TW201331710A - Colored resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

Abstract

The subject of the present invention is to provide a colored resin composition for enabling the cross-section of the pixel to be formed in a forward cone shape, which is difficult to simultaneously achieve in the prior art due to a trade-off relationship, and having a higher solubility in developer solution. The colored resin composition of this invention is characterized in including (A) a dye, (B) a solvent, (C) a binder resin, and (D) a polymerizable monomer, where the (C) adhesive resin includes specific resin that contains unsaturated group-containing, and (D) polymerizable monomer includes monomer that contains acid group.

Description

Colored resin composition, color filter, liquid crystal display device, and organic EL display device

The present invention relates to a coloring resin composition, a color filter, a liquid crystal display device, and an organic electroluminescence (EL) display device.

In recent years, color filters have been used in liquid crystal display (LCD) applications, and are not limited to monitors, and their use has expanded to television. Along with the trend of expansion and energy saving of this application, the industry requires high color characteristics of color filters in terms of chromaticity and contrast. In addition, the color filter used for the image sensor (solid-state imaging device) also has a tendency to have a higher color characteristic such as a decrease in color unevenness and an improvement in color resolution, and is also expected to be high-definition.

As described above, in recent years, the demand for high color reproducibility of color filters has increased, and the colored resin composition tends to have a high pigment concentration. However, when a colored resin composition having a high pigment concentration is used to form a colored pattern by photolithography, the pigment hinders the penetration of ultraviolet rays or absorbs them, so that there is a significant lack of exposure, and sufficient exposure cannot be obtained. The tendency of deep hardenability. As a result, in the development step, undercutting is likely to occur, and a colored pattern having a cross-sectional shape of a reverse taper shape is formed, and when a conductive film such as ITO (Indium Tin Oxides) is formed, problems such as disconnection occur.

In order to solve this problem, for example, Patent Document 1 discloses a coloring resin composition containing a specific polymerizable compound.

However, in Patent Document 1, there is a problem in that the dissolution time in the developer becomes long, and the yield is prone to decrease due to a long dissolution time.

On the other hand, in order to shorten the dissolution time, for example, Patent Document 2 discloses that a photopolymerization initiator having a tertiary amine structure and light having one or more acidic functional groups and three or more photocurable functional groups are used. A hardening compound.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-288313

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-287230

However, the colored resin composition described in Patent Document 2 has been found to have a problem such as a disconnection caused by a tapered shape.

That is, in the prior art as described above, for the coloring resin composition having a high pigment concentration, the breakage caused by the tapered shape is suppressed, and even if the cross-sectional shape becomes a forward taper and the solubility in the developing solution is improved The relationship between trade-offs is difficult to achieve at the same time.

Accordingly, an object of the present invention is to provide a colored resin composition in which a cross-sectional shape of a obtained pixel which is difficult to be simultaneously achieved in a trade-off relationship is a forward taper and has high solubility in a developer.

Still another object of the present invention is to provide a color filter having a pixel formed using the above colored resin composition, and a high quality liquid crystal display device. The organic EL display device is placed.

As a result of intensive studies, the present inventors have found that (C) the binder resin contains a specific unsaturated group-containing resin, and (D) the polymerizable monomer contains a coloring resin composition of an acid group-containing monomer, The above problems can be solved, and the present invention has been completed.

That is, the present invention has the following constitution.

(1) A colored resin composition comprising: (A) a pigment, (B) a solvent, (C) a binder resin, and (D) a polymerizable monomer, wherein the (C) binder resin contains at least The unsaturated group-containing resin obtained by the addition of the copolymer (C-4) and (C-5) obtained by copolymerization of the following (C-1) and (C-3) (hereinafter, sometimes referred to as " a specific unsaturated group-containing resin"), and (D) the polymerizable monomer contains an acid group-containing monomer,

(C-1): a compound having an unsaturated bond and an epoxy group in one molecule

(C-3): a compound having an unsaturated bond copolymerizable with the above (C-1)

(C-4): unsaturated carboxylic acid

(C-5): polybasic acid anhydride.

(2) The colored resin composition according to the above (1), wherein the copolymerization system obtains a copolymer obtained by copolymerizing (C-1), (C-3) and (C-2) below,

(C-2): a compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule.

(3) The colored resin composition according to (1) or (2) above, wherein the acid group is contained The acid value of the monomer is 10 mg-KOH/g or more and 150 mg-KOH/g or less.

(4) The colored resin composition according to any one of the above (1) to (3) wherein the (C-4) unsaturated carboxylic acid is methacrylic acid.

(5) The colored resin composition according to any one of (1) to (4) above, wherein the content P of the solid content of the polymer in the colored resin composition and the content of the solid content of the monomer in the colored resin composition are The specific P/M ratio of M is 0.5 or more and 4.5 or less.

(6) The coloring resin composition according to any one of the above (1) to (5), wherein the (A) pigment is contained in an amount of 28% by weight or more and 45% by weight or less based on the total solid content.

(7) The colored resin composition according to any one of the above (1), wherein the (A) pigment comprises a zinc bromide phthalocyanine pigment.

(8) The colored resin composition according to any one of the above (1) to (7) further comprising (E) at least one of a photopolymerization starting component and a thermal polymerization starting component.

(9) A color filter comprising a pixel formed using the colored resin composition according to any one of (1) to (8) above.

(10) A liquid crystal display device comprising the color filter of (9) above.

(11) An organic EL (electroluminescence) display device comprising the color filter of (9) above.

Cross-sectional shape of a pixel formed using the colored resin composition of the present invention In the case of forming a conductive film such as ITO, it is less likely to cause problems such as disconnection, and the dissolution time in the developer is short. Therefore, the yield on the production which is affected by the dissolution time is liable to lower.

That is, the colored resin composition of the present invention can simultaneously realize the cross-sectional shape of the obtained pixel which is previously in a trade-off relationship, and has a high taper shape and a high solubility in a developing solution.

Further, the color filter including the pixel formed using the colored resin composition of the present invention, and the liquid crystal display device and the organic EL display device including the color filter are of high quality.

Hereinafter, the embodiments of the present invention will be described in detail, but the following description is an example of the embodiment of the present invention, and the present invention is not limited to the contents.

Further, in the present invention, "(meth)acryloyl group", "(meth)acrylate" and the like means "acryloyl group and/or methacrylic acid group", "acrylate" and/or nail "Acrylate" or the like, for example, "(meth)acrylic" means "acrylic acid and/or methacrylic acid".

In addition, the "all solid content" means the total component of the colored resin composition of the present invention other than the solvent component described below.

The term "color material" as used in the present invention means both "dye" and "pigment".

Further, the term "aromatic ring" means both "aromatic hydrocarbon ring" and "aromatic heterocyclic ring".

Further, terms such as "C.I. Pigment Green" mean a color index (C.I.).

<Colored resin composition>

The colored resin composition of the present invention comprises (A) a pigment, (B) a solvent, (C) a binder resin, and (D) a polymerizable monomer, the (C) binder resin comprising a specific unsaturated group-containing resin, and (D) The polymerizable monomer contains an acid group-containing monomer. Further, (E) a photopolymerization starting component and/or a thermal polymerization starting component, and other optional components are optionally contained.

First, the (C) binder resin will be described in detail.

[(C) Binder Resin]

In the colored resin composition of the present invention, the (C) binder resin contains a copolymer addition (C-4) and (C-) obtained by copolymerizing at least the following (C-1) and (C-3). 5) An unsaturated group-containing resin obtained.

(C-1): a compound having an unsaturated bond and an epoxy group in one molecule

(C-3): a compound having an unsaturated bond copolymerizable with the above (C-1)

(C-4): unsaturated carboxylic acid

(C-5): polybasic anhydride

The compound having an unsaturated bond and an epoxy group in the above (C-1) molecule may specifically be a glycidyl (meth)acrylate or a 3,4-epoxy (meth)acrylate. Cyclohexyl ester, methyl glycidyl (meth)acrylate. Preferred is glycidyl (meth)acrylate. These may be used alone or in combination of two or more.

Specific examples of the compound (C-3) having an unsaturated bond copolymerizable with the above (C-1) include methyl (meth)acrylate and ethyl (meth)acrylate. Unsubstituted or substituted alkyl ester of an unsaturated carboxylic acid such as butyl acrylate, 2-hydroxyethyl (meth)acrylate and aminoethyl (meth)acrylate; (meth)acrylic acid Cyclopentyl ester, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, menthyl (meth)acrylate, Cyclopentenyl (meth)acrylate, cyclohexene (meth)acrylate, cycloheptenyl (meth)acrylate, cyclooctene (meth)acrylate, pentadienyl (meth)acrylate, (meth)acrylic acid Ester, decyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylate An ester compound containing an alicyclic group of an unsaturated carboxylic acid such as an enoyl ester or a decene ester of (meth) acrylate; a diol such as an oligoethylene glycol monoalkyl (meth) acrylate a saturated carboxylic acid ester compound; an unsaturated carboxylic acid such as benzyl (meth) acrylate or phenoxy (meth) acrylate; an aromatic ring-containing ester compound; styrene, α-methyl styrene, and vinyl An aromatic vinyl compound such as toluene; a vinyl carboxylate such as vinyl acetate or vinyl propionate; a vinyl cyanide compound such as (meth)acrylonitrile or α-chloroacrylonitrile; N-benzene A maleimide compound such as a cis-butenylene imine or the like.

These may be used alone or in combination.

Furthermore, the copolymer of the present invention (co-polymerizes at least (C-1) and (C-3) The obtained copolymer) is one in which one of (C-1), (C-3) and (C-2) has at least one selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton. In the case of a copolymer obtained by copolymerizing a compound having a skeleton and an unsaturated bond, the strength of the obtained pixel can be improved, which is preferable in this respect.

Specific examples of (C-2) include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentyloxyethyl (meth)acrylate. Dicyclopentenyloxyethyl (meth)acrylate, a compound represented by the following formula (1). These may be used alone or in combination.

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group)

As the above unsaturated carboxylic acid (C-4), specifically, acrylic acid or methacrylic acid is preferred. Acrylic acid and methacrylic acid can be used individually or in combination of both. Further, other acids may be used in addition to the acrylic or methacrylic acid. As the other acid, specifically, at least one type of carboxylic acid selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid, and fumaric acid may be used in combination. Further, a monomer having a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid may be used in combination.

The polybasic acid anhydride (C-5) is used to impart alkali developability to the binder resin. Specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. a dibasic acid anhydride such as chloro bridge anhydride; a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride or biphenyl tetracarboxylic anhydride. Preferred is tetrahydrophthalic anhydride or succinic anhydride. These may be used alone or in combination of two or more.

In the copolymer obtained by copolymerizing (C-1) to (C-3) in the present invention, the ratio of the constituent components introduced from each of (C-1) to (C-3) is preferred. The total number of moles with respect to the constituent components constituting the above-mentioned copolymerized product is in the range of the following by the molar fraction.

The constituent units imported from (C-1): 2~98 mol%

The constituent units introduced from (C-2): 2~90 mol%

The constituent units introduced from (C-3): 2~65mol%

Further, the ratio of the above constituent components is more preferably in the following range.

The constituent unit introduced from (C-1): 40~80 mol%

The constituent units introduced from (C-2): 5~40 mol%

The constituent units introduced from (C-3): 5~30 mol%

Further, the resin is added to the copolymer (C-4) and (C-5) to impart solubility and light/thermosetting properties to the resin in the developer.

The amount of addition of (C-4) is from 0.5 to 1.0 equivalent, preferably from 0.7 to 1.0 equivalent, per equivalent of the epoxy group in the resin obtained by polymerizing (C-1) to (C-3).

When the composition ratio of (C-4) is within the above range, sufficient photocurability or thermosetting property can be obtained, and sensitivity or reliability is excellent, which is preferable.

The amount of addition of (C-5) is from 50 to 100%, preferably from 60 to 100%, based on the molar fraction of the hydroxyl group formed during the reaction of (C-4).

When the composition ratio of (C-5) is within the above range, the solubility in an alkaline developing solution is excellent, and residue is less likely to occur, which is preferable.

The polyunsaturated group-containing resin has a weight average molecular weight of 4,000 or more, preferably 4,500 or more, and more preferably 5,000 or more, as measured by gel permeation chromatography (GPC, Gel Permeation Chromatography). Further, it is usually 100,000 or less, preferably 20,000 or less, and more preferably 15,000 or less.

When it is in the above range, film formation is less likely to occur at the time of development, and the non-pixel portion is excellent in detachment at the time of development, which is preferable.

The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the specific unsaturated group-containing resin is preferably from 1.5 to 6.0, more preferably from 2.0 to 4.0. When the molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) is from 1.5 to 6.0, the developability is excellent, which is preferable.

(other resin)

The colored resin composition of the present invention may contain other binder resins in addition to the specific unsaturated group-containing resin, and for example, Japanese Patent Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. Hei 8-259876, and Japanese Patent No. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A polymer compound described in the publication or the like.

(content)

The (C) binder resin used in the colored resin composition of the present invention is usually contained in an amount of from 5 to 90% by weight, preferably from 10 to 70% by weight, based on the total solid content of the colored resin composition.

In the above range, the solubility in the developer is sufficient, and development residue is less likely to occur on the substrate of the non-pixel portion, and the film portion of the pixel portion of the exposed portion is less likely to be generated during development, and the non-pixel is formed. Part of the detachment is good, so it is preferred.

Further, in the present invention, it is preferred that the resin contained as the (C) binder resin is a specific unsaturated group-containing resin, that is, a resin containing a specific unsaturated group in the above range is preferable.

[(D) Polymerizable monomer]

In the colored resin composition of the present invention, the (D) polymerizable monomer contains an acid group-containing monomer.

(D) The polymerizable monomer is a polymerizable low molecular compound, and is preferably a compound capable of undergoing addition polymerization having at least one ethylenic double bond (hereinafter sometimes referred to as "ethylenic compound").

In other words, the acid group-containing monomer in the present invention may be a polymerizable low molecular compound and may contain an acid group, and is preferably an acid group-containing ethylenic compound.

The acid group is preferably a carboxyl group in terms of good compatibility with other components contained in the colored resin composition, particularly a specific unsaturated group-containing resin.

That is, the acid group-containing monomer is preferably a low molecular compound containing a carboxyl group and an ethylenic double bond.

Examples of the acid group-containing monomer include ester compounds of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid.

A compound in which a hydroxyl group of an aliphatic polyhydroxy compound is modified by a dibasic acid anhydride to introduce a carboxyl group, and a photocurable functional group having three or more layers by using concentrated sulfuric acid or fuming sulfuric acid may be mentioned. The aromatic compound is modified to introduce a compound having a sulfonic acid group or the like.

The photocurable functional group is preferably an acrylonitrile group, and particularly preferably an aliphatic polyhydroxy compound is a compound of pentaerythritol and/or dipentaerythritol.

Further, in terms of good alkali developability, the acid group to be introduced is preferably a carboxyl group.

Preferred examples of the acid group-containing monomer include pentaerythritol or dipentaerythritol having one or more acidic groups and three or more photocurable functional groups in one molecule, and acrylic acid and succinic anhydride or orthobenzene. A compound of diacetic anhydride or trimellitic anhydride, or a mixture of dipentaerythritol and succinic anhydride, phthalic anhydride or trimellitic anhydride.

Among them, the acid anhydride to be added is preferably succinic anhydride or phthalic anhydride in terms of the balance between the solubility in the developer and the photocurability.

The acid group-containing monomer is preferably a compound represented by the following formula (2) (hereinafter sometimes referred to as "compound (2)") or a compound represented by the following formula (3) ( Next, sometimes called "compound (3)").

(About Compound (2))

(In the above formula (2), X ¹ represents a direct bond, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent or an aromatic hydrocarbon ring group which may have a substituent; R ² represents a hydrogen atom or may have The alkyl group having 1 to 4 carbon atoms of the substituent.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a C 1 to 4 alkyl group which may have a substituent. However, R ¹¹ and R ¹² may be bonded to each other to form a ring; further, when a plurality of -CR ¹¹ R ¹² - are contained in one molecule, they may be the same or different; l represents 1~ An integer of 12, where n represents an integer from 0 to 12, and m represents an integer from 1 to 3)

(about X ¹ )

X ¹ represents a direct bond, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or an aromatic hydrocarbon ring group which may have a substituent.

The hydrocarbon group in X ¹ may be any of a linear chain, a branched chain, or a cyclic group, and examples thereof include a hydrocarbon having a carbon number of usually 1 or more, and usually 8 or less, preferably 5 or less. base.

Specific examples thereof include a methylene group, an ethylidene group, an exo-propyl group, a 2-extended propyl group, an exo-butyl group, an exo-butyl group, a tert-butyl group, and a cyclohexyl group.

The heterocyclic group in X ¹ may be a ring containing at least one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom, and means both an aromatic ring group and a non-aromatic ring group.

The heterocyclic group in X ¹ may be a monocyclic ring or a condensed ring, and the number of carbon atoms forming the ring is not particularly limited as long as it is 3 to 10. Further, when the heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.

Examples of the heterocyclic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring. Diazole ring, anthracene ring, indazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanfuran ring, thiophene Furan ring, benzopyrene Oxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridyl Ring, 嗒 Ring, pyrimidine ring, three Ring, quinoline ring, isoquinoline ring, porphyrin ring, quin a porphyrin ring, a pyridine ring, an acridine ring, a quinazoline ring, a quinazolinone ring, an anthracene ring, a thiazole ring, Oxazole ring, thiadiazole ring, phthalimide ring, piperidine ring, pyrrolidine ring, imidazolidinium ring, pyrazolidine ring, piperazine ring, A porphyrin ring, a porphyrin ring, an isoindoline ring, a piperidine ring or the like.

The aromatic hydrocarbon ring group in X ¹ may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 18, and examples thereof include one free valence. Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, anthracene ring, benzofluorene ring, A ring such as a ring, a benzene ring, an ethane naphthalene ring, a propadiene ring, an anthracene ring or the like.

Furthermore, the free price in the present invention is based on the "organic chemistry, biochemical nomenclature" (Nanjiangtang, issued on May 20, 1992, Hirayama Kenzo, Hirayama Kazuo, 11-11 pages). .

X ^{1 is} preferably an aromatic hydrocarbon ring, and particularly preferably a benzene ring, in terms of ease of synthesis and the like.

The hydrocarbon group, the heterocyclic group and the aromatic hydrocarbon ring group in X ¹ may have a substituent, and examples thereof include the following (substituent group W).

(substituent group W)

a fluorine atom, a chlorine atom, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, Base, tolyl, naphthyl, cyano, ethoxycarbonyl, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonylamino group, sulfonylalkylamine group having 2 to 9 carbon atoms, carbon number 2 to 9 a dialkylaminoethyl group, a trifluoromethyl group, and a carbon number of 1 to 8 bonded by an alkylcarbonyl group, a phenethyl group, a hydroxyethyl group, an acetamino group, an alkyl group having 1 to 4 carbon atoms. An alkylalkyl group, a nitro group, an alkylthio group having 1 to 8 carbon atoms.

(about R ¹ )

R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.

In terms of the crosslinking reaction, a hydrogen atom or a methyl group is particularly preferable.

Examples of the substituent which the alkyl group in R ¹ may have include the above (substituent group W).

(About R ¹¹ and R ¹² )

R ¹¹ and R ¹² each independently represent a hydrogen atom or a C 1 to 4 alkyl group which may have a substituent. Further, R ¹¹ and R ¹² may be bonded to each other to form a ring.

Further, in the case where a molecule contains a plurality of -CR ¹¹ R ¹² -, R ¹¹ and R ¹² may be the same or different, but in terms of the ease of synthesis of the compound, Several -CR ¹¹ R ¹² - are preferably the same.

(about l and n)

l represents an integer from 1 to 12, and n represents an integer from 0 to 12.

In terms of ease of synthesis, l is preferably from 1 to 5, and more preferably from 1 to 2.

Further, n is preferably 2 to 5, and more preferably 2, in terms of ease of synthesis.

Furthermore, when a plurality of l and n are contained in one molecule, they may be the same or different.

(about m)

m represents an integer from 1 to 3.

Among them, m is preferably 1 or 2, and particularly preferably 1 in terms of solubility in an alkaline developing solution and good hardenability of the obtained pixel.

(molecular weight)

The molecular weight of the compound (2) is usually 400 or more, preferably 500 or more, and usually 2,000 or less, preferably 1800 or less.

If it is in the above range, the production of the compound is relatively easy, and it is preferable in this respect.

(About Compound (3))

(In the above formula (3), R ⁴ and R ⁵ , R ³¹ and R ³² , R ⁴¹ and R ⁴² , R ⁵¹ and R ⁵² , and R ⁶¹ and R ⁶² each independently represent a hydrogen atom or may have a substituent. a carbon number of 1 to 4 alkyl groups; however, R ³¹ and R ³² , R ⁴¹ and R ⁴² , R ⁵¹ and R ⁵² , and R ⁶¹ and R ⁶² may be independently bonded to each other to form a ring; The plurality of -CR ³¹ R ³² -, -CR ⁴¹ R ⁴² -, -CR ⁵¹ R ⁵² -, -CR ⁶¹ R ⁶² -, R ⁴ and R ⁵ may be the same or different, respectively; a and b each independently represent an integer of 1 to 3, and l ³ to ¹⁶ each independently represent an integer of 1 to 12, and n ³ to n ⁶ independently represent an integer of 0 to 12)

(About R ⁴ and R ⁵ , R ³¹ and R ³² , R ⁴¹ and R ⁴² , R ⁵¹ and R ⁵² , and R ⁶¹ and R ⁶² )

R ⁴ and R ⁵ have the same meanings as R ² in the above compound (2). The preferred form is also the same.

R ³¹ and R ³² , R ⁴¹ and R ⁴² , R ⁵¹ and R ⁵² , and R ⁶¹ and R ⁶² have the same meanings as R ¹¹ and R ¹² in the compound (2). The preferred form is also the same.

(About l ³ ~l ⁶ and n ³ ~n ⁶ )

l ³ ~ l ⁶ has the same meaning as l in compound (2). The preferred form is also the same.

Further, n ³ to n ⁶ have the same meaning as n in the compound (2). The preferred form is also the same.

(About a and b)

a and b each independently represent an integer from 1 to 3.

A and b are preferably 1 to 2, and particularly preferably 1.

Furthermore, a and b may be the same or different.

(molecular weight)

The compound (3) in the present invention has a molecular weight of usually 400 or more, preferably 500 or more, and usually 1,000 or less, preferably 800 or less.

If it is in the above range, the synthesis of the compound is relatively easy, and it is preferable in this respect.

Hereinafter, preferred specific examples of the acid group-containing monomer are exemplified, but the present invention is not limited thereto.

(Specific example)

These monomers may be used singly or in combination, but it is difficult to obtain a single compound in the production. Therefore, a mixture of two or more kinds may be used.

When the acid group-containing monomer is a mixture, the acid value is usually 10 mg-KOH/g or more, preferably 15 mg-KOH/g or more, more preferably 20 mg-KOH/g or more, and usually, It is 150 mg-KOH/g or less, preferably 110 mg-KOH/g or less, and further preferably 100 mg-KOH/g or less.

When it is in the above range, the balance between the solubility in the developer and the photocurability is easily obtained, which is preferable.

(other monomers)

In the colored resin composition of the present invention, the (D) polymerizable monomer may further contain a monomer other than the acid group-containing monomer.

The other monomer is not particularly limited as long as it is a polymerizable low molecular compound, and examples thereof include pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

(content)

The content of the (D) polymerizable monomer in the colored resin composition of the present invention is usually 1% by weight or more, preferably 5% by weight or more, and more preferably 8% by weight or more, based on the total solid content. It is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and still more preferably 40% by weight or less.

Further, the content of the acid group-containing monomer in the colored resin composition of the present invention is usually 10% by weight or more, preferably 30% by weight or more based on the total of the (D) polymerizable monomer.

Further, it is preferred that all (D) polymerizable monomers are monomers containing an acid group, and the upper limit is 100% by weight or less.

(P/M ratio)

The P/M ratio in the colored resin composition of the present invention is usually 0.5 or more, preferably 1.0 or more, and usually 5.0 or less, preferably 4.5 or less.

When it is in the above range, it is easy to obtain a balance between alkali development solubility, hardenability, and cross-sectional shape, which is preferable.

Further, P represents the content of the polymer in the colored resin composition, and M represents the content of the monomer in the colored resin composition.

[(A) pigment]

In the colored resin composition of the present invention, as the (A) pigment, a pigment of various colors such as a red pigment, a green pigment, a yellow pigment, a violet pigment, an orange pigment, or a brown pigment can be usually used.

Examples of the chemical structure of various pigments include an azo type, a quinophthalone type, a phthalocyanine type, a benzimidazole type, an isoindolinone type, and two. Organic pigments such as linden, indanthrene, and lanthanide. In addition to these, various inorganic pigments and the like can be used.

Among the above, in particular, when a phthalocyanine-based pigment is used, the pigment concentration tends to be high, and the adjustment of the dissolution time in the alkaline developer is difficult, so that the effects of the present invention can be easily obtained. Especially in the case of using a halogenated metal phthalocyanine pigment, this tendency is strong, and the effect of the present invention can be remarkably obtained.

The metal phthalocyanine usually has 16 hydrogen atoms in one molecule, and the hydrogen atom is substituted with a bromine atom or a chlorine atom to form a metal halide phthalocyanine. In the present invention, a metal phthalocyanine pigment can be preferably used. .

Among them, a metal bromide phthalocyanine having an average of 13 or more bromine atoms in one molecule exhibits an extremely high transmittance, and is preferable in that it is suitable for forming a green pixel of a color filter. Further preferably, there are 13 to 16 bromines in one molecule. Zinc bromide phthalocyanine which does not contain chlorine or has an average of 3 or less chlorine in one molecule, and particularly preferably has 14 to 16 bromine atoms in one molecule and does not contain a chlorine atom in one molecule or has an average of 2 The following metal bromide phthalocyanine of a chlorine atom. As the metal bromide phthalocyanine, copper bromide phthalocyanine and zinc bromide phthalocyanine are preferably mentioned. As the copper bromide phthalocyanine, C.I. Pigment Green 36 is preferred. Further, as the zinc bromide phthalocyanine, C.I. Pigment Green 58 is preferable.

Further, specific examples of other green pigments represented by pigment numbers include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 45, 48, 50, 51, 54, 55, etc.

Further, specific examples of the pigments other than the green pigment of the present invention are indicated by the pigment number, but are not limited to these examples.

First, as the red pigment, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32 , 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53 , 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81 , 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123 , 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 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, etc. Among these, CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc. are preferred, and CI Pigment Red 177, 209, 224, 242 are further preferred. , 254, etc.

As the blue pigment, for example, CI Pigment Blue 1, 1, 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19 , 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76 , 78, 79, etc.

As the yellow pigment, CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81 , 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133 , 134, 136, 138, 139, 142, 147, 148, 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, and a pigment defined by the following <Pigment Y> (hereinafter referred to as "Pigment Y").

<Pigment Y>

A compound obtained by inserting another compound into a 1:1 complex of azo barbituric acid and nickel or an interchange isomer thereof represented by the following structural formula.

In addition, examples of the other compound include a compound represented by the following formula (I-1).

Among these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and Pigment Y are preferable, and C.I. Pigment Yellow 138, 139, Pigment Y, etc. are further preferable.

As the purple pigment, CI 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, etc. Among these, C.I. Pigment Violet 19, 23, etc. are preferable, and C.I. Pigment Violet 23 etc. are further preferable.

As an orange pigment, CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62 , 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, etc. Among these, C.I. Pigment Orange 38, 71 and the like are preferred.

Further, as described below, a resin black matrix in which a colored resin composition is formed to form a color filter may be prepared, and in this case, a black pigment may be used. Further, the black pigment may be used singly or in combination with a pigment such as red, green or blue. Further, it may be an inorganic pigment or an organic pigment.

Further, when the pigment in the present invention is C.I. (color index) Pigment Red 58, the effect of the present invention is easily obtained, and it is particularly preferable in this respect.

Further, examples of the inorganic pigment which can be used in the present invention include barium sulfate, lead sulfate, titanium oxide, yellow dan, iron oxide, and chromium oxide.

Further, several kinds of the above various pigments may be used in combination. For example, in order to adjust the chromaticity, as the (A) pigment, a red pigment and a yellow pigment may be used in combination, or a green pigment and a yellow pigment may be used in combination.

Further, the average primary particle diameter of the (A) pigment of the present invention is usually 100 nm or less, preferably 80 nm or less, more preferably 20 nm or more and 70 nm or less. The present invention is particularly effective in the case of a composition containing a highly micronized pigment, and therefore it is particularly preferable to contain a pigment having an average primary particle diameter of 20 nm or more and 60 nm or less.

By setting the average primary particle diameter of the (A) pigment to be used in the above range, the depolarization property can be favorably maintained, a high contrast ratio, a transmittance, and the like can be achieved, and dispersion stability can be obtained, and heat resistance can be obtained. A colored resin composition excellent in properties or light resistance.

Further, the primary particle diameter of the pigment can be obtained by the following method.

First, the pigment is ultrasonically dispersed in chloroform, dropped onto a mesh to which a colloidion film is adhered, dried, and observed by a transmission electron microscope (TEM) to obtain a pigment. The first particle image. In the case of an organic pigment, the diameter of the projection area converted into the diameter of a circle having the same area is calculated from the particle diameter of each pigment particle, and the particle diameter is determined for each of a plurality of pigment particles (usually about 200 to 300). Using the obtained value of the primary particle diameter, the average value is obtained by calculating the average value based on the calculation formula of the following formula.

Particle size of each pigment particle: X ₁ , X ₂ , X ₃ , X ₄ ,. . . . , X _i ,. . . . . . X _m

The (A) pigment thus obtained may be used singly, but one or two or more kinds of pigments may be used in combination insofar as the effects of the present invention are not impaired.

The content of the (A) pigment in the colored resin composition of the present invention is usually 60% by weight or less, preferably 50% by weight or less, more preferably 45% by weight or less, and usually 10% based on the total amount of the solid content. The weight% or more is preferably 20% by weight or more, and more preferably 28% by weight or more.

When the content of the (A) pigment is in the above range, the film thickness with respect to the color density does not become excessively large, and the gap control or the like at the time of liquid crystal cell formation is not adversely affected, and sufficient image formation property can be obtained. Moreover, the dispersion state of the pigment is also maintained, and aggregation or precipitation is less likely to occur, and as a result, problems such as thickening or reduction in brightness/contrast can be eliminated.

[(B) Solvent]

(B) The solvent has a function of dissolving or dispersing each component contained in the colored resin composition to adjust the viscosity. The solvent (B) may be any component which can dissolve or disperse the constituent resin composition, and it is preferred to select a boiling point of 100 to 200 °C. More preferably, it has a boiling point of 120 to 170 °C.

As such a solvent, the following are mentioned, for example.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol a diol such as alcohol monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol or tripropylene glycol monomethyl ether Monoalkyl ethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Ester, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl a glycol alkyl ether acetate such as ether acetate or 3-methyl-3-methoxybutyl acetate; diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl Ether, dihexyl ether Ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isobutyl Amyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl ketone ketone, methyl decyl ketone Ketones; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol; n-pentane, n-octane Aliphatic hydrocarbons such as alkane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; cyclohexane, methylcyclohexane, methylcyclohexene, and cyclohexane An alicyclic hydrocarbon such as an alkane; an aromatic hydrocarbon such as benzene, toluene, xylene or cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentane acetate Ester, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate Ester, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, a chain or cyclic ester such as butyrolactone; an alkoxycarboxylic acid such as 3-methoxypropionic acid or 3-ethoxypropionic acid; halogenation such as chlorobutane or chloropentane; A hydrocarbon; an ether ketone such as methoxymethylpentanone; a nitrile such as acetonitrile or benzonitrile; and the solvent may be used alone or in combination of two or more.

Among the above solvents, those having a good dispersibility of the (A) pigment are preferably diol monoalkyl ethers. Among them, propylene glycol monomethyl ether is particularly preferable in terms of solubility of various constituent components in the colored resin composition.

In addition, the balance between the coatability and surface tension of the colored resin composition is good, and the solubility of the constituent components in the composition is relatively high, and it is more preferable to further mix and use the glycol alkyl ether acetate. As a solvent.

Further, the use amount of the diol monoalkyl ether is preferably from 5 to 50% by weight, more preferably from 5 to 50% by weight, based on the viscosity of the colored resin composition and the storage stability. It is 5 to 30% by weight.

Further, from the viewpoint of adaptability to the slit coating method of the recent large substrate or the like, it is also preferred to use a solvent having a boiling point of 150 ° C or higher. In this case, the content of the high boiling point solvent is preferably from 3 to 50% by weight, more preferably from 5 to 40% by weight, even more preferably from 5 to 30% by weight, based on the total of the solvent (B).

When it is in the above range, foreign matter defects such as precipitation and solidification of the pigment nozzle are less likely to occur, and the drying speed is moderate. Therefore, the vacuum drying process is less likely to occur in the color filter manufacturing step described below. Poor contact or pre-baked stomata marks.

Further, the solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, a solvent having a boiling point of 150 ° C or higher may not be additionally contained.

In the colored resin composition of the present invention, (B) the solvent content is not particularly The limitation is usually 99% by weight or less, and usually 75% by weight or more, preferably 80% by weight or more, and more preferably 82% by weight or more.

When it is in the above range, it is preferable to form a coating film in order to be suitable for coating viscosity.

[Dispersant]

The dispersing agent in the present invention is not particularly limited as long as it can disperse the pigment and remains stable. For example, a cationic, anionic, nonionic or amphoteric dispersing agent can be used, and a polymer dispersing agent is preferred. Specific examples thereof include a modified acrylic copolymer, an acrylic copolymer, a polyurethane, a polyester, an alkylammonium salt or a phosphate salt of a polymer copolymer, and a cationic comb-type graft. Polymers, etc. Among these dispersants, a modified acrylic copolymer, a polyurethane, and a cationic comb graft polymer are preferred. More preferably, it is a modified acrylic copolymer, and particularly preferably a block copolymer comprising a block having a solvophilic A block and a B block having a functional group containing a nitrogen atom, and an amine value of 80 mg- KOH/g or more, 150 mg-KOH/g or less (converted in effective solid content). More preferably, it is 100 to 140 mg-KOH/g.

When it is in the above range, the adsorption force to the surface of the pigment is sufficient, and the dispersion stability is good.

Among them, the (meth)acrylic block copolymer described in JP-A-2009-025813 is preferably used.

The acrylic block copolymer can disperse the (A) pigment extremely efficiently. Speculate The reason for this is that the molecular arrangement is controlled, whereby the structure in which the dispersing agent is hindered when adsorbed to the pigment is less.

Further, in the present invention, the acrylic block copolymer is preferably an AB block and/or an ABA block copolymer comprising an A block and a B block.

The B block constituting the above acrylic block copolymer has an amine group, and the amine group is preferably -NR ⁷¹ R ⁷² (wherein R ⁷¹ and R ⁷² each independently represent a cyclic or chain group which may have a substituent) The alkyl group, the aryl group which may have a substituent, or the aralkyl group which may have a substituent is represented by a partial structure including it, and is preferably represented by the following formula, for example.

(wherein R ⁷¹ and R ⁷² have the same meanings as R ⁷¹ and R ⁷² described above, R ⁷³ is an alkylene group having 1 or more carbon atoms, and R ⁷⁴ represents a hydrogen atom or a methyl group)

Wherein R ⁷¹ and R ^{72 are} preferably a methyl group, R ^{73 is} preferably a methylene group or an ethyl group, and R ^{74 is} preferably a methyl group. As such a compound, a partial structure represented by the following formula can be mentioned.

The partial structure containing an amine group as described above may be contained in two or more B blocks. In this case, two or more kinds of amine-containing moiety structures may be contained in the B block in any of the states of random copolymerization or block copolymerization. Further, in the range which does not impair the effects of the present invention, a part of the structure in which the amine group is not contained in the B block may be contained. Examples of such a partial structure include a (meth) acrylate-based single sheet. Part of the body structure.

On the other hand, in the present invention, the A block of the dispersing agent is not particularly limited as long as it is solvophilic and contains a monomer copolymerizable with the monomer constituting the B block.

Examples of the A block include a styrene monomer, a (meth) acrylate monomer, a (meth) acrylate monomer, a vinyl acetate monomer, and a glycidyl ether. A polymer structure obtained by copolymerizing a comonomer such as a body.

The dispersing agent in the present invention is an AB block or ABA block copolymer type polymer compound containing an A block and a B block as described above. Among them, an AB block copolymer is preferred. Such a block copolymer can be produced, for example, by a living polymerization method.

Examples of the living polymerization method include an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Specifically, for example, a Japanese patent can be cited. The method described in JP-A-2007-270147.

Further, the amine value (converted in terms of effective solid content) of the dispersing agent is expressed by the weight of KOH equivalent to the amount of alkali per 1 g of the solid content other than the solvent in the dispersant sample, and is measured by the following method. Accurately weigh 0.5~1.5 g of the dispersant sample into a 100 mL beaker and dissolve it with 50 mL of acetic acid. The solution was neutralized and titrated using a 0.1 mol/L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve was set as the end point of the titration, and the amine value was determined by the following formula.

Amine value [mg-KOH/g] = (561 × V) / (W × S)

(W, W represents the amount of dispersant sample weighed [g], V represents the titer [mL] at the end of the titration, and S represents the solid concentration [% by weight] of the dispersant sample)

Further, the acid value of the block copolymer depends on the presence or absence of the acidic group which is the source of the acid value, and the lower the better, it is usually 50 mg-KOH/g or less, preferably 40 or less, more preferably It is 30 or less.

When the average primary particle diameter of the pigment is small, the specific surface area is increased, and the amount of the dispersant adsorbed per unit area is small. In this case, since the effect of the dispersing agent containing the above-mentioned copolymer is larger than that of other dispersing agents, it can be preferably used.

The dispersing agent in the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and usually 200% by weight or less, more preferably 200% by weight or less, based on the total amount of the (A) pigment in the colored resin composition. It is 100% by weight or less.

The colored resin composition of the present invention may contain other dispersing agents as long as the effects of the present invention are not impaired. As another dispersing agent, for example, Japanese specializing is mentioned The person described in Japanese Patent Publication No. 2006-343648.

[Dispersing Aid]

The colored resin composition of the present invention may further contain a dispersing aid. The dispersing aid herein may also be a pigment derivative, and as a pigment derivative, for example, JP-A-2001-220520, JP-A-2001-271004, and JP-A-2002-179976 may be used. Various compounds and the like described in Japanese Laid-Open Patent Publication No. 2007-186681, and the like.

Further, the content of the dispersing aid in the colored resin composition of the present invention is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less, based on the total (A) pigment. It is preferably 10% by weight or less, and more preferably 5% by weight or less.

When it is in the above range, the effect as a dispersing aid can be effectively obtained, and the dispersibility and dispersion stability are good, and it is preferable in this respect.

[dispersion resin]

The colored resin composition of the present invention may contain a part or all of a resin selected from the above (C) binder resin as the above-mentioned dispersion resin.

Specifically, in the following [method of preparing a colored resin composition], the (C) binder resin is synergized with a dispersing agent by containing a component such as the above dispersing agent and (C) a binder resin. The effect contributes to (A) the dispersion stability of the pigment. As a result, it is possible to reduce the amount of the dispersant added, which is preferable. Moreover, the effect is also improved: the developability is improved, and the non-pixel portion of the substrate is not It is preferable that the undissolved matter remains, and the adhesion between the pixel and the substrate is improved.

Thus, the (C) binder resin used in the dispersion treatment step is sometimes referred to as a dispersion resin. The amount of the dispersion resin in the pigment dispersion liquid is preferably from 0 to 200% by weight, more preferably from 10 to 100% by weight.

As the dispersion resin, various (C) binder resins described above can be used.

The acid value of the dispersion resin is preferably 0.5 mg-KOH/g or more, more preferably 1 mg-KOH/g or more, most preferably 5 mg-KOH/g or more, and more preferably 300 mg-KOH/g or less. More preferably, it is 200 mg-KOH/g or less, and it is preferably 150 mg-KOH/g or less. By controlling the acid value to the above range, the alkali developability becomes good, and the synthesis becomes easy to handle.

Further, the polystyrene-equivalent weight average molecular weight of the dispersion resin measured by GPC is preferably 1,000 or more, more preferably 1,500 or more, most preferably 2,000 or more, further preferably 200,000 or less, more preferably 50,000 or less. The best is below 30,000. By controlling the molecular weight to the above range, the alkali developability is improved, and the dispersion stability can be prevented from being lowered.

[(E) Photopolymerization starting component and thermal polymerization starting component]

In order to harden the coating film, the colored resin composition of the present invention preferably contains at least one of (E) a photopolymerization starting component and a thermal polymerization starting component. However, the method of hardening may be a method other than the method of using the initiator.

In particular, the colored resin composition of the present invention contains an ethylenic double bond. When the resin is used as the component (C) or when the ethylenic compound is contained as the component (D), it is preferred to contain a light having a direct absorption or a photo-sensitization to cause a decomposition reaction or a hydrogen abstraction reaction to produce a polymerization activity. A photopolymerization starting component which functions as a radical and/or a thermal polymerization starting component which generates a living active radical by heat. In the present invention, the component (E) as a photopolymerization starting component means a polymerization accelerator (hereinafter, also referred to as "(E1) component arbitrarily"), and a polymerization accelerator is used in combination (hereinafter, Also, it is arbitrarily referred to as "(E2) component"), and a mixture of an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as "(E3) component").

[(E) Photopolymerization starting ingredients]

The (E) photopolymerization starting component in the present invention is usually a mixture of an (E1) photopolymerization initiator, and optionally an (E2) polymerization accelerator and an (E3) sensitizing dye. The form is used as a component which directly absorbs light or undergoes a decomposition reaction or a hydrogen abstraction reaction by light sensitization to produce a function of polymerizing active radicals.

The (E1) photopolymerization initiator which is a photopolymerization initiation component, for example, is described in JP-A-59-152396, JP-A-61-151197, and the like. a hexaarylbiimidazole derivative described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The halomethylation described in Japanese Laid-Open Patent Publication No. Hei 10-39503, etc. Diazole derivatives, halomethyl groups Free derivatives such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters The pharmaceutically acceptable agent, the α-aminoalkyl phenone derivative, and the oxime ester derivative described in JP-A-2000-80068.

Specifically, for example, a photopolymerization initiator described in International Publication No. WO 2009/107734 or the like can be mentioned.

Among the photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and 9-oxosulfuric acid are more preferred. Derivatives.

Further, examples of the oxime ester-derived derivatives include 1-[4-(phenylthio)phenyl]-2-(o-benzamide) 1,2-octanedione and 1-[ 9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(o-acetamidine)ethanone, and represented by the following formula (XI) Compounds, etc.

(In the formula (XI), R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms or a heteroaryl group having 4 to 25 carbon atoms. Or an alkyl group, which may have a substituent; or R ¹⁰¹ may be bonded to X or Z to form a ring; R ¹⁰² represents an alkanoyl group having 2 to 20 carbon atoms, an olefin group having 3 to 25 carbon atoms, 4 to 8 cycloalkyl fluorenyl groups, 7 to 20 aryl fluorenyl groups, 2 to 10 carbon alkoxycarbonyl groups, 7 to 20 carbon aryloxycarbonyl groups, carbon number 2 to 20 An aryl group, a heteroaryl group having 3 to 20 carbon atoms or an alkylaminocarbonyl group having 2 to 20 carbon atoms, which may have a substituent; and X represents a condensation of two or more rings which may have a substituent. a divalent aromatic hydrocarbon ring group and/or an aromatic hetero group; Z represents an aromatic ring group which may have a substituent)

In addition, among the compounds represented by the above formula (XI), X is a compound of a carbazole ring which may have a substituent, and specifically, a compound represented by the following formula (XII), etc. Among them, a compound represented by the following formula (XIII) is particularly preferred.

(wherein R ¹⁰¹ , R ¹⁰² and Z have the same meanings as in the above formula (XI); and R ¹⁰³ to R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent)

(wherein R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (XIIIa))

(wherein R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom, a phenyl group or an N-ethinyl-N-acetoxyamino group; * represents a bonding site)

R ^102a represents a cycloalkyl group having 2 to 4 carbon atoms, X ^a represents ^a 3,6-carbazolyl group in which ^a nitrogen atom may be substituted with an alkyl group having 1 to 4 nitrogen atoms; and Z ^a represents a phenyl group which may be substituted by an alkyl group. Or can be Polinyl substituted naphthyl)

In addition, benzoin alkyl ethers, anthracene derivatives, 2-methyl-(4'-methylthiophenyl)-2- Acetophenone derivatives such as phenyl-1-propanone, 2-ethyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 9-oxosulfur Derivatives, benzoate derivatives, acridine derivatives, brown Derivatives, anthrone derivatives, and the like.

Among the photopolymerization initiators, α-aminoalkylphenone derivatives and 9-oxosulfuric acid are more preferred. Derivatives, oxime ester derivatives. It is especially preferred to be an oxime ester derivative.

Examples of the (E2) polymerization accelerator to be used, for example, N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester; 2-mercapto Benzothiazole, 2-mercaptobenzophenone a mercapto compound having a heterocyclic ring such as an azole or a 2-mercaptobenzimidazole; or a mercapto compound such as an aliphatic polyfunctional mercapto compound.

These (E1) photopolymerization initiators and (E2) polymerization accelerators may be used alone or in combination of two or more.

Moreover, (E3) sensitizing dye is used for the purpose of improving induction sensitivity as needed. The sensitizing dye can be used in accordance with the wavelength of the image-exposure light source. For example, the dibenzopyran series described in JP-A-4-221958, JP-A-4-219756, and the like can be used. a coumarin-based dye having a heterocyclic ring as described in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. -3-keto-coumarin-based dyes, which are described in Japanese Laid-Open Patent Publication No. Hei. No. 6-19240, and the like. Japanese Patent Laid-Open No. Sho 54-155292, Japanese Patent Laid-Open No. Sho 45-37377, Japanese Patent Laid-Open No. Sho 48-84183, Japanese Patent Laid-Open No. Sho 52-112681, Japanese Patent Laid-Open No. Sho 58-15503, Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Japanese Patent Laid-Open No. 5-210240, Japanese Patent Laid-Open No. 4-288818 As described in the newspaper and other dye having the dialkylamino benzene skeleton and the like.

(E3) The sensitizing dye may be used alone or in combination of two or more.

In the colored resin composition of the present invention, the (E) photopolymerization starting component The content is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, and usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content. It is preferably in the range of 20% by weight or less.

If it is in the above range, the sensitivity to the exposure light is good, and the solubility of the unexposed portion in the developer is also good, which is less likely to cause development failure, etc., and is preferable in this respect.

((E) Thermal polymerization starting component)

Specific examples of the (E) thermal polymerization starting component which can be contained in the colored resin composition of the present invention include an azo compound, an organic peroxide, and hydrogen peroxide. Among these, an azo compound can be preferably used. More specifically, for example, a thermal polymerization starting component described in International Publication No. 2009/107734 or the like can be used.

These thermal polymerization starting components may be used alone or in combination of two or more.

[(F) chain transfer agent]

In view of the fact that the effects of the present invention are more easily obtained, the colored resin composition of the present invention preferably contains (F) a chain transfer agent.

The (F) chain transfer agent in the present invention means a compound which accepts the generated radical and delivers the radical to other compounds.

The colored resin composition of the present invention contains a compound represented by the following formula (4) as a (F) chain transfer agent.

(In the above formula (4), p represents an integer of 2 to 4; R ³ represents a hydrogen atom or an alkyl group which may have a substituent; X ² represents a direct bond, a secondary to a quaternary carbon atom, and a 2 to 4 valence a heterocyclic group or a 2 to 4 valent aromatic hydrocarbon ring group; a plurality of ones contained in one molecule

Can be the same, but also different)

(about R ³ )

R ³ represents a hydrogen atom or an alkyl group which may have a substituent.

As the above alkyl group, the carbon number is usually from 1 to 8, more preferably from 1 or 2.

R ³ is preferably a hydrogen atom from the viewpoint that the reactivity of the compound is high and the surface hardenability of the obtained film is high.

Further, examples of the substituent which the alkyl group in R ³ may have include, for example, those described in the above (Substituent Group Z).

(substituting group Z)

a fluorine atom, a chlorine atom, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, Base, tolyl, naphthyl, ethoxycarbonyl, alkoxycarbonyl group having 2 to 9 carbon atoms, phenoxycarbonyl group, amine methyl sulfonyl group, alkylamine carbhydryl group having 2 to 9 carbon atoms, phenylamine Mercapto, amidoxime, alkylamine sulfonyl group having 1 to 8 carbon atoms, phenylamine sulfonyl group, alkylcarbonyl group having 2 to 9 carbon atoms, benzamidine group, carbon number 1-8 Alkylsulfonyl, trifluoromethanesulfonyl, phenethyl, hydroxyethyl, ethylamino, a C1-C4 alkyl group bonded dialkylaminoethyl, trifluoro A methyl group, a trialkylsulfonyl group having 1 to 8 carbon atoms, a nitro group, a cyano group, a carboxyl group, and an alkylthio group having 1 to 8 carbon atoms.

(about X ² )

X ² represents a direct bond, a secondary to quaternary carbon atom, a 2 to 4 valent aromatic hydrocarbon ring group or a 2 to 4 valent heterocyclic group.

Examples of the aromatic hydrocarbon ring group and the heterocyclic group in X ² include those described above in relation to the compound (2) (in respect to X ¹ ). The preferred form is also the same.

In the case of X ² , in terms of good storage stability of the compound (4), a secondary to quaternary carbon atom is preferred, and a quaternary carbon atom is preferred.

In addition, the carbon atom, the heterocyclic group, and the aromatic hydrocarbon ring group in X ² may have a substituent represented by a structural formula other than the following structural formula (hereinafter, referred to as "structure containing a sulfur-containing group") Examples of the substituent include those described in the above (Substituent Group Z).

In the present invention, it is preferred that the structure containing only the above-mentioned sulfur-containing group is a substituent, and the number of stages of the carbon atom, the heterocyclic group and the aromatic hydrocarbon ring group in X ² is preferably the same as p.

(about p)

p represents an integer from 2 to 4.

In the compound (4), the amount of the sulfur group as the reaction site is increased, the reactivity of the compound is increased, and the hardenability of the obtained pixel is particularly preferably 4.

Specific examples of the compound (4) in the present invention are exemplified below, but the present invention is not limited thereto.

[Specific example]

a compound having two sulfur-containing structures: 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5 - pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,3-dimercapto-1-propanol, dithiobacillus Sugar alcohol, 1,2-benzenedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 3,4-dimercaptotoluene, 4-chloro-1,3-benzenedisulfide Alcohol, 2-hexylamino-4,6-dimercapto-1,3,5-three 2-Diethylamino-4,6-dimercapto-1,3,5-three 2-cyclohexylamino-4,6-dimercapto-1,3,5-three , ethylene glycol bis(3-mercaptopropionate), 2,5-dimercapto-1,3,4-thiadiazole, 2,2-bis(2-hydroxy-3-mercaptopropoxyphenyl) Propane or the like; a compound having three sulfur-containing structures: trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tridecyl acetate, 1,2,6-hexanetriol Mercaptoacetate or the like; a compound having four sulfur-containing structures: pentaerythritol tetradecyl acetate, pentaerythritol tetrakis(3-mercaptopropionate), and the like.

(about content)

The content of the (F) chain transfer agent in the present invention is usually 0.5% by weight or more, preferably 1% by weight or more, more preferably 1.5% by weight or more, based on the solid content of the colored resin composition, and is usually 10% by weight or less, preferably 8% by weight or less, further preferably 6% by weight or less.

When it is in the above range, the obtained colored resin composition is sufficiently cured, and the colored resin composition is excellent in storage stability and is less likely to affect the brightness of the obtained pixel, and is preferable in this respect.

In addition, the coloring resin composition of the present invention may contain a chain transfer agent other than the compound (4). In this case, the total content of the chain transfer agent may be contained within the above range.

However, it is particularly preferred to contain only the compound (4) as a chain transfer agent, and it is preferred to contain the compound (4) in the above range.

[Other optional ingredients]

The colored resin composition of the present invention may contain, in addition to the above components, a surfactant, an organic carboxylic acid, and/or an organic carboxylic anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, and a surface protective agent. , adhesion improver, development improver, and the like. As the optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Preparation method of colored resin composition]

In the present invention, the colored resin composition can be produced by a suitable method. For example, the (A) pigment, the (C) binder resin containing a specific unsaturated group-containing resin, and the (D) polymerizable monomer including the acid group-containing monomer, and (B) a solvent and, if necessary, The ingredients used are mixed together and prepared.

Further, it is preferred to use, for example, a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill in (B) a solvent, in the presence of a dispersant and optionally a dispersing aid. In a jet mill, a homogenizer, or the like, a pigment dispersion liquid is prepared by mixing and dispersing (A) a pigment, as appropriate, and a part of the (C) binder resin. A method of adding (C) a binder resin containing a specific unsaturated group-containing resin and a (D) polymerizable monomer containing an acid group-containing monomer to the pigment dispersion liquid, if necessary, may be mentioned. The (E) photopolymerization starting component and/or the thermal polymerization starting component, and other components are mixed and prepared.

[Application of colored resin composition]

The colored resin composition of the present invention is usually in a state in which all constituent components are dissolved or dispersed in a solvent. The colored resin composition is supplied onto a substrate to form a constituent member such as a color filter, a liquid crystal display device, or an organic EL display device.

In the following, as an application example of the colored resin composition of the present invention, a liquid crystal display device (panel) and an organic EL display device using the same as a pixel of a color filter will be described.

<Color Filter>

The color filter of the present invention has the composition of the colored resin of the present invention The pixels formed.

Hereinafter, a method of forming the color filter of the present invention will be described.

The pixels of the color filter can be formed by various methods. Here, a case where the photopolymerizable coloring resin composition is formed by photolithography will be described as an example, but the production method is not limited thereto.

First, a black matrix is formed on the surface of the substrate as needed to form a portion of the pixel, and after coating the colored resin composition of the present invention on the substrate, prebaking is performed to evaporate the solvent to form a coating film. Then, after exposing the coating film through a photomask, development is performed using an alkaline developing solution, and the unexposed portion of the coating film is dissolved and removed, and then post-baking is performed to form respective pixels of red, green, and blue. Pattern, and make color filters.

The substrate to be used for forming the pixel is not particularly limited as long as it is transparent and has moderate strength. Examples thereof include a polyester resin, a polyolefin resin, a polycarbonate resin, and an acrylic resin. A thermoplastic resin sheet, an epoxy resin, a thermosetting resin, various glasses, and the like.

In addition, appropriate pretreatment such as a film formation treatment such as a decane coupling agent or an urethane-based resin, or a surface treatment such as a corona discharge treatment or an ozone treatment may be carried out as necessary.

When the colored resin composition is applied onto a substrate, a spin coating method, a wire bar coating method, a flow coating method, a squeeze and spin coating method, a die coating method, and the like are mentioned. Roll coating method, spray coating method, and the like. Among them, extrusion and spin coating methods and die coating methods are preferred.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, and more preferably 0.8 to 5.0 μm, in terms of film thickness after drying.

If it is in the above range, the gap adjustment in the pattern development or liquid crystal unitization step is easy, and the desired color is easily formed, which is preferable in this respect.

As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

The light source used for the exposure of the image to use radiation having a wavelength of 190 to 450 nm is not particularly limited, and examples thereof include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide lamp. Medium-pressure mercury lamp, low-pressure mercury lamp, carbon arc lamp, fluorescent lamp, etc.; argon ion laser, YAG, Yttrium Aluminum Garnet laser, excimer laser, nitrogen laser, 氦- Laser light sources such as cadmium lasers and semiconductor lasers. An optical filter can also be used when it is used to illuminate light of a specific wavelength.

The amount of radiation exposure is preferably from 10 to 10,000 J/m ² .

Further, as the alkaline developing solution, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate or metasilicate is preferred. Inorganic basic compounds such as sodium, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-, di- or triethanolamine, mono-, di- or trimethylamine , single, two or three Ethylamine, mono-, di- or triisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyl imine, ethyl diimide, tetramethylammonium hydroxide (TMAH An aqueous solution of an organic basic compound such as choline.

A suitable amount of a water-soluble organic solvent or interface such as isopropanol, benzyl alcohol, ethyl sirolius, butyl sirlo, phenyl sirolimus, propylene glycol, diacetone alcohol or the like may be added to the above alkaline developing solution. Active agent, etc. Further, after alkaline development, water washing is usually carried out.

As the development treatment method, any one of a dipping development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The developing conditions are preferably carried out at room temperature (23 ° C) for 5 to 300 seconds.

The conditions of the development treatment are not particularly limited, and the development temperature is usually 10 ° C or higher, and preferably 15 ° C or higher, more preferably 20 ° C or higher, and usually 50 ° C or lower, and preferably 45 ° C or lower. Further, it is preferably in the range of 40 ° C or lower.

The developing method may be any one of a dipping development method, a spray development method, a brush development method, an ultrasonic development method, and the like.

When a color filter produced in this manner is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image in an intrinsic state, and is used as a part of a color display or a liquid crystal display device. However, in order to improve surface smoothness or durability, it is also possible to provide a top coat of polyimide, polyimide or the like on the image as needed. In addition, some of them are used in a planar alignment type driving method (intra-electric field switching (IPS) mode). In the middle, a transparent electrode is sometimes not formed. Further, in the vertical alignment type drive mode (Multi-Domain Vertical Alignment (MVA) mode), ribs may be formed. Further, in place of the bead-dispersion type spacer, a trabecular structure (photosensitive spacer) may be formed by photolithography.

<Liquid crystal display device>

The liquid crystal display device of the present invention uses the above-described color filter of the present invention. The type or configuration of the liquid crystal display device of the present invention is not particularly limited, and can be assembled according to a conventional method using the color filter of the present invention.

For example, the liquid crystal display device of the present invention can be formed by the method described in "Liquid Crystal Equipment Handbook" (Japanese Journal of Industry News, issued on September 29, 1989, and the Japanese Society for the Promotion of Science, 142th Committee).

<Organic EL display device>

In the case of producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a pixel 20 is formed on the transparent supporting substrate 10 by the colored resin composition of the present invention. On the blue color filter, the organic light-emitting body 500 is laminated via the organic protective layer 30 and the inorganic oxide film 40 to produce a multi-color organic EL device.

As a method of laminating the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode are sequentially formed on the upper surface of the color filter. The method of 55, or bonding the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40 Method and so on. The organic EL element 100 fabricated in this manner can be applied to an organic EL display device of a passive driving method, and can also be applied to an organic EL display device of an active driving method.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples as long as the scope of the present invention is not exceeded.

[1] Synthesis of resin <Synthesis Example 1: Synthesis of Resin P-1>

A separable flask equipped with a cooling tube was prepared as a reaction vessel, and 400 parts by weight of propylene glycol monomethyl ether acetate was added thereto, and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C while stirring in an oil bath while stirring.

On the other hand, 30 parts by weight of 2,2'-[oxybis(methylene)]bis-2-acrylic acid dimethyl ester, 60 parts by weight of methacrylic acid, and cyclohexyl methacrylate 110 are added to the monomer tank. 5.2 parts by weight of dibutyl acrylate 2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, and 4.2 parts by weight of n-dodecyl mercaptan in the chain transfer agent tank, propylene glycol After 27 parts by weight of methyl ether acetate, the temperature of the reaction vessel was stabilized at 85 ° C, and the polymerization was started from the monomer tank and the chain transfer agent tank. While maintaining the temperature at 85 ° C, the dropwise addition was carried out for 135 minutes, and after the completion of the dropwise addition for 60 minutes, the temperature was raised to adjust the reaction vessel to 110 ° C.

After maintaining at 110 ° C for 3 hours, a gas introduction tube was attached to the separable flask to start foaming of a mixed gas of oxygen/nitrogen = 5/95 (v/v). Then, 39.6 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were added to the reaction vessel. The reaction was carried out directly at 110 ° C for 9 hours.

After cooling to room temperature, a resin P-1 having a weight average molecular weight of 12,000 and an acid value of 90 mg-KOH/g in terms of polystyrene measured by GPC was obtained.

<Synthesis Example 2: Synthesis of Resin P-2>

One of the 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 °C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, followed by dropwise addition for 3 hours. 2.00 parts by weight of 2,2'-azobis(2-methylbutyronitrile), and further stirring was continued at 90 ° C for 2 hours. Then, the inside of the reaction vessel was replaced with air, and 0.7 parts by weight of tris(dimethylaminomethyl)phenol and 0.12 parts by weight of hydroquinone were placed in 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C for 12 hours. Thereafter, 68.5 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours to add propylene glycol monomethyl ether acetate in such a manner that the solid content became 40%. The ester is prepared. The resin P-2 thus obtained had a weight average molecular weight Mw of about 5,500 in terms of polystyrene measured by GPC, and an acid value of 92 mg-KOH/g.

<Synthesis Example 3: Synthesis of Resin P-3>

One of the 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 °C. 10 parts by weight of styrene was added thereto, 85.2 parts by weight of glycidyl methacrylate and 66 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, followed by dropwise addition of 2,2'-azobis (2) over 3 hours -methylbutyronitrile) 8.47 parts by weight, and further stirring was continued at 100 ° C for 2 hours. Then, the reaction vessel was replaced with air, and 0.7 parts by weight of tris(dimethylaminomethyl)phenol and 0.12 parts by weight of hydroquinone were added to 51.7 parts by weight of methacrylic acid, and the reaction was continued at 100 ° C for 12 hours. . Thereafter, 27.0 parts by weight of succinic anhydride and 0.7 parts by weight of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours to prepare propylene glycol monomethyl ether acetate so that the solid content concentration became 40%. The resin P-3 thus obtained had a weight average molecular weight Mw of about 5,500 in terms of polystyrene measured by GPC, and an acid value of 80 mg-KOH/g.

<Synthesis Example 4: Synthesis of Resin P-4>

93.6 parts by weight of a monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 36.4 parts by weight of methacrylic acid were dissolved in 150 parts by weight of propylene glycol monomethyl ether acetate, and added in a nitrogen atmosphere. 1.25 parts by weight of nitrogen diisobutyronitrile was reacted at 80 ° C for 7 hours. Thereafter, nitrogen gas bubbling was stopped, the temperature was raised to 100 ° C, and the mixture was stirred for 1 hour. 0.124 g of tetraethylammonium chloride was added thereto, and the mixture was stirred at 80 ° C to dissolve it, and 23.4 g of glycidyl methacrylate and 23.90 g of propylene glycol monomethyl ether acetate were added dropwise over 1 hour. The solution was further prepared by adding propylene glycol monomethyl ether acetate so that the solid content concentration became 40%. The thus obtained resin P-4 has a weight average molecular weight of about 8,000 in terms of polystyrene measured by GPC, and is acid. The value is 100 mg-KOH/g.

<Synthesis Example 5: Synthesis of Resin P-5>

The methacrylic acid of the resin P-4 was changed to acrylic acid, and the synthesis was carried out in the same manner to obtain a resin having a weight average molecular weight of about 8000 and an acid value of 100 mg-KOH/g in terms of polystyrene measured by GPC. P-5.

<Synthesis Example 6: Synthesis of Resin P-6>

In Synthesis Example 3, 27.0 parts by weight of the succinic anhydride of the resin P-3 was changed to 68.5 parts by weight of tetrahydrophthalic anhydride (THPA), and the reaction was carried out in the same manner to obtain polystyrene measured by GPC. The converted weight average molecular weight Mw was about 5,500, and the acid value was about 80 mg-KOH/g of the resin P-6.

<Synthesis Example 7: Synthesis of Resin P-7>

In Synthesis Example 2, 68.5 parts by weight of tetrahydrophthalic anhydride (THPA) of the resin P-2 was changed to 27.0 parts by weight of succinic anhydride, and the reaction was carried out in the same manner to obtain polystyrene measured by GPC. The converted weight average molecular weight Mw was about 5,500, and the acid value was about 90 mg-KOH/g of resin P-7.

[2] Preparation of pigment dispersion

74 parts by weight of propylene glycol monomethyl ether acetate, 6.5 parts by weight of CI pigment green, 6.5 parts by weight of pigment Y, and 3.25 parts by weight of an acrylic dispersing agent LPN6919 (manufactured by BYK-Chemie Co., Ltd.) in terms of solid content 3.25 parts by weight of the resin P-1 synthesized in the above Synthesis Example 1 was mixed, and stirred for 3 hours with a stirrer to prepare a solid concentration of 20 Amount of slurry. 100 parts by weight of this mixed solution and 300 parts by weight of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container, and dispersed by a paint shaker for 6 hours to prepare a pigment dispersion liquid.

[3] Preparation of colored resin composition

In the pigment dispersion prepared in the above "[2] Preparation of Pigment Dispersion", the agitation binder resin, the polymerizable monomer, the photopolymerization starting component, and the like are mixed so as to have the composition shown in Table 1 below. As a surfactant of the other component, a solvent (propylene glycol monomethyl ether acetate) was added so that the solid content concentration became 20% by weight to obtain a colored resin composition.

Furthermore, the foreign matter was finally removed by filtration using a 5 μm wedge type filter (a circular small disposable filter: Disposable syringe filter unit).

Each of the compounds in Table 1 is as follows.

M-520: a pentafunctional acrylate containing a carboxyl group, an acid value of 25 mg-KOH/g, M-520 (manufactured by Toagosei Co., Ltd.)

M-510: a trifunctional acrylate containing a carboxyl group, acid value 95 mg-KOH/g, M-510 (manufactured by Toagosei Co., Ltd.)

Monomer mixture A: a mixture of DPHA and a compound represented by the following structural formula (acid value: 35 mg-KOH/g)

CBX-1N: (2,2,2-tripropenyloxymethylethyl phthalate) Acid value 85 mg-KOH/g (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

OXE-02: 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidine)ethanone (manufactured by BASF Corporation) )

Irgacure 907: 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one (manufactured by BASF Corporation)

PET-P: pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by Dian Chemical Co., Ltd.)

MEGAFAC F475: Fluorine-based surfactant (manufactured by DIC Corporation)

[4] Evaluation method [4-1] Determination of Dissolution Time of Colored Resin Composition

The colored resin compositions described in Table 1 were spin-coated on a glass substrate on which chromium was deposited, and prebaked for 3 minutes using a hot plate at 80 °C. The coating rotation speed was prepared in such a manner that it became a color coordinate y=0.594 after baking. When spray-developing using a 0.04% by weight aqueous potassium hydroxide solution at a developer temperature of 23 ° C and a pressure of 0.25 MPa, the unexposed portion of the colored resin composition is completely dissolved in the developer, and the substrate is exposed. It is the dissolution time of the colored resin composition.

The results are summarized in Table 2.

[4-2] Determination of profile shape

The colored resin composition described in Table 1 was applied onto a glass substrate (AN100) in the same manner as in [4-1], and pre-baked, followed by high pressure, using a pattern mask of a color filter. The mercury lamp was exposed at 60 mj/cm ² . Thereafter, spray development was carried out for 40 seconds using a 0.04% by weight aqueous potassium hydroxide solution at a developer temperature of 23 ° C and a pressure of 0.25 MPa. After the substrate is developed, it is rinsed with sufficient water and then dried with clean air. Then, it was baked in an oven at 230 ° C for 30 minutes. The film thickness of the colored resin composition was 2.0 μm. The position of the pattern obtained in this manner was changed, and the shape of each section was observed by an electron microscope at 10,000 times.

The results are summarized in Table 2.

Further, the evaluation of the cross-sectional shape is as follows, and is the shape described in Fig. 2, respectively.

◎: Super positive cone

○: Positive cone

△: roughly vertical

×: inverted cone

[5] Results

As shown in Table 2, the pixel formed using the colored resin composition of the present invention has a short solubility in a developing solution and a cross-sectional shape of a forward taper.

Therefore, since the cross section of the pixel formed by using the colored resin composition of the present invention has a forward taper shape, when a conductive film such as ITO is formed, problems such as disconnection are less likely to occur, and the dissolution time in the developer is short. Therefore, the manufacturing yield is affected by the dissolution time.

That is, it is a colored resin composition in which the cross-sectional shape of the obtained pixel which is previously difficult to achieve at the same time in the trade-off relationship is a forward taper and a dissolution time in the developer is short.

Therefore, the color filter having the pixel formed using the colored resin composition of the present invention, and the liquid crystal display device and the organic EL display device having the color filter are of high quality.

10‧‧‧ Transparent support substrate

20‧‧ ‧ pixels

30‧‧‧Organic protective layer

40‧‧‧Inorganic oxide film

50‧‧‧Anode

51‧‧‧ hole injection layer

52‧‧‧ hole transport layer

53‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL device having a color filter of the present invention.

Fig. 2 is a representative micrograph of the cross-sectional shape of a pixel after development.

10‧‧‧ Transparent support substrate

20‧‧ ‧ pixels

30‧‧‧Organic protective layer

40‧‧‧Inorganic oxide film

50‧‧‧Anode

51‧‧‧ hole injection layer

52‧‧‧ hole transport layer

53‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

Claims (11)

A colored resin composition comprising: (A) a pigment, (B) a solvent, (C) a binder resin, and (D) a polymerizable monomer, the (C) binder resin comprising at least a lower layer The unsaturated group-containing resin obtained by the addition of the copolymer (C-4) and (C-3) obtained by copolymerization (C-4) and (C-5), and (D) a polymerizable monomer a monomer containing an acid group, (C-1): a compound having an unsaturated bond and an epoxy group in one molecule (C-3): a compound having an unsaturated bond copolymerizable with the above (C-1) (C-4): Unsaturated carboxylic acid (C-5): polybasic acid anhydride. The colored resin composition of the first aspect of the invention, wherein the copolymerization system obtains a copolymer obtained by copolymerizing (C-1), (C-3) and (C-2), (C- 2) A compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond in one molecule. The colored resin composition of the first aspect of the invention, wherein the acid group-containing monomer has an acid value of 10 mg-KOH/g or more and 150 mg-KOH/g or less. The colored resin composition of claim 1, wherein the (C-4) unsaturated carboxylic acid is methacrylic acid. The colored resin composition of the first aspect of the invention, wherein the ratio P of the polymer solid content P in the colored resin composition to the content M of the solid content of the colored resin composition is 0.5. Above, 4.5 or less. The colored resin composition of the first aspect of the invention, wherein the (A) pigment is contained in an amount of 28% by weight or more and 45% by weight or less based on the total solid content. The colored resin composition of claim 1, wherein the (A) pigment comprises a zinc bromide phthalocyanine pigment. The colored resin composition of claim 1, further comprising (E) at least one of a photopolymerization starting component and a thermal polymerization starting component. A color filter comprising a pixel formed using the colored resin composition according to any one of claims 1 to 8. A liquid crystal display device characterized by having the color filter of claim 9th. An organic EL display device characterized by having a color filter of claim 9th.