KR101519428B1 - Colored curable resin composition method for forming colored pattern colored pattern method for producing color filter color filter and liquid crystal display - Google Patents

Abstract

(C) at least two kinds of binder resins, (d) a photopolymerization initiator, and (e) a surfactant for providing a colored curable resin composition having good coating properties, Wherein at least two of the binder resins are a resin having a (meth) acryloyl group in an amount of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g, a coloring pattern forming method using the same , A coloring pattern, a method of manufacturing a color filter, a color filter, and a liquid crystal display element.

A coloring pattern, a color filter, a liquid crystal display element

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring curable resin composition, a coloring pattern forming method, a coloring pattern, a method of manufacturing a color filter, a color filter, and a liquid crystal display element, AND LIQUID CRYSTAL DISPLAY}

 The present invention relates to a colored curable resin composition, a colored pattern forming method, a colored pattern, a method of producing a color filter, a color filter, and a liquid crystal display element.

The color filter contains a binder resin and / or a monomer, a photopolymerization initiator, and other components in a solvent-dispersed composition of a coloring material such as an organic pigment and an inorganic pigment to form a colored photosensitive composition, and the color filter is manufactured by a photolithography method or the like.

In recent years, the color filter tends to be used not only for a monitor but also for a television (TV) in the use of a liquid crystal display device (LCD), and a high color characteristic is required in chromaticity, contrast, have. In addition, in the use of an image sensor (solid-state image pickup device), similarly, color characteristics are required to be high.

Further, as the size of the substrate is increased, the method of applying the colored photosensitive composition for improving the productivity has been carried out from the spin coating method to the slit coating method (also referred to as die coating or flexible coating). Among them, a composition suitable for the application method is required, and a composition whose specific property is controlled as such a composition is disclosed (for example, see WO2005 / 078524 A1).

In recent years, with the spread of large-sized liquid crystal displays and the like, the size of the substrate has been further increased, and high-speed coating which is not conventionally required in the slit coating method is required. However, in these techniques, there is a problem that there are still many coating defects when the slit coating speed is set at a high speed of 200 mm / sec on a glass substrate in order to manufacture a color filter.

On the other hand, a technique of controlling the unevenness of the coating film thickness by using a specific binder is also disclosed, but there is a problem that there is still no way to cope with the application of the high-speed coating slit (see, for example, Japanese Patent Application Laid-Open No. 2002-20442).

It is an object of the present invention to provide a colored curable resin composition having good coating properties, a colored pattern forming method including a slit coating step using the colored curable resin composition, and a colored pattern formed by the colored pattern forming method.

It is still another object of the present invention to provide a method of manufacturing a color filter having the colored pattern with a good film surface shape, a color filter manufactured by the manufacturing method, and a liquid crystal display element using the color filter.

In view of the above circumstances, the inventors of the present invention have conducted intensive studies, and found that the above problems can be solved, and completed the present invention.

That is, the present invention is achieved by the following means.

A colored curable resin composition comprising (a) a colorant, (b) a solvent, (c) at least two binder resins, (d) a photopolymerization initiator, and (e) a surfactant, Is a resin having a (meth) acryloyl group in an amount of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g.

Here, having a (meth) acryloyl group means having either an acryloyl group or a methacryloyl group.

&Lt; 2 > The colored curable resin composition according to < 1 >, wherein at least one kind of the binder resin contains a (meth) acrylic copolymer having an alicyclic (meth) acryloyl group in the side chain.

<3> The toner according to any one of <1> or <2>, wherein at least one kind of the binder resin is any one selected from the following formulas (1-1), (1-2) &Lt; / RTI &gt;

R ₁ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group having 1 to 4 carbon atoms or an alkoxy group, an aryl group having 6 to 12 carbon atoms, or an aryl group having 7 to 12 carbon atoms R ₂ represents a carbamate ester containing an alkylene group having 1 to 18 carbon atoms, a phenylcarbamate ester containing an alkyl group having 1 to 4 carbon atoms, or an alicyclic group having 3 to 18 carbon atoms, R ₃ represents a straight chain or branched alkylene group having 2 to 16 carbon atoms.

The repeating units a to d in the general formula (1-1), a to e in the general formula (1-2), and a to e in the general formula (1-3) B represents 3 to 50, c represents 3 to 40, d represents 2 to 60, and a + b + c + d = 100. B in the general formulas (1-2) and (1-3) represents 0 to 85, c represents 3 to 50, d represents 3 to 40, e represents 2 to 60, a + b + c + d + e = 100. n is an integer of 2 to 16;

In the general formulas (1-1) to (1-3), R ₁ represents an aralkyl group, R ₂ represents an alkylene group having 2 to 16 carbon atoms, a residue other than (NCO) of the following diisocyanate, Tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and R ₃ is a divalent hydrocarbon group having 2 to ₆ carbon atoms, Is - (CH ₂ ) _n -, which is an integer of 1 to 10.

&Lt; 5 > The colored curable resin composition according to < 1 >, further comprising a compound having an ethylenic unsaturated group.

&Lt; 6 > A method for forming a coloring pattern, which comprises applying the colored curable resin composition according to any one of < 1 > to < 3 >

&Lt; 7 > A coloring pattern formed by the coloring pattern forming method according to < 6 >.

&Lt; 8 > A method for producing a color filter having the coloring pattern according to < 7 >.

<9> A color filter manufactured by the manufacturing method described in <8>, wherein the contrast is 5000 or more.

&Lt; 10 > A liquid crystal display element using the color filter according to < 9 >.

According to the present invention, it is possible to provide a colored curable resin composition having good coating properties, a colored pattern forming method including a slit coating step using the colored curable resin composition, and a colored pattern formed by the colored pattern forming method .

Further, according to the present invention, it is possible to provide a method of manufacturing a color filter having the colored pattern with a good film surface shape, and a color filter manufactured by the manufacturing method. Further, a liquid crystal display element using the color filter can be provided.

Hereinafter, the present invention will be described in detail.

&Lt; Coloring curable resin composition &

 The colored curable resin composition of the present invention is a colored curable resin composition containing (a) a colorant, (b) a solvent, (c) at least two kinds of binder resins, (d) a photopolymerization initiator, and (e) a surfactant, Wherein at least two of the resins have a (meth) acryloyl group in an amount of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g.

Here, having a (meth) acryloyl group means having at least one of an acryloyl group and a methacryloyl group.

In addition to the essential components, other optional components may be added to the colored curable resin composition.

The colored curable resin composition preferably has a total solid content in the total colored curable resin composition of 2 to 50 mass%, more preferably 10 to 30 mass%, and particularly preferably 15 to 25 mass% Do.

Hereinafter, the components and the like of the above-mentioned colored curable resin composition will be described in detail.

< (c) Binder resin &

The colored curable resin composition contains (c) at least two kinds of binder resins (hereinafter referred to as &quot; resins of the present invention &quot;) as the binder resin, and the binder resin has a (meth) acryloyl group in a range of from 0.0005 to 0.0050 eq / g, and an acid value of 15 to 150 mgKOH / g.

In addition, the binder resin in the present invention is a polymer which satisfies the above-mentioned properties which are soluble in an organic solvent and a weakly alkaline aqueous solution. In these polymers, the (meth) acryloyl group is 0.0005 to 0.0050 eq / g, preferably 0.0007 to 0.0020 eq / g, more preferably 0.0010 to 0.0020 eq / g.

The (meth) acryloyl group in the polymer is preferably 0.0005 eq / g or more and 0.0050 eq / g or less, because curing property is good and a proper developing region can be obtained.

The acid value of the resin in the present invention is 15 to 150 mgKOH / g, preferably 35 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g.

By setting these ranges, it is preferable that proper coating property and proper developing area tend to be ensured. In order to keep the acid value of the polymer within the above range, for example, a method of binding an acid group (carboxyl group, sulfonic acid group, phosphoric acid group, etc.) to the side chain is listed. The acid group is preferably a carboxyl group.

Further, it is preferable to have a hydroxy group from the viewpoint of substrate adhesion irrespective of the acid value. As the hydroxy group, recurring units derived from hydroxymethyl methacrylate are listed. In this case, the content is preferably 3 to 40, more preferably 10 to 30, in terms of the molar percentage of units.

At least one kind of the binder resin in the present invention preferably contains a (meth) acrylic copolymer having an alicyclic (meth) acryloyl group in its side chain. It is preferable that at least one kind of the binder resin contains any one selected from the following general formulas (1-1) to (1-3).

&Lt; (Meth) acrylic copolymer having alicyclic (meth) acryloyl group in side chain >

As the binder resin in the present invention, it is preferable to contain a (meth) acrylic copolymer (hereinafter also referred to as &quot; binder resin c1 &quot;) having an alicyclic (meth) acryloyl group as a polymerization group in its side chain.

As a synthesizing means for introducing such a polymerization reactor into a resin, there is known a method described in Japanese Patent Publication No. 50-34443, Japanese Patent Publication No. 50-34444, and the like.

Specifically, a resin having a polymerization group in its side chain can be obtained by reacting a carboxyl group or a hydroxy group in the resin with a compound having an alicyclic epoxy group such as an epoxycyclohexyl group or an epoxycyclopentyl group and a (meth) acryloyl group together have.

Preferred examples of the compound include epoxycyclohexylmethyl (meth) acrylate and epoxycyclopentylmethyl (meth) acrylate, and the most preferred is (3,4-epoxycyclohexyl) methyl (meth) acrylate .

In the present invention, since the alicyclic group is introduced into the side chain of the binder resin, a photocurable resin composition having excellent adhesion with a substrate and having high chemical resistance can be obtained, and particularly, it is suitable for a color filter.

As the resin skeleton into which the (meth) acryloyl group is introduced as the polymerization unit, a (meth) acrylic copolymer is used. As the monomer copolymerized with (meth) acrylic acid, an alkyl group is substituted at the a position such as styrene and? (Meth) acrylate, glycidyl (meth) acrylate, propyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate, allyl glycidyl ether, glycidyl ethylacrylate, crotonyl glycidyl ether, crotonic acid glycidyl ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, Acrylate, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, And copolymers obtained by copolymerizing monomers such as acrylamide and acrylamide. In particular, a copolymer containing (meth) acrylic acid and styrene which may have an alkyl group substituted at the? -Position as a copolymerization component is preferable.

The ratio of the (meth) acrylic acid in the (meth) acrylic copolymer into which the (meth) acryloyl group is introduced as the polymerizer is preferably 0.2 to 0.8, more preferably 0.3 to 0.7 in terms of the molar ratio. The content of the copolymerization component such as styrene in the copolymer is preferably 0.8 to 0.2, more preferably 0.7 to 0.3.

The binder resin c1 used in the present invention, that is, the weight average molecular weight of the (meth) acrylic copolymer as measured by GPC is preferably from 5,000 to 100,000, and more preferably from 10,000 to 70,000 from the viewpoint of coating ability. But is preferably from 1,000 to 70,000, more preferably from 1,000 to 50,000 from the viewpoint of liquid storage stability.

&Lt; Resin selected from general formulas (1-1) to (1-3)

The binder resin constituting the composition of the present invention is a resin having a (meth) acryloyl group in an amount of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g, but at least one kind of the binder resin (hereinafter also referred to as "binder resin c2" ) Preferably includes any one selected from the following formulas (1-1) to (1-3).

In the present invention, in addition to the resin component, other resins may be added to the composition within the range that does not impair the effects of the present invention, for example, for improving developability, improving physical properties (mechanical properties, adhesion, etc.).

(Meth) acrylate / (meth) acrylic acid copolymer with benzyl (meth) acrylate / (meth) acrylate / (meth) acrylic acid / and other monomers such as benzyl Molar ratio is 5/5 to 9/1) can be used in combination with other thermoplastic resins.

In the general formulas (1-1) to (1-3), R represents a hydrogen atom or a methyl group. R ₁ is an alkyl group having 1 to 18 carbon atoms (C ₁ to C ₁₈ ), a phenyl group having an alkyl or alkoxy group having 1 to 4 carbon atoms (C ₁ to C ₄ ), a C ₆ to C ₁₂ ) Or an aralkyl group having 7 to 12 carbon atoms (C ₇ to C ₁₂ ).

The C ₁ -C ₁₈ alkyl group represented by R ₁ may be any of linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group, , A hexadecyl group, an octadecyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-cyanoethyl group, a 2-methoxycarbonylethyl group, a 2-methoxyethyl group, .

C ₁ ~ with an alkyl group of C ₄ is that having from 1 to 4 carbon atoms listed in examples of the alkyl groups of the C ₁ ~ C ₁₈ for example, C alkoxy group of ₁ ~ C ₄ contained in the phenyl group contained in a phenyl group is a methoxy group, Ethoxy group, propoxy group, butoxy group, and the like.

As the C ₆ to C ₁₂ aryl group of R ₁ , a phenyl group, a tolyl group, a naphthyl group and the like can be exemplified.

Examples of the C ₇ -C ₁₂ aralkyl group include benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, , A methoxybenzyl group, a dimethylbenzyl group, and a dimethoxybenzyl group.

Further, in the formula (1-1) to formula (1-3), R ₂ is phenyl carbamic acid ester comprising an alkyl group of C ₁ ~ C ₁₈ alkylene group, C ₁ ~ C _4, C ₃ Lt; RTI ID = 0.0 &gt; _{C18 &lt}; / RTI &gt;

The C ₁ - C ₁₈ alkylene group includes those in which the C ₁ - C ₁₈ alkyl group represented by R ₁ is transposed, and the C ₁ - C ₄ alkyl group contained in the phenylcarbamate group includes the above R ₁ Of the specific examples of the C ₁ - C ₁₈ alkyl group of 1 to 4 carbon atoms, those having 1 to 4 carbon atoms are listed.

Carbamic acid phenyl ester _{(-OCO-NH-C 6 H} 4 -) and the structure represented by the alkyl group is a substituent of the phenylene group of the.

Examples of the C ₃ to C ₁₈ alicyclic group contained in the carbamic acid ester include a cyclopentyl group, a cyclobutyl group, a cyclohexyl group, an isophorone group, and a dicyclohexyl group. The carbamic acid ester is a structure represented by (-NH-COO-), and the alicyclic group together with this structure forms a divalent group.

R ₃ represents a linear or branched alkylene group having 2 to 16 carbon atoms, specifically, 2 to 16 carbon atoms in the C ₁ to C ₁₈ alkyl group of R ₁ .

(A) to (d) in the formula (1-1), a to e in the formula (1-2) and a to e in the formula (1-3) B represents 3 to 50, preferably 5 to 40, c represents 3 to 40, preferably 10 to 30, d represents 2 to 60, Preferably 5 to 50, and a + b + c + d = 100. n is an integer of 2 to 16, preferably 4 to 12.

B in the formulas (1-2) and (1-3) represents 0 to 85, preferably 0 to 80, c represents 3 to 50, preferably 5 to 40, and d represents 3 to 40 , Preferably 8 to 30, e represents 2 to 60, preferably 2 to 50, and a + b + c + d + e = 100. n is an integer of 2 to 16, preferably 4 to 12.

In the general formulas (1-1) to (1-3), R ₁ is preferably an aralkyl group, more preferably a benzyl group, and R ₂ is preferably a group having 2 to 16 carbon atoms (NCO) of the following diisocyanate can be exemplified. Preferably, it is preferably a diisocyanate such as diphenylmethane diisocyanate, tolylene diisocyanate, xylene diisocyanate, 2,4-toluylene diisocyanate, o-toluylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, Include hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate.

R ₃ is the n is an integer of _{2 ~ 10 - (CH 2)} n - are preferred, and, n is an integer of _{2 ~ 6 - (CH 2)} n - is preferred.

In the colored curable resin composition of the present invention, each of the above-mentioned c1 and c2 may be used singly, or two or more of the above c1 and c2 may be used in combination, or a combination thereof may be used.

The content of the binder resin in the colored curable resin composition of the present invention is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and still more preferably from 30 to 75% by mass, based on the total solid content (concentration) Mass%.

 The content of the binder resin in the colored curable resin composition is preferably 10 to 90% by mass, because it is easy to form a coating film having a good coated surface shape.

In the present invention, in addition to the above-mentioned resin component, other resins may be added to the composition within the range that does not impair the effect of the present invention, such as improvement in developability, improvement in physical properties (mechanical properties, adhesion, etc.).

(Meth) acrylate / (meth) acrylic acid copolymer with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers (benzyl Molar ratio is 5/5 to 9/1) can be used in combination with other thermoplastic resins.

<(c3) Compound having an ethylenically unsaturated group>

The colored curable resin composition of the present invention may contain (c3) a compound having an ethylenically unsaturated group (hereinafter referred to as a polymerizable compound, as appropriate).

The polymerizable compound usable in the present invention is an addition-polymerizable compound having at least one ethylenic unsaturated double bond and is selected from compounds having at least one terminal ethylenic unsaturated bond, preferably two or more terminal ethylenic unsaturated bonds. Such a group of compounds is widely known in the industrial field, and in the present invention, these compounds can be used without any particular limitation. They have chemical forms such as monomers, prepolymers, i.e., dimers, trimer and oligomers, or mixtures thereof and copolymers thereof.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, An ester of a carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent group such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxide, and a monofunctional or polyfunctional carboxylic acid And a dehydration condensation reaction product of water. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols and also a leaving group such as a halogen group or a tosyloxy group Substitution reactions of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional alcohols, amines, thiols are also suitable. As another example, it is also possible to use a compound group modified with an unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

Specific examples of the monomers of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexane diol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, Sorbitol triacrylate Agent, and the like sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate.

Examples of the methacrylic esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol Dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate , Dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- Methacryloxyethoxy) phenyl] dimethylmethane and the like.

Examples of itaconic acid esters include ethylene glycol diacetonate, propylene glycol diacetonate, 1,3-butanediol diacetonate, 1,4-butanediol diacetonate, tetramethylene glycol diacetonate, pentaerythritol diacetonate, sorbitol tetra And taconate. Examples of the crotonic acid esters include ethylene glycol dichlortonate, tetramethylene glycol dichlonate, pentaerythritol dichlonate, and sorbitol tetracrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in Japanese Patent Application Laid-Open Nos. 51-47334 and 57-196231, Japanese Laid-Open Patent Application Nos. 59-5240, 59-5241, Those having an aromatic skeleton as disclosed in JP-A No. 2-226149, those containing an amino group as described in JP-A No. 1-165613, and the like are also suitably used. The above-mentioned ester monomer can also be used as a mixture.

Specific examples of the amide monomer of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebisacrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis -Methacrylamide, diethylene triamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, and the like. Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726.

Further, urethane-based addition polymerizable compounds prepared by the addition reaction of isocyanate with a hydroxy group are also suitable. Examples of such urethane-based addition polymerizable compounds include two or more isocyanate groups in a molecule described in Japanese Patent Publication No. 48-41708 , A vinyl urethane compound having two or more polymerizable vinyl groups in a molecule to which a vinyl monomer having a hydroxyl group represented by the following general formula (A) is added, and the like.

CH ₂ = C (R) COOCH ₂ CH (R ') OH (A)

(Provided that R and R 'represent H or CH ₃ ).

Urethane acrylates as described in JP-A-51-37193, JP-A-2-32293, JP-A-2-16765, JP-A-58-49860, JP-B-56-17654, JP-A-62-39417, and JP-A-62-39418 are also suitable for urethane compounds having an ethylene oxide skeleton. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 1-105238, Can be obtained.

Other examples include polyester acrylates, epoxy resins and (meth) acrylates as described in JP-B-48-64183, JP-B-49-43191, JP-A-52-30490, And polyfunctional acrylates or methacrylates such as epoxy acrylates obtained by reacting acrylic acid. Also, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-43946, 1-40337 and 1-40336 and vinylphosphonic acid compounds described in Japanese Patent Application Laid-Open No. 25493 Can be listed. In addition, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is suitably used. Also, those which have been introduced as photocurable monomers and oligomers in Japan Adhesion Society vol.20, No. 7, pages 300 to 308 (1984) can be used.

The structure of the photopolymerizable compound (addition polymerizable compound), details of the usage, such as the use alone or in combination, and the amount of addition, can be arbitrarily set in accordance with the performance design of the final coloring pattern. For example, it is selected from the following viewpoints.

From the viewpoint of sensitivity, a structure having a large amount of unsaturated group per molecule is preferable, and in many cases, a bifunctionality or more is preferable. Further, in order to increase the coloring pattern, that is, the strength of the cured film, it is preferable to use trifunctional or more functional groups. In addition, the combination of other functional groups and other polymerizable groups (for example, acrylate ester, methacrylate ester, styrene group compound and vinyl ether group compound) A method of adjusting both the sensitivity and the intensity is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and a compound containing four or more Most preferred. In addition, from the viewpoints of curing sensitivity and developability of the unexposed portion, it is preferable to contain an EO-modified product. In addition, from the viewpoints of curing sensitivity and exposure part strength, it is preferable to contain a urethane bond.

The compatibility and dispersibility of the other components in the colored curable resin composition of the present invention (for example, the colorant, (d) the photopolymerization initiator and (c) the binder resin (alkali-soluble resin) The selection and use of the polymerization compound is an important factor. For example, the compatibility may be improved by using a low-purity compound or by combining two or more compounds. Further, when the colored curable resin composition is applied to a substrate or the like, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.

From the above viewpoints, it is preferable that bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, tetra But are not limited to, ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate , Sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO-modified product, and dipentaerythritol hexaacrylate EO- UH-140 (manufactured by Sanyo-Kokusaku Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA -306T, UA-306I, AH-600, T-600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate , DPA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I (manufactured by Nippon Kayaku Co., Ltd.) are commercially available products, and pentaerythritol tetraacrylate EO modified product and dipentaerythritol hexaacrylate EO- , AH-600, T-600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) are more preferable.

In the present invention, the (c3) polymerizable compound may be used singly or in combination of two or more.

The content of the (c3) polymerizable compound in the colored curable resin composition of the present invention is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, More preferably 70% by mass. When the content of the polymerizable compound is within the above range, the curing reaction is sufficiently carried out.

In particular, when the color-curable resin composition of the present invention is used for forming a coloring pattern of a color filter, it is preferably in the range of 5 to 50 mass%, more preferably 7 to 40 mass%, and more preferably 10 to 35 mass% More preferably, it is in mass%.

<(a) Colorant>

(a) a coloring material means a coloring of the colored curable resin composition of the present invention. As a coloring material, a salt pigment can be used, but a pigment is preferable in view of heat resistance, light resistance and the like.

As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. Examples of the structure include azo, anthraquinone, phthalocyanine, quinacridone, benzimidazolone, isoindolin, dioxazine, indanthrene, perylene, diketopyrrolopyrrole, quinophthalone And various inorganic pigments can also be used.

Specific examples of usable pigments are shown below as pigment numbers. In addition, &quot; C.I. &quot; listed below means color index (C.I.).

The red pigments include C.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 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 48: 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, : 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254 , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276.

Of these, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment Red 177, 209, 224, 254 can be listed.

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

Among them, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. Pigment Blue 15: 3, 15: 6.

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

Of these, C.I. Pigment Green 7, 36 can be listed.

The yellow pigments include C.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, 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: , 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174 , 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 , 204, 205, 206, 207, 208, FAST Yellow Y-5688, Yellow Pigment E4GN and Yellow 5GN-01.

Among them, C.I. Pigment Yellow, 117, 129, 138, 139, 150, 154, 155, 180, 185, FAST Yellow Y-5688, Yellow Pigment E4GN, Yellow 5GN-01, Pigment Yellow 138, 139, 150, 180, 185, FAST Yellow Y-5688, Yellow Pigment E4GN, Yellow 5GN-01.

The orange pigments include C.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,

Among them, C.I. Pigment Orange 38, 71 can be listed.

Examples of the purple pigment include C.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 can be listed.

Among them, C.I. Pigment Violet 19, 23, more preferably C.I. Pigment Violet 23 can be listed.

When the colored curable resin composition of the present invention is a colored curable resin composition for a black matrix of a color filter, a black coloring material may be used as the coloring material. The black material may be a black material alone or a mixture of red, green, and blue. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic pigments and organic pigments, it is preferable to disperse the pigment in an average particle size of 1 μm or less, preferably 0.5 μm or less.

In order to prepare a black coloring material, a mixture of available colors such as Victorian Pure Blue (42595), Oramin O (41000), Cationic Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B Simulfast Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simulfast Red 4015 (12355) , Lionol Blue ES (Pigment Blue 15: 6), Lyonogen Red (Liongreen Red), Lionol Blue (R) ) GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), and the like. (The numbers in parentheses indicate color index (CI)).

Further, for another mixed usable pigment, C.I. When displayed in numbers, for example, C.I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, Purple pigments 19, 23, 29, 30, 37, 40, 50, C.I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. Green pigment 7, C.I. Brown pigments 23, 25, 26, and the like.

Examples of the black color material which can be used alone include carbon black, acetylene black, lamp black, black black, graphite, iron black, aniline black, cyanine black, titanium black and metal particles such as silver or metal.

Examples of preferable metals constituting these metal-based fine particles include copper, silver, gold, platinum, vanadium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, , Antimony, and alloys of these metals. More preferred metals are at least one kind selected from copper, silver, gold, platinum, vanadium, tin, calcium, and their alloys, and particularly preferred metals are copper, silver, gold, platinum, tin and alloys thereof At least one species is preferable, and a compound with an element other than metal is also preferable.

Examples of the compound of the metal and other elements include oxides, sulfides, sulfates, and carbonates of metals, and these metal compounds are suitable as the metal compound particles. Among them, particles of sulfide are preferable from the viewpoint of easiness of color tone and formation of fine particles.

The metal, the alloy, and the metal compound may be used in combination, or two or more metals may be used. Of these, silver or an alloy thereof and a sulfide thereof are particularly preferred because of their high shielding effect. As examples of the alloys, silver tin alloys are listed as preferred examples.

Of these black coloring materials, alloys such as carbon black, titanium black, silver and silver tin, and their sulfides are preferred because of their high shielding effect. Examples of the carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation Products: 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, OIL 7B, OIL 9B, OIL 11B, OIL 30B,

Printex S, Printex 3OP, Printex SO, Pril: itex30OP, Printex 40, Printex 45, Printex 55, Printex GO, Printex 75, Printex SO, Printex 85, Printex 9O, Printex, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, , Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

 Cabot Corporation Products: Monarch 120, Monarch 280, Monarch 4, 60, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN XC72R, ELFTEX-8

Colombia Carbon Co. Products: RAVEN 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22 RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020 , RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN S750, RAVEN 7000

The titanium black is listed below.

Examples of the method for producing titanium black include a method of reducing a mixture of titanium dioxide and titanium metal by heating in a reducing atmosphere (Japanese Patent Application Laid-Open No. 49-5432), a method of producing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride (Japanese Patent Application Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide in the presence of ammonia at a high temperature (JP-A-60-65069, Japanese Patent Publication JP-A 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide, and a method in which the mixture is subjected to high-temperature reduction in the presence of ammonia (Japanese Patent Application Laid-open No. 61-201610), but the present invention is not limited thereto .

Examples of commercially available products of titanium black include Mitsubishi Material Co., Ltd. Products of titanium black 10S, 12S, 13R, 13M, 13M-C, and the like are listed.

Examples of other black pigments include aniline black, iron oxide black pigments, and organic pigments of three colors of red, green and blue, and can be used as a black pigment.

As the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, spinach, chromium oxide and the like may be used.

A plurality of the above-mentioned various pigments may be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment may be used together as a pigment, or a blue pigment and a purple pigment may be used in combination.

The average primary particle diameter of these pigments is preferably 10 nm to 100 nm, more preferably 10 nm to 50 nm.

The content of the pigment is preferably 30 mass% or more and 70 mass% or less, more preferably 38 mass% or more and 60 mass% or less, further preferably 42 mass% or more and 60 mass% or less, relative to the total solid content of the colored curable resin composition Do.

(D) a photopolymerization initiator, (e) a surfactant, and (f) at least two kinds of binder resins. The term &quot; total solids content &quot; ) &Lt; / RTI &gt; other components than the solvent.

As described above, a pigment is preferable as a coloring material from the viewpoints of heat resistance, light resistance and the like, but a dye may also be used.

Examples of the dyes usable as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

As the azo dyes, for example, C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Bayle Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5, C.I. Mordant Black 7, and the like.

As the anthraquinone-based dye, for example, C.I. Bat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60 and the like.

In addition, as phthalocyanine dyes, for example, C.I. Pad Blue 5 and the like, as quinone imine dye, for example, C.I. Basic Blue 3, C.I. Basic Blue 9 and the like, and quinoline dyes such as C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I., Disperse Yellow 64 and the like, and nitro-based dyes such as C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42 and the like.

<(b) Solvent>

In order to dissolve or disperse the constituent components such as (a) a colorant, (c) at least two kinds of binder resins, (d) a photopolymerization initiator and (e) a surfactant, use.

Examples of the solvent include glycol ethers and / or alkoxy esters.

Specific examples of the glycol ethers include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono- Butyl ether, ethylene glycol acetate, ethylene glycol diacetate, ethylene glycol diethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, and tripropylene glycol methyl ether. do.

Specific examples of the alkoxy esters include ethyl acetate, methyl isobutylate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, , Butyl 3-methoxypropionate, butyl acetate, (n, sec, t-) butyl acetate, butyl stearate, ethyl propionate, ethyl benzoate, ethyl orthoformate, ethyl caprylate and propyl acetate do.

Other solvents such as diisopropyl ether, mineral spirits, n-pentane, amyl ether, n-hexane, diethyl ether, isoprene, ethylisobutyl ether, n-octane, Amyl acetate, amphocin, butyl ether, diisobutyl ketone, methylcyclohexene, methylnonyl ketone, propyl ether, dodecane, sorbitol solvents No.1 and No.2, amyl formate, dihexyl ether, Diisopropyl ketone, Solvesso # 150, hexene, cell TS 28 solvent, butyl chloride, ethyl amyl ketone, amyl chloride, butylene glycol diacetate, methoxymethylpentanone, methyl butyl ketone, methylhexyl ketone, Methyl isobutyl ketone, amyl acetate, amyl formate, bicyclohexyl, dipeptide, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, methyl ethyl ketone, Methylcellulose Ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl lactate, propylene glycol, 3-methoxypropionic acid, 3-ethoxypropionic acid, diglyme, ethylcarbitol, butylcarbitol, 3 Methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, and the like.

The solvent may be used alone, or two or more solvents may be used in combination.

The content of the solvent in the entirety of the colored curable resin composition of the present invention is appropriately set in the range of usually 50 to 95 mass% in accordance with the ratio (concentration) of the total solid content. More preferably, it is in the range of 70 to 90 mass%, particularly preferably in the range of 75 to 90 mass%.

By setting this range, the coatability and the film formability of the coating film are improved.

<(d) Photopolymerization initiator>

The colored curable resin composition of the present invention contains a photopolymerization initiator having a function of directly absorbing light or causing photo decomposition and decomposition reaction and hydrogen withdrawing reaction to generate a polymerizable radical. The photopolymerization initiator preferably has absorption in a wavelength range of 300 to 500 nm.

The photopolymerization initiator may be used alone, or two or more thereof may be used in combination.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 20% by mass, based on the total solid content of the colored curable resin composition. Within this range, good sensitivity and pattern formability are obtained.

When a black photopolymerizable layer is formed by the colored curable resin composition, since the image is exposed through the pattern mask from above the photopolymerizable layer, the photopolymerization initiator means a compound exhibiting sensitivity to ultraviolet light to visible light, It is preferable to use an exposure light source corresponding thereto.

Also, in each of the red, green and blue photocomposition layers, the red, green, and blue color image patterns are formed between the black matrix patterns by exposure through a pattern mask of each color or other methods, As a photopolymerization initiator as in the case of a pattern, a compound exhibiting sensitivity to ultraviolet to visible light, particularly a compound exhibiting spectral sensitivity at a wavelength of 450 nm or less, particularly 400 nm or less, is preferable.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Hexaarylbimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds and acylphosphine (oxide) compounds.

More preferred examples include trihalomethyltriazine compounds,? -Amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, At least one compound selected from the group consisting of trihalomethyl triazine compounds,? -Amino ketone compounds, oxime compounds, triarylimidazole dimers and benzophenone compounds is the most preferable Do.

Examples of the photopolymerization initiator include a metallocene compound containing a titanocene compound described in each of Japanese Patent Application Laid-open Nos. 59-152396 and 61-151197, a hexacyanocaprolactone compound disclosed in Japanese Patent Application Laid-open No. Hei 10-39503 N-aryl-α-amino acids such as arylimidazole derivatives, halomethyl-s-triazine derivatives and N-phenyl-glycine, N-aryl-α-amino acid salts, N-aryl- Amino-alkylphenone-based compounds, oxime ester-based initiators described in JP-A-2000-80068, and the like.

Specific examples of the organic halogenated compound include Wakabayashi Co., Ltd., Bull Chem. Soc Japan "42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Application Laid-Open No. 48-36281, Japanese Patent Application Laid-open No. 55-32070, Japanese Patent Laid- Japanese Patent Application Laid-Open Nos. 239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, Japanese Patent Open No. 63-298339, MP Hutt, "Journal of Heterocyclic Chemistry 1 (No. 3), (1970) &quot;, and particularly oxazole compounds and s-triazine compounds in which a trihalomethyl group is substituted are listed.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

(Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s- Bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloro Trimethylsilyl) aminomethyl) -s-triazine.

As s-triazine compounds, more preferably, s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to a s-triazine ring, specifically, 2,4,6-tris (Trichloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (?,?,? - trichloroethyl 4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6- (Trichloromethyl) -s-triazine, 2- (p-chlorophenyl) - 4,6-bis (Trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis -Triazine, 2-styryl-4,6-bis (trichloro Methyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio- (trichloromethyl) -s-triazine, 2,4,6-trimethylpyridine, 2,4,6-trimethoxyphenyl) -2,6-di (trichloromethyl) Tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) Triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, and the like.

2-trichloromethyl-5- [beta - (2-benzofuryl) vinyl] -1,3, 4-oxadiazole, 2-trichloromethyl-5- [β- (2 '- (6'-benzofuryl) vinyl] Oxalate derivatives such as furyl-1,3,4-oxadiazole.

 Examples of the oxadiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole , 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) -Oxodiazole, and the like.

(2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- A dimer of 2- (2'-fluorophenyl) -4,5-diphenyl-imidazole, a dimer of 2- (2'-methoxyphenyl) Methoxyphenyl) -4,5-diphenyl-imidazole dimer.

Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether.

Anthraquinone derivatives such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone.

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone.

2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone,? -Hydroxy-2-methylphenylpropanone, 1-hydroxy- Ethyl (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthio) , 1,1,1-trichloromethyl- (p-butylphenyl) ketone, and other acetophenone derivatives.

2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-di Thioxanthone derivatives such as isopropyl thioxanthone.

benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine, and the like.

Phenazine derivatives such as 9,10-dimethylbenzophenazine.

Anthrone derivatives such as benzoanthrone.

Bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl , Dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl- Yl, dicyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl Bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopentadiene Yl-Ti-2,6-difluoro-3- (pyr-1-yl) -phenyl-1-yl.

2-methyl-1- [4- (methyl-thio) phenyl] -2-morpholinopropane- Benzyl-2-dimethyl-amino-1- (4-morpholinophenyl-) butanone-on, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, Diethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- Amino-alkylphenone compounds such as 3- (4-diethylaminobenzoyl) coumarin and 4- (diethylamino) chalcone.

Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-benzoyloxymethyl] Oxazol-3-yl] -, 1- (O-acetyloxime).

Examples of the carbonyl compound include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Benzophenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone,? -Hydroxy-2-methylphenylpropanone, (P-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2- 1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) , Acetophenone derivatives such as 1,1-trichloromethyl- (p-butylphenyl) ketone and 2-benzyl-2-dimethylamino-4-morpholinobutylophenone, , 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Thioxanthone derivatives such as 4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

Examples of the ketal compound include benzyl dimethyl ketal, benzyl-beta-methoxyethyl ethyl acetal, and the like.

Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoyl benzoate.

As the acridine compound, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane and the like can be opened.

Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Butyl peroxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5- Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert- 2-ethylhexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, Di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, ter butyl peroxy pivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxy octanoate, tert-butyl peroxy laurate, 3,3 ', 4,4'- Butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p- Benzophenone, carbonyldi (t-butylperoxy hydrogen di 2-phthalate), carbonyl di (t-hexylperoxy dihydrogen 2-phthalate), and the like.

Examples of the azo compound include azo compounds described in JP-A-8-108621.

Examples of coumarin compounds include 3-methyl-5-amino- ((s-triazin-2-yl) amino) 2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino- ((s-triazin-2-yl) amino) -3-phenyl coumarin and the like.

Examples of the azide compound include organic azide compounds described in the specification of USP 2848328, USP 2852379 and USP 2940853, 2,6-bis (4-azidobenzylidene) -4-ethylcyclo Hexanone (BAC-E), and the like.

Examples of the metallocene compound include compounds disclosed in Japanese Patent Application Laid-Open Nos. 59-152396, 61-151197, 63-41484, 2-249, 2-4705 and JP-A 5-83588, for example, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,6- Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-tri Yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dimethylcyclopentadienyl- , 6-trifluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoro Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, JP-A-1-304453, Japanese Patent Iron-arsenic complexes described in JP-A-1-152109 are heated.

Examples of the hexaarylbimidazole compound include various compounds described in each specification such as Japanese Patent Publication Nos. 6-29285, 3,479,185, 4,311,783 and 4,622,286, specifically 2, (O-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl)) - 4,4', 5,5 (O, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) ) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, Tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.

Examples of the organic borate compound include compounds described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710 Japanese Patent Application Laid-Open No. 2000-131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and Kunzmann's "Rad Tech '98. ProceEding April 19-22, 1998, Chicago &quot;, JP-A-6-157623, JP-A-6-175564 and JP-A-6-175561, organic boron sulphonium complexes or organic boron oxo sulphates An organoboron phosphonium complex described in Japanese Patent Application Laid-Open No. H09-188710, and an organoboron phosphonium complex described in Japanese Patent Application Laid-Open No. Hei 9-188710, Japanese Patent Publication No. 6-348011 Organic boron transition metal coordination complexes such as those described in JP-A 7-128785, JP 7-140589 A, JP 7-306527 A and JP 7-292014 A, do.

Examples of disulfone compounds include compounds described in JP-A-61-166544 and JP-A-2002-328465.

As the oxime ester compounds, there are listed JCS Perkin II (1979), 1653-1660, JCS Perkin II (1979), 156-162, Journal of Photopolymer Science and Technology (1995), 202-232 and Japanese Patent Application Laid- Compounds described in Japanese Patent Application Laid-Open Nos. 2000-80068 and 2004-534797, and the like. Specific examples include Ciba Specialty Chemical Co., Ltd. IRGACURE OXE-01 and OXE-02 are suitable.

As the onium salt compounds, for example, S.I. Schlesinger, Photogr. Sci. Ammonium salts described in U.S. Patent No. 4,069,055, JP-A-4-365049, etc., U.S. Patent No. 4,069,055 (U.S. Patent No. 4,069,055), U.S. Patent No. 4,069,055 4,069,056, EP 104,143, US 339,049, EP 410,201, JP 2-150848, JP 2-296514 And iodonium salts described in the respective publications.

The iodonium salt which can be suitably used in the present invention is a diaryliodonium salt. From the standpoint of stability, it is preferable that two or more thereof are substituted with an electron-donating group such as an alkyl group, an alkoxy group or an aryloxy group. As other preferable types of iodonium salts, iodonium salts having one substituent group of a triaryl iodonium salt having a coumarin or anthraquinone structure and having absorption at 300 nm or more are preferable.

Examples of sulfonium salts that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, U.S. Patents 4,933,377, 161,811, 410,201, 339,049 Sulfonium salts described in the specification of each of U.S. 4,760,013, U.S. 4,734,444, U.S. 2,833,827, German Patent 2,904,626, U.S. 3,604,580, U.S. 3,604,581, and the substitution of an electron-withdrawing group . As the electron-withdrawing group, it is preferable that the Hammett value is larger than zero. Preferred examples of the electron-withdrawing group include a halogen atom and a carboxylic acid.

Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorption at 300 nm or more. Other preferred sulfonium salts include sulfonium salts in which the triarylsulfonium salt has an absorption at 300 nm or more having an aryloxy group or arylthio group as a substituent.

The onium salt compounds may also be prepared according to J. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), C. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, Oct (1988), and the like.

Acylphosphine (oxide) compounds include Ciba Specialty Chemical Co., Ltd. Products IRGACURE 819, DAROCUR 4265, DAROCUR TPO are listed.

As the photopolymerization initiator (D) used in the present invention, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds,? -Hydroxyketone compounds,? -Aminoketone compounds, acylphosphine compounds, Based compounds, benzophenone-based compounds, acetophenone-based compounds and derivatives thereof, cyclopentadiene-benzene-based compounds, cyclopentadiene-based compounds, Iron complexes and salts thereof, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds.

< (e) Surfactant >

As the surfactant, various kinds of anionic, cationic, non-ionic (non-ionic), and amphoteric surfactant can be used, but it is preferable to use a nonionic surfactant because the effect on various characteristics is low.

Examples of the anionic surfactant include an alkyl sulfate ester salt surfactant such as EMAL 10 manufactured by Kao Corporation, an alkyl naphthalenesulfonate surfactant such as PELEX NB-L, a special high molecular weight surfactant such as HOMOGENOL L-18 and L-100 Surfactants, and the like.

Of these, a special polymer type surfactant is preferable, and a special polycarboxylic acid type polymer type surfactant is more preferable.

Examples of the cationic surfactant include alkylamine salt surfactants such as ACETAMIN 24 from Kao Corporation and quaternary ammonium salt surfactants such as QUARTAMIN 24P and 86W.

Of these, quaternary ammonium salt surfactants are preferred, and stearyltrimethylammonium salt based surfactants are more preferred.

As the nonionic surfactant, it is preferable to use at least one kind selected from the group of compounds represented by the following formulas (A) to (D).

In the general formulas (A) to (D), PO represents propylene oxide and EO represents ethylene oxide. Propylene in propylene oxide includes - (CH ₂ ) ₃ -, -CH ₂ CH (CH ₃ ) -.

In the general formulas (A) and (B), (Styryl) represents ph-CH = CH- and (benzyl) represents ph-CH ₂ -. Here, ph is a phenyl group.

N is an integer of 1 to 3, preferably 1. m is an integer of 7 to 30, preferably an integer of 8 to 20; L is an integer of 0 to 10, preferably 0 to 5. a is an integer of 0 to 20, b is 0 to 20, and c is an integer of 6 to 30. Preferably, a is 0 to 10, b is 0 to 10, and c is 10 to 20.

In the general formulas (C) and (D), x is an integer of 5 to 100, preferably an integer of 5 to 50. And y is an integer of 20 to 100. Also, x and y satisfy 0.1? X / y? 2.0, and preferably 0.2? X / y? 1.0.

Here, the four x and y in the general formula (C) and the general formula (D) are the same or different from each other. That is, although there are four ethylene oxide blocks in the general formula (C) and the general formula (D), the number of the ethylene oxide units constituting each of the four blocks may be the same or different. Although there are four propylene oxide blocks in the general formula (C) and the general formula (D), the number of the propylene oxide units constituting each of the four blocks may be the same or different.

In the present invention, among the compounds represented by the general formulas (A) to (D), the compound represented by the general formula (A) and the compound represented by the general formula (B) are preferable.

More specifically, in the general formula (A), n is 1, l is 0 to 5, and m is an integer of 8 to 20, and specific examples include ethylene oxide 8 adduct of styrylphenol, 10 adducts, 12 adducts, 16 adducts and 20 adducts are preferable.

In the general formula (B), a compound in which n is 1 to 3, a is 0 to 10, b is 0 to 10, and c is an integer of 10 to 20 is preferable, and specific examples include monostyrylbenzylphenyl A is 4, b is 2 and c is 10, adducts in which a is 0, b is 0, and c is 16 in the tristyrylbenzylphenyl, a is 6 in the tristyrylbenzylphenyl, b is 2 , adduct of c = 10, adduct of tristyrylbenzylphenyl having a = 8, b = 6, and c = 18 are preferred.

In the present invention, well-known surfactants other than the compounds represented by the general formulas (A) to (D) may be used, or they may be used in combination.

As the surfactant to be used, surfactants disclosed in JP-A-2003-337424 and JP-A-11-133600 are suitable.

Examples of the nonionic surfactant include nonionic surfactants such as polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers, poly Polyoxypropylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters and the like are preferable.

Specific examples include polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; Polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether and polyoxyethylene nonyl phenyl ether; Nonionic surfactants such as polyoxyalkylene dialkyl esters such as polyoxyethylene distearate and polyoxyethylene distearate, sorbitan fatty acid esters and polyoxyalkylene sorbitan fatty acid esters.

Specific examples of the nonionic surfactant include, for example, ADEKA PLURONIC series, ADEKANOL series, TETRONIC series (manufactured by Adeka. Co., Ltd.), Emalgen series, REODOL series (Kao Corporation), ELEMINOL series, Nonipol series , Octapol series, Dodekapol series, Newpol series (manufactured by Sanyo Chemical Industries Co., Ltd.), Paionin series (above, TAKEMOTO OIL & FAT CO., LTD.), Nissan Nonion series . Those commercially available can be suitably used.

The preferred HLB value is 8 to 20, more preferably 10 to 17.

As the silicon-based surfactant, for example, Toray Dow Corning Silicone Co., Ltd. The product SH8400, Shin-Etsu Chemical Co., Ltd. KP341 of the product can be enumerated.

Examples of the fluorine surfactant include Megafac F172, Copper F173, Copper F176, Copper F177, Copper F183, Copper 470, Copper F475, Copper F780, Copper F781 (manufactured by Dainippon Ink and Chemicals, Incorporated), Fluorad FC 430, (Manufactured by Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106. Eftop EF351, 352, 801 and 802 (manufactured by JEMCO).

When a fluorochemical surfactant is used as the surfactant, the blending amount of the surfactant is preferably 0.01% by mass or more and 1.00% by mass or less, more preferably 0.1% by mass or more and 3.0% by mass or less based on the total solid content of the colored curable resin composition. When the blending amount of the surfactant is within the above range, hygroscopicity and leveling property are improved.

When a surfactant other than the fluorine surfactant is used, the blending amount thereof is preferably 0.001% by mass or more and 1.0% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less based on the total solid content of the colored curable resin composition.

<(f) Other ingredients>

- (f-1) Dispersant (dispersion resin) -

Examples of the dispersing agent include polymeric dispersants such as acrylic acid and styrene, acrylic acid esters and methacrylic acid, acrylic acid and methacrylic acid esters, copolymers such as styrene and maleic acid, amide compounds, urethane compounds, lactam compounds, barbituric acid compounds (Bik-Chemie Japan KK Disperbyk 130, Disperbyk 161, Disperbyk 182, Disperbyk 170, commercially available products such as Efka 46, Efka 47 from EFKA, etc.) can be used as the polyamide compound or the polyurethane compound have.

Among these, a dispersant having a nitrogen-containing functional group is preferable, and an acrylic dispersant, a urethane dispersant, and a graft copolymer dispersant are more preferable.

As the acrylic dispersant, an A-B block copolymer and / or a B-A-B block copolymer composed of an A block having a quaternary ammonium salt group in the side chain and a B block having no quaternary ammonium salt group is preferable.

The block A constituting the block copolymer of the acrylic dispersant is a quaternary ammonium salt group, preferably -N ⁺ R _1a R _2a R _3a · Y ^- (wherein R _1a , R _2a and R _3a are each independently a hydrogen atom Or two or more of R _1a , R _2a and R _3a may be bonded to each other to form a cyclic structure, and Y ^- represents a counter anion). Having a quaternary ammonium salt group. The quaternary ammonium salt group may be bonded directly to the main chain, but may be bonded to the main chain through a divalent linking group.

In ^{_{-N + R 1a R 2a R 3a}} , R 1a, R 2a, R a cyclic structure in which at least two of _3a dog is formed by combining each other, for example, a nitrogen-containing heterocyclic monocyclic or these 5 to 7-membered ring 2 Ring condensed rings are listed. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a nitrogen-containing heterocycle. Specifically, the following are listed.

In the above formulas, R represents any one of R _1a to R _3a .

These cyclic structures may further have substituents. -N ⁺ R _1a R _2a R More preferable R _1a ~ R _3a as in _3a is a good benzyl group which may have a substituent which may have a good carbon number of 1 to 3 alkyl group, or a phenyl group which may have a substituent, or a substituent .

As the A block, it is particularly preferable to include a partial structure represented by the following general formula (9).

In the general formula (9), R _1a , R _2a , and R _3a each independently represent a hydrogen atom or a cyclic or a straight chain hydrocarbon group which may be substituted. Or two or more of R _1a , R _2a and R _3a may be bonded to each other to form a cyclic structure. R _4a represents a hydrogen atom or a methyl group. X represents a divalent linking group, and Y ^- represents a counter anion.

Examples of the divalent linking group X in the general formula (9) include an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-R _5a -, -COO-R _6a - in which R _5a and R _6a are , An alkylene group having 1 to 10 carbon atoms or an ether group having 1 to 10 carbon atoms (-R _7a -OR _8a - wherein R _7a and R _8a each independently represents an alkylene group), and the like, -COO-R &lt; _6a &gt; -.

The counter anions Y ^- include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , PF ₆ ^- and the like.

The partial structure containing a specific quaternary ammonium salt group as represented by the general formula (9) may contain two or more species in one A block. In this case, two or more kinds of quaternary ammonium group-containing partial structures may be contained in any of the above-mentioned A blocks in random copolymerization or block copolymerization. A partial structure not containing the quaternary ammonium salt group may be contained in the A block. Examples of the partial structure include a partial structure derived from the (meth) acrylate monomer described later.

The content of the quaternary ammonium salt group-free partial structure in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. However, the quaternary ammonium salt group-free partial structure is contained in the A block Most preferably.

On the other hand, examples of the B block constituting the block copolymer of the dispersant include styrene monomers such as styrene and? -Methylstyrene; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (Meth) acrylate monomers such as (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate and N, N-dimethylaminoethyl (meth) acrylate; (Meth) acrylic acid salt type monomers such as (meth) acrylic acid chloride; (Meth) acrylamide monomers such as (meth) acrylamide, N-methylol acrylamide, N, N-dimethyl-acrylamide and N, N-dimethylaminoethyl acrylamide; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; And a polymer structure obtained by copolymerizing a comonomer such as N-methacryloylmorpholine.

The B block is preferably a partial structure derived from a (meth) acrylic acid ester-based monomer represented by the following general formula (10).

In the general formula (10), R _9a represents a hydrogen atom or a methyl group. R _10a represents a cyclic or straight-chain alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent.

The partial structure derived from the (meth) acrylate-based monomer may contain two or more kinds in one B block. Of course, the B block may further include partial structures other than these. When the partial structure derived from two or more kinds of monomers is present in a B block not containing a quaternary ammonium salt group, the respective partial structures may be contained in any of the above-mentioned B blocks in random copolymerization or block copolymerization.

When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate-based monomer, the content of the partial structure other than the (meth) acrylic ester-based monomer in the B block is preferably 0 to 50 mass% , And more preferably 0 to 20 mass%. Most preferably, the partial structure other than the (meth) acrylate monomer is not contained in the B block.

The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymerized polymer compound composed of the A block and the B block, but such a block copolymer is produced by, for example, the following living polymerization method.

Examples of the living polymerization method include anion living polymerization method, cationic living polymerization method, and radical living polymerization method. The anionic living polymerization method is a polymerizable active species anion, and is represented by the following scheme, for example.

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

When synthesizing such an acrylic dispersant, JP-A-9-62002 and P. Lutz. P. Massoneta., Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. et al. Andrewseta 1, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. 36, 366 (1987), Hikashisontoshinofu, Sawakimitsuo, Polymer Journal, 46 (1987), 17, 977 , 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. (1987), DY Sogoh, WR Hertiereta 1, Macromolecules, 20, 1473 (1987), etc. .

Even if the dispersant used in the present invention is an AB block copolymer or a BAB block copolymer, the A block / B block ratio (mass ratio) constituting the copolymer is usually 1/99 or more, more preferably 5/95 or more, Preferably 80/20 or less, and more preferably 60/40 or less. Outside this range, good heat resistance and dispersibility may not be obtained.

The amount of the quaternary ammonium salt group in 1 g of the A-B block copolymer and the B-A-B block copolymer according to the present invention is preferably in the range of usually 0.1 to 10 mmol. Outside this range, good heat resistance and dispersibility can not be obtained.

In addition, the block copolymer usually contains an amino group generated during the production process, but the amine value thereof is about 1 to 100 mg-KOH / g. Also, the amine value is a value expressed in terms of mg acid of KOH corresponding to the acid value by neutralizing the basic amino group with an acid.

The acid value of the block copolymer is preferably low, generally 100 mg-KOH / g or less, although the acid value depends on the presence or absence of the acidic group causing the acid value and the kind thereof, and the molecular weight is the polystyrene Weight average molecular weight (Mw) in the range of 1000 to 100,000. When the molecular weight of the block copolymer is too small, the dispersion stability is deteriorated. When the molecular weight is too large, the developability and resolution tend to decrease.

In the present invention, commercially available urethane-based and / or acrylic-based dispersants having the above-described structure may be used as the dispersant.

Examples of the urethane-based dispersing agent include (1) a polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule, (3) a dispersion resin obtained by reacting a compound having an active hydrogen and a tertiary amino group in the same molecule .

(1) Polyisocyanate compound

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as tolylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, lidin methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimeric acid diisocyanate, isophorone diisocyanate, 4, Alicyclic diisocyanates such as 4'-methylenebis (cyclohexylisocyanate),?,? '- diisocyanate trimethylcyclohexane, and the like; and aromatic diisocyanates such as xylene diisocyanate,?,?',? '- tetramethylxylene diisocyanate Aliphatic diisocyanate having an aromatic ring, lysine ester triisocyanate, 1,6,11-unde (Isocyanate phenyl) thiophosphate, and the like can be used as the polyisocyanate compound, such as 1,1-diisocyanate, 1,6-hexamethylene triisocyanate, 1,6-hexamethylene triisocyanate, Triisocyanates of these, and trimer thereof, adducts thereof, and polyol adducts thereof, and the like.

As the polydiisocyanate, preferred is a trimer of an organic diisocyanate, and most preferable is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used singly or in a mixture of two or more kinds.

As a method for producing an isocyanate trimer, a method of partially trimerizing an isocyanate group using a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts and the like can be used And the polyisocyanate in the terminal reaction is removed by solvent extraction or thin-film distillation to obtain the objective isocyanurate group-containing polyisocyanate.

(2) a compound having one or two hydroxyl groups in the same molecule

Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols and the like, and those obtained by alkoxylating the terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms and Mixtures of two or more of these are listed.

The polyether glycol includes polyether diol, polyether ester diol, and mixtures of two or more thereof.

As the polyether diol, there may be mentioned those obtained by singly or copolymerizing an alkylene oxide such as polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, Mixtures of more than two species are listed.

The polyetheresterdiols include those obtained by reacting a mixture of an ether group-containing diol or another glycol with a dicarboxylic acid or an anhydride thereof, or by reacting an alkylene oxide with a polyester glycol such as poly (polyoxytetra Methylene) adipate, and the like.

Polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds in which the terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms is most preferable as the polyether glycol.

Examples of the polyester glycol include dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid and the like) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2 Propyl-1,3-propane-diol, 2-butyl-2-ethyl-1,3-propane-diol, 1,5-pentanediol, Methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5- Aliphatic glycols such as 2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, Aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, Dialkylamine such as N-methyl-diethanolamine, etc.), such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or Polylactone diols or polylactone monools obtained by using the diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator such as polycaprolactone glycol, polymethylvalerolactone glycol, and mixtures of two or more thereof.

Most preferred as the polyester glycol is a polycaprolactone glycol or a polycaprolactone glycol having an alcohol of 1 to 25 carbon atoms as an initiator, more specifically, a compound obtained by polymerizing? -Caprolactone at a ring-opening portion in a monool.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene Glycol, and the like.

Among the compounds having one or two hydroxy groups in the same molecule, polyether glycol and polyester glycol are particularly preferable.

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

(3) a compound having an active hydrogen and a tertiary amino group in the same molecule

Compounds having active hydrogen and tertiary amino groups in the same molecule used in the present invention will be described. As active hydrogen atoms, that is, hydrogen atoms directly bonded to oxygen atom, nitrogen atom or sulfur atom, hydrogen atoms in functional groups such as hydroxyl group, amino group and thiol group are enumerated, and among them, hydrogen atoms of amino group, particularly primary amino group are preferable.

The tertiary amino group is not particularly limited. Examples of the tertiary amino group 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 active hydrogen and tertiary amino groups in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl- 1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-diethylethylenediamine, N-dibutyl-1,4-butanediamine, and the like.

The tertiary amino group is a nitrogen-containing heterocyclic ring, and examples thereof include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring Containing hetero-6-membered rings such as an N-containing hetero five-membered ring such as a benzothiadiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring and an isoquinoline ring. Preferred as these nitrogen-containing heterocyclic rings are imidazole ring or triazole ring.

Specific examples of the compound having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like.

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) 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino- -1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, -Triazole is preferred.

The preferable mixing ratio of the urethane-based dispersant raw material is 10 to 200 parts by mass, preferably 20 to 190 parts by mass of a compound having a number average molecular weight of 300 to 10,000, which has 1 or 2 hydroxy groups in the same molecule per 100 parts by mass of the polyisocyanate compound More preferably 30 to 180 parts by mass, and the compound having an active hydrogen and a tertiary amino group in the same molecule in an amount of 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass.

The weight average molecular weight (Mw) of the urethane dispersant in terms of polystyrene measured by GPC is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. In the range of the molecular weight, the dispersibility and dispersion stability are excellent, the solubility and dispersibility are excellent, and the reaction is easy to control.

The production of such a urethane-based dispersing agent is carried out according to a known method for producing a polyurethane resin. Examples of the solvent for use in the preparation include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve, , Alcohols such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, aliphatic hydrocarbons such as dimethylformamide, tetrahydrofuran and dioxane, alcohols such as benzene, toluene and xylene, hydrocarbons such as toluene, xylene, and hexane, diacetone alcohol, isopropanol, And aprotic polar solvents such as N-methylpyrrolidone and dimethylsulfoxide. These solvents are used alone or in combination of two or more.

In the above preparation, a conventional urethane-forming reaction catalyst is used. Examples of the catalyst include iron-based catalysts such as tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannous octoate, iron acetylacetonate and ferric chloride, Tertiary amines such as ethylamine and triethylenediamine, and the like.

The introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg-KOH / g of the amine after the reaction. And more preferably in the range of 5 to 95 mg-KOH / g. The amine value is a value expressed in terms of the number of mg of KOH corresponding to the acid value by neutralizing the basic group with an acid. By setting this range, dispersion capability and developability are improved.

When the isocyanate group remains in the dispersion resin obtained in the above reaction, the isocyanate group in the alcohol or the amino compound is destroyed, so that the stability of the product with time is improved.

The graft copolymer dispersing agent preferably has a repeating unit containing a nitrogen atom in its main chain. Among them, those having a repeating unit represented by the following general formula (11) and / or a repeating unit represented by the following general formula (12) are preferable.

In the general formula (11), R ¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following general formulas (13) to (15).

In the general formula (11), R ¹ represents an alkylene group of 1 to 5 carbon atoms, straight or branched chain such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably an ethylene group. A represents a hydrogen atom or any one of the following general formulas (13) to (15), but is preferably a general formula (13).

In the above general formula (12), R ^1, A is the same as R ^1, A in formula (11).

In the formula (13), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene and hexylene is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10;

In the formula (14), Y ₁ represents a divalent linking group, and among these, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy are preferable.

W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, and butylene. Of these, an alkylene group having 2 to 3 carbon atoms such as ethylene and propylene is preferable.

Y ₂ represents a hydrogen atom or -CO-R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl or hexyl, and particularly preferably has 2 to 5 carbon atoms such as ethyl, Lt; / RTI &gt; alkyl groups are preferred).

q represents an integer of 1 to 20, preferably an integer of 5 to 10;

In the formula (15), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxy groups, among which an alkyl group having 10 to 20 carbon atoms such as stearyl, Hydroxyalkyl groups having 1 to 2 hydroxy groups such as hydroxyethyl group and hydroxyethyl group, and hydroxyethyl group.

The content of the repeating unit represented by the formula (11) or (12) in the graft copolymer is preferably high, usually 50 mol% or more, and preferably 70 mol% or more. The repeating unit represented by the formula (11) and the repeating unit represented by the formula (12) may be both noxious and harmful, and the content thereof is not particularly limited, but preferably the repeating unit represented by the formula (11) Is preferable.

The total number of the repeating units represented by the formula (11) or (12) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50.

The repeating unit may contain repeating units other than the formulas (11) and (12), and examples of the other repeating units include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention preferably has at its terminals -NH ₂ and -R ₁ -NH ₂ (R ₁ has the same meaning as R ₁ ).

Further, in the case of the graft copolymer, the main chain may be linear or branched.

The amine value of the graft copolymer is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, and more preferably 15 to 40 mgKOH / g. When the amine value is within this range, the dispersion stability is good, the viscosity is stable, the residual liquid is small, and the electric characteristics after the liquid crystal panel is formed are also improved.

The weight average molecular weight of the dispersant as measured by GPC is preferably from 3,000 to 100,000 and particularly preferably from 5,000 to 50,000 from the viewpoints of dispersibility and developability. When the weight average molecular weight is within this range, solubility in an organic solvent is good.

The dispersant may be synthesized by a known method, for example, the method described in Japanese Patent Publication No. 63-30057.

These dispersants may be used singly or in combination of two or more kinds.

The blending amount of the dispersing agent is preferably selected in the range of 0 to 30 mass% with respect to the total solid content in the colored curable resin composition.

In the colored curable resin composition of the present invention, the content of the dispersing agent is usually 10 to 300 mass%, preferably 20 to 100 mass%, and particularly preferably 30 to 80 mass% with respect to the coloring material. When the content of the dispersing agent is within this range, cohesion can be suppressed and the film thickness can be set to an appropriate thickness, and cell gap control defects in the liquid crystal cell formation process can be suppressed when used in a color filter.

In the colored curable resin composition of the present invention, conventionally known dispersants (pigment dispersants) described below may be used in combination in addition to the above polymer dispersant.

Examples of known dispersants (pigment dispersants) include polymer dispersants (e.g., polyamide amines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) And polyoxyethylene alkylphosphoric acid esters, polyoxyethylene alkylamine, alkanolamine, pigment derivatives, and the like.

Polymeric dispersants can be further divided into linear polymers, end-modified polymers, graft-type polymers, and block-type polymers from the structure.

The polymeric dispersant is adsorbed on the surface of the pigment to prevent re-aggregation. Therefore, a terminal modified polymer, graft polymer, and block polymer having an anchor site on the surface of the pigment can be listed as preferable structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Specific examples of known dispersants (pigment dispersants) usable in the present invention include BIK Chemie Japan K.K. (EFKA 4047, 4050, 4010, 4165 (trade name), manufactured by EFKA), "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166, (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 ), Ajinomoto Fine-Techno Co., Ltd. "AJISPER PB821, PB822" manufactured by Kyoeisha Chemical Co., Ltd., "Florene TG-710 (urethane oligomer)", "Polyflow No.50E, No.300 . "Disparlon # 7004 (polyetherester), DA-703-50, DA-705, DA-725" manufactured by Kao Corporation, "Emalgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) &Quot; ACETAMIN 86 (stearylamine acetate) &quot;, Lubrizol Advanced Materials, Inc. (Polymer having functional groups at the terminals), 24000, 28000, 32000, 38500 (graft-type polymer), "SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 ), Nikko Chemicals Co., Ltd. Quot; Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) &quot;, and the like.

In the present invention, when a known dispersant as described above is used, it is preferable that the above-mentioned acid value is 20 to 300 mg-KOH / g, the amount of the compound is 10 to 100% by mass, That is, it can be used in a range of 1/10 to 1/1 (equivalent).

(f-2) Dispersion preparation

As the dispersion aid, for example, pigment derivatives are listed.

Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, Pyrrole-based pigments, and dioxazine-based pigments.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxy group, a carboxyl group, an amide group, etc. directly to the pigment skeleton or through an alkyl group, Sulfonamido group and quaternary salt thereof, sulfonic acid group are preferable, and sulfonic acid group is more preferable. These substituents may be substituted in a single pigment skeleton, or may be a mixture of compounds having different substitution numbers.

Specific examples of the pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments , Sulfonic acid derivatives of dioxazine pigments, and the like.

Commercially available pigment derivatives include azo type Abisia Co., Ltd. SOLSPERSE 22000 of the product, SOLSPERSE 5000 of the phthalocyanine series, and EFKA 475 of the EFKA product. These pigment derivatives may be used singly or in combination of two or more kinds.

The blending amount of the dispersing aid is preferably selected in the range of 0 to 20 mass% with respect to the total solid content in the colored curable resin composition.

[Preparation of colored curable resin composition]

The colored curable resin composition of the present invention can be prepared by previously preparing a pigment dispersion as described below and then adding (b) a binder resin and (c) a photopolymerization initiator to the pigment dispersion, (b) For example, by adding an additive such as a polymerizable compound or a surfactant.

Hereinafter, a method for producing a pigment dispersion used in the colored curable resin composition of the present invention will be described.

The pigment dispersion in the present invention can be obtained by dispersing a mixture of the above-mentioned (a) color material, (f-1) dispersion resin and (b) organic solvent in a vertical or horizontal sand grinder, pin mill, slit mill, And then performing micro-dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

Before the bead dispersion is carried out, a strong shear force is applied by using two rolls, three rolls, a ball mill, a thrommill, a Dispers, a kneader, a cone, a homogenizer, a blender, a single shaft or a biaxial extruder It is also possible to carry out the kneading dispersion treatment.

Further, details concerning kneading and dispersing are described in T. C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964).

The colored curable resin composition of the present invention thus obtained contains the above-mentioned respective components, and (a) the colorant is maintained in a good dispersed state in the composition to obtain good color characteristics, and a color filter A high contrast can be obtained.

<Coloring Pattern Forming Method, Color Filter Manufacturing Method, and Color Filter>

Next, the coloring pattern forming method, the color filter manufacturing method, and the color filter of the present invention will be described.

The coloring pattern forming method of the present invention includes a step of applying the colored curable resin composition of the present invention by a slit coating method at a coating speed of 200 mm / sec to 400 mm / sec, whereby a desired coloring pattern can be formed.

Since the colored curable resin composition of the present invention has predetermined physical properties, even when the slit coating is performed at a high speed of 200 to 400 mm / sec from the application speed, the coating unevenness is small, the occurrence of coating defects is suppressed, It has become possible to form the photosensitive film with high efficiency.

The coloring pattern forming method is preferably applied to a method of manufacturing a color filter.

Hereinafter, a method of manufacturing a color filter (a method of manufacturing a color filter of the present invention) to which the coloring pattern forming method of the present invention is applied will be described.

The method for producing a color filter of the present invention is characterized in that the step of forming a photosensitive film by providing the colored curable resin composition of the present invention directly or through another layer on a substrate (hereinafter referred to as a "photosensitive film forming step" A step of exposing the film to a pattern exposure (exposure through a mask) (hereinafter, appropriately referred to as an &quot; exposure step &quot;) and a step of developing a photosensitive film after exposure to form a coloring pattern ).

Hereinafter, each step in the production method of the present invention will be described.

(Photosensitive film forming step)

In the photosensitive film forming step, the photosensitive curable resin composition of the present invention is applied (applied) directly or on a substrate having another layer to form a photosensitive film.

Examples of the substrate that can be used in the present process include soda glass, Pyrex (registered trademark) glass, quartz glass, a transparent conductive film adhered thereto, and a photoelectric conversion element substrate used for an image pickup device, A silicon substrate, and a complementary metal oxide semiconductor (CMOS). These substrates may be formed with black stripes for isolating each pixel.

In addition, a primer layer (other layer) may be formed on these substrates in order to improve adhesion with the upper layer, prevent diffusion of the material, or planarize the surface of the substrate, if necessary.

In the method for producing a color filter of the present invention, a method of applying the colored curable resin composition of the present invention onto a substrate includes a step of applying the resin composition at a coating speed of 200 mm / sec to 400 mm / sec using a slit coating method It is preferable from the viewpoint of efficiency. According to the colored curable resin composition of the present invention, a uniform photoresist film free from coating defects can be formed with high productivity by such high-speed slit coating, so that the effect is remarkable when used in the method for producing a color filter of the present invention, Needless to say, the photosensitive film can be formed by applying various coating methods such as the ink jet method, spin coating, flexible coating, roll coating, and screen printing.

The coating thickness of the colored curable resin composition is preferably 0.1 to 10 占 퐉, more preferably 0.2 to 5 占 퐉, and still more preferably 0.2 to 3 占 퐉.

Drying (prebaking) of the photosensitive film applied on the substrate can be performed in a hot plate, an oven or the like at a temperature of 50 to 140 ° C for 10 to 300 seconds.

(Exposure step)

 In the exposure step, the photosensitive film formed in the photosensitive film formation step is exposed through a mask having a predetermined mask pattern, that is, pattern exposure is performed.

In this step, only the coated film portion irradiated with light can be cured by exposing the photosensitive film as a coating film through a predetermined mask pattern.

As the radiation which can be used at the time of exposure, ultraviolet rays such as g line and i line are preferably used. The irradiation dose is preferably 5 to 1500 mJ / cm 2, more preferably 10 to 1000 mJ / cm 2, and most preferably 10 to 500 mJ / cm 2.

When the color filter to be manufactured is for a liquid crystal display device, it is preferably 5 to 200 mJ / cm 2, more preferably 10 to 150 mJ / cm 2, and most preferably 10 to 100 mJ / cm 2 in the above range. When the color filter to be manufactured is a solid-state image pickup device, it is preferably 30 to 1500 mJ / cm 2, more preferably 50 to 1000 mJ / cm 2, and most preferably 80 to 500 mJ / cm 2 in the above range.

(Developing step)

Subsequently, by performing the developing treatment, only the unexposed portion of the unexposed portion in the exposure process is left in the developer and the photocured portion remains. Any developer may be used as long as it dissolves the film of the photo-curable composition in the un-cured portion and does not dissolve the cured portion. Concretely, a combination of various organic solvents or an alkaline aqueous solution can be used.

The developing temperature is usually 20 to 30 ° C, and the developing time is 20 to 90 seconds.

Examples of the organic solvent include the above-mentioned solvents that can be used in producing the colored curable resin composition of the present invention.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline compounds such as benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, By mass is preferably used as the developing solution.

Further, when a developer composed of such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with pure water after development.

After the development process, the excess developer is washed away, dried, and then heat-treated (post-baked).

The post-baking is a post-development heat treatment for complete curing, and usually a heat curing treatment at 100 to 240 캜 is performed. When the substrate is a glass substrate or a silicon substrate, it is preferably 200 DEG C to 240 DEG C in the above temperature range.

This post-baking treatment can be carried out continuously or collectively using heating means such as a hot plate, a convection oven (hot-air circulation type drier), a high-frequency heater or the like so that the coated film after development becomes the above-

By repeating the photosensitive film forming process, the exposure process, and the developing process (and the heating process as needed) as described above for the desired number of colors, a color filter (color filter of the present invention) made of a desired color is produced.

The color filter obtained by the method of producing a color filter of the present invention as described above has a coloring pattern formed by using the colored curable resin composition of the present invention on a substrate and surprisingly has a high contrast of 5000 or more.

Here, the contrast indicates the contrast evaluated separately for each color for R (red), G (green), and B (blue) constituting the color filter.

The method of measuring the contrast is as follows. A polarizing plate is superimposed on both sides of the object to be measured and a backlight is irradiated from the side of the polarizing plate on one side and the luminance Y1 of the light passing through the polarizing plate on the other side is measured while the polarizing direction of the polarizing plate is parallel to each other. Next, in a state where the polarizing plates are orthogonal to each other, the backlight is irradiated from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. Using the obtained measurement values, the contrast is calculated as Y1 / Y2. As the polarizing plate, Nitto Denko Corp. G1220DUN of the product was used, and a colorimetric BM-5 (manufactured by Topcone Co., Ltd.) was used as the measuring device.

When a film is formed by applying the colored curable resin composition of the present invention on a substrate, the dry thickness of the film is generally from 0.3 to 5.0 mu m, preferably from 0.5 to 3.5 mu m, and most preferably from 1.0 to 2.5 mu m.

Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and a photoelectric conversion element substrate which can be used for a solid-state image pickup device, A silicon substrate, and the like, and a plastic substrate. On these substrates, a black stripe for isolating each pixel is usually formed.

The plastic substrate preferably has a gas barrier layer and / or a solvent-resistant layer on its surface.

The use of the color-curable resin composition of the present invention has been mainly described as a pixel of a color filter, but it goes without saying that it can also be applied to a black matrix provided between pixels of a color filter. The black matrix is subjected to pattern exposure and alkali development in the same manner as the above-mentioned pixel manufacturing method, except that a black colorant such as carbon black or titanium black is added to the colored curable resin composition of the present invention as a coloring agent, Baking is further performed to promote curing of the film.

<Liquid crystal display element>

The liquid crystal display element of the present invention is provided with the color filter of the present invention.

More specifically, an orientation film is formed on the inner surface side of the color filter, and the liquid crystal is filled in the gap portion by facing the electrode substrate, thereby sealing the liquid crystal display device of the present invention.

According to the aspect of the present invention, there is provided a colored curable resin composition having a coating property capable of achieving a good film surface shape even at high speed application, a coloring pattern forming method including a slit coating step using the colored curable resin composition, The coloring pattern formed by the forming method can be provided.

Further, according to the present invention, it is possible to provide a method of manufacturing a color filter having the colored pattern with a good film surface shape even at high speed application, and a color filter manufactured by the manufacturing method. In particular, it is possible to provide a color filter with less film thickness unevenness and film defects and high contrast.

Further, a liquid crystal display element using the color filter can be provided.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. Unless otherwise stated, &quot;% &quot; and &quot; part &quot; are based on mass.

(Example 1)

The following components were mixed to prepare a pigment dispersion.

[Pigment dispersion]

Pigment (a)

C.I. Pigment Red 254 ... Part 5

C.I. Pigment Red 177 ... Part 5

· Dispersion resin

Bik-Chemie Japan K.K. byk-161 (active ingredient 30% by mass) ... 13.3 part

(B) Solvent

Propylene glycol monomethyl ether acetate ... 32.7 parts

Separately, the following components were mixed to prepare a transparent resist solution.

[Composition of transparent resist solution]

(C) binder resin

The acrylic resin (c1) represented by the following formula (6): 2.0 parts

The acrylic resin (c2) (A) shown in Table 1 2.0 parts

(C3) monomer

Dipentaerythritol hexaacrylate ... 4.0 parts

(D) Photopolymerization initiator

2- (2-Chlorophenyl) -4,5-diphenylimidazole dimer ... 0.4 part

4,4'-bis (diethylamino) benzophenone ... 0.2 part

2-Methylbenzothiazole ... 0.4 part

(E) Surfactant

Sumitomo 3M Limited products FC430 ... 0.04 part

(B) Solvent

Propylene glycol monomethyl ether acetate ... 50 parts

The pigment dispersion and the transparent resist solution were mixed, homogenized with stirring, 300 g of zirconium oxide beads having a particle diameter of 0.5 mm was added, and dispersed by shaking in a paint conditioner for 5 hours. Thereafter, the mixture was filtered to obtain a composition for forming a uniform colored pattern (colored curable resin composition).

The obtained composition for forming a color pattern was subjected to the following evaluations.

(Evaluation 1)

The obtained composition for forming a color pattern was coated on a 550 mm x 650 mm glass substrate (1737, Corning product) at a coating speed of 200 mm / sec using a slit coater (Head Coater, FAStar, Ltd., head mounted). Thereafter, it was dried in an oven at 90 캜 for 60 seconds (prebaking). The film thickness of the dried film was 1.2 탆.

(Coated surface shape)

Under the above conditions, application of 200 sheets (application interval of 20 seconds: dummy ejection of 2 seconds) was performed, and the shape of the 200th application side was observed with an optical microscope.

The evaluation criteria are as follows, and &Dgr; is the lower limit of the practical allowable range.

○: The number of defects is less than 1 per 0.25 square meters

B: The number of defects is not less than 1 and not more than 5 per 0.25 square meter

X: The number of defects is more than 5 per 0.25 square meters

(Film thickness unevenness)

The composition for forming a color pattern 16 obtained above was extruded from a discharge port of a slit die 12 having a width of 550 mm sandwiching a padding 10 (0.05 mm thick) as shown in Fig. 1 as shown in Fig. 2 (Corning product, 1737, 0.7 mm thick) so that the coating speed was 100 mm / s, the coating gap was 100 占 퐉, and the film thickness after the post-baking treatment was 2.0 占 퐉. In Fig. 1, the unit of dimension is mm, a represents the manifold edge, and b represents the tip position of the slit die.

At this time, the fluctuation of the stripe-shaped film thickness unevenness 18 caused by the projection of the shim 10 was measured by ULVAC Co., Ltd. after the post-baking treatment. The measurement was carried out with a contact-type membrane thickness meter DECTAC-3. The results are shown in Table 2.

The evaluation criteria are as follows, and? Is the lower limit of the practical allowable range.

?: Film thickness unevenness within ± 1%

?: The film thickness unevenness exceeds ± 1% and is within ± 2%

X: Film thickness unevenness exceeding ± 2%.

(Contrast)

Using the slit coater (head coater, head manufactured by FAStar, Ltd.), a composition for forming a color pattern was coated on a 550 mm x 650 mm glass substrate (1737, Corning) at a coating speed of 200 mm / sec. Thereafter, it was dried in an oven at 90 캜 for 60 seconds (prebaking). The film thickness of the dried film was 1.2 탆.

The coated film was exposed on the entire surface of the coated film at 200 mJ / cm 2 (roughness: 20 mW / cm 2), covered with a 1% aqueous solution of alkali developer CDK-1 (FUJIFILM Electronic Materials) and stopped for 60 seconds. After stopping, pure water was sprayed in a shower shape to wash the developer. Then, the film subjected to the exposure and development as described above was heat-treated in an oven at 220 캜 for one hour (post baking) to form a colored resin film (coloring pattern) for a color filter on a glass substrate, Filter).

The polarizing plate was placed on the colored resin film (coloring pattern) of the colored filter substrate, the colored resin film was sandwiched therebetween, and the luminance when the polarizing plate was perpendicular to the luminance at the time of parallelization was measured by Topcon Co., Ltd. The value obtained by dividing the luminance at the time of parallelism by the luminance at the time of orthogonality (the luminance at the time of parallelism / the luminance at the time of orthogonality) was measured as an index of the contrast evaluation.

The higher the contrast, the better the contrast.

(Examples 2 to 4)

A composition for forming a coloring pattern was prepared and evaluated in the same manner as in Example 1 except that the binder resin (c2) in Example 1 was changed to each of the compounds shown in Table 2.

(Comparative Examples 100 to 103)

A composition for forming a coloring pattern was prepared in the same manner as in Example 1 except that the binder resin (c2) in Example 1 was changed to each of the compounds shown in Table 2, and the same evaluations as in Example 1 were carried out.

The acrylic resins (c2) A to G used above were synthesized as follows.

The synthesis scheme of the acrylic resin (c2) A is shown below. The weight average molecular weight, (meth) acryloyl group content and acid value were obtained as follows.

Resin A

(Weight average molecular weight)

Was measured by GPC (gel permeation chromatography) measurement under the following conditions in terms of polystyrene conversion.

Use column: TSKgel Multipore HXL-M (multi-dispersed linear column) TOSOH Co., Ltd. product

Eluent: THF

Flow rate: 1.0 ml / min

Temperature: 40 ° C

Detection condition: RI

System: High speed GPC system (TOSOH-HLC-8220)

As a result, the weight average molecular weight was 45,000.

((Meth) acryloyl group content)

40 g of benzyl methacrylate (BzMA), 20 g of acrylic acid (AA), 40 g of hydroxyethyl methacrylate (HEMA) and 50 g of mono adduct of hydroxyethyl acrylate of hexamethylene diisocyanate (HMDI) were used as monomers , And their weight, molecular weight, moles before reaction and moles after reaction are summarized in the following table.

Resin A BzMA AA HEMA HMDI HEMA + IPDI Addition weight (g) 40 20 40 50 - Molecular Weight 176 72 130 284 - Before the reaction
(= Weight / molecular weight) 0.227 0.278 0.308 0.176 - After the reaction, 0.227 0.278 0.132 - 0.176 After the reaction, 27.96% 34.18% 16.20% - 21.66%

Considering the number of moles after the reaction, the unit having the allyloxyl group is (HEMA + HMDI). When the number of moles after the reaction is considered, the weight of the entire resin when the unit is 0.176 mole is 40 + 20 + 40 + 50 = 150 (g) , The number of moles of the corresponding unit becomes 0.176 / 150 = 0.00117 mol / g. 1 equivalent = 1 mol, and 0.00117 eq / g.

(Acid value)

In the above table, KOH for neutralizing 0.278 moles of the AA-derived unit is 56.11 x 0.278 = 15.59858 g = 15598.58 mg. Using 150 g of resin, 15598.58 / 150 = 103.99, that is, the acid value is 104 mgKOH / g.

(Synthesis of acrylic resin (c2) A)

40 g of benzyl methacrylate, 20 g of acrylic acid, 40 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate and 80 g of cyclohexanone were placed in a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas introducing tube and a stirrer. 0.5 g of azoisobutyronitrile as a polymerization initiator was added, and the mixture was heated and stirred at 80 캜 for 8 hours to complete polymerization. 50 g of a mono-adduct of hydroxyethyl acrylate of hexamethylene diisocyanate was further added and the mixture was heated and stirred at 60 DEG C for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) B)

40 g of benzyl methacrylate, 20 g of acrylic acid, 40 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate and 80 g of cyclohexanone were placed in a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas introducing tube and a stirrer. 0.5 g of azoisobutyronitrile as a polymerization initiator was added, and the mixture was heated and stirred at 80 캜 for 8 hours to complete polymerization. 60 g of a mono-adduct of hydroxyethyl acrylate of isophorone diisocyanate was further added and the mixture was heated and stirred at 60 DEG C for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) C)

40 g of benzyl methacrylate, 20 g of acrylic acid, 40 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate and 80 g of cyclohexanone were placed in a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas introducing tube and a stirrer. 0.5 g of azoisobutyronitrile as a polymerization initiator was added, and the mixture was heated and stirred at 80 캜 for 8 hours to complete polymerization. 30 g of methacryloyloxyethyl isocyanate was further added, and the mixture was heated and stirred at 60 DEG C for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) D)

In a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas introducing tube and a stirrer, 78 g of styrene, 2 g of benzyl methacrylate, 5 g of acrylic acid, 15 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate, Respectively. 0.5 g of azoisobutyronitrile as a polymerization initiator was added, and the mixture was heated and stirred at 80 캜 for 8 hours to complete polymerization. 5 g of a mono-adduct of hydroxyethyl acrylate of isophorone diisocyanate was further added and the mixture was heated and stirred at 60 DEG C for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) E)

In a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas introducing tube and a stirrer, 25 g of styrene, 30 g of benzyl methacrylate, 5 g of acrylic acid, 40 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate, Respectively. 0.5 g of azoisobutyronitrile as a polymerization initiator was added, and the mixture was heated and stirred at 80 캜 for 8 hours to complete polymerization. 100 g of a mono-adduct of hydroxyethyl acrylate of isophorone diisocyanate was further added and the mixture was heated and stirred at 60 DEG C for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) F)

In a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas introducing tube and a stirrer, 20 g of styrene, 5 g of benzyl methacrylate, 50 g of acrylic acid, 25 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate, Respectively. 0.5 g of azoisobutyronitrile as a polymerization initiator was added, and the mixture was heated and stirred at 80 DEG C for 8 hours to complete polymerization. 67 g of a mono-adduct of hydroxyethyl acrylate of isophorone diisocyanate was further added and the mixture was heated and stirred at 60 DEG C for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) G)

In a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas introducing tube and a stirrer, 40 g of benzyl methacrylate, 3 g of acrylic acid, 2 g of methacrylic acid, 5 g of hydroxyethyl acrylate, 155 g of ethyl ethoxypropionate, . 0.5 g of azoisobutyronitrile was further added as a polymerization initiator, and the mixture was heated and stirred at 80 DEG C for 8 hours to complete polymerization to obtain an acrylic resin.

As apparent from the results in Table 2, the composition for forming a color pattern in Examples 1 to 4 had no film surface unevenness when the slit coater was applied using the composition for forming a color pattern, and the coated surface shape was good. On the other hand, the compositions for forming coloring patterns of Comparative Examples 100 to 103 are found to be inferior in film surface unevenness and coated surface shape compared to the examples.

Therefore, it can be seen that the color filter of the present invention having a coloring pattern formed by using the compositions for forming coloring patterns of Examples 1 to 4 is superior in contrast to the comparative example.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing a shim used for applying a color resist in the embodiment; Fig.

2 is a perspective view showing a state of application by a slit die with a shim shown in Fig.

Claims (10)

A colored curable resin composition comprising (a) a colorant, (b) a solvent, (c) two or more binder resins, (d) a photopolymerization initiator, and (e) Wherein at least two of the binder resins have a (meth) acryloyl group in an amount of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g, Wherein at least one of the binder resins is any one selected from the following general formulas (1-1) to (1-3).

R ₁ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group having 1 to 4 carbon atoms or an alkoxy group, an aryl group having 6 to 12 carbon atoms, or an aryl group having 7 to 12 carbon atoms R ₂ represents a carbamate ester containing an alkylene group having 1 to 18 carbon atoms, a phenylcarbamate ester containing an alkyl group having 1 to 4 carbon atoms, or an alicyclic group having 3 to 18 carbon atoms, R ₃ represents a straight chain or branched alkylene group having 2 to 16 carbon atoms. The repeating units a to d in the general formula (1-1), a to e in the general formula (1-2), and a to e in the general formula (1-3) B represents 3 to 50, c represents 3 to 40, d represents 2 to 60, and a + b + c + d = 100. B in the general formulas (1-2) and (1-3) represents 0 to 85, c represents 3 to 50, d represents 3 to 40, e represents 2 to 60, a + b + c + d + e = 100. and n is an integer of 2 to 16.) The colored curable resin composition according to claim 1, wherein at least one of the binder resins contains a (meth) acrylic copolymer having an alicyclic (meth) acryloyl group in its side chain. delete delete The colored curable resin composition according to claim 1, further comprising a compound having an ethylenic unsaturated group. A method for forming a coloring pattern, which comprises applying the colored curable resin composition according to any one of claims 1 to 3 by a slit coating method. A coloring pattern formed by the coloring pattern forming method according to claim 6. A manufacturing method of a color filter, characterized by having the coloring pattern according to claim 7. A color filter manufactured by the method of manufacturing a color filter according to claim 8, wherein the contrast is 5000 or more. A liquid crystal display element using the color filter according to claim 9.

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