KR20070056962A - Coloring photosensitive resin composition - Google Patents

Abstract

Provided is a colored photosensitive resin composition, which leaves little residue after development in developing a pattern for forming a color filter for image sensors or various display devices. The colored photosensitive resin composition comprises: (A) a colorant; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the photopolymerizable compound comprises 2,2,2-tris(acryloyloxy)methylethyl phthalate. In the photopolymerizable compound, 2,2,2-tris(acryloyloxy)methylethyl phthalate is used in an amount of at least 10 wt%, and preferably of at least 30 wt%.

Description

Colored photosensitive resin composition {COLORING PHOTOSENSITIVE RESIN COMPOSITION}

[Patent Document 1] Japanese Patent Publication No. 8-271723

[Patent Document 2] Japanese Patent Publication No. 10-332929

The present invention relates to a colored photosensitive resin composition.

Colored photosensitive resin compositions are used in the production of color filters used in display devices such as liquid crystals, electroluminescent or plasma display panels, as well as image sensors for charge coupled devices (CCD) and complementary metal oxide semiconductors (CMOS).

Among these, the color filter for image sensors is required to make the film thinner. In order to reduce the film thickness while maintaining the color density at a high level, the pigment concentration in the color filter must be increased. However, when a colored photosensitive resin composition containing a high concentration of pigment is used to prepare a film, and subsequently exposed, and the unnecessary portion is removed with a developer to form a pattern for producing a color filter, There was a problem in that there was a residue generated by failure (see Japanese Patent Laid-Open No. 8-271723).

Japanese Patent Application Laid-Open No. 10-332929 discloses a colored photosensitive resin composition comprising 2,2,2-tris (acryloyloxy) methylethyl succinate, a photopolymerization initiator and a solvent as a colorant, a binder resin, and a photopolymerizable compound. It is proposed. However, when developing a pattern for manufacturing a color filter, there was a problem that a residue remained after development.

The present invention has been studied to find a colored photosensitive resin composition having little of the above-mentioned problems, and is a colored photosensitive resin composition comprising 2,2,2-tris (acryloyloxy) methylethyl phthalate as a photopolymerizable compound. It has been found that when developing to form a pattern for producing a color filter, little residue remains after development.

An object of the present invention is to provide a colored photosensitive resin composition in which, when developing a pattern for producing a color filter, almost no residue remains after development.

That is, this invention provides following (1)-(4).

[1] A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the photopolymerizable compound (C) is 2,2,2-tris. Colored photosensitive resin composition containing (acryloyloxy) methylethyl phthalate.

[2] A pattern formed using the colored photosensitive resin composition according to [1].

[3] A color filter comprising the pattern according to [2].

[4] An image sensor comprising the color filter according to [3].

The colored photosensitive resin composition of this invention contains a coloring agent (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The said photopolymerizable compound (C) is 2, 2,2-tris (acryloyloxy) methylethyl phthalate is included as an essential component.

The photopolymerizable compound I is a compound polymerizable with an active radical or an acid generated from the initiator (D) for photopolymerization upon light irradiation.

The photopolymerizable compound I contains 2,2,2-tris (acryloyloxy) methylethyl phthalate as an essential component. The amount of 2,2,2-tris (acryloyloxy) methylethyl phthalate in the photopolymerizable compound I is preferably 10% by weight or more, more preferably 30% by weight or more.

In the present invention, the photopolymerizable compound I can also be used in combination with other photopolymerizable compounds. The other photopolymerizable compound is preferably a multifunctional photopolymerizable compound having three or more functional groups. Examples of the polyfunctional photopolymerizable compound having three or more such functional groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, and dipentaerythritol hexamethacrylate. do.

The amount of the photopolymerizable compound I is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, even more preferably 20 to 70% by mass relative to the total solids content of the colored photosensitive resin composition. When the amount of the photopolymerizable compound I is in the above range, it is preferable in that the colored photosensitive resin composition tends to be sufficiently cured and adhered to withstand formation of undercuts in the pattern.

The coloring photosensitive resin composition of this invention contains a coloring agent (A). Examples of the colorant (A) include at least one colorant selected from the group of pigments and dyes.

Pigments specifically include compounds classified as pigments in color indices (The Society of Dyers and Colourists).

Specific examples of the pigment include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 194, 214, CI Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like orange pigments, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. , CI Pigment blue 15, 15: 3, 15: 4, 15: 6, 60, etc. Blue pigment, C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like purple pigments, C.I. Green pigments such as Pigment Green 7, 36, and C.I. Pigment pigments such as Pigment Brown 23 and 25, and C.I. Black pigments, such as pigment black 1 and 7, etc. are contained.

Among them, C.I. Pigment Yellow 138, 139 and 150, C.I. Pigment Red 177, 209 and 254, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3 and 15: 6, and C.I. At least one pigment selected from the group consisting of Pigment Greens 7 and 36 is preferably contained.

Examples of dyes include oil-soluble dyes, acid dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes.

Examples of such dyes include C.I. Solvent Yellow 4 (hereinafter, CI solvent yellow is omitted and only numbers are shown. Similarly omitted herein for other dye types and colors), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 and 162, CI Solvent Red 45 and 49, C.I. Solvent orange 2, 7, 11, 15, 26 and 56, C.I. Solvent Blue 35, 37, 59 and 67, C.I. Acid yellow 17, 29, 40 and 76, C.I. Acid red 91, 92, 97, 114, 138 and 151, C.I. Acid oranges 51 and 63, C.I. Acid blue 80, 83 and 90, and C.I. Acid greens 9, 16, 25, and 27.

In addition, the dye (A) to be used may include, for example, amine salts of acidic dyes of the following formulas (VII) to (iii) and sulfonamide derivatives of acidic dyes of the following formulas (VII) to (iii).

In the formulas (i) to (iii), D represents a dye matrix. M represents the integer of 1-20. n represents the integer of 1-20. e and f each independently represent an integer of 1 to 10. Ph represents a phenyl group. Py represents a pyridine ring residue or a methylpyridine ring residue bonded to C _n H _{2n +1} via a nitrogen atom. P represents the integer of 1-8. q represents the integer of 0-8. L represents a hydrogen atom or a monovalent cation.

Embodiments of D include azo dye matrices, xanthene dye matrices, anthraquinone dye matrices, triphenylmethane dye matrices and copper phthalocyanine dye matrices.

M preferably represents an integer of 1 to 10, more preferably an integer of 1 to 8.

N preferably represents an integer of 1 to 10, more preferably an integer of 1 to 8.

E and f each independently preferably represent an integer of 1 to 8, more preferably an integer of 1 to 6;

Py preferably represents a methylpyridine ring residue.

P preferably represents an integer of 1 to 6, more preferably an integer of 1 to 5.

Q preferably represents an integer of 0-6, more preferably an integer of 0-5.

Examples of monovalent cations in L include lithium ions, sodium ions, potassium ions, tetravalent ammonium ions such as (C ₂ H ₅ ) ₃ HN ^+, and the like, with sodium ions being preferred.

Examples of azo dyes include dyes of the following general formula (I) or dyes of the following general formulas (11) to (13).

In said general formula (I), R <^30> represents a C1-C15 alkyl group, a C2-C15 alkenyl group, a C6-C21 aryl group, or a C7-C21 aralkyl group.

The alkyl group, alkenyl group, aryl group and aralkyl group may be unsubstituted or have a substituent. R ³¹ to R ³⁴ each independently represent a hydrogen atom, a halogen atom and a C1 to C4 alkyl group.

Examples of the C1 to C15 alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-de Linear alkyl groups, such as a real group, n-undecyl group, and n-dodecyl group, isopropyl group, sec-butyl group, tert- butyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2- Branched alkyl groups, such as an ethylheptyl group, 2-ethyloctyl group, 2-ethylnonyl group, and 2-ethyldecyl group, and cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, are included. .

The alkyl group may contain an oxygen atom as an ether bond. Examples of the alkyl group containing an oxygen atom as the ether bond include methoxymethylene group, methoxyethylene group, ethoxyethylene group, butoxyethylene group and butoxybutylene group.

Examples of the C2 to C15 alkenyl group include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group , 2-octenyl group, 1-nonenyl group, 2-nonenyl group, 1-decenyl group, 2-decenyl group, 1-undecenyl group, 2-undecenyl group, 1-dodecenyl group, 2-dodecenyl Groups, 1-tridecenyl group, 2-tridecenyl group, 1-tetradecenyl group, 2-tetradecenyl group, 1-pentadecenyl group, 2-pentadedecenyl group and the like.

Examples of C6 to C21 aryl groups include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 2-furyl group, 3-furyl group, 2- Pyrrolyl group, 3-pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thienyl group, 3-thienyl group, 2-pyrimidyl group, 2-quinolyl group, 3-quinolyl group , 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group and the like.

Examples of the C7 to C21 aralkyl group include benzyl, diphenylmethyl, 1,2-diphenylethyl, phenylcyclopentylmethyl, α-methylbenzyl, phenylethyl, α-methylphenylethyl, β-methylphenylethyl and 3-phenyl Propyl group, 3,3-diphenylpropyl group, 4-phenylbutyl group, naphthylmethyl group, styryl group, cinnamil group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydro Naphthyl group, piperonyl group, pyrenemethyl group and the like.

Among them, benzyl group, phenylcyclopentylmethyl group, α-methylbenzyl group, phenylethyl group, α-methylphenylethyl group, β-methylphenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, styryl group, cinnamil group, fluore More preferred are a silyl group, 1-benzocyclobutenyl group and 1,2,3,4-tetrahydronaphthyl group, and a-methylbenzyl group, phenylethyl group, α-methylphenylethyl group, β-methylphenylethyl group, and 3-phenylpropyl group. , Styryl group, cinnamil group, fluorenyl group, 1-benzocyclobutenyl group and 1,2,3,4-tetrahydronaphthyl group are even more preferable.

Examples of R ³⁰ preferably include a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, sec-butyl group , tert-butyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethylheptyl group and 2-ethyloctyl group, more preferably isopropyl group and tert-butyl group , 2-ethylbutyl group, 2-ethylpentyl group and 2-ethylhexyl group.

Examples of R ³¹ to R ³⁴ include hydrogen atom, methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert-butyl group, fluorine atom, chlorine atom, bromine atom and iodine valence It is contained, Preferably a hydrogen atom, a methyl group, an ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert- butyl group, a fluorine atom, and a chlorine atom are mentioned.

Specific examples of the preferred dyes among the dyes of formula (I) include the compound of formula (14). As an example of xanthene dye, the compound of General formula (15) is mentioned. Examples of copper phthalocyanine dyes include compounds of formula (16).

Such dyes may be appropriately selected depending on the solubility in the solvent used for the coloring composition, and the photochromic resistance and spectrum in the formation of the color filter pattern using the coloring photosensitive composition containing the coloring composition. Combinations of two or more of these can be used.

When forming a red pixel using the coloring photosensitive resin composition containing the coloring composition of this invention, the combination of dye of General formula (13), (14), and (15) is preferably chosen.

In order to form a blue pixel, preferably, the dye of formula (16) and C.I. Acid blue 90 and C.I. The combination of Solvent Blue 67 is selected.

In order to form green pixels, preferably C.I. Solvent Blue 67, C.I. Acid Green 9, C.I. Acid Green 16, C.I. Solvent Yellow 82 and C.I. The combination of Solvent Yellow 162 is selected.

Combinations of red, blue and green dyes are not limited to the combinations mentioned above, and each dye may be suitably formulated to match the spectrum of the desired pixel.

Such dyes (A) are, if necessary, treated with rosin or surface treatment with pigment derivatives containing acidic or basic groups introduced, graft treatment with the surface of dye particles using polymer compounds, washing with organic solvents or water for removal of impurities. Treatment, or treatment by ion exchange for removing ionic impurities can be performed. Such treatment may be performed alone or in combination.

The colorant (A) may be dispersed in part or all of the dispersant or binder resin (B), if necessary, to obtain a dispersion in which the pigment or dye is uniformly dispersed.

Examples of the dispersant include cationic, anionic, nonionic, amphoteric polyester-based or polyamine-based surfactants, which may be used alone or in combination of two or more thereof.

Examples of such surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, modified fatty acid polyesters, modified tert-amine polyurethanes and polyethyleneimines.

Specific examples include KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (registered trademark, Kyoeisha Chemical Co., Ltd.) as trade names. Ftop (registered trademark, Tohchem Products Co., Ltd.), Megapack (registered trademark, Dainippon Ink & Chemicals Inc.) .)), Fluorad (registered trademark, Sumitomo 3M Co., Ltd.), Asahi Guard (registered trademark) and Surfron (registered trademark) (Asahi Asahi Glass Co. Ltd.), Solsperse®, Zeneca Co., Ltd., EFKA (registered trademark, EFKA Chemicals Co., Ltd.) EFKA Chemicals Co., Ltd.) and PBS821 (Ajinomoto Co., Inc.).

When the dispersant is used, the amount thereof is preferably 0.1 to 100 mass%, more preferably 5 to 50 mass%, in mass ratio with respect to 100 mass% of the colorant. When the amount of the dispersant is used within the above range, a uniformly dispersed solution tends to be preferably obtained.

The amount of the colorant (A) used in the colored photosensitive resin composition of the present invention is preferably 20 to 65 mass%, more preferably 25 to 60 mass%, even more preferably in mass ratio with respect to the solid content of the colored photosensitive resin composition. Is 27-55 mass%, Most preferably, it is 30-50 mass%.

The term solid content, as used herein, refers to 25 ° C. (room temperature) in colorants (A), binder resins (B), photopolymerizable compounds (C), photopolymerization initiators (D), and other components added in the colored photosensitive resin composition, if necessary. ) Is the total amount of non-liquid components.

When the content of the colorant (A) is within the above range, the color density formed in the color filter to be formed is sufficient, and since the composition may contain more binder resin than the required amount, the formed pattern is preferable in that it has sufficient mechanical strength. .

The coloring photosensitive resin of this invention contains binder resin (B). The binder resin (B) preferably contains a structural unit derived from (meth) acrylic acid. The term (meth) acrylic acid refers to acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% to 40 mol%, more preferably 18 mol% to 38 mol, in molar ratio with respect to the amount of the total structural units composed of the binder resin (B). %to be. If the content of the structural unit derived from (meth) acrylic acid is within the above range, it is preferable in that the non-pixel portion becomes soluble during development and there is a tendency that little residue remains in the non-pixel region after development.

Examples of monomers derived from structural units of binder resins other than those derived from (meth) acrylic acid include aromatic vinyl compounds, unsaturated carboxylates, aminoalkyl unsaturated carboxylates, glycidyl unsaturated carboxylates, vinyl unsaturated carboxyls Laterates, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes and macromonomers having monoacryloyl or monomethacryloyl groups at the ends of the polymer chains. The structural units represented by the following formula (II) or (III) can also be listed as the structural units.

In the formulas (II) and (III), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a C1 to C6 alkyl group.

R ¹⁰ and R ¹¹ include a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2- Methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group , 1-ethylbutyl group, 2-ethylbutyl group and 3-ethylbutyl group, preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert- Butyl groups, more preferably hydrogen atoms, methyl groups and ethyl groups are included.

Specific examples of the binder resin preferably include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate air Copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, structural units of methacrylic acid / formula (V) wherein R ¹⁰ and R ¹¹ in formula (II) are each a methyl group and Hydrogen atom) / benzyl methacrylate copolymer, structural unit of formula (II), wherein R ¹⁰ and R ¹¹ in formula (II) each represent a methyl group and a hydrogen atom) / benzyl methacrylate copolymer And structural units of methacrylic acid / formula (III), wherein R ¹⁰ and R ¹¹ in formula (III) each represent a methyl group and a hydrogen atom) / styrene / tricyclodecanyl methacrylate copolymer.

The acid value of the binder resin (B) used in the present invention is preferably 50 to 150, more preferably 60 to 135, even more preferably 70 to 135. When the acid value is within the above range, the solubility of the resin in the developing solution tends to be improved to promote dissolution of the non-exposed sites, the sensitivity of the resin is increased to maintain the pattern of the exposed sites during development, and the residual film thickness It is preferable at the point that the ratio of is improved. The acid value herein is the value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of acrylic acid polymer and is usually determined by titration using an aqueous potassium hydroxide solution.

The content of the binder resin (B) is preferably 15 to 40% by mass, more preferably 18 to 38% by mass, even more preferably 21 to 36% by mass relative to the solids content of the colored photosensitive resin composition. When the content of the binder resin (B) is within the above range, a sharp pattern is formed, which is preferable in that the high ratio of pattern resolution and residual film thickness tends to be improved.

Binder resin comprising structural component of formula (II), such as methacrylic acid / structural component of formula (II), wherein R ¹⁰ and R ¹¹ in formula (II) each represent a methyl group and a hydrogen atom) / benzyl The methacrylate copolymer copolymerizes methacrylic acid and benzyl methacrylate to obtain a bicomponent polymer, and then reacts with a compound of formula (II-1) (wherein R ¹¹ represents a hydrogen atom in formula (II-1)) It is prepared by making.

Methacrylic acid / Structural component of formula (III) (R ¹⁰ and R ¹¹ in formula (III) each represent a methyl group and a hydrogen atom) / benzyl methacrylate / tricyclodecanyl methacrylate copolymer is benzyl methacryl It can be obtained by reacting a copolymer of monomethacrylate having a rate, methacrylic acid, and tricyclodecane structure with glycidyl methacrylate.

The weight average molecular weight based on the polystyrene assay standard of the binder resin (B) is preferably 5,000 to 100,000, more preferably 6,000 to 90,000, even more preferably 7,000 to 80,000. When the molecular weight is in the above range, the film hardness tends to be improved, and since the solubility of the non-exposed sites in the developer is good, the ratio of the residual film thickness and the pattern resolution tend to be high.

The coloring photosensitive resin composition of this invention contains a photoinitiator (D). Examples of the initiator (D) for the photopolymerization include triazine compounds, acetophenone compounds, biimidazole compounds, active radical generators and acid generators.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl ) Ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-tria Jeans are included.

Examples of the acetophenone compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one, and 2-hydroxy-2-methyl-1-phenylpropane -1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2 Oligomers of -hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and the like; and 2-methyl-2-morpholino-1- (4-methylthio Phenyl) propan-1-one is preferred.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl)- 4,4 ', 5,5'-tetra (4-carboethoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (4 -Bromophenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (2,4-dichlorophenyl) biimidazole, 2,2' -Bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5 ' -Tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (2 , 6-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,4', 5,5'-tetraphenylbiimi Dazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.

Active radical generators generate active radicals upon light irradiation. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds and the like.

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

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert- Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-prop Foxy thioxanthones and the like.

Examples of the triazine compound include the same compounds as those listed above.

Examples of such oxime compounds include O-acyl oxime compounds, specifically 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4- Phenylsulfanylphenyl) octane-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) octan-1-one-oxime-O-acetate, 1- (4-phenyl Sulfanylphenyl) butan-1-one-oxime-O-acetate and the like.

Examples of active radical generators other than the active radical generators exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxylate, titanocene compound, and the like.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyl Onium salts such as iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate and the like.

Among the active radical generators, some compounds are compounds which simultaneously generate an active radical and an acid, for example, a triazine-based photopolymerization initiator may also be used as the acid generator.

The content of the photopolymerization initiator (D) is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, based on the total amount of both the binder resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is in the above range, the photosensitivity is improved to shorten the exposure time, thus increasing the productivity, while the minimum line width at the resolution of the line-and-space in the pattern is widened due to the very large photosensitivity. Is preferable in that it is prevented.

The coloring photosensitive resin composition of this invention can further contain a photoinitiator adjuvant (G). The photopolymerization initiation aid (G) is usually used in combination with the photopolymerization initiator (D) and functions to promote polymerization of the photopolymerizable compound initiated by the photopolymerization initiator.

Examples of the photopolymerization initiation assistant (G) include an amine compound, an alkoxy anthracene compound, a thioxanthone compound, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate , 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and 4 , 4'-bis (ethylmethylamino) benzophenone and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. .

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-prop Foxy thioxanthones and the like.

Photopolymerization start adjuvant (G) can be used individually or in combination of 2 or more types. Commercially available photopolymerization initiation aid (G) can be used. Examples of commercially available photopolymerization initiation aids (G) include organic amines such as EAB-F (4,4'-bis (diethylamino) benzophenone from Hodogaya Chemical Co., Ltd.) Compound is included.

Examples of the combination of the photopolymerization initiator (D) / photopolymerization initiation aid (G) used in the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone and 2-methyl- 2-morpholino-1- (4-methylthiophenyl) propane-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropane-1 -One / 4,4'-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- ( 2-hydroxyethoxy) phenyl] propane-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylketone / 4,4'-bis (diethylamino) benzo Phenone, oligomer / 4,4'-bis (diethylamino) benzophenone, 2-benzyl- of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone and the like. Among them, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one / 4,4'-bis (diethylamino) benzophenone is preferably used.

The amount of such photopolymerization initiation aid (G) used is preferably 0.01 to 10 parts, more preferably 0.01 to 5 parts per 1 part of the photopolymerization initiator (D).

Examples of the solvent (E) used in the colored photosensitive resin composition of the present invention include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

Examples of such ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methylcellosolve acetate, ethylcellosolve acetate, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether acetate, methoxy And the like ethyl acetate, methoxy pentyl acetate, anisole, phenetole, methyl anisole.

Examples of the aromatic hydrocarbon include benzene, toluene, xylene, mesitylene and the like.

Examples of the ketone include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and the like.

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

Examples of such esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropio Nate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxy Propionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methock Propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate Nate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate Bate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, etc. This includes.

Examples of such amides include N, N-dimethylformamide, N, N-dimethylacetamide, and the like.

Examples of other solvents include N-methylpyrrolidone, dimethyl sulfoxide and the like.

The said solvent can be used individually or in combination of 2 or more types.

Among the solvents, a solvent containing propylene glycol monomethyl ether acetate is preferably used. When the solvent (E) contains propylene glycol monomethyl ether acetate, the content thereof is preferably 50 to 97 mass%, more preferably 60 to 95 mass% in mass ratio with respect to the total amount of the solvent.

The content of the solvent (E) is preferably 70 to 90% by weight, more preferably 75 to 88% by weight in mass ratio with respect to the total amount of the colored photosensitive resin composition. When the content of the solvent (E) is within the above range, the in-plane uniformity at the time of coating is good, the color density is sufficient at the time of forming the color filter, and the display properties are preferable.

The coloring photosensitive resin composition of this invention can contain surfactant. Examples of surfactants include silicone-based surfactants, fluoro surfactants and silicone-based surfactants containing fluorine atoms.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond. Specific examples of commercially available products include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, and polyether-modified silicone oil SH8400 (Toray Silicone Co., Ltd.) , KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (Shin-Etsu Silicone Co., Ltd.), and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (GE TOSHIBA Silicone Co., Ltd.) Limited (GE Toshiba Silicone Co., Ltd.)).

Examples of such fluorosurfactants include surfactants having a fluorocarbon chain. Specific examples of commercially available products include fluoride (registered trademark) FC430 and FC431 (Sumitomo 3M Co., Limited), Megapack (registered trademark) F142D, F171, F172, F173, F177, F183, F470, F475, and R30 (Daninip Ink) And Chemicals Inc.), F-Top® EF301, EF303, EF351 and EF352 (New Akita Chemical Co., Ltd.), Surfron® S381 , S382, SC101 and SC105 (Asahi Glass Co., Limited), E5844 (Daikin Fine Chemical Laboratory), BM-1000 and BM-1100 (BM Chemie), etc. Included.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having both a siloxane bond and a fluorocarbon chain. Specifically, MegaPack® R08, BL20, F475, F477, and F443 (Daniyek Ink and Chemicals Inc.) are included.

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

The coloring photosensitive resin composition of this invention can contain the organic acid whose molecular weight is 1,000 or less. Examples of the organic acid include those disclosed in Japanese Patent Application Laid-Open No. 5-343631. Specific examples include malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid and methacrylic acid, preferably Preferably malonic acid, oxalic acid, fumaric acid and phthalic acid. When the molecular weight contains an organic acid of 1,000 or less, the residue after development tends to exhibit good characteristics.

The colored photosensitive resin composition of the present invention may further contain additives such as fillers, polymer compounds other than binder resins, adhesion promoters, antioxidants, uv absorbers, coagulation inhibitors, organic amines, curing agents and the like.

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

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 vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy Silanes and the like.

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

Examples of the uv absorbents include benzotriazole type such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole and the like; Benzophenones such as 2-hydroxy-4-octyloxybenzophenone and the like; Benzoate-based such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and the like; And triazine-based, such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

Examples of such coagulation inhibitors include sodium polyacrylates and the like.

The addition of the organic amine compound prevents the deposition of residues on the unexposed areas of the substrate during development, so that the pixels adhere well to the base substrate.

Examples of such organic amine compounds include monoalkylamines such as n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine , n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine and the like; Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine and the like; Dialkylamines such as methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine , Di-sec-butylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine and the like; Monoalkylmonocycloalkylamines such as methylcyclohexylamine, ethylcyclohexylamine and the like; Dicycloalkylamines such as dicyclohexylamine and the like; Trialkylamines such as dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyl-di-n-propylamine, ethyl-di-n-propylamine , Tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri tert-butylamine, tri-n-pentylamine, tri-n-hexyl Amines and the like; Dialkylmonocycloalkylamines such as dimethylcyclohexylamine, diethylcyclohexylamine and the like; Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine and the like; Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1- Hexanol and the like; Monocycloalkanolamines such as 4-amino-1-cyclohexanol and the like; Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine and the like; Dicycloalkanolamines such as di (4-cyclohexanol) amine and the like; Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine and the like; Tricycloalkanolamines such as tri (4-cyclohexanol) amine and the like; Aminoalkanediols such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethyl Amino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol and the like; Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol and the like; Amino group-containing cycloalkanonemethanols such as 1-aminocyclopentanonemethanol, 4-aminocyclopentanonmethanol and the like; Amino group-containing cycloalkanethanols such as 1-aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclohexanemethanol, 4 Diethylaminocyclohexanemethanol and the like; Aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6 Aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid and the like; Aromatic amines such as aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1 Naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline and the like; Aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol and the like; Aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethyl aminophenol, p-diethylaminophenol and the like; Aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and the like.

Examples of the curing agent include a compound that reacts with a carboxyl group of a binder resin by heating and crosslinks, and a compound that is polymerized alone to cure a colored pattern. Examples of the compound include an epoxy compound and an oxetane compound, preferably an oxetane compound is used.

Examples of the epoxy compound include epoxy resins such as 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, aliphatic Aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins and epoxidized oils, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof , Epoxidized butadiene (co) polymers, epoxidized isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylates, triglycidyl isocyanurates, and the like.

Examples of the oxetane compound include carbonate-bisoxetane, xylylene-bisoxetane, adipate-bisoxetane, terephthalate-bisoxetane, cyclohexanecarboxylic acid-bisoxetane, and the like. .

When it contains an epoxy compound or an oxetane compound as a hardening | curing agent, the coloring photosensitive resin composition of this invention can contain the compound which can cause ring-opening polymerization of the epoxy group of an epoxy compound, and the oxetane ring of an oxetane compound. Examples of such compounds include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, acid generators, and the like.

Examples of such polyvalent carboxylic acids include aromatic polyhydric carboxylic acids such as phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid , 3,3'4,4'-benzophenonetetracarboxylic acid; Aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid; Alicyclic polyhydric carboxylic acids such as hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclo Hexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and the like.

Examples of the polyhydric carboxylic anhydride include aromatic polyhydric carboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3'4,4'-benzophenonetetracarboxylic dianhydride and the like; Aliphatic polyhydric carboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Water and the like; Alicyclic polyhydric carboxylic anhydrides such as hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid Anhydrides, cyclopentanetetracarboxylic dianhydrides, 1,2,4,5-cyclohexanetetracarboxylic dianhydrides, himic anhydrides, nadic anhydrides, and the like; And ester group-containing carboxylic acid anhydrides such as ethylene glycol bis (trimelitate), glyceryl tris (trimelitate) anhydride and the like.

Commercially available curing agents for epoxy resins can be used as the carboxylic acid anhydride. Examples of the curing agent for the epoxy resin include Adeka Hardener (registered trademark) EH-700 (ADEKA Corp.) and Rikacid (registered trademark) HH, MH-700 (both New Japan Chemical) Co., Limited (New Japan Chemical Co., Ltd.) and the like.

The acid generator is the same as described above.

The said hardening | curing agent can be used individually or in combination of 2 or more types.

As a manufacturing method of the coloring photosensitive resin composition of this invention, a coloring agent (A), such as a pigment, is disperse | distributed in a solvent (E) in presence of a dispersing agent, to form a coloring agent dispersion liquid, and binder resin (B) melt | dissolves in a solvent, for example. After adding the prepared solution, a photopolymerizable compound (C), a photoinitiator (D), and the other additive melt | dissolved in a solvent as needed, the method of adding a solvent further if needed is mentioned.

The colored photosensitive resin composition of the present invention is usually sealed in a container for transportation and storage.

The general method of manufacturing the color filter for image sensors using the coloring photosensitive resin composition of this invention is described below. This method is a sequence of applying and drying the colored photosensitive resin composition to a base substrate, pattern exposing the dry coated film obtained by using an I line stepper, alkali developing the post-exposure image, and heat treating the post-exposure image. Phosphorus process. The above process is repeated for each color (three or four colors) sequentially to form a pixel to obtain a color filter.

More specifically, after applying the colored photosensitive resin composition of the present invention to a suitable base substrate by a spin coater or the like so that the dry film has a thickness of generally 0.1 to 5 탆, preferably 0.2 to 2 탆, the coated substrate is 100 Drying in an oven at 3 ° C. for 3 minutes yields a flat coated film.

The base substrate is not particularly limited, and glass plates, plastic sheets, aluminum plates, base substrates for electronic components such as silicon wafers for image elements, transparent plastic sheets, resin films, cathode ray tube screens, light receiving planes of solid state images, solid images Wafers made of devices, such as CCDs, BBDs, CIDs and BASIS on wafers, including contact image sensors using thin film semiconductors, liquid crystal display planes, photoreceptors for color electrophotography and base substrates for electrochromic (EC) displays do. It is also desirable to apply a high degree of adhesion treatment to the base substrate in order to improve the adhesion between the base substrate and the color filter layer. Specifically, the silane coupling agent may be previously applied thinly to the base substrate, and then a pattern of the colored photosensitive resin composition may be formed, or the silane coupling agent may be previously contained in the colored photosensitive resin composition.

When the base substrate is not flat, a flattening film is applied to the base substrate in order to remove the unevenness to form a flat surface for coating, and then the colored photosensitive resin composition of the present invention can be applied thereto. For example, the sensor portion of an image sensor such as a CCD is composed of a photoelectric conversion portion (photodiode) for generating electrons corresponding to the amount of received light on the silicon base substrate and a reading gate part for outputting the generated electrons. . However, when light collides with the read gate portion, noise is generated and accurate data is not output, so a light shading layer is formed on the upper portion of the read gate portion, and the unevenness is formed in the photodiode portion having no light shielding layer. do. When the color resist is applied on the uneven surface to form the color filter directly, the light path is long and the formed image is darkened and the light focusing is also poor. In order to improve this problem, it is desirable to form a transparent flattening film between the CCD and the color filter to fill in the uneven portion. Examples of the material for the flattening film include a photocurable resin composition of the present invention, a thermosetting resin such as acrylic acid or an epoxy resin, and a photocurable resin.

After application of the photosensitive resin composition, the coated base substrate is usually pre-baked under reduced pressure to evaporate the solvent to obtain a dried coated film. For example, a method of maintaining the coated substrate at a temperature of 50 to 120 ° C. under a pressure of 0.1 to 10 Torr may be enumerated. Examples of the pre-baking method include a method of heating and drying with hot air, and a method of heating or drying (80 to 140 ° C., 50 to 200 seconds) on a hot plate.

In addition, post-baking is usually performed to sufficiently cure the coated resin composition and to improve the mechanical strength of the pattern obtained after development to form a permanent film. For example, in the production of a color filter having three colors, the first formed pattern is then subjected to two application, exposure and image development processes with colored photosensitive resin compositions of different colors. In this process, it is preferable to perform post-baking in order to prevent color mixing and pattern loss by exposure and image development in the coated and colored photosensitive resin composition. This post-baking is performed similarly to the method of pre-baking, but for a longer time at high temperature than the pre-baking. For example, post-baking is performed at 100 to 250 ° C. for 1 to 60 minutes.

The developing solution for developing the colored photosensitive resin composition is not particularly limited, and a known developing solution can be used. Among them, aqueous organic alkali solutions of tetravalent ammonium salts such as tetramethylammonium hydroxide (TMAH) and the like are preferred.

The image sensor with a color filter in the present invention forms, for example, a flattening film on the sensor portion formed on the base substrate, and then the color filter of the present invention is placed on the film according to the above method, and then the lens material is applied. By patterning the lens pattern by a photolithography process and a heat treatment, and then performing an etch back process on all regions to form an on-chip lens.

When a thin color filter containing a high concentration of pigment is produced according to the present invention, the residue after development can be reduced to obtain a color filter having a high color purity and few defects during manufacture. The coloring photosensitive resin composition of this invention is especially suitable for manufacture of the color filter for image sensors.

<Example>

The present invention will be described based on the following examples, of course, the present invention is not limited to these examples.

<Synthesis of Resin (B1)>

333 g of propylene glycol monomethyl ether acetate were introduced into a 1 L flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas introduction tube. Nitrogen gas was then introduced into the flask through a gas introduction tube to replace the atmosphere in the flask with nitrogen gas. The solution in the flask was then heated to 100 ° C., after which dicyclopentenyl methacrylate (FA-513M; Hitachi Chemical Co., Ltd.) 22.0 g (0.10 mol), benzyl meta A mixture consisting of 70.5 g (0.40 mol) of methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate was added to the flask using a dropping funnel over 2 hours. Was added. After the addition was complete, the mixture was further stirred at 100 ° C. for 5 hours.

After stirring was complete, air was introduced into the flask through a gas introduction tube to replace the atmosphere in the flask with air, followed by 35.5 g [0.25 moles of glycidyl methacrylate (molar ratio relative to methacrylic acid used in this reaction). 50 mol%)], 0.9 g of tris (dimethylamino) methylphenol and 0.145 g of hydroquinone were added. The reaction was continued at 110 ° C. for 6 hours to obtain a solution containing Resin B1 (solid content 38.5 mass% and acid value 80 mg KOH / g).

The acid value here is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of a polymer containing an acidic group such as carboxylic acid. This is usually measured by titration with aqueous potassium hydroxide solution of known concentration.

The weight average molecular weight of Resin B1 was 9,000 based on the polystyrene assay standard.

The weight average molecular weight based on the polystyrene assay standard of the binder resin was determined by the GPC method under the following conditions.

Equipment: HLC-8120 GPC (Tosoh Co., Ltd.)

Column: TSK-GEL G2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate; 1.0 ml / min

Solids content of the test sample solution: 0.001 to 0.01 mass%

Injection volume: 50 μl

Detector: Refractometer

Standards for Assay: TSK Standard Polystyrene F-40, F-4, F-1, A-2500 and A-500 (Doso Co., Limited)

The components used in this example are described below and may be represented by abbreviations below.

(A-1) Colorant: C.I. Pigment Blue 15: 6

(A-2) Colorant: C.I. Pigment Violet 23

(B-1) Resin B1 (Solution of 38.5% by mass of solids in propylene glycol monomethyl ether acetate)

(C-1) photopolymerizable compound: DPHA (Dipentaerythritol hexaacrylate; Nippon Kayaku Co., Ltd.)

(C-2) photopolymerizable compound: 2,2,2-tris (acryloyloxy) methylethyl phthalate; Shin-Nakamura Chemical Co., Ltd.

(C-3) photopolymerizable compound: 2,2,2-tris (acryloyloxy) methylethyl succinate; Shin-Nakamura Chemical Co., Limited)

(D-1) Photoinitiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine

(D-2) Photoinitiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one

(G-1) Photopolymerization Initiation Aid: 4,4'-bis (diethylamino) benzophenone

(E-1) Solvent: Propylene Glycol Monomethyl Ether Acetate

(E-2) solvent: ethyl 3-ethoxypropionate

(F-1) Mega Pack F475 (Dainitung Ink and Chemicals Co., Limited)

<Example 1>

[Production of Colored Photosensitive Resin Composition 1]

(A-1) 4.968 parts by mass,

(A-2) 1.242 parts by mass,

2.174 parts by mass of an acrylic dispersant,

(B-1) 16.569 parts by mass,

(C-2) 2.126 parts by mass,

(D-1) 0.425 parts by mass,

(D-2) 0.510 parts by mass,

(G-1) 0.170 parts by mass,

(E-1) 63.610 parts by mass,

(E-2) 8.200 parts by mass, and

(F-1) 0.005 parts by mass

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

[Pattern Formation 1]

SumiResist® PR-1300Y-PG (Sumitomo Chemical Co., Ltd.) was spin coated on a glass plate, and then heated at 100 ° C. for 1 minute to remove volatile components, which had a thickness of 0.5 μm. The resin layer was formed. The glass plate was heated at 230 ° C. for 15 minutes to cure the resin layer to form a support medium having a coated flattening film. The colored photosensitive resin composition (red) obtained above was spin coated onto the support medium and heated at 100 ° C. for 3 minutes to remove volatile components to form a colored photosensitive resin composition film. After cooling, the colored photosensitive resin composition film was irradiated through a photomask using an I line (wavelength 365 nm). An ultrahigh pressure mercury lamp was used as the light source for the I line, and the light before irradiation was parallel. The irradiated light intensity was 150 mJ / cm ² . Photomasks have color pixels in the form of lines with line widths 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 It was used to form a. The glass substrate (on the surface on which the colored photosensitive resin composition film is formed) is developed by exposure to a developer (CIS DEVELOPER; ENF Technology Co.) at 80 ° C. for 80 seconds after exposure. , Washed with purified water to obtain a glass plate patterned in a line-and-space pattern.

[Evaluation 1]

The light transmittance (average of 400 nm to 780 nm) of the coated base substrate on which the coated film was dissolved was 99.9%.

[Pattern Formation 2]

Semiresist PR-1300Y-PG (Sumitomo Chemical Co.) was spin coated on a silicon wafer, and then heated at 100 ° C. for 1 minute to remove volatile components to form a resin layer having a thickness of 0.5 μm. This silicon wafer was then heated at 230 ° C. for 15 minutes to cure the resin layer to form a support medium with the coated flattening film. The colored photosensitive resin composition 1 obtained above was spin coated onto the support medium and heated at 100 ° C. for 1 minute to remove volatile components to form a colored photosensitive resin composition layer. The obtained colored photosensitive resin composition layer was subjected to 20 to 310 milliseconds from an exposure machine (Nikon NSR I9C; Nikon Corp.) through a patterning mask (pixels of 2 μm ² were formed into a checkerboard). Were investigated using I lines at positions of 30 armies at 10 millisecond intervals. The exposed support medium was developed by immersion in a developer (cis developer; ENF Technology Co.) at 23 ° C. for 60 seconds. After the development, the support medium was washed with water and dried to obtain a color filter having pixels in a check pattern having a line width of 2.0 m and a thickness of 0.7 m.

[Evaluation 2]

The cross section of the pattern was observed with a scanning electron microscope (S-4500; Hitachi Ltd.) to confirm that there was no residue in the dissolved portion during development and that the pattern was adhered well.

Comparative Example 1

[Production of Colored Photosensitive Resin Composition 2]

Colored photosensitive resin composition 2 was prepared by mixing similar components to Example 1 except that C-2 in Example 1 was changed to C-3.

[Evaluation 1]

A method similar to Example 1 was used except that the colored photosensitive resin composition 1 in Example 1 was changed to the colored photosensitive resin composition 2. The light transmittance (average of 400 nm to 780 nm) of the coated base substrate after the coating layer was dissolved was 98.9%.

[Evaluation 2]

A test specimen was prepared in a similar manner to Example 1 except that the colored photosensitive resin composition 1 in Example 1 was changed to the colored photosensitive resin composition 2. Observation of the cross section of the pattern with a scanning electron microscope revealed the presence of delamination in part of the pattern and the attachment of residue to the dissolved part during development.

Comparative Example 2

[Production of Colored Photosensitive Resin Composition 3]

Colored photosensitive resin composition 3 was prepared by mixing similar components to Example 1 except that C-2 in Example 1 was changed to C-1.

[Evaluation 1]

A method similar to Example 1 was used except that the colored photosensitive resin composition 1 in Example 1 was changed to the colored photosensitive resin composition 3. The light transmittance (average of 400 nm to 780 nm) of the coated base substrate after the coating layer was dissolved was 98%.

[Evaluation 2]

A test specimen was prepared in a similar manner to Example 1 except for changing the colored photosensitive resin composition 1 in Example 1 to the colored photosensitive resin composition 3. Observation of the cross section of the pattern with a scanning electron microscope revealed that the adhesion of the pattern was good, but the residue adhered to the dissolved portion during development.

Industrial availability

The colored photosensitive resin composition of the present invention can be used to form a thin color filter containing a pigment at a high concentration, and the color filter obtained can be suitably used for image sensors and liquid crystal display equipment.

According to the present invention, in the case of developing a pattern for producing a color filter, a colored photosensitive resin composition in which almost no residue remained after development was provided.

Claims (4)

A coloring agent (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E) are included, The said photopolymerizable compound (C) is a 2,2, 2- tris (acryl A coloring photosensitive resin composition containing iloxy) methylethyl phthalate. The pattern formed using the coloring photosensitive resin composition of Claim 1. A color filter comprising the pattern of claim 2. An image sensor comprising the color filter according to claim 3.