TW201604247A - Photosensitive resin composition for color filter, color filter and method for manufacturing the same, liquid crystal display apparatus - Google Patents

Abstract

A photosensitive resin composition for color filter, which is capable of forming to a pixel layer with low surface roughness and good development resistance, a color filter and a method for manufacturing the same, and a liquid crystal display apparatus are provided. The photosensitive resin composition for color filter includes a dye (A), a pigment (B), an alkali-soluble resin (C), a compound (D) containing an ethylenically unsaturated group, a photoinitiator (E), and an organic solvent (E). The dye (A) includes a compound represented by formula (1), and the pigment (B) includes a first pigment (B-1) represented by formula (2).

Description

Photosensitive resin composition for color filter, color filter, method of manufacturing the same, and liquid crystal display device

The present invention relates to a photosensitive resin composition for a color filter, a color filter, a method for producing the same, and a liquid crystal display device. In particular, the present invention relates to a photosensitive resin composition for a color filter which can form a pixel layer having a low surface roughness and excellent development resistance, a color filter, a method for producing the same, and a liquid crystal display device.

Currently, color filters have been widely used in applications such as color liquid crystal displays, color facsimile machines, and color cameras. Moreover, as the market demand for image devices such as color liquid crystal displays is expanding, the production techniques of color filters are also diversified to meet the above market demands.

The color filter can usually be formed on a transparent glass substrate by a method such as a dyeing method, a printing method, an electrophoresis method, or a pigment dispersion method to obtain a color filter. In general, a light shielding layer (or a black matrix) may be further disposed between the pixel layers (also referred to as pixel coloring layers) forming the pixels.

In general, the photosensitive resin composition used for the red pixel is CI Pigment Red 254 (that is, a chlorinated diketopyrrolopyrrole pigment), which can improve the brightness, but is easy to have the surface roughness of the pixel layer. High problem.

Further studies by Japanese Patent Laid-Open No. 2003-504480 disclose that the use of the diketopyrrolopyrrole pigment and the dye can simultaneously improve the brightness and the surface roughness of the pixel layer, but it has the disadvantage of poor development resistance.

Therefore, how to improve the surface roughness of a cured product (such as a pixel layer) formed by the photosensitive resin composition, and to improve the problem of poor development resistance, in order to meet the requirements of the current industry, it is currently One of the problems that the field technicians want to solve.

In view of the above, the present invention provides a photosensitive resin composition for a color filter which is capable of improving the above-mentioned poor development resistance while reducing the surface roughness of the formed cured product (for example, a pixel layer). problem.

The present invention provides a photosensitive resin composition for a color filter comprising a dye (A), a pigment (B), an alkali-soluble resin (C), an ethylenically unsaturated group-containing compound (D), and a photoinitiator. (E) and an organic solvent (F), wherein the dye (A) includes a compound represented by the formula (1).

In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; R ⁷ represents a group having a polymerizable unsaturated group; and a represents an integer of 1 to 5.

Further, the pigment (B) includes the first pigment (B-1) represented by the formula (2).

In an embodiment of the invention, the compound represented by the formula (1) above includes a compound represented by the formula (3).

In the formula (3), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; R ⁸ represents a group having a polymerizable unsaturated group.

In an embodiment of the invention, the above polymerizable unsaturated group is an acrylonitrile group or a methacryl group.

In an embodiment of the invention, the above R ⁸ is a group represented by the formula (4) or a group represented by the formula (5).

In the formulae (4) and (5), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group; and Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a substituted or unsubstituted carbon number of 1 Alkanediyl to 12; Z ¹ represents or Z ² represents a divalent alicyclic hydrocarbon group; b represents an integer of 0 to 12; and c and d each independently represent an integer of 0 to 6.

In one embodiment of the present invention, the dye (A) is obtained by reacting a compound having a hydroxyl group and a polymerizable unsaturated group with a compound represented by the formula (6). The polymerizable unsaturated group is an acrylonitrile group or a methacryl group.

In the formula (6), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; X ^- represents an anion.

In one embodiment of the present invention, the amount of the dye (A) used is 5 parts by weight to 50 parts by weight, and the amount of the pigment (B) used is 40 parts by weight based on 100 parts by weight of the alkali-soluble resin (C). The amount of the first pigment (B-1) used is from 40 parts by weight to 400 parts by weight, and the amount of the compound (D) containing an ethylenically unsaturated group is used in an amount of 500 parts by weight. The photoinitiator (E) is used in an amount of 5 parts by weight to 50 parts by weight, and the organic solvent (F) is used in an amount of 500 parts by weight to 5000 parts by weight, based on 50 parts by weight to 500 parts by weight.

In an embodiment of the invention, the above alkali-soluble resin (C) comprises a first alkali-soluble resin (C-1), and the first alkali-soluble resin (C-1) is obtained by reacting the first mixture. The first mixture includes an epoxy compound (c-1) having at least two epoxy groups and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group.

In one embodiment of the present invention, the above epoxy compound (c-1) having at least two epoxy groups includes a compound represented by the formula (7), a compound represented by the formula (8) or both combination.

In the formula (7), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number of An aryl group of 6 to 12 or an aralkyl group having a carbon number of 6 to 12.

In the formula (8), R ¹⁵ to R ²⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and e represents an integer of 0 to 10.

In one embodiment of the present invention, the first alkali-soluble resin (C-1) is used in an amount of 10 parts by weight to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (C).

The present invention further provides a method of producing a color filter comprising the pixel layer formed using the photosensitive resin composition for a color filter described above.

The present invention further provides a color filter which is produced by the above-described manufacturing method.

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

According to the above, when the photosensitive resin composition for a color filter of the present invention is used for forming a color filter, the problem of poor development resistance can be improved while reducing the surface roughness of the formed cured product. Further, it is applicable to color filters and liquid crystal display devices.

The above described features and advantages of the present invention will be more apparent from the following description.

<Photosensitive Resin Composition for Color Filters>

The present invention provides a photosensitive resin composition for a color filter comprising a dye (A), a pigment (B), an alkali-soluble resin (C), an ethylenically unsaturated group-containing compound (D), and a photoinitiator. (E) and organic solvent (F). Further, if necessary, the photosensitive resin composition for a color filter may further include an additive (G).

Each component of the photosensitive resin composition for color filters (hereinafter, also referred to as "photosensitive resin composition") used in the present invention will be described in detail below.

Here, it should be noted that the following is (meth)acrylic acid and acrylic acid and/or methacrylic acid, and (meth)acrylate is used to represent acrylate and/or methacrylate; likewise, (methyl) The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group.

Further, alkanoyl refers to a divalent radical obtained by removing two hydrogen atoms from an alkane.

Dye (A)

The dye (A) includes a compound represented by the formula (1).

In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; R ⁷ represents a group having a polymerizable unsaturated group; and a represents an integer of 1 to 5.

Specific examples of the alkyl group having 1 to 8 carbon atoms in R ¹ , R ² , R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group and a third butyl group. Base, isobutyl, pentyl, third amyl, hexyl, heptyl, octyl, isooctyl, trioctyl or 2-ethylhexyl, and the like. R ¹ , R ² , R ³ and R ^{4 are} preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the cycloalkyl group having 3 to 8 carbon atoms in R ¹ , R ² , R ³ and R ⁴ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. R ¹ , R ² , R ³ and R ^{4 are} preferably a cycloalkyl group having a carbon number of 5 to 7, and more preferably a cyclohexyl group.

The alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, and the phenyl group in R ¹ , R ² , R ³ and R ⁴ may have a substituent, and the substituent is preferably a halogen atom. -R ^a , -OH, -OR ^a , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ^a , -SO ₃ R ^a , -SO ₂ NHR ^b , -SO ₂ NR ^b R ^c or -SO ₃ -.

Here, R ^a represents a saturated hydrocarbon group having ^a carbon number of 1 to 10. Here, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom, a carbonyl group or -NR ^a -.

R ^b and R ^c each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having a carbon number of 3 to 30 (preferably 3 to 8) or -G, or A heterocyclic group having 2 to 10 carbon atoms formed by bonding R ^b and R ^{c to} each other. Wherein the hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted by a hydroxyl group, a halogen atom, -G, -CH=CH ₂ or -CH=CHR ^a , and the methylene group contained in the alkyl group and the cycloalkyl group The group may be substituted by an oxygen atom, a carbonyl group or -NR ^a -, and the hydrogen atom contained in the heterocyclic group may be substituted by -R ^a , -OH or -G.

M represents a sodium atom or a potassium atom.

G represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. Here, the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted by -OH, -R ^a , -OR ^a , -NO ₂ , -CH=CH ₂ , -CH=CHR ^a or a halogen atom.

The saturated hydrocarbon group in R ^a may be any of a linear chain, a branched chain, and a cyclic chain as long as the carbon number is from 1 to 10, and may have a bridged structure. Specifically, in addition to the alkyl group similar to the above R ¹ , R ² , R ³ and R ⁴ , specific examples of R ^a may further include an anthracenyl group, a fluorenyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, Cyclooctyl or tricyclic fluorenyl. Further, specific examples of the group in which the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group or a methoxyhexyl group.

Further, specific examples of the alkyl group, the cycloalkyl group and the substituent of the phenyl group -CO ₂ R ^a in R ¹ , R ² , R ³ and R ⁴ include a methyloxycarbonyl group and an ethyloxycarbonyl group. Propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, cyclohexyloxycarbonyl or methoxy propyloxycarbonyl. Further, specific examples of -SO ₃ R ^a include a methanesulfonyl group, a ethanesulfonyl group, a hexanesulfonyl group, or a decanesulfonyl group.

Specific examples of the heterocyclic group in which R ^b and R ^c are bonded to each other include pyrrole, pyridine, indole, isoindole, quinoline, isoquinoline. (isoquinoline), carbazole, phenanthridine, acridine or phenothiazine.

Specific examples of the aromatic hydrocarbon group in G include a phenyl group, a naphthyl group, an azulenyl group, and the like. Further, specific examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyridyl group, a pyrrolyl group, an oxazolyl group, and an isoxazole. An isothiazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group or a pyrimidyl group.

Specific examples of the alkyl group having 1 to 8 carbon atoms in R ⁵ and R ⁶ are the same as the specific examples of the alkyl group having 1 to 8 carbon atoms in R ¹ , R ² , R ³ and R ⁴ , and Will be described separately.

a represents an integer of 1 to 5, and when a is an integer of 2 or more, a plurality of R ⁷ may be the same or different, and a is preferably 1 or 2, more preferably 1.

The compound represented by the formula (1) preferably includes a compound represented by the formula (3). Further, the compound represented by the formula (3) is preferably a compound in which the -COOR ⁸ group in the formula (3) is substituted at the ortho position on the benzene ring.

In the formula (3), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; R ⁸ represents a group having a polymerizable unsaturated group.

The polymerizable unsaturated group in R ⁷ and R ⁸ is preferably an acryl fluorenyl group or a methacryl fluorenyl group in view of easiness of the crosslinking reaction. Specific examples of R ⁸ are preferably a group represented by the formula (4) or a group represented by the formula (5).

In the formulae (4) and (5), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group; and Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a substituted or unsubstituted carbon number of 1 Alkanediyl group to 12; Z ¹ represents or Z ² represents a divalent alicyclic hydrocarbon group; b represents an integer of 0 to 12; and c and d each independently represent an integer of 0 to 6.

R ⁹ and R ^{10 are} preferably a methyl group.

Specific examples of the alkanediyl group having 1 to 12 carbon atoms in Y ¹ , Y ² , Y ³ and Y ⁴ include a methylene group, an ethyl group, an ethane-1,1-diyl group, and a propane-1,1. -diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl Butane-1,4-diyl, pentane-1,2-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-1,5-diyl Hexane-1,5-diyl, hexane-1,6-diyl, octane-1,8-diyl or decane-1,10-diyl. Y ¹ , Y ² , Y ³ and Y ^{4 are} preferably an alkanediyl group having a carbon number of 2 to 8, and more preferably an alkanediyl group having a carbon number of 2 to 6.

The substituent of the alkanediyl group includes a hydroxyl group, a halogen atom, a (meth)acryloxy group or a phenoxy group, and is preferably a hydroxyl group.

The divalent alicyclic hydrocarbon group in Z ² is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Further, the alicyclic hydrocarbon group may be a 2 to 4 ring crosslinked cyclic hydrocarbon group.

Specifically, R ^{8 is} preferably a (meth) propylene decyloxyalkyl group. Further, the (meth) propylene decyloxyalkyl group has a total carbon number of preferably 4 to 16, particularly preferably 4 to 10.

b is preferably an integer representing 0 to 3, and c and d are preferably integers each independently representing 0 to 3.

The compound represented by the formula (1) is obtained by reacting a compound having a hydroxyl group and a polymerizable unsaturated group with a compound represented by the formula (6), wherein the polymerizable unsaturated group is an acryloyl group or a methacryloyl group. . A well-known method can be used for this esterification reaction. Further, the -COOH group in the formula (6) is preferably substituted with an ortho position on the benzene ring.

In the formula (6), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; X ^- represents an anion.

The compound having a hydroxyl group and a polymerizable unsaturated group may have one or more hydroxyl groups and a (meth) acrylonitrile group in the compound, and the number of bonds and bonds of the hydroxy group and the (meth) acryl fluorenyl group. The knot position is not particularly limited. Further, as the hydroxyl group, any of an alcoholic hydroxyl group and a phenolic hydroxyl group can be used. Further, when other substituents are contained in addition to the hydroxyl group and the (meth)acrylonium group, the kind, the bonding position, and the number of bonds are not limited.

A specific example of the compound having a hydroxyl group and a (meth)acrylinyl group is preferably a compound represented by the formula (4a) or (5a).

In the formulas (4a) and (5a), R ⁹ , R ¹⁰ , Y ¹ , Y ² , Y ³ , Y ⁴ , Z ¹ , Z ² , b, c and d are the same as in the formulas (4) and (5) R ⁹ , R ¹⁰ , Y ¹ , Y ² , Y ³ , Y ⁴ , Z ¹ , Z ² , b, c and d are synonymous and will not be further described herein.

Specific examples of the compound having a hydroxyl group and a (meth)acrylinyl group preferably include at least one of the compounds represented by the formula (3-1) to the formula (3-4).

In the formula (3-1), R ^d represents a hydrogen atom or a methyl group; f and g each independently represent an integer of 0 to 2; and h represents an integer of 1 to 6. When at least one of f and g is an integer of 1 or more, the -CH(OH)- group, the -CH(CH ₃ )- group, and the -CH ₂ - group may be bonded in an arbitrary order.

In the formula (3-2), R ^e represents a hydrogen atom or a methyl group; and i and j each independently represent an integer of 1 to 12.

In the formula (3-3), R ^f represents a hydrogen atom or a methyl group; and k and m each independently represent an integer of 1 to 12.

In the formula (3-4), R ^g represents a hydrogen atom or a methyl group; W represents a divalent group selected from the group consisting of the groups represented by the following formulas (I) to (IV); n and q each independently represent 0. An integer of up to 6.

Specific examples of the compound represented by the formula (3-1) include 2-hydroxyethyl (meth)acrylate, 1-methyl-2-hydroxyethyl (meth)acrylate, and 2-methyl (meth)acrylate. 2-hydroxyethyl ester, 3-hydroxypropyl (meth)acrylate, 1-glycerol (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (A) 5-hydroxypentyl acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 9-hydroxyl (meth) acrylate An oxime ester, 10-hydroxydecyl (meth)acrylate, 11-hydroxyundecyl (meth)acrylate or 12-hydroxydodecyl (meth)acrylate.

Further, specific examples of the compound represented by the formula (3-2) include (meth)acrylic acid 2-(6-hydroxyhexyloxy)ethyl ester, 3-(6-hydroxyhexyloxy)propyl (meth)acrylate, 4-(6-hydroxyhexyloxy)butyl (meth)acrylate Ester, 5-(6-hydroxyhexyloxy)pentyl (meth)acrylate or (meth)acrylic acid (6-hydroxyl) such as 6-(6-hydroxyhexyloxy)hexyl (meth)acrylate Commercially available products of (meth)acrylic acid (6-hydroxyhexyloxy) alkyl esters include the trade names PLACCEL FM1D, PLACCEL FM2D (above, DAICEL chemistry) Industrial (share) system, etc.

Further, specific examples of the compound represented by the formula (3-3) include 2-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)ethyl (meth)acrylate and (meth)acrylic acid. 3-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)propyl ester, 4-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)(meth)acrylate Butyl ester, 5-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)pentyl (meth)acrylate or 6-(3-hydroxy-2,2-dimethyl (meth)acrylate (3-hydroxy-2,2-dimethylpropoxycarbonyloxy)alkyl (meth)acrylate, etc.; (meth)acrylic acid (3-hydroxyl) Commercial products of the -2,2-dimethylpropoxycarbonyloxy)alkyl esters include the trade name HEMAC1 (manufactured by DAICEL Chemical Industry Co., Ltd.) and the like.

Further, specific examples of the compound represented by the formula (3-4) include 4-hydroxycyclohexyl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, and (meth)acrylic acid. 2-[4-(2-hydroxyethyl)cyclohexyl]ethyl ester, 3-hydroxybicyclo(2.2.1)hept-5-en-2-yl (meth)acrylate, (meth)acrylic acid (3) -Hydroxymethylbicyclo[2.2.1]hept-5-en-2-yl)methyl ester, 2-[3-(2-hydroxyethyl)bicyclo[2.2.1]hept-5-(meth)acrylate Alken-2-yl]ethyl ester, 8-hydroxybicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, 2-hydroxyoctahydro-4,7-arylene (meth)acrylate Methyl 茚-5-yl ester (meth)acrylic acid 2-hydroxy Octahydro-4,7-methanoindene-5-yl ester), (meth)acrylic acid (2-hydroxymethyl octahydro-4,7-methylene fluoren-5-yl)methyl ester, (meth)acrylic acid 2 -[2-(2-hydroxyethyl) octahydro-4,7-methylene fluoren-5-yl]ethyl ester, 3-hydroxyadamantan-1-yl (meth)acrylate, (methyl) Acrylic acid (3-hydroxymethyladamantan-1-yl)methyl ester or 2-[3-(2-hydroxyethyl)adamantan-1-yl]ethyl (meth)acrylate or the like.

Among these compounds having a hydroxyl group and a (meth)acrylinyl group, from the viewpoint of reactivity, the following compounds are preferable: f and g in the formula (3-1) are 0, and h is 2 to a compound of 6; wherein, in the formula (3-1), f is 1, g is 0, and h is a compound of 1 to 5; wherein i in the formula (3-2) is 2 or 3, and j is 1; In the formula (3-3), k is 2 or 3, and m is a compound of 1; n in the formula (3-4) is 1 or 2, or q is 1 or 2, and W is a formula (I) Or a compound of the formula represented by the formula (IV).

The compound having a hydroxyl group and a (meth)acrylinyl group preferably includes 2-hydroxyethyl (meth)acrylate, 1-glyceryl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. 2-(6-hydroxyhexyloxy)ethyl acrylate, 2-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)ethyl (meth)acrylate, (methyl) (4-Hydroxymethylcyclohexyl)methyl acrylate or (3-hydroxymethyladamantan-1-yl)methyl (meth) acrylate.

Specific examples of the compound having a hydroxyl group and a (meth)acrylinyl group, in addition to the compound represented by the formula (3-1) to the formula (3-4), include 4-hydroxyphenyl (meth) acrylate and pentaerythritol. (pentaerythritol tri(meth)acrylate), dipentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, a compound represented by formula (3-5) or formula (3-6) The compound represented.

In the present invention, a compound having a hydroxyl group and a (meth)acrylinyl group may be a single Use alone or in combination of two or more.

Next, X ^- in the above formula (6) will be described.

Specific examples of X ^- include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion or amethide anion.

Halogen ions include fluoride ions, chloride ions, bromide ions or iodide ions.

Further, specific examples of the boron anion include inorganic boron anions such as BF ₄ ^- ; (CF ₃ ) ₄ B ^- , (CF ₃ ) ₃ BF ^- , (CF ₃ ) ₂ BF ₂ ^- , (CF ₃ ) BF ₃ ^- , ( C ₂ F ₅ ) ₄ B ^- , (C ₂ F ₅ ) ₃ BF-, (C ₂ F ₅ ) BF ₃ ^- , (C ₂ F ₅ ) ₂ BF ₂ ^- , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ^- , (C ₆ F ₅ ) ₄ B ^- , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ^- , (CF ₃ C ₆ H ₄ ) ₄ B ^- , (C ₆ F ₅ ) ₂ BF ₂ ^- , (C ₆ F ₅ )BF ₃ ^- , (C ₆ H ₃ F ₂ ) ₄ B ^- , B(CN) ₄ ^- , B(CN)F ₃ ^- , B(CN) ₂ F ₂ ^- , B( CN) ₃ F ^- , (CF ₃ ) ₃ B(CN) ^- , (CF ₃ ) ₂ B(CN) ₂ ^- , (C ₂ F ₅ ) ₃ B(CN) ^- , (C ₂ F ₅ ) ₂ B (CN) ₂ ^- , (nC ₃ F ₇ ) ₃ B(CN) ^- , (nC ₄ F ₉ ) ₃ B(CN) ^- , (nC ₄ F ₉ ) ₂ B(CN) ₂ ^- , (nC ₆ F ₁₃ ) ₃ B(CN) ^- , (CHF ₂ ) ₃ B(CN) ^- , (CHF ₂ ) ₂ B(CN) ₂ ^- , (CH ₂ CF ₃ ) ₃ B(CN) ^- , (CH ₂ CF _{3 2} B(CN) ₂ ^- , (CH ₂ C ₂ F ₅ ) ₃ B(CN) ^- , (CH ₂ C ₂ F ₅ ) ₂ B(CN) ₂ ^- , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B(CN) ₂ ^- , (nC ₃ F ₇ CH ₂ ) ₂ B(CN) ₂ ^- , (C ₆ H ₅ ) ₃ B(CN) ^- , tetraphenylborate, tetrakis(monofluorophenyl) Borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl) Acid salt, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(dimethylphenyl)borate Salt, (triphenyl, pentafluorophenyl) borate, [e (pentafluorophenyl), phenyl] borate or tridecahydro-7,8-dicarbonyl undecanoate (tridecahydride-7,8) In addition to the organic-boron anion, it is also disclosed in Japanese Laid-Open Patent Publication No. Hei 10-195119, JP-A-2010-094807, JP-A-2006-243594, and JP-A-2002- A boron anion described in Japanese Laid-Open Patent Publication No. Hei. No. 041-533.

Further, specific examples of the phosphate anion include inorganic phosphate anions such as HPO ₄ ^2- , PO ₄ ^3- , PF ₆ ^- ; (C ₂ F ₅ ) ₂ PF ₄ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , [( CF ₃ ) ₂ CF] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (nC ₃ F ₇ ) ₂ PF ₄ ^- , (nC ₃ F ₇ ) ₃ PF ₃ ^- , (nC ₄ F _{9 3} PF ₃ ^- , (C ₂ F ₅ )(CF ₃ ) ₂ PF ₃ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ^- , ( nC ₄ F ₉ ) ₂ PF ₄ ^- , (nC ₄ F ₉ ) ₃ PF ₃ ^- , (C ₂ F ₄ H)(CF ₃ ) ₂ PF ₃ ^- , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ^- , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ^- , an octyl phosphate anion, a dodecyl phosphate anion, an octadecyl phosphate anion, a phenyl phosphate anion or a nonylphenyl phosphate anion.

Further, specific examples of the carboxylic acid anion include CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- and the like, and in addition to Japanese Patent Laid-Open Publication No. 2009-265641 or JP-A-2008- A carboxylic acid anion described in Japanese Patent No. 096680.

Further, specific examples of the sulfate anion include a sulfate anion and a sulfite anion.

Specific examples of the organic sulfonic acid anion include an alkylsulfonic acid anion such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid or nonafluorobutanesulfonic acid; benzenesulfonic acid and benzenedisulfonate An arylsulfonic acid anion such as ion, p-toluenesulfonic acid, p-trifluoromethanesulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid or naphthalene disulfonate ion, in addition to 2-(methyl) Propylene oxime-1,1,2,2-tetrafluoroethanesulfonic acid, 2-(4-vinylphenoxy)-1,1,2,2-tetrafluoroethanesulfonic acid, in International Publication No. 2011 An organic sulfonic acid anion described in Japanese Patent No. 3,736,221, or Japanese Patent Application Laid-Open No. 2011-070172.

Further, specific examples of the nitrogen anion include [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ )N(CF ₃ SO ₂ )] ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , [(FSO ₂ )N(CF ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ^- , [ (FSO ₂ )N{CF ₃ CF ₂ (CF ₃ )CFSO ₂ }] ^- , [(FSO ₂ )N{(CF ₃ ) ₃ CSO ₂ }] ^-, etc., in addition to The nitrogen anions described in JP-A-2010-090341, and JP-A-2010-090341.

Further, specific examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ^- , (CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ^- , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ^- , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ^- , (FSO ₂ ) ₃ C ^- and the like, in addition to Japanese Patent Laid-Open No. 2011-145540, No. 5,554,664 The methide anion described in JP-A-2005-309657, JP-A-2004-085657, and JP-A-2010-505787.

The dye (A) may be used in an amount of 5 parts by weight to 50 parts by weight, based on the amount of the alkali-soluble resin (C) to be described later, preferably 6 parts by weight to 40 parts by weight, and more preferably 7 parts by weight. Parts by weight to 30 parts by weight.

It is to be noted that when the photosensitive resin composition does not contain the dye (A), the development resistance of the photosensitive resin composition is not good.

The dye (A) may include a dye other than the compound represented by the formula (1), and may also include a red dye such as CI Solvent Red 45, CI Solvent Red 49; CI Solvent Blue 35, CI Solvent Blue 37, CI Solvent Blue 59 , blue dye such as CI Solvent Blue 67; acid red dye such as CI Acid Red 91, CI Acid Red 92, CI Acid Red 97, CI Acid Red 114, CI Acid Red 138, CI Acid Red 151, CI Acid Red 289; Acid blue dyes such as CI Acid Blue 80, CI Acid Blue 83, and CI Acid Blue 90.

Pigment (B)

The pigment (B) includes the first pigment (B-1). In addition, the pigment (B) can be selectively A second pigment (B-2) is included.

First pigment (B-1)

The first pigment (B-1) is a red pigment, and the first pigment (B-1) is a compound represented by the formula (2).

The first pigment (B-1) represented by the formula (2) is a brominated diketopyrrolopyrrole pigment, which can be produced by a synthesis method disclosed in a known patent document (Publication No. WO 2009/144115).

The above synthesis method is, for example, a method for synthesizing a brominated diketopyrrolopyrrole pigment using a succinic acid diester as a raw material. Specifically, 2 moles of 4-bromobenzonitrile and 1 mole of succinic acid diester are added to an inert organic solvent (for example, tert-amylalcohol). Next, the condensation reaction is carried out in the presence of an alkali metal or an alkali metal alkoxide and at a high temperature of 80 ° C to 110 ° C to An alkali metal salt of a brominated diketopyrrolopyrrole compound is formed. Then, an alkali metal salt of a brominated diketopyrrolopyrrole compound is protonated using water, an alcohol or an acid or the like to obtain a brominated diketopyrrolopyrrole pigment. At the stage of protonation, the size of the primary particle size can be controlled by the temperature of protonation, the water used, the ratio of alcohol to acid, and the amount of addition. The above synthesis method is merely illustrative, and the synthesis method of the brominated diketopyrrolopyrrole pigment of the present invention is not limited thereto.

The first pigment (B-1) may be used in an amount of 40 parts by weight to 400 parts by weight, preferably 50 parts by weight to 350 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C) to be described later, and More preferably, it is 60 parts by weight to 300 parts by weight.

It is to be noted that when the photosensitive resin composition does not contain the first pigment (B-1), the cured product formed has a problem that the surface roughness is high.

Second pigment (B-2)

In addition to the above-mentioned first pigment (B-1), the pigment (B) of the present invention may be optionally mixed with two or more kinds of the second pigments (B-2). The second pigment (B-2) is usually an organic pigment or an inorganic pigment, and it is preferred to use a pigment having high coloring property and high heat resistance.

Specific examples of the second pigment (B-2) include a diketopyrrolopyrrole pigment other than the first pigment (B-1); azo (Azo), disazo (Disazo) or polyazo (Polyazo) Azo pigment; copper phthalocyanine, copper phthalocyanine (Halogenated copper) Phthalocyanine pigments such as phthalocyanine or metal-free phthalocyanine; aminoguanidine (Aminoanthraquinone), diamino dianthraquinone, anthrapyrimidine, Flavanthrone, and ruthenium Anthraquinone pigments such as Anthanthrone, Indanthrone, Pyranthrone or Violanthrone; Quinacridone pigment; Dioxazine Pigment; Perynone pigment; Perylene pigment; thioindigo pigment; Isoindoline pigment; Isoindolinone pigment; Quinophthalone pigment ; Threne pigment; Quinoline pigment; Benzimidazolone pigment, metal complex pigment or a combination of the above pigments.

The second pigment (B-2) is preferably different from the first pigment (B-1). Further, the second pigment (B-2) is preferably selected from the group consisting of diketopyrrolopyrrole pigments, azo pigments, anthraquinone pigments, anthraquinone pigments, quinacridone pigments, benzimidazolone pigments. And a group consisting of quinoline pigments. The pigment can be adjusted by adjusting the mixing ratio of the first pigment (B-1) and the second pigment (B-2) in the pigment (B) and the mixing ratio of the various pigments in the second pigment (B-2). )s color.

Specific examples of the red pigment of the second pigment (B-2) include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 41, 47, 48, 48:1, 48:2, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53 53:1, 53: 2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81: 2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, Red pigment of 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275 or 276.

In order to obtain a better brightness, the red pigment is preferably CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254, and more preferably CI Pigment Red 177, 209, 224, 242 or 254. It is to be noted that C.I. Pigment Red 254 is a chlorinated diketopyrrolopyrrole pigment (the substituent on the benzene ring is chlorine), which can improve the brightness, but the formed cured product has a problem of high surface roughness. In contrast, the first pigment (B-1) in the present case is a brominated diketopyrrolopyrrole pigment (the substituent on the benzene ring is bromine), which not only improves the brightness but also the surface roughness of the formed cured product. low.

Specific examples of the yellow pigment of the second pigment (B-2) include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, Yellow of 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207 or 208 pigment.

In order to obtain a preferred brightness, the yellow pigment is preferably CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185, and more preferably CI Pigment Yellow 83, 138, 139, 150 or 180.

The specific color of the orange pigment of the second pigment (B-2) includes CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79.

For better brightness, the orange pigment is preferably C.I. Pigment Orange 38 or 71.

The inorganic pigment of the second pigment (B-2) specifically includes barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide red [red iron oxide (III)], cadmium red, ultramarine blue, and low iron cyanide. Metal oxide powder of iron, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, titanium dioxide or triiron tetroxide, gold It is a sulfide powder or a metal powder.

In order to obtain a balance between brightness and saturation, and to obtain good coatability, sensitivity, and development resistance, an inorganic pigment may be used in combination with an organic pigment.

The pigment (B) may be used in an amount of 40 parts by weight to 500 parts by weight, preferably 60 parts by weight to 360 parts by weight, and more preferably 80, based on 100 parts by weight of the alkali-soluble resin (C) to be described later. Parts by weight to 320 parts by weight.

Alkali soluble resin (C)

The alkali-soluble resin (C) includes a first alkali-soluble resin (C-1). Further, the alkali-soluble resin (C) may further include a second alkali-soluble resin (C-2).

First alkali soluble resin (C-1)

The first alkali-soluble resin (C-1) is obtained by reacting the first mixture. The first mixture includes an epoxy compound (c-1) having at least two epoxy groups and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. Further, the first mixture may more optionally include a carboxylic anhydride compound (c-3), an epoxy group-containing compound (c-4), or a combination of the two.

Epoxy compound having at least two epoxy groups (c-1)

The epoxy compound (c-1) having at least two epoxy groups includes a compound represented by the formula (7), a compound represented by the formula (8), or a combination of the two.

Specifically, the compound represented by the formula (7) is as follows.

In the formula (7), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number of An aryl group of 6 to 12 or an aralkyl group having a carbon number of 6 to 12.

The compound represented by the formula (7) can be obtained by reacting a bisphenol fluorene with a halogenated propylene oxide (epihalohydrin).

In detail, specific examples of the bisphenol quinoid type compound include: 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyl) 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)indole (9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene), 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene (9,9-bis(4-hydroxy) -3,5-dibromophenyl)fluorene) or an analog thereof, or a combination of the above compounds.

Specific examples of the epoxidized propylene oxide (epihalohydrin) include 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-epoxyhydrin or the like, or a combination thereof. .

Specific examples of the bisphenol quinoid compound having an epoxy group include (1) a product manufactured by Nippon Steel Chemical Co., Ltd.: ESF-300 or the like; (2) Osaka Natural Gas (Osaka) Goods manufactured by Gas Co., Ltd.: for example, PG-100, EG-210 or the like; (3) Goods manufactured by SMS Technology Co., Ltd.: for example, SMS-F9PhPG, SMS-F9CrG, SMS -F914PG or an analogue thereof.

Further, specifically, the compound represented by the formula (8) is as follows.

In the formula (8), R ¹⁵ to R ²⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and e represents an integer of 0 to 10.

The compound represented by the formula (8) can be made in the presence of an alkali metal hydroxide The compound represented by the formula (8-1) is obtained by reacting with a halogenated propylene oxide.

In the formula (8-1), and are respectively of formula (. 8) and R ¹⁵ to R ²⁸ are the same as defined in R ¹⁵ to R e and ²⁸ e is defined, which is not further described herein.

The method for synthesizing the compound represented by the formula (8-1) is as follows. First, a compound represented by the formula (8-2) is subjected to a condensation reaction with a phenol in the presence of an acid catalyst to form a formula. The compound represented by (8-1). Next, an excess amount of halogenated propylene oxide is added to carry out dehydrohalogenation of the halogenated propylene oxide with the compound represented by the formula (8-1) to obtain a compound represented by the formula (8).

In the formula (8-2), the same as defined in R ¹⁷ to R ²⁰ defined in formula (. 8) of the R ¹⁷ to R ^20, which is not further described herein. X ¹ and X ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. The above halogen atom may be chlorine or bromine. The above alkyl group is preferably a methyl group, an ethyl group or a tert-butyl group. The above alkoxy group is preferably a methoxy group or an ethoxy group.

Specific examples of the phenols include: phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol , octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol, propylene Propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol, cyclohexylcresol or the like. The above phenols may be used singly or in combination of two or more.

The compound represented by the formula (8-2) is used in an amount of 1 mol, and the phenol is used in an amount of from 0.5 mol to 20 mol, and preferably from 2 mol to 15 mol.

Specific examples of the acid catalyst include: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous, chlorination Zinc chloride or an analogue thereof. The acid catalyst is preferably p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or a combination of the above compounds. The acid catalysts may be used singly or in combination of two or more.

Further, the amount of the above acid catalyst used is not particularly limited. However, the amount of the compound represented by the above formula (8-2) is 100% by weight (% by weight), and the acid catalyst is preferably used in an amount of 0.1% by weight to 30% by weight.

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

The organic solvent is used in an amount of 50% by weight to 300% by weight, based on the total weight of the compound represented by the formula (8-2) and the phenol, of 100% 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 condensation reaction has an operation time of 1 hour to 8 hours.

After completion of the above condensation reaction, a neutralization treatment or a water washing treatment may be performed. 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 above water washing treatment can be carried out using a neutralizing agent, wherein the neutralizing agent is an alkaline substance, and specifically includes: an alkali metal hydrogen of sodium hydroxide, potassium hydroxide or the like. Oxide; alkaline earth metal hydroxide of calcium hydroxide, magnesium hydroxide or the like; diethylene triamine, triethylenetetramine, aniline (aniline), an organic amine of phenylene diamine or an analogue thereof; ammonia, sodium dihydrogen phosphate or a combination of the above. The above neutralizing agents may be used singly or in combination of two or more. The above water washing treatment can be carried out by a conventional method, for example, by adding an aqueous solution containing a neutralizing agent to the solution after the reaction, and carrying out the extraction repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off under reduced pressure and concentrated, whereby the compound represented by the formula (8-1) can be obtained.

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or a combination of the above compounds. 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 one embodiment, the alkali metal hydroxide added in the dehydrohalogenation reaction may also be an aqueous solution thereof. In this embodiment, while the above 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, and the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or its The quaternary ammonium salt of the analog is used as a catalyst, and after reacting at 50 ° C to 150 ° C for 1 hour to 5 hours, an alkali metal hydroxide or an aqueous solution thereof is added. Next, the reaction is allowed to proceed for 1 hour to 10 hours at a temperature of from 20 ° C to 120 ° C to carry out a dehydrohalogenation reaction.

The above-mentioned halogenated propylene oxide is used in an amount of 1 equivalent to 20 equivalents, and preferably 2 equivalents to 10 equivalents, based on the total equivalent of the hydroxyl group in the compound represented by the formula (8-1). The total hydroxyl group equivalent weight in the compound having the structure of the above formula (8-1) is 1 equivalent, and the alkali metal hydroxide added in the above dehydrohalogenation reaction is used in an amount of 0.8 to 15 equivalents, and preferably From 0.9 equivalents to 11 equivalents.

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

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 distillation under reduced pressure, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg).

In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the dehydrohalogenated reaction solution may be added to a solvent such as toluene or methyl isobutyl ketone, or an alkali metal such as sodium hydroxide or potassium hydroxide. An aqueous hydroxide solution is used and the dehydrohalogenation reaction is carried out again. In the dehydrohalogenation reaction, the total hydroxyl group equivalent weight in the compound represented by the formula (8-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, and preferably 0.05 moles to 0.2 moles. 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 the dehydrohalogenation reaction is completed, the salt is removed by filtration, washing, and the like. class. Further, a solvent such as toluene or methyl isobutyl ketone is removed by distillation under reduced pressure to obtain a compound represented by the formula (8). Specific examples of the compound represented by the above formula (8) include those commercially available from Nippon Kayaku, such as NC-3000, NC-3000H, NC-3000S, and NC-3000P.

a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (c-2)

Specific examples of the compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group are selected from the group consisting of (1) to (3): (1) acrylic acid, methyl group Acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyloxyethyl adipate, 2-methyl Acryloxybutylene adipate, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl malay Acid, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropenyloxypropyl Tetrahydrophthalic acid, 2-methylpropenyl propyl phthalate, 2-methylpropenyl butyl phthalate or 2-methyl propylene oxybutyl phthalic acid; (2) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound comprises adipic acid, succinic acid, maleic acid or phthalic acid; (3) by hydroxyl group-containing (methyl) Ester with the carboxylic acid anhydride compound (c-3) obtained by reacting a half ester compound, wherein the hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl acrylate [(2-hydroxyethyl) Acrylate], 2-hydroxyethylmethacrylate [2-hydroxyethyl) methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate [(2- Hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate, and the like. Further, the carboxylic anhydride compound described herein may be the same as the carboxylic anhydride compound (c-3) contained in the first mixture of the aforementioned first alkali-soluble resin (C-1).

Carboxylic anhydride compound (c-3)

The carboxylic anhydride compound (c-3) may be selected from the group consisting of (1) to butanedioic anhydride, maleic anhydride, and itacona. Anitaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, methyl endo-methylene tetrahydrophthalic anhydride, chlorendic anhydride, glutaric anhydride, trimellitic anhydride a dicarboxylic anhydride compound such as 1,2,4-benzenetricarboxylic anhydride; and (2) benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride, double A tetracarboxylic anhydride compound such as phenyl ether tetracarboxylic dianhydride.

Epoxy group-containing compound (c-4)

The epoxy group-containing compound (c-4) may be selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, and an epoxy group. A group of unsaturated compounds or a combination of the above compounds. The above-mentioned unsaturated group-containing glycidyl ether compound is manufactured by Nagase Chemical Co., Ltd., and is modeled as Denacol EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX-146, and Denacol EX-171. Or products such as Denacol EX-192.

The first alkali-soluble resin (C-1) may be an epoxy compound (c-1) having at least two epoxy groups and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. The hydroxyl group-containing reaction product formed by the polymerization reaction, wherein the epoxy compound (c-1) having at least two epoxy groups is a compound represented by the formula (7). Next, the carboxylic anhydride compound (c-3) is added to the reaction solution to carry out a polymerization reaction. The number of equivalents of the hydroxyl group of the hydroxy group-containing reaction product is 1 equivalent, and the number of equivalents of the acid anhydride group contained in the carboxylic anhydride compound (c-3) is preferably from 0.4 equivalents to 1 equivalent, more preferably from 0.75 equivalents to 1 equivalent. . When a plurality of carboxylic anhydride compounds (c-3) are used, these carboxylic anhydride compounds 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 (c-3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is preferably from 1/99 to 90/10. And More preferably 5/95 to 80/20. Further, the above reaction may be operated at a temperature of from 50 ° C to 130 ° C.

The first alkali-soluble resin (C-1) may be an epoxy compound (c-1) having at least two epoxy groups and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. The hydroxyl group-containing reaction product formed by the reaction, wherein the epoxy compound (c-1) having at least two epoxy groups is a compound represented by the formula (6). Next, a polymerization reaction is carried out by adding a carboxylic anhydride compound (c-3), an epoxy group-containing compound (c-4), or a combination of the two to the reaction solution. The total number of equivalents of the epoxy groups in the compound represented by the formula (6) is 1 equivalent, and the number of acid equivalents of the compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is preferably the same. It is from 0.8 equivalents to 1.5 equivalents, and more preferably from 0.9 equivalents to 1.1 equivalents. The total amount of the hydroxyl group based on the above hydroxyl group-containing reaction product is 100 mol%, and the carboxylic anhydride compound (c-3) is used in an amount of 10 mol% to 100 mol%, preferably 20 mol% to 100%. Mohr%, and more preferably 30 mol% to 100 mol%.

When the first alkali-soluble resin (C-1) described above is prepared, in order to shorten the reaction time, a basic compound is generally added to the reaction solution as a reaction catalyst. The reaction catalyst includes triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethylammonium chloride or benzyl chloride. Benzylethylethylammonium chloride or the like. The reaction catalysts may be used singly or in combination of two or more.

The total amount of the epoxy compound (c-1) having at least two epoxy groups and the compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 parts by weight, and the reaction is carried out. The amount of the catalyst used is preferably from 0.01 part by weight to 10 parts by weight, and 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 may be added to the reaction solution. Polymerization inhibitors include methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di-t-butyl-p -cresol), phenothiazine, and the like. The polymerization inhibitors may be used singly or in combination of two or more.

The total amount of the epoxy compound (c-1) having at least two epoxy groups and the compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 parts by weight, polymerized. The inhibitor is preferably used in an amount of from 0.01 part by weight to 10 parts by weight, and more preferably from 0.1 part by weight to 5 parts by weight.

When the first alkali-soluble resin (C-1) is prepared, a polymerization solvent can be optionally used. The polymerization solvent includes an alcohol solvent such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; a ketone solvent such as methyl ethyl ketone or cyclohexanone; toluene; An aromatic hydrocarbon solvent such as xylene; a cellophane solvent such as cellosolve or butyl cellosolve; carbitol and butyl carbitol Carbene-like solvent; propylene glycol monomethyl ether a propylene glycol alkyl ether solvent such as monomethyl ether); a poly(propylene glycol alkyl ether) solvent such as di(propylene glycol) methyl ether; ethyl acetate, acetic acid Acetate solvent such as butyl ester, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; ethyl lactate, butyl lactate ( A solvent such as an alkyl lactate such as butyl lactate; or a solvent of a dialkyl glycol ether. The polymerization solvent may be used singly or in combination of two or more. Further, the acid value of the first alkali-soluble resin (C-1) is preferably from 50 mgKOH/g (mgKOH/g) to 200 mgKOH/g, and more preferably from 60 mgKOH/g to 150 mgKOH/g. .

The first alkali-soluble resin (C-1) may be used in an amount of 10 parts by weight to 100 parts by weight, preferably 12 parts by weight to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C), and More preferably, it is 15 parts by weight to 60 parts by weight. When the alkali-soluble resin (C) contains the first alkali-soluble resin (C-1), the obtained photosensitive resin composition is preferably excellent in developability.

Second alkali soluble resin (C-2)

The second alkali-soluble resin (C-2) is a total of ethylenically unsaturated monomers (c-5) having at least one carboxylic acid group and other copolymerizable ethylenically unsaturated monomers (c-6). Polymerized, wherein the ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group and the other copolymerizable ethylenically unsaturated monomer (c-6) are used in a total amount of 100 Quantities.

Specific examples of the ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acrylonitrile ethoxylate Unsaturated monocarboxylic acid compound such as butyl succinate, 2-methyl propylene ethoxy succinate, 2-isobutyl hydrazide ethoxy succinic acid monoester; maleic acid, maleic anhydride An unsaturated dicarboxylic acid (anhydride) compound such as fumaric acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride; or a trivalent or higher unsaturated polyvalent carboxylic acid (anhydride) compound. The above ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group may be used singly or in combination of two or more.

The ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group is preferably acrylic acid, methacrylic acid, 2-propenyl ethoxy succinate, 2-methyl propylene ethoxy ethoxylate An acid ester, 2-isobutylene ethoxylate succinate or a combination of the above compounds.

Specific examples of the other copolymerizable ethylenically unsaturated monomer (c-6) include dicyclopentyl acrylate, dicyclopentyl ethoxy acrylate, dicyclopentenyl acrylate (hereinafter referred to as FA-511A). , dicyclopentenyloxyethyl acrylate (hereinafter referred to as FA-512A), dicyclopentyl methacrylate, dicyclopentyl ethoxy methacrylate, dicyclopentenyl methacrylate, Dicyclopentenyl ethoxy methacrylate, styrene, α-methyl styrene, vinyl toluene, p-chlorostyrene, methoxybenzene An aromatic vinyl compound such as ethylene; N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyl Phenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-cyclohexyl Maleimide compound such as imine or the like; methyl acrylate, methyl methacrylate, benzyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, methacrylic acid Propyl ester, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, methacrylic acid second Butyl ester, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy methacrylate Propyl ester, propylene Acid-3-hydroxypropyl ester, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, methacrylic acid-3- Hydroxybutyl ester, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, Phenyl methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, lauryl methacrylate , tetradecyl methacrylate (tertadecyl Methacrylate), cetyl methacrylate, octadecylmethacrylate, eicosyl methacrylate, behenyl methacrylate (Unsaturated carboxylic acid ester compound of (docosyl methacrylate); N-N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N-N-N-ethyl acrylate Aminopropyl acrylate, N,N-dimethylaminopropyl methacrylate, N-N-dibutylaminopropyl acrylate, N-isobutylaminoethyl methacrylate; Epoxypropyl acrylate An unsaturated carboxylic acid glycidyl ester compound such as an ester or a glycidyl methacrylate; a vinyl carboxylate compound such as vinyl acetate, vinyl propionate or vinyl butyrate; vinyl methyl ether or ethylene An unsaturated ether group compound such as ethyl ether, allyl epoxypropyl ether or methallyl epoxypropyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinyl cyanide, etc. Vinyl cyanide compound; acrylamide, methacrylamide, α-chloropropenylamine, N-hydroxyethyl propylene An unsaturated decylamine compound such as guanamine or N-hydroxyethyl methacrylamide; an aliphatic conjugated diene compound such as 1,3-butadiene, isoamylene or chlorinated butadiene or the above compound The combination. Specific examples of the other copolymerizable ethylenically unsaturated monomer (c-6) may be used singly or in combination of two or more.

The other copolymerizable ethylenically unsaturated monomer (c-6) is preferably selected from the group consisting of dicyclopentyl acrylate, dicyclopentyl ethoxy acrylate, dicyclopentenyl acrylate, dicyclopentenyl ethoxylate. Acrylate, biscyclopentyl methacrylate, dicyclopentylethoxy methacrylate, dicyclopentenylmethyl Acrylate, dicyclopentenyl ethoxy methacrylate, styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid - A group consisting of 2-hydroxyethyl ester, benzyl acrylate, and benzyl methacrylate.

Solvents for preparing the second alkali-soluble resin (C-2) include 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 methyl 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, condensate (poly)alkylene glycol monoalkyl ether solvent such as tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol (poly)alkylene glycol monoalkyl ether acetate solvent such as monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diglyme, diethylene glycol methyl ether, digan Other ether solvents such as alcohol diethyl ether and tetrahydrofuran; ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate and 2-hydroxypropionic acid Alcoholic acid alkyl ester solvent such as ester; methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyl Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, acetic acid Ethyl ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, N-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, acetone Other ester solvents such as n-propyl acrylate, ethyl acetoacetate, ethyl acetate, ethyl 2-oxybutyrate; aromatic hydrocarbon solvents such as toluene and xylene; or N-methyl A carboxylic acid guanamine solvent such as pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide. The above solvents may be used singly or in combination of two or more.

The solvent for preparing the second alkali-soluble resin (C-2) is preferably propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate or a combination of the two.

The initiator used to prepare the second alkali-soluble resin (C-2) is generally a radical polymerization initiator. The radical polymerization initiator includes 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile) [2, 2'-azobis-(2,4-dimethylvaleronitrile)], 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)[2,2'-azobis-(4- Azo (azo) compound such as methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile; a peroxy compound such as benzoylperoxide or a combination of the above compounds.

The second alkali-soluble resin (C-2) may be used in an amount of from 0 part by weight to 100 parts by weight, preferably from 15 parts by weight to 90 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C). More preferably, it is 30 parts by weight to 80 parts by weight.

Compound containing ethylenically unsaturated group (D)

The ethylenically unsaturated group-containing compound (D) may be selected from a compound having one ethylenically unsaturated group or a compound having two or more (including two) ethylenically unsaturated groups.

Specific examples of the compound having one ethylenically unsaturated group include (meth)acrylamide, (meth)acrylium morpholine, (meth)acrylic acid-7-amino-3,7 - dimethyloctyl ester, isobutoxymethyl (meth) acrylamide, isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate-2- Ethylhexyl ester, ethyl diethylene glycol (meth) acrylate, trioctyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylamino (meth) acrylate Ethyl ester, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl (methyl) Acrylamide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (methyl) ) tetrabromophenyl acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, ( 2-tribromophenoxyethyl methacrylate, 2-hydroxy-(meth) acrylate , 2-hydroxy-(meth)acrylic acid propyl ester, vinyl caprolactam, nitrogen-vinyl pyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, (methyl) Pentabromophenyl acrylate, polyethylene mono(meth)acrylate, propylene mono(meth)acrylate, borneol (meth)acrylate, and the like. The above compound (D-1) having one ethylenically unsaturated group may be used singly or in combination of two or more.

Specific examples of the compound having two or more (including two) ethylenically unsaturated groups include ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, and triethylene glycol di(a) Acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate Acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tris(meth)acrylic acid trimethylolpropyl ester, ethylene oxide , EO) modified tris (meth) acrylate trimethylol propyl acrylate, propylene oxide (PO) modified tris (meth) acrylate trimethylol propyl ester, tripropylene glycol di (methyl) Acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tris (a) Acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol five ( Methyl) acrylate, two Pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, tetra(meth)acrylic acid Di(trimethylolpropane)tetra(meth)acrylate, epoxide-modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A II Acrylate, ethylene oxide modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, modified with propylene oxide Triglyceride (meth) acrylate, ethylene oxide modified bisphenol F di(meth) acrylate, novolac polyglycidyl ether (meth) acrylate or the like, or the above compounds combination. The above compound having two or more (including two) ethylenically unsaturated groups may be used singly or in combination of plural kinds. use.

Specific examples of the above ethylenically unsaturated group-containing compound (D) include trimethylolpropyl acrylate, trimethylolpropyl triacrylate modified with ethylene oxide, and modified with propylene oxide. Trimethylolpropyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, four Ditrimethylolpropyl acrylate, propylene oxide modified glycerol triacrylate or the like, or a combination of the above compounds.

The ethylenically unsaturated group-containing compound (D) is preferably dipentaerythritol hexaacrylate, trimethylolpropyl triacrylate, ditrimethylolpropyl methacrylate or a combination of the above compounds.

The ethylenically unsaturated group-containing compound (D) may be used in an amount of 50 parts by weight to 500 parts by weight, preferably 80 parts by weight to 400 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C). More preferably, it is 100 parts by weight to 300 parts by weight.

Photoinitiator (E)

The photoinitiator (E) may be a radical photoinitiator. Specifically, the photoinitiator (E) is, for example, an O-oxime compound, a triazine compound, or a benzene. An acetophenone-based compound, a biimidazole-based compound, or a benzophenone-based compound.

Specific examples of the O-mercaptoquinone compound include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-phenylhydrazinium), 1-[ 4-(phenylthio)phenyl]- Octane-1,2-dione-2-(O-phenylhydrazinium), 1-[4-(phenylhydrazino)phenyl]-heptane-1,2-dione-2-(O- Phenylhydrazinium), 1-[9-ethyl-6-(2-methylphenylindenyl)-9H-indazol-3-yl]-ethanone-1-(O-ethylindenyl) , 1-[9-ethyl-6-(3-methylphenylindenyl)-9H-indazol-3-yl]-ethanone-1-(O-ethylindenyl), 1-[9 -ethyl-6-phenylhydrazino-9H-indazol-3-yl]-ethanone-1-(O-acetamidoxime), ethane ketone-1-[9-ethyl-6-( 2-methyl-4-tetrahydrofuranylphenyl)]-9H-carbazol-3-yl]-1-(O-acetamidoxime), ethane ketone-1-[9-ethyl-6-( 2-methyl-5-tetrahydropyranylphenyl)]-9H-indazol-3-yl]-1-(O-acetamidoxime), ethane ketone-1-[9-ethyl- 6-(2-Methyl-4-tetrahydrofuranylmethoxyphenyl)]-9H-indazol-3-yl]-1-(O-ethylindenyl), ethane ketone-1-[9- Ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzoyl)-9H-indazol-3-yl]-1-(O-acetamidoxime), ethane ketone-1- [9-Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoinyl}-9H-indazol-3-yl] -1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxo Pentyl) methoxybenzoin}-9H-indazol-3-yl]-1-(O-B Oxime group), or a combination of the above compounds.

Specific examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine [2,4-bis(trichloromethyl)-6-( P-methoxy)styryl-s-triazine], 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s- Triazine [2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine], 2-trichloromethyl-4-amino-6-pair-A Oxystyryl-s-triazine [2-trichloromethyl-4-amino-6-(p-methoxy) Styryl-s-triazine] or a combination of the above compounds.

Specific examples of the acetophenone compound include p-dimethylacetonone, α , α' -dimethoxy oxy acetophenone, 2,2'-dimethyl-2-phenylbenzene Ethyl ketone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N N-dimethylamine-1-(4-morpholinylphenyl)-1-butanone or a combination of the above compounds.

Specific examples of the diimidazole compound include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl) -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2 , 2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4' , 5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-double (2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4 , 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole or the above compounds The combination.

Specific examples of the benzophenone compound include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-anthracene, benzophenone, and 4,4'-bis(dimethylamine) Benzophenone, or 4,4'-bis(diethylamine)benzophenone or a combination of the above compounds.

The photoinitiator (E) is preferably 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylindenyl), 1-[9 -ethyl-6-(2-methylphenylindenyl)-9H-indazol-3-yl]-ethanone-1-(O-acetamidoxime), ethane ketone-1-[9- Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)-9H-indazol-3-yl]-1-(O-B Ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxy Benzoyl}-9H-carbazol-3-yl]-1-(O-ethylindenyl), 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl -s-triazine, 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinyl)-1-butanone, 2,2'-bis(2,4-dichloro Phenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -biimidazole], 4,4'-bis(diethylamine)benzophenone or a combination of the above compounds.

The above photoinitiators (E) may be used singly or in combination of two or more.

Further, in the range without affecting the physical properties of the photosensitive resin composition of the present invention can also need to add a further photoinitiator other than the above (E) an initiator, for example: α - dione (α -diketone) compound, A acyloin-based compound, a acyloin ether-based compound, an acylphosphine oxide-based compound, a quinone-based compound, a halogen-containing compound, or a peroxide.

Specific examples of the α -diketone compound include a benzil or an acetyl group-based compound or a combination of the above compounds.

Specific examples of the ketol compound include benzoin or a combination of the above compounds.

Specific examples of the ketol ether compound include benzoin methylether, benzoin ethylether, benzoin isopropyl ether or a combination of the above compounds.

Specific examples of the phosphonium oxide compound include 2,4,6-trimethyl-benzoyl diphenylphosphine oxide, bis-(2,6-dimethoxy Bismuthene-2,4,4-trimethoxy-benzoyl-2,4,4-trimethylbenzyl phosphineoxide or a combination of the above compounds.

Specific examples of the quinone compound include anthraquinone or 1,4-naphthoquinone or a combination of the above compounds.

Specific examples of the halogen-containing compound include phenacyl chloride, tribromomethyl phenylsulfone, tris(trichloromethyl)-s-triazine [tris(trichloromethyl)-s-triazine Or a combination of the above compounds.

Specific examples of the peroxide include di-tertbutylperoxide or a combination of the above compounds.

The photoinitiator (E) may be used singly or in combination of two or more.

The photoinitiator (E) is preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2,2'-bis (2,4-di) Chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 4,4'-bis(diethylamine)benzophenone 1-[4-(phenylthio)phenyl] - Octane-1,2-dione-2-(O-phenylhydrazinium) or a combination of the above compounds.

When the photoinitiator (E) is not used, the development resistance of the photosensitive resin composition is not good.

The photoinitiator (E) may be used in an amount of 5 parts by weight to 50 parts by weight, preferably 6 parts by weight to 40 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C). The amount is, and more preferably, 7 parts by weight to 30 parts by weight.

Organic solvent (F)

The organic solvent (F) means that the dye (A), the pigment (B), the alkali-soluble resin (C), the ethylenically unsaturated group-containing compound (D), and the photoinitiator (E) can be dissolved, but not An organic solvent which reacts with the above components, and preferably has a suitable volatility.

Further, the organic solvent (F) may be the same as the organic solvent used to prepare the second alkali-soluble resin (C-2), and will not be described herein. The organic solvent (F) is preferably propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate or a combination of the above solvents.

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

Additive (G)

The photosensitive resin composition of the present invention can be further optionally further added with the additive (G) without affecting the efficacy of the present invention. Specific examples of the additive (G) include a filler, a polymer (refer to a polymer other than the above-described alkali-soluble resin (C)), an adhesion promoter, an antioxidant, an ultraviolet absorber, or an anti-aggregation agent.

Specific examples of the filler include glass or aluminum and the like.

Specific examples of the polymer include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate or a combination of the above polymers.

Specific examples of the adhesion promoter include vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, and N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxy Propyl propyl trimethoxy decane, 3-glycidyl propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, 3-chloropropyl group Dimethoxy decane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane or a combination of the above compounds.

Specific examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol or a combination of the above compounds.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone or the above compounds. combination.

Specific examples of the anti-agglomerating agent include sodium polyacrylate and the like.

The amount of the additive (G) to be used is 0.01 parts by weight to 10 parts by weight, preferably 0.05 parts by weight to 8 parts by weight, and more preferably 0.1 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C). 6 parts by weight.

<Preparation Method of Photosensitive Resin Composition for Color Filter>

A method which can be used for preparing a photosensitive resin composition, for example, a dye (A), a pigment (B), an alkali-soluble resin (C), an ethylenically unsaturated group-containing compound (D), and light The initiator (E) and the organic solvent (F) are placed in a stirrer and stirred to be uniformly mixed into a solution state, and if necessary, an additive (G) may be added, and evenly mixed, the photosensitivity in a solution state can be obtained. Resin composition.

Further, the method for preparing the photosensitive resin composition is not particularly limited. The photosensitive resin composition is prepared by, for example, dispersing a part of the alkali-soluble resin (C) and the ethylenically unsaturated group-containing compound (D) in a part of the organic solvent (F) to form a dispersion solution; and then The remaining dye (A), pigment (B), alkali-soluble resin (C), ethylenically unsaturated group-containing compound (D), photoinitiator (E), and organic solvent (F) are mixed.

Alternatively, the photosensitive resin composition may be obtained by dispersing a part of the pigment (B) in a part of the organic solvent (F) to form a pigment dispersion liquid; and mixing the remaining dye (A), pigment (B), The alkali-soluble resin (C), the ethylenically unsaturated group-containing compound (D), the photoinitiator (E), and the organic solvent (F) are prepared. Further, the dispersion step of the above pigment (B) can be carried out by mixing, for example, a mixer such as a beads mill or a roll mill.

<Method for Manufacturing Pixel Layer and Color Filter>

The color filter is prepared by sequentially pre-baking, exposing, developing, and baking the photosensitive filter with a photosensitive composition on a substrate on which a black matrix has been formed, wherein the black matrix is used to isolate each Picture layer. The preparation method of the color filter will be described in detail below.

First, by spin coating or cast coating or roll coating, etc. In the formula, a photosensitive resin composition for a color filter in a solution state is uniformly applied onto a substrate to form a coating film. The substrate is, for example, an alkali-free glass, a soda-lime glass, a hard glass (Pyles glass), a quartz glass, and the like to which a transparent conductive film is attached, which is used for a liquid crystal display device, and the like, and is used for a photoelectric conversion device (such as a solid). A substrate (for example, a germanium substrate) of the photographing device; or a substrate having a black matrix for shielding light from which a pixel layer such as red, green or blue is isolated.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and then the residual solvent is completely removed by pre-baking to form a pre-baked coating film. It is worth noting that the conditions of drying under reduced pressure and pre-baking vary depending on the type and ratio of each component. In general, the vacuum drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the prebaking is performed at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes. Heat treatment.

Next, the prebaked coating film is exposed by a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet irradiation device may be a (ultra) high-pressure mercury lamp or a metal halide lamp.

Then, the exposed prebaked coating film is immersed in a developing solution at a temperature of 23 ± 2 ° C to remove an unnecessary portion of the prebaked coating film, whereby a specific pattern can be formed on the substrate. Specific examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, dimethyl Basicity of basic compounds such as ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine or 1,8-diazabicyclo-(5.4.0)-7-undecene Aqueous solution. The developer concentration is from 0.001% by weight to 10% by weight %, preferably from 0.005 wt% to 5 wt%, and more preferably from 0.01 wt% to 1 wt%.

After the prebaked coating film is developed, the substrate having the specific pattern is washed with water, and the above specific pattern is air-dried with compressed air or compressed nitrogen. Then, post-bake (that is, heat treatment) is performed by a heating device such as a hot plate or an oven. The post-baking temperature is from 100 ° C to 280 ° C, and the heating time is from 1 minute to 15 minutes to remove volatile components in the coating film and to carry out a thermosetting reaction of the unreacted ethylenically unsaturated double bond. After the above-described processing steps, a specific pattern can be fixed on the substrate, thereby forming a pixel layer. Repeat the above steps to form red, green, blue and other pixel layers on the substrate in sequence.

Finally, an ITO (Indium Tin Oxide) protective film (evaporated film) was formed on the surface of the pixel layer by sputtering in a vacuum environment at a temperature of 220 ° C to 250 ° C. When necessary, the ITO protective film is etched and wired, and a liquid crystal alignment film (polyimine for liquid crystal alignment film) is applied onto the surface of the ITO protective film, thereby forming a color filter having a pixel layer.

<Method of Manufacturing Liquid Crystal Display Device>

First, a color filter formed by the above-described method of forming a color filter and a substrate provided with a thin film transistor (TFT) are disposed oppositely, and a gap is provided between the two (crystal) Cell gap). Next, the color filter is attached to the peripheral portion of the above substrate with an adhesive and the injection hole is left. Then, by the injection of the surface of the substrate and the gap separated by the adhesive The holes are injected into the liquid crystal, and the injection holes are sealed to form a liquid crystal layer. Subsequently, a polarizing plate is provided by contacting the other side of the color filter in contact with the other side of the liquid crystal layer in the color filter to form a liquid crystal display element. Next, a surface light source is provided on one side of the liquid crystal display element to form a liquid crystal display device. The liquid crystal used, that is, the liquid crystal compound or the liquid crystal composition, is not particularly limited herein, and any liquid crystal compound and liquid crystal composition can be used.

Further, the liquid crystal alignment film used in the production of the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and any of inorganic substances or organic substances may be used, and the present invention is not limited thereto.

Synthesis example of dye (A)

Synthesis Example A-1 to Synthesis Example A-8 of the dye (A) will be described below:

Synthesis Example A-1

170 parts by mass of anhydrous chloroform, 1.0 part by mass of camphorsulfonic acid, 1.4 parts by mass of 4-(N,N-dimethylamino)pyridine, and 18 parts by mass of basic violet 10 were added. 18 parts by mass of 2-hydroxyethyl methacrylate and stirred for about 30 minutes. Thereafter, 47 parts by mass of anhydrous chloroform was added to 10.5 parts by mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and preliminarily dissolved. After the solution, it was stirred at room temperature for about 2 hours. After two times of liquid separation operation using 150 parts by mass of 1N aqueous hydrochloric acid solution, the organic layer was washed twice with 150 parts by mass of 10% saline. Next, after adding 43 parts by mass of anhydrous magnesium sulfate and stirring for about 30 minutes, The desiccant was filtered and the solvent was distilled off to obtain 20.6 parts by mass of a compound represented by the formula (A1) (recovery rate: 90%) (hereinafter referred to as dye A-1).

Synthesis Example A-2

20 parts by mass of the dye A-1 and 14.5 parts by mass of lithium bis(trifluoromethanesulfonyl) ruthenium, and 130 parts by mass of chloroform and 100 parts by mass were placed in a 500 mL Erlenmeyer flask to which a stir bar was placed. The ion exchanged water was then stirred at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with 200 parts by mass of ion-exchanged water. After concentrating the organic layer under reduced pressure, the residue was dried under reduced pressure at 50 ° C for 12 hours to obtain 26.6 parts by mass of the compound represented by formula (A2) (recovery rate 94%) (hereinafter referred to as dye A-2) ). In addition, it was confirmed to be a target compound by ¹ H-NMR (solvent: deuterated chloroform).

Synthesis Example A-3

A dye was synthesized in the same manner as in Synthesis Example A-2 except that potassium tetracyanoborate was used instead of lithium bis(trifluoromethanesulfonyl) ruthenium in Synthesis Example A-2. The target compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform). The resulting compound is referred to as dye A-3.

Synthesis Example A-4

A dye was synthesized in the same manner as in Synthesis Example A-2 except that potassium trifluoromethanesulfonate was used instead of lithium bis(trifluoromethanesulfonyl) ruthenium imine in Synthesis Example A-2. The target compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform). The resulting compound is referred to as dye A-4.

Synthesis Example A-5

In the synthesis example A-2, potassium 2-propenyloxy-1,1,2,2-tetrafluoroethanesulfonate was used in place of lithium bis(trifluoromethanesulfonyl) ruthenium, in addition to The dye was synthesized in the same manner as in Synthesis Example A-2. The target compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform). The resulting compound is referred to as dye A-5.

Synthesis Example A-6

In the synthesis example A-2, potassium 2-(4-vinylphenoxy)-1,1,2,2-tetrafluoroethanesulfonate was used instead of lithium bis(trifluoromethanesulfonyl) ruthenium. Further, a dye was synthesized in the same manner as in Synthesis Example A-2, and it was confirmed to be a target compound by ¹ H-NMR (solvent: chloroform). The obtained compound was designated as Dye A-6.

Synthesis Example A-7

In the synthesis example A-2, tris(trifluoromethylsulfonyl)methylhydrazine was used instead of lithium bis(trifluoromethanesulfonyl)phosphonium, and the same as in Synthesis Example A-2. The synthetic dye was identified as a target compound by ¹ H-NMR (solvent: deuterated chloroform). The obtained compound was designated as Dye A-7.

Synthesis Example A-8

In Synthesis Example A-1, a dye was synthesized in the same manner as in Synthesis Example A-1 except that 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate, by ¹ H-NMR ( Solvent: deuterated chloroform) was determined to be the target compound. The obtained compound was designated as Dye A-8.

Synthesis example of first alkali soluble resin (C-1)

Synthesis Example C-1-1 to Synthesis Example C-1-3 of the first alkali-soluble resin (C-1) will be described below:

Synthesis Example C-1-1

First, 100 parts by weight of a ruthenium epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, and 0.3 parts by weight Benzyltriethylammonium chloride, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous addition to a 500 ml four-necked flask. . The feed rate was controlled at 25 parts by weight/min, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid content of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was added to 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 heated to 110 ° C to 115 ° C. After reacting for 2 hours, the first alkali-soluble resin C-1-1 having an acid value of 98 mgKOH/g and a weight average molecular weight of 2,205 was obtained.

Synthesis Example C-1-2

100 parts by weight of ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., model ESF-300; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were continuously added to a 500-mL four-necked flask. The feed rate was controlled at 25 parts by weight/min, and the temperature of the reaction was maintained at 100 ° C to 110 ° C. After 15 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 13 parts by weight of benzophenonetetracarboxylic dianhydride was added, and heated to 90 ° C to 95 ° C. After 2 hours of reaction, add 6 weights The amount of tetrahydrophthalic anhydride is adjusted at 90 ° C to 95 ° C for 4 hours to obtain a first alkali-soluble resin C-1-2 having an acid value of 99.0 mgKOH/g and a weight average molecular weight. For 2630.

Synthesis Example C-1-3

400 parts by weight of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd., model: NC-3000; epoxy equivalent: 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight A portion of triphenylphosphine and 264 parts by weight of propylene glycol monomethyl ether acetate were added to the 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 mgKOH/g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a first alkali-soluble resin C-1-3 having an acid value of 102 mgKOH/g. And the weight average molecular weight was 3,200.

Synthesis example of second alkali soluble resin (C-2)

Synthesis Example C-2-1 to Synthesis Example C-2-4 of the second alkali-soluble resin (C-2) will be described below:

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, 45 parts by weight of 2-methylpropenyl ethoxy succinate (hereinafter abbreviated as HOM) S), 15 parts by weight of dicyclopentenyl acrylate (hereinafter abbreviated as FA-511A), 20 parts by weight of styrene monomer (hereinafter abbreviated as SM), and 5 parts by weight of benzyl methacrylic acid An ester (hereinafter abbreviated as BzMA) and 15 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 the monomer mixture The way of feeding is continuous addition.

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-2-4

The second alkali-soluble resin of Synthesis Example C-2-2 to Synthesis Example C-2-4 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, once again after the reaction is complete material.

Example of photosensitive resin composition

Hereinafter, Examples 1 to 10 and Comparative Examples 1 to 7 of the photosensitive resin composition will be described:

Example 1

5 parts by weight of the dye (A-1), 40 parts by weight of the compound represented by the formula (2) (hereinafter abbreviated as B-1), and 100 parts by weight of the first alkali-soluble resin C-1-1 (hereinafter referred to as C-1-1), 50 parts by weight of dipentaerythritol hexaacrylate, and 3 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone ( Hereinafter referred to as E-1), 1 part by weight of 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (hereinafter referred to as E-) 2), 1 part by weight 4,4'-bis(diethylamine)benzophenone (hereinafter abbreviated as E-3), 0.01 part by weight of 3-mercaptopropyltrimethoxydecane (hereinafter abbreviated as G-1), 500 parts by weight In the propylene glycol monomethyl ether acetate (hereinafter abbreviated as F-1), and the mixture was uniformly stirred by a shaking type stirrer, the photosensitive resin composition of Example 1 was obtained. The obtained photosensitive resin composition was evaluated for each evaluation method described later, and the results are shown in Table 2.

Embodiment 2 to Embodiment 10

The photosensitive resin compositions of Examples 2 to 10 were prepared in the same manner as in Example 1, and were different in that the composition of the photosensitive resin composition and the amount thereof were changed (as shown in Table 2). ), wherein the compounds corresponding to the labels in Table 2 are as follows. The obtained photosensitive resin composition was evaluated for each evaluation method described later, and the results are shown in Table 2.

Comparative Example 1 to Comparative Example 7

The photosensitive resin compositions of Comparative Examples 1 to 7 were prepared in the same manner as in Example 1, and were different in that the kinds of components of the photosensitive resin composition and the amounts thereof were changed (as shown in Table 3). ). The obtained photosensitive resin composition was evaluated for each evaluation method described later, and the results are shown in Table 3.

The compounds corresponding to the abbreviations in Table 2 and Table 3 are as follows.

Evaluation method

(a) Resistance to development

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 for about 30 seconds. Next, the glass substrate was prebaked at a temperature of 80 ° C for 2 minutes to form a prebaked film having a film thickness of 2.5 μm. Thereafter, the chromaticity (L*, a*, b*) was measured with a colorimeter (manufactured by Otsuka Electronics Co., model MCPD).

Next, the above prebaked coating film was irradiated with ultraviolet light of 100 mJ/cm ² (mJ/cm ² ) using an exposure machine (manufactured by Canon, model: PLA-501F). After irradiation with ultraviolet light, the prebaked coating film was immersed in a developing solution at 23 °C. After 1 minute, it was washed with pure water. Then, the chromaticity was measured again, and the chromaticity change (ΔEab*) was calculated by the following formula (9). The smaller the measured chromaticity change (ΔEab*), the better the developability of the photosensitive resin composition, and the evaluation was performed based on the following criteria.

△Eab*=[(ΔL) ² +(Δa) ² +(△b) ² ] ^1/2 (9)

◎: △Eab*<2

○: 2≦△Eab*<4

△: 4≦△Eab*<6

×: 6≦△Eab*

(b) Surface roughness

The pre-baked coating film of the above evaluation mode (a) having a film thickness of 2.5 μm was irradiated with ultraviolet light of 100 mJ/cm ² (mJ/cm ² ) using an exposure machine (manufactured by Canon, model: PLA-501F), and then The prebaked coating film was immersed in a developing solution at 23 ° C for 1 minute, and washed with pure water. Then, by baking at 235 ° C for 30 minutes, a pixel layer having a film thickness of 2.0 μm was formed on the glass substrate. The surface roughness of the pixel layer was measured using an Atomic Force Microscope (AFM) (Dimension 3100, manufactured by Veeco Instruments Inc.). The measurement area was 10 μm ² . The surface roughness was evaluated based on the following criteria. The smaller the measured surface roughness, the better the surface roughness of the cured product formed of the photosensitive resin composition is.

◎: Surface roughness ≦ 6nm

○: 6 nm < surface roughness ≦ 8 nm

△: 8 nm < surface roughness ≦ 10 nm

×: 10 nm < surface roughness

<evaluation result>

Table 2 and Table 3 show that the photosensitive resin composition containing no dye (A) is composed of the photosensitive resin composition containing the dye (A) (Examples 1 to 10, Comparative Examples 5 and 6). The materials (Comparative Examples 1 to 4 and Comparative Example 7) had poor development resistance.

Further, compared with the photosensitive resin composition containing the first pigment (B-1) (Examples 1 to 10 and Comparative Examples 1 to 4), the first pigment (B-1) was not contained. The surface roughness of the pixel layer formed of the resin composition (Comparative Example 5 to Comparative Example 7) was not preferable.

Further, the photosensitive resin composition containing the first alkali-soluble resin (C-1) is compared with the photosensitive resin composition (Example 4 to Example 7) which does not contain the first alkali-soluble resin (C-1). (Examples 1, 2, 3, 8, 9, and 10) are preferably resistant to development.

As described above, the present invention can reduce the surface roughness of the formed pixel layer by adding a xanthene dye having a specific structure and a brominated diketopyrrolopyrrole pigment to the photosensitive resin composition. Next, the problem of poor development resistance is solved. Further, in the present invention, the development resistance can be further improved by adding an alkali-soluble resin having a specific structure to the photosensitive resin composition. In other words, since the photosensitive resin composition of the present invention contains a specific composition, it has the characteristics of being able to form a pixel layer having a low surface roughness and excellent development resistance, and is therefore suitable for use in a color filter and a liquid crystal display device.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art without departing from the invention. In the spirit and scope, the scope of protection of the present invention is subject to the definition of the appended patent application.

Claims (12)

A photosensitive resin composition for a color filter comprising: a dye (A); a pigment (B); an alkali-soluble resin (C); an ethylenically unsaturated group-containing compound (D); and a photoinitiator (E) And an organic solvent (F), wherein the dye (A) comprises a compound represented by the formula (1), In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; R ⁷ represents a group having a polymerizable unsaturated group; a represents an integer of 1 to 5, and the pigment (B) includes the first pigment (B-1) represented by the formula (2), The photosensitive resin composition for a color filter according to the first aspect of the invention, wherein the compound represented by the formula (1) includes a compound represented by the formula (3), In the formula (3), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; R ⁸ represents a group having a polymerizable unsaturated group. The photosensitive resin composition for a color filter according to the above aspect of the invention, wherein the polymerizable unsaturated group is an acrylonitrile group or a methacrylonitrile group. The photosensitive resin composition for color filters according to the second aspect of the invention, wherein R ⁸ is a group represented by the formula (4) or a group represented by the formula (5). In the formulae (4) and (5), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group; and Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a substituted or unsubstituted carbon number of 1 Alkanediyl group to 12; Z ¹ represents or Z ² represents a divalent alicyclic hydrocarbon group; b represents an integer of 0 to 12; and c and d each independently represent an integer of 0 to 6. The photosensitive resin composition for a color filter according to the first aspect of the invention, wherein the dye (A) is a compound having a hydroxyl group and a polymerizable unsaturated group and a compound represented by the formula (6) According to the reaction, the polymerizable unsaturated group is an acrylonitrile group or a methacryl group. In the formula (6), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, and a carbon number of 3 a cycloalkyl group to 8, a substituted cycloalkyl group having a carbon number of 3 to 8, a phenyl group or a substituted phenyl group; and R ⁵ and R ⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; Or a chlorine atom; X ^- represents an anion. The photosensitive resin composition for color filters according to claim 1, wherein the amount of the dye (A) used is 5 based on 100 parts by weight of the alkali-soluble resin (C). The pigment (B) is used in an amount of 40 parts by weight to 500 parts by weight, and the first pigment (B-1) is used in an amount of 40 parts by weight to 400 parts by weight, based on 50 parts by weight, The ethylenically unsaturated group-containing compound (D) is used in an amount of from 50 parts by weight to 500 parts by weight, the photoinitiator (E) is used in an amount of from 5 parts by weight to 50 parts by weight, and the organic solvent (F) The amount used is from 500 parts by weight to 5000 parts by weight. The photosensitive resin composition for color filters 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 obtained by reacting the first mixture, wherein The first mixture includes: an epoxy compound (c-1) having at least two epoxy groups; and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. The photosensitive resin composition for color filters according to claim 7, wherein the epoxy compound (c-1) having at least two epoxy groups includes a compound represented by the formula (7), a compound represented by the formula (8) or a combination of the two, In the formula (7), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number of An aryl group of 6 to 12 or an aralkyl group having a carbon number of 6 to 12, In the formula (8), R ¹⁵ to R ²⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and e represents an integer of 0 to 10. The photosensitive resin composition for color filters according to claim 7, wherein the amount of the alkali-soluble resin (C) used is 100 parts by weight. The first alkali-soluble resin (C-1) is used in an amount of 10 parts by weight to 100 parts by weight. A method of producing a color filter comprising the pixel layer formed of the photosensitive resin composition for a color filter according to any one of the first to ninth aspects of the invention. A color filter produced by the manufacturing method described in claim 10 of the patent application. A liquid crystal display device comprising the color filter according to claim 11 of the patent application.