JP4184365B2 - Photosensitive resin composition for color filter - Google Patents

Description

  The present invention relates to a resin composition applied to a liquid crystal display (LCD), a charge coupled device (CCD) or the like, and more particularly to a photosensitive resin composition for a color filter that can be applied to a liquid crystal display. The photosensitive resin composition for a color filter has good sensitivity at the time of exposure, and does not produce a residue on a substrate in an unexposed area after development processing, and the formed pixel has a saturation and contrast. It is a photosensitive resin composition obtained by dispersing a highly concentrated pigment that is good and does not cause an undercut in the pattern.

  Color filters are widely applied to office automation equipment such as color liquid crystal displays, color facsimiles, and color photographing machines. As the application of color filters to OA equipment expands in this way, the production techniques for color filters themselves are diversified.

  Usually, a color filter in which pixels such as red, green, and blue are formed on a transparent substrate such as glass by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method, or the like is used. Among these, the pigment dispersion method has become the mainstream method for producing industrial color filters. In general, in order to improve the contrast of a color filter, a light shielding layer (black pattern) called a black matrix may be disposed between colored pixels.

  In the pigment dispersion method, a pixel colored layer is formed using a colored photosensitive composition in which a pigment is dispersed in a photocurable resin. The color filter manufactured by this manufacturing method has advantages such as high heat resistance and no need for dyeing, and can form a highly accurate pixel coloring layer.

  In the pigment dispersion method, usually, for example, a photosensitive resin (color resist) in which a red pigment is dispersed is rotated on a transparent substrate such as a glass substrate or a glass substrate on which a black matrix is formed. A red pixel can be obtained by applying to the entire surface of the substrate by a method such as a coating method or a cast coating method, exposing through a mask, and developing after exposure. When green, blue pixels are coated, exposed, and developed in the same procedure, red, green, and blue three-color pixels are formed on the substrate.

  Examples of the photosensitive resin composition used in the pigment dispersion method include a photosensitive resin composition comprising an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, a pigment, and a solvent. Here, as the photopolymerization initiator used, a generally known photopolymerization initiator, for example, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer was used. (Refer to Examples of Kaihei 10-260309 and JP-A-10-288837).

In recent years, for example, the use of color liquid crystal displays has expanded not only for personal computers but also for televisions, monitors, etc. (especially large color liquid crystal televisions), and in order to achieve high saturation, generally, It is necessary to increase the concentration of pigment in the photosensitive resin composition for color filters.
Japanese Patent Laid-Open No. 10-260309 Japanese Patent Laid-Open No. 10-288837

  However, when a photosensitive resin composition in which a highly concentrated pigment is dispersed is used, the sensitivity at the time of exposure is poor, and residues are often generated on the unexposed substrate and black matrix after development. In addition, it has a problem that undercut is likely to occur.

  Therefore, the problem to be solved by the present invention is that the sensitivity at the time of exposure is good even when the concentration of the pigment is increased, and the saturation and contrast of the pixel formed after development are good, there is no undercut, It is an object of the present invention to provide a photosensitive resin composition that can be used for a liquid crystal display, a charge-coupled device, and the like without causing a residue and using a color filter having the colored pixel layer as a color pixel layer.

  The present inventor has found that the above-described problems can be completed by using a photosensitive resin composition having the following constitution, and has completed the present invention.

  That is, this invention is invention which provides the photosensitive resin composition for color filters (henceforth this photosensitive resin composition) characterized by containing the following (A)-(E). .

(A) Alkali-soluble resin [The alkali-soluble resin (A) contains an alkali-soluble resin (A1) having no ethylenically unsaturated bond and an alkali-soluble resin (A2) having an ethylenically unsaturated bond, and The alkali-soluble resin (A1) accounts for 40 to 95% by mass with respect to the total mass of the alkali-soluble resin (A1) and the alkali-soluble resin (A2).

(B) Polymerizable compound having an ethylenically unsaturated bond

(C) a photopolymerization initiator (C1) of biimidazoles and a photopolymerization initiator (C2) represented by the following general formula (c2-1) [the photopolymerization initiator (C ), The photopolymerization initiator (C2) accounts for 10 to 98% by mass relative to the total mass of the photopolymerization initiator (C1) and the photopolymerization initiator (C2)]

Wherein, Z ₁ represents a hydrogen atom, an alkyl group, an aryl group, a mercapto group, an alkylthio group, an arylthio group, a benzylthio group, a hydroxyl group, an alkyloxy group, an aryloxy group, or a benzyloxy group, Z ₂ Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom]

(D) Pigment [In the case where the color filter resin composition is a red photosensitive resin composition, the pigment (D) is an alkali-soluble resin (A), a polymerizable compound having an ethylenically unsaturated bond (B ), 28 to 46% by mass based on the total mass of the photopolymerizable initiator (C) and the pigment (D), and in the green photosensitive resin composition, 32 to 51% by mass, In the case of a blue photosensitive resin composition, 25 to 45% by mass is blended]

(E) Organic solvent

  Furthermore, the present invention provides a color filter (hereinafter also referred to as the present color filter) using the photosensitive resin composition as a raw material for the pixel colored layer.

  According to the present invention, the sensitivity at the time of exposure is good even when the concentration of the pigment is increased, and the saturation and contrast of the pixel formed after development are good, there is no undercut, no residue is produced, There are provided a photosensitive resin composition for a color filter in which a color filter using this as a colored pixel layer can be used for a liquid crystal display, a charge coupled device, and the like, and a color filter using the photosensitive resin.

  The photosensitive resin composition is a photosensitive resin compound that can exhibit the desired effect in a color filter or the like by containing the above (A) to (E).

[Alkali-soluble resin (A)]
The alkali-soluble resin (A) includes one or two or more types of ethylenically unsaturated bonds (A1) and one or two or more types of ethylenically unsaturated bonds (A2). ) And the alkali-soluble resin (A1) accounts for 40 to 95% by mass, more preferably 50 to 90%, based on the total mass of the alkali-soluble resin (A1) and the alkali-soluble resin (A2). % By weight, most preferably from 52 to 88% by weight. If the mass ratio of the alkali-soluble resin (A1) is less than 40% by mass with respect to the total amount of the alkali-soluble resin (A1) and the alkali-soluble resin (A2), residues and undercuts are likely to occur. On the other hand, if it exceeds 95% by mass, the sensitivity of the photosensitive resin composition deteriorates.

  Alkali-soluble resin (A1) is an ethylenically unsaturated monomer (M1-1) containing 1 or 2 or more carboxyl groups (hereinafter referred to as monomer (M1-1)) 5-50 parts by mass And 95 to 50 parts by mass of other copolymerizable ethylenically unsaturated monomer (M1-2) (hereinafter referred to as monomer (M1-2)). The total amount of the monomer (M1-1) and the monomer (M1-2) is 100 parts by mass. Specific examples of the monomer (M1-1) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethylacrylic acid and cinnamic acid; maleic acid and maleic anhydride Examples thereof include unsaturated dicarboxylic acids (anhydrides) such as acid, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; trivalent or higher unsaturated polycarboxylic acids (anhydrides).

  Of the above monomers (M1-1), unsaturated monocarboxylic acids are preferred, and acrylic acid and methacrylic acid are particularly preferred. The monomer (M1-1) can be used alone or in combination of two or more.

  Specific examples of the monomer (M1-2) include aromatic vinyl group compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, methoxystyrene; N-phenylmaleimide, N-o- Hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenyl Maleimides such as maleimide and N-cyclohexylmaleimide; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, s-butyl acrylate, s-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl Acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate Unsaturated carboxylic acid esters such as phenyl acrylate, phenyl methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, docosyl methacrylate; N, N -Non-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminopropyl methacrylate, N, N-dibutylaminopropyl acrylate, Nt-butylaminoethyl methacrylate, etc. Saturated carboxylic acid aminoalkyl esters; unsaturated glycated glycates such as glycidyl acrylate and glycidyl methacrylate Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; acrylonitrile, methacrylonitrile, vinyl cyanide compounds such as α-chloroacrylonitrile and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide; 1,3-butadiene, And aliphatic conjugated dienes such as isoprene and chloroprene.

  Of the above monomers (M1-2), aromatic vinyl group compounds and unsaturated carboxylic acid esters are preferred, and in particular, styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl. Acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate and benzyl methacrylate are preferred. Monomers (M1-2) can be used alone or in combination of two or more.

  Specific examples of the solvent used in the production of the alkali-soluble resin (A1) include ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether, diethylene glycol mono n-butyl ether. , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol Mono n-butyl ether, tripropylene glycol monomethyl (Poly) alkylene glycol monoalkyl ethers such as ether, tripropylene glycol monoethyl ether; (poly) such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate , Ethyl 2-hydroxypropionate Lactic acid alkyl esters; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, acetic acid n-butyl, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvine Ethyl acetate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutyric acid ethyl Other esters and the like; toluene, aromatic hydrocarbon compounds such as xylene; N- methylpyrrolidone, N, N- dimethylformamide, N, a carboxylic acid amides such as N- dimethylacetamide.

  These solvents can be used alone or in admixture of two or more. Among these solvents, propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate are exemplified as preferred solvents.

  The polymerization initiator used when producing the alkali-soluble resin (A1) is usually a free radical polymerization initiator. Specific examples thereof include 2,2′-azobisisobutyronitrile, 2,2 ′. -Azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile, etc. Compound: Examples of the peroxide compound include benzoyl peroxide.

  In order to achieve the object of the present invention, the alkali-soluble resin (A) includes an alkali-soluble resin (A2) containing at least one ethylenically unsaturated bond. Here, the alkali-soluble resin (A2) having an ethylenically unsaturated bond refers to one having an ethylenically unsaturated bond that can participate in the photopolymerization reaction of the alkali-soluble resin. Specific examples thereof include a product obtained by reacting a carboxyl group of a part of a resin containing a carboxyl group with an epoxy compound containing a carbon-carbon double bond, a compound containing an acid anhydride group and a carbon. A half-esterified compound obtained by reacting a compound containing a double bond and a hydroxy group simultaneously, an acid anhydride-modified resin of epoxy acrylate resin, an ester compound obtained from acrylic acid and allyl alcohol, and an ethylenic compound. Examples thereof include products obtained by reacting with saturated carboxylic acid compounds. Among these alkali-soluble resins (A2), it is preferable to select an alkali-soluble resin containing bisphenol fluorene in the molecule.

  The alkali-soluble resin (A2) ′ containing bisphenolfluorene in the molecule is obtained by reacting a compound containing a functional group represented by the following general formula (a2-11) with another copolymerizable compound. It is an alkali-soluble resin.

(In the formula, each R independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom.)

  Specific examples of the functional group-containing compound represented by the general formula (a2-11) include an epoxy group-containing bisphenolfluorene compound represented by the following general formula (a2-12) [hereinafter also referred to as a compound (A2-12)] And a hydroxyl group-containing bisphenolfluorene compound represented by general formula (a2-13) [hereinafter also referred to as compound (A2-13)].

[Wherein, R is the same as in general formula (a2-11). ]

[Wherein, R is the same as in formula (a2-11), and R ¹ and R ² are each independently an alkylene group having 1 to 20 carbon atoms and an alicyclic group having 1 to 20 carbon atoms. It represents at least one group selected from groups of the formula. k and m each independently represent an integer of 1 or more. ]

  Other copolymerizable compounds include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethylacrylic acid and cinnamic acid; maleic acid, succinic acid, itaconic acid, phthalic acid , Tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, glutaric acid and other dicarboxylic acids and their anhydrides; trimellitic acid and other tricarboxylic acids And acid anhydrides thereof: tetramellitic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid dianhydrides thereof.

  The production method for obtaining the alkali-soluble resin (A2) 'is not particularly limited. Hereinafter, production methods (Production Method I to Production Method III) of the alkali-soluble resin (A2) ′ will be exemplified.

[Production method I]
First, a compound (A2-12) is reacted with (meth) acrylic acid to give a bisphenolfluorene-based epoxy (meth) acrylate compound represented by the following general formula (a2-14) [hereinafter also referred to as compound (A2-14)] ] Is obtained.

[Wherein, R is the same as in formula (a2-11), and R ³ is independently a hydrogen atom or a methyl group. ]

Further, the compound (A2-14) is reacted with a polybasic carboxylic acid or an anhydride thereof (provided that the number of carboxylic acid molecules is the same (that is, “the same basic”) polybasic carboxylic acid or anhydride thereof). Select a thing. For example, one or more selected from the group of the number of carboxylic acid molecules among the group of dicarboxylic acid or its anhydride, the group of tricarboxylic acid or its anhydride, the group of tetracarboxylic acid or its anhydride, Can be used. ].
Specific examples of this reaction include, for example, the above compound (A2-14) and the following general formula (a2-15):

[Wherein Y represents a carboxylic anhydride residue]
In the presence of a dicarboxylic acid anhydride represented by the following formula, it has an ethylenically unsaturated bond and a carboxylic acid molecule, by heating in a cellosolve solvent such as ethyl cellosolve acetate and butyl cellosolve acetate, and reacting. An alkali-soluble resin (A2-16) represented by (a2-16) can be produced.

[Wherein X is a divalent group represented by the following general formula (a2-17):

{Wherein R and R ³ are the same as in general formula (a2-14)}
Y is the same as in the general formula (a2-15), and n is an integer of 1 or more, preferably an integer of 1-20. ]

[Production II]
The above compound (A2-14), the dicarboxylic acid anhydride represented by the above general formula (a2-15), and the following general formula (a2-18):

[Wherein Z represents a residue of tetracarboxylic dianhydride]
A mixture of tetracarboxylic dianhydrides represented by the following formula is heated in a cellosolve solvent such as ethyl cellosolve acetate, butyl cellosolve acetate, and reacted to produce ethylenic acid represented by the following general formula (a2-19) An alkali-soluble resin (A2-19) having an unsaturated bond and a carboxylic acid can be produced.

 [Wherein X is the same as in general formula (a2-16), Y is the same as in general formula (a2-15), Z is the same as in general formula (a2-18), p And q each represent a degree of polymerization, and each independently represents an integer of 1 or more, preferably an integer of 1 to 20. ]

[Production III]
The compound (A2-14) and the tetracarboxylic dianhydride represented by the formula (a2-18) are heated in a cellosolve solvent such as ethyl cellosolve acetate and butyl cellosolve acetate, reacted, and then reacted. Producing an alkali-soluble resin having an ethylenically unsaturated bond and a carboxylic acid represented by the following general formula (a2-20) by reacting the carboxylic acid anhydride represented by the formula (a2-15) Can do.

 [Wherein X is the same as in general formula (a2-16), Y is the same as in general formula (a2-15), Z is the same as in general formula (a2-18), and r Is an integer of 1 or more, preferably an integer of 1-20. ]

  In the synthesis reaction of the alkali-soluble resin (A2) in the above production methods I to III, the reaction temperature when the compound (A2-14) is reacted with the polybasic carboxylic acid or its anhydride is preferably 50 to 130 ° C., more Preferably it is 70-120 degreeC.

  In the synthesis reaction of the alkali-soluble resin (A2) in the above production methods I to III, the reaction between the polybasic carboxylic acid or its anhydride and the compound (A2-14) is carried out with 1 equivalent of the hydroxyl group of the compound (A2-14). On the other hand, the polybasic carboxylic acid or its anhydride is reacted at a ratio of 0.4 to 1 equivalent, preferably 0.75 to 1 equivalent, as the total of acid anhydride groups when all are converted as anhydride.

  In the synthesis reaction of the alkali-soluble resin (A2) of the above production method II and production method III, the dicarboxylic acid anhydride represented by the general formula (a2-15) and the tetracarboxylic acid dicarboxylic acid represented by the above formula (a2-18) The reaction molar ratio with the anhydride is preferably 1/99 to 90/10 [(a2-15) / (a2-18)], and more preferably 5/95 to 80/20. .

[Unsaturated polymerizable compound (B)]
The unsaturated polymerizable compound (B) is an ethylenically unsaturated compound having at least one ethylenically unsaturated bond.

  Examples of the unsaturated polymerizable compound (B) having one ethylenically unsaturated bond include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, Isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) ) Acrylamide, dimethylaminoethyl (meth) acrylate, dodecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, Trachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (Meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, Phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate , Polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate.

  Specific examples of the ethylenically unsaturated compound having two or more ethylenically unsaturated bonds among the unsaturated polymerizable compound (B) include, for example, ethylene glycol di (meth) acrylate and dicyclopentenyl di (meth). Acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter abbreviated as “EO”) modified trimethylolpropane tri (meth) acrylate, pro Ren oxide (hereinafter abbreviated as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate , Caprolactone modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (Meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified glycerol triacrylate, EO-modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, and the like.

  Particularly preferred among the unsaturated polymerizable compounds (B) are trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta. Examples include erythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, and PO-modified glycerol triacrylate.

    In the present photosensitive resin compound, the unsaturated polymerizable compound (B) can be used by containing one or more kinds, and the content is 100 parts by mass of the alkali-soluble resin (A). The amount is preferably 30 to 400 parts by mass, particularly preferably 50 to 300 parts by mass.

[Photoinitiator (C)]
As described above, the photopolymerization initiator (C) contains a biimidazole photopolymerization initiator (C1) and a photopolymerization initiator (C2) represented by the following general formula (c2-1). It is a photopolymerization initiator.

Wherein, Z ₁ represents a hydrogen atom, an alkyl group, an aryl group, a mercapto group, an alkylthio group, an arylthio group, a benzylthio group, a hydroxyl group, an alkyloxy group, an aryloxy group, or a benzyloxy group, Z ₂ Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom]

  Specific examples of the photopolymerization initiator (C1) include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methylphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (2,4-dichlorophenyl) -4,5-diphenylimidazole dimer, 2- And (2-chlorophenyl) -4,5-diphenylimidazole dimer.

  Specific examples of the photopolymerization initiator (C2) include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) (product) Name: CGI-242, manufactured by Ciba Specialty Chemicals, shown in general formula (C2-1-1)), ethanone, 1- [9-ethyl-6- (2-chloro-4-benzyl-thiobenzoyl)- 9H-carbazol-3-yl], 1- (O-acetyloxime) (manufactured by Asahi Denka Co., Ltd. and represented by the general formula (C2-1-2)).

 Photopolymerization initiators (C1) and (C2) can be used as the photopolymerization initiator (C) by selecting one or more of them from each group. Further, the content of the photopolymerization initiator (C2) in the photosensitive resin composition is 10 to 98% by mass with respect to the total mass composed of the photopolymerization initiator (C1) and the photopolymerization initiator (C2), Preferably it is 20-95 mass%, More preferably, it is 35-92 mass%. When the content of the photopolymerization initiator (C2) is less than 10% by mass, the sensitivity of the color filter using the photosensitive resin composition tends to deteriorate. When the content exceeds 98% by mass, an undercut occurs. It tends to occur.

  The total content of the photopolymerization initiators (C1) and (C2) in the present photosensitive resin composition is 1 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the unsaturated polymerizable compound (B). Parts, particularly preferably 10 to 100 parts by mass. When the total content is less than 1 part by mass with respect to 100 parts by mass of the unsaturated polymerizable compound (B), curing by exposure becomes insufficient, and a pixel array in which pixel patterns are arranged according to a predetermined arrangement is obtained. On the other hand, if it exceeds 200 parts by mass, a residue may be formed on the substrate in the unexposed area, and an undercut may be generated in the pattern.

  The photopolymerization initiator (C) can contain one or more photopolymerization initiators (C ′) other than the photopolymerization initiators (C1) and (C2) as necessary. . Examples of the corresponding photopolymerization initiator (C ′) include oxime compounds other than the photopolymerization initiator (C2), acetophenone compounds, benzophenone compounds, α-diketone compounds, acyloin compounds, acyloin ether compounds, and acylphosphine oxides. Quinones, halogen compounds, peroxides and the like.

  Examples of oxime compounds other than the photopolymerization initiator (C2) include 1- (4-phenylthiophenyl) -butane-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylthiophenyl) ) -Octane-1,2-dione-2-oxime-O-benzoate (trade name: CGI-124, manufactured by Ciba Specialty Chemicals), 1- (4-phenylthiophenyl) -octane-1-one-oxime- O-acetate, 1- (4-phenylthiophenyl) -butan-1-one-oxime-O-acetate and the like. As acetophenone compounds, p-dimethylaminoacetophenone, α, α'-dimethoxyazoxyacetophenone, 2,2'-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- (4-methylthiophenyl) -2 -Morpholino-1-propane, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone and the like.

  Examples of the benzophenone compound include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and the like. Examples of α-diketone compounds include benzyl and acetyl. Benzoin etc. are mentioned as an acyloin compound. Examples of the acyloin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Examples of the acylphosphine oxide include 2,4,6-trimethyl-benzoyldiphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylbenzylphosphine oxide. Examples of the quinone compound include anthraquinone and 1,4-naphthoquinone. Examples of the halogen compound include phenacyl chloride, tribromomethylphenylsulfone, and tris (trichloromethyl) -s-triazine. Examples of the peroxide include di-t-butyl peroxide.

  The content of the photopolymerization initiator (C ′) in the photosensitive resin composition is 0 to 150 parts by mass, preferably 0 to 80 parts by mass with respect to 100 parts by mass of the unsaturated polymerizable compound (B). Yes, particularly preferably 0 to 50 parts by mass.

[Pigment (D)]
The pigment (D) is blended to make the photosensitive resin composition a photosensitive resin composition for a color filter having a desired color. Here, the desired color is usually one of red, green and blue, but is not limited thereto. For example, the pigment contained in the photosensitive resin composition may be a red pigment, a green pigment, and a blue pigment (herein, “red,” “green,” and “blue” pigments may be blended as a whole) For example, “red pigment” is blended with a photosensitive resin composition, and the photosensitive resin composition is added to the colored pixel of the color filter. When the raw material is used, this means that the colored pixel is a pigment capable of developing a “red” color.), The photosensitive resin composition has a red photosensitive resin composition, A green photosensitive resin composition and a blue photosensitive resin composition can be prepared, and these photosensitive resin compositions are respectively a red pixel colored layer, a green pixel colored layer, and a blue pixel of a color filter. It can be a raw material for the color layer.

  As the pigment having a desired color, known inorganic pigments or organic pigments can be used alone or in combination.

    Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, etc. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal complex oxides.

  Examples of the organic pigment include CIPigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; CI Pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43 , 46, 49, 51, 61, 63, 64, 71, 73;

  CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32 , 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57 : 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104 , 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179 , 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265;

  CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39; CI pigment blue 1, 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 66; CI Pigment green 7, 36, 37; CI Pigment Brown 23, 25, 28; CI Pigment black 1, 7 and the like.

  When the present photosensitive resin composition is the above-mentioned red photosensitive resin composition, the content of the red pigment is alkali-soluble resin (A), polymerizable compound (B) having an ethylenically unsaturated bond, and photopolymerization initiation. It is 28-46 mass% with respect to the total mass of an agent (C) and a pigment (D), Preferably it is 32-44 mass%, More preferably, it is 36-42 mass%. Moreover, in the case of the same green photosensitive resin composition, content of a green pigment is 32-51 mass% with respect to the same total mass, Preferably it is 36-50 mass%, More preferably, it is 38-49 mass%. Moreover, in the same blue photosensitive resin composition, content of a blue pigment is 25-45 mass% with respect to the same total mass, Preferably it is 30-42 mass%, More preferably, it is 25-45 mass%. By including the pigment of each color in the photosensitive resin composition in the blending amount as described above, the sensitivity at the time of exposure after application of the resin composition is good, and after performing the development treatment, Residues on the unexposed portion of the substrate or on the black matrix do not occur, there is no undercut, and the color filter formed using the resin compound can have good saturation and contrast.

  In the present photosensitive resin composition, the average particle diameter of the primary particles of the pigment (D) is preferably 10 to 200 nm, more preferably 20 to 150 nm, and most preferably 30 to 100 nm. In particular, when the present photosensitive resin composition is applied to a high-saturation liquid crystal display or television, it is preferable to increase the concentration of the pigment in the photosensitive resin composition and use a pigment having a small average particle size of primary particles. It is.

  As a means of reducing the average particle size of the primary particles of the pigment (D), a method of reducing the particle size by mechanically pulverizing the pigment (grinding method), a particle dissolved in a good solvent is added to the poor solvent Examples thereof include a method for precipitating a pigment having a small diameter (precipitation method), a method for producing particles having a small particle diameter at the time of synthesis (synthetic precipitation method), and the like.

  Note that “high saturation” satisfies the following criteria. That is, a photosensitive resin composition is applied onto a substrate, and steps such as drying under reduced pressure, pre-baking and post-baking are performed to form a photosensitive resin layer having a thickness of 2.0 μm on the substrate. Using a chromaticity meter (C light source), chromaticity coordinates (x, y) of the photosensitive resin layer are made and evaluated. The chromaticity coordinates deserving “high saturation” are in the following ranges, respectively.

(1) Red photosensitive resin layer
(0.62 ≦ x ≦ 0.67) and (0.26 ≦ y ≦ 0.41),
More preferably, (0.65 ≦ x ≦ 0.67) and (0.29 ≦ y ≦ 0.37)
(2) Green photosensitive resin layer
(0.11 ≦ x ≦ 0.32) and (0.58 ≦ y ≦ 0.75),
More preferably, (0.12 ≦ x ≦ 0.29) and (0.60 ≦ y ≦ 0.75)
(3) Blue photosensitive resin layer
(0.10 ≦ x ≦ 0.21) and (0.04 ≦ y ≦ 0.13)
More preferably, (0.11 ≦ x ≦ 0.19) and (0.04 ≦ y ≦ 0.10)

The pigment (D) can be used together with a dispersant if desired. Such a dispersant typically includes a surfactant, but is not limited thereto. As the surfactant, a cationic, anionic, nonionic, amphoteric, silicone, or fluorine-based surfactant can be selected and used as necessary. More specifically,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene Polyethylene glycol diesters such as glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethane; the following are trade names: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427 (Toray Industries, Inc.)・ Dow Corning), Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), F Top (manufactured by Gemco Co., Ltd.), MegaFuck (manufactured by Dainippon Ink & Chemicals), Florard 3M Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co.) and the like. These surfactants can be used alone or in combination of two or more.

  The usage-amount of these dispersing agents, such as surfactant, is 0-6 mass parts with respect to alkali-soluble resin (A), Preferably it is 0-4 mass parts, More preferably, it is 0-3 mass parts.

[Organic solvent (E)]
The photosensitive resin composition is a composition in which the organic solvent (E) is contained and each of the above components (A) to (D) is dissolved. Usually, components (A) to (C) other than the pigment (D) are dissolved in the organic solvent (E) to prepare a liquid composition, and then the pigment (D) is added and mixed uniformly. The photosensitive resin composition is produced.

  As the organic solvent (E), at least one of the above-described components (A) to (C) can be dissolved, and one having appropriate volatility without reacting with these components is used. Or it can select and use 2 or more types. Specifically, it is the same as the solvent that can be used for the alkali-soluble resin (A) described above, but propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate is particularly preferable.

  The content of the organic solvent (E) in the photosensitive resin composition [including the solvent used for the alkali-soluble resin (A)] is preferably 500 to 5000 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). Is 800 to 4500 parts by mass, more preferably 1000 to 4000 parts by mass.

[Other additives]
(1) Surfactant In the present photosensitive resin composition, it is possible to contain a surfactant in order to improve the coating property. The surfactant that can be contained is the same as the surfactant that can be used as the dispersant for the pigment (D). The content of the surfactant in the photosensitive resin composition is 0 to 6 parts by mass, preferably 0 to 4 parts by mass, and more preferably 0 to 3 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). Part by mass.

(2) Various additives The present photosensitive resin composition may contain various additives as required. For example, fillers such as glass and alumina; polymer compounds other than alkali-soluble resins (A) such as polyvinyl alcohol, polyethylene glycol monoalkyl ether and polyfluoroalkyl acrylate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2 -Methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane Adhesion promoters such as 3-mercaptopropyltrimethoxysilane; antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol; 2- (3- and ultraviolet absorbers such as t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

  Although the compounding quantity of these additives can be set according to the kind and purpose of an additive, it is 0-10 mass parts with respect to 100 mass parts of alkali-soluble resin (A), Preferably it is 0-6 mass. Part, more preferably 0 to 3 parts by mass.

  The present photosensitive resin composition containing the above components (A) to (E) as essential components has good sensitivity at the time of exposure even when the concentration of the pigment (D) is increased, and is formed after development. Photosensitive resin composition that has good saturation and contrast of pixels, no undercuts, no residue, and can be used in liquid crystal displays, charge coupled devices, etc. It is a thing.

[Color filter]
As described above, the color filter is a color filter using the photosensitive resin composition as a raw material for the pixel colored layer.

Examples of the method for producing the color filter include a method using the following steps.
(1) Formation process of prebaked coating film This photosensitive resin composition is apply | coated on a board | substrate by application | coating means, such as spin coating, cast coating, or roll coating. After the application, the solvent is almost removed by drying under reduced pressure or the like, and then the solvent is almost completely removed by pre-baking, whereby a pre-baked coating film is formed on the substrate. The substrate used here is, for example, a glass substrate such as non-alkaline glass, soda glass, Pyrex (registered trademark) glass, or quartz glass used for a liquid crystal display or the like, and a transparent conductive film attached to these glass substrates, Examples include a photoelectric conversion element substrate (for example, a silicon substrate) used for a solid-state imaging element or the like. On these substrates, generally, a black matrix for isolating each pixel is formed. The conditions for vacuum drying and pre-baking vary depending on the constituent components and blending ratio of the photosensitive resin composition, but usually vacuum drying is performed for about 1 to 60 seconds under a pressure of 0 to 200 mmHg, while pre-baking is 70 ˜110 ° C. for about 1 to 15 minutes.

(2) Pattern forming process After performing the pre-baking process, the pre-baked coating film formed on the substrate is exposed through a predetermined pattern mask, and developed with a developer at a temperature of 23 ± 2 ° C. for 15 seconds to 5 minutes. By doing so, an unnecessary part can be removed and a predetermined pattern can be formed on a coating film. The light rays used for exposure are preferably ultraviolet rays such as g-line, h-line and i-line. Examples of the ultraviolet irradiation device include a high-pressure mercury lamp and a metal halide lamp.

  Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethyl. Concentration of an alkaline compound such as ammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo (5,4,0) -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0 An alkaline aqueous solution dissolved in water can be used so that the amount is 0.005 to 5% by mass, more preferably 0.01 to 1% by mass.

  When the above development is performed using a developer composed of such an alkaline aqueous solution, it is preferable to wash with water after completion of the development and to air dry with compressed air or compressed nitrogen. By performing such a process, the pattern can be easily formed on the coating film.

(3) Post-bake process After performing the above-mentioned pattern formation process, it is heated at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 60 minutes on a hot plate, and 15 to 150 minutes in an oven. By processing (post-baking), a pattern composed of pixels having a target colored pixel layer can be obtained.

(4) Formation of colored pixel layer of each color By repeating this process for each color (mainly three colors of red, green, and blue), a color filter in which a pixel pattern of each color is formed can be manufactured. Furthermore, an ITO (indium tin oxide) vapor deposition film is formed on the colored pixel layer thus formed under a vacuum of about 220 ° C. to 250 ° C., and etched into the ITO film as necessary. After the wiring is formed, a color filter that can be suitably used for a liquid crystal display can be manufactured by applying and baking a polyimide varnish for a liquid crystal alignment film.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited by the examples.

[Synthesis of alkali-soluble resin (A)]
[Synthesis Example a]
In a 500 ml separable flask equipped with an air inlet, a stirrer, a heater, a cooling tube and a thermometer under an air atmosphere, the raw material composition [100 parts by mass of an epoxy group-containing bisphenolfluorene compound (general formula) a compound represented by (a2-21), epoxy equivalent 230), 0.3 part by mass of tetramethylammonium chloride, 0.1 part by mass of 2,6-di-t-butyl-p-cresol, 30 parts by mass of acrylic acid, and Propylene glycol monomethyl ether acetate consisting of 130 parts by mass] was continuously added, and the reaction was performed at a flow rate of 25 ml / min and a temperature of 100 to 110 ° C. for 15 hours.

  As a result, a bisphenolfluorene type epoxy acrylate compound was obtained as a light yellow transparent mixed solution (EA) having a solid content concentration of 50% by mass.

  Then, in a 300 ml separable flask, 100 parts by mass of the above EA, 25 parts by mass of propylene glycol monomethyl ether acetate, 13 parts by mass of benzophenone tetracarboxylic dianhydride, and 1,2,3,6-tetrahydrophthalic anhydride 6 parts by mass were charged and reacted at a temperature of 110 to 115 ° C. for 2 hours to obtain a yellow transparent alkali-soluble resin solution. After completion of the polymerization reaction, the polymerization product was taken out from the separable flask and the solvent was devolatilized to obtain an alkali-soluble resin (A2-1) having an ethylenically unsaturated bond. The obtained resin had an acid value of 98.4 mgKOH / g and a weight average molecular weight of 4,200.

[Synthesis Example b]
In a 300 ml separable flask, 100 parts by weight of a light yellow transparent mixed solution (EA) obtained in the process of Synthesis Example a, 25 parts by weight of propylene glycol monomethyl ether acetate, and 13 parts by weight of benzophenone tetracarboxylic dianhydride The reaction mixture was reacted at 90 to 95 ° C. for 2 hours. After confirming the disappearance of the acid anhydride group in the reaction solution by IR spectrum, 6 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride was added. The mixture was reacted at a temperature of 90 to 95 ° C. for 4 hours to obtain a pale yellow transparent alkali-soluble resin solution. After completion of the polymerization reaction, the polymerization product was taken out from the separable flask and the solvent was devolatilized to obtain an alkali-soluble resin (A2-2) having an ethylenically unsaturated bond. The obtained resin had an acid value of 99.3 mg KOH / g and a weight average molecular weight of 4000.

[Synthesis Example c]
Under a nitrogen gas atmosphere, a raw material composition [35 parts by weight of methacrylic acid monomer, benzyl methacrylate] was added to a 300 ml four-necked flask equipped with a nitrogen gas inlet, a stirrer, a heater, a condenser tube and a thermometer. 40 parts by weight of monomer, 10 parts by weight of styrene monomer, 15 parts by weight of methyl acrylate monomer, 3.8 parts by weight of 2,2′-azobis-2-methylbutyronitrile as a photopolymerization initiator -Consisting of 210 parts by mass of ethyl ethoxypropionate] was added all at once and the polymerization reaction was carried out. In the polymerization reaction, the reaction temperature was 100 ° C., and the reaction time was 6 hours. After completion of the polymerization, the polymerization product was taken out from the four-necked flask and the solvent was devolatilized to obtain an alkali-soluble resin (A1-1) containing no ethylenically unsaturated bond.

[This photosensitive resin composition]
[Example 1]
70 parts by mass (solid content) of the alkali-soluble resin (A1-1) obtained in Synthesis Example c, and 30 parts by mass (solid content) of the alkali-soluble resin (A2-2) obtained in Synthesis Example b. 130 parts by mass of dipentaerythritol hexaacrylate (DPHA) shown in Table 1, 15 parts by mass of 2- (2,4-dichlorophenyl) -4,5-diphenylimidazole dimer of photopolymerization initiator (C1), photopolymerization Initiator (C2), ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) 35 parts by mass, photopolymerization initiator ( C ′) 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone (hereinafter referred to as “369”), 20 parts by mass, green pigment (CI36 / CI150 = 75 / 25) Using 250 parts by mass, 1300 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as solvent and 3-ethoxypropion After addition of ethyl (EEP) 1000 parts by mass, a vibration stirrer, dissolution, be mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was evaluated by each evaluation method (below). The results are also shown in Table 1. In Table 1, A1 / (A1 + A2) mass% represents the mass% that the alkali-soluble resin (A1) accounts for the total amount of the alkali-soluble resin (A1) and the alkali-soluble resin (A2), and C2 / ( C1 + C2) mass% represents the mass% of the photopolymerization initiator (C2) with respect to the total mass of the photopolymerization initiator (C1) and the photopolymerization initiator (C2), and D / (A + B + C + D)% by mass is the total amount of pigment (D) consisting of an alkali-soluble resin (A), a polymerizable compound (B) having an ethylenically unsaturated bond, a photopolymerization initiator (C), and a pigment (D). The mass% occupied with respect to is expressed.

[Examples 2 to 10]
The same operation method as in Example 1 was followed. The blending contents and evaluation results are shown in Table 1.

[Comparative Examples 1 to 11]
The same operation method as in Example 1 was followed. The blending contents and evaluation results are shown in Table 1.

[Evaluation methods]
(1) Sensitivity The photosensitive resin composition to be tested was applied on a 100 mm × 100 mm glass substrate by a spin coating method, and the coating film was dried under reduced pressure for 30 seconds under a pressure of 100 mmHg, and then at 80 ° C. Pre-baking was performed for 3 minutes to form a pre-baked coating film having a thickness of 2.5 μm.

A T2115 type negative film (21 steps of different optical density steps) made by Stouffer was adhered to the above pre-baked coating film, and a light amount of 800 mJ / cm ² was irradiated using a 20 W high-pressure mercury lamp toward this, After immersing in a 23 ° C. developer (0.04 mass% potassium hydroxide aqueous solution) for 2 minutes, it was rinsed with pure water. Next, the number of steps of the negative film with respect to the developer was examined for this coating film and evaluated according to the following criteria (in this evaluation method, the higher the sensitivity, the greater the number of remaining steps).

○: Number of steps 9 to 21
Δ: 7 to 8 steps
X: Number of stages 1-6

(2) Saturation After irradiating the coating film with an amount of ultraviolet light (exposure machine: Canon PLA-501F) of 300 mJ / cm ² using the same pre-baking coating film as that used in the sensitivity test of (1) above. , Immersed in a developer at 23 ° C., developed for 2 minutes, washed with pure water, further post-baked at 200 ° C. for 80 minutes to form a photosensitive resin layer having a thickness of 2.0 μm on the glass substrate. Formed.

  Subsequently, the colorimetric coordinate (x, y) of the photosensitive resin layer was measured with a C light source using a colorimeter (manufactured by Otsuka Electronics Co., Ltd., model number MCPD), and a determination was made based on the following criteria. .

Red ○: (0.65 ≦ x ≦ 0.67) and (0.29 ≦ y ≦ 0.37)
Green ○: (0.12 ≦ x ≦ 0.29) and (0.60 ≦ y ≦ 0.75)
Blue ○: (0.11 ≦ x ≦ 0.19) and (0.04 ≦ y ≦ 0.10)

Red △: (0.62 ≦ x <0.65) and (0.26 ≦ y ≦ 0.41)
Green △: (0.11 ≦ x ≦ 0.32) and (0.58 ≦ y <0.60)
Blue △: (0.10 ≦ x ≦ 0.21) and (0.10 <y ≦ 0.13)

Red ×: Range other than red ○ and Δ above Green ×: Range other than the above green ○ and Δ Blue ×: Range other than the above blue ○ and Δ

(3) Contrast Contrast was measured by the method shown in FIGS. That is, between the two polarizing plates 2 and 3, the same photosensitive resin layer 1 as the photosensitive resin layer used in the saturation test of the above (2) is placed, and light is irradiated from the light source 4, and the polarizing plate 2. The amount of light (cd / cm ² ) transmitted through the photosensitive resin layer 1 and the polarizing plate 3 was measured with a luminance meter 5 (“BM-5A” manufactured by Topcon Japan).

  The amount of light A (parallel) when the polarization direction of the polarizing plate 3 is parallel to the polarization direction of the polarizing plate 2 as shown in FIG. 1, and the polarization direction of the polarizing plate 3 is changed to the polarization of the polarizing plate 2 as shown in FIG. The amount of light B (cross) in the case of being perpendicular to the direction was measured, the contrast was calculated as a ratio value (light amount A / light amount B) of the light amount A and the light amount B, and evaluation was performed according to the following criteria.

○: Red 1200 ≦ Contrast ○: Green 1500 ≦ Contrast ○: Blue 1000 ≦ Contrast

Δ: Red 700 ≦ Contrast <1200
Δ: Green 900 ≦ Contrast <1500
Δ: Blue 600 ≦ Contrast <1000

×: Red contrast <700
×: Green contrast <900
×: Blue contrast <600

(4) Undercut The pattern on the surface of the photosensitive resin layer used in the saturation test of (2) above is undercut on the basis of the following criteria based on the shape of the edge profile using a scanning electron microscope (SEM). Evaluated.

◯: As shown in FIG. 3, the taper angle (angle with respect to the substrate 14) of the line of the photosensitive resin pattern 12 is 0 ° ≦ θ ₁ ≦ 60 °.
Δ: As shown in FIG. 4, the taper angle of the line of the photosensitive resin pattern 22 is 60 ° <θ ₂ ≦ 90 ° ×: As shown in FIG. The taper angle of the line is 90 ° <θ ₃ <180 °.

(5) Residue Using the same pre-baked coating film as the pre-baked coating film used in the sensitivity test in (1) above, a predetermined mask is installed, and the amount of ultraviolet light (exposure machine: Canon PLA-501F) is 300 mJ / cm ² . After being immersed in a developer at 23 ° C. (0.04 mass% potassium hydroxide aqueous solution), developed for 2 minutes, washed with pure water, and further post-baked at 200 ° C. for 80 minutes. A required photosensitive resin design pattern was formed on a glass substrate. The obtained pattern was observed with a microscope, it was confirmed whether or not there was a residue in the unexposed portion, and evaluation was performed according to the following criteria.

○: There is no residue.
Δ: There is a little residue.
X: There are many residues.

The evaluation results obtained in the above tests are shown in Table 1.

  As is apparent from Table 1, the tests (1) to (5) conducted using the photosensitive resin compositions (Examples 1 to 10) within the specified range of the present invention are the same in any test items. The highest evaluation was obtained.

  On the other hand, Comparative Example 1 in which the content of the red pigment is too small was inferior in the evaluation of saturation. On the contrary, Comparative Example 2 in which the content of the red pigment is too large was inferior in sensitivity and contrast, and a residue was observed. Moreover, the tendency for the undercut to be inferior was recognized. Moreover, the comparative example 3 with too little content of the green pigment was inferior in the evaluation of saturation. On the contrary, Comparative Example 4 in which the content of the green pigment is too large was inferior in sensitivity, contrast and undercut, and a residue was also observed. In addition, Comparative Example 5 in which the content of the blue pigment was too small was inferior in the evaluation of saturation. On the contrary, Comparative Example 6 in which the content of the green pigment is too large is inferior in contrast and undercut, tends to be inferior in sensitivity, and tends to recognize residues.

Furthermore, the undercut was inferior in Comparative Example 7 in which (C1) was not used as the photopolymerization initiator (C). Moreover, the comparative example 8 in which the ratio of (A1) in the alkali-soluble resin (A) is too small relative to (A2) was inferior in contrast and undercut, and a residue was also observed. On the contrary, Comparative Example 9 in which all of the alkali-soluble resin (A) is (A1) was inferior in sensitivity.
Further, Comparative Example 10 in which the ratio of the initiator (C2) in the photopolymerization initiator (C) was too high was found to be inferior in undercut and inferior in saturation and contrast. Conversely, Comparative Example 11 in which the ratio of the initiator (C2) is too small was inferior in sensitivity and undercut.

It is a sketch (1) of the measurement state with respect to the contrast of the photosensitive resin layer. It is a sketch (2) of the measurement state with respect to the contrast of the photosensitive resin layer. It is drawing which showed the 1st type edge side state of the photosensitive resin pattern. It is drawing which showed the 2nd type edge side surface state of the photosensitive resin pattern. It is drawing which showed the 3rd type edge side surface state of the photosensitive resin pattern.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive resin layer 2 Polarizing plate 3 Polarizing plate 4 Light source 5 Luminance (light quantity) meter 12 Photosensitive resin pattern 14 Substrate 22 Photosensitive resin pattern 32 Photosensitive resin pattern

Claims (3)

A photosensitive resin composition for a color filter, comprising the following (A) to (E):
(A) Alkali-soluble resin [The alkali-soluble resin (A) contains an alkali-soluble resin (A1) having no ethylenically unsaturated bond and an alkali-soluble resin (A2) having an ethylenically unsaturated bond, and The alkali-soluble resin (A1) accounts for 40 to 95% by mass with respect to the total mass of the alkali-soluble resin (A1) and the alkali-soluble resin (A2).
(B) a polymerizable compound having an ethylenically unsaturated bond (C) a photopolymerization initiator (C1) of biimidazoles and a photopolymerization initiator (C2) represented by the following general formula (c2-1) [In the photopolymerization initiator (C), the photopolymerization initiator (C2) is 10 to 10% of the total mass of the photopolymerization initiator (C1) and the photopolymerization initiator (C2). Occupies 98% by mass]
Wherein, Z ₁ represents a hydrogen atom, an alkyl group, an aryl group, a mercapto group, an alkylthio group, an arylthio group, a benzylthio group, a hydroxyl group, an alkyloxy group, an aryloxy group, or a benzyloxy group, Z ₂ Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom]
(D) Pigment [In the case where the color filter resin composition is a red photosensitive resin composition, the pigment (D) is an alkali-soluble resin (A), a polymerizable compound having an ethylenically unsaturated bond (B ), 28 to 46% by mass based on the total mass of the photopolymerizable initiator (C) and the pigment (D), and in the green photosensitive resin composition, 32 to 51% by mass, In the case of a blue photosensitive resin composition, 25 to 45% by mass is blended]
(E) Organic solvent 2. The color filter photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A2) having an ethylenically unsaturated bond is an alkali-soluble resin containing bisphenolfluorene in the molecule. Photosensitive resin composition. A color filter using the photosensitive resin composition for a color filter as a raw material for a pixel colored layer.