JP2013167687A - Photosensitive coloring resin composition, color filter, and liquid-crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring resin composition which exhibits high adhesion with a glass substrate, causes no surface defect having nonuniformity in a surface of a color pattern, and is excellent in productivity.SOLUTION: A photosensitive coloring resin composition contains (a) a photopolymerizable monomer, (b) an organic binder, (c) a photoinitiator and (d) a black color material. The (a) photopolymerizable monomer contains a compound with a structure represented by any of the specified general formulas (a1) to (a3).

Description

  The present invention relates to a photosensitive colored resin composition, a color filter, and a liquid crystal display device. Specifically, the present invention relates to a photosensitive colored resin composition that is excellent in adhesiveness with a glass substrate, hardly causes development unevenness when forming a color filter, and has excellent productivity. The present invention also relates to a cured product of this photosensitive colored resin composition and its use.

  Conventionally, as a method for producing a color filter using a pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method and the like are known.

  In the case of production of a color filter by the pigment dispersion method, usually a photosensitive resin obtained by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. to a colored resin composition obtained by dispersing a pigment with a dispersant or the like. The resin composition is coated on a glass substrate, dried, exposed using a mask, and developed to form a colored pattern, which is then heated to fix the pattern and form pixels. These steps are repeated for each color to form a color filter.

  When a photosensitive layer is formed on a glass substrate using a photosensitive colored resin composition, the adhesion strength between the photosensitive layer and the glass substrate is low, and the glass substrate is affected by external forces when bonded to the liquid crystal drive side substrate. In some cases, peeling occurs between the photosensitive layer and the photosensitive layer, causing light leakage and the like.

  Conventionally, a photosensitive colored resin composition having high sensitivity has been used. However, the conventional photosensitive colored resin composition is frequently sensitive to the surface of the colored pattern despite its high sensitivity. Surface defects that cause unevenness occurred, and there was a defect that productivity could not be increased.

  Therefore, there has been a demand for a photosensitive colored resin composition having high productivity and a photosensitive colored resin composition having high adhesion to a glass substrate, and a surface defect that does not cause unevenness on the surface of the colored pattern.

  On the other hand, as a photopolymerizable monomer contained in the photosensitive colored resin composition used for forming a color filter, a (meth) acrylate compound of a polyhydric alcohol is generally used. It is known that a compound in which part or all of the hydroxyl groups of a polyhydric alcohol are (meth) acrylated via a divalent linking group is used instead. Here, as examples of the divalent linking group, lactones (for example, Patent Document 1) and alkylene oxides (for example, Patent Documents 1 to 3) are known. However, these conventional techniques have room for improvement in the performance and productivity of the color filter.

JP 2005-189720 A JP 2008-107773 A JP 2009-175724 A

  The present invention is a photosensitive colored resin composition that has high adhesion to a glass substrate, does not cause surface defects that cause unevenness on the surface of the colored pattern, and is excellent in productivity, and a cured product, a color filter, and the like. It is another object of the present invention to provide a liquid crystal display device.

The inventor has analyzed in detail the cause of the occurrence of unevenness on the surface of the colored pattern, and it has been found that the surface of the coating film is roughened during the development process and appears as unevenness.
As a result of intensive studies, the inventor can improve the adhesion with the glass substrate by using a photopolymerizable monomer having a specific structure and a resin having a specific structure, It has been found that roughness of the coating film surface in the development process can be suppressed, that is, the above-mentioned problems can be solved, and the present invention has been achieved.

  The first gist of the present invention is a photosensitive coloring composition containing (a) a photopolymerizable monomer, (b) an organic binder, (c) a photopolymerization initiator, and (d) a black color material. (A) the photopolymerizable monomer contains a compound having a structure represented by any one of the following general formulas (a1) to (a3), and (b) the organic binder contains the following alkali-soluble resin (b1 And / or an alkali-soluble resin (b2).

(In the general formula (a1), A is composed of A1 and A2 below, and the molar ratio of A1 and A2 in the formula (a1) is A1: A2 = 2: 2 to 4: 0.)

(In the general formula (a2), A consists of A1 and A2 below, and the molar ratio of A1 and A2 in the formula (a2) is A1: A2 = 3: 3 to 6: 0.)

(In the general formula (a3), A consists of A1 and A2 below, the molar ratio of A1 and A2 in the formula (a3) is A1: A2 = 2: 1 to 3: 0, and R ⁴ is carbon. Represents an alkyl group of 1-6.)

(In the above A1 and A2, R ¹ represents an alkylene group which may have 2 to 6 carbon atoms in the main chain, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and n is Represents an integer of 1 to 3. When n is 2 or 3, a plurality of R ¹ may be the same or different from each other.
<Alkali-soluble resin (b1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (b2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

  The second gist of the present invention resides in a cured product obtained by curing the photosensitive colored resin composition.

  The third gist of the present invention resides in a color filter formed using the photosensitive colored resin composition.

  The fourth gist of the present invention resides in a liquid crystal display device manufactured using the color filter.

  According to the photosensitive colored resin composition of the present invention, the adhesion to the glass substrate is high, and there is no unevenness on the surface in the development process, and pixels without unevenness can be formed.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”. In addition, “(acid) anhydride” and “(anhydrous)... Acid” mean that both an acid and its anhydride are included.
Further, in the present invention, “total solid content” means all components other than the solvent contained in the photosensitive colored resin composition or in the ink described later.

Moreover, in this invention, a weight average molecular weight means the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).
Further, in the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

[Photosensitive colored resin composition]
The photosensitive colored resin composition of the present invention is
(A) a photopolymerizable monomer,
(B) an organic binder,
(C) contains a photopolymerization initiator and (d) a black color material as an essential component, preferably further,
(E) Contains a dispersant, and if necessary, adhesion improvers such as organic solvents and silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigments It contains other compounding components such as derivatives, and each compounding component is usually used in a state dissolved or dispersed in an organic solvent.

<Photopolymerizable monomer (a)>
The photopolymerizable monomer (a) used in the present invention contains a compound having a structure represented by any one of the following general formulas (a1) to (a3).

(In the general formula (a1), A is composed of A1 and A2 below, and the molar ratio of A1 and A2 in the formula (a1) is A1: A2 = 2: 2 to 4: 0.)

(In the general formula (a2), A consists of A1 and A2 below, and the molar ratio of A1 and A2 in the formula (a2) is A1: A2 = 3: 3 to 6: 0.)

(In the general formula (a3), A consists of A1 and A2 below, the molar ratio of A1 and A2 in the formula (a3) is A1: A2 = 2: 1 to 3: 0, and R ⁴ is carbon. Represents an alkyl group of 1-6.)

(In the above A1 and A2, R ¹ represents an alkylene group which may have 2 to 6 carbon atoms in the main chain, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and n is Represents an integer of 1 to 3. When n is 2 or 3, a plurality of R ¹ may be the same or different from each other.

The ratio of A1 to A2 is preferably 4: 0 in the general formula (a1), 6: 0 in the general formula (a2), and 3: 0 in the general formula (a3). In general formula (a3), R ⁴ is particularly preferably an alkyl group having 1 or 2 carbon atoms.

Moreover, in A1, the carbon number of the main chain of R ¹ is preferably 3 to 5, and particularly preferably 5. When R ¹ has a branch, the total carbon number including the branch of R ¹ is preferably 4 to 7. N is preferably 1 to 2.
In the general formulas (a1), (a2), and (a3), when a plurality of A1 and / or A2 are present, the plurality of A1 and / or A2 may be the same or different.

  The photopolymerizable monomer (a) is obtained by adding a lactone to a part or all of the hydroxyl groups of the polyhydric alcohol represented by the following general formulas (a1 ′) to (a3 ′), and then (meth) acrylated It is preferable that the compound be synthesized.

(In the general formula (a3 ′), the definition of R ^{4 is the same as} the definition in the general formula (a3).)

  Examples of lactones to be added to polyhydric alcohol include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, α, α-dimethyl- Examples include γ-butyrolactone, ε-caprolactone, δ-hexanolactone, γ-hexanolactone, and γ-heptanolactone. Among these, γ-butyrolactone, δ-valerolactone, and ε-caprolactone are preferable, and ε-caprolactone is particularly preferable.

  The photopolymerizable monomer (a) having a structure represented by any one of these general formulas (a1) to (a3) may be used alone or in combination with a plurality of compounds. Moreover, it can also be used in combination with a photopolymerizable monomer other than the compound having a structure represented by any one of the general formulas (a1) to (a3) such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. However, when a photopolymerizable monomer other than the compound having a structure represented by any one of the general formulas (a1) to (a3) is used in combination, the general formula (a1) in the photopolymerizable monomer (a) The proportion of the photopolymerizable monomer other than the compound having the structure represented by any one of (a3) is preferably 50% by weight or less, particularly preferably 0 to 25% by weight.

<Organic binder (b)>
The organic binder (b) used in the present invention includes the following alkali-soluble resin (b1) and / or alkali-soluble resin (b2) (hereinafter sometimes referred to as “carboxyl group-containing epoxy (meth) acrylate resin”). .
<Alkali-soluble resin (b1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (b2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol A type epoxy, etc. Epoxy obtained by reaction of alcoholic hydroxyl group of resin and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin (for example, oily shell epoxy) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc.") manufactured by the company, epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and epichlorohydrin (for example, Japan “NER-740” manufactured by Kayaku Co., Ltd. (Epoxy equivalent 350, softening point 66 ° C.), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg “YX-4000” manufactured by Yuka Shell Epoxy), phenol novolac type epoxy resin (eg Nippon Kayaku) "EPPN-201", Yuka Shell Epoxy "EP-152", "EP-154", Dow Chemical "DEN-438"), (o, m, p-) cresol novolak Type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), trisphenol Methane type epoxy resin (for example, “EPPN-501”, “EPN-502”, “E” manufactured by Nippon Kayaku Co., Ltd.) PN-503 "), cycloaliphatic epoxy resins (" Celoxide 2021P "," Celoxide EHPE "manufactured by Daicel Chemical Industries, Ltd.), epoxy resins obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, Dainippon "EXA-7200" manufactured by Ink Company, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (B1) to (B4), and the like can be suitably used. Specifically, “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1), and “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B2) As an epoxy resin represented by “NC-3000” and the following general formula (B4), “ESF-300” manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned.

(In the general formula (B1), a represents an average value and represents a number of 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Represents a phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ¹¹ present in one molecule may be the same as or different from each other.

(In the above general formula (B2), b represents an average value and represents a number from 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Represents a phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ²¹ present in one molecule may be the same as or different from each other.

(In the general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), provided that the molecular structure includes one or more adamantane structures. Represents an integer of 2 or 3.)

(In the above general formulas (B3-1) and (B3-2), R ^{31 to} R ³⁴ and R ^{35 to} R ³⁷ are each independently an adamantyl group optionally having a substituent, a hydrogen atom, and a substituent. The alkyl group having 1 to 12 carbon atoms which may have a group, or a phenyl group which may have a substituent.

(In the above general formula (B4), d and e each independently represent an integer of 0 to 4, R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ each independently And x and y each independently represents an integer of 0 or more.)

  Among these, it is preferable to use epoxy resins represented by general formulas (B1) to (B4).

  Examples of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) a Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone, γ-butyrolactone, Monomers added with lactones such as δ-valerolactone, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate with (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) Monomers added with acid (anhydride) such as maleic acid, (meth) acrylic acid dimer, etc. And the like.

  Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method of adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin, a known method can be used. For example, reacting an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used. .
In addition, the epoxy resin, the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two types. You may use the above together.

  The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid and / or anhydride thereof The reaction with is also insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

  Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

  A known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having carboxyl group to epoxy resin. The target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mg KOH / g, and further 20 It is preferable that it is a grade which becomes the range of -140 mgKOH / g. When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is less than the above range, the alkali developability tends to be poor, and when it exceeds the above range, the curing performance tends to be poor.

  In addition, it is good also as what introduce | transduced polyfunctional alcohol, such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce | transduced the multibranched structure at the time of addition reaction of this polybasic acid and / or its anhydride.

  The carboxyl group-containing epoxy (meth) acrylate resin is usually a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with a polybasic acid and / or Or it is obtained by heating after mixing the anhydride and polyfunctional alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating. To the polybasic acid and / or its anhydride.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the carboxyl group-containing epoxy (meth) acrylate resin is usually 1000 or more, preferably 1500 or more, and usually 10,000 or less, preferably 8000. Below, more preferably 6000 or less. If the weight average molecular weight is small, the solubility in the developer is high, and if it is too large, the solubility in the developer is low.

  The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.

  Moreover, as long as the organic binder (b) used by this invention does not impair the performance of this invention, you may substitute a part of above-mentioned carboxyl group-containing epoxy (meth) acrylate resin. That is, a carboxyl group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination. In this case, the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in the organic binder (b) is preferably 50% by weight or more, particularly 80% by weight or more.

As long as the performance of the present invention is not impaired, other binder resins that can be used in combination with the carboxyl group-containing epoxy (meth) acrylate resin are not limited, and can be selected from resins that are usually used in photosensitive colored resin compositions for color filters. good. Examples thereof include binder resins described in JP 2007-271727 A, JP 2007-316620 A, JP 2007-334290 A, and the like.
In addition, all other binder resins may be used alone or in combination of two or more.

<Photopolymerization initiator (c)>
The photopolymerization initiator (c) is a component having a function of directly absorbing light and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. If necessary, additives such as accelerators and sensitizing dyes may be added and used.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbi compounds described in JP-A-2000-56118. Imidazole derivatives; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N-aryl-α-amino acid salts, Radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750 A, and the like. .

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

  Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is.

  Examples of the oxime ester derivatives include the following compounds (in the following, “Me” represents “methyl group”).

  Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p- Methoxyph Acridine derivatives such as benzyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone.

  Among these photopolymerization initiators, oxime ester derivatives (oxime ester compounds) are particularly preferable from the viewpoint of sensitivity.

  A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of the accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, complex such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. A mercapto compound having a ring or an aliphatic polyfunctional mercapto compound is used. Accelerators may be used alone or in combination of two or more.

  If necessary, the photopolymerization initiator can be mixed with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred.

  A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

<Black color material (d)>
In the present invention, the black color material (d) may be a black color material alone, a mixture of color materials such as red, green and blue, or a mixture of both. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  Examples of the black color material used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  Among these, carbon black is preferable from the viewpoint of few surface defects and further from the viewpoint of light shielding rate and image characteristics. Examples of commercially available carbon black include the following.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

  Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, C lor Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

  Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

  From the viewpoint of high adhesion to the glass substrate, it is preferable to use carbon black coated with a resin. By using carbon black coated with resin, there is also an effect of improving the volume resistance value. As carbon black coated with resin, for example, carbon black described in JP-A No. 09-71733 can be suitably used.

As carbon black to be subjected to a coating treatment with a resin, the total content of Na and Ca is preferably 100 ppm or less. This is because the total content of Na and Ca in the carbon black coated with the resin needs to be 100 ppm or less.
That is, carbon black is usually made from raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al. , Fe and the like are contained in the order of percent. Of these, Na and Ca are generally contained in a few hundred ppm or more, but if many of these are present, they penetrate into the transparent electrode (ITO) and other electrodes, causing electrical shorts. Become.
Even if the content of carbon black to be used for resin coating is more than 100 ppm, and even if it exceeds 100 ppm in the coated carbon black, the content should be reduced by the time of resin coating treatment. You can also.

  As a method for reducing the content of ash containing these Na and Ca in carbon black, these contents are used as much as possible as raw material oil, fuel oil (or gas) and reaction stop water when producing carbon black. Examples include a method of carefully selecting a small amount and a method of minimizing the addition amount of an alkaline substance for adjusting the structure. As another method, there is a method in which Na or Ca is dissolved and removed by washing carbon black produced from a furnace with water or hydrochloric acid.

  Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide solution, when a solvent that is hardly soluble in water is added, the carbon black moves to the solvent side and completely separates from water. Most of Na and Ca present in carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there may be a case where a carbon black production process alone or a water or acid dissolution method alone with carefully selected raw materials may be possible. The total amount of Na and Ca can be easily made 100 ppm or less.

  The carbon black used for the resin coating is preferably so-called acidic carbon black having a pH of 6 or less. Such carbon black is suitable because it has a small dispersed diameter (agglomerated diameter) in water, and can cover even fine units. Furthermore, the carbon black used for the resin coating preferably has a particle size of 40 nm or less and a dibutyl phthalate (DBP) absorption of 140 ml / 100 g or less. If the particle size is larger than 40 nm and the DBP absorption is larger than 140 ml / 100 g, the dispersibility when made into a paste is excellent, but the coating film does not have a sufficient concentration feeling, and the film thickness of about 1 to 2 μm is light-shielding. This is because there is a risk of becoming scarce.

  The type of resin used to coat carbon black is not particularly limited, but synthetic resins are common, and resins with benzene nuclei in the structure function more as amphoteric active surfactants. Is preferable from the viewpoint of dispersibility and dispersion stability.

Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfone, polyphenylene sulfone, polyarylate, and polyether ether ketone can be used.
These may be used alone or in combination of two or more.

  The coating amount of the resin on the carbon black is preferably 1 to 30% by weight with respect to the total amount of the carbon black and the resin. When the coating amount of the resin with respect to carbon black is less than 1% by weight, there is a possibility that only dispersibility and dispersion stability similar to those of untreated carbon black can be obtained. On the other hand, if it exceeds 30% by weight, the adhesiveness between the resins is strong, and it becomes a dumpling-like lump, which may prevent the dispersion from proceeding.

  The carbon black formed by coating with a resin can be used as a black matrix shading material according to a conventional method, and a color filter having this black matrix as a constituent element can be prepared by a conventional method. When such carbon black is used, a black matrix having a high light shielding rate, a low surface reflectance, and a thin film thickness can be achieved at a low cost. This is presumably because the dispersibility and dispersion stability of carbon black was significantly improved compared to the resin and solvent that make up the black matrix liquid. As a result, it is difficult to disperse to 0.1 μm or less, and even if dispersed, the stability is poor and the aggregation increases with time.) It is also presumed that by coating the carbon black surface with a resin, Ca and Na can be contained in the carbon black.

  In the present invention, as the black color material (d), various colors such as a pigment other than black, for example, a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment, as necessary. The pigment may be added. Examples of pigments that may be added include various inorganic pigments in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Is available.

Specific examples of pigments that may be added are shown below by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 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, 175, 176, 177, 178, 17 , 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, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55.

  Examples of yellow pigments include C.I. I. 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, 128, 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, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208.

  Examples of orange pigments include C.I. I. 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, 79.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.

These pigments of each color may be used alone or in combination of two or more.
In order to obtain the above-mentioned effects more effectively by using the resin-coated carbon black, in the present invention, the ratio of the resin-coated carbon black in the black color material (d) is 30% by weight or more, particularly 50 to 100. It is preferable that it is weight%.

<Dispersant (e)>
In the present invention, it is important to finely disperse the black color material (d) and stabilize the dispersion state, so that it is important to ensure the stability of the quality. Therefore, the dispersant (e) is preferably included.

  The dispersing agent (e) is preferably a polymer dispersing agent having a functional group, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary A polymeric dispersant having a functional group such as a quaternary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, is preferred. Of these, basic polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine, etc. are particularly preferred. .

  Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

Specific examples of such a dispersant include trade names of EFKA (manufactured by BASF), Disperbyk (manufactured by Big Chemie), disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (Shin-Etsu Chemical) (Manufactured by Ajinomoto Co., Inc.)
These polymer dispersants may be used alone or in combination of two or more.

  The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.

  Among these, it is particularly preferable that the dispersant (e) contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group in terms of adhesion and linearity.

  Examples of urethane and acrylic polymer dispersants include Disperbyk 160 to 166, 182 series (both urethane), Disperbyk 2000, 2001, etc. (both acrylic) (all manufactured by BYK Chemie).

  If a chemical structure preferable as a urethane polymer dispersant is specifically exemplified, for example, the same as a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule.

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.

  Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.

  These may be used alone or in combination of two or more.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, when the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo N-containing hetero 5-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., nitrogen-containing hetero 6-membered ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

  These may be used alone or in combination of two or more.

  The preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. -200 parts by weight, preferably 20-190 parts by weight, more preferably 30-180 parts by weight, 0.2-25 parts by weight of a compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 -24 parts by weight.

  Manufacture of a urethane type polymer dispersing agent is performed in accordance with the well-known method of polyurethane resin manufacture. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.

  In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. 1 type, or 2 or more types, such as a class amine system, are mentioned.

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

  In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.

  The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.

  As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid. Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohe N-substituted maleimides such as silmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Examples thereof include macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers. These may be used alone or in combination of two or more.

  The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group. In addition to the unsaturated group-containing monomer containing the functional group, the block may contain an unsaturated group-containing monomer that does not contain the functional group. It may be contained in any form of polymerization or block copolymerization. Further, the content of the partial structure containing no functional group in the A block is usually 80% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less.

  The B block is composed of an unsaturated group-containing monomer that does not contain the above functional group. However, two or more types of monomers may be contained in one B block. It may be contained in any form of random copolymerization or block copolymerization in the block.

  The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.

  The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

  In synthesizing this acrylic polymer dispersant, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al. , Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right hand, Koichi Hatada, Polymer processing, 36 , 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida Inoue Shohei, Synthetic Organic Chemistry, 43, 300 (1985), DYSogoh, WRHertler et al, Macromolecules, 20, 1473 (1987), etc. can be employed.

  Whether the acrylic polymer dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio constituting the copolymer Is preferably 1/99 to 80/20, and more preferably 5/95 to 60/40 (weight ratio). Outside this range, it may not be possible to combine good heat resistance and dispersibility.

  In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer according to the present invention is preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.

  Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mgKOH / g.

Here, the amine value of the dispersant such as these block copolymers is expressed by the weight of KOH equivalent to the base amount per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [wt%] of the dispersant sample. ]

  The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1000, the dispersion stability tends to decrease, and when it exceeds 100,000, the developability and resolution tend to decrease.

  From the viewpoint of improving dispersion stability, the dispersant (e) is preferably used in combination with a pigment derivative described later.

<Other compounding components of photosensitive colored resin composition>
In addition to the above-mentioned components, the photosensitive coloring resin composition of the present invention includes an adhesion improver such as an organic solvent and a silane coupling agent, a coating property improver, a development improver, an ultraviolet absorber, an antioxidant, and a surface activity. An agent, a pigment derivative, and the like can be appropriately blended.

(1) Organic solvent The photosensitive colored resin composition of the present invention usually comprises a photopolymerizable monomer (a), an organic binder (b), a photopolymerization initiator (c), a black color material (d), and The dispersant (e) and other various materials used as necessary are used in a state dissolved or dispersed in an organic solvent.

  As the organic solvent, it is preferable to select an organic solvent having a boiling point in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.

  Examples of such organic solvents include the following.

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

  Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

  Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

  Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;

  Alkyl acetates such as cyclohexanol acetate;

  Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

  Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;

  Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;

  aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;

  Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

  Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;

  Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;

  Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

  Halogenated hydrocarbons such as butyl chloride and amyl chloride;

  Ether ketones such as methoxymethylpentanone;

  Nitriles such as acetonitrile and benzonitrile;

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

  These organic solvents may be used alone or in combination of two or more.

  When a pixel or black matrix of a color filter is formed by photolithography, the boiling point of the organic solvent is 100 to 200 ° C. (under a pressure of 101.25 [hPa]. Hereinafter, all of the boiling points are the same). It is preferable to select one. More preferably, it has a boiling point of 120 to 170 ° C.

  Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by weight to 30% by weight, and more preferably 5% by weight to 20% by weight.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation and solidification of a coloring material at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight. If the amount of the high boiling point solvent is too small, for example, a coloring material may precipitate and solidify at the tip of the slit nozzle to cause a foreign matter defect, and if it is too much, the drying temperature of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

(2) Adhesion improver The photosensitive colored resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.

  As the type of the silane coupling agent, various types such as epoxy-based, (meth) acrylic-based, and amino-based ones can be used alone or in admixture of two or more.

  Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Epoxyglycans such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Although isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, the silane coupling agent of epoxy silanes is mentioned.

  As the phosphoric acid group-containing compound, (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (f1), (f2), and (f3) are preferable.

(In the general formulas (f1), (f2), and (f3), R ⁵¹ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 10, and q is 1, 2 or 3.)

  These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

(3) Surfactant As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.

  Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (Dainippon Ink & Chemicals), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 Nippon Unicar Co., Ltd.), FC4430 (Sumitomo 3M Co., Ltd.) and the like.

  In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

(4) Pigment derivatives As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketo Derivatives such as pyrrolopyrrole and dioxazine are listed, but quinophthalone is preferred.

  Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.

  Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.

<Ingredient compounding amount in photosensitive colored resin composition>
In the photosensitive colored resin composition of the present invention, the content of the photopolymerizable monomer (a) is usually 90% by weight or less, preferably 80% by weight, based on the total solid content of the photosensitive colored resin composition. It is as follows. When there is too much content of a photopolymerizable monomer (a), the permeability of the developing solution to an exposed part will become high, and it may become difficult to obtain a favorable image. In addition, the minimum of content of a photopolymerizable monomer (a) is 1 weight% or more normally with respect to the total solid of a photosensitive coloring resin composition normally, Preferably it is 5 weight% or more.

  The content of the organic binder (b) is usually 5% by weight or more, preferably 10% by weight or more, and usually 85% by weight or less, preferably based on the total solid content of the photosensitive colored resin composition of the present invention. Is 80% by weight or less. When the content of the organic binder (b) is extremely small, the solubility of the unexposed portion in the developer is lowered, and it becomes easy to induce development failure. On the other hand, when the content of the organic binder (b) is too large, the permeability of the developer into the exposed area tends to be high, and the sharpness and adhesion of the pixel may be lowered.

  The content of the photopolymerization initiator (c) is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0%, based on the total solid content of the photosensitive colored resin composition of the present invention. 0.7% or more, usually 30% by weight or less, preferably 20% by weight or less. When the content of the photopolymerization initiator (c) is too small, the sensitivity may be lowered. On the other hand, when the content is too large, the solubility of the unexposed portion in the developer is lowered, and development failure is likely to be induced.

  When using an accelerator with a photoinitiator (c), content of an accelerator is 0 weight% or more normally with respect to the total solid of the photosensitive coloring resin composition of this invention, Preferably it is 0.02 weight. %, Usually 10% by weight or less, preferably 5% by weight or less, and the accelerator is 0.1 to 50% by weight, particularly 0.1 to 10% by weight, based on the photopolymerization initiator (c). It is preferable to use in proportion.

  When the blending ratio of the photopolymerization initiator component composed of the photopolymerization initiator (c) and the accelerator is extremely low, the sensitivity to the exposure light may be lowered. The solubility in the liquid may be reduced, leading to poor development.

The blending ratio of the sensitizing dye in the photosensitive colored resin composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, based on the total solid content in the photosensitive colored resin composition. Preferably it is 0 to 10% by weight.

  The content of the black color material (d) can be selected in the range of usually 1 to 70% by weight with respect to the total solid content in the photosensitive colored resin composition. In this range, 10 to 70% by weight is more preferable, and 20 to 60% by weight is particularly preferable. If the content of the black color material (d) is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control during liquid crystal cell formation. Conversely, if the content of the black color material (d) is too large, sufficient image formability may not be obtained.

  In the photosensitive colored resin composition, the amount of the organic binder (b) to the black color material (d) is usually 20 to 500% by weight, preferably 30 to 300% by weight, more preferably 50 to 200% by weight. Range. If the content of the organic binder (b) with respect to the black color material (d) is too low, the solubility of the unexposed portion in the developer is lowered, and it is easy to induce development failure. Is difficult to obtain.

  The content of the dispersant (e) is usually 50% by weight or less, preferably 30% by weight or less, usually 1% by weight or more, preferably 3% by weight or more in the solid content of the photosensitive colored resin composition. Further, the content of the dispersant (e) is usually 5% by weight or more, particularly 10% by weight or more, and usually 200% by weight or less, particularly 80% by weight or less with respect to the black color material (d). Is preferred. If the content of the dispersant (e) is too small, sufficient dispersibility may not be obtained. If the content is too large, the proportion of other components is relatively reduced, resulting in a decrease in color density, sensitivity, film formability, and the like. Tend to.

  In particular, as the dispersant (e), it is preferable to use a polymer dispersant and a pigment derivative together. In this case, the blending ratio of the pigment derivative is based on the total solid content of the photosensitive colored resin composition of the present invention. Thus, it is usually 1% by weight or more, usually 10% by weight or less, preferably 5% by weight or less.

  When using an adhesion improver, the content thereof is usually 0.1 to 5% by weight, preferably 0.2 to 3% by weight, more preferably 0.00%, based on the total solid content in the photosensitive colored resin composition. 4 to 2% by weight. If the content of the adhesion improver is less than the above range, the effect of improving the adhesion may not be sufficiently obtained. If the content is too large, the sensitivity may be lowered, or the residue may remain as a defect after development. .

  Moreover, when using surfactant, the content is 0.001-10 weight% normally with respect to the total solid in a photosensitive coloring resin composition, Preferably it is 0.005-1 weight%, More preferably 0.01 to 0.5% by weight, most preferably 0.03 to 0.3% by weight. If the surfactant content is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the content is too high, the smoothness and uniformity of the coating film may not be expressed, and other characteristics deteriorate. There is a case.

  In addition, the photosensitive coloring resin composition of this invention is prepared using the above-mentioned organic solvent so that the solid content concentration may become 5 to 50 weight% normally, Preferably it is 10 to 30 weight%.

<Method for producing photosensitive colored resin composition>
The photosensitive colored resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.

  Usually, it is preferable to disperse the black color material (d) in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the black color material (d) is finely divided by the dispersion treatment, the resist coating characteristics are improved. Further, the black color material (d) contributes to the improvement of the light shielding ability.

  In the dispersion treatment, a part of or all of the black color material (d), the organic solvent, and optionally the dispersant (e), and the epoxy acrylate resin having a carboxyl group and / or other binder resin are used in combination. It is preferable to carry out in a system. (Hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink”.) In particular, when a polymer dispersant is used as the dispersant (e), the obtained ink and This is preferable since the thickening of the resist over time is suppressed (excellent dispersion stability).

In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the colored resin composition,
Due to the heat generated during the dispersion process, highly reactive components may be denatured. Therefore, it is preferable to perform the dispersion treatment in a system containing the above-described components.

  When the black color material (d) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

  Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.

[Color filter]
Next, a color filter using the photosensitive colored resin composition of the present invention will be described according to its production method.

(1) Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meta ) Thermosetting resin sheets such as acrylic resins, or various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, silane coupling agents, thin film formation treatment of various resins such as urethane resins, etc. May be performed.

  The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Black matrix By providing a black matrix on a transparent substrate and usually forming red, green, and blue pixel images, the color filter of the present invention can be produced, and the photosensitive colored resin of the present invention. The composition is used as at least one resist forming coating solution of black, red, green, and blue. For the black resist, on the transparent glass surface on the transparent substrate, on the resin black matrix forming surface formed on the transparent substrate for red, green, and blue, each process of coating, heat drying, image exposure, development and thermosetting is performed. The pixel image of each color is formed. A black matrix can be formed in the same manner as described below for forming red, green, and blue pixel images.

(3) Pixel formation
(3-1) Application of photosensitive colored resin composition The photosensitive colored resin composition of the present invention is applied on a transparent substrate and dried, and then a photomask is stacked on the coating film. Then, a pixel image is formed by image exposure, development, and heat curing or photocuring as necessary to produce a black matrix. Subsequently, a color filter image can be formed by performing the same operation for each of the three colored photosensitive colored resin compositions of red, green, and blue.

  The photosensitive colored resin composition for color filters can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. May become impossible. The thickness of the coating film is preferably in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.5 to 5 μm, as the film thickness after drying. It is a range.

(3-2) Drying of the coating film The drying of the coating film after applying the photosensitive colored resin composition to the substrate is preferably performed by a drying method using a hot plate, IR oven, or convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

  The higher the drying temperature is, the better the adhesion of the coating film to the transparent substrate is. However, when the drying temperature is too high, the organic binder (b) may be decomposed to induce thermal polymerization and cause poor development. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

(3-4) Development The color filter according to the present invention contains an organic solvent or a surfactant and an alkaline compound after image-exposing the coating film of the photosensitive colored resin composition with the above-mentioned light source. An image can be formed on a substrate by development using an aqueous solution. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The color filter substrate after development is subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

(3-6) Formation of transparent electrode The color filter is used as a part of components such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image as it is. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described color filter of the present invention.

  A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8 μm is preferable. A photo spacer (PS) of a transparent resin film is formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[Organic EL display]
An organic EL display can be produced using the color filter of the present invention.

  When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the pixel 20 and adjacent) formed on the transparent support substrate 10 by the colored resin composition. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is manufactured, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. By laminating, the organic EL element 100 can be manufactured. In addition, at least one of the pixel 20 and the resin black matrix is produced using the photosensitive colored resin composition of the present invention. As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

  Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[Synthesis of raw materials]
<Synthesis Example 1-1: Synthesis of carboxyl group-containing epoxy (meth) acrylate resin (b-I)>

50 g of epoxy compound having the above structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were attached to a thermometer, a stirrer and a cooling pipe. The reaction was continued at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by weight of the above epoxy acrylate solution, 0.76 parts by weight of trimethylolpropane (TMP), 3.3 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts by weight of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with methoxybutyl acetate and prepared to have a solid content of 50% by weight, and the carboxyl group having an acid value of 131 mg KOH / g and a polystyrene-equivalent weight average molecular weight (Mw) of 2600 measured by GPC. The containing epoxy (meth) acrylate resin (b-I) was obtained.

<Synthesis Example 1-2: Synthesis of carboxyl group-containing epoxy (meth) acrylate resin (b-II)>
“XD1000” (polyglycidyl ether of dicyclopentadiene / phenol polymer, epoxy equivalent 252) 300 parts by weight, 87 parts by weight of methacrylic acid, 0.2 parts by weight of p-methoxyphenol, triphenylphosphine manufactured by Nippon Kayaku Co., Ltd. 5 parts by weight and 255 parts by weight of propylene glycol monomethyl ether acetate were charged in a reaction vessel and stirred at 100 ° C. until the acid value became 3.0 mgKOH / g. Subsequently, 145 parts by weight of tetrahydrophthalic anhydride was further added and reacted at 120 ° C. for 4 hours. The solid content was 50% by weight, the acid value was 100 mgKOH / g, and the carboxyl of polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 2600. A group-containing epoxy (meth) acrylate resin (b-II) was obtained.

<Synthesis Example 2: Synthesis of photopolymerization initiator (c-I)>
(Diketone body)
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then AlCl ₃ (3. 41 g, 25.61 mmol) was added. Further, after stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, then AlCl ₃ (4.1 g, 30.73 mmol) was added, and another 1 hour 30 hours. Stir for minutes. The reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a diketone body as a white solid (10 g).

(Oxime body)
Diketone (3.00 g, 7.19 mmol), NH ₂ OH · HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 ml of isopropanol and refluxed for 3 hours. .
After completion of the reaction, the reaction mixture was concentrated, 30 ml of ethyl acetate was added to the resulting residue, washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82 g of a solid. This was purified by column chromatography to obtain 2.22 g of an oxime compound as a pale yellow solid.

(Oxime ester)
The oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, and the mixture was ice-cooled. Triethylamine (1.77 g, 17.5 mmol) was added dropwise, and 1 Reacted for hours. After confirming disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of saturated aqueous sodium hydrogen carbonate solution and twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate / hexane = 2/1) to give 0.79 g of a light yellow solid photopolymerization initiator (c-I). ) The structure of the photopolymerization initiator (c-I) is shown below.

<Production Example 1: Preparation of coated carbon black>
Carbon black was produced by a normal oil furnace method. However, ethylene bottom oil with a small amount of Na, Ca, and S was used as the raw material oil, and combustion was performed using gas fuel. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. 540 g of the obtained carbon black was stirred at 5,000 to 6,000 rpm for 30 minutes together with 14500 g of pure water using a homomixer to obtain a slurry. The slurry was transferred to a container with a screw type stirrer, and 600 g of toluene in which 60 g of epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water was transferred to the toluene side, and became particles of about 1 mm.
Next, after draining with a 60 mesh wire net, it put into the vacuum dryer, and it dried at 70 degreeC for 7 hours, and removed toluene and water.
The resin coating amount of the obtained coated carbon black is 10% by weight with respect to the total amount of carbon black and resin.

<Production Example 2-1: Preparation of coated carbon black ink (d-I)>
To 20 parts by weight of the coated carbon black prepared in Production Example 1, 4.5 parts by weight of Disperbyk-167 (manufactured by Big Chemie) as a dispersant and 1 part by weight of S12000 (manufactured by Lubrizol) as a pigment derivative are added to form a solid. Propylene glycol monomethyl ether acetate (PGMEA) was added so that the partial concentration was 35% by weight.
This was sufficiently stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As the beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion, the beads and the dispersion were separated by a filter to prepare ink (d-I).

<Production Example 2-2: Preparation of coated carbon black ink (d-II)>
To 20 parts by weight of the coated carbon black prepared in Production Example 1, 4.5 parts by weight of EFKA4046 (manufactured by BASF) as a dispersant and 1 part by weight of S12000 (manufactured by Lubrizol) as a pigment derivative are added, and the solid content concentration Of propylene glycol monomethyl ether acetate (PGMEA) was added so as to be 25% by weight.
This was sufficiently stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As the beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare ink (d-II).

<Production Example 2-3: Preparation of carbon black ink (d-III)>
Carbon black for color (“MA-8” manufactured by Mitsubishi Chemical Corporation, average particle size 24 μm, DBP oil absorption 58 ml / 100 g), 5 parts by weight of EFKA4046 (manufactured by BASF) as a dispersant, and S12000 as a pigment derivative 1 part by weight (manufactured by Lubrizol) was added, and propylene glycol monomethyl ether acetate (PGMEA) was further added so that the solid content concentration was 30% by weight. The total weight of the dispersion was 181 g.
This was sufficiently stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As the beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare ink (d-III).

[Photopolymerizable monomer]
The following photopolymerizable monomers (a-I) to (a-IV) were prepared.
a-I: acrylic acid ester of dipentaerythritol caprolactone represented by the following structure (a11) (DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.))
a-II: Dipentaerythritol hexaacrylate a-III: Acrylic ester of trimethylolpropane caprolactone represented by the following structure (a12) a-IV: Trimethylolpropane triacrylate

[Examples and Comparative Examples]
(1) Preparation of resist (photosensitive colored resin composition) <Examples 1 and 4 and Comparative Examples 1 and 3>
Add each component so that the ratio in the solid content is the following ratio as the solid content, and further add an organic solvent (propylene glycol monomethyl ether acetate (PGMEA)) so that the solid content concentration is 15% by weight. The black resist was prepared by stirring and dissolving.

<Formulation>
Ink (d-I) prepared in Production Example 2-1: 30.5% by weight
Ink (d-III) prepared in Production Example 2-3: 26.4% by weight
Carboxyl group-containing epoxy (meth) acrylate resin (b-I) synthesized in Synthesis Example 1-1: 24.2% by weight
Carboxyl group-containing epoxy (meth) acrylate resin (b-II) synthesized in Synthesis Example 1-2: 2.7% by weight
Photopolymerization initiator (c-I) synthesized in Synthesis Example 2: 7.0% by weight
Silane coupling agent (SH6040 (manufactured by Toray Dow Corning)): 0.5% by weight
Surfactant (F-475 (manufactured by Dainippon Ink and Chemicals)): 0.1% by weight
Photopolymerizable monomer (described in Table 1): 8.6% by weight

<Examples 2 and 3 and Comparative Example 2>
Each component is added so that the ratio in the solid content is the following ratio as the solid content, and further an organic solvent (propylene glycol monomethyl ether acetate (PGMEA)) is added so that the solid content concentration is 14.5% by weight, A black resist was prepared by stirring and dissolving with a stirrer.

<Formulation>
Ink (d-II) prepared in Production Example 2-2: 61.2% by weight
Carboxyl group-containing epoxy (meth) acrylate resin (b-I) synthesized in Synthesis Example 1-1: 15.0% by weight
Carboxyl group-containing epoxy (meth) acrylate resin (b-II) synthesized in Synthesis Example 1-2: 10.0% by weight
Photopolymerization initiator (c-I) synthesized in Synthesis Example 2: 6.0% by weight
Phosphoric acid group-containing compound (PM-21 (manufactured by Nippon Kayaku Co., Ltd.)): 0.5% by weight
Surfactant (F-475 (manufactured by Dainippon Ink and Chemicals)): 0.1% by weight
Photopolymerizable monomer (described in Table 2): 7.2% by weight

(2) Evaluation of resist
(2-1) Coating Film Surface Roughness Evaluation in Development Step The black resist prepared in (1) was applied to a glass substrate with a spin coater and dried on a hot plate at 80 ° C. for 2.5 minutes. The film thickness of the resist after drying was measured with a stylus type film thickness meter (“α-step” manufactured by Tencor), and it was 1.6 μm. Next, this sample was image-exposed with a high-pressure mercury lamp through a linear mask having an opening of 26.5 μm. Then, a resist pattern was obtained by spray development using a KOH aqueous solution having a concentration of 0.05% by weight at a temperature of 23 ° C. The line width of the obtained pattern was 29.5 μm.
The surface roughness Sa [nm] of the resist pattern before and after development is measured by a non-contact surface / layer cross-sectional shape measurement system (“Vert Scan” manufactured by Ryoka System Co., Ltd.) Was evaluated by the difference between Sa after development and before development: ΔSa. The results are shown in Tables 1 and 2.

(2-2) Evaluation of Adhesiveness with Glass Substrate The black resist prepared in (1) was applied to a glass substrate with a spin coater and dried on a hot plate at 80 ° C. for 2.5 minutes. The film thickness of the resist after drying was measured with a stylus type film thickness meter (“α-step” manufactured by Tencor), and it was 1.6 μm. Subsequently, it was heat-cured at 230 ° C. for 30 minutes to obtain an evaluation substrate.
A stud pin having a diameter of 2.7 mm is bonded to the obtained evaluation substrate using an adhesive (Struct Bond XN-21-S (manufactured by Mitsui Chemicals)), heated at 150 ° C. for 1 hour, and then returned to room temperature. Allowed to cool. The adhesion strength of the obtained evaluation substrate with stud pins was measured using a thin film adhesion strength measuring device “ROMULUS” (manufactured by QUAD GROUP). The force applied to the stud pin was 2 kg / second. The results are shown in Tables 1 and 3.

From Tables 1 to 3, according to the photosensitive colored resin composition of the present invention, the adhesiveness with the glass substrate is high, and the difference ΔSa between the surface roughness Sa after development and before development is small. It can be seen that pixels can be formed with no roughness on the surface.
On the other hand, in Comparative Examples 1 to 3 that do not contain the compounds represented by the general formulas (a1) to (a3) as the photopolymerizable monomer, the adhesion to the glass substrate is low, and after development And the difference ΔSa in surface roughness Sa before development is large.

DESCRIPTION OF SYMBOLS 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (7)

A photosensitive coloring composition containing (a) a photopolymerizable monomer, (b) an organic binder, (c) a photopolymerization initiator, and (d) a black color material,
(A) The photopolymerizable monomer includes a compound having a structure represented by any one of the following general formulas (a1) to (a3),
(B) The photosensitive colored resin composition, wherein the organic binder contains the following alkali-soluble resin (b1) and / or alkali-soluble resin (b2).

(In the general formula (a1), A is composed of A1 and A2 below, and the molar ratio of A1 and A2 in the formula (a1) is A1: A2 = 2: 2 to 4: 0.)

(In the general formula (a2), A consists of A1 and A2 below, and the molar ratio of A1 and A2 in the formula (a2) is A1: A2 = 3: 3 to 6: 0.)

(In the general formula (a3), A consists of A1 and A2 below, the molar ratio of A1 and A2 in the formula (a3) is A1: A2 = 2: 1 to 3: 0, and R ⁴ is carbon. Represents an alkyl group of 1-6.)

(In the above A1 and A2, R ¹ represents an alkylene group which may have 2 to 6 carbon atoms in the main chain, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and n is Represents an integer of 1 to 3. When n is 2 or 3, a plurality of R ¹ may be the same or different from each other.
<Alkali-soluble resin (b1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (b2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this. (B) The organic binder contains the following alkali-soluble resin (b1 ′) and / or alkali-soluble resin (b2 ′), the photosensitive colored resin composition according to claim 1.
<The following alkali-soluble resin (b1 ′)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin of any one of B1 to B4 below, and a polybasic acid and / or anhydride thereof An alkali-soluble resin obtained by reacting.
<The following alkali-soluble resin (b2 ′)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin of any one of B1 to B4 below, and a polyhydric alcohol, a polybasic acid, Or alkali-soluble resin obtained by making the anhydride react.
B1: Epoxy resin represented by the following general formula (B1)

(In the general formula (B1), a represents an average value and represents a number of 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Represents a phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ¹¹ present in one molecule may be the same as or different from each other.
B2: Epoxy resin represented by the following general formula (B2)

(In the above general formula (B2), b represents an average value and represents a number from 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Represents a phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ²¹ present in one molecule may be the same as or different from each other.
B3: Epoxy resin represented by the following general formula (B3)

(In the general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), provided that the molecular structure includes one or more adamantane structures. Represents an integer of 2 or 3.)

(In the above general formulas (B3-1) and (B3-2), R ^{31 to} R ³⁴ and R ^{35 to} R ³⁷ are each independently an adamantyl group optionally having a substituent, a hydrogen atom, and a substituent. The alkyl group having 1 to 12 carbon atoms which may have a group, or a phenyl group which may have a substituent.
B4: Epoxy resin represented by the following general formula (B4)

(In the above general formula (B4), d and e each independently represent an integer of 0 to 4, R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ each independently And x and y each independently represents an integer of 0 or more.)   (C) The photopolymerization initiator is an oxime ester compound, The photosensitive colored resin composition according to claim 1 or 2.   The photosensitive colored resin composition according to any one of claims 1 to 3, wherein (d) the black color material includes carbon black coated with a resin.   Hardened | cured material formed by hardening | curing the photosensitive colored resin composition in any one of Claims 1 thru | or 4.   A color filter formed using the photosensitive colored resin composition according to claim 1.   A liquid crystal display device produced using the color filter according to claim 6.

Images