JP2013140346A - Colored resin composition, color filter, liquid crystal display device and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition having a forward tapered cross-section of an obtained pixel and high solubility to a developer which are in a trade-off relation and hard to be achieved simultaneously.SOLUTION: A colored resin composition contains (A) a pigment, (B) a solvent, (C) a binder resin and (D) a polymerizable monomer. The (C) binder resin contains a specific unsaturated group-containing resin and the (D) polymerizable monomer contains an acid group-containing monomer.

Description

  The present invention resides in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

  In recent years, color filters tend to be used not only for monitors but also for televisions in liquid crystal display (LCD) applications. With the trend of the expansion of applications and energy saving, color filters are required to have high color characteristics in terms of chromaticity and contrast. In addition, color filters for image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction of color unevenness and improvement of color resolution, and high definition is also desired. ing.

  As described above, in recent years, the demand for high color reproducibility of color filters has increased, and colored resin compositions tend to have high pigment concentrations. However, when a colored pattern is formed by a photolithographic method using a colored resin composition having a high pigment concentration, the pigment is not sufficiently exposed because it prevents or absorbs the transmission of ultraviolet rays. There is a tendency that deep curability is not obtained. As a result, an undercut is likely to occur in the development process, and a colored pattern having a reverse tapered shape in cross section is formed. When a conductive film such as ITO is formed, problems such as disconnection occur.

In order to solve this problem, for example, Patent Document 1 discloses the use of a colored resin composition containing a specific polymerizable compound.
However, in Patent Document 1, there is a problem that the dissolution time in the developer becomes long, and the dissolution time tends to decrease due to the long dissolution time.
On the other hand, in order to shorten the dissolution time, for example, Patent Document 2 discloses a photopolymerization initiator having a tertiary amine structure, one or more acidic functional groups, and three or more photocurable functional groups. It is disclosed about using an organic compound.

JP 2009-288313 A JP 2004-287230 A

However, in the colored resin composition described in Patent Document 2, on the contrary, it has been found that problems such as disconnection due to the tapered shape may occur.
That is, in the conventional technology as described above, in the colored resin composition having a high pigment concentration, the disconnection suppression due to the taper shape, that is, the cross-sectional shape is a forward taper, and the solubility in the developer is improved. It was a trade-off relationship and it was difficult to achieve both.

Therefore, the present invention has a trade-off relationship, and it has been difficult to achieve both of them, and it is an object to provide a colored resin composition in which the cross-sectional shape of the obtained pixel has a forward taper and is highly soluble in a developer. And
Another object of the present invention is to provide a color filter having pixels formed using the colored resin composition, a high-quality liquid crystal display device, and an organic EL display device.

As a result of intensive studies, the present inventors, as a result, are (C) a binder resin containing a specific unsaturated group-containing resin, and (D) a polymerizable monomer containing a acid group-containing monomer. The present inventors have found that the above problems can be solved and have reached the present invention.
That is, the present invention has the following configuration.
(1) It contains (A) pigment, (B) solvent, (C) binder resin and (D) polymerizable monomer, and (C) binder resin is at least the following (C-1) and (C-3) An unsaturated group-containing resin obtained by adding (C-4) and (C-5) to a copolymer obtained by copolymerizing (hereinafter, referred to as “specific unsaturated group-containing resin”). And (D) the polymerizable monomer contains an acid group-containing monomer.
(C-1); Compound (C-3) having an unsaturated bond and an epoxy group in one molecule; Compound (C-4) having an unsaturated bond copolymerizable with the above (C-1); Unsaturated carboxylic acid (C-5); polybasic acid anhydride (2) A copolymer obtained by copolymerizing the copolymer (C-1), (C-3) and the following (C-2) It is a polymer, The colored resin composition as described in said (1) characterized by the above-mentioned.
(C-2); a compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in one molecule and an unsaturated bond.
(3) The colored resin composition according to (1) or (2) above, wherein the acid value of the acid group-containing 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 (1) to (3), wherein the (C-4) unsaturated carboxylic acid is methacrylic acid.
(5) Ratio of polymer solid content P in the colored resin composition to monomer solid content M in the colored resin composition, P / M ratio is 0.5 or more and 4.5 or less The colored resin composition according to any one of (1) to (4), wherein the colored resin composition is any one of the above.
(6) The colored resin composition according to any one of (1) to (5), wherein the pigment (A) is contained in a total solid content of 28% by weight to 45% by weight. object.
(7) The colored resin composition according to any one of (1) to (6), wherein the (A) pigment contains a brominated zinc phthalocyanine pigment.
(8) The colored resin composition according to any one of (1) to (7), further comprising (E) at least one of a photopolymerization initiation component and a thermal polymerization initiation component. object.
(9) A color filter comprising a pixel formed using the colored resin composition according to any one of (1) to (8).
(10) A liquid crystal display device comprising the color filter according to (9). (11) An organic EL display device comprising the color filter according to (9).

The pixel formed using the colored resin composition of the present invention has a forward tapered cross-sectional shape, and when a conductive film such as ITO is formed, problems such as disconnection hardly occur and the dissolution time in the developer Therefore, the production yield due to the dissolution time is likely to decrease.
In other words, the colored resin composition of the present invention can satisfy both a trade-off relationship between the cross-sectional shape of the obtained pixel and a forward taper and high solubility in a developing solution. .

  Moreover, the color filter containing the pixel formed using the colored resin composition of this invention, the liquid crystal display device and organic electroluminescent display device containing this color filter are high quality.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention. It is a typical microscope picture of the cross-sectional shape in the pixel after image development.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".

Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.
In the present invention, “coloring material” means both “dye” and “pigment”. Furthermore, “aromatic ring” means “aromatic hydrocarbon ring” and “aromatic heterocyclic ring”. It shall mean both.
Moreover, terms such as “CI Pigment Green” mean a color index (CI).

<Colored resin composition>
The colored resin composition of the present invention contains (A) a pigment, (B) a solvent, (C) a binder resin and (D) a polymerizable monomer, and the (C) binder resin contains a specific unsaturated group-containing resin. And (D) the polymerizable monomer contains an acid group-containing monomer. Moreover, it contains (E) a photopolymerization initiation component and / or a thermal polymerization initiation component, and other optional components as necessary.

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

[(C) Binder resin]
In the colored resin composition of the present invention, the (C) binder resin is obtained by copolymerizing (C-4) and (C-) with at least the following copolymer (C-1) and (C-3). 5) containing an unsaturated group-containing resin obtained by adding.
(C-1); Compound (C-3) having an unsaturated bond and an epoxy group in one molecule; Compound (C-4) having an unsaturated bond copolymerizable with the above (C-1); Unsaturated carboxylic acid (C-5); polybasic acid anhydride

  Specific examples of the compound (C-1) having an unsaturated bond and an epoxy group in one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate. Is mentioned. Preferably, it is glycidyl (meth) acrylate. These can be used alone or in combination of two or more.

Specific examples of the compound (C-3) having an unsaturated bond copolymerizable with (C-1) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 -Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meta) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate An ester compound containing an alicyclic group of an unsaturated carboxylic acid such as
Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;
Ester compounds containing an aromatic ring of an unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
And maleimide compounds such as N-phenylmaleimide.
These can be used alone or in combination.

  The copolymers in the present invention (copolymers obtained by copolymerizing at least (C-1) and (C-3)) are (C-1), (C-3) and (C-2). ): It is a copolymer obtained by copolymerizing a compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in one molecule and an unsaturated bond, This is preferable in terms of improving the strength of the obtained pixel.

  As (C-2), specifically, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, The compound represented by following formula (1) is mentioned. These can be used alone or in combination.

(In formula (I), R ¹ represents a hydrogen atom or a methyl group.)
Specifically, the unsaturated carboxylic acid (C-4) is preferably acrylic acid or methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. In addition to these acrylic acid and methacrylic acid, other acids can be used. Specifically, as the other acid, at least one carboxylic acid selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid can be used in combination. A monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can also be used in combination.

The polybasic acid anhydride (C-5) is used for imparting alkali developability to the binder resin. Specifically, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride Examples thereof include polybasic acid anhydrides such as acid, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Tetrahydrophthalic anhydride or succinic anhydride is preferable. These can 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 components derived from each of (C-1) to (C-3) is as described above. It is preferable to be in the following range in terms of mole fraction with respect to the total number of moles of the constituent components constituting the copolymer.
Structural units derived from (C-1); 2-98 mol%
Structural units derived from (C-2); 2 to 90 mol%
Structural units derived from (C-3); 2 to 65 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (C-1); 40 to 80 mol%
Structural units derived from (C-2); 5 to 40 mol%
Structural units derived from (C-3); 5 to 30 mol%
Further, next, (C-4) and (C-5) are added to the copolymer to give the resin solubility in a developer and light / thermosetting.

The addition amount of (C-4) is 0.5 to 1.0 equivalent with respect to 1.0 equivalent of epoxy group in the resin obtained by polymerizing (C-1) to (C-3). Preferably it is 0.7-1.0 equivalent.
When the composition ratio of (C-4) is within the above range, sufficient photocurability and thermosetting properties can be obtained, and sensitivity and reliability are excellent.
The addition amount of (C-5) is 50 to 100%, preferably 60 to 100%, in terms of a molar fraction with respect to the amount of hydroxyl group produced when (C-4) is reacted.

When the composition ratio of (C-5) is within the above range, it is preferable because it is excellent in solubility in an alkali developer and hardly generates a residue.
The polystyrene-reduced weight average molecular weight measured by GPC in the specific unsaturated group-containing resin is usually 4,000 or more, preferably 4,500 or more, more preferably 5,000 or more, and usually 100,000 or less, preferably 20 15,000 or less, more preferably 15,000 or less.

Within the above range, it is preferable because film loss is unlikely to occur during development, and the non-pixel portion can be easily removed during development.
The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the specific unsaturated group-containing resin is preferably 1.5 to 6.0, and more preferably 2.0 to 4.0. The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) is preferably from 1.5 to 6.0 because the developability is excellent.

(Other resins)
The colored resin composition of the present invention may contain other binder resins in addition to the specific unsaturated group-containing resin. For example, JP-A-7-207211, JP-A-8-259876, JP-A-10 -300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, etc. can do.

(Content)
The binder resin (C) used in the colored resin composition of the present invention is usually contained in the range of 5 to 90% by weight, preferably 10 to 70% by weight, based on the total solid content in the colored resin composition. .
If it is within the above range, the solubility in the developer is sufficient, development residue is not easily generated on the substrate of the non-pixel portion, and the film thickness of the pixel portion of the exposed portion is difficult to occur during development. This is preferable because the slipperiness tends to be good.
In the present invention, it is preferable that all of the resins contained as the binder resin (C) are specific unsaturated group-containing resins, that is, the specific unsaturated group-containing resin is contained within the above range. preferable.

[(D) Polymerizable monomer]
The colored resin composition of the present invention includes an acid group-containing monomer in (D) the polymerizable monomer.

(D) The polymerizable monomer is a polymerizable low-molecular compound, preferably an addition-polymerizable compound having at least one ethylenic double bond (hereinafter sometimes referred to as “ethylenic compound”). .
That is, the acid group-containing monomer in the present invention is a polymerizable low molecular compound and may contain an acid group, and is preferably an ethylenic compound containing an acid group.

The acid group is preferably a carboxyl group in terms of good compatibility with other components contained in the colored resin composition, particularly with the 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.
As an acid group containing monomer, the ester compound of an aliphatic polyhydroxy compound and unsaturated carboxylic acid is mentioned, for example.

A compound obtained by modifying an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a dibasic acid anhydride to introduce a carboxyl group, or an aromatic compound having three or more photocurable functional groups with concentrated sulfuric acid or fuming sulfuric acid Examples thereof include compounds in which a sulfonic acid group has been introduced by modification.
The photocurable functional group is preferably an acryloilo group, and particularly preferably a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

  The acid group to be introduced is preferably a carboxyl group from the viewpoint of good alkali developability. As particularly preferred acid group-containing monomers, pentaerythritol having one or more acidic groups and three or more photocurable functional groups in one molecule, or dipentaerythritol with acrylic acid and succinic anhydride or phthalic anhydride, anhydrous Examples include those obtained by adding trimellitic acid, and those obtained by adding acrylic acid and succinic anhydride or phthalic anhydride or trimellitic anhydride to dipentaerythritol.

Of these, succinic anhydride or phthalic anhydride is preferred as the acid anhydride to be added because it is easy to balance the solubility in the developer and the photocurability.
Examples of the acid group-containing monomer include a compound represented by the following formula (2) (hereinafter sometimes referred to as “compound (2)”) or a compound represented by the following formula (3) (hereinafter referred to as “compound (3)”. ) ”May be preferred).
(About compound (2))

(In the above formula (2),
X ¹ represents a direct bond, a hydrocarbon group that may have a substituent, a heterocyclic group that may have a substituent, or an aromatic hydrocarbon ring group that may have a substituent. .
R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent. However, R ¹¹ and R ¹² may be bonded to each other to form a ring.

In addition, when several -CR < ¹¹ > R < ¹² >-is contained in 1 molecule, each may be the same and may differ.
l is an integer from 1 to 12,
n is an integer from 0 to 12,
m represents an integer of 1 to 3. )

(For ^{X 1)}
X ¹ represents a direct bond, a hydrocarbon group that may have a substituent, a heterocyclic group that may have a substituent, or an aromatic hydrocarbon ring group that may have a substituent. .
The hydrocarbon group for X ¹ may be linear, branched or cyclic, and includes an alkylene group having usually 1 or more, usually 8 or less, preferably 5 or less. .
Specific examples include a methylene group, an ethylene group, an n-propylene group, a 2-propylene group, an n-butylene group, an isobutylene group, a tert-butylene group, and a cyclohexylene group.

The heterocyclic group in X ¹ may be any 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 for 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 3 to 10. 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 furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolo Pyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring , Isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, thiazole ring, oxazole ring, thiadiazole ring, phthalimide ring, piperidine , Pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperazine ring, morpholine ring, indoline ring, isoindoline ring, piperidine ring and the like.

The aromatic hydrocarbon ring group for X ¹ may be a single ring or a condensed ring, and is not particularly limited as long as it has 5 to 18 carbon atoms to form the ring. Examples thereof include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring having a free valence.

The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.
X ¹ is preferably an aromatic hydrocarbon ring, and particularly preferably a benzene ring from the viewpoint of easy synthesis.
Examples of the substituent that the hydrocarbon group, heterocyclic group, and aromatic hydrocarbon ring group in X ¹ may have include the following (substituent group W).

(Substituent group W)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy group, alkyl having 2 to 9 carbon atoms A carboxyl group, a sulfonic acid amide group, a sulfone alkylamide group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, and an alkyl group having 1 to 4 carbon atoms are bonded. A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and 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.
A hydrogen atom or a methyl group is particularly preferable because a crosslinking reaction easily occurs.
Examples of the substituent that the alkyl group in R ¹ may have include those described above (Substituent Group W).

(About R ¹¹ and R ¹² )
R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a ring.
In addition, when a plurality of —CR ¹¹ R ¹² — is contained in one molecule, R ¹¹ and R ¹² may be the same or different from each other, but the compound can be easily synthesized. It is preferable that a plurality of —CR ¹¹ R ¹² — are the same.

(About l and n)
l represents an integer of 1 to 12, and n represents an integer of 0 to 12.
In terms of easy synthesis, l is preferably 1 to 5, more preferably 1 to 2.
N is preferably 2 to 5 and more preferably 2 in terms of easy synthesis.
When a plurality of l and n are contained in one molecule, each may be the same or different.

(About m)
m represents an integer of 1 to 3.
Among these, m is preferably 1 or 2, particularly preferably 1, in terms of good solubility in an alkali developer and curability of the obtained pixel.
(Molecular weight)
The molecular weight of the compound (2) is usually 400 or more, preferably 500 or more, and usually 2000 or less, preferably 1800 or less.

It is preferable at the point which is easy to manufacture a compound as it is in the said range.
(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 are each independently a carbon atom that may have a hydrogen atom or a substituent. Represents a 1-4 alkyl group.
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.

In addition, a 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 in each molecule. Or different.
a and b each independently represent an integer of 1 to 3,
l ^{3 to} l ⁶ each independently represents an integer of 1 to 12,
n ³ ~n ⁶ each independently represents an integer of 0 to 12. )
(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 meaning as R ² in the compound (2). The preferred embodiment 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 are synonymous with R ¹¹ and R ¹² in the compound (2). The preferred embodiment is also the same.
(About l ^{3 to} l ⁶ and n ^{3 to} n ⁶ )
l ^{3 to} l ⁶ have the same meaning as l in the compound (2). The preferred embodiment is also the same.
^Moreover, n 3 ~n ⁶ has the same meaning as n in the compound (2). The preferred embodiment is also the same.

(About a and b)
a and b each independently represent an integer of 1 to 3.
a and b are preferably 1 to 2, particularly preferably 1.
A and b may be the same or different.
(Molecular weight)
The molecular weight of the compound (3) in the present invention is usually 400 or more, preferably 500 or more, and usually 1000 or less, preferably 800 or less.

It is preferable at the point which is easy to synthesize | combine a compound within the said range.
Although the preferable specific example of an acid group containing monomer is shown below, this invention is not limited to these.
(Concrete example)

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
The acid value when the acid group-containing monomer is a mixture 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 150 mg-KOH / g or less. Preferably it is 110 mg-KOH / g or less, More preferably, it is 100 mg-KOH / g or less.

Within the above range, it is preferable to easily balance the solubility in the developer and the photocurability.
(Other monomers)
The colored resin composition of the present invention may contain a monomer other than the acid group-containing monomer in the (D) polymerizable 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 polymerizable monomer (D) in the colored resin composition of the present invention is usually 1% by weight or more, preferably 5% by weight or more, more preferably 8% by weight or more in the total solid content. It is 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly 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 in the total (D) polymerizable monomer.
In addition, it is preferable that the whole quantity of (D) polymerizable monomer is an acid group containing monomer, and an upper limit is 100 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.

Within the above range, it is easy to balance alkali development solubility and curability and cross-sectional shape, which is preferable.
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, pigments of various colors such as a red pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be usually used as the (A) pigment.

Examples of chemical structures of various pigments include organic pigments such as azo, quinacridone, phthalocyanine, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used.
Among these, in particular, when a phthalocyanine pigment is used, the pigment concentration tends to be high, and it is difficult to adjust the dissolution time in an alkali developer, and thus the effect of the present invention is easily obtained. In particular, when a metal halide phthalocyanine pigment is used, the tendency is strong, and the effect of the present invention is remarkably obtained.

Ordinary metal phthalocyanines have 16 hydrogen atoms in one molecule, and these hydrogen atoms are substituted with bromine atoms or chlorine atoms in halogenated metal phthalocyanines, which are preferably used in the present invention. Is a brominated metal phthalocyanine pigment.
Of these, a brominated metal phthalocyanine having an average of 13 or more bromine atoms in one molecule is preferable because it exhibits extremely high transmittance and is suitable for forming a green pixel of a color filter. Furthermore, brominated zinc phthalocyanine having 13 to 16 bromine atoms in one molecule and not containing chlorine or having an average of 3 or less in one molecule is preferable, and in particular, an average of 14 bromine atoms in one molecule is 14 Brominated metal phthalocyanine having ˜16 and containing no chlorine atom in one molecule or having an average of 2 or less is preferred. Preferred brominated metal phthalocyanines include brominated copper phthalocyanine and brominated zinc phthalocyanine. The brominated copper phthalocyanine is preferably C.I. I. Pigment Green 36. The brominated zinc phthalocyanine is preferably C.I. I. Pigment Green 58.

In addition, specific examples of other green pigments represented by pigment numbers are C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 45, 48, 50, 51, 54, 55, and the like.
Furthermore, although the specific example of pigments other than the green pigment which can be used for this invention is shown by a pigment number, it is not limited by these illustrations.

  First, as a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, and the like.

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

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 17 175, 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 <Pigment Y> below (hereinafter referred to as “Pigment Y”).

<Pigment Y>
A compound obtained by inserting another compound into a 1: 1 complex of azobarbituric acid with nickel represented by the following structural formula or a compatible isomer thereof.

  Examples of the other compounds include compounds represented by the following formula (I-1).

Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, pigment Y, and the like, more preferably C.I. I. Pigment Yellow 138, 139 and Pigment Y.
Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Of these, C.I. I. Pigment violet 19, 23, etc., more preferably C.I. I. Pigment violet 23 and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, C.I. I. Pigment orange 38, 71 and the like.

Further, as described later, a colored resin composition may be prepared to form a resin black matrix of a color filter. In that case, a black pigment can be used. In addition, a black pigment may be used independently and may mix and use pigments, such as red, green, and blue. Further, it may be an inorganic pigment or an organic pigment.
The pigment in the present invention is C.I. I. (Color index) Pigment Red 58 is particularly preferable because the effects of the present invention can be easily obtained.

Examples of inorganic pigments that can be used in the present invention include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.
In addition, the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, as the (A) pigment, a red pigment and a yellow pigment can be used in combination, or a green pigment and a yellow pigment can be used in combination.

The average primary particle size of the pigment (A) according to 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. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 20 nm to 60 nm is particularly preferable.
By making the average primary particle size of the pigment (A) used within the above range, the depolarization characteristics are kept good, high contrast and transmittance are realized, dispersion stability is good, heat resistance and light resistance A colored resin composition having excellent properties can be obtained.

The primary particle diameter of the pigment can be determined by the following method.
First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). However, in the case of organic pigments, the particle diameter of each pigment particle is the diameter corresponding to the area circle converted to the diameter of a circle having the same area, and the particle diameter of each of plural (usually about 200 to 300) pigment particles. Ask for. Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.

The pigment (A) thus obtained may be used alone, but one or two or more pigments can be mixed and used within a range not impairing the effects of the present invention.
The content of the pigment (A) 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% by weight based on the total solid content. % By weight or more, preferably 20% by weight or more, more preferably 28% by weight or more.

(A) By setting the pigment content within the above range, the film thickness with respect to the color density does not become too large, and there is no adverse effect on the gap control during the formation of a liquid crystal cell, and sufficient image formability is obtained. In addition, the dispersed state of the pigment is maintained, and aggregation and sedimentation are unlikely to occur. As a result, problems such as thickening and lowering of brightness and contrast can be solved.
[(B) Solvent]
(B) The solvent has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition. The solvent (B) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin composition, and a solvent having a boiling point in the range of 100 to 200 ° C. is preferably selected. More preferably, it has a boiling point of 120-170 ° C.

Examples of such solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;

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, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;

Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

In the solvent, glycol monoalkyl ethers are preferable in that the dispersibility of the pigment (A) is good. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
Also, from the viewpoint of good balance of coating properties and surface tension of the colored resin composition and relatively high solubility of the constituent components in the composition, it is possible to use a mixture of glycol alkyl ether acetates as a solvent. More preferred.

In addition, the use amount of glycol monoalkyl ethers is preferably 5 to 50% by weight in the total amount of the solvent (B) in that the viscosity of the colored resin composition is appropriate and the storage stability is good. 30% by weight is more preferred.
Moreover, from the viewpoint of suitability for the slit coat method corresponding to the recent large substrates, etc., 1
It is also preferable to use a solvent having a boiling point of 50 ° C. or higher in combination. In this case, the content of such a high boiling point solvent is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight based on the total amount of the solvent (B).

Within the above range, foreign matter defects due to precipitation and solidification of pigments and the like at the slit nozzle tip are difficult to occur, and the drying speed is moderate. , Pre-baked pin marks are difficult to occur.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .

In the colored resin composition of the present invention, the content of the solvent (B) is not particularly limited, but is usually 99% by weight or less, usually 75% by weight or more, preferably 80% by weight or more, more preferably 82% by weight or more. It is.
Within the above range, the viscosity is suitable for coating and is preferable in that it is suitable for forming a coating film.

[Dispersant]
The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability. For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, a polymer copolymer alkylammonium salt or phosphate ester salt, a cationic comb graft polymer, and the like can be given. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable. In particular, a modified acrylic copolymer is preferable. Among these, a block copolymer composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom has an amine value of 80 mg-KOH / g or more and 150 mg. What is -KOH / g or less (effective solid content conversion) is especially preferable. More preferably, it is 100-140 mg-KOH / g.

Within the above range, the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.
Of these, the (meth) acrylic block copolymer described in JP-A-2009-025813 is preferable. The acrylic block copolymer can disperse the pigment (A) very efficiently. This is presumably because the molecular arrangement is controlled, so that there are few structures that obstruct the dispersant when adsorbing to the pigment.

In the present invention, the acrylic block copolymer is preferably an AB block comprising an A block and a B block and / or an ABA block copolymer.
The B block constituting the acrylic block copolymer has an amino group, and the amino group is preferably —NR ⁷¹ R ⁷² (provided that R ⁷¹ and R ⁷² each independently have a substituent). A cyclic or chain alkyl group which may be substituted, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. A preferable example is represented by the following formula, for example.

^{(However, R 71} and ^{R 72} has the same meaning as above ^{R 71} and ^{R 72, R 73} is one or more alkylene groups having a carbon ^{number, R 74} represents a hydrogen atom or a methyl group.)
Among them, R ⁷¹ and R ⁷² are preferably methyl groups, R ⁷³ is preferably a methylene group or an ethylene group, and R ⁷⁴ is preferably a methyl group. Examples of such a compound include a partial structure represented by the following formula.

  Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B block within a range not impairing the effects of the present invention. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer.

On the other hand, in the present invention, the A block of the dispersant is not particularly limited as long as the A block is solvophilic and is composed of a monomer copolymerizable with the monomer constituting the B block described above.
Examples of the A block include polymer structures obtained by copolymerizing comonomers such as styrene monomers, (meth) acrylate monomers, (meth) acrylate monomers, vinyl acetate monomers, glycidyl ether monomers, and the like. It is done.

The dispersant in the present invention is an AB block or ABA block copolymerized polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

The amine value of the dispersant (in terms of effective solid content) is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mg-KOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
Further, the acid value of this block copolymer is preferably lower, although it depends on the presence and type of acidic groups that form the acid value, and is usually 50 mg-KOH / g or less, preferably 40 or less, more preferably. Is 30 or less.

When the average primary particle size of the pigment is small, the specific surface area increases and the amount of adsorbing dispersant per unit area decreases. In this case, the dispersant made of the copolymer is preferably used because it is more effective than the other dispersants.
The dispersant 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 100% by weight or less, based on the total amount of the pigment (A) in the colored resin composition. It is.
The colored resin composition of the present invention may contain other dispersants as long as the effects of the present invention are not impaired. Examples of other dispersants include those described in JP-A-2006-343648, for example.

[Dispersion aid]
The colored resin composition of the present invention may further contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total (A) pigment. More preferably, it is 10 weight% or less, More preferably, it is 5 weight% or less.
Within the above range, the effect as a dispersion aid is effectively obtained, and this is preferable in terms of good dispersibility and dispersion stability.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of the resin selected from the above-mentioned (C) binder resin as the following dispersion resin.
Specifically, in [Preparation Method of Colored Resin Composition], which will be described later, by adding (C) binder resin together with the components such as the above-mentioned dispersant, the (C) binder resin is combined with the dispersant. It contributes to the dispersion stability of the pigment (A) by a synergistic effect. As a result, the amount of dispersant added may be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the pigment dispersion.
As the dispersion resin, the above-mentioned various (C) binder resins 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 preferably 300 mg-KOH / g or less, 200 mg-KOH / G or less is more preferable, and 150 mg-KOH / g or less is most preferable. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

  The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

[(E) Photopolymerization initiation component and thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains at least one of (E) a photopolymerization initiation component and a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, when the colored resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (D), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (E) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(E1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(E2) component”). ")" And a sensitizing dye (hereinafter also referred to as "(E3) component").

[(E) Photopolymerization initiation component]
The (E) photopolymerization initiating component in the present invention is usually a mixture of (E1) a photopolymerization initiator and, if necessary, (E2) a polymerization accelerator and (E3) an additive such as a sensitizing dye. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of (E1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-
Acetyloxime), and compounds represented by the following formula (XI).

(In 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. An alkyl group, each of 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 alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.
X represents a divalent aromatic hydrocarbon ring group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.

Z represents an aromatic ring group which may have a substituent. )
Of the compounds represented by the formula (XI), compounds in which X is a carbazole ring which may have a substituent are preferable. Specifically, compounds represented by the following formula (XII) Among them, the compound represented by the following formula (XIII) is particularly preferable.

(In the formula, R ¹⁰¹ , R ¹⁰² and Z have the same meanings as in formula (XI). R ^{103 to} R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent.)

(In the formula, 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-acetyl-N-acetoxyamino group.
* Represents a binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group. )
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (E2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.
Further, (E3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(E3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content of these (E) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight in the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less.
Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed portion in the developer is good, and it is preferable in that it is difficult to induce poor development.

((E) Thermal polymerization initiation component)
Specific examples of the (E) thermal polymerization initiating component that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiating component described in International Publication No. 2009/107734 can be used.
These thermal polymerization initiating components may be used alone or in combination of two or more.

[(F) Chain transfer agent]
The colored resin composition of the present invention preferably contains (F) a chain transfer agent in that the effects of the present invention are more easily obtained.
The (F) chain transfer agent in the present invention refers to a compound that receives a generated radical and transfers the radical to another compound.
The colored resin composition of the present invention contains a compound represented by the following formula (4) as a chain transfer agent (F).

(In said formula (4), p represents the integer of 2-4.
R ³ represents a hydrogen atom or an alkyl group which may have a substituent.
X ² represents a direct bond, a 2-4 quaternary carbon atom, a 2-4 valent heterocyclic group or a 2-4 valent aromatic hydrocarbon ring group.
Multiple contained in one molecule

May be the same or different. )
(For ^{R 3)}
R ³ represents a hydrogen atom or an alkyl group which may have a substituent.
As said alkyl group, carbon number is 1-8 normally, Most preferably, it is 1 or 2.
R ³ is preferably a hydrogen atom from the viewpoint that the reactivity of the compound is high and the surface curability of the resulting film is high.
As the substituent that the alkyl group have in R ^3, for example, those described in the item of the (substituent group Z).

(Substituent group Z)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, acetyloxy group, alkoxycarbonyl group having 2 to 9 carbon atoms, Phenoxycarbonyl group, carbamoyl group, alkyl carbamoyl group having 2 to 9 carbon atoms, phenyl carbamoyl group, sulfamoyl group, alkyl sulfamoyl group having 1 to 8 carbon atoms, phenyl sulfamoyl group, alkyl carbonyl having 2 to 9 carbon atoms Group, benzoyl group, alkylsulfonyl group having 1 to 8 carbon atoms, trifluoromethanesulfonyl group, phenethyl group, hydroxyethyl group, acetylamino group, dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms, Fluoromethyl group, C1-C8 trialkylsilyl group, nitro group A cyano group, a carboxy group, an alkylsulfanyl group having 1 to 8 carbon atoms.

(For ^{X 2)}
X ² represents a direct bond, a 2-4 quaternary carbon atom, a 2-4 valent aromatic hydrocarbon ring group or a 2-4 valent heterocyclic group.
Examples of the aromatic hydrocarbon ring group and the heterocyclic group in X ² include those described in the above section (for compound (2)) (for X ¹ ). The preferred embodiment is also the same.

X ² is preferably a secondary to quaternary carbon atom, and particularly preferably a quaternary carbon atom, from the viewpoint of good storage stability of the compound (4).
In addition, the carbon atom, heterocyclic group and aromatic hydrocarbon ring group in X ² have a substituent represented by other than the following structural formula (hereinafter sometimes referred to as “sulfanyl group-containing structure”). In addition, examples of the substituent include those described in the above section (Substituent group Z).

In the present invention, it is preferable that only the above-described sulfanyl group-containing structure is used as a substituent, and the series of carbon atoms, heterocyclic groups and aromatic hydrocarbon ring groups in X ² is preferably the same as p.
(About p)
p represents an integer of 2 to 4.
In the compound (4), a sulfanyl group that is a reactive site is increased, the reactivity of the compound is increased, and 4 is particularly preferable in that the resulting pixel has sufficient curability.
Specific examples of the compound (4) in the present invention are shown below, but the present invention is not limited thereto.

[Concrete example]
Compounds having two sulfanyl group-containing structures: 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexane Dithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 1,2-benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzene Dithiol, 3,4-dimercaptotoluene, 4-chloro-1,3-benzenedithiol, 2-hexylamino-4,6-dimercapto-1,3,5-triazine, 2-diethylamino-4,6-dimercapto- 1,3,5-triazine, 2-cyclohexylamino-4,6-dimercapto-1,3 5-triazine, ethylene glycol bis (3-mercaptopropionate), 2,5-dimercapto-1,3,4-thiadiazole, 2,2-bis (2-hydroxy-3-mercapto-propoxyphenyl propane,
Compounds having three sulfanyl group-containing structures: trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, 1,2,6-hexanetriol trithioglycolate, etc.
Compounds having four sulfanyl group-containing structures: pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakis (3-mercaptopropionate), etc.
Is mentioned.

(About content)
The content of the chain transfer agent (F) 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 in the solid content of the colored resin composition. It is 10% by weight or less, preferably 8% by weight or less, more preferably 6% by weight or less.
Within the above range, the resulting colored resin composition is preferable in terms of sufficient curability, excellent storage stability of the colored resin composition, and hardly affects the luminance of the obtained pixel.
In addition, the colored resin composition of this invention may contain chain transfer agents other than a compound (4), and should just contain so that the total content of a chain transfer agent may become in the said range. .
However, it is particularly preferable to contain only the compound (4) as the chain transfer agent, and it is preferable to contain the compound (4) within the above range.

[Other optional ingredients]
In addition to the above components, the colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may contain a protective agent, an adhesion improver, a development improver, and the like. As these 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 prepared by an appropriate method. For example, the colored resin composition includes (A) a pigment, (C) a binder resin containing a specific unsaturated group-containing resin, and an acid group-containing monomer ( D) The polymerizable monomer can be prepared by mixing with (B) a solvent and optional components used as necessary.

  Preferably, (A) a pigment is added in (B) a solvent, in the presence of a dispersing agent and, if necessary, a dispersing aid, optionally with (C) a part of a binder resin, for example, a paint shaker, Using a sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like, a pigment dispersion is prepared by mixing and dispersing while grinding. The pigment dispersion contains (C) a binder resin containing a specific unsaturated group-containing resin, and (D) a polymerizable monomer containing an acid group-containing monomer, and (E) a photopolymerization initiating component and / or heat, if necessary. The method of preparing by adding a polymerization start component, another component, etc., and mixing can be mentioned.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display device using them will be described.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made, an epoxy resin, a thermosetting resin, and various glasses.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.

Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
As the radiation used in 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 image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Further, a column structure (photo spacer) by a photolithography method may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
[1] Synthesis of Resin <Synthesis Example 1: Synthesis of Resin P-1>
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction tank to 90 ° C. did.

  Meanwhile, 30 parts by weight of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, 60 parts by weight of methacrylic acid, 110 parts by weight of cyclohexyl methacrylate, t-butylperoxy-2-ethyl Charge 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, and 4.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate in a chain transfer agent tank. Was stabilized at 85 ° C., dripping was started from the monomer tank and the chain transfer agent tank, and polymerization was started. While maintaining the temperature at 85 ° C., dropping was carried out over 135 minutes, and after 60 minutes from the completion of dropping, the temperature was raised to 110 ° C.

  After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 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 charged into the reaction vessel at 110 ° C. as it was. For 9 hours.

After cooling to room temperature, a resin P-1 having a weight-average molecular weight of 12,000 in terms of polystyrene measured by GPC and an acid value of 90 mg-KOH / g was obtained.
<Synthesis Example 2: Synthesis of Resin P-2>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging 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, and then 2.2′-azobis-2-methyl was added. 9.00 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 68.5 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, reacted at 100 ° C. for 3.5 hours, and adjusted by adding propylene glycol monomethyl ether acetate to a solid content concentration of 40%. did. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the resin P-2 thus obtained was about 5500, and the acid value was 92 mg-KOH / g.

<Synthesis Example 3: Synthesis of Resin P-3>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging 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, and then 2.2′-azobis-2-methyl was added. 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was further continued at 100 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol 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 reacted at 100 ° C. for 3.5 hours, and propylene glycol monomethyl ether acetate was added to adjust the solid content concentration to 40%. G of resin P-3 thus obtained
The polystyrene-equivalent weight average molecular weight Mw measured by PC was about 5500, and the acid value was 80 mg-KOH / g.

<Synthesis Example 4: Synthesis of Resin P-4>
93.6 parts by weight of monoacrylate FA-513M having a tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd.) and 36.4 parts by weight of methacrylic acid are dissolved in 150 parts by weight of propylene glycol monomethyl ether acetate, and azobisiso 1.25 parts by weight of butyronitrile was added and reacted at 80 ° C. for 7 hours. Thereafter, nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. To this was added 0.124 g of tetraethylammonium chloride, and the mixture was stirred and dissolved at 80 ° C. Then, a solution in which 23.4 g of glycidyl methacrylate and 23.90 g of propylene glycol monomethyl ether acetate were mixed was added dropwise over 1 hour. Propylene glycol monomethyl ether acetate was added to adjust the partial concentration to 40%. The weight average molecular weight in terms of polystyrene measured by GPC of the resin P-4 thus obtained was about 8000, and the acid value was 100 mg-KOH / g.

<Synthesis Example 5: Synthesis of Resin P-5>
Resin P-4 was synthesized in the same manner using methacrylic acid as acrylic acid, and a resin P-5 having a weight average molecular weight of about 8000 and an acid value of 100 mg-KOH / g as measured by GPC was obtained.
<Synthesis Example 6: Synthesis of Resin P-6>
In Synthesis Example 3, 27.0 parts by weight of succinic anhydride in Resin P-3 was replaced with 68.5 parts by weight of tetrahydrophthalic anhydride (THPA) and reacted in the same manner. The weight average molecular weight Mw in terms of polystyrene measured by GPC Obtained a resin P-6 having an acid value of about 5500 and an acid value of about 80 mg-KOH / g.

<Synthesis Example 7: Synthesis of Resin P-7>
In Synthesis Example 2, 68.5 parts by weight of tetrahydrophthalic anhydride (THPA) in resin P-2 was replaced with 27.0 parts by weight of succinic anhydride, and reacted in the same manner. The weight average molecular weight Mw in terms of polystyrene measured by GPC Obtained a resin P-7 having an acid value of about 5500 and an acid value of about 90 mg-KOH / g.

[2] Preparation of pigment dispersion 74 parts by weight of propylene glycol monomethyl ether acetate, C.I. I. 6.5 parts by weight of Pigment Green 58, 6.5 parts by weight of Pigment Y, 3.25 parts by weight of an acrylic dispersant LPN6919 (manufactured by Big Chemie) in terms of solid content, Resin P-1 synthesized in Synthesis Example 1 Was mixed with 3.25 parts by weight in terms of solid content and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by weight. A stainless steel container was filled with 100 parts by weight of this mixed liquid and 300 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed for 6 hours with a paint shaker to prepare a pigment dispersion.

[3] Preparation of Colored Resin Composition In the pigment dispersion prepared in “[2] Preparation of pigment dispersion”, a binder resin, a polymerizable monomer, and a photopolymerization initiating component are prepared so as to have the composition shown in Table 1 below. In addition, a surfactant was mixed and stirred as a component, and a solvent (propylene glycol monomethyl ether acetate) was added so that the solid content concentration was 20% by weight to obtain a colored resin composition.
In addition, finally, it filtered with the 5 micrometers piece filter, and removed the foreign material.

Each compound in Table 1 is as follows.
M-520: Carboxyl group-containing pentafunctional acrylate, acid value 25 mg-KOH / g, M-520 (manufactured by Toagosei Co., Ltd.)
M-510: carboxyl group-containing trifunctional acrylate, acid value of 95 mg-KOH / g, M-
510 (manufactured by Toagosei)
Monomer mixture A: mixture of DPHA and a compound represented by the following structural formula (acid value: 35 mg-KOH / g)

CBX-1N: (2,2,2-trisacryloyloxymethylethylphthalic acid) acid value 85 mg-KOH / g (manufactured by Shin-Nakamura Chemical Co., Ltd.)
DPHA: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
OXE-02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF)
Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF)
PET-P: pentaerythritol-tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd.)
MegaFuck F475: Fluorosurfactant (manufactured by DIC)
[4] Evaluation Method [4-1] Measurement of Dissolution Time of Colored Resin Composition Each of the colored resin compositions shown in Table 1 was spin-coated on a glass substrate on which chromium was vapor-deposited and applied to a hot plate at 80 ° C. For 3 minutes. The coating rotation speed was adjusted so that the color coordinate y = 0.594 after post-baking. When this was spray-developed using a 0.04 wt% 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 was completely dissolved in the developer, and the substrate The time at which was exposed was defined as the dissolution time of the colored resin composition.

The results are summarized in Table 2.
[4-2] Measurement of cross-sectional shape Using a color filter pattern mask, the colored resin composition shown in Table 1 is applied to a glass substrate (AN100) and prebaked in the same manner as in [4-1]. Then, exposure was performed at 60 mj / cm ² with a high-pressure mercury lamp. Thereafter, spray development was performed for 40 seconds using a 0.04 wt% aqueous potassium hydroxide solution at a developer temperature of 23 ° C. and a pressure of 0.25 MPa. After development, the substrate was rinsed with sufficient water and then dried with clean air. Subsequently, it was post-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 thus obtained was changed, and each cross-sectional shape was observed with an electron microscope at a magnification of 10,000 times.

The results are summarized in Table 2.
In addition, evaluation regarding a cross-sectional shape is as follows, and is a shape as shown in FIG.
◎: Super forward taper ○: Forward taper △: Almost vertical ×: Reverse taper [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 has a forward tapered cross section.
Therefore, the pixel formed using the colored resin composition of the present invention has a forward taper cross section, so that problems such as disconnection are less likely to occur when a conductive film such as ITO is formed, and development. Since the dissolution time in the liquid is short, the production yield due to the dissolution time is high.

In other words, it is a colored resin composition that has a trade-off relationship and has been difficult to achieve in the past, and the cross-sectional shape of the obtained pixel is a forward taper and the dissolution time in the developer is short.
From this, the color filter which has the pixel formed using the colored resin composition of this invention, and the liquid crystal display device and organic electroluminescence display which have this color filter are high quality.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (11)

(A) a pigment, (B) a solvent, (C) a binder resin and (D) a polymerizable monomer,
The (C) binder resin is obtained by adding (C-4) and (C-5) to a copolymer obtained by copolymerizing at least the following (C-1) and (C-3). Including unsaturated group-containing resins,
And (D) the polymerizable monomer contains an acid group-containing monomer.
(C-1); Compound (C-3) having an unsaturated bond and an epoxy group in one molecule; Compound (C-4) having an unsaturated bond copolymerizable with the above (C-1); Unsaturated carboxylic acid (C-5); polybasic acid anhydride The colored resin according to claim 1, wherein the copolymer is a copolymer obtained by copolymerizing (C-1), (C-3) and the following (C-2). Composition.
(C-2): Compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton in one molecule and an unsaturated bond   The colored resin composition according to claim 1, wherein an acid value of the acid group-containing monomer is 10 mg-KOH / g or more and 150 mg-KOH / g or less. (C-4) The colored resin composition according to claim 1, wherein the unsaturated carboxylic acid is methacrylic acid.   The ratio of the polymer solid content P in the colored resin composition to the monomer solid content M in the colored resin composition, and the P / M ratio is 0.5 or more and 4.5 or less. The colored resin composition according to claim 1, wherein:   2. The colored resin composition according to claim 1, wherein the pigment (A) is contained in a total solid content of 28 wt% or more and 45 wt% or less.   The colored resin composition according to claim 1, wherein the pigment (A) contains a brominated zinc phthalocyanine pigment.   The colored resin composition according to claim 1, further comprising (E) at least one of a photopolymerization initiation component and a thermal polymerization initiation component.   It has a pixel formed using the colored resin composition as described in any one of Claims 1-8, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 9. An organic EL display device comprising the color filter according to claim 9.