TWI537348B - Photosensitive resin composition for color filter and its application - Google Patents

Description

Photosensitive resin composition for color filter and application thereof

The present invention relates to a photosensitive resin composition for a color filter of a liquid crystal display and a color filter formed therefor. In particular, a photosensitive resin composition for a color filter having a high-definition pattern linearity, a good thermal solvent film thickness change rate, and a good surface roughness is provided.

At present, color filters have been widely used in applications such as color liquid crystal displays, color facsimile machines, color cameras, and the like. With the increasing market demand for image devices such as color liquid crystal displays, the production techniques of color filters are also diversified.

The color filter can be generally obtained by forming a red, green, blue or the like on a transparent glass substrate by a method such as a dyeing method, a printing method, an electrophoresis method, or a pigment dispersion method. In general, in order to improve the contrast of the color filter, a light shielding layer (or a black matrix) may be disposed between the pixel colored layers.

The process of the above pigment dispersion method is to form a colored photosensitive resin composition by dispersing a pigment in a photocurable resin, and finally forming the resin composition into a pixel colored layer. Further, in the process of the pigment dispersion method, a black matrix is usually formed on a transparent support such as a glass substrate by using a metal such as chromium or chromium oxide or a photosensitive resin light-shielding film. Then, the photosensitive resin (color resist) in which the red pigment is dispersed is applied onto the transparent support by spin coating, exposed by a photomask, and developed after exposure. You can get red pixels. Then, in the same operation mode, that is, the coating, exposure, and development can be repeatedly used to obtain three-color pixels such as red, green, and blue on the support.

In recent years, the use of color liquid crystal displays is no longer limited to personal computers, but also widely used in color TVs and various surveillance screens (especially large-size color LCD screens), so the requirements for color saturation of liquid crystal displays are increasing. high. Therefore, the proportion of the pigment contained in the photosensitive resin composition is also higher and higher, and the relative use amount of the alkali-soluble resin and the photosensitive monomer is decreased, resulting in a decrease in the degree of crosslinking after exposure, resulting in problems such as poor surface roughness. .

In the content disclosed in Japanese Laid-Open Patent Publication No. 2004-138950, a specific color-soluble resin having a good surface roughness and a color filter excellent in pattern shape and brightness can be formed by using a specific alkali-soluble resin. It is easy to cause a change in the film thickness of the thermal solvent film of the photosensitive resin composition, and the pattern linearity of high definition is not good.

In view of the above, there is an urgent need to develop a photosensitive resin composition for a color filter having a high-definition pattern linearity, a thermal solvent film thickness change rate, and a good surface roughness to overcome the conventional color filter. The above problem of the film.

The present invention provides a photosensitive resin for a color filter having a high-definition pattern linearity, a thermal solvent film thickness change rate, and a surface roughness by providing a special alkali-soluble resin and a compound component having an ethylenically unsaturated group. Composition.

The present invention provides a photosensitive resin composition for a color filter, the composition comprising: an organic pigment (A); a dye (B); an alkali-soluble resin (C); a compound (D) having an ethylenically unsaturated group; a photoinitiator (E); and an organic solvent (F); wherein: the compound (D) having an ethylenically unsaturated group contains the first compound (D-1), and the first compound (D-1) is The polyfluorenyl compound represented by the formula (b) is formed by reacting with a polyfunctional (meth) acrylate represented by the formula (a). In the formula (a): X ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and X ² represents a residue after esterification of n hydroxyl groups in a hydroxyl group-containing compound having m hydroxyl groups, wherein m≧ n, m and n each independently represent an integer of 2 to 20; the hydroxyl group-containing compound having m hydroxyl groups is X ³ (OH) _m or X ³ (OH) _m via propylene oxide, epoxy chloride a compound modified with epichlorohydrin, an alkyl group, an alkoxy group or a hydroxypropyl acrylate; and X ³ (OH) _m is a polyalcohol having a carbon number of 2 to 18, from which the poly a polyhydric alcohol ethers formed by an alcohol, an ester formed by reacting the polyol with an acid, or a silicone; In the formula (b): X ⁴ represents a single bond, a hydrocarbon group having a carbon number of 1, or a linear or branched hydrocarbon group having a carbon number of 2 to 22, and the skeleton of X ⁴ may further include a sulfur atom or constitute an ester group. An oxygen atom; and p represents an integer of 2 to 6, wherein when X ⁴ represents a single bond, p represents 2; when X ⁴ represents a hydrocarbon group having a carbon number of 1, p represents an integer of 2 to 4; when X ⁴ represents When the carbon number is a linear or branched hydrocarbon group of 2 to 22, p represents an integer of 2 to 6.

The present invention also provides a method of producing a color filter which forms a pixel layer using the photosensitive resin composition for a color filter described above.

The present invention further provides a color filter which is produced by the aforementioned method.

The present invention further provides a liquid crystal display device comprising the above-described color filter.

The present invention provides a photosensitive resin composition for a color filter, the composition comprising: an organic pigment (A); a dye (B); an alkali-soluble resin (C); a compound (D) having an ethylenically unsaturated group; a photoinitiator (E); and an organic solvent (F); wherein: the compound (D) having an ethylenically unsaturated group contains the first compound (D-1), and the first compound (D-1) is The polyfluorenyl compound represented by the formula (b) is formed by reacting with a polyfunctional (meth) acrylate represented by the formula (a). In the formula (a): X ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and X ² represents a residue after esterification of n hydroxyl groups in a hydroxyl group-containing compound having m hydroxyl groups, wherein m≧ n, m and n each independently represent an integer of 2 to 20; the hydroxyl group-containing compound having m hydroxyl groups is X ³ (OH) _m or X ³ (OH) _m via propylene oxide, epoxy chloride a compound modified with epichlorohydrin, an alkyl group, an alkoxy group or a hydroxypropyl acrylate; and X ³ (OH) _m is a polyalcohol having a carbon number of 2 to 18, from which the poly a polyhydric alcohol ethers formed by an alcohol, an ester formed by reacting the polyol with an acid, or a silicone; In the formula (b): X ⁴ represents a single bond, a hydrocarbon group having a carbon number of 1, or a linear or branched hydrocarbon group having a carbon number of 2 to 22, and the skeleton of X ⁴ may further include a sulfur atom or constitute an ester group. An oxygen atom; and p represents an integer of 2 to 6, wherein when X ⁴ represents a single bond, p represents 2; when X ⁴ represents a hydrocarbon group having a carbon number of 1, p represents an integer of 2 to 4; when X ⁴ represents When the carbon number is a linear or branched hydrocarbon group of 2 to 22, p represents an integer of 2 to 6.

The organic pigment (A) according to the present invention provides a blue pigment.

In one embodiment of the present invention, the organic pigment (A) is used in an amount ranging from 50 parts by weight to 500 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably 60 parts by weight. Parts to 400 parts by weight; more preferably 70 parts by weight to 300 parts by weight.

Preferably, the organic pigment (A) comprises a blue organic pigment (A-1) mainly composed of a copper phthalocyanine structure. The blue pigment (A-1) mainly composed of a copper phthalocyanine structure may be used singly or in combination, and the blue pigment (A-1) mainly composed of a copper phthalocyanine structure includes, but is not limited to, CI Pigment Blue 15: 1 (CIPB 15:1), CI Pigment Blue 15:2 (CIPB 15:2), CI Pigment Blue 15:3 (CIPB 15:3), CI Pigment Blue 15:4 (CIPB 15:4), CI Pigment Blue 15:5 (CI PB15: 5), or C.I. Pigment Blue 15:6 (C.I.PB15:6).

In a specific example of the present invention, the total amount of the alkali-soluble resin (C) used is 100 parts by weight, and the amount of the blue organic pigment (A-1) mainly composed of the copper phthalocyanine structure is 40. The parts by weight to 400 parts by weight; preferably 45 parts by weight to 320 parts by weight; more preferably 50 parts by weight to 240 parts by weight.

Preferably, the organic pigment (A) further comprises a purple organic pigment (A-2). The purple pigment (A-2) may be used singly or in combination, and the purple pigment (A-2) includes, but is not limited to, CI Pigment Violet 14 (CIPV14), CI Pigment Violet 19 (CIPV19), CI Pigment Violet 23 ( CIPV23), CI Pigment Violet 29 (CIPV29), CI Pigment Violet 32 (CIPV32), CI Pigment Violet 33 (CIPV33), CI Pigment Violet 36 (CIPV36), CI Pigment Violet 37 (CIPV37), CI Pigment Violet 38 (CIPV38), CI Pigment Violet 40 (CIPV40), or CI Pigment Violet 50 (CIPV50).

In a specific example of the present invention, the purple organic pigment (A-2) is used in an amount ranging from 10 parts by weight to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); It is from 15 parts by weight to 80 parts by weight; more preferably from 20 parts by weight to 60 parts by weight.

The organic pigment (A) may contain a blue pigment (A-3) other than (A-1).

The blue pigment (A-3) other than the (A-1) includes, but is not limited to, CI Pigment Blue 1, CI Pigment Blue 21, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 61, CI Pigment Blue 64, Or such a combination. The blue pigment (A-3) other than the (A-1) may be used singly or in combination.

In another embodiment of the present invention, in order to adjust the chromaticity, the organic pigment (A) may comprise a green pigment mainly composed of a halogenated phthalocyanine structure.

Preferably, the green pigment mainly composed of a halogenated phthalocyanine structure includes, but not limited to, C.I. Pigment Green 07, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 42, or C.I. Pigment Green 58. More preferably, the green pigment component mainly composed of a halogenated phthalocyanine structure is C.I. Pigment Green 07, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 42, C.I. Pigment Green 58, or such combinations. The green pigment mainly composed of a halogenated phthalocyanine structure may be used singly or in combination.

The photosensitive resin composition for a color filter according to the present invention contains the dye (B). Preferably, the dye (B) comprises a red dye having the structure of formula (I): In the formula (I), R ¹ to R ⁴ each independently represent hydrogen, -R ⁶ , C ₆ to C ₁₀ aromatic hydrocarbon group, or a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -COOH, -COOR ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ substituted C ₆ to C ₁₀ aromatic hydrocarbon group; R ⁵ Represents -SO ₃ ^- , -SO ₃ H, -SO ³ M, -COOH, -COOR ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ; m represents an integer from 0 to 5 When m represents 2 to 5, a plurality of R ⁵ are the same or different; X represents a halogen atom; a represents 0 or 1; and R ⁶ represents a C ₁ to C ₁₀ alkyl group or a C ₁ to C substituted by a halogen atom; An alkyl group of ₁₀ , wherein the C ₁ to C ₁₀ alkyl group or the -CH ₂ - group in the C ₁ to C ₁₀ alkyl group substituted by a halogen atom is unsubstituted or substituted with -O-, a carbonyl group or - NR ⁷ -; R ⁷ represents a C ₁ to C ₁₀ alkyl group of the halogen atom or substituted C ₁ to C ₁₀ alkyl group of; R ⁸ and R ⁹ each independently represents a linear chain of C ₁ to C ₁₀ alkyl, C branched alkyl of ₁ to C _10, cycloalkyl group of C ₃ to C _30, or -Q is; wherein, C straight chain alkyl of ₁ to C _10, C branched alkyl of ₁ to C ₁₀ or C ₃ system to a hydrogen atom of the cycloalkyl group of C ₃₀ without A substituted or substituted by a substituent group, the substituent is selected from the group consisting of a hydroxyl group, the group consisting of a halogen atom, -Q, -CH = CH ₂ and -CH = CH-R ^6; C straight-chain alkyl of ₁ to C ₁₀ The -CH ₂ - group in the C ₁ to C ₁₀ branched alkyl group or the C ₃ to C ₃₀ cycloalkyl group is unsubstituted or substituted with -O-, carbonyl or -NR ⁷ -; or R ⁸ and R ⁹ combine to form a C ₁ to C ₁₀ heterocyclic group, the heterocyclic group wherein the C ₁ to C ₁₀ in the hydrogen system of unsubstituted or R ^6, -OH, substituted or -Q; Q represents C ₆ to C ₁₀ aromatic hydrocarbon group, C ₅ to C ₁₀ heteroaryl group, via halogen atom, -R ⁶ , -OH, -OR ⁶ , -NO ₂ , -CH=CH ₂ or -CH=CH-R ⁶ the substitution of C ₆ to C ₁₀ aromatic hydrocarbon group, or a halogen ^{atom, -R 6, -OH, -OR 6} , -NO 2, -CH = CH 2 and -CH = CH-R ⁶ substituents of C ₅ to C _a heteroaromatic group of ₁₀ ; and M represents potassium or sodium.

Preferably, the R ⁶ includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl. , cyclohexyl, heptyl, cycloheptane, octyl, cyclooctyl, 2-ethylhexyl, decyl, decyl, tricyclo [5.3.0.0 ^3,10 ] fluorenyl [tricycle (5.3.0.0 ^{3, 10} ) decanyl], methoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, or epoxypropyl.

Preferably, the C ₆ to C ₁₀ aromatic hydrocarbon group includes, but is not limited to, a phenyl group or a naphthyl group and the like.

Preferably, the -SO ₃ R ⁶ includes, but is not limited to, methanesulfonyl, ethanesulfonyl, hexanesulfonyl, or decanesulfonyl.

Preferably, the -COOR ⁶ includes, but is not limited to, methyloxycarbonyl, ethyloxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, Pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptoxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, Cyclooctyloxycarbonyl, 2-ethylhexyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl, tricyclo[5.3.0.0 ^3,10 ]decylcarbonyl, methoxypropoxycarbonyl, hexyloxy Propyloxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, or methoxyhexyloxycarbonyl.

Preferably, the -SO ₂ NHR ⁸ includes, but is not limited to, sulfamoyl, methylamine sulfonyl, ethylamine sulfonyl, propylamine sulfonyl, isopropylamine sulfonyl , butylamine sulfonyl, isobutylamine sulfonyl, pentylamine sulfonyl, isoamylamine sulfonyl, neopentylamine sulfonyl, cyclopentylamine sulfonyl, hexylamine sulfonate Mercapto, cyclohexylamine sulfonyl, heptylamine sulfonyl, cycloheptylamine sulfonyl, octylamine sulfonyl, cyclooctylamine sulfonyl, 2-ethylhexylamine sulfonyl, Hydrazinylsulfonyl, decylamine sulfonyl, tricyclo[5.3.0.0 ^3,10 ]decylamine sulfonyl, methoxypropylamine sulfonyl, hexyloxypropylamine sulfonyl , 2-ethylhexyloxypropylamine sulfonyl, methoxyhexylamine sulfonyl, epoxy propyl sulfonyl, 1,5-dimethylhexylamine sulfonyl, propoxy Propylsulfonyl, isopropoxypropylamine sulfonyl, 3-phenyl-1-methylpropylamine sulfonyl, (R ^a represents a substituted alkyl group of C ₁ to C _3, the C ₁ to C ₃ alkoxy group, the substituted alkyl group or a halogen atom of the halogen atom C ₁ to C ₃ of the C ₁ to C ₃ alkyl-oxy base), (R ^b represents a substituted alkyl group of C ₁ to C _3, the C ₁ to C ₃ alkoxy group, the substituted alkyl group or a halogen atom of the halogen atom C ₁ to C ₃ of the C ₁ to C ₃ alkyl-oxy base),

Preferably, the -SO ₂ NR ⁸ R ⁹ includes but is not limited to (R ^b represents a substituted alkyl group of C ₁ to C _3, the C ₁ to C ₃ alkoxy group, the substituted alkyl group or a halogen atom of the halogen atom C ₁ to C ₃ of the C ₁ to C ₃ alkyl-oxy base),

Preferably, the dye (B) comprises a red dye having the structure of formula (I-1): In the formula (I-1), R ¹¹ to R ¹⁴ each independently represent hydrogen, -R ⁶ , C ₆ to C ₁₀ aromatic hydrocarbon group, or a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO _a C ₆ to C ₁₀ aromatic hydrocarbon group substituted with ₃ ^- , -SO ₃ H, -SO ₃ Na, -COOH, -COOR ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ; R ¹⁵ represents hydrogen, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ; R ¹⁶ represents -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ; X ¹ represents a halogen atom; a ¹ represents 0 or 1.

Preferably, the dye (B) comprises a red dye having the structure of formula (I-2): In the formula (I-2), R ²¹ to R ²⁴ each independently represent hydrogen, -R ²⁶ , C ₆ to C ₁₀ aromatic hydrocarbon group, or a halogen atom, -R ²⁶ , -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ Na, -COOH, -COOR ²⁶ , -SO ₃ R ²⁶ , or -SO ₂ NHR ²⁸ substituted C ₆ to C ₁₀ aromatic hydrocarbon group; R ²⁵ represents -SO ₃ ^- , -SO ₃ Na, -COOH, -COOR ²⁶ , -SO ₃ H, or -SO ₂ NHR ²⁸ ; m ¹ represents an integer from 0 to 5; when m ¹ represents 2 to 5, a plurality of R ²⁵ are the same or Different; X ² represents a halogen atom; a ² represents 0 or 1; R ²⁶ represents a C ₁ to C ₁₀ alkyl group; or a C ₁ to C ₁₀ alkyl group substituted by a halogen atom or -OR ²⁷ ; R ²⁷ represents C An alkyl group of ₁ to C ₁₀ ; and R ²⁸ represents hydrogen, -R ²⁶ , -COOR ²⁶ , a C ₆ to C ₁₀ aromatic hydrocarbon group, or a C ₆ to C ₁₀ aromatic hydrocarbon group substituted by -R ²⁶ or -OR ²⁶ .

Preferably, the dye (B) comprises a red dye having the structure of formula (I-3): In the formula (I-3), R ³¹ and R ³² each independently represent a phenyl group, or are substituted by a halogen atom, -R ²⁶ , -OR ²⁶ , -COOR ²⁶ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ Phenyl group; R ³³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ ; R ³⁴ represents hydrogen, -SO ₃ ^- or -SO ₂ NHR ²⁸ ; X ³ represents a halogen atom; a ³ represents 0 or 1; ²⁶ represents a C ₁ to C ₁₀ alkyl group, the halogen atom or -OR ²⁷ or a substituted alkyl group of C ₁ to C ₁₀ of; R ²⁷ represents a C ₁ to C ₁₀ alkyl group of; and R ²⁸ represents hydrogen, -R ^26, -COOR ^26, C ₆ to C ₁₀ aromatic hydrocarbon group of, by -R ²⁶ or -OR ^26, or the substituted C ₆ to C ₁₀ aromatic hydrocarbon group of.

Preferably, the dye (B) comprises a red dye having the structure of formula (I-4): In the formula (I-4), R ⁴¹ and R ⁴² each independently represent a phenyl group or a phenyl group substituted with -R ²⁶ or -SO ₂ NHR ²⁸ ; and R ⁴³ represents -SO ₃ -, or -SO ₂ NHR ²⁸ X ⁴ represents a halogen atom; a ⁴ represents 0 or 1; R ²⁶ represents a C ₁ to C ₁₀ alkyl group; or a C ₁ to C ₁₀ alkyl group substituted by a halogen atom or -OR ²⁷ ; R ²⁷ represents C ₁ the alkyl to C _10; and R ²⁸ represents hydrogen, -R ^26, -COOR ^26, C ₆ to C ₁₀ aromatic hydrocarbon group of, by -R ²⁶ or -OR ^26, or the substituted C ₆ to C ₁₀ aromatic hydrocarbon group of.

In a specific example of the present invention, the dye (B) includes, but is not limited to, the following formulas (1) to (31): R ^c and R ^d each independently represent hydrogen, -SO ₃ ^- , -COOH or -SO ₂ NHR ⁸¹ ; R ⁸¹ represents 2-ethylhexyl; X represents a halogen atom; and a represents 0 or 1.

R ^e represents hydrogen, -SO ₃ ^- , -COOH or -SO ₂ NHR ⁸¹ ; R ⁸¹ represents 2-ethylhexyl; X represents a halogen atom; and a represents 0 or 1.

R ^e represents hydrogen, -SO ₃ ^- , -COOH or -SO ₂ NHR ⁸¹ ; R ⁸¹ represents 2-ethylhexyl; X represents a halogen atom; and a represents 0 or 1.

R ^f , R ^g and R ^h each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ⁸¹ ; R ⁸¹ represents 2-ethylhexyl.

R ^f , R ^g and R ^h each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ⁸¹ ; and R ⁸¹ represents 2-ethylhexyl.

R ⁱ , R ^j and R ^k each independently represent hydrogen, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ⁸¹ ; and R ⁸¹ represents 2-ethylhexyl.

R ⁱ , R ^j and R ^k each independently represent hydrogen, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ⁸¹ ; and R ⁸¹ represents 2-ethylhexyl.

R ^l , R ^m and R ⁿ each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ⁸¹ ; and R ⁸¹ represents 2-ethylhexyl.

R ^l , R ^m and R ⁿ each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ⁸¹ ; and R ⁸¹ represents 2-ethylhexyl.

R ^p , R ^q and R ^r each independently represent hydrogen, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ⁸¹ ; and R ⁸¹ represents 2-ethylhexyl.

R ^p , R ^q and R ^r each independently represent hydrogen, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ⁸¹ ; and R ⁸¹ represents 2-ethylhexyl.

A preferred specific example of the dye (B) of the present invention is a formula (1) (R ^c and R ^d are -SO ₃ ^- , a is 0) [CI acid red dye 52], formula (22) [CI acid red dye 289], formula (28), formula (31), or a combination of these.

In a specific example of the present invention, the total amount of the alkali-soluble resin (C) used is 100 parts by weight, and the dye (B) is used in an amount ranging from 10 parts by weight to 100 parts by weight; preferably 12 parts by weight to 80 parts by weight; more preferably 15 parts by weight to 60 parts by weight. When the dye (B) is not used, there is a problem that the surface roughness is poor.

The alkali-soluble resin (C) according to the present invention comprises a first alkali-soluble resin (C-1) which is obtained by polymerization of a mixture, and the mixture contains one At least two epoxy-based epoxy compounds (i), and a compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group. In addition to the above, the above mixture may more optionally comprise a carboxylic anhydride compound (iii) and/or an epoxy group-containing compound (iv).

The epoxy compound (i) having at least two epoxy groups according to the present invention may have a structure represented by the following formula (CI) or the following formula (C-II). Here, the description that the epoxy compound (i) may have a structure represented by the following formula (CI) or the following formula (C-II) also encompasses a compound having a structure represented by the following formula (CI) and having A compound having a structure represented by the following formula (C-II) exists simultaneously as a case of the epoxy compound (i). Specifically, the epoxy compound (i) having at least two epoxy groups described above has, for example, a structure represented by the following formula (CI): In the formula (CI), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are the same or different and each represents a hydrogen atom, a halogen atom, a C ₁ to C ₅ alkyl group, a C ₁ to C ₅ alkoxy group, C ₆ to C ₁₂ aryl or C ₆ to C ₁₂ aralkyl.

The epoxy compound (i) having at least two epoxy groups of the above formula (CI) may include an epoxy group-containing double obtained by reacting a bisphenol fluorene with an epoxidized propylene oxide (epihalohydrin). A phenolphthalein type compound, but is not limited thereto.

Specific examples of the above bisphenol quinoid type compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyl group). -3-methylphenyl)fluorene [9,9-bis(4-hydroxy-3-methylphenyl)fluorene], 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene [9,9-bis (4-hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9 - bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl) [9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9-bis(4-hydroxy) -3,5-dimethylphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, a compound such as 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene.

The above-mentioned epihalohydrin may include, but is not limited to, 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-propylene oxide (epibromohydrin).

The epoxy group-containing bisphenol quinone type compound obtained by reacting the bisphenol quinoid compound with the halogenated propylene oxide includes, but is not limited to: (1) a product manufactured by Nippon Steel Chemical Co., Ltd. : for example, ESF-300, etc.; (2) goods manufactured by Osaka Gas Co., Ltd.: for example, PG-100, EG-210, etc.; (3) manufactured by SMS Technology Co., Ltd. Goods such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, and the like.

Next, the epoxy compound (i) having at least two epoxy groups may have a structure represented by the following formula (C-II): In the formula (C-II), R ⁶⁵ to R ⁷⁸ are the same or different and each represents a hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aromatic group, and n represents 0 to An integer of 10.

The epoxy compound (i) having at least two epoxy groups of the above formula (C-II) is, for example, a compound having a structure of the following formula (C-II-1) by using an alkali metal hydroxide in the presence of an alkali metal hydroxide The halogenated propylene oxide is reacted to obtain: In the above formula (C-II-1), R 65 to R ⁷⁸ and n are as defined to R ⁶⁵ are the same, and ⁷⁸ in formula (C-II) R n is defined, which is not repeated herein.

Further, the epoxy compound (i) having at least two epoxy groups of the above formula (C-II) is, for example, a compound having a structure of the following formula (C-II-2) and a phenol in the presence of an acid catalyst. After the condensation reaction of the (phenol) type, a compound having the structure of the formula (C-II-1) is formed. Next, an dehydrohalogenation reaction is carried out by adding an excess of halogenated propylene oxide to obtain an epoxy compound (i) having at least two epoxy groups as shown in the formula (C-II): In the above formula (C-II-2), R ⁷⁹ and R ⁸⁰ are each the same or different hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aromatic group; X ¹ and X ² is the same or different halogen atom, C ₁ to C ₆ alkyl group or C ₁ to C ₆ alkoxy group, respectively. Preferably, the above halogen atom may be, for example, chlorine or bromine, and the above alkyl group may be, for example, a methyl group, an ethyl group or a third butyl group, and the above alkoxy group may be, for example, a methoxy group or an ethoxy group.

Specific examples of the phenols include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, and t-butyl phenol. (t-butylphenol), octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol (vinylphenol), propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol. The above phenols can be generally used singly or in combination of two or more.

The compound having the structure of the above formula (C-II-2) is used in an amount of 1 mol, and the phenol is used in an amount of 0.5 mol to 20 mol, and preferably 2 mol to 15 mol.

Specific examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, and boron trifluoride (boron). Trifluoride), aluminum chloride anhydrous, zinc chloride, etc., of which p-toluenesulfonic acid, sulfuric acid or hydrochloric acid is preferred. The above acid catalysts may be used singly or in combination of two or more.

Further, although the amount of the acid catalyst used is not particularly limited, the amount of the acid catalyst used is preferably based on 100 parts by weight (wt%) of the compound having the structure of the formula (C-II-2). It is from 0.1 wt% to 30 wt%.

The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent include toluene, xylene, and methyl isobutyl ketone. The above organic solvents may be used singly or in combination of two or more.

The total amount of the compound and the phenol used based on the structure of the formula (C-II-2) is 100% by weight, and the above organic solvent is used in an amount of 50% by weight to 300% by weight, preferably 100% by weight to 250% by weight. Further, the above condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the operation time of the condensation reaction is 1 hour to 8 hours.

After completion of the above condensation reaction, a neutralization treatment or a water washing treatment may be carried out. The above neutralization treatment adjusts the pH of the solution after the reaction to pH 3 to pH 7, and preferably pH 5 to pH 7. The water washing treatment may be carried out using a neutralizing agent, and the neutralizing agent is an alkaline substance, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and hydrogen; Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylenetetramine, aniline, phenylenediamine (diethyltetramine) Organic amines such as phenylene diamine; and ammonia, sodium dihydrogen phosphate, and the like. The above washing treatment can be carried out by a conventional method. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be carried out repeatedly. After neutralization treatment or water washing treatment, the unreacted phenols and solvent are distilled off by heat treatment under reduced pressure, and concentrated. By shrinking, a compound having the structure of the formula (C-II-1) can be obtained.

Specific examples of the above halogenated propylene oxide include 3-chloro-1,2-epoxypropane and 3-bromo-1,2-epoxypropane (3). -bromo-1, 2-epoxypropane) or any combination of the above. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added to the reaction before the dehydrohalogenation reaction. The above dehydrohalogenation reaction has an operating temperature of from 20 ° C to 120 ° C and an operation time ranging from 1 hour to 10 hours.

In a specific example of the present invention, an aqueous solution of the alkali metal hydroxide added to the dehydrohalogenation reaction may be used. In this specific example, while the aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing water. At the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or the like may be added. The ammonium salt is used as a catalyst, and reacted at 50 ° C to 150 ° C for 1 hour to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof is added thereto, and the reaction is carried out at a temperature of 20 ° C to 120 ° C for 1 hour. 10 hours for the dehydrohalogenation reaction.

The halogenated propylene oxide may be used in an amount of from 1 equivalent to 20 equivalents, preferably from 2 equivalents to 10 equivalents, based on 1 equivalent of the total hydroxyl group in the compound of the above formula (C-II-1). The alkali metal hydroxide added in the above dehydrohalogenation reaction may be used in an amount of from 0.8 equivalents to 15 equivalents, based on 0.9 equivalents based on the total hydroxyl group equivalent of the above compound having the structure of the formula (C-II-1). Equivalent to 11 equivalents is preferred.

Further, in order to smoothly carry out the above-described dehydrohalogenation reaction, an aprotic such as dimethyl sulfone or dimethyl sulfoxide may be added in addition to an alcohol such as methanol or ethanol. A polar solvent or the like is used to carry out the reaction. In the case of using an alcohol, the alcohol may be used in an amount of 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight based on the total amount of the above-mentioned halogenated propylene oxide being 100% by weight. In the case of using an aprotic polar solvent, the total amount of the aprotic polar solvent may be from 5 wt% to 100 wt%, wherein 10 wt% to 90 wt%, based on the total amount of the halogenated propylene oxide, is 100 wt%. good.

After completion of the dehydrohalogenation reaction, a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by heating and decompression. The heating and depressing is performed, for example, in an environment having a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the solution after the dehydrohalogenation reaction may be added to a solvent such as toluene or methyl isobutyl ketone, and a base such as sodium hydroxide or potassium hydroxide may be added. The metal hydroxide aqueous solution is again subjected to a dehydrohalogenation reaction. In the dehydrohalogenation reaction, the total equivalent weight of the hydroxyl group in the compound having the structure of the above formula (C-II-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, wherein 0.05 moles to 0.2 moles are preferred. Further, the above dehydrohalogenation reaction has an operating temperature in the range of 50 ° C to 120 ° C and an operation time ranging from 0.5 hour to 2 hours.

After completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, a solvent such as toluene or methyl isobutyl ketone may be distilled off by heating and pressure reduction to obtain an epoxy compound having at least two epoxy groups as shown in the formula (C-II). (i). The epoxy compound (i) having at least two epoxy groups of the above formula (C-II) may include, but is not limited to, a Japanese chemical such as NC-3000, NC-3000H, NC-3000S, and NC-3000P. (Nippon Kayaku Co. Ltd.) manufactured goods.

The aforementioned compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is, for example, selected from the group consisting of (1) to (3): (1) acrylic acid, methacrylic acid, 2 -methacryloxyethyl succinic acid (2- Methacryloyloxyethylbutanedioic acid), 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyl oxyethyl adipate, 2-methylpropenyloxybutyl adipate, 2-methylpropene oxime Ethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl maleic acid, 2-methylpropenyloxybutyl maleic acid, 2- Methyl propylene oxypropyl succinic acid, 2-methyl propylene sulfoxypropyl adipate, 2-methyl propylene oxypropyl tetrahydrophthalic acid, 2-methyl propylene oxypropyl butyl Phthalic acid, 2-methylpropenyloxybutylphthalic acid, or 2-methylpropenyloxybutylphthalic acid; (2) Hydroxyl-containing (meth)acrylate and binary a compound obtained by reacting a carboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, phthalic acid; (3) a hydroxyl group-containing (meth) acrylate and A half ester compound obtained by reacting a carboxylic anhydride compound (iii), wherein the hydroxyl group-containing (meth) acrylate includes, but not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate base 2-hydroxyethylmethacrylate, 2-hydroxypropylacrylate, 2-hydroxypropylmethacrylate, 4-hydroxybutyrate Alkyl acrylate [(4-hydroxybutyl)acrylate], 4-hydroxybutyl methacrylate, or pentaerythritol trimethacrylate. Further, the carboxylic anhydride compound herein may be the same as the carboxylic anhydride compound (iii) contained in the mixture of the first alkali-soluble resin (C-1) described below, and thus will not be described herein.

The mixture of the above first alkali-soluble resin (C-1) may more optionally contain a carboxylic anhydride compound (iii) and/or an epoxy group-containing compound (iv). The above carboxylic anhydride compound (iii) may be selected from the group consisting of (1) to (2): (1) butanedioic anhydride, maleic anhydride, itaconic anhydride (Itaconic) Anhydride), phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl hexahydrate Hydrogen phthalic anhydride, methyl endo-methylene tetrahydro phthalic acid An carboxylic acid anhydride compound such as chlorendic anhydride, glutaric anhydride or 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic acid A tetracarboxylic carboxylic anhydride compound such as benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or diphenyl ether tetracarboxylic dianhydride.

The epoxy group-containing compound (iv) is, for example, selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, and an epoxy group-containing compound. A group of unsaturated compounds or any combination of the above. The unsaturated group-containing glycidyl ether compound includes, but is not limited to, the trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, and Denacol EX-192. Compound (the above is a product of Nagase Chemical Industry Co., Ltd.).

The aforementioned first alkali-soluble resin (C-1) may be an epoxy compound (i) having at least two epoxy groups of the formula (CI) and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (ii) The polymerization reaction is carried out to form a hydroxyl group-containing reaction product, followed by addition of a carboxylic anhydride compound (iii) to carry out a reaction. The equivalent weight of the acid group based on the above hydroxyl group-containing reaction product is 1 equivalent, and the equivalent amount of the acid anhydride group contained in the carboxylic anhydride compound (iii) is preferably from 0.4 equivalent to 1 equivalent, more preferably from 0.75 equivalent to 1 equivalent. When a plurality of carboxylic anhydride compounds (iii) are used, they may be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (iii), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is preferably from 1/99 to 90/10, more preferably It is from 5/95 to 80/20. Further, the operating temperature range of the above reaction is, for example, in the range of 50 ° C to 130 ° C.

The aforementioned first alkali-soluble resin (C-1) may be an epoxy compound (i) having at least two epoxy groups of the formula (C-II) and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. (ii) performing a reaction to form a hydroxyl-containing reaction product, and then borrowing It is obtained by carrying out a polymerization reaction by adding a carboxylic anhydride compound (iii) and/or an epoxy group-containing compound (iv). The epoxy group compound (i) having at least two epoxy groups having a total equivalent weight of 1 equivalent based on the formula (C-II), the above compound having at least one carboxylic acid group and at least one ethylenically unsaturated group The acid value equivalent of (ii) is preferably from 0.8 equivalents to 1.5 equivalents, more preferably from 0.9 equivalents to 1.1 equivalents. The total amount of hydroxyl groups based on the above hydroxyl group-containing reaction product is 100 mol% (mol%), and the carboxylic anhydride compound (iii) is preferably used in an amount of 10 mol% to 100 mol%, more preferably 20 mol%. % to 100% by mole, particularly preferably 30% by mole to 100% by mole.

In the preparation of the above first alkali-soluble resin (C-1), in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The above reaction catalysts may be used singly or in combination, and the above reaction catalysts include, but are not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine. , tetramethylammonium chloride, benzyltriethylammonium chloride, and the like. The use of the reaction catalyst is based on the total amount of the epoxy compound (i) having at least two epoxy groups and the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group in an amount of 100 parts by weight. The amount is preferably from 0.01 part by weight to 10 parts by weight, more preferably from 0.3 part by weight to 5 parts by weight.

Further, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The above polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di) -t-butyl-p-cresol) or phenothiazine. In general, the above polymerization inhibitors may be used singly or in combination of two or more. The use of the polymerization inhibitor is based on the total amount of the epoxy compound (i) having at least two epoxy groups and the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group in an amount of 100 parts by weight. The amount is preferably from 0.01 part by weight to 10 parts by weight, more preferably from 0.1 part by weight to 5 parts by weight.

In the preparation of the first alkali-soluble resin (C-1), a polymerization solvent can be used as necessary. Specific examples of the polymerization reaction solvent include alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; methyl ethyl ketone or cyclohexanone; Ketone compounds; aromatic hydrocarbon compounds such as toluene or xylene; celecin compounds such as cellosolve or butyl cellosolve; carbitol or butyl carbene a carbaryl compound such as butyl carbitol; a propylene glycol alkyl ether compound such as propylene glycol monomethyl ether; and a polypropylene glycol alkyl ether such as di(propylene glycol) methyl ether [poly(propylene glycol) alkyl ether] compound; acetate such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate a compound; an alkyl lactate compound such as ethyl lactate or butyl lactate; or a dialkyl glycol ether. The above polymerization solvent can be generally used singly or in combination of two or more. Further, the acid value of the above first alkali-soluble resin (C-1) is preferably from 50 mgKOH/g to 200 mgKOH/g, more preferably from 60 mgKOH/g to 150 mgKOH/g.

Further, the first alkali-soluble resin (C-1) has a polystyrene-equivalent number average molecular weight of from 800 to 8,000, more preferably from 1,000 to 6,000, as measured by Gel Permeation Chromatography (GPC). .

The first alkali-soluble resin (C-1) is used in an amount ranging from 4 parts by weight to 100 parts by weight, based on the total amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight; preferably from 5 parts by weight to 80 parts by weight. More preferably, it is 6 parts by weight to 60 parts by weight. When the first alkali-soluble resin (C-1) is used, a change rate of the film thickness of the hot solvent is preferable.

Preferably, the alkali-soluble resin (C) according to the present invention comprises a second alkali-soluble resin (C-2) which is firstly composed of a carboxylic acid-containing group. Unsaturated monomer (c-2-1), a second unsaturated monomer containing a maleimide structure (c- 2-2), and a polymerization reaction product of a mixture of a third unsaturated monomer (c-2-3) having an alicyclic structure.

Wherein the carboxylic acid group-containing first unsaturated monomer (c-2-1) is selected from the group consisting of acrylic acid, methacrylic acid, 2-methylpropenyl ethoxy succinate, crotonic acid, and α. - chloroacrylic acid, ethacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, or a combination thereof. Preferably, the carboxylic acid group-containing first unsaturated monomer (c-2-1) is selected from the group consisting of acrylic acid, methacrylic acid, 2-methylpropenyl ethoxy succinate, or the like. One combination.

The second unsaturated monomer (c-2-2) containing a maleimide structure is selected from the group consisting of nitrogen-cyclohexylmaleimide, nitrogen-phenylmaleimide, nitrogen-ortho- Hydroxyphenylmaleimide, nitrogen-m-hydroxyphenylmaleimide, nitrogen-p-hydroxyphenylmaleimide, nitrogen-o-methylphenylmaleimide, nitrogen -m-methylphenylmaleimide, nitrogen-p-methylphenylmaleimide, nitrogen-o-methoxyphenylmaleimide, nitrogen-m-methoxybenzene A combination of maleimide, nitrogen-p-methoxyphenylmaleimide, or the like, or a combination thereof. Wherein the second unsaturated monomer (c-2-2) containing a maleimide structure is nitrogen-phenylmaleimide, nitrogen-o-hydroxyphenylmaleimide, nitrogen- m-Hydroxyphenylmaleimide, nitrogen-p-hydroxyphenylmaleimide, nitrogen-o-methylphenylmaleimide, nitrogen-m-methylphenyl malayan Amine, nitrogen-p-methylphenylmaleimide, nitrogen-o-methoxyphenylmaleimide, nitrogen-m-methoxyphenylmaleimide, nitrogen-p- Maleic imides such as methoxyphenylmaleimide are preferred.

The third unsaturated monomer (c-2-3) having an alicyclic structure is selected from the group consisting of an unsaturated compound having a dicyclopentanyl group and a dicyclopentenyl group. Saturated compound, or a combination of these.

Specifically, the third unsaturated monomer (c-2-3) having an alicyclic structure may be dicyclopenteny acrylate (FA-511A) or dicyclopentenyloxyethyl acrylate (dicyclopentenyloxyethyl acrylate). , FA-512A), dicyclopentan Alkenyl acrylate, dicyclopentenyl ethoxy acrylate, dicyclopentanyl methacrylate (FA-513M), dicyclopentyl ethoxy methacrylate, dicyclopentenyl methacrylate , dicyclopentenyloxyethyl methacrylate FA-512M, or a combination of these.

Further, the mixture of the above second alkali-soluble resin (C-2) further has a first unsaturated monomer (c-2-1) having a carboxylic acid group and a second unsaturated monomer having a maleimide structure. a body (c-2-2), and a fourth unsaturated monomer (c-2-4) other than the third unsaturated monomer (c-2-3) having an alicyclic structure.

The fourth unsaturated monomer (c-2-4) is selected from the group consisting of styrene, α-methyl styrene, vinyl toluene, p-chlorostyrene, divinyl benzene, benzyl methacrylate, Benzene methacrylate, phenyl methacrylate, phenyl acrylate, 2-nitrophenyl acrylate, 4-nitrophenyl acrylate, 2-nitrophenyl methacrylate, 2-nitro Benzyl methacrylate, 2-nitrophenyl methacrylate, 2-chlorophenyl methacrylate, 4-chlorophenyl methacrylate, 2-chlorophenyl acrylate, 4-chloro Phenyl acrylate, phenoxyethyl methacrylate, phenoxy polyethylene glycol acrylate, phenoxy polyethylene glycol methacrylate, nonyl phenoxy polyethylene glycol acrylate, hydrazine Phenoxyethylene glycol methacrylate, o-vinyl phenol, m-vinyl phenol, p-vinyl phenol, 2-methyl-4-vinyl phenol, 3-methyl-4-ethylene Phenolic, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, 2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2 -naphthol, 3-vinyl-2-naphthalene Phenol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- Methoxymethylstyrene, m-methoxymethylstyrene, p-methoxymethylstyrene, o-(vinylbenzyl)epoxypropyl ether, m-(vinylstyrene) Epoxy propyl ether, p-(vinylbenzyl)epoxypropyl ether, hydrazine, acetyl phthalene, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylic acid Butyl ester, isobutyl acrylate, second butyl acrylate, third butyl acrylate, 2-hydroxy acrylate Ethyl ethyl ester, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, allyl acrylate, triethylene glycol methacrylate Oxygen ester, nitrogen, nitrogen-dimethylaminoethyl acrylate, nitrogen, nitrogen-diethylaminopropyl acrylate, nitrogen, nitrogen-dibutylamino propyl acrylate, glycidyl acrylate, methacrylic acid Ester, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third methacrylate Ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, methacrylic acid 4-hydroxybutyl ester, allyl methacrylate, triethylene glycol methacrylate, dodecyl methacrylate, tetradecyl methacrylate, cetyl methacrylate , octadecyl methacrylate, eicosyl methacrylate, methyl propyl Tetylene dicarboxylate, nitrogen methacrylate, nitrogen-dimethylaminoethyl ester, nitrogen, nitro-dimethylaminopropyl methacrylate, nitrogen-iso-butylaminoethyl methacrylate, Epoxypropyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl ethyl ether, allyl epoxypropyl ether, methallyl propyl propyl Methallyl glycidyl ether, acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, vinyl cyanide, acrylamide, methacrylamide, alpha-chloropropenylamine, nitrogen-hydroxyethyl propylene oxime Amine, nitrogen-hydroxyethyl methacrylamide, 1,3-butadiene, isoamylene, chlorinated butadiene, or a combination of these, in which methyl acrylate, ethyl acrylate, acrylic acid N-propyl ester, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, tert-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate , ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methyl Isobutyl acrylate, second butyl methacrylate, third butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, vinyl acetate Esters, acrylonitrile, methacrylonitrile, 1,3-butadiene, and isoamylene are preferred.

The second alkali-soluble resin (C-2) is used in an amount ranging from 30 parts by weight to 100 parts by weight, based on the total amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight; preferably 40 parts by weight to 96 parts by weight. More preferably, it is 50 parts by weight to 94 parts by weight. When the second alkali-soluble resin (C-2) is used, the film thickness change rate of the hot solvent is preferable.

Further, when the first alkali-soluble resin (C-1) and the second alkali-soluble resin (C-2) are used at the same time, the film thickness change rate of the hot solvent is more preferable.

In a preferred embodiment of the present invention, the photosensitive resin composition for a color filter contains the compound (D) having an ethylenically unsaturated group. The compound (D) having an ethylenically unsaturated group contains a first compound (D-1) which is a polyfluorenyl compound represented by the formula (b) and represented by the formula (a) a polyfunctional (meth) acrylate is formed by reaction, In the formula (a): X ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and X ² represents a residue after esterification of n hydroxyl groups in a hydroxyl group-containing compound having m hydroxyl groups, wherein m≧ n, m and n each independently represent an integer of 2 to 20; the hydroxyl group-containing compound having m hydroxyl groups is X ³ (OH) _m or X ³ (OH) _m via propylene oxide, epoxy chloride a compound modified with epichlorohydrin, an alkyl group, an alkoxy group or a hydroxypropyl acrylate; and X ³ (OH) _m is a polyalcohol having a carbon number of 2 to 18, from which the poly a polyhydric alcohol ethers formed by an alcohol, an ester formed by reacting the polyol with an acid, or a silicone; In the formula (b): X ⁴ represents a single bond, a hydrocarbon group having a carbon number of 1, or a linear or branched hydrocarbon group having a carbon number of 2 to 22, and the skeleton of X ⁴ may further include a sulfur atom or constitute an ester group. An oxygen atom; and p represents an integer of 2 to 6, wherein when X ⁴ represents a single bond, p represents 2; when X ⁴ represents a hydrocarbon group having a carbon number of 1, p represents an integer of 2 to 4; when X ⁴ represents When the carbon number is a linear or branched hydrocarbon group of 2 to 22, p represents an integer of 2 to 6.

Another preferred embodiment of the present invention, wherein the first compound (D-1) is the polyfluorenyl compound represented by the formula (b) and the polyfunctional (meth) acrylate represented by the formula (a) The (meth) acrylate group remaining after the reaction is further formed by reacting with a thiol compound having a carboxyl group represented by the formula (c). In the formula (c), X ⁵ represents an alkylene group having a carbon number of 1 to 12, and q represents an integer of 1 to 3.

In the first compound (D-1), the fluorenyl group contained in the polyfluorenyl compound represented by the formula (b) and the fluorenyl compound having a carboxyl group represented by the formula (c) is added to the photoreaction via photoreaction. The polyfunctional (meth) acrylate represented by the formula (a) has a carbon-carbon double bond. In general, in the carbon-carbon double bond of the polyfunctional (meth) acrylate represented by the formula (a), the photoreactive carbon-carbon double bond is preferably relative to all carbon-carbon double bonds. 0.1% to 50%.

Further, the fluorenyl group of the polyfluorenyl compound represented by the formula (b), or the fluorenyl group of the fluorenyl compound having a carboxyl group represented by the formula (c), or the fluorenyl group of the fluorenyl compound having a carboxyl group represented by the formula (c) The molar ratio of the carbon-carbon double bond in the polyfunctional (meth) acrylate represented by the formula (a) is from 1/200 to 1/2; preferably from 1/100 to 1/3; more preferably It is 1/50 to 1/5; especially preferably 1/20 to 1/8.

The first compound (D-1) preferably has a sufficient photopolymerization functional group. For example, a carbon-carbon double bond. Specifically, the molecular weight of the first compound (D-1) per 1 mol of the carbon-carbon double bond is preferably from 100 to 100,000. Further, the molecular weight of the first compound (D-1) of the present invention is preferably from 1,000 to 50,000, more preferably from 1,500 to 40,000, still more preferably from 2,000 to 30,000.

Further, in order to produce an alkali-developable photosensitive resin composition, the first compound (D-1) preferably has a sufficient carboxyl group. Specifically, the molecular weight of the first compound (D-1) per 1 mol of the carboxyl group is preferably from 200 to 20,000, more preferably from 250 to 6,000.

In the polyfunctional (meth) acrylate represented by the formula (a), the number of the acrylate groups is preferably from 2 to 20; more preferably from 2 to 10, still more preferably from 2 to 6. When X ¹ in the formula (a) represents an alkyl group having 1 to 4 carbon atoms, X ¹ may be a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group. Further, the carbon number of the hydrocarbon group in X ³ (OH) _m of the formula (a) is preferably 2 to 18; more preferably 2 to 14, particularly preferably 4 to 12.

Specific examples of the polyfunctional (meth) acrylate represented by the formula (a) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di( Methyl) acrylate, tetraethylene glycol di(meth) acrylate, tetramethylene glycol di(meth) acrylate, trimethylolpropane tri(meth) acrylate, ethylene oxide Modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, Pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentolide tetraol (meth) acrylate modified by caprolactone, pentaerythritol tetra (meth) acrylate modified by caprolactone, Caprolactone modified dipentaerythritol hexa(meth) acrylate, epichlorohydrin modified hexahydrophthalic acid (meth) acrylate, hydroxy pivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di(meth) acrylate, epoxy Ethyl modified neopentyl glycol Di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, caprolactone modified hydroxypivalate neopentyl glycol di(meth)acrylate Pentaerythritol di(meth)acrylate modified with stearic acid, di(meth)acrylate phthalate modified with epichlorohydrin, poly(ethylene glycol tetramethylene glycol) (Meth) acrylate, poly(propylene glycol tetramethylene glycol) di(meth) acrylate, polyester (meth) acrylate, polyethylene glycol di(meth) acrylate, polyethylene glycol Polypropylene glycol polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, epichlorohydrin modified propylene glycol di(meth)acrylate, propylene oxide modified bisphenol A diglycidyl ether di(meth) acrylate, fluorenone di(meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclic fluorene Alkanediethanol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, tripropylene glycol di(meth)acrylate, modified with ethylene oxide three Propylene glycol di(meth)acrylate, triglycerin di(meth)acrylate, dipropylene glycol di(meth)acrylate, epichlorohydrin-modified tris(meth)acrylate, epoxy B Alkyl modified tris(meth)acrylate, propylene oxide modified tris(meth)acrylate, ethylene oxide modified tris(meth)acrylate, caprolactone Modified trimethylolpropane tri(meth)acrylate, hydroxypropyl acrylate (HPA) modified trimethylolpropane tri(meth)acrylate, modified with ethylene oxide Trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolpropane benzoate (meth) acrylate, Tris((meth)acryloylethyl)isocyanurate, alkoxy-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkane a (meth) acrylate such as di-pentaerythritol tri(meth)acrylate or ditrimethylolpropane tetra(meth)acrylate, which is modified by a base group. ) Acrylates may be used alone or in combination.

In the polyfluorenyl compound represented by the formula (b), X ⁴ preferably has a carbon number of from 0 to 22 (when the carbon number is 0, X ⁴ is a single bond, and the formula (b) represents HS-CH ₂ - CH ₂ -SH) is more preferably from 1 to 16, particularly preferably from 2 to 12. Specific examples of the polyfluorenyl compound represented by the formula (b) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-didecylbutane, bisdidecylethanethiol (HS- CH ₂ CH ₂ -S-CH ₂ CH ₂ -SH), dimercaptotriethylene glycol, trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionate), pentaerythritol tetra ( Mercaptoacetate), pentaerythritol tris(mercaptoacetate), pentaerythritol tetrakis(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), the polythiol compound may be used alone or in combination use.

In the mercapto compound having a carboxyl group represented by the formula (c), X ^{5 is} preferably a linear or branched alkylene group having from 1 to 12 carbon atoms. Specifically, the alkylene group is, for example, a methylene group, an ethylidene group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a octyl group, a hydrazine group, a hydrazine group, and a hydrazine group. An undecyl or a dodecyl group. The mercapto compound having a carboxyl group represented by the formula (c) is exemplified by thioglycolic acid.

In the present invention, the above-mentioned addition reaction may firstly mix a polyfunctional (meth) acrylate represented by the formula (a) with a polyfluorenyl compound represented by the formula (b), and add an alkali at room temperature of 100 ° C. Catalyst to carry out. The reaction time is usually from 30 minutes to about 6 hours. Thus, the first compound (D-1) can be obtained.

Next, a mercapto compound having a carboxyl group represented by the formula (c) may be added to the first compound (D-1), followed by a single addition reaction. Thus, a multi-branched polymer having a carboxyl group can be obtained.

Further, when the reaction is completed, the synthesis of the first compound (D-1) can be confirmed by a general analytical instrument such as liquid chromatography, gel filtration chromatography or iodine titration. End.

Among them, the reaction may be added with a polymerization inhibitor if necessary. As the polymerization inhibitor, a hydroquinone-based compound generally used for suppressing polymerization of a (meth) acrylate compound, a phenol compound, or a combination thereof can be used. Specific examples of the polymerization inhibitor include, but are not limited to, p-benzoic acid Phenol, methoxy hydroquinone, catechol, p-tert-butyl catechol, cresol, dibutylhydroxytoluene, 2,4,6-tri-tert-butylphenol (BHT ), or a combination of the above compounds.

The first compound (D-1) is used in an amount ranging from 10 parts by weight to 100 parts by weight, preferably 15 parts by weight to 80 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (C). More preferably, it is 20 parts by weight to 60 parts by weight. When the first compound (D-1) is not used, the high-definition pattern is inferior in linearity.

The compound (D) having an ethylenically unsaturated group according to the present invention may further comprise a second compound (D-2) and a third compound (D-3).

The second compound (D-2) according to the present invention is a (meth) acrylate-based compound obtained by reacting a caprolactone-modified polyol with (meth)acrylic acid.

The caprolactone-modified polyol is obtained by reacting the caprolactone with a polyol having four or more functional groups, wherein the caprolactone may be γ-caprolactone or δ-caprolactone. Or ε-caprolactone, and preferably ε-caprolactone. The polyol having four or more functional groups may be pentaerythritol, ditrimethylolpropane, dipentaerythritol or the like. Preferably, the content of the caprolactone ranges from 1 to 12 moles based on the content of the polyol having 4 functional groups or more.

Specific examples of the second compound include: pentaerythritol caprolactone modified tetra(meth)acrylate compound, ditrimethylolpropane caprolactone modified tetra(meth)acrylate compound, dipentaerythritol a lactone modified poly(meth) acrylate compound, etc., wherein the dipentaerythritol caprolactone modified poly(meth) acrylate compound may be the second modification of dipentaerythritol caprolactone ( Methyl) acrylate compound, dipentaerythritol caprolactone modified tri(meth) acrylate compound, dipentaerythritol caprolactone modified tetra(meth) acrylate compound, dipentaerythritol caprolactone A hexa (meth) acrylate compound modified with a pentaerythritol (meth) acrylate compound or dipentaerythritol caprolactone.

Further, the structure of the poly(meth)acrylate modified by the above dipentaerythritol caprolactone may be represented by the formula (d): In the formula (d), X ⁶ and X ⁷ each represent hydrogen or a methyl group; m is an integer of 1 to 2; a is an integer of 1 to 6, and b is an integer of 0 to 5, wherein a+b=2~ 6. Preferably, a+b=3~6, more preferably a+b=5~6, and most preferably a+b=6.

More specifically, the second compound is manufactured by Nippon Kayaku Co., Ltd. under the names KAYARAD® DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

The third compound has a functional group as shown in formula (e): In the formula (e), X ⁸ represents hydrogen or a methyl group, respectively.

The third compound may, for example, be acrylamide, (meth) propylene morpholine, (meth) acrylate-7-amino-3,7-dimethyloctyl, isobutoxymethyl (methyl) Propylene amide, isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diglycol (meth) acrylate , third octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethyl amino (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylate Cyclopenteneoxyethyl ester, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl(meth)acrylamide, tetrachlorophenyl (meth)acrylate, (meth)acrylic acid-2 -tetrachlorophenoxyethyl ester, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, (meth)acrylic acid -2-three Chlorophenoxyethyl ester, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid -2-hydroxypropyl ester, vinyl caprolactam, nitrogen-vinyl tyrosinone, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, (meth) acrylate Bromophenyl ester, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, borneol (meth)acrylate, ethylene glycol di(meth)acrylate, di(methyl) Dicyclopentenyl acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth) acrylate, tris(2-hydroxyethyl)isocyanate di(meth) acrylate, tris(2-hydroxyethyl) Isocyanate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tris(meth)acrylate trimethylolpropylate, ethylene oxide ( Hereinafter referred to as EO) modified tris (meth) acrylate trimethylol propyl acrylate, propylene oxide (hereinafter referred to as PO) modified tris (meth) acrylate trimethylol propyl ester, triethylene glycol di (a) 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, tetrakis (meth) acrylate ditrimethylol propyl ester, 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 triglyceride, EO-modified bisphenol F di(meth)acrylate, phenolic polyglycidyl ether (meth)acrylate, and the like.

Preferably, the third compound is selected from trimethylol propyl triacrylate, EO modified trimethylol propyl triacrylate, PO modified trimethylol propyl triacrylate, pentaerythritol triacrylate Ester, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, ditrimethylolpropyl methacrylate, PO modified tripropionate, Japan East Asia Synthetic Co., Ltd. TO-1382, or a combination of these.

The compound (D) having an ethylenically unsaturated group is used in an amount ranging from 40 parts by weight to 400 parts by weight, preferably 50 parts by weight to 350 parts by weight based on the total amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight. The parts by weight are more preferably from 60 parts by weight to 300 parts by weight.

The photoinitiator (E) of the present invention may be selected from the group consisting of an acetophenone compound, a biimidazole compound, an acyl oxime compound, or a combination thereof.

The acetophenone-based compound referred to is: p-dimethylamino-acetophenone, α,α'-dimethoxyazoxy-acetophenone (α,α'-dimethoxyazoxy-acetophenone) , 2,2'-dimethyl-2-phenyl-acetophenone, p-methoxy-acetophenone, 2-A 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1 -butanone].

The diimidazole compound referred to is: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(o-chlorophenyl) -4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenyldiimidazole [2,2'- Bis(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl 2,2'-bis(o-methyl phenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methoxyphenyl)-4,4 ',5,5'-o-methoxyphenyl-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-double (o-B 2,2',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole 2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(p-methoxyphenyl)-4,4',5,5' -tetraphenyl-biimidazole], 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)- 4,4',5,5'-tetraphenyl-biimidazole [2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole] , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2-chlorophenyl)-4,4',5, 5'-tetraphenyl-biimidazole], 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis (2, 4-dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole] and the like.

The lanthanide compound referred to is: ethane ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-oxazol-3-substituted group]-, 1-( Othanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), such as the name of Ciba Specialty Chemicals For CGI-242, the structure is shown in formula (32)], 1-(4-phenyl-thio-phenyl)-octane-1,2-dione 2-(O-phenylhydrazinium) [1-(4-phenyl-thio-phenyl)-octane-1,2-dion 2-oxime-O-benzoate, as manufactured by Ciba Specialty Chemicals under the trade name CGI-124, the structure of which is shown in formula (33) Ethyl ketone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzhydryl)-9hydro-oxazol-3-substituted group]-, 1-(9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-, 1-(O- Acetyl oxime), manufactured by Asahi Chemical Co., Ltd., whose structure is shown in formula (34).

Preferably, the photoinitiator (E) is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-nitrogen. Nitro-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl Diimidazole, ethane ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9hydro-oxazol-3-substituted]-, 1-(oxy-acetamidine) , or a combination of these.

The photoinitiator (E) of the present invention may further contain the following compounds: thioxanthone, 2,4-diethyl-thioxanthanone, thioxanthone- 4-碸(thioxanthone-4-sulfone), benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 A benzophenone compound such as '-bis(diethylamino)benzophenone; a benzil or a acetyl group -a-diketones; acyloins of benzoin; benzoin methylether, benzoin ethylether, diphenylethanol Acetone ethers such as benzoin isopropyl ether; 2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide , bis-(2,6-dimethoxybenzoquinone)-2,4,4-trimethylphenylphosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4- Trimethyl-benzyl- Phosphine oxide, etc.; acylphosphine oxide; anthraquinone, 1,4-naphthoquinone, etc.; quinacyl chloride, tribromide a halide such as tribromomethyl-phenylsulfone, tris(trichloromethyl)-s-triazine, or a di-tertbutylperoxide ) and other peroxides. Among them, a benzophenone-based compound is preferred, and 4,4'-bis(diethylamine)benzophenone is particularly preferred.

The photoinitiator (E) is used in an amount ranging from 10 parts by weight to 150 parts by weight, preferably 20 parts by weight to 120 parts by weight, based on the total amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight. It is 30 parts by weight to 90 parts by weight.

The organic solvent (F) of the present invention can dissolve the alkali-soluble resin (C), the ethylenically unsaturated group-containing compound (D) and the photoinitiator (E) without reacting therewith, and With appropriate volatility.

The organic solvent (F) is more commonly used, for example, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol Ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether ( Tripropylene glycol mono methyl ether), (poly)alkylene glycol monoalkyl ethers such as tripropylene glycol mono ethyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol (poly)alkylene glycol monoalkyl ether acetates such as methyl ether acetate, propylene glycol ethyl ether acetate; diglyme, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionic acid Methyl ester, ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-B Methyl propionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, acetic acid Propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate , other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate; toluene, An aromatic hydrocarbon such as xylene; and a carboxylic acid amide such as nitrogen-methylpyrrolidone, nitrogen, nitrogen-dimethylformamide, nitrogen or nitrogen-dimethylacetamide.

Preferably, the organic solvent (F) is used propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate alternatively or in combination.

The organic solvent (F) is used in an amount ranging from 500 parts by weight to 5000 parts by weight, preferably from 800 parts by weight to 4,500 parts by weight, based on the total amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight, more preferably 1000 parts by weight to 4000 parts by weight.

In a preferred embodiment of the present invention, the photosensitive resin composition for a color filter further includes an additive (G), for example, a filler, a polymer compound other than the alkali-soluble resin (C), an adhesion promoter, An antioxidant, an ultraviolet absorber, an anti-aggregation agent, or the like is provided to provide physical properties and chemical properties of the color filter segment obtained from the photosensitive resin composition.

The additive (G) may be used singly or in combination, and the additive (G) includes, but is not limited to, a filler such as glass or aluminum; an alkali-soluble resin such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate. Polymer compound other than (C); vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, nitrogen-(2-aminoethyl)-3 -Aminopropylmethyldimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-ring Oxypropanol propyl trimethoxy decane, 3-glycidyl propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-chloropropyl Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, a adhesion promoter such as 3-methacryloxypropyltrimethoxydecane or 3-thiolpropyltrimethoxydecane; 2,2-thiobis(4-methyl-6-t-butyl group) Antioxidant such as phenol), 2,6-di-tert-butylphenol; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxy An ultraviolet absorber such as benzophenone; and an anti-aggregation agent such as sodium polyacrylate.

The present invention also provides a method of producing a color filter which forms a pixel layer using the photosensitive resin composition for a color filter described above.

Preferably, the color filter includes a pixel layer, and the pixel layer is formed using the photosensitive resin composition for the color filter.

The method for forming a color filter of the present invention is mainly a method of mixing into a solution state by a coating method such as rotary coating, cast coating, ink-jet coating or roll coating. The color filter is coated on the substrate with a photosensitive composition. After coating, most of the solvent is removed by drying under reduced pressure, and the solvent is removed by pre-bake to form a pre-baked coating film. The conditions for drying under reduced pressure and pre-baking vary depending on the type of each component and the blending ratio. Usually, the drying under reduced pressure is carried out at a pressure of 0 to 200 mmHg for 1 second to 60 seconds, and the pre-baking is It is carried out at a temperature of 70 to 110 ° C for 1 minute to 15 minutes. After prebaking, the prebaked coating film is exposed to a designated mask, immersed in a developing solution at a temperature of 23 ± 2 ° C for 15 seconds to 5 minutes for development, and the unnecessary portion is removed to form a pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet device may be a (super) high-pressure mercury lamp or a metal halide lamp.

Specific examples of the substrate include: alkali-free glass, soda-lime glass, hard glass (Pyrus glass), quartz glass, and the like, and a transparent conductive film attached to the glass; or a solid-state imaging device; A photoelectric conversion device substrate (such as a germanium substrate) or the like. These substrates generally form a black matrix that separates the colored layers of each pixel.

Further, specific examples of the developing solution are: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia water, and Amine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine, 1,8-diazabicyclo-(5,4,0)-7 The alkaline aqueous solution composed of a basic compound such as undecene generally has a concentration of 0.001 to 10% by weight, preferably 0.005 to 5% by weight, more preferably 0.01 to 1% by weight.

When the developer composed of the alkaline aqueous solution is used, it is usually washed with water after development, and then air-dried with compressed air or compressed nitrogen.

After drying, the substrate having the photo-curing coating layer is heated by a heating means such as a hot plate or an oven at a temperature of 100 to 280 ° C for 1 to 15 minutes to remove volatile components in the coating film, and the coating film is not The reacted ethylenically unsaturated double bond undergoes a thermosetting reaction. The photosensitive resin composition of each color (mainly including red, green, and blue colors) is repeatedly operated in the same step three times on a predetermined pixel to obtain a light-hardened pixel coloring layer of red, green, and blue colors. .

Next, on the pixel colored layer, an ITO (indium tin oxide) deposited film is formed under vacuum at a temperature of 220 ° C to 250 ° C, and if necessary, after etching and wiring the ITO deposited film, the liquid crystal alignment film is coated. The quinone imine, which is then fired, can be used as a color filter for liquid crystal displays.

It is still another object of the present invention to provide a liquid crystal display element comprising the aforementioned color filter.

The liquid crystal display device of the present invention is mainly composed of a color filter substrate formed by the above-described color filter forming method and a driving substrate provided with a thin film transistor (TFT), wherein The inter-substrate gap (cell gap) is arranged in the opposite direction, and the peripheral portions of the two substrates are bonded together with a sealing agent, and the liquid crystal is filled in the gap between the surface of the substrate and the sealing agent to seal the injection. The holes constitute a liquid crystal cell. Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, to obtain a liquid crystal display element.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

[Preparation of First Alkali Soluble Resin (C-1)] <Synthesis Example C-1-1> Method for producing first alkali-soluble resin (C-1-1)

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500-mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min, and the temperature was maintained at 100 ° C. After reacting for 15 hours in the range of 110 ° C, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heating to 110 ° C to 115 ° C, after 2 hours of reaction, the acid value of 98.0 mg KOH / g, obtained by gel permeation chromatography (GPC) and polystyrene-converted number average molecular weight of 1,623 The first alkali-soluble resin (C-1-1).

<Synthesis Example C-1-2> Method for producing first alkali-soluble resin (C-1-2)

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500-mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min, and the temperature was maintained at 100 ° C. After reacting for 15 hours in the range of 110 ° C, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 13 parts by weight of benzophenone tetracarboxylic dianhydride was added, and the reaction was carried out at 90 ° C to 95 ° C for 2 hours. Next, 6 parts by weight of tetrahydrophthalic anhydride is added, and After reacting at 90 ° C to 95 ° C for 4 hours, a first alkali-soluble resin having an acid value of 99.0 mg KOH/g and having a polystyrene-converted number average molecular weight of 2,162 can be obtained by a gel permeation chromatography (GPC). (C-1-2).

<Synthesis Example C-1-3> Method for producing first alkali-soluble resin (C-1-3)

400 parts by weight of an epoxy compound (Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight Triphenylphosphine and 264 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.2 mg KOH / g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added, and the reaction was carried out at 95 ° C for 4 hours to obtain an acid value of 102 mgKOH/g, which was measured by a gel permeation chromatography (GPC). The polystyrene-converted number average molecular weight was 2,589 of the first alkali-soluble resin (C-1-3).

<Synthesis Example C-1-4> Method for producing first alkali-soluble resin (C-1-4)

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 96 parts by weight of 2-methylpropenyloxyethyl succinic acid, 0.3 parts by weight of chlorinated Benzyltriethylammonium, 0.1 parts by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 The temperature was maintained in the range of 100 ° C to 110 ° C in parts per minute, and after 18 hours of reaction, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heating to 110 ° C to 115 ° C, after 2 hours of reaction, the acid value of 90.0 mg KOH / g, obtained by gel permeation chromatography (GPC) and polystyrene-converted number average molecular weight of 3,101 First alkali soluble resin (C-1-4).

[Preparation of second alkali-soluble resin (C-2)] <Synthesis Example C-2-1>

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed in a four-necked flask having a volume of 1000 ml, and nitrogen gas was introduced. Then, 10 parts by weight of 2-methylpropenyl ethoxy succinate (hereinafter abbreviated as HOMS), 20 parts by weight of nitrogen-cyclohexylmaleimide (hereinafter abbreviated as N-CMI), 30 Parts by weight of nitrogen-m-methylphenylmaleimide (hereinafter abbreviated as N-MPMI), 10 parts by weight of dicyclopenteny acrylate (hereinafter abbreviated as FA-511A), and 10 parts by weight Styrene (hereinafter abbreviated as SM) and 20 parts by weight of methyl methacrylate (hereinafter abbreviated as MMA) are dissolved in 200 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as EEP), wherein monomer The mixture was fed in such a manner that the reaction temperature was 100 ° C and the reaction time was 6 hours.

After stirring evenly, the temperature of the oil bath was raised to 100 °C. Then, 6 parts by weight of a polymerization initiator 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as AMBN) was dissolved in the EEP, and added in an interval of one hour in five equal parts. Into a four-necked flask.

The reaction temperature of the polymerization process was maintained at 100 °C. After 6 hours, the polymerization product was taken out from the four-necked flask, and the solvent was devolatilized to obtain a second alkali-soluble resin C-2-1.

<Synthesis Example C-2-2 to Synthesis Example C-2-7>

The second alkali-soluble resin of Synthesis Example C-2-2 to Synthesis Example C-2-7 was prepared in the same manner as in Synthesis Example C-2-1, and was distinguished by changing the second alkali-soluble resin. The types of components and their amounts used, the reaction time, the reaction temperature, and the reaction addition time (as shown in Table 1), wherein the compounds corresponding to the reference numerals in Table 1 are shown below. Further, in Table 1, "continuous addition" means that the monomer for copolymerization is continuously fed to the reactor, and the reaction is continuously carried out and continuously discharged; and "one-time addition" means that the monomer for copolymerization is completely fed at one time. To the reactor, the reaction is completely discharged after the reaction is completed.

[Preparation of First Compound (D-1)] <Synthesis Example D-1-1>

In a four-necked flask having a capacity of 1 L, 25 g of trimethylolpropane tris(mercaptoacetate) (fluorenyl 0.28 mol), 177 g of pentaerythritol tetraacrylate (carbon-carbon double bond 2.01 mol), 0.1 g of hydroquinone and 0.01 g of benzyl dimethyl amine were reacted at 60 ° C for 12 hours. For each of the reaction products, the first compound (D-1-1) was obtained by confirming the disappearance of the thiol group by iodine titration. The molecular weight of the first compound (D-1-1) measured by gel filtration chromatography was 4,400.

<Synthesis Example D-1-2>

In a four-necked flask having a capacity of 1 L, 20 g of pentaerythritol tetrakis(mercaptoacetate) (mercapto-based 0.19 mol), 212 g of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (carbon-carbon double bond) were added. 2.12 moles, 0.1 grams of hydroquinone and 0.01 grams of benzyl dimethylamine were reacted at 60 ° C for 12 hours. For each of the reaction products, the first compound (D-1-2) was obtained by confirming the disappearance of the thiol group by iodine titration. The molecular weight of the first compound (D-1-2) as measured by gel filtration chromatography was 11,000.

<Synthesis Example D-1-3>

In a four-necked flask having a capacity of 1 L, 20 g of pentaerythritol tetrakis(mercaptoacetate) (mercapto-based 0.19 mol), 212 g of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (carbon-carbon double bond 2.12) were added. Mohr), 58 g of propylene glycol monomethyl ether acetate, 0.1 g of hydroquinone and 0.01 g of benzyl dimethylamine were reacted at 60 ° C for 12 hours. For each of the reaction products, an intermediate product was obtained by confirming the disappearance of the sulfhydryl group by iodine titration. The molecular weight of this intermediate product as measured by gel filtration chromatography was 11,000. Next, 20 g (0.22 mol) of thioglycolic acid was placed in a four-necked flask, and reacted at 60 ° C for 12 hours. For each reaction product, confirm the sulfhydryl group by iodine titration When disappeared, the first compound (D-1-3) was obtained. The molecular weight of the first compound (D-1-3) as measured by gel filtration chromatography was 12,000.

[Preparation of photosensitive resin composition] <Examples and Comparative Examples>

100 parts by weight of the first alkali-soluble resin (hereinafter referred to as C-1-1) obtained in the above Synthesis Example, and 50 parts by weight of the organic pigment CI Pigment Blue 15:6 (hereinafter abbreviated as A-1-1), and the formula (1) 10 parts by weight of the dye (B-1), 10 parts by weight of the first compound (hereinafter referred to as D-1-1) obtained in the above Synthesis Example, and 30 parts by weight of the second compound DPCA-20 (hereinafter referred to as D-2-1) , 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (hereinafter referred to as E-1) 5 parts by weight, 2,2'-bis (2,4 -dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (hereinafter referred to as E-2) 3 parts by weight, 4,4'-bis(diethylamine)benzophenone (below) (E-3) 2 parts by weight, 3-thiol propyl trimethoxy decane (hereinafter referred to as G-1) 0.1 parts by weight, added to the organic solvent 3-ethoxypropionate ethyl ester (hereinafter referred to as F-1) After 500 parts by weight, a photosensitive resin composition for a color filter is prepared by dissolving and mixing with a shaker, and the blue photosensitive resin composition for the color filter is evaluated by the following respective measurements. The evaluation was carried out in the manner, and the results obtained are shown in Table 2.

<Examples 2 to 11 and Comparative Examples 1 to 6>

In Examples 2 to 11 and Comparative Examples 1 to 6, the same operation method as that of the method for producing a blue photosensitive resin composition for a color filter of Example 1 was used, except that Examples 2 to 11 and Comparative Example 1 were used. The type and amount of the raw materials in the blue photosensitive resin composition for the color filter were changed, and the formulation and the following evaluation results are shown in Tables 2 and 3.

In Table 2 and Table 3:

[Evaluation method] a. Thermal solvent film thickness change rate:

The color filter of the solution state was applied onto a glass substrate having a size of 100 mm × 100 mm by spin coating using a photosensitive resin composition, and dried under reduced pressure at a pressure of about 100 mmHg for about 30 seconds. Then, it was prebaked at a temperature of 80 ° C for 2 minutes to form a prebaked coating film having a film thickness of 2.5 μm. Next, the prebaked coating film having a thickness of 2.5 μm was irradiated onto the prebaked coating film with ultraviolet light having an energy of 60 mJ/cm ² , and then the prebaked coating film was immersed in a developing solution at 23 ° C for 1 minute. After washing with water, followed by post-baking, the post-baking temperature was 230 ° C, and the post-baked film was immersed in a solvent of propylene glycol methyl ether acetate at 60 ° C for 6 minutes, and the film thickness change rate was calculated according to the following formula:

Film thickness change rate = [│ (film thickness after immersion - film thickness before immersion) │ / film thickness before immersion] × 100%

A preferred film thickness variation rate is preferably less than 1%.

◎: film thickness change rate <1%; ○: 1% ≦ film thickness change rate < 3%; △: 3% ≦ film thickness change rate < 5%; ×: 5% ≦ film thickness change rate.

b. Surface roughness:

The prebaked coating film having a film thickness of 2.5 μm in the above evaluation method was irradiated with ultraviolet light (external lens Canon PLA-501F) at a light amount of 100 mJ/cm ² , and then immersed in a developing solution at 23 ° C. In a minute, it was washed with pure water and baked at 235 ° C for 30 minutes to form a pixel-colored layer having a thickness of 2.0 μm on a glass substrate, followed by AFM (Dimension 3100, manufactured by Veeco Instruments Co., Ltd.) to measure surface roughness. . The measurement area was 10 μm ² .

The surface roughness was evaluated according to the following criteria: ◎: less than 6 nm; ○: more than 6 nm, less than 8 nm; Δ: more than 8 nm, less than 10 nm; ×: more than 10 nm.

c. High definition pattern linearity:

The photosensitive resin compositions of the above respective Examples and Comparative Examples were applied by spin coating to a glass substrate having a length and a width of 100 mm. Then, it was dried under reduced pressure at a pressure of about 100 mmHg (mmHg) for about 30 seconds. Next, the above glass substrate was prebaked at 80 ° C for 3 minutes to form a prebaked coating film having a film thickness of 2.5 μm. Next, using a photomask having a strip pattern of 25 μm width (pitch 50 μm), an exposure machine (manufactured by Canon, model: PLA-501F) was used at 300 mJ/cm ² (mJ/cm ² ). The ultraviolet light illuminates the above pre-baked coating film. After irradiation with ultraviolet light, the prebaked coating film was immersed in a developing solution at 23 ° C for 2 minutes. Thereafter, the prebaked coating film was washed with pure water, and the prebaked coating film was post-baked at 200 ° C for 80 minutes to form a photosensitive resin layer having a film thickness of 2.0 μm on the glass substrate.

The strip pattern formed by the above method was observed by an optical microscope, and the linearity of the pattern with high definition was evaluated according to the following criteria: ◎: 90% or more of the strip pattern was linear; ○: 80% or more, less than 90% The strip pattern is linear; Δ: 70% or more, less than 80% of the strip pattern is linear; ×: less than 70% of the strip pattern is linear.

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (13)

A photosensitive resin composition for a color filter, the composition comprising: an organic pigment (A); a dye (B); an alkali-soluble resin (C); a compound having an ethylenically unsaturated group (D); (E); and an organic solvent (F); wherein: the compound (D) having an ethylenically unsaturated group contains the first compound (D-1), and the first compound (D-1) is represented by the formula (b) a (meth) acrylate group remaining after reacting the polyfluorenyl compound represented by the polyfunctional (meth) acrylate represented by the formula (a), and further a thiol compound having a carboxyl group represented by the formula (c) Formed by reaction, In the formula (a): X ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and X ² represents a residue after esterification of n hydroxyl groups in a hydroxyl group-containing compound having m hydroxyl groups, wherein m≧ n, m and n each independently represent an integer of 2 to 20; the hydroxyl group-containing compound having m hydroxyl groups is X ³ (OH) _m or X ³ (OH) _m via propylene oxide, epoxy chloride a compound modified with epichlorohydrin, an alkyl group, an alkoxy group or a hydroxypropyl acrylate; and X ³ (OH) _m is a polyalcohol having a carbon number of 2 to 18, from which the poly a polyhydric alcohol ethers formed by an alcohol, an ester formed by reacting the polyol with an acid, or a silicone; In the formula (b): X ⁴ represents a single bond, a hydrocarbon group having a carbon number of 1, or a linear or branched hydrocarbon group having a carbon number of 2 to 22, and the skeleton of X ⁴ may further include a sulfur atom or constitute an ester group. An oxygen atom; and p represents an integer of 2 to 6, wherein when X ⁴ represents a single bond, p represents 2; when X ⁴ represents a hydrocarbon group having a carbon number of 1, p represents an integer of 2 to 4; when X ⁴ represents When a carbon number is 2 to 22 linear or branched hydrocarbon groups, p represents an integer of 2 to 6; In the formula (c), X ⁵ represents an alkylene group having a carbon number of 1 to 12, and q represents an integer of 1 to 3. The photosensitive resin composition for a color filter according to claim 1, wherein in the first compound (D-1), the fluorenyl group in the polyfluorenyl compound represented by the formula (b) is relative to the formula ( The molar ratio of the carbon-carbon double bond in the polyfunctional (meth) acrylate represented by a) is from 1/200 to 1/2. The photosensitive resin composition for a color filter according to claim 1, wherein in the first compound (D-1), the polyfluorenyl compound represented by the formula (b) and the compound represented by the formula (c) The mercapto group in the mercapto compound having a carboxyl group has a molar ratio of from 1/200 to 1/2 with respect to the carbon-carbon double bond in the polyfunctional (meth)acrylate represented by the formula (a). The photosensitive resin composition for a color filter according to claim 1, wherein the first compound (D- is based on the total amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight. 1) The amount used is in the range of 10 parts by weight to 100 parts by weight. The photosensitive resin composition for a color filter according to claim 1, wherein the alkali-soluble resin (C) comprises a first alkali-soluble resin (C-1), and the first alkali-soluble resin (C-1) is a mixture The polymerization is carried out, and the mixture contains an epoxy compound (i) having at least two epoxy groups, and a compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group. The photosensitive resin composition for a color filter according to claim 5, wherein the epoxy compound (i) having at least two epoxy groups has a structure represented by the following formula (CI) or the following formula (C-II) : In the formula (CI), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are the same or different and each represents a hydrogen atom, a halogen atom, a C ₁ to C ₅ alkyl group, a C ₁ to C ₅ alkoxy group, a C ₆ to C ₁₂ aryl group or a C ₆ to C ₁₂ aralkyl group; In the formula (C-II), R ⁶⁵ to R ⁷⁸ are the same or different and each represents a hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aromatic group, and n represents 0 to An integer of 10. The photosensitive resin composition for a color filter according to claim 5, wherein the first alkali-soluble tree is 100 parts by weight based on the total amount of the alkali-soluble resin (C) used. The fat (C-1) is used in an amount ranging from 4 parts by weight to 100 parts by weight. The photosensitive resin composition for a color filter according to claim 1, wherein the alkali-soluble resin (C) comprises a second alkali-soluble resin (C-2), and the second alkali-soluble resin (C-2) has one a carboxylic acid group-containing first unsaturated monomer (c-2-1), a maleic imide-containing second unsaturated monomer (c-2-2), and a alicyclic ring-containing structure A polymerization reaction product of a mixture of trisaturated monomers (c-2-3). The photosensitive resin composition for a color filter according to claim 8, wherein the second alkali-soluble resin (C-2) is used in an amount of 100 parts by weight based on the total amount of the alkali-soluble resin (C) used. It is 30 parts by weight to 100 parts by weight. The photosensitive resin composition for a color filter according to claim 1, wherein the organic pigment (A) is used in an amount of 50 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C). 500 parts by weight; the dye (B) is used in an amount ranging from 10 parts by weight to 100 parts by weight; the ethylenically unsaturated group-containing compound (D) is used in an amount ranging from 40 parts by weight to 400 parts by weight; The starting agent (E) is used in an amount ranging from 10 parts by weight to 150 parts by weight; the organic solvent (F) is used in an amount ranging from 500 parts by weight to 5000 parts by weight. A method of producing a color filter, which comprises forming a pixel layer using a photosensitive resin composition for a color filter according to any one of claims 1 to 10. A color filter produced by the method of claim 11. A liquid crystal display device comprising a color filter according to claim 12.