WO2013080964A1

WO2013080964A1 - Colored composition for color filter, and color filter

Info

Publication number: WO2013080964A1
Application number: PCT/JP2012/080601
Authority: WO
Inventors: 深雪田中; 三上　譲司; 鈴木　雄太; 奈津子小久保; 章乃宮川; 由昌宮沢
Original assignee: 東洋インキＳｃホールディングス株式会社
Priority date: 2011-11-30
Filing date: 2012-11-27
Publication date: 2013-06-06
Also published as: TWI504691B; TW201343806A; KR20140100519A; CN103959109B; KR102004436B1; CN103959109A

Abstract

A colored composition for a color filter, which comprises a coloring agent (A), a binder resin and an organic solvent, said colored composition being characterized by containing a salt-forming compound produced by reacting an acrylic resin having a cationic group and a thermally crosslinkable functional group as side chain groups with an anionic dye and/or a salt-forming compound produced by reacting an acrylic resin having a caionic group as a side chain group and having a glass transition temperature of 50˚C or highr with an anionic dye.

Description

Coloring composition for color filter, and color filter

The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

In recent years, liquid crystal display devices have been evaluated for their space-saving properties, light weight, and power-saving properties due to their thinness, and recently they are rapidly spreading to television applications. For television applications, it is required to further improve the performance such as brightness and contrast, and further improvement of the transmittance and enhancement of the contrast are desired for the color filter which is a member of the color liquid crystal display device. ing.

As a method for producing the color filter, after forming a pattern with a photoresist, a dyeing method for dyeing the pattern, or by forming a transparent electrode of a predetermined pattern in advance, and using a pigment-containing resin dissolved and dispersed in a solvent by voltage application Electrodeposition method for ionization and pattern formation, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curable resin, pigment dispersion using color resist agent in which colorant such as pigment is dispersed in photoresist material Laws, etc. are known. Recently, the pigment dispersion method has become mainstream. However, in a color filter using a pigment as a colorant, the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by pigment particles. As a result, there is a problem that the luminance and contrast of the color liquid crystal display device are likely to be reduced.

As a technique for solving this problem, the practical application of a dye-based curable composition using a dye that can exist in a dissolved state in a medium of the curable composition as a colorant has been studied and proposed (for example, patents). Reference 1). However, the dye used for the color resist agent has problems related to heat resistance, light resistance, and solubility in the resin and the organic solvent used for the resin.

Thus, in order to improve the solubility, a color filter using a salt of an anionic dye and a cationic surfactant as a colorant has been proposed (for example, see Patent Documents 2 and 3). In general, it is known that the solubility of an anionic dye in an organic solvent is increased by changing the sodium sulfonate group (—SO ₃ Na) of the anionic dye to an organic amine salt. In the above colorant, the solubility of the anionic dye in an organic solvent is increased by changing the sodium sulfonate group of the anionic dye to the base salt of the cationic surfactant. However, in these methods, sufficient solubility cannot be obtained with respect to the solvent used when producing the color filter. In addition, since the compatibility with the resin is poor, it is difficult to provide long-term storage stability of the color filter coloring composition and strong adhesion between the coating film and a transparent substrate such as glass. It has not been possible to solve important problems in color filters such as solvent resistance and alkali developability of the film.

Further, as salt forming compounds of anionic dyes, those using a cationic resin as a counter have been studied as crystalline aqueous coloring materials (see, for example, Patent Document 4). In color filter applications that require use in a dissolved state, detailed studies have not been made.

On the other hand, a colored resin composition in which an anionic dye is added to a copolymer solution obtained by copolymerizing a monomer having an amide structure has also been proposed (for example, see Patent Document 5). This is because the amide structure acts as a dyeing point with the anionic dye, thereby stabilizing the dye in the coating film and improving the resistance. However, the method disclosed here has a problem in that since a copolymer and an anionic dye are mixed in an organic solvent, a highly polar dye is not sufficiently dissolved and foreign matter is generated.

On the other hand, in order to improve heat resistance and light resistance, a coloring composition in which a dye is chemically bonded to a polymer has been proposed (for example, see Patent Document 6). However, the solvent resistance and resistance are insufficient only by simply combining the polymer and the dye, and the recent required level of alkali developability could not be satisfied.

JP 1994-75375 A JP 1993-333207 JP 2004-307391 A JP 2005-350648 A JP 2000-352819 A JP 2000-162429 A

The object of the present invention is to provide a color filter coloring composition having excellent storage stability, and no foreign matter is generated in the coating film, and has strong adhesiveness with a transparent substrate such as glass, and has excellent heat resistance and resistance. The object is to provide a color filter having high solvent properties and excellent alkali solubility.

As a result of intensive studies to solve the above problems, the present inventors have found that the resin (B) having a cationic group in the side chain, that is, having a cationic group in the side chain, and having a crosslinkable functional group. A coloring composition for a color filter containing a salt-forming compound (D) obtained by reacting an acrylic resin satisfying at least one having a glass transition temperature of 50 ° C. or higher and an anionic dye (C) However, it has been found that it has high storage stability, no foreign matter is generated on the coating film, is excellent in adhesion, and exhibits high heat resistance in a heat resistance test, and the present invention has been made based on this finding.

That is, the present invention is a color filter coloring composition comprising at least a colorant (A), a binder resin, and an organic solvent,
The colorant (A) contains a salt-forming compound (D) obtained by reacting a resin (B) having a cationic group in the side chain with an anionic dye (C),
The resin (B) having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (1), and the acrylic resin has an acrylic resin having a thermally crosslinkable functional group, The present invention relates to a coloring composition for a color filter, which is selected from an acrylic resin having a glass transition temperature of 50 ° C. or higher and an acrylic resin having a thermally crosslinkable functional group and a glass transition temperature of 50 ° C. or higher.

(In general formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂ , R ₃ , and R ₄ are each independently substituted with a hydrogen atom or an arbitrary substituent. Represents an alkyl group that may be substituted, an alkenyl group that may be substituted with any substituent, or an aryl group that may be substituted with any substituent; ₂ of R ₂ , R ₃ , and R ₄ _May be bonded to each other to form a ring, Q represents an alkylene group, an arylene group, —CONH—R ₅ —, or —COO—R ₅ —, R ₅ represents an alkylene group, and Y ⁻ represents Represents an inorganic or organic anion.)
Further, the present invention is characterized in that the thermally crosslinkable functional group is at least one selected from the group consisting of hydroxyl group, carboxyl group, oxetane group, t-butyl group, isocyanate group, and (meth) acryloyl group. It is related with the coloring composition for said color filters.

Further, in the present invention, the acrylic resin including the structural unit represented by the general formula (1) is a copolymer including a structural unit having a thermally crosslinkable functional group, and the copolymer is the thermal crosslinked The color filter coloring composition according to the invention, which contains 10 to 35% by weight of a structural unit having a functional functional group out of a total of 100% by weight.

Furthermore, the present invention relates to the coloring composition for a color filter, wherein the thermally crosslinkable functional group contains a hydroxyl group.

Furthermore, the present invention relates to the coloring composition for a color filter, wherein the thermally crosslinkable functional group is a hydroxyl group and a carboxyl group.

Furthermore, the present invention relates to the color composition for color filters, wherein the acrylic resin containing the structural unit represented by the general formula (1) has an ammonium salt value of 10 to 200 mgKOH / g.

Further, in the present invention, the salt-forming compound (D) is a mixture of a resin (B) having a cationic group in the side chain and an anionic dye (C) in an aqueous solution, and having a cationic group in the side chain. The present invention relates to the coloring composition for a color filter, which is a compound prepared by removing a salt composed of a counter anion of a resin (B) and a counter cation of an anionic dye (C).

Furthermore, the present invention relates to the coloring composition for a color filter, wherein the main component of the organic solvent is propylene glycol monomethyl ether acetate.

The present invention also relates to the color filter coloring composition, wherein the colorant further contains a pigment.

The present invention also relates to the color filter coloring composition, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

The present invention also relates to a color filter formed from the coloring composition for a color filter.

In the present invention, the resin (B) having a cationic group in the side chain, that is, at least one having a cationic group in the side chain and a crosslinkable functional group, or having a glass transition temperature of 50 ° C. or higher. By using a coloring composition for a color filter containing a salt-forming compound (D) obtained by reacting a filling acrylic resin with an anionic dye (C), it has high storage stability and forms a coating film. There is no generation of foreign matter at the time, and it is possible to obtain a color filter which is excellent in adhesion, exhibits high heat resistance and solvent resistance, and exhibits excellent alkali development.

Hereinafter, the present invention will be described in detail.

The coloring composition for a color filter of the present invention is obtained by reacting a resin (B) having a cationic group in a side chain with an anionic dye (C) in a colorant carrier containing a binder resin and an organic solvent. It is a coloring composition for color filters containing the obtained salt-forming compound (D). First, the resin (B) having a cationic group in the side chain will be described.

<Resin (B) having cationic group in side chain>
The resin (B) having a cationic group in the side chain of the present invention is an acrylic resin containing a structural unit represented by the following general formula (1), an acrylic resin having a thermally crosslinkable functional group, and a glass transition temperature. Is selected from an acrylic resin having a thermal crosslinkable functional group and a glass transition temperature of 50 ° C. or higher. The acrylic resin is preferably an acrylic resin having a thermally crosslinkable functional group and a glass transition temperature of 50 ° C. or higher.

The salt-forming compound (D) of the present invention can be obtained when the cationic group represented by the following general formula (1) forms a salt with the anionic group of the anionic dye (C).

(In general formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂ , R ₃ , and R ₄ are each independently substituted with a hydrogen atom or an arbitrary substituent. Represents an alkyl group that may be substituted, an alkenyl group that may be substituted with any substituent, or an aryl group that may be substituted with any substituent; ₂ of R ₂ , R ₃ , and R ₄ _May be bonded to each other to form a ring, Q represents an alkylene group, an arylene group, —CONH—R ₅ —, or —COO—R ₅ —, R ₅ represents an alkylene group, and Y ⁻ represents Represents an inorganic or organic anion.)
In general formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group represented by R ₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, R ₁ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, an alkyl group that may be substituted with an arbitrary substituent, or an arbitrary substituent. It may be an alkenyl group or an aryl group optionally substituted by any substituent.

Here, as an example of the alkyl group in R ₂ , R ₃ , and R ₄ , a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n- Dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1, 3,3-tetramethylbutyl and the like), cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl) and bridged cyclic alkyl groups (such as norbornyl, adamantyl and pinanyl). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of alkenyl groups for R ₂ , R ₃ and R ₄ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1- Methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.) Can be mentioned. The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of aryl groups in R ₂ , R ₃ , and R ₄ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocycles Ring hydrocarbon group (thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (Groups derived from xanthone) and 9-oxothioxanthenyl (groups derived from thioxanthone)).

When the alkyl group, alkenyl group, and aryl group represented by R ₂ , R ₃ , and R ₄ have a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, and an alkenyl group. And a substituent selected from an acyl group, an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these, the substituent is particularly preferably a halogen atom, a hydroxyl group, an alkoxyl group, or a phenyl group.

R ₂ , R ₃ and R ₄ are preferably an alkyl group which may be substituted, and more preferably an unsubstituted alkyl group, from the viewpoint of stability.

_Two of R ₂ , R ₃ and R ₄ may be bonded to each other to form a ring.

In the general formula (1), Q connecting the acrylic moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ₅ —, or —COO—R ₅ —, and R ₅ represents an alkylene group. Among these, Q is preferably —CONH—R ₅ — or —COO—R ₅ —, more preferably —COO—R ₅ —, from the viewpoints of polymerizability and availability. R ₅ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The component Y ⁻ in the general formula (1) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, a halogen ion or a carboxylate ion is preferable, and a halogen ion is most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

The acrylic resin containing the structural unit represented by the general formula (1) can be obtained by carrying out a copolymerization reaction using an ethylenically unsaturated monomer having an ammonium base as a monomer component. Alternatively, the acrylic resin is synthesized by carrying out a copolymerization reaction using an ethylenically unsaturated monomer having an amino group as a monomer component, and then synthesizing an acrylic resin having an amino group. It can be obtained by reacting with A and carrying out ammonium chloride.

Specific examples of the ethylenically unsaturated monomer having an ammonium base, the ethylenically unsaturated monomer having an amino group, and an onium chlorinating agent are shown below. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

Examples of ethylenically unsaturated monomers having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyl Alkyl (meth) acrylate quaternary ammonium salts such as oxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Alkyl (meth) acryloylamide quaternary ammonium salts such as dimethyldi Lil ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

Examples of ethylenically unsaturated monomers having amino groups include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (Meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylamino Propyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylamino Examples include (meth) acrylic acid esters having a dialkylamino group such as propyl (meth) acrylamide or (meth) acrylamide, styrenes having a dialkylamino group such as dimethylaminostyrene, dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

Examples of onium chlorinating agents include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or octyl. Examples thereof include alkyl chlorides such as chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, particularly about 30 ° C. or less when the vinyl monomer is ammonium chlorinated, and the reaction time is about 1 to 4 hours.

Separately, an alkoxycarbonylalkyl halide can also be used as an onium chloride agent. The alkoxycarbonylalkyl halide is represented by the following general formula (2).

Z—R ⁶ —COOR ⁷ general formula (2)
(In the general formula (2), Z is a halogen such as chlorine or bromine, preferably bromine, and R ⁶ has 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to carbon atoms. 3 is an alkylene group, and R ⁷ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.)
Reaction of the ethylenically unsaturated monomer and alkoxycarbonylalkyl halide with an amino group, after equimolar following alkoxycarbonylalkyl halide was reacted in the same manner as in the above onium chloride agent to an amino group, a -COOR ⁷ It is obtained by hydrolysis and conversion to carboxylate ions (—COO ⁻ ). Thereby, an ethylenically unsaturated monomer having a carboxybetaine structure represented by the general formula (2) and having an ammonium base can be obtained.

Subsequently, the thermally crosslinkable functional group in the resin (B) having a cationic group in the side chain used in the present invention will be described.

(Crosslinkable functional group)
The acrylic resin having a thermally crosslinkable functional group of the present invention forms a crosslink with an acrylic resin having a thermally crosslinkable functional group or a binder resin in a heating step in the production of a color filter. Thereby, a strong film is formed and the color change of the film is prevented. That is, heat resistance can be improved. Moreover, solvent resistance can also be improved.

The suitable structure of the thermally crosslinkable functional group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic acid anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a t-butyl group, Examples thereof include an epoxy group, a mercapto group, an isocyanate group, an allyl group, and a (meth) acryl group.

Among these, from the viewpoint of storage stability and reactivity with other materials in the use of a coloring composition for a color filter, a hydroxyl group, a carboxyl group, an oxetanyl group, a t-butyl group, an isocyanate group, and a (meth) acryl group are preferable. In particular, it preferably has a hydroxyl group.

Moreover, it is preferable to have a carboxyl group from the viewpoint of alkali developability.

One method for introducing a thermally crosslinkable functional group into an acrylic resin is to convert an ethylenically unsaturated monomer having a thermally crosslinkable functional group into an ethylenically unsaturated group corresponding to the cationic group represented by the general formula (1). This is a method of copolymerizing with a saturated monomer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (addition mole number is preferably 1 to 5).

Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc., and ethylenic having a carboxylic anhydride group. Examples of the unsaturated monomer include maleic anhydride and itaconic anhydride.

Examples of the ethylenically unsaturated monomer having an oxetanyl group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (Methacryloyloxymethyl) 3-hexyloxetane and the like.

Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate, and the like.

The isocyanate group in the present invention includes a blocked isocyanate group and can be preferably used. Under normal conditions, the blocked isocyanate group can protect the isocyanate group with other functional groups to suppress the reactivity of the isocyanate group, and can be deprotected by heating to regenerate the active isocyanate group. The isocyanate block body is shown.

Examples of commercially available ethylenically unsaturated monomers having such a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, Showa Denko); Examples include 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko).

Further, as the ethylenically unsaturated monomer having a blocked isocyanate group, a commercially available product can be used, and it can also be prepared and used by a known method. For example, an isocyanate compound having an ethylenically unsaturated bond and a blocking agent are stirred in a solvent at a temperature of about 0 to 200 ° C., and known separation and purification means such as concentration, filtration, extraction, crystallization, distillation, etc. are performed. It can obtain by separating using.

Another method for introducing a heat-crosslinkable functional group into an acrylic resin is to obtain a functional group that can react with the functional group and a heat-crosslinkable functional group on the functional group of the acrylic resin after obtaining the acrylic resin. It is the method of making the compound which has it react. For example, by reacting a glycidyl group of an ethylenically unsaturated monomer having a glycidyl group with a carboxyl group in an acrylic resin having a carboxyl group, an acrylic resin having a (meth) acryloyl group as a thermally crosslinkable functional group is obtained. Obtainable.

少なくとも At least one kind of the above heat-crosslinkable functional group needs to be contained in the resin, and two or more kinds may be contained.

Furthermore, when two or more types of thermally crosslinkable functional groups are contained, there is a preferable combination among the thermally crosslinkable functional groups. This is a combination in which heat-crosslinkable functional groups are more likely to react with each other when heated. In this case, the effect of crosslinking is improved. For example, it is effective to use an oxetanyl group and a carboxyl group at the same time. Similarly, since a t-butyl group becomes a carboxyl group when heated, a combination of an oxetanyl group and a t-butyl group is also effective. A combination of a hydroxyl group, a blocked isocyanate group and an isocyanate group is also effective. In particular, the combination of a hydroxyl group and a carboxyl group is most preferable because not only a strong film can be obtained by thermal crosslinking, but also in the alkali development step before thermal crosslinking, alkali developability is improved by the presence of carboxyl groups.

Subsequently, the glass transition temperature of the resin (B) having a cationic group in the side chain will be described.

(Glass-transition temperature)
When synthesizing the resin (B) having a cationic group in the side chain used in the present invention, the glass transition temperature (hereinafter abbreviated as Tg) is 50 ° C. by selecting the ethylenically unsaturated monomer to be used. The above acrylic resin can be obtained. It is possible to control the Tg of the acrylic resin by appropriately selecting the ethylenically unsaturated monomer to be used within a range that does not affect other physical properties. Since Tg of the acrylic resin directly affects the heat resistance of the color filter, when this Tg is less than 50 ° C. and does not have a thermally crosslinkable functional group, a color change at high temperature, that is, poor heat resistance occurs.

Considering use in the field of electronics such as a color filter having a heating step of 200 ° C. or higher, the Tg of the acrylic part is more preferably 70 ° C. or higher. The upper limit of Tg is not particularly limited, but if it exceeds 150 ° C., there may be practical problems in workability and film-forming properties, and therefore it is preferably less than 150 ° C.

The Tg of the acrylic resin of the present invention indicates a value calculated from the Tg of the homopolymer of each of the ethylenically unsaturated monomers to be copolymerized by the Fox formula shown below.

Fox formula 1 / Tg = W1 / Tg1 + W2 / Tg2 +... + Wn / Tgn
W1 to Wn represent the weight fraction of the monomer used, and Tg1 to Tgn represent the glass transition temperature of the monomer homopolymer (unit is absolute temperature “K”).
Tg (glass transition temperature) of the homopolymer of the main monomer used for calculation is illustrated below.

Ethyl acrylate: -22 ° C (251K)
Butyl acrylate: -54 ° C (219K)
Benzyl methacrylate: 55 ° C (328K)
Acrylic acid: 106 ° C (379K)
Methyl methacrylate: 105 ° C (378K)
n-Butyl methacrylate: 20 ° C (293K)
2-Ethylhexyl methacrylate: -10 ° C (263K)
Hydroxyethyl methacrylate: 55 ° C (328K)
Methacrylic acid: 130 ° C (403K)
3- (Methacryloyloxymethyl) 3-ethyloxetane: 105 ° C. (378 K)
2-Isocyanate ethyl methacrylate: 60 ° C. (333 K)
t-Butyl methacrylate: 107 ° C (380K)
Dimethylaminoethyl methyl chloride salt: 58 ° C (331K)

For example, when the calculation is performed by the above method, the glass transition temperature of the vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer synthesized using 90 parts by weight of methyl methacrylate and 10 parts by weight of ethyl acrylate is 86. 8 ° C.

In order to increase the Tg, it is necessary to include an ethylenically unsaturated monomer having a high homopolymer Tg in the copolymer composition. Among the ethylenically unsaturated monomers, the following are high in Tg and are effective for increasing the Tg of the acrylic resin.

Monomers with relatively high Tg of homopolymer are listed.
Methyl methacrylate: 105 ° C (378K)
t-Butyl methacrylate: 107 ° C (380K)
Methacrylic acid: 130 ° C (403K)
Acrylic acid: 106 ° C (379K)
3- (Methacryloyloxymethyl) 3-ethyloxetane: 105 ° C. (378 K)
Isobornyl acrylate: 94 ° C (367K)
Isobornyl methacrylate: 180 ° C (453K)
Dicyclopentanyl acrylate: 120 ° C (393K)
Dicyclopentanyl methacrylate: 175 ° C (448K)
Adamantyl acrylate: 153 ° C (426K)
Adamantyl methacrylate: 250 ° C (523K)
Among these, t-butyl methacrylate and methacrylic acid are particularly preferred because they can increase the Tg and introduce a thermally crosslinkable functional group. Further, methyl methacrylate is preferable from the viewpoint of versatility.

Other examples of the ethylenically unsaturated monomer that can be used other than the ethylenically unsaturated monomer include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, Preference is given to fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like.

Specific examples of such vinyl monomers include the following compounds.

Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2- (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (Meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (2-methoxy) Toxi) ethyl, (meth) acrylic acid benzyl, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol mono Ethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β-phenoxyethoxyethyl, (meth) acrylic acid nonylphenoxy polyethylene glycol, (meth) acrylic acid Dicyclopentenyl, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropenti (meth) acrylate , Perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of crotonates include butyl crotonate and hexyl crotonate.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butylacrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

As a method for obtaining the resin (B) having a cationic group in the side chain, known methods such as anion polymerization, living anion polymerization, cation polymerization, living cation polymerization, free radical polymerization, and living radical polymerization can be used. Of these, free radical polymerization or living radical polymerization is preferred.

In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

In the living radical polymerization method, side reactions occurring in general radical polymerization are suppressed, and further, the growth of polymerization occurs uniformly, so that block polymers and resins with uniform molecular weight can be easily synthesized.

Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in References 1 to 8 below.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101,
2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995
, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Scien
ce, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-411117

It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited. For example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

The amount of the ammonium base present in the resin (B) having a cationic group in the side chain is not particularly limited, but the ammonium salt value of the resin is preferably 10 to 200 mgKOH / g, 20 to More preferably, it is 130 mgKOH / g. When the ammonium salt value is less than 10 mgKOH / g, the ratio of the anionic dye (C) to be reacted is reduced, so that the coloring power is lowered, and more salt-forming compound (D) is required in the resist material. Therefore, the binder resin, the curable resin, or the like originally added to the resist material is reduced, and the glass adhesion of the resist film may be deteriorated or the coating film resistance of the resist film may be deteriorated. On the other hand, when it exceeds 200 mgKOH / g, the solvent solubility of the salt-forming compound (D) deteriorates and precipitates as a foreign substance in the resist material.

In order for the ammonium salt value of the resin to satisfy the above range, the preferable content of the structural unit having a quaternary ammonium base is 4 to 74% by weight in a total of 100% by weight of the structural units constituting the resin, A more preferred range is 8 to 48% by weight.

The molecular weight of the resin (B) having a cationic group in the side chain used in the present invention is not particularly limited, but the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is 1, It is preferably from 000 to 500,000, more preferably from 1,000 to 80,000, still more preferably from 2,000 to 20,000, and most preferably from 3,000 to 15,000.

Further, it is preferable that the resin (B) having a cationic group in the side chain to be used has a property of being dissolved in a solvent widely used in the color filter coloring composition. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

(Anionic dye (C))
Next, the anionic dye (C) for obtaining the salt-forming compound (D) of the present invention will be described. The anionic dye (C) may be a colored compound having an anionic group that is ionically bonded to the cationic group described above. Such a coloring compound is not particularly limited as long as it has a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group, or a metal salt thereof in the molecule, and an organic solvent or developer. Can be appropriately selected in consideration of all the required performance such as solubility in water, salt-forming property, absorbance, interaction with other components in the composition, light resistance, heat resistance and the like.

Examples of the anionic dye (C) include an anthraquinone anionic dye, a monoazo anionic dye, a disazo anionic dye, an oxazine anionic dye, an aminoketone anionic dye, a xanthene anionic dye, and a quinoline anion. Dyes, triphenylmethane anionic dyes and the like. Below, the specific example of the anionic dye which can be used for the synthesis | combination of a salt-forming compound (D) is shown by a color index number.

As red dyes, C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 13 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299 , 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388, etc. .

Also, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. can also be used.

¡As yellow dyes, C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 19 Etc. The.

Also, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, etc. can also be used.

As orange dyes, C.I. I. Acid Orange candy 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1, 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like.

Also, C.I. I. Direct orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114, etc. can also be used.

青色 As the blue dye, C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41: 1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 14 150,155,159,169,174,175,176,183,198,203,204,205,206,208,213,227,230,231,232,233,235,239,245,247,253 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

Also, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 2 3,215,225,226,229,230,231,242,243,244,253,254,260,263 and the like can also be used.

As purple dye, C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. Is mentioned.

Also, C.I. I. Direct violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc. can also be used.

As green dye, C.I. I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, 95 and the like.

Also, C.I. I. Direct green coffee 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, etc. can also be used.

(Salt formation)
The salt-forming compound (D) of the present invention is prepared by stirring or vibrating an aqueous solution in which a resin (B) having a cationic group in the side chain and an anionic dye (C) are dissolved, or cationic in the side chain. It can be easily obtained by mixing an aqueous solution of the resin (B) having a group and an aqueous solution of the anionic dye (C) under stirring or vibration. In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the acidic dye is water-soluble and can be removed by washing or the like. As the resin (B) having a cationic group in the side chain to be used and the anionic dye (C), only a single type or a plurality of types having different structures may be used.

As the aqueous solution used for salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the resin (B) having a cationic group in the side chain and an anionic dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone, and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the mixed solution (100% by weight).

The ratio of the resin (B) having a cationic group in the side chain and the anionic dye (C) is such that the molar ratio of the total cationic unit of the resin to the total anionic group of the anionic dye (C) is 10: 1. In the range of ˜1: 4, the salt-forming compound (D) of the present invention can be suitably adjusted, and the range of 2: 1 to 1: 2 is more preferable.

<Pigment>
The coloring composition for a color filter of the present invention can be used as a coloring composition for a color filter by further adding a pigment.

As the pigment, organic or inorganic pigments can be used alone or in combination of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for the coloring composition for color filters is shown by a color index number.

Examples of the red coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 97, 122, 123, 146, 149, 150, 168, 169, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, Red pigments such as 286 or 287 can be used. The red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 or the like and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 76,177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220, or a yellow pigment 221 and the like can be used in combination.

Examples of the green coloring composition for forming the green filter segment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37, 58 can be used. The green coloring composition includes C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or a yellow pigment 221 and the like can be used in combination.

The blue coloring composition for forming the blue filter segment includes, for example, C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 60, 61, 62, 64, etc. Can be used. The blue coloring composition includes C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

Examples of cyan coloring compositions for forming cyan filter segments include C.I. I. Blue pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used alone or in combination.

Examples of the magenta colored composition for forming the magenta color filter segment include C.I. I. Pigment Violet 1, 19, C.I. I. Pigment Red 144, 146, 177, 169, 81, etc. Purple pigments and red pigments can be used alone or in combination. A yellow pigment can be used in combination with the magenta composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

(Miniaturization of pigment)
The pigment added to the coloring composition of the present invention is preferably refined by a salt milling process or the like in order to correspond to high transmittance and high contrast. The primary particle diameter of the pigment is preferably 10 nm or more because of good dispersion in the colorant carrier. Moreover, since a filter segment with high contrast can be formed, it is preferable that it is 80 nm or less. A particularly preferred range is 20 to 60 nm.

Salt milling is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on the total weight of the pigment (100 parts by weight) in terms of both processing efficiency and production efficiency.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on the total weight of the pigment (100 parts by weight).

When the salt is milled with a pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight based on the total weight of the pigment (100 parts by weight).

<Binder resin>
The binder resin is one that disperses a colorant, particularly a salt-forming compound (D) and a pigment, or one that dyes and penetrates a salt-forming compound, and examples thereof include thermoplastic resins and thermosetting resins.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, since the coloring composition for color filters of the present invention is in the form of an alkali development type colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

In order to improve the photosensitivity of the alkali-soluble resin copolymerized with the acidic group-containing ethylenic non-monomer, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used. In addition, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain because it has an effect of improving the solvent resistance of the resist material.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted products, etc. A monocarboxylic acid etc. are mentioned. These may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. These may be used alone or in combination of two or more. For example, a tricarboxylic acid anhydride such as trimellitic acid anhydride may be used as necessary, for example, by increasing the number of carboxyl groups. Alternatively, the remaining anhydride group may be hydrolyzed using tetracarboxylic dianhydride such as pyromellitic dianhydride. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Polyether mono (meth) acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate added with (poly) 12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

The binder resin has an affinity for a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, a colorant carrier, and a solvent from the viewpoint of dispersibility, penetrability, developability, and heat resistance of the pigment and salt-forming compound. The balance between the aliphatic group and aromatic group acting as a functional group is important for the dispersibility, penetrability, developability and durability of the pigment and salt-forming compound, and a resin having an acid value of 20 to 300 mgKOH / g is used. It is preferable. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

The binder resin is preferably used in an amount of 30 parts by weight or more based on the total weight of the colorant (100 parts by weight) because of good film formability and various resistances. Since the colorant concentration is high and good color characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl 1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among them, since the dispersion and dissolution of the pigment of the present invention and the salt-forming compound (D) are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether It is preferable to use glycol acetates such as acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoints of health and safety and low viscosity.

These organic solvents may be used alone or in combination of two or more. The mixed solvent in which two or more kinds are mixed preferably contains 65 to 95% by weight of the above-mentioned preferred organic solvent.

In addition, the organic solvent can adjust the colored composition to an appropriate viscosity to form a filter segment having a desired uniform film thickness, so that 800 to 4000 weights based on the total weight of the colorant (100 parts by weight). It is preferable to use in the amount of parts.

<Dispersion>
The colored composition of the present invention comprises a salt-forming compound (D) obtained by reacting a resin (B) having a cationic group in the side chain with an anionic dye (C), the binder resin and a solvent. When a pigment is further included in the colorant carrier, the pigment is preferably used together with a dispersing aid such as a dye derivative, and various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor are used. Then, the colored composition can be produced by finely dispersing. The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds (D), and other colorants separately dispersed in a colorant carrier.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

In the present invention, the salt-forming compound (D) is also expected to play a role as a pigment dispersion aid.

Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469 and the like can be used. These may be used alone or in combination of two or more.

The blending amount of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably from the viewpoint of improving the dispersibility of the additive pigment, based on the total amount of the additive pigment (100 parts by weight). 3 parts by weight or more. From the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, based on the total amount (100 parts by weight).

The resin-type dispersant has a pigment-affinity part that has the property of adsorbing to the additive pigment and a part that is compatible with the colorant carrier, and adsorbs to the additive pigment to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Water-soluble dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester, modified poly A acrylate system, an ethylene oxide / propylene oxide addition compound, a phosphate ester system, and the like are used. These may be used alone or in combination of two or more, but are not necessarily limited thereto. is not.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen, etc. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 44 manufactured by Japan
01, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc. are mentioned.

Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, which may be used alone or in admixture of two or more, but are not necessarily limited thereto. Absent.

The amount of the resin type dispersant or surfactant added is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on the total amount of the added pigment (100 parts by weight). It is. When the blending amount of the resin-type dispersant or the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is adversely affected by the excessive dispersant. May have an effect.

<Photopolymerizable monomer>
The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

The photopolymerizable monomer of the present invention includes a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin. These may be used alone or in combination of two or more. The blending amount of the monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. preferable.

Monomers and oligomers that are cured by ultraviolet rays or heat to produce transparent resins include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyme Diether ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy Examples include, but are not necessarily limited to, methyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
The colored composition for a color filter of the present invention is a solvent development type or alkali development type colored resist material added with a photopolymerization initiator or the like when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method. It can be prepared in the form of The blending amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight based on the total amount of the colorant, and 10 to 150 parts by weight from the viewpoint of photocurability and developability. More preferred.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-
Triazine compounds such as trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O— Oxime ester compounds such as (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Or use titanocene compounds I can.

These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200 parts by weight based on the total amount of the colorant in the color filter coloring composition (100 parts by weight), and are 10 from the viewpoint of photocurability and developability. More preferably, it is ˜150 parts by weight.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.

Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives Tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Enone, 4,4′-diethylaminobenzophenone, and the like.

More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Two or more kinds of sensitizers may be used in any ratio as necessary. The blending amount when using the sensitizer is preferably 3 to 60 parts by weight based on the total weight (100 parts by weight) of the photopolymerization initiator contained in the colored composition. From the viewpoint of developability, the amount is more preferably 5 to 50 parts by weight.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

A leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, has a hydrophilic group, but has low solubility in water, and when added to a coloring composition, its surface tension decreases. Those with low performance are preferred. Furthermore, it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and those that can sufficiently suppress the chargeability in an added amount that does not cause defects in the coating film due to foaming are suitable. is there. Examples of the leveling agent having these preferable characteristics include dimethylpolysiloxane having a polyalkylene oxide unit. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit. Dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but is not limited thereto.

¡Anionic, cationic, nonionic or amphoteric surfactants can be supplementarily added to the leveling agent. Two or more surfactants may be used as a mixture.

Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

Examples of chaotic surfactants that are supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- And methacryloyloxyethyl-S-triazine / isocyanuric acid adduct). These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15% by weight with respect to the total amount of the thermosetting resin.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on the total amount of the colorant (100 parts by weight).

Examples of the adhesion improver include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltri Toxisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on the total amount of the colorant in the coloring composition (100 parts by weight).

<Removal of coarse particles>
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of this invention comprises the filter segment formed using the coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment, or those having a magenta filter segment, a cyan filter segment, and a yellow filter segment.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender.

When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, it is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In the development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise indicated, “parts” means “parts by weight”.

First, the binder resin, the refined pigment, the resin (B) having a cationic group in the side chain, and the production method of the salt-forming compound (D) used in Examples and Comparative Examples will be described.

<Method for preparing binder resin solution>
(Preparation of binder resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The binder resin solution 1 was prepared by adding. Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Preparation of binder resin solution 2)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.

Next, after the nitrogen gas was stopped and the mixture was stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.

About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of binder resin solution 3)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate, and 1.33 of 2,2′-azobisisobutyronitrile Part of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.

Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 6.5 parts of 2-methacryloyloxyl ethyl isocyanate. A mixture of 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.

About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin solution 4)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and the reaction was terminated when the solid content acid value reached 0.5 to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a carboxyl group and a copolymer solution.

After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, a binder resin solution 4 was prepared. The weight average molecular weight (Mw) was 19000.

<Production method of fine pigment>
(Blue refined pigment (P-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“Rionol Blue ES” manufactured by Toyo Ink Mfg. Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. for 12 hours. Kneaded. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain 98 parts of a blue fine pigment (P-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

Here, the average primary particle diameter of the pigment was measured using a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.) by measuring the primary particle diameter of all pigment particles in the observation sample at 50,000 times. Average values were used. In addition, when the particle shape was not spherical, the major axis and the minor axis were measured, and the value obtained by (major axis + minor axis) / 2 was defined as the particle diameter.

(Purple refined pigment (P-2))
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain 118 parts of purple fine pigment (P-2). The average primary particle diameter of the obtained pigment was 26.4 nm.

(Red fine pigment (P-3))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan Co., Ltd.), 1400 parts of ground sodium chloride and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was poured into 8000 parts of warm water, heated to about 80 ° C., stirred with a high speed mixer for about 2 hours to form a slurry, filtered and washed repeatedly to remove salt and solvent, then at 85 ° C. for 24 hours. Drying gave 190 parts of red fine pigment (P-3). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Red fine pigment (P-4))
Red pigment C.I. I. 200 parts of Pigment Red 242 (“NOVOPERM SCARLET 4RF” manufactured by Clariant), 1400 parts of ground sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture is poured into 8000 parts of warm water, stirred for 2 hours with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 85 ° C. for 24 hours. 190 parts of red fine pigment (P-4) were obtained. The average primary particle diameter of the obtained pigment was 28.5 nm.

<Preparation method of resin (B) having cationic group in side chain>
(Production Example 1; Preparation of resin B-1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 75.1 parts of isopropyl alcohol was charged, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 18.2 parts methyl methacrylate, 27.3 parts n-butyl methacrylate, 27.3 parts 2-ethylhexyl methacrylate, 15.0 parts hydroxyethyl methacrylate, 12.2 parts dimethylaminoethyl methyl methacrylate salt, and separately 7.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 23.4 parts of methyl ethyl ketone was homogenized, charged into a dropping funnel and attached to a four-necked separable flask for 2 hours. It was dripped over. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content, and the weight average molecular weight (Mw) was 7330, and the mixture was cooled to 50 ° C. Thereafter, 14.3 parts of methanol was added to obtain Resin B-1 having a Tg of 32 ° C. having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 32 mgKOH / g.

Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The ammonium salt value of the resin (B) having a cationic group in the side chain was determined by titrating with a 0.1N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator, and then the equivalent of potassium hydroxide. It is the converted value and indicates the ammonium salt value of the solid content.

(Production Example 2 to Production Example 17, Production Example 19 to Production Example 24; Preparation of resins B-2 to 17 and B-19 to 24 having a cationic group in the side chain)
Hereinafter, resins B-2 to 17 and B-19 to 24 having cationic groups in the side chains were prepared in the same manner as in Production Example 1 except that the monomers, polymerization initiator, and reaction temperature were changed to the compositions shown in Table 1. Obtained.

(Production Example 18; Preparation of resin B-18 having a cationic group in the side chain)
Resin B-18 having a cationic group in the side chain was synthesized by synthesizing a carboxyl group-containing acrylic resin in the same manner as in Production Example 1 except that a monomer other than GMA (glycidyl methacrylate) shown in Table 1 was used. By reacting the glycidyl group of GMA with the glycidyl group of GMA, Resin B-18 having a heat-crosslinkable group (methacryloyl group) and a cationic group in the side chain was obtained. The procedure is shown below.

Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 75.1 parts of isopropyl alcohol was charged, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 18.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 15.0 parts of methacrylic acid, 12.2 parts of dimethylaminoethyl methyl chloride salt, and separate methyl ethyl ketone 7.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 23.4 parts was homogenized and charged into a dropping funnel and attached to a four-necked separable flask over 2 hours. And dripped. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content, and a resin B-18 ′ having a Tg of 40 ° C. having a cationic group in the side chain as an intermediate was obtained. Next, after adding 107.1 parts of butyl cellosolve, it heated at 80 degreeC or more, isopropyl alcohol and methyl ethyl ketone were azeotroped with butyl cellosolve, and isopropyl alcohol and methyl ethyl ketone were distilled off. When the internal temperature reached 100 ° C., 1 g of this was sampled, heated and dried at 180 ° C. for 20 minutes, and the non-volatile content was measured to confirm that the non-volatile content of the resin solution was 50%. Thereafter, 24.8 parts of glycidyl methacrylate, 1.0 part of dimethylbenzylamine and 0.2 part of methoquinone were charged, and oxygen was bubbled at 100 ml / min. Then, it heated up at 100 degreeC and stirred for 6 hours. After 6 hours, sample 1g, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, confirm that the reaction rate is 90% or more, cool to 50 ° C, resin B having a cationic group in the side chain -18 was obtained. The ammonium salt value of the obtained resin was 26.4 mgKOH / g.

The following monomers were used in Table 1. Shown with glass transition temperature.

MMA: Methyl methacrylate (105 ° C)
n-BMA: n-butyl methacrylate (20 ° C)
2-EHMA: 2-ethylhexyl methacrylate (-10 ° C)
2-EHA: 2-ethylhexyl acrylate (-85 ° C)
CHMA: cyclohexyl methacrylate (66 ° C)
i-BuMA: Isobutyl methacrylate (48 ° C)
HEMA: hydroxyethyl methacrylate (55 ° C)
HEA: hydroxyethyl acrylate (-15 ° C)
4HBA: 4-hydroxybutyl acrylate (-80 ° C)
MAA: Methacrylic acid (130 ° C)
AA: Acrylic acid (106 ° C)
OXMA: 3- (methacryloyloxymethyl) 3-ethyloxetane (ETERRNACOLL OXMA (manufactured by Ube Industries)) (105 ° C)
t-BuMA: Tertiary butyl methacrylate (107 ° C)
DMC78: Dimethylaminoethyl methyl chloride salt of methacrylate (acrylic ester DMC (manufactured by Mitsubishi Rayon)) (58 ° C)
MOI-BM: 2- [O- (1′-methylpropylideneamino) carboxyano] ethyl methacrylate (Karenz MOI-BM (manufactured by Showa Denko) (60 ° C.)
GMA: Glycidyl methacrylate (Blemmer G (manufactured by NOF Corporation))

The value of Tg in Table 1 is a value calculated using the above formula. However, the value of the glass transition temperature of MOI-BM in Production Example 17 was the value of 2-isocyanatoethyl methacrylate instead. In addition, Production Example 18 is the value of Resin B-18 ′ before being modified with glycidyl methacrylate.

<Method for Producing Salt-Forming Compound (D)>
(Production Example 25; Preparation of Salt-Forming Compound D-1)
In the following procedure, C.I. I. A salt-forming compound (D-1) comprising Acid Red 289 and Resin B-1 having a cationic group in the side chain was produced.

The resin B-1 having a cationic group in the side chain of 51 parts is added to 2000 parts of water, sufficiently mixed with stirring, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which acid red candy 289 is dissolved is prepared, and the resulting solution is added dropwise to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, a counter anion of the resin having a cationic group in the side chain and C.I. I. After removing the salt consisting of the counter cation of Acid Red 289, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound D-1 between Acid Red candy 289 and resin B-1 having a cationic group in the side chain was obtained.

(Production Examples 29 to 41, 43 to 47, 49 to 59; Preparation of salt-forming compounds D-5 to 17, 19 to 23, 25 to 35)
Hereinafter, salt-forming compounds D-5 to 17, 19 to 23, and 25 to 35 were produced in the same manner as in Production Example 25 except that the resin and dye having a cationic group in the side chain were changed to those shown in Table 2. did.

(Production Example 26; Preparation of salt-forming compound D-2)
Thereafter, a salt-forming compound D-2 was produced in the same manner as in Production Example 25 except that 24 parts of the resin B-2 having a cationic group in the side chain was used.

(Production Example 27; Preparation of salt-forming compound D-3)
Thereafter, a salt-forming compound D-3 was produced in the same manner as in Production Example 25 except that 17 parts of resin B-3 having a cationic group in the side chain was used.

(Production Example 28; Preparation of salt-forming compound D-4)
Thereafter, a salt-forming compound D-4 was produced in the same manner as in Production Example 25 except that 10 parts of the resin B-4 having a cationic group in the side chain was used.

(Production Example 42; Preparation of salt-forming compound D-18)
Thereafter, a salt-forming compound D-18 was produced in the same manner as in Production Example 25 except that 64 parts of the resin B-18 having a cationic group in the side chain was used.

(Production Example 48; Preparation of salt-forming compound D-24)
Hereinafter, 17 parts of resin B-3 having a cationic group in the side chain, C.I. I. A salt-forming compound D-24 was produced in the same manner as in Production Example 25 except that 10 parts of Acid Red 52 was used.

(Salt-forming compound (H-1))
In the following procedure, C.I. I. A salt-forming compound (H-1) consisting of Acid Red 289 and distearyldimethylammonium chloride (Coatamine D86P) was produced.

11.5 parts of Cotamine D86P is added to 2000 parts of a 10% aqueous sodium hydroxide solution, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which acid red candy 289 is dissolved is prepared and added dropwise to the previous solution little by little. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 17 parts of C.I. I. A salt-forming compound (H-1) of Acid Red 289 and Coatamine D86P was obtained.

(Salt making compound (H-2))
In the following procedure, C.I. I. A salt-forming compound (H-2) consisting of Acid Red 52 and monolauryltrimethylammonium chloride (Cotamine 24P) was produced.

8.1 parts of Cotamine 24P is added to 2000 parts of a 7% aqueous sodium hydroxide solution, and after sufficient stirring and mixing, the mixture is heated to 50 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 is dissolved is prepared and added dropwise little by little to the previous solution. After the dropping, the mixture is stirred at 50 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound (H-2) of acid red 52 and coatamine 24P was obtained.

[Examples 1 to 49, Comparative Examples 1 to 11]
[Example 1]
(Preparation of blue coloring composition (DB-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (DB-1) was produced by filtration using a filter.

Salt-forming compound (D-1) 4.0 parts Fine pigment (P-1) 7.0 parts Binder resin solution 1 40.0 parts Cyclohexanone 10.0 parts Propylene glycol monomethyl ether acetate (PGMAC) 38.0 parts Resin 1.0 part of dispersant ("EFKA4300" manufactured by Ciba Japan)

[Examples 2 to 49, Comparative Examples 1 to 9]
(Blue coloring composition (DB-2 to 31, DB-50 to 52), purple coloring composition (DB-32, 33, DB-53, 54), red coloring composition (DB-34 to 49, DB- 55-58))
A colored composition (DB-2 to 58) was produced in the same manner as in Example 1 except that the salt-forming compound and the finer pigment were changed to the compositions shown in Table 3.

[Comparative Example 10]
(Preparation of blue coloring composition (DB-59))
A blue colored composition (DB-59) was produced in the same manner as in Example 1 except that 3 parts of the salt-forming compound H-1 and 8 parts of the refined pigment P1 were used.

[Comparative Example 11]
(Preparation of blue coloring composition (DB-60))
A blue colored composition (DB-60) was produced in the same manner as in Example 1 except that 5 parts of the salt-forming compound H-1 and 6 parts of the refined pigment P1 were used.

The obtained colored compositions (DB-1 to 60) were subjected to the following methods for evaluating the heat resistance of the coating film, the foreign matter test, and the storage stability of the colored composition with time. The results of the test are shown in Table 3.

(Evaluation of heat resistance of coating film)
The coloring composition (DB-1 to 60) is applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. The coated substrate was prepared by heating and allowing to cool. The coating film substrate thus prepared was subjected to heat treatment at 220 ° C., and the spin coater coating rotation speed was adjusted so that the film thickness was 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined.

ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
If ΔEab * is less than 3.0, there is no practical problem as a color filter. ΔEab is more preferably 1.5 or less, and most preferably 1.0 or less.

(Test on storage stability over time)
The coloring composition (DB-1 to 60) stored for 6 months under a cold-reserving condition at 10 ° C. was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then 20 ° C. at 70 ° C. The film was dried for a while, then heated at 220 ° C. for 30 minutes and allowed to cool to produce a coated substrate, and this coated substrate was observed at 500 times using an optical microscope.

<Evaluation criteria>
◎: Generation of foreign matter is not recognized at all ○: Generation of foreign matter is recognized but allowable range ×: Excessive generation of foreign matter is outside the allowable range (Coating foreign matter test method)
A test substrate was prepared with the colored composition (DB-1 to 60) immediately after preparation, and the evaluation was performed by counting the number of particles. First, a colored composition is applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying is about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes. A test substrate was obtained. Then, surface observation was performed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of particles that can be observed in any five visual fields by transmission was counted and evaluated according to the following criteria. did. In the evaluation results, ◎ and ○ are good with a small number of foreign matters, △ is a level where there is a large number of foreign matters, but there is no problem in use, and × is a state where it cannot be used because uneven coating due to foreign matters occurs. Equivalent to.

◎: Less than 5 ○: 5 or more, less than 20 △: 20 or more, less than 100 ×: 100 or more

AR289: C.I. I. Acid Red 289
AR52: C.I. I. Acid Red 52

As in Examples 1 to 49, containing a salt-forming compound (D) obtained by reacting a resin (B) having a cationic group in the side chain with an anionic dye (C), the cationic group The resin having a quaternary ammonium salt and a thermally crosslinkable functional group or an acrylic resin satisfying at least one of Tg of 50 ° C. or higher has good heat resistance, and ΔEab is It was 3.0 or less. Moreover, it was excellent in storage stability, and the coating film foreign matter was in a range that can be used as a color filter.

Regarding Examples 10 to 15, 26 to 30, 36, 40, 44 and 48, the heat-crosslinkable functional groups contained in the resin having a cationic group are a hydroxyl group and a carboxyl group, and therefore, heat resistance is further improved. Yes, ΔEab was 1.5 or less. Among them, Examples 12 and 27 are acrylic resins having a glass transition temperature of 50 ° C. or higher, and thus have very good heat resistance, and ΔEab was 1.0 or less.

In Example 5, the heat-crosslinkable functional group contained in the resin having a cationic group is a hydroxyl group, and is an acrylic resin having a glass transition temperature of 50 ° C. or higher. Therefore, the heat resistance is very good. , ΔEab was 1.0 or less.

In Comparative Examples 1 to 9, since the resin having a cationic group does not contain a thermally crosslinkable functional group, and the glass transition temperature of the resin having a cationic group is lower than 50 degrees, all of them have heat resistance. Unfortunately, ΔEab exceeded 3.

Further, Comparative Examples 10 and 11 were not only poor in heat resistance but also poor in storage stability with time, and the coating film foreign matter test was slightly inferior.

[Example 50]
(Preparation of blue photosensitive coloring composition (R-1))
The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali developing resist material R-1.

Blue coloring composition (DB-1) 60.0 parts Binder resin solution 1 11.0 parts Trimethylolpropane triacrylate 4.2 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan) 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Cyclohexanone 5.2 parts Propylene glycol monomethyl ether acetate (PGMAC 18.0 parts

[Examples 51 to 101, Comparative Examples 12 to 22]
(Blue photosensitive coloring composition (R-2 to 34, R-53 to 55, R-62, 63), Purple photosensitive coloring composition (R-35 to 36, R-56 to 57), Red photosensitive property Coloring composition (production of R-37 to 52, R-58 to 61))
Alkaline development type photosensitive coloring compositions (R-2 to 63) were prepared in the same manner as in Example 50 except that the coloring composition and the binder resin solution were changed to the coloring compositions shown in Table 4.

(Evaluation of photosensitive coloring composition)
About the obtained photosensitive coloring composition (R-1 to 63), heat resistance evaluation of coating film, foreign matter test, storage stability with time, test on adhesion to a transparent substrate such as glass, solvent resistance test An alkali developability test was conducted. A foreign matter test, an adhesion test with a transparent substrate such as glass, a solvent resistance test, and an alkali developability test method were performed by the following methods. Other evaluation / test methods were the same as those described in Examples 1 to 49 and Comparative Examples 1 to 11.

(Coating foreign material test method)
A test substrate was prepared using the photosensitive coloring composition (R-1 to 63) immediately after preparation, and the evaluation was performed by counting the number of particles. First, a photosensitive coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying was about 2.0 μm, dried at 70 ° C. for 20 minutes, UV exposure is performed with an integrated light quantity of 150 mJ / cm ² using an ultrahigh pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm, and unexposed with a 0.05% potassium hydroxide aqueous solution containing a surfactant. The part was washed off and developed, and placed in a hot air oven at 230 ° C. for 20 minutes to form a stripe pattern having a width of 100 μm on the substrate to obtain a test substrate. Then, surface observation was performed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of particles that can be observed in any five visual fields by transmission was counted and evaluated according to the following criteria. did. In the evaluation results, ◎ and ○ are good with a small number of foreign matters, △ is a level where there is a large number of foreign matters, but there is no problem in use, and × is a state where it cannot be used because uneven coating due to foreign matters occurs. Equivalent to.

(Glass adhesion test method)
Evaluation was performed by forming a test substrate in the same procedure as the coating film foreign matter test and confirming the chemical resistance. The obtained test substrate was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C. for 30 minutes, and the adhesion to the glass before and after immersion was evaluated in three stages by visual observation.

○: No peeling at all Δ: Slight peeling is observed ×: Peeling is observed (solvent resistance test)
A test substrate obtained by the same procedure as the coating film foreign matter test described above was immersed in an N-methylpyrrolidone solution for 30 minutes, then washed with ion-exchanged water, air-dried, and the pattern on the 100 μm photomask portion was examined using an optical microscope Evaluation was made by observation. The rank of evaluation is as follows.

◎: Appearance and color are good ○: Some wrinkles are generated, but color is good without change △: Slight color fading occurs ×: Peeling or color fading occurs (alkali developability test)
The photosensitive coloring composition (R-1 to 63) was applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying was about 2.0 μm, at 70 ° C. After drying for 20 minutes, UV exposure was performed with an integrated light amount of 150 mJ / cm ² using a super high pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm. When developing with a 0.05% aqueous potassium hydroxide solution containing a surfactant, the unexposed area is washed away, the development is performed at an appropriate development time of +10 seconds and +20 seconds, and the developed glass surface is subjected to a microspectrophotometer ( Measured using "OSP-SP200" manufactured by Olympus Optical Co., Ltd.

◎: No residue at appropriate development time ○: No residue at appropriate development time + 10 seconds △: No residue at appropriate development time + 20 seconds ×: Residue at appropriate development time + 20 seconds

As in Examples 50 to 101, containing a salt-forming compound (D) obtained by reacting a resin (B) having a cationic group in the side chain with an anionic dye (C), and the cationic group The resin having a quaternary ammonium salt and containing a heat-crosslinkable functional group or an acrylic resin satisfying at least one of Tg of 50 ° C. or higher has good heat resistance, and ΔEab is It was 3.0 or less. Moreover, it was excellent in storage stability, the coating-film foreign material was in the range which can be used as a color filter, and it was a result with favorable glass adhesiveness, solvent resistance, and alkali developability.

Regarding Examples 62 to 67, 78 to 82, 88, 92 and 96, since the thermally crosslinkable functional groups contained in the resin having a cationic group are a hydroxyl group and a carboxyl group, the heat resistance is further improved. ΔEab was 1.5 or less. Among them, Examples 64 and 79 were acrylic resins having a glass transition temperature of 50 ° C. or higher, and thus had very good heat resistance, and ΔEab was 1.0 or less.

In Example 50, the heat-crosslinkable functional group contained in the resin having a cationic group is an acrylic resin having a hydroxyl group and a glass transition temperature of 50 ° C. or higher, so that the heat resistance is very good. , ΔEab was 1.0 or less.

Regarding Examples 62 to 67, 78 to 82, 88, 92 and 96, since a hydroxyl group and a carboxyl group are contained as the thermally crosslinkable functional group, a strong film is formed by thermal crosslinking, and the solvent resistance is extremely high. Excellent results. Moreover, since the carboxyl group was contained, there was no residue residue and the result was very excellent in alkali developability.

In Comparative Examples 12 to 20, since the resin having a cationic group does not contain a thermally crosslinkable functional group, and the glass transition temperature of the resin having a cationic group is lower than 50 degrees, all of them have heat resistance. Unfortunately, ΔEab exceeded 3. Also, the solvent resistance was poor.

Comparative Examples 21 and 22 were not only poor in heat resistance but also poor in storage stability over time, glass adhesion and solvent resistance, and the coating film foreign matter test was slightly inferior.

<Production of color filter>
In combination with the photosensitive coloring composition of the present invention, a red photosensitive coloring composition, a blue photosensitive coloring composition and a green photosensitive coloring composition used for the preparation of a color filter were prepared.

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A red colored composition (DR-1) was prepared by filtration through a 0.0 μm filter.

Red pigment (CI Pigment Red 254) 9.6 parts Red Pigment (CI Pigment Red 177) 2.4 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Binder resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a red photosensitive coloring composition (RR). -1) was produced.

Red coloring composition (DR-1) 42.0 parts Binder resin solution 1 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A blue colored composition (DB-100) was produced by filtration through a 0.0 μm filter.

Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Binder resin solution 1 17.5 parts Propylene glycol monomethyl ether acetate 69.5 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).

Blue coloring composition (DB-100) 34.0 parts Binder resin solution 1 7.6 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907", manufactured by 2.0) Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part 52.7 parts ethylene glycol monomethyl ether acetate

(Preparation of green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A green colored composition (DG-1) was prepared by filtration through a 0.0 μm filter.

Green pigment (CI Pigment Green 58) 12.0 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 parts Binder resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a green photosensitive coloring composition (RG-1).

Green coloring composition (DG-1) 34.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 45.1 parts

A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied on the substrate with a spin coater to a thickness of x = 0.640 to form a colored film. The coating was irradiated with 300 mJ / cm 2 of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. Formed. By the same method, a blue filter segment is formed so that the film thickness of the blue photosensitive coloring composition (R-2) of the present invention is 2.0 μm, and then the green photosensitive coloring composition (RG-1) is formed. ) To form a green color filter segment to obtain a color filter.

Similarly, using the red photosensitive coloring composition (R-47), blue photosensitive coloring composition (RB-1), and green photosensitive coloring composition (RG-1) of the present invention, a color filter Got.

By using the photosensitive coloring composition of the present invention, the heat resistance of the color filter, the foreign matter test, the adhesion to a transparent substrate such as glass, the solvent resistance, and the alkali developability are improved and preferably used. I was able to.

Claims

A color filter coloring composition comprising a colorant (A), a binder resin, and an organic solvent,
The colorant (A) contains a salt-forming compound (D) obtained by reacting a resin (B) having a cationic group in the side chain with an anionic dye (C),
The resin (B) having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (1), and the acrylic resin has an acrylic resin having a thermally crosslinkable functional group, Coloring composition for color filters, characterized in that it is selected from acrylic resins having a glass transition temperature of 50 ° C. or higher and acrylic resins having a thermally crosslinkable functional group and a glass transition temperature of 50 ° C. or higher.

(In General Formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. R 2 , R 3 , and R 4 are each independently a hydrogen atom or an optionally substituted alkyl. A group, an alkenyl group which may be substituted, or an aryl group which may be substituted, two of R 2 , R 3 and R 4 may be bonded to each other to form a ring. Represents an alkylene group, an arylene group, —CONH—R 5 —, or —COO—R 5 —, wherein R 5 represents an alkylene group, and Y − represents an inorganic or organic anion.)
2. The heat-crosslinkable functional group is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetane group, a t-butyl group, an isocyanate group, and a (meth) acryloyl group. The coloring composition for color filters as described.
The acrylic resin containing the structural unit represented by the general formula (1) is a copolymer containing a structural unit having a thermally crosslinkable functional group, and the copolymer has a structure having the thermally crosslinkable functional group. The coloring composition for a color filter according to claim 1, wherein the unit contains 10 to 35% by weight out of a total of 100% by weight.
The colored composition for a color filter according to any one of claims 1 to 3, wherein the thermally crosslinkable functional group contains a hydroxyl group.
The colored composition for a color filter according to any one of claims 1 to 4, wherein the thermally crosslinkable functional group is a hydroxyl group and a carboxyl group.
The colored composition for a color filter according to any one of claims 1 to 5, wherein the ammonium salt value of the acrylic resin containing the structural unit represented by the general formula (1) is 10 to 200 mgKOH / g. object.
The salt-forming compound (D) is a mixture of a resin (B) having a cationic group in the side chain and an anionic dye (C) in an aqueous solution, and a resin (B) pair having a cationic group in the side chain. The colored composition for a color filter according to any one of claims 1 to 6, which is a compound prepared by removing a salt composed of an anion and a counter cation of an anionic dye (C).
The coloring composition for a color filter according to any one of claims 1 to 7, wherein a main component of the organic solvent is propylene glycol monomethyl ether acetate.
The colored composition for a color filter according to any one of claims 1 to 8, wherein the colorant further contains a pigment.
The colored composition for a color filter according to any one of claims 1 to 9, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.
A color filter formed from the coloring composition for a color filter according to any one of claims 1 to 10.