etc. are illustrated.

As the pigment dispersant (E), it is preferable to use at least one surfactant selected from the group consisting of a polyester-based surfactant, a polyethyleneimine-based surfactant, a polyurethane-based surfactant, and an acrylic acid-based surfactant. It is more preferable to use surfactant.

The usage-amount of a pigment dispersant (E) is 1 mass part or less normally per 1 mass part of coloring agents (A), Preferably they are 0.05 mass part or more and 0.5 mass part or less. When the usage-amount of a pigment dispersant (E) is 1 mass part or less per 1 mass part of coloring agents (A), since there exists a tendency which can obtain the pigment of a uniform particle size, it is preferable.

It is preferable that the binder resin (B) used for the coloring photosensitive resin composition of this invention contains the structural unit guide | induced from (meth) acrylic acid. As for binder resin (B), it is more preferable that it is an acryl-type copolymer of the structural unit derived from (meth) acrylic acid, and the other monomer copolymerizable with these.

Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. It is preferable that content of the structural unit guide | induced from said (meth) acrylic acid is 16 mol% or more and 40 mol% or less in all the structural units which comprise binder resin (B). When content of a meta (acrylic) acid unit exists in the said range, since the solubility of a non-pixel part in a resin layer at the time of image development is favorable, and there exists a tendency for a residue to remain in the non-pixel part after image development, it is preferable.

As another copolymerizable monomer, an aromatic vinyl compound, unsaturated carboxylic acid ester, unsaturated carboxylic acid amino alkyl ester, unsaturated carboxylic acid glycidyl ester, carboxylic acid vinyl ester, unsaturated ether is mentioned, for example. And macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecule chains, and vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes.

As said acrylic copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate air, for example The copolymer containing the copolymer, the methacrylic acid / styrene / benzyl methacrylate / N-phenyl maleimide copolymer, and the structural component represented by following formula (I), etc. are mentioned.

(Ⅰ)

In formula (I), R^OneAnd R²Is Each independently represents a hydrogen atom or a methyl group.

Among these, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid / the above Constituent components represented by formula (I) ((R^OneSilver methyl group, R²Is hydrogen atom ) / Benzyl methacrylate copolymer and the constituents represented by formula (I)^OneSilver methyl group, R²Is a hydrogen atom) / benzyl methacrylate copolymer is preferably used.

Binder resin which has a structural component represented by (I) Formula, For example, methacrylic acid / structural component represented by said (I) Formula (R)^OneSilver methyl group, R²Is hydrogen atom The benzyl methacrylate copolymer can be obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and reacting the obtained two-component polymer with the component represented by the following formula (II).

(Ⅱ)

In formula (II), R <^2> represents a hydrogen atom.

The acid value of binder resin (B) used by this invention is 50-150 normally, Preferably it is 60-135, More preferably, it is 70-135. When the acid value is 50 to 150, the solubility in the developing solution is improved, so that the unexposed portion is easily dissolved, and the sensitivity is increased, so that the pattern of the exposed portion remains during development, so that the residual film ratio tends to be improved. Here, an acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of acrylic acid polymers, and can usually be calculated | required by titration using the potassium hydroxide aqueous solution.

Moreover, the polystyrene reduced weight average molecular weight of binder resin (B) is 5,000-35,000 normally, Preferably it is 6,000-30,000, More preferably, it is 7,000-28,000. When the molecular weight is 5,000 to 35,000, the hardness of the cured resin layer (coating film) is improved, the residual film ratio is also high, solubility in the developing solution of the unexposed part is good, and the resolution tends to be improved.

Said binder resin (B) is 5 mass% or more and 50 mass% or less normally in mass fraction with respect to solid content of a coloring photosensitive resin composition, It is preferable that they are 10 mass% or more and 40 mass% or less, It is 15 mass% or more and 35 mass% or less More preferred. If content of said binder resin is 5 mass% or more and 50 mass% or less, since pattern formation is possible and since there exists a tendency for the resolution and a residual film rate to improve, it is preferable.

The photopolymerizable compound (C) used in the present invention is a compound capable of initiating polymerization by active radicals generated from the photopolymerization initiator upon irradiation with light. As a photopolymerizable compound (C), the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned, for example. The compound may be a monofunctional photopolymerizable compound or may be a bifunctional or trifunctional or higher polyfunctional photopolymerizable compound.

Examples of the monofunctional photopolymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxy propyl acrylate, 2-ethylhexyl carbitol acrylate 2-hydroxy ethyl acrylate, and N-vinyl. Pyrrolidone 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 diacryl Latex, neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methyl Pentanediol dimethacrylate etc. are mentioned.

Examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetra Methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like.

Said photopolymerizable compounds can be used individually or in combination of 2 or more types, respectively. The content of the photopolymerizable compound (C) is usually 16% by mass or more and 31% by mass or less, preferably 18% by mass or more and 30% by mass or less, more preferably 19% by mass or more, based on the mass fraction of the colored photosensitive resin composition. It is 29 mass% or less. When content of a photopolymerizable compound (C) is 16 mass% or more and 31 mass% or less, since hardening arises sufficiently and a residual film rate improves, it is preferable.

As a photoinitiator (D) used for this invention, an acetophenone type compound, a triazine type compound, a biimidazole type compound, an oxime compound, 2 or more types of mixtures of these compounds, etc. are mentioned, for example.

As an acetophenone type compound, for example, diethoxy acetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1-phenyl propane-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-4- ( 2-hydroxy ethoxy) phenyl] propan-1-one, 1-hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1- And oligomers of on. Among them, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one is preferably used. Moreover, you may use combining a plurality of acetophenone series and other photoinitiators.

As another photoinitiator, the active radical generator, an acid generator, etc. which generate | occur | produce an active radical by irradiating light are mentioned.

As a triazine type compound, 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- (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 etc. are mentioned.

As a biimidazole compound, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole and 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-carboethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-bromo Phenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o -Bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimi Dazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenyl biimidazole, 2, 2'-bis (o-methylphenyl) -4,4 ', 5,5'- tetraphenyl biimidazole etc. are mentioned.

Examples of the oxime compound include O-acyl oxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O-benzoate and 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 etc. are mentioned.

Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and the like.

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

Examples of the benzophenone compounds include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t-butylper Oxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- pro, for example A fox city oxanthone etc. are mentioned.

The same thing as the above is mentioned as a triazine type compound.

As active radical generators other than the above, for example, 2,4,6-trimethyl benzoyl diphenyl phosphine 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, etc. Can be mentioned.

As the acid generator, for example, 4-hydroxy phenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxy phenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl benzylsulfonium hexafluoro antimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexa fluoro antimonate, diphenyl iodonium p-toluenesulfonate, Onium salts such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzointosylates and the like.

In addition, among the compounds described above as an active radical generator, there are also compounds which generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

Content of said photoinitiator (D) is 0.1 mass part or more and 30 mass parts or less normally with respect to 100 mass parts of total amounts of binder resin (B) and a photopolymerizable compound (C), Preferably 1 mass part or more and 25 mass parts or less to be. When content of a photoinitiator is 0.1 mass part or more and 30 mass parts or less, since it becomes high sensitivity and shortens an exposure time, productivity improves, and since it is very high sensitivity, since there exists a tendency which does not become poor in resolution, it is preferable.

Examples of the photopolymerization initiator (D) include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl). Butan-1-one and 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine are preferably used.

In this invention, you may use photoinitiator adjuvant. It is preferable to use a photoinitiator adjuvant in combination with a photoinitiator, and it is a compound used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started with a photoinitiator. As photopolymerization start adjuvant, an amine compound, an alkoxy anthracene type compound, a thioxanthone type compound, etc. are mentioned.

As the amine compound, for example, triethanol amine, methyl diethanol amine, triisopropanol amine, 4-dimethyl amino benzoate methyl, 4-dimethyl amino benzoate ethyl, 4-dimethyl amino benzoate isoamyl, benzoic acid 2-dimethyl amino ethyl, 4- Dimethyl amino benzoic acid 2-ethyl hexyl, N, N-dimethyl paratolizine, 4,4'-bis (dimethyl amino) benzophenone (commonly known as Mihilus ketone), 4,4'-bis (diethyl amino) benzophenone And 4,4'-bis (ethyl methyl amino) benzophenone. Among these, 4,4'-bis (diethyl amino) benzophenone is used preferably.

Examples of the alkoxy anthracene-based compound include 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, and the like. Can be mentioned.

Examples of the thioxanthone compound include those mentioned above.

Photopolymerization start adjuvant can be used individually or in combination of multiple. Moreover, what is marketed as a photoinitiator can also be used, As a commercial photoinitiator, a brand name "EAB-F" (made by Hodogaya Chemical Co., Ltd.) etc. is mentioned, for example.

As a combination of the photoinitiator and photoinitiator in the coloring photosensitive start composition of this invention, diethoxy acetophenone / 4,4'-bis (diethyl amino) benzophenone, 2-methyl- 2-mor Polyno-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethyl amino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4'-bis (diethyl amino) benzophenone, benzyldimethyl ketal / 4,4'-bis (diethyl amino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxy Oxyethoxy) phenyl] propan-1-one / 4,4'-bis (diethyl amino) benzo phenone, 1-hydroxy cyclohexyl phenyl ketone / 4,4'-bis (diethyl amino) benzophenone, 2 Oligomers of -hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one- / 4,4'-bis (diethyl amino) benzophenone, 2-benzyl-2- Dimethyl amino-1- (4-morpholino phenyl) butan-1-one / 4,4'-bis (diethyl amino) benzophenone etc. are mentioned. Among them, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone is preferably used.

When using these photoinitiators, the usage-amount is 10 mol or less normally per 1 mol of photoinitiators, Preferably they are 0.01 mol or more and 5 mol or less.

Examples of the solvent (F) used in the present invention include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.

As esters, for example, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ethyr, diethylene glycol Monomethyl ether, diethyl glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Ethyl Carbitol Acetate, Butyl Carbitol Acetate, Propylene Glycol Methyl Ether Acetate, Methoxy Butyl Acetate Tate, methoxy pentyl acetate, anisole, phentol, methyl anisole and the like.

As aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

As ketones, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, etc. are mentioned, for example.

Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and the like.

Examples of the esters include ethyl acetate, acetic acid-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, methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl, ethoxy methyl acetate, ethyl ethoxy acetate, 3-oxypropionate methyl, 3-oxypropionic acid Ethyl, Methyl 3-methoxy Propionate, Ethyl 3-methoxy Propionate, Methyl 3-ethoxy Propionate, Ethyl 3-ethoxy Propionate, Methyl 2-oxy Propionate, Ethyl 2-oxy Propionate, 2-oxy Propionate Profile, 2- Methyl methoxy propionate, 2-methoxy ethyl propionate, 2-methoxy propionic acid propyl, 2-in Methyl propionate, 2-ethoxy ethyl propionate, 2-oxy-2-methyl methyl propionate, 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2-methyl Ethyl propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxy butyl acetate, 3-methyl-3-methoxy butyl Acetate, (gamma) -butyrolactone, etc. are mentioned.

Examples of the amides include N, N-dimethylholm amide, N, N-dimethylacetamide, and the like.

As another solvent, N-methyl pyrrolidone, dimethyl sulfooxide, etc. are mentioned, for example.

Said solvent can also be used individually or in combination of 2 or more types, respectively. Content in a coloring photosensitive resin composition is 70 mass% or more and 95 mass% or less by mass fraction normally, Preferably they are 75 mass% or more and 90 mass% or less. When content of the solvent (F) exists in the said range, since flatness at the time of application | coating is favorable and display characteristic is favorable when a color filter is formed, it is preferable.

It is preferable that a solvent (F) contains at least 1 sort (s) chosen from the group which consists of propylene glycol monomethyl ether acetate and 3-ethoxy ethyl propionate. When at least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl 3-ethoxy propionate and other solvents is used in combination, the mixing ratio is propylene glycol monomethyl based on the total amount of the solvent used. It is preferable that it is 50-100 mass% normally, and, as for at least 1 sort (s) chosen from the group which consists of ether acetate and ethyl 3-ethoxy propionate, it is more preferable that it is 60-100 mass%. If the at least one solvent selected from the group consisting of propylene glycol mono methyl ether acetate and ethyl 3-ethoxy propionate is 50 to 100% by mass in terms of mass fraction with respect to the exclusive agent, the flatness tends to be good, which is preferable.

The colored photosensitive resin composition used for this invention may contain the epoxy compound. As an epoxy compound, the epoxy compound etc. which can crosslink binder resin in the post-baking process (heating process) of the coloring pattern after image development, etc. are mentioned, for example. Moreover, it may be an epoxy compound which can be polymerized alone as it is heated. Since this epoxy compound hardens a coloring pattern by crosslinking binder resin or superposing | polymerizing itself, since it is hard to generate | occur | produce a sublimation from a coloring pattern in said post baking, it is used preferably.

As said 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 epoxidized oils;

Brominated derivatives of the above 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) acrylate ) Polymer, triglycidyl isocyanurate, etc. are mentioned.

The content of the epoxy compound in the colored photosensitive resin composition is usually 15% or less, preferably 0.5% or more and 12% or less, more preferably 1% or more and 10% or less in terms of mass fraction with respect to the solid content of the colored photosensitive resin composition. When content of the said epoxy compound is 15 mass% or less, since hardening arises enough and a residual film rate improves, it is preferable.

The coloring photosensitive resin composition of this invention may contain additives, such as surfactant, a filler, polymeric compounds other than binder resin, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amino compound, and a hardening | curing agent.

As surfactant, at least 1 sort (s) chosen from the group which consists of silicone type surfactant, a fluorochemical surfactant, and the silicone type surfactant which has a fluorine atom can be used.

Examples of the silicone surfactant include a surfactant having a siloxane bond. Specifically, Torre silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (brand name: product made by Torre silicon, KP321, KP322, KP323, KP324) And KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 TSF4460 (manufactured by JI TOSHIBA Silicone Co., Ltd.), and the like.

As a fluorine type surfactant, surfactant which has a fluorocarbon chain is mentioned. Specifically, Florinate (trade name) FC430, copper FC431 (product of Sumitomo 3M Co., Ltd.), mega pack (brand name) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30 (Japan ink) Chemical industry Co., Ltd.), F-top (brand name) EF301, copper EF303, copper EF351, copper EF352 (product of Shin Akita Hwaseong Co., Ltd.), Supron (trade name) S381, copper S382, copper SC101, copper SC105 (Asahi Glass, Co., Ltd., E5844 (made by Daikin Fine Chemical Research Institute), BM-1000, BM-1100 (all are brand name: BM Chemie), etc. are mentioned.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain is mentioned. Specifically, mega pack (brand name) R08, copper BL20, copper F475, copper F477, copper F443 (made by Japan Nippon Ink Chemical Co., Ltd.), etc. are mentioned.

These surfactant can be used individually or in combination of 2 or more types.

These surfactant is 0.6 mass parts or less with respect to 100 mass parts of coloring photosensitive resin compositions except surfactant, Preferably it is used in 0.001 mass part or more and 0.5 mass part. If content of surfactant is 0.6 mass part or less, since flatness tends to improve, it is preferable.

As a filler, microparticles | fine-particles, such as glass and alumina, are mentioned, for example.

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

Examples of the adhesion promoter include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-amino propyl methyl dimethoxy silane, and N-. (2-amino ethyl) -3-amino propyl trimethoxy silane, 3-amino propyl triethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy methyl dimethoxy silane, 2- (3 , 4-epoxy cyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyl dimethoxy silane, 3-chloropropyl trimethoxy silane, 3-methacryloxy propyl trimethoxy silane, 3-mercapto propyl trimethoxy Silane and the like.

As antioxidant, 4,4'- thiobis (6-t- butyl- 3-methyl phenol), 2, 6- di- t- butyl- 4-methyl phenol, etc. are mentioned, for example.

As a ultraviolet absorber, for example, benzo triazole type, such as 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chlorobenzo triazole, 2-hydroxy-4-octyloxy benzophenone, etc. Benzoates, such as benzophenone series and 2, 4- di- t-butyl phenyl-3, 5- di- t- butyl- 4-hydroxy benzoate, 2- (4, 6- diphenyl- 1, 3 And triazines such as, 5-triazin-2-yl) -5-hexyloxyphenol, and the like.

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, capronic acid, diethyl acetic acid, enanthic acid and caprylic acid;

Oxalic acid, melonic acid, succinic acid, tartaric acid, adipic acid, pimeline acid, sperinic acid, azeline acid, sebacic acid, brasylic acid, methylmelonic acid, ethylmelonic acid, dimethyl melonic acid Aliphatic dicarboxylic acids such as acid, methyl succinic acid, tetramethyl succinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;

Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid;

Aromatic monocarboxylic acids such as benzoic acid, toluic acid, tomic acid, hemelic acid and mesitylene acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;

Aromatic polycarboxylic acids, such as trimellitic acid, trimesic acid, a melanoic acid, and pilomellitic acid, etc. are mentioned.

Examples of the organic amino compound include n-propyl amine, i-propyl amine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptyl Mono alkyl amines such as amine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;

Monocyclo alkyl amines such as cyclohexyl amine, 2-methylcyclohexylamine, 3-methyl cyclohexyl amine, and 4-methyl cyclohexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, din-propylamine, dii-propylamine, din-butylamine, dii-butylamine, disec-butylamine, Dialkyl amines such as dit-butylamine, din-pentylamine and din-hexylamine;

Monoalkyl monocycloalkyl amines such as methylcyclohexylamine and ethylcyclohexylamine;

Dicyclo alkylamines such as dicyclo hexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldin-propylamine, ethyldin-propylamine, trin-propylamine, trii-propyl Trialkylamines such as amine, trin-butylamine, trii-butylamine, trisec-butylamine, trit-butylamine, trin-pentylamine and trin-hexylamine;

Dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;

Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

Monoalkanes such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol Olamines;

Monocycloalkanolamines such as 4-amino-1-cyclohexanol;

Dialkanolamines such as diethanolamine, din-propanolamine, dii-propanolamine, din-butanolamine, di i-butanolamine, din-pentanolamine, and din-hexanolamine;

Dicycloalkanolamines such as di (4-cyclohexanol) amine;

Trialkanolamines such as triethanolamine, trin-propanolamine, trii-propanolamine, trin-butanolamine, trii-butanolamine, trin-pentanolamine, and trin-hexanolamine;

Tricycloalkanol amines 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 Amino alkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, and 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;

1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanmethanol, 4-diethyl aminocyclopentanmethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol Amino group-containing cycloalkane methanols;

β-alanine, 2-amino butyric acid, 3-amino butyric acid, 4-amino butyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-amino valeric acid, 5-amino valeric acid, 6-amino caproic acid, 1 Aminocarboxylic acids such as aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid;

Aniline, o-methyl aniline, m-methyl aniline, p-methyl aniline, p-ethyl aniline, pn-propyl aniline, pi-propyl aniline, pn-butyl aniline, pt-butyl aniline, N, N-dimethyl aniline, N Aromatic amines such as, N-diethyl aniline and p-methyl-N, N-dimethyl aniline;

aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol;

aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;

and amino benzoic acids such as m-amino benzoic acid, p-amino benzoic acid, p-dimethylamino benzoic acid and p-diethylamino benzoic acid.

As a hardening | curing agent, the compound which can crosslink binder resin by reacting with the carboxyl group in binder resin as it heats, for example is mentioned. Moreover, the compound which can superpose | polymerize by itself and harden a coloring pattern is also mentioned. As said compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example.

Examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, and alicyclic systems. Epoxy resins such as epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxidized oils, aliphatic, alicyclic or aromatic groups other than brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof The epoxy compound of the, the epoxide of the (co) polymer of butadiene, the epoxide of the (co) polymer of isoprene, the (co) polymer of glycidyl (meth) acrylate, triglycidyl isocyanurate, etc. are mentioned. .

As an oxetane compound, carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, a terephthalate bis oxetane, a cyclohexane dicarboxylic acid bis oxetane, etc. are mentioned, for example.

When the coloring photosensitive composition of this invention contains an epoxy compound, an oxetane compound, etc. as a hardening | curing agent, the compound which can ring-open-polymerize the epoxy group of an epoxy compound and the oxetane skeleton of an oxetane compound may be contained. As said 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-dimethyl phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3 Aromatic polyhydric carboxylic acids such as, 3 ', 4,4'-benzophenone tetracarboxylic acid;

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

Hexahydrophthalic acid, 3,4-dimethyl tetrahydrophthalic acid, hexahydro isophthalic acid, hexahydro telephthalic acid, 1,2,4-cyclopentane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, cyclo Alicyclic polyhydric carboxylic acids, such as a pentane tetra carboxylic acid and a 1,2,4, 5- cyclohexane tetra carboxylic acid, etc. are mentioned.

As polyhydric carboxylic anhydride, aromatic polyhydric carboxylic anhydrides, such as phthalic anhydride, a pyromellitic dianhydride, trimellitic anhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, for example. logistics;

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

Hexahydrophthalic anhydride, 3,4-dimethyl tetrahydrophthalic anhydride, 1,2,4-cyclopentane tricarboxylic anhydride, 1,2,4-cyclohexane tricarboxylic anhydride, cyclopentane tetracarboxylic acid 2 Alicyclic polyhydric carboxylic acid anhydrides such as anhydrides, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, hymic anhydride and nadine 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 also be used. As said epoxy resin hardening | curing agent, for example, brand name "adekahardner-EH-700" (product of Asahi Electrochemical Industry Co., Ltd.), brand name "Likaside HH" (New Nippon Ewha Co., Ltd. product), brand name "MH- 700 "(new Nippon Ewha Co., Ltd. product) etc. are mentioned.

The same thing as the above is mentioned as an acid generator.

Said hardening | curing agent can be used individually or in combination of 2 or more types, respectively.

As a method of forming a color filter using the coloring photosensitive resin composition of this invention, the coloring photosensitive resin composition of this invention is a board | substrate or the other colored photosensitive resin composition layer of the solid formed on the board | substrate (Hereinafter, this is also called a board | substrate.). After apply | coating on and prebaking the apply | coated resin layer, removing volatile components, such as a solvent, exposing the resin layer from which the volatile component was removed through the photomask, developing with post-baking solution, such as aqueous alkali solution, The process of forming a cured resin layer is made into one process, and this method is repeated using the coloring photosensitive resin composition containing a different color, and the method of finally forming the color filter which has three colors of RGB, etc. are mentioned.

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

In order to apply | coat a coloring photosensitive resin composition on said board | substrate, for example, the coloring photosensitive resin composition of this invention is spin-coating method (spin coat method), cast method, roll coating method, slit & spin coating method, slit coat method. What is necessary is just to apply | coat on board | substrates etc. by normal coating methods, such as these, and then volatilize volatile components, such as a solvent, by heating (prebaking). In this way, the resin layer which consists of solid content of a coloring photosensitive resin composition is formed on substrates etc.

Next, the resin layer which consists of solid content of a coloring photosensitive resin composition is exposed. Exposure may be performed by the method of irradiating a light ray through a photomask. As a light ray used, ultraviolet rays etc. which are normally called g line | wire (wavelength 436 nm) and i line | wire (wavelength 365 nm) are mentioned. The light is irradiated through the photo mask, but the photo mask is provided with, for example, a light shielding layer that blocks the light on the surface of the glass plate. The part in which the light shielding layer is not provided in a glass plate is a light transmission part which a light ray permeate | transmits, The coloring photosensitive resin composition layer is exposed by the pattern according to the pattern of this light transmission part, the unirradiated area | region to which no light beam was irradiated, and the irradiation area | region to which the light beam was irradiated. This happens. The irradiation amount of the light ray in an irradiation area is suitably selected according to the weight average molecular weight, monomer ratio, content of a binder resin, the kind and content of a photopolymerizable compound, the kind and content of a photoinitiator, the kind and content of a photoinitiator, etc.

It develops after exposure. In order to develop, what is necessary is just to contact the developing resin layer with a developing solution, for example, and, specifically, what is necessary is just to immerse the board | substrate of the state in which the resin layer was formed on the surface.

As a developing solution, aqueous solution of alkaline compounds, such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, etc. are mentioned, for example. By development, the unirradiated area | region to which the light ray in the resin layer was not irradiated is removed. On the other hand, the light irradiation area remains as it is and a pattern is formed.

The target pattern can be obtained by washing with water normally after image development and drying. Furthermore, after developing and drying, a cured resin layer is formed by post-baking in apparatus, such as a baking. By the post bake, the mechanical strength of the pattern is improved. When using what contains a hardening | curing agent further as a coloring photosensitive resin composition, a coloring pattern can harden further and the mechanical strength can be improved more. The temperature of a postbaking is 180 degreeC or more and 250 degrees C or less normally, Preferably they are 200 degreeC or more and 230 degrees C or less. If the temperature of the postbaking is in the above-mentioned range, curing is sufficiently performed, and thus it is preferable. In addition, the time of post-baking is 5 to 40 minutes normally, Preferably it is 10 to 36 minutes, More preferably, it is 15 to 30 minutes. If time of post-baking is the said range, since hardening arises enough, it is preferable.

Thus, the desired coloring pattern is formed, but the color of the coloring agent contained in a coloring photosensitive resin composition is replaced, and a resin layer is formed again on a board | substrate similarly to the above, and it develops after exposing the said resin layer. Then, post-baking can further form a coloring pattern. By performing the said operation repeatedly, replacing the color of the coloring agent contained in a coloring photosensitive resin composition, a coloring pattern can be formed further and the target color filter can be manufactured.

Next, an ITO film is vapor-deposited on the obtained Curley filter. The color filter obtained in this way contains the said coloring pattern, and a suitable liquid crystal display device can be manufactured by using this color filter.

The colored photosensitive resin composition of this invention is excellent in developability by the point that a residue level is good, and can form the cured resin layer of a high surface hardness, and also the cured resin layer is excellent in solvent resistance, and it has a pure tapered cross-sectional shape. Since the cured resin layer without surface roughening can be formed into a spherical shape, it can be used suitably for formation of the coloring pattern used for a color liquid crystal display device, an imaging element, etc., and the color filter using the same.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the Examples.

First embodiment

[Preparation of Colored Photosensitive Resin Composition 1]

(A) C.I. pigment blue 15: 6 (1.967 parts by mass),

(A) C.I. pigment violet 23 (0.030 parts by mass)

(E) Polyester type dispersing agent (0.599 mass part)

(B) Copolymer of methacrylic acid and benzyl methacrylate [The composition ratio of the methacrylic acid unit and the benzyl methacrylate unit is 3: 7 and the weight average molecular weight (Mw) is 25,000] in the mass ratio (mol ratio) (1.764 mass part),

(C) dipentaerythritol hexaacrylate (`` KAYARAD DPHA '', Nippon Kayaku Co., Ltd.) (1.176 parts by mass),

(D) 2-benzyl-2-dimethyl amino-1- (4-morpholino phenyl) butan-1-one (0.353 parts by mass),

(D2) 4,4'-bis (diethyl amino) benzophenone ("EAB-F") (product of Hodogaya Chemical Co., Ltd.) (0.118 mass part),

Epoxy compound [Orsocresol novolak-type epoxy resin, "Sumi epoxy ESCN-195XL-80" (product of Sumitomo Chemical Industry)) (0.294 mass parts) and

(F) propylene glycol monomethyl ether acetate (23.700 parts by mass)

Was mixed and the coloring photosensitive resin composition 1 was obtained.

[Formation of colored layer]

After apply | coating the coloring photosensitive resin composition 1 obtained above by the spin coat method on the surface of a glass substrate (The product made by Corning Corporation, "# 1737"), the volatile component was volatilized for 3 minutes at 100 degreeC, and the coloring photosensitive resin composition layer 1A was formed. . After cooling, this colored photosensitive resin composition layer was irradiated i line | wire (wavelength 365nm) over the whole surface, without passing through a photomask. An ultrahigh pressure mercury lamp was used for the light source of i line | wire, and the irradiation light quantity was 150 mJ / cm <2>. Subsequently, the solution was immersed in a developer at 25 ° C. (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalene sulfonate in mass fraction each) for 120 seconds, developed, washed with pure water, and then formed over the entire surface of the glass substrate. The colored layer of was obtained. This coating film substrate was baked at 220 degreeC for 20 minutes, and the coloring photosensitive resin composition layer 1B was formed. After cooling the layer 1A, the colored photosensitive resin composition layer was irradiated with an i-line (wavelength of 365 nm) through a photomask and exposed. The light source of i line | wire was irradiated after making into parallel light using the ultrahigh pressure mercury lamp. The irradiation light amount was 150 mJ / cm 2. As the photo mask, 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 are formed. Used a photo mask. Subsequently, the glass substrate (the colored photosensitive resin composition layer is formed on the surface) after exposure was immersed in 25 degreeC developer (Aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalene sulfonates by mass fraction) for 120 second, After developing and washing with pure water, it was heated at 220 ° C. for 20 minutes to form a blue pixel 1C.

〔evaluation〕

The layer 1A was immersed in a 25 ° C. developer (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalene sulfonate in mass fraction) for 120 seconds under agitation, and washed with pure water. The coating layer was dissolved. The particle size distribution of the developer in which the coating layer was dissolved was measured by the light scattering method using a micro track particle size measuring apparatus (manufactured by UPA 150,9230 UPA, manufactured by LEED & NORTHRUP COMPANY), and the maximum particle size was 1.0 µm or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Subsequently, in accordance with the test method described in JIS K 5400, using a pencil "Mitsubishi High Uni" on a pencil hardness tester, the highest hardness at which no scratch was generated on the coating film was measured as a measured value. The pencil strength of the 1B layer of the previously formed coating film was measured by the above method, and the pencil strength was 4H.

In addition, in the formed blue pixel 1C, the cross-sectional shape was a forward tapered shape, there was no surface roughness on the surface, and the performance of the colored photosensitive resin composition 1 was favorable.

Second embodiment

[Preparation of Colored Photosensitive Resin Composition 2]

A colored photosensitive resin composition 2 was obtained in the same manner as in the first example except that the polyethyleneimine dispersant was used in place of the polyester dispersant used in the first example.

〔evaluation〕

Except for using the coloring photosensitive resin composition 2 obtained above instead of the coloring photosensitive resin composition 1 obtained by the 1st Example, it operated similarly to Example 1, the 2A layer was immersed in the developing solution of 25 degreeC under stirring for 120 second, After developing and washing with pure water, no lump appeared in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component dissolved in the developing solution was measured, and the maximum particle size thereof was 1.0 µm or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Next, the pencil strength of the 2B layer was measured in the same manner as in the first example, and the pencil strength was 4H. In addition, in the formed blue pixel 2C, the cross-sectional shape was a forward taper shape, and there was no surface roughness on the surface, and the performance of the colored photosensitive resin composition 2 was favorable.

Third embodiment

[Preparation of Colored Photosensitive Resin Composition 3]

A colored photosensitive resin composition 3 was obtained in the same manner as in Example 1 except that a polyurethane-based dispersant was used instead of the polyester-based dispersant used in the first example.

〔evaluation〕

Except for using the coloring photosensitive resin composition 3 obtained above instead of the coloring photosensitive resin composition 1 obtained by the 1st Example, it operated similarly to Example 1, the 3A layer was immersed in the developing solution of 25 degreeC under stirring for 120 second, After developing and washing with pure water, no lump appeared in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component dissolved in the developing solution was measured, and the maximum particle size thereof was 1.0 µm or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Next, the pencil strength of the 3B layer was measured in the same manner as in the first example, and the pencil strength was 4H. In addition, in the formed blue pixel 3C, the cross-sectional shape was a forward taper shape, and there was no surface roughness on the surface, and the performance of the coloring photosensitive resin composition 3 was favorable.

Comparative Example 1

[Preparation of Colored Photosensitive Resin Composition 4]

In place of the binder resin (B) used in the first embodiment, a copolymer of methacrylic acid and benzyl methacrylate [the composition ratio of the methacrylic acid unit and the benzyl methacrylate unit is 3: 7 in the material amount ratio (mol ratio); And mass average molecular weight (Mw) were mixed like Example 1 except having used 36,000] (1.764 mass parts), and the coloring photosensitive resin composition 4 was obtained.

〔evaluation〕

Except for using the coloring photosensitive resin composition 4 obtained above instead of the coloring photosensitive resin composition 1 obtained by the 1st Example, it operated similarly to Example 1, and a 4A layer is immersed in the developing solution of 25 degreeC under stirring for 120 second. After developing, washing with pure water showed no lump in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component dissolved in the developing solution was measured, and the maximum particle size thereof was 1.0 µm or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or less and 95%.

Subsequently, the pencil strength was 5H as the 4B layer measured the pencil strength similarly to the 1st Example. Moreover, in the formed blue pixel 4C, the cross-sectional shape showed a forward data type | mold or the form which a lower hem is dragged to one side, and the performance of the coloring photosensitive resin composition 4 was bad.

2nd comparative example

[Preparation of Colored Photosensitive Resin Composition 5]

In place of the binder resin (B) used in the first embodiment, a copolymer of methacrylic acid and benzyl methacrylate [the composition ratio of methacrylic acid unit and benzyl methacrylate unit is 3: 7, The weight average molecular weight (Mw) was mixed like Example 1 except having used 4,800], and the coloring photosensitive resin composition 5 was obtained.

〔evaluation〕

Except for using the coloring photosensitive resin composition 5 obtained above instead of the coloring photosensitive resin composition 1 obtained by the 1st Example, it operated similarly to Example 1, and a 5A layer was immersed for 120 second in 25 degreeC developing solution under stirring. After developing, washing with pure water showed no lump in the developing solution, and the coating layer was dissolved. When the particle size distribution of the coating film layer melt | dissolved in the developing solution was measured, the maximum particle diameter was 1.0 micrometer or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Next, the pencil strength of the 5B layer was measured in the same manner as in the first example, and the pencil strength was 1H. The cross-sectional shape of the formed blue pixel 5C was a forward tapered shape, but surface roughness was observed on the surface. Moreover, the residual film rate was also low, and the performance of the colored photosensitive resin composition 5 was bad.

Fourth embodiment

[Preparation of Colored Photosensitive Resin Composition 6]

An acrylic acid dispersant was used in place of the polyester dispersant used in Example 1, and the binder resin (B) was copolymerized with methacrylic acid and benzyl methacrylate [The composition ratio of methacrylic acid unit and benzyl methacrylate unit is 35:65 and weight average molecular weight (Mw) were changed to material quantity ratio (mol ratio) to 10,000], and it mixed like Example 1 except having added no epoxy compound, and colored photosensitive resin composition 6 was obtained.

〔evaluation〕

Except for using the coloring photosensitive resin composition 6 obtained above instead of the coloring photosensitive resin composition 1 obtained by the 1st Example, it operated similarly to Example 1, 6A layer was immersed in the developing solution of 25 degreeC under stirring for 120 second, After developing and washing with pure water, no lump appeared in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component dissolved in the developing solution was measured, and the maximum particle size thereof was 1.0 µm or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Next, the pencil strength of the 6B layer was measured in the same manner as in the first example, and the pencil strength was 9H. In addition, in the formed blue pixel 6C, the cross-sectional shape was a pure tapered shape, there was no surface roughness, and the performance of the coloring photosensitive resin composition 6 was favorable.

Fifth Embodiment

[Preparation of Colored Photosensitive Resin Composition 7]

In place of the binder resin (B) used in Example 4, methacrylic acid, benzyl methacrylate and formula (I) (In formula (I), R ¹ represents a methyl group and R ² represents a hydrogen atom.) Copolymer with the component represented by [The composition ratio of the methacrylic acid unit, the benzyl methacrylate unit, and the component represented by said Formula (I) is 25:60:15 in weight ratio (mol ratio), polystyrene conversion weight average Molecular weight (Mw) is 9,000], and the mixture was mixed in the same manner as in the first example except that the epoxy compound was not added to obtain a colored photosensitive resin composition 7.

(Ⅰ)

〔evaluation〕

Except for using the colored photosensitive resin composition 7 obtained above instead of the colored photosensitive resin composition 1 obtained in Example 1, it operated similarly to Example 1, the 7A layer was immersed in the developing solution of 25 degreeC under stirring for 120 second, After developing and washing with pure water, no lump appeared in the developing solution, and the coating layer was dissolved. The particle size distribution of the coating layer component dissolved in the developing solution was measured, and the maximum particle size thereof was 1.0 µm or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Next, the pencil strength of the 7B layer was measured in the same manner as in the first example, and the pencil strength was 9H. In addition, in the formed blue pixel 7C, the cross-sectional shape was a forward taper shape, there was no surface roughness, and the performance of the coloring photosensitive resin composition 7 was favorable.

Sixth embodiment

[Preparation of Colored Photosensitive Resin Composition 8]

The colored photosensitive resin composition 8 was obtained by mixing similarly to Example 1 except changing the binder resin (B) of Example 4 into the binder resin (B) used in Example 5, and adding no epoxy compound. .

〔evaluation〕

Except for using the colored photosensitive resin composition 8 obtained above instead of the colored photosensitive resin composition 1 obtained by the 1st Example, it operated similarly to Example 1, and 8A layer was immersed in the developing solution of 25 degreeC under stirring for 120 second, After developing and washing with pure water, no lump appeared in the developing solution, and the coating layer was dissolved. When the particle size distribution of the coating film layer melt | dissolved in the developing solution was measured, the maximum particle diameter was 1.0 micrometer or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Next, the pencil strength of the 8B layer was measured in the same manner as in the first example, and the pencil strength was 9H. In addition, in the formed blue pixel 8C, the cross-sectional shape was a forward taper shape, there was no surface roughness, and the performance of the coloring photosensitive resin composition 8 was favorable.

Seventh embodiment

[Preparation of Colored Photosensitive Resin Composition 9]

In place of the binder resin (B) of the first embodiment, a copolymer of methacrylic acid, benzyl methacrylate, and styrene [the composition ratio of the methacrylic acid unit, the benzyl methacrylate unit, and the styrene unit is represented by a mass amount ratio (mol ratio). 30:60:10, polystyrene reduced weight average molecular weight (Mw) is 16,000], and was mixed in the same manner as in the first example to obtain a colored photosensitive resin composition 9.

〔evaluation〕

Except for using the coloring photosensitive resin composition 9 obtained above instead of the coloring photosensitive resin composition 1 obtained by the 1st Example, it operated similarly to Example 1, 9A layer was immersed for 120 second in 25 degreeC developing solution under stirring, After developing and washing with pure water, no lump appeared in the developing solution, and the coating layer was dissolved. When the particle size distribution of the coating film component dissolved in the developing solution was measured, the maximum particle diameter was 1.0 micrometer or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Next, the pencil strength of the 9B layer was measured in the same manner as in the first example, and the pencil strength was 6H. In addition, in the formed blue pixel 9C, the cross-sectional shape was a forward taper shape, there was no surface roughness, and the performance of the coloring photosensitive resin composition 9 was favorable.

Eighth embodiment

[Preparation of Colored Photosensitive Resin Composition 10]

Copolymer with methacrylic acid, benzyl methacrylate and isobornyl methacrylate instead of the binder resin (B) of the first embodiment [methacrylic acid unit, benzyl methacrylate unit and isobornyl methacrylate The composition ratio of the unit was 30:60:10 and the polystyrene reduced weight average molecular weight (Mw) was 16,000 in terms of the material amount ratio (mol ratio)], except that the mixture was mixed in the same manner as in Example 1 to obtain a colored photosensitive resin composition 10.

〔evaluation〕

Except for using the colored photosensitive resin composition 10 obtained above instead of the colored photosensitive resin composition 1 obtained by the 1st Example, it operated similarly to Example 1, the 10A layer was immersed in the developing solution of 25 degreeC under stirring for 120 second, After developing and washing with pure water, no lump appeared in the developing solution, and the coating layer was dissolved. When the particle size distribution of the coating film component dissolved in the developing solution was measured, the maximum particle diameter was 1.0 micrometer or less. In addition, the transmittance | permeability (average of 400 nm-780 nm) of the glass part after melt | dissolving a coating film layer was 98% or more.

Next, the pencil strength of the 10B layer was measured in the same manner as in the first example, and the pencil strength was 7H. In addition, in the formed blue pixel 10C, the cross-sectional shape was a forward taper shape, there was no surface roughness, and the performance of the coloring photosensitive resin composition 10 was favorable.

According to this invention, the coloring photosensitive resin composition which is excellent in developability and which can form a cured resin layer with high surface hardness can be provided.

Claims (11)

As a coloring photosensitive resin composition containing a coloring agent (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), a pigment dispersant (E), and a solvent (F), When the said colored photosensitive resin composition is apply | coated on a glass substrate, a resin layer is formed, and when the said resin layer is prebaked, exposure through a mask, image development, and postbaking, the hardness of the cured resin layer obtained after postbaking is set to pencil hardness. Transmittance of the part in which the non-exposed part of the photosensitive resin layer melt | dissolved in the 25 degreeC alkali aqueous solution which is 3H or more and 9H or less and obtained after exposure through a prebaking and a mask and stirred at 100 rpm ( Colored photosensitive resin composition whose average of 400-780 nm) is 98% or more and 100% or less. The coloring photosensitive resin composition of Claim 1 whose binder resin (B) is resin containing the structural unit guide | induced from (meth) acrylic acid. The coloring photosensitive resin composition of Claim 1 or 2 whose content of the structural unit guide | induced from (meth) acrylic acid in all the structural units which comprise binder resin (B) is 16 mol% or more and 40 mol% or less. The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the binder resin (B) further comprises a structural unit derived from benzyl (meth) acrylate. The coloring photosensitive resin composition of any one of Claims 1-4 whose binder resin (B) is resin which further contains the structural unit represented by following formula (I). (I) (In formula (I), R^OneAnd R²Each independently represents a hydrogen atom or a methyl group.) The colored photosensitive resin composition of any one of Claims 1-5 whose polystyrene conversion weight average molecular weight of binder resin (B) is 5,000 or more and 35,000 or less. The coloring photosensitive resin of any one of Claims 1-6 whose pigment dispersant (E) is at least 1 type of surfactant chosen from the group which consists of polyester type, polyethyleneimine type, polyurethane type, and acrylic acid type. Composition. The coloring photosensitive resin composition of any one of Claims 1-7 whose pigment dispersant (E) is an acrylic acid type surfactant. After forming the resin layer which consists of the coloring photosensitive resin composition in any one of Claims 1-8 on a board | substrate, exposing the said resin layer through a mask, developing, and then post-baking, It is characterized by the above-mentioned. Method of forming a coloring pattern. The formation method of the coloring pattern of Claim 9 whose temperature of a post-baking process is 180 degreeC or more and 250 degrees C or less. The color filter containing the coloring pattern formed by the method of Claim 9 or 10.