JP2015129927A - Coloring composition for color filters, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for color filters that has excellent dispersibility, temporal stability, and heat resistance, is further excellent in developability with respect to alkali aqueous solution, and achieves high resolution and high brightness, and a color filter prepared using the same.SOLUTION: A coloring composition for color filters comprises a resin dispersant (A) having a hindered amine skeleton represented by the general formula (1) and a vinyl resin [B1] comprising a constitutional unit (b1) and (b2).

Description

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

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a colorant is mainly used.

  In general, when producing a pigment composition, it is known that it is difficult to stably disperse the pigment at a high concentration, which causes various problems to the production process and the product itself.

  Therefore, in general, a dispersant is used in order to keep the dispersion state good. The dispersant has a structure of a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance of these two functional sites.

  A pigment composition with excellent dispersibility, fluidity and storage stability is proposed for use in color filters in combination with a dispersant having an aromatic carboxyl group and a vinyl resin (dispersant) having a tertiary amino group. (See Patent Document 1). However, the tertiary amino group-containing basic resin described herein has a problem that the basicity is low compared to the primary or secondary amine, but the amine value is high and the brightness is lowered. It was not possible to achieve a high-intensity color filter that is increasing.

  In addition, a coloring composition for a color filter using a binder resin derived from an ethylenically unsaturated monomer having a hindered amine structure that is an alicyclic tertiary amino group has been proposed (see Patent Document 2). However, Patent Document 2 does not use the specific vinyl resin of the present application in combination, and cannot achieve excellent dispersibility, stability over time, heat resistance, developability, and resolution at the same time.

JP 2009-185277 A JP 2010-54808 A

  An object of the present invention is to provide a coloring composition for a color filter that has excellent dispersibility, stability over time, and heat resistance, and further has excellent developability with respect to an aqueous alkali solution and achieves high resolution and high brightness, and To provide a color filter using

  As a result of intensive studies to solve the above problems, the present inventors have found that when a specific resin-type dispersant and a specific binder resin are used as a color filter coloring composition, dispersibility, The present inventors have found that a color filter excellent in stability, heat resistance, developability, resolution, and brightness can be produced.

  That is, the present invention contains a colorant, a resin-type dispersant (A) having a hindered amine skeleton represented by the following general formula (1), and a binder resin, and the binder resin has an ethylenically unsaturated double bond. The present invention relates to a colored composition for a color filter, which is a vinyl resin [B1] which is an introduced vinyl resin and contains the following structural units (b1) and (b2).

［式（１）中、Ｒ¹は水素原子、炭素数１〜１８のアルキル基、炭素数６〜２０のアリール基、炭素数７〜１２のアラルキル基、アシル基、オキシラジカル基、または、ＯＲ⁴を表し、Ｒ⁴は、水素原子、炭素数１〜１８のアルキル基、炭素数６〜２０のアリール基、炭素数７〜１２のアラルキル基、アシル基、を表し、Ｒ²、及び、Ｒ³はそれぞれ独立にメチル基、エチル基、または、フェニル基を示す。「＊」は結合手であることを示す。］
（ｂ１）；カルボキシル基を有する構成単位：
ビニル系樹脂［Ｂ１］の全構成単位の重量を基準として２〜６０重量％
（ｂ２）；一般式（２）または一般式（３）に示す芳香族環基を有する構成単位：
ビニル系樹脂［Ｂ１］の全構成単位の重量を基準として２〜８０重量％ General formula (1)

[In the formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. ⁴ and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an acyl group, and R ² and R ³ each independently represents a methyl group, an ethyl group, or a phenyl group. “*” Indicates a bond. ]
(B1); a structural unit having a carboxyl group:
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]
(B2): a structural unit having an aromatic ring group represented by the general formula (2) or the general formula (3):
2 to 80% by weight based on the weight of all structural units of the vinyl resin [B1]

［一般式（２）及び（３）中、Ｒ¹⁵は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。］

[In General Formulas (2) and (3), R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

In the present invention, the vinyl resin [B1]
The precursor of the structural unit (b2) is reacted with an ethylenically unsaturated monomer having an epoxy group to obtain a copolymer (i1-1), and then the copolymer (i1-1) obtained ) And an unsaturated monobasic acid to obtain a copolymer (i1-2), and a resin obtained by reacting the obtained copolymer (i1-2) with a polybasic acid anhydride ,
Or
The precursor of the structural unit (b1) and the precursor of the structural unit (b2) are reacted to obtain a copolymer (i2-1), and then the copolymer (i2-1) and epoxy obtained A resin obtained by reacting an ethylenically unsaturated monomer having a group,
It is related with the said coloring composition for color filters characterized by these.

In addition, the present invention relates to the colored composition for a color filter, wherein the vinyl resin [B1] further contains the following structural unit (b3).
(B3): a structural unit having an aliphatic cyclic group represented by formula (4) or formula (5):
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]

  The present invention also relates to the color composition for a color filter, further comprising a resin type dispersant (C) having no hindered amine structure represented by the formula (1).

  The present invention also relates to the colored composition for a color filter, wherein the resin-type dispersant (C) having no hindered amine structure has a glass transition temperature of 40 to 170 ° C.

  In the present invention, the vinyl resin [B1] is obtained by reacting the precursor of the structural unit (b2) with an ethylenically unsaturated monomer having an epoxy group to obtain a copolymer (i1-1). Next, the copolymer (i1-1) obtained is reacted with an unsaturated monobasic acid to obtain a copolymer (i1-2), and the copolymer (i1-2) further obtained It is related with the said coloring composition for color filters characterized by being a resin obtained by making a succinic anhydride react.

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  Furthermore, the present invention relates to a color filter comprising a filter segment formed from the colored composition for a color filter on a substrate.

  According to the present invention, by using a specific resin-type dispersant and a specific vinyl resin as a color filter coloring composition, dispersibility, stability over time, heat resistance, developability, resolution, brightness It is possible to provide a coloring composition for a color filter and a color filter excellent in the above.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” mentioned in the present specification means a color index (CI).

  The present invention is a coloring composition containing a colorant, a resin-type dispersant, a binder resin, and an organic solvent, wherein the resin-type dispersant has a hindered amine skeleton represented by the general formula (1), and the binder The resin is a vinyl resin into which an ethylenically unsaturated double bond is introduced, and is a vinyl resin [B1] containing structural units (b1) and (b2).

  The colored composition of the present invention includes a resin-type dispersant having a hindered amine skeleton and a vinyl resin into which an ethylenically unsaturated double bond is introduced, so that the dispersibility (lower viscosity) of the colored composition and the time-lapse It has the effect which was excellent in stability, heat resistance, developability, and resolution.

  Furthermore, the colored composition of the present invention is colored by including a resin-type dispersant having a high glass transition temperature and a vinyl resin into which an ethylenically unsaturated double bond containing an acid group derived from succinic anhydride is introduced. The composition has excellent effects on brightness and developability.

<Resin type dispersant having hindered amine skeleton (A)>
The resin-type dispersant having a hindered amine skeleton of the present invention is characterized by having a hindered amine structure represented by the general formula (1), and has a structure as long as it has a hindered amine structure represented by the general formula (1). There is no limitation. In particular, a vinyl polymer obtained by polymerizing an ethylenically unsaturated monomer having a hindered amine skeleton represented by the general formula (1) and another ethylenically unsaturated monomer as required is suitably used. it can. Specific examples of suitable vinyl polymers include an ethylenically unsaturated monomer represented by the following general formula (6-1) or (6-2), and a general formula (6-1) or ( 6-2) and copolymers with other ethylenically unsaturated monomers copolymerizable.
As the polymerization method, the desired effect can be obtained regardless of whether random polymerization or block polymerization is used. The same effect can be obtained with a so-called comb copolymer polymerized using a macromer (a high molecular weight monomer having a polymerizable functional group) as a copolymerization partner.

［式（１）中、Ｒ¹は水素原子、炭素数１〜１８のアルキル基、炭素数６〜２０のアリール基、炭素数７〜１２のアラルキル基、アシル基、オキシラジカル基、または、ＯＲ⁴を表し、Ｒ⁴は、水素原子、炭素数１〜１８のアルキル基、炭素数６〜２０のアリール基、炭素数７〜１２のアラルキル基、または、アシル基を表し、Ｒ²、及び、Ｒ³はそれぞれ独立にメチル基、エチル基、または、フェニル基を示す。「＊」は結合手であることを示す。］ General formula (1)

[In the formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. ⁴ and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, R ² , and R ³ each independently represents a methyl group, an ethyl group, or a phenyl group. “*” Indicates a bond. ]

In the above general formula (1), examples of the alkyl group having 1 to 18 carbon atoms of R ¹ and R ⁴ include linear, branched, and cyclic alkyl groups, specifically, methyl group, ethyl group Group, normal propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like.

In the general formula (1), examples of the aryl group having 6 to 20 carbon atoms of R ¹ and R ⁴ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

In the general formula (1), examples of the aralkyl group having 7 to 12 carbon atoms of R ¹ and R ⁴ include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specific examples include benzyl group, phenethyl group, α-methylbenzyl group, 2-phenylpropan-2-yl group and the like.

In the general formula (1), examples of the acyl group of R ¹ and R ⁴ include alkanoyl groups having 2 to 8 carbon atoms and aroyl groups, and specific examples include acetyl groups and benzoyl groups. I can do it.
In the present invention, R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an oxy radical group, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

[An ethylenically unsaturated monomer having a hindered amine skeleton represented by the general formula (1)]
As specific examples of the ethylenically unsaturated monomer having a group represented by the general formula (1),
For example, the compound represented with the following general formula (6-1), the compound represented with the following general formula (6-2), etc. can be mentioned.

General formula (6-1), (6-2)

[In General Formula (6-1) and General Formula (6-2), R ⁵ and R ⁷ each represent a hydrogen atom or a methyl group, R ⁶ represents an alkylene group having 1 to 5 carbon atoms, X is the above general formula (1)
Y represents —CONH— *, —SO ₂ —, —SO ₂ NH— * (where a bond marked with “*” is bonded to X), and n is 0. Integer of ~ 9 is shown. ]

R ⁶ is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. n is preferably an integer of 0 to 8, particularly preferably an integer of 0 to 6.

  Specific examples of the monomer represented by the general formula (6-1) include compounds represented by the following general formulas (7-1) to (7-7).

General formula (7-1)-general formula (7-7)

(In the general formula (7-1) to formula (7-7), R ⁵ has the same meaning as R ⁵ in the general formula (6-1).)

  Specific examples of the monomer represented by the general formula (6-2) include compounds represented by the following general formulas (8-1) to (8-4).

General formula (8-1)-General formula (8-4)

[In the general formula (8-1) to formula (8-4), R ⁷ has the same meaning as R ⁷ in the general formula (6-2). ]

Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound in which R ⁵ is a methyl group in the above general formula (7-1)), 1,2,2,6,6-pentamethylpiperidyl Methacrylate (a compound in which R ⁵ is a methyl group in the above general formula (7-2)) is preferable, and 1,2,2,6,6-pentamethylpiperidyl methacrylate (the above general formula (7-2)) is particularly preferable. .

[Other ethylenically unsaturated monomers]
The other ethylenically unsaturated monomer is not particularly limited as long as it is a monomer copolymerizable with an ethylenically unsaturated monomer having a hindered amine skeleton, and can be appropriately selected according to the use. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrene And (meth) acrylonitrile.

Specific examples of such a monomer include the following compounds.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiarybutylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meth) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl Ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol Monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (Meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, (Poly) alkylene glycol monoalkyl ether (meth) acrylates;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, and nonylphenoxypoly (ethylene glycol-propylene glycol) (meth) ) Having an aromatic ring such as acrylate (poly) Ruki glycol (meth) acrylates;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine;
Nitriles such as (meth) acrylonitrile are exemplified.
Styrenes such as styrene and α-methylstyrene;
Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate; and the like can also be used.

  Furthermore, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2 -(Meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth) acrylate, and ω-carboxypoly Examples include caprolactone (meth) acrylate.

  One or more types can be selected from the ethylenically unsaturated monomers listed above, and at least benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and methoxy It is preferred to use an ethylenically unsaturated monomer selected from the group consisting of ethyl (meth) acrylate.

[About polymerization method]
(Random polymerization)
The resin-type dispersant (A) of the present invention is particularly preferably a random copolymer. When the resin-type dispersant (A) of the present invention is a random copolymer, a free radical polymerization method can be suitably used. 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 the 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.

  It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but 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 resin-type dispersant (A), which is a random polymer using an ethylenically unsaturated monomer having a group represented by the general formula (1), is ethylene from the viewpoint of viscosity and viscosity stability of the pigment dispersion. The ethylenically unsaturated monomer having a group represented by the general formula (1) is preferably contained in an amount of 1% by weight to 100% by weight, and more preferably 25% by weight to the solid content of the unsaturated unsaturated monomer. The content is preferably 100% by weight, and particularly preferably 40% by weight to 100% by weight.

  Since the group represented by the general formula (1) has an antioxidant function, it is possible to prevent oxidation of the color filter material by including even a small amount, and as a result, to prevent a decrease in brightness.

  Furthermore, the resin type dispersant (A), which is a random polymer using an ethylenically unsaturated monomer having a group represented by the general formula (1) of the present invention, has an amine value of 50 to 350 mgKOH / g. Preferably there is. If the amine value is less than 50 mgKOH / g, the viscosity and viscosity stability of the pigment dispersion may be deteriorated. If it exceeds 350 mgKOH / g, the brightness may decrease.

  The number average molecular weight of the resin type dispersant (A) which is a random polymer using an ethylenically unsaturated monomer having a group represented by the general formula (1) of the present invention is preferably 500 to 30,000. . If it is less than 500 or exceeds 30,000, the viscosity and viscosity stability of the pigment dispersion may be deteriorated.

(Block polymerization)
When the resin-type dispersant (A) of the present invention is a block copolymer, a copolymer comprising an A block having a hindered amine structure represented by the general formula (1) in the side chain and a B block not having a hindered amine structure. Any polymer may be used, and an AB block, a B-A-B block, or an A-B-A block is preferable, and an AB block or a B-A-B block can be more preferably used.
Such a block copolymer is prepared, for example, by the living polymerization method shown below. Here, the living polymerization is a polymerization method in which side reactions occurring in general radical polymerization are suppressed, and further, the growth of the polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight is easily synthesized. Depending on the charge ratio of the polymerization initiator and vinyl monomer added during polymerization, the molecular weight of the polymer and the ratio of monomers copolymerized with the block can be freely controlled, including block polymers, gradient polymers, star polymers, comb polymers, Can be used for the production of terminal functional polymers and the like.

  The block copolymer of the present invention can be synthesized by a known radical living polymerization method. As specific examples, the methods listed below have been developed, and extensive research and development has been conducted. Nitroxide mediated polymerization (NMP method) using dissociation and bonding of amine oxide radicals (see Reference 1). Atom transfer radical polymerization (ATRP method) using a heavy metal such as copper, ruthenium, nickel and iron and a ligand that forms a complex with the heavy metal as a starting compound (Atom transfer radical polymerization: ATRP method) (Reference 2, Reference 3 and Reference 4). Reversible addition-fragmentation chain transfer (RAFT method) in which dithiocarboxylic acid ester or xanthate compound is used as the starting compound and polymerized using an addition polymerizable monomer and a radical initiator (references) 5) and Macromolecular Designvia Interchange of Xanthate (MADIX method) (see Reference 6). Method using heavy metal such as organic tellurium, organic bismuth, organic antimony, antimony halide, organic germanium, germanium halide (Degenerative transfer: DT method) (see Reference 7 and Reference 8)

(Reference document 1) Chemical Review (2001) 101,3661
(Reference 2) JP 2000-500516 A (Reference 3) JP 2000-514479 A (Reference 4) Chemical Review (2001) 101, 3690
(Reference 5) Japanese translations of PCT publication No. 2000-515181 (Reference 6) pamphlet of International Publication No. 1999-05099 (Reference 7) JP 2007-277533 A (Reference 8) Journal of American Chemical Society (2002) 124, 2874

  Among these radical living polymerizations, the atom transfer radical polymerization method (ATRP method) in which an organic halide or a sulfonyl halide compound is used as an initiator and a metal complex having a transition metal as a central metal as a catalyst is used for the molecular weight of the polymer. This is preferable not only in terms of controlling the molecular weight distribution, but also in that it can be applied to a wide range of monomers and a polymerization temperature that can be applied to existing equipment.

  In the atom transfer radical polymerization method, a transition metal complex such as copper, ruthenium, iron and nickel is used as a redox polymerization catalyst. Specific examples of the transition metal complex include low-valent transition metal halides such as copper (I) chloride and copper (I) bromide.

  An organic ligand is used for the transition metal complex. Organic ligands are used to allow for reversibility of the solubility in the polymerization solvent and the redox polymerization catalyst. Examples of the coordination atom of the transition metal include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom.

  As the initiator used in the atomic radical polymerization method, known initiators can be used, and mainly organic halides having a highly reactive carbon halogen bond, halogenated sulfonyl compounds, and the like are used. Specific examples include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, paratoluenesulfonic acid chloride, 1-bromoethylbenzene, chloroethylbenzene, and the like. These are used alone or in combination.

  The content of the partial structure (A block) having a hindered amine structure represented by the general formula (1) in the side chain with respect to the block copolymer solid content is preferably 1 to 99% by weight, and more preferably 20% by weight. % To 50% by weight is preferable, and 20% to 30% by weight is particularly preferable. When the A block contains 20 wt% to 30 wt%, the remaining 70 wt% to 80 wt% constitutes the B block. Therefore, the pigment can be stably present in the dispersion medium by the affinity of the B block with the solvent as the dispersion medium.

  The block copolymer used in the present invention may be an AB block copolymer or a B-A-B block copolymer, and the A block / B block ratio (weight) constituting the copolymer. The ratio is usually in the range of 1/99 or more, especially 20/80 or more, and usually 80/20 or less, especially 60/40 or less. Outside this range, it may not be possible to achieve both good brightness and dispersibility.

  Further, the amount of the group represented by the general formula (1) in 1 g of the AB block copolymer and the BAB block copolymer used in the present invention is usually 0.1 to 5 mmol. Preferably, outside this range, good brightness and dispersibility may not be compatible.

The block copolymer of the present invention preferably has an amine value of 50 to 350 mgKOH / g, although it depends on the type of hindered amine group represented by the general formula (1) that is the basis of the amine value. If the amine value is less than 50 mgKOH / g, the viscosity and viscosity stability of the pigment dispersion may be deteriorated. If it exceeds 350 mgKOH / g, the brightness may decrease.

  Moreover, the molecular weight of the block copolymer of the present invention is preferably a range of 1,000 or more and 100,000 or less in terms of polystyrene weight average. When the molecular weight of the block copolymer is less than 1,000, the dispersion stability is lowered, and when it exceeds 100,000, the developability tends to be lowered.

The A block constituting the block copolymer has the hindered amine structure represented by the general formula (1), and the same one as already explained in the explanation section of the resin-type dispersant having a hindered amine skeleton can be used.
On the other hand, the A block having a partial structure not containing the group represented by the general formula (1) and the B block not having a hindered amine structure may be a polymer structure obtained by copolymerizing a copolymerizable monomer. If it is not specifically limited, it can select suitably according to a use. As the copolymerizable monomer, the same monomers as those already explained in the explanation section of the random polymer can be used.

<Resin type dispersant (C) not having hindered amine structure>
The colored composition of the present invention is preferably further used in combination with another resin-type dispersant (C) that does not have a hindered amine structure represented by the general formula (1). The resin-type dispersant shown below has a colorant-affinity part that has the property of adsorbing to the additive colorant and a part that is compatible with the colorant carrier, and adsorbs to the additive colorant to form a colorant carrier. It works to stabilize the dispersion.

  Specific examples of the resin-type dispersant include a dispersant (D) having an aromatic carboxyl group, a dispersant having a phosphate group, a dispersant having a sulfate group or a sulfonate group, a polycarboxylic acid such as polyurethane and polyacrylate Esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, , These modified products, oil-based dispersants such as amides and salts thereof formed by the reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, (meth) acrylic acid-styrene copolymers, (meta ) Acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer Body, polyvinyl alcohol, polyvinyl pyrrolidone and other water-soluble resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, etc. are used alone or in combination of two or more. Although it can be used, it is not necessarily limited to these.

  As other commercially available resin type dispersants (C), Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165 manufactured by Big Chemie Japan Co., Ltd. 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163 , 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, or LACTIMON, LACTIMON-WS or BYKUMEN, etc. -3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, manufactured by BASF Corp., 41000, 41090, 53095, 55000, 56000, 76500, etc. 4401, 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. Can be mentioned.

  The resin type dispersant (C) can be roughly classified into an acidic resin type dispersant and a basic resin type dispersant, and an acidic resin type dispersant can be preferably used. Among these, a dispersant (D) having an aromatic carboxyl group, a dispersant having a phosphoric acid group, a dispersant having a sulfuric acid group or a sulfonic acid group are preferable, and a dispersant (D) having an aromatic carboxyl group is most preferable.

Moreover, it is preferable that a resin type dispersing agent (C) has a polymer site | part, and it is preferable that the glass transition temperature (Tg) of this polymer site | part is 40-170 degreeC from a lightness and developability viewpoint.
More preferably, the polymer portion is a vinyl polymer obtained by polymerizing an ethylenically unsaturated monomer from the viewpoint of the viscosity and storage stability of the pigment dispersion.

Here, the Tg (glass transition temperature) of the polymer part referred to in the present invention can be calculated from the Tg of each homopolymer of the monomer to be polymerized by the following Fox equation.

Formula of Fox 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”).

[Dispersant (D) having aromatic carboxyl group]
The dispersant (D) having an aromatic carboxyl group of the present invention has an aromatic carboxyl group in the molecule. The production method includes, for example, production method 1 in which aromatic tricarboxylic acid anhydride (D1) and / or aromatic tetracarboxylic dianhydride (D2) is reacted with polymer (E) having a hydroxyl group, aromatic carboxyl Production method 2 for producing a polymer using a monomer having a group, aromatic tricarboxylic acid anhydride (D1) and / or aromatic tetracarboxylic dianhydride (D2) while polymerizing a monomer having a hydroxyl group Any one of production methods 3 in which is reacted. Among these, from the viewpoint of pigment dispersibility, those produced by the production method 1 in which the number of aromatic carboxyl groups in the dispersant (D) can be more easily controlled are preferable.

  That is, as the dispersant (C) having an aromatic carboxyl group, a polymer (E) having a hydroxyl group, an aromatic tricarboxylic acid anhydride (D1) and / or an aromatic tetracarboxylic acid dianhydride (D2), Preferably, the polymer (E) having a hydroxyl group is a polymer having a hydroxyl group at one end, and more preferably a polymer having a hydroxyl group at one end. (E) can be made excellent in stability by using a dispersant which is a polymer having two hydroxyl groups at one end.

  Further, the polymer having a hydroxyl group at one end is preferably a polyester and / or polyether polymer having a hydroxyl group at one end, or a vinyl polymer having a hydroxyl group at one end, particularly preferably, This is the case where a vinyl polymer having a hydroxyl group at one end is used from the viewpoint of dispersion stability.

  Moreover, as aromatic tricarboxylic acid anhydride (D1) and / or aromatic tetracarboxylic acid dianhydride (D2), especially aromatic tetracarboxylic acid dianhydride (D2) is effective in the storage stability of the pigment dispersion. It is preferable because of its superiority.

  Among such dispersants (D) having an aromatic carboxyl group, the polymer part has a glass transition temperature (Tg) of 40 to 170 ° C. from the viewpoint of brightness and developability. Preferably there is. More preferably, it is 50-150 degreeC, More preferably, it is 70-130 degreeC. When the temperature is lower than 40 ° C., the developability is improved, but the brightness is lowered. When the temperature is higher than 170 ° C., the developability may be deteriorated.

The dispersant (D) having an aromatic carboxyl group of the present invention preferably has a number average molecular weight of 500 to 30,000. If it is less than 500 or more than 30,000, the viscosity and viscosity stability of the pigment dispersion may be deteriorated.
Moreover, it is preferable that the dispersing agent (D) which has an aromatic carboxyl group of this invention has an acid value of 10-200 mgKOH / g.

  For the dispersant (D) having an aromatic carboxyl group, known techniques described in International Publication No. 2008/007776 pamphlet, Japanese Unexamined Patent Application Publication No. 2009-185277, Japanese Unexamined Patent Application Publication No. 2008-029901 can be used. .

<Colorant>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. The following are typical pigments and dyes that can be used in the present invention.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208,209,210,216,220,221,224,226,242,246,254,255,264,270,272,273,274,276,277,278,279,280,281,2 2,283,284,285,286,287 or diketopyrrolopyrrole pigment described in JP-T 2011-523433 discloses the like, but not particularly limited thereto. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.

  Yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes , Naphthoquinone dyes and oxazine dyes.

  Therefore, specific examples of yellow dyes include 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, 199 Etc.

In addition, C.I. I. Direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 2
4, 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 and the like.

  In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

  In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like are also included.

  In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

  As the yellow pigment, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include 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, Yellow pigments such as 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable.
These yellow pigments can be used alone or in combination of two or more depending on the desired color characteristics.

  Examples of the green pigment that can be used in the present invention include C.I. I. Examples thereof include zinc phthalocyanine pigments described in CI Pigment Green 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like. It is not limited to.

  Examples of blue pigments that can be used in the present invention include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not limited thereto.

  The preferred colorant content in all the non-volatile components of the colored composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of sufficient color reproducibility and stability. Most preferably, it is 20 to 80% by weight.

(Miniaturization of pigment)
When the colorant used in the coloring composition of the present invention is a pigment, it can be refined by a salt milling process or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated 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 cost. 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 with respect to 100 parts by weight of the pigment, from the viewpoint 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 100 parts by weight of the pigment.

  When the salt is milled, 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 the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Binder resin>
(Vinyl resin [B1])
The binder resin contained in the colored composition of the present invention is a vinyl resin into which an ethylenically unsaturated double bond is introduced, and includes a vinyl resin [B1] containing the following structural units (b1) and (b2). It is characterized by containing.
(B1); a structural unit having a carboxyl group:
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]
(B2): a structural unit having an aromatic ring group represented by the general formula (2) or the general formula (3):
2 to 80% by weight based on the weight of all structural units of the vinyl resin [B1]

[一般式（２）及び（３）中、Ｒ¹⁵は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。]

[In General Formulas (2) and (3), R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

Hereinafter, the structural unit (b1), the structural unit (b2), other structural units, and a method for introducing an ethylenically unsaturated double bond will be described in order.
In the present specification, the content% by weight of each structural unit is the weight% of the precursor that brings each structural unit to the vinyl resin [B1].

[Structural unit (b1)]
The structural unit (b1) has a carboxyl group and functions as an alkali-soluble site during development. Based on the weight of all the structural units of the vinyl resin [B1], the structural unit (b1) is 2 to 60% by weight from the viewpoint of developability. If it is less than 2% by weight, the removability of the unexposed part by the alkaline developer becomes insufficient, and if it exceeds 60% by weight, the dissolution rate in the alkali developer is increased and the exposed part is dissolved.

  The structural unit (b1) corresponds to a carboxyl group that is not used for an addition reaction with an epoxy group by a method using a precursor of the structural unit (b1) having a carboxyl group and a method (i-1) described later. The unit may be the structural unit (b1) in the vinyl resin.

  Examples of the precursor of the structural unit (b1) having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, and unsaturated dicarboxylic acids such as maleic acid or fumaric acid. And compounds containing a carboxyl group such as an acid and having an ethylenically unsaturated double bond. Moreover, what half-esterified the anhydride of unsaturated dicarboxylic acid, such as maleic anhydride, with the (meth) acrylic compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, can also be used. Among these, (meth) acrylic acid is more preferable, and methacrylic acid is most preferable from the viewpoint of polymerizability (ease of control of molecular weight and the like). These can be used alone or in combination of two or more.

[Structural unit (b2)]
The structural unit (b2) has a cyclic structure with an aromatic ring group represented by the general formula (2) and the general formula (3), and functions as an affinity site for a pigment or a pigment composition comprising a pigment and a dispersant. To do. Based on the weight of all structural units of the vinyl resin [B1], the structural unit (b2) is 2 to 80% by weight from the viewpoints of developability, dispersion stability, and chemical resistance. If it is less than 2% by weight, the developability, dispersion stability and chemical resistance are lowered. If it exceeds 80% by weight, the dissolution rate in an alkaline developer is slowed, the development time is long, and the productivity is deteriorated. .
(B2): a structural unit having an aromatic ring group represented by the general formula (2) or the general formula (3):
2 to 80% by weight based on the weight of all structural units of the vinyl resin [B1]

[一般式（２）及び（３）中、Ｒ¹⁵は、水素原子、またはベンゼン環を有していてもよい
炭素数１〜２０のアルキル基である。]

[In General Formulas (2) and (3), R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

  As the precursor of the structural unit (b2), styrene, α-methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, bisphenol A diglycidyl ether di (meth) acrylate, (meth) of methylolated melamine Examples thereof include monomers / oligomers such as acrylic acid esters, and ethylenically unsaturated monomers represented by the general formula (9).

[一般式（９）中、Ｒ¹⁶は、水素原子、またはメチル基であり、Ｒ¹⁷は、炭素数２若しくは３のアルキレン基であり、Ｒ¹⁸は、ベンゼン環を有していてもよい炭素数１〜２０のアルキル基であり、ｎは、１〜１５の整数である。]

[In General Formula (9), R ¹⁶ is a hydrogen atom or a methyl group, R ¹⁷ is an alkylene group having 2 or 3 carbon atoms, and R ¹⁸ is a carbon that may have a benzene ring. It is a C1-C20 alkyl group, and n is an integer of 1-15. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (9) include:
New Frontier CEA [EO-modified cresol acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : methyl group, n = 1 or 2], NP-2 [n-nonylphenoxy polyethylene] Glycol acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : n-nonyl group, n = 2], N-177E [n-nonylphenoxypolyethylene glycol acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene Group, R ¹⁸ : n-nonyl group, n = 16 to 17], or PHE [phenoxyethyl acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1],
Made by Daicel, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1], or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 2],
Aronix M-101A manufactured by Toagosei Co., Ltd. [phenol EO modified (n≈2) acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n≈2], M-102 [phenol EO modified ( n≈4) acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n≈4], M-110 [paracumylphenol EO modified (n≈1) acrylate, R ¹⁶ : hydrogen atom , R ¹⁷ : ethylene group, R ¹⁸ : paracumyl, n≈1], M-111 [n-nonylphenol EO-modified (n≈1) acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : n− Nonyl group, n≈1], M-113 [n-nonylphenol EO-modified (n≈4) acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : n-nonyl group, n≈4], or M-117 [ n-nonylphenol PO-modified (n≈2.5) acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : propylene group, R ¹⁸ : n-nonyl group, n≈2.5],
Kyoeisha light acrylate PO-A [phenoxyethyl acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1], P-200A [phenoxypolyethylene glycol acrylate, R ¹⁶ : hydrogen atom, R ^17: an ethylene group, R ^18: a hydrogen atom, n ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R ^16: a hydrogen atom, R ^17: an ethylene group, R ^18: n-nonyl group, n ≒ 4 Or NP-8EA [[nonylphenol EO adduct acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R ¹⁶ : Methyl group, R ¹⁷ : propylene group, R ¹⁸ : hydrogen atom, n = 1],
NIPPON BLEMER ANE-300 [nonylphenoxypolyethylene glycol acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : -nonyl group, n≈5], ANP-300 [nonylphenoxypolypropylene glycol acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : propylene group, R ¹⁸ : n-nonyl group, n≈5], 43ANEP-500 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group And propylene group, R ¹⁸ : -nonyl group, n≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group and propylene group, R ¹⁸ : n -Nonyl group, n≈9 + 3], 75ANEP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group and propylene group, R ¹⁸ : n-nonyl group, n≈5 + 2], AAE-50 [phenoxypolyethylene glycol Acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1], AAE-300 [phenoxypolyethylene glycol acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen Atom, n≈5.5], PAE-50 [phenoxypolyethylene glycol methacrylate, R ¹⁶ : methyl group, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1], PAE-100 [phenoxypolyethylene glycol methacrylate, R ¹⁶ : methyl group, R ¹⁷ : ethylene group, R ^{1 8} : hydrogen atom, n = 2] or 43PAPE-600B [phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R ¹⁶ : methyl group, R ¹⁷ : ethylene group and propylene group, R ¹⁸ : hydrogen atom, n≈6 + 6] ,
NK ESTER AMP-10G [phenoxyethylene glycol acrylate (EO 1 mol), Shin Nakamura Chemical Co., Ltd., R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1], AMP-20G [phenoxyethylene glycol acrylate (EO 2 mol), R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n≈2], AMP-60G [phenoxyethylene glycol acrylate (EO 6 mol), R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group , R ¹⁸ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ¹⁶ : methyl group, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1],
Biscoat # 192 [phenoxyethyl acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1] manufactured by Osaka Organic Chemical Co., Ltd.
SR-339A [2-phenoxyethylene glycol acrylate, R ¹⁶ : hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : hydrogen atom, n = 1], or SR-504 (ethoxylated nonylphenol acrylate, R ¹⁶ : Hydrogen atom, R ¹⁷ : ethylene group, R ¹⁸ : n-nonyl group] and the like, but not limited thereto, two or more kinds may be used in combination.

In the ethylenically unsaturated monomer represented by the general formula (9), the alkyl group of R ¹⁸ has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the carbon number of the alkyl group of R ¹⁸ is 1 to 10, the alkyl group becomes an obstacle and the penetration of ITO etching solution, Metal etching solution, etc. is suppressed and the chemical resistance is increased. The steric hindrance effect increases, and the adhesion with the base material tends to be hindered. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ¹⁸ becomes longer. When the carbon number exceeds 20, the adhesion with the substrate is extremely lowered. Examples of the alkyl group having a benzene ring represented by R ¹⁸ include a benzyl group and a 2-phenyl (iso) propyl group. By adding one side chain benzene ring, chemical resistance is further improved and developability is also improved.

  In the ethylenically unsaturated monomer represented by the general formula (9), n is preferably an integer of 1 to 15. When n exceeds 15, the hydrophilicity increases and the effect of solvation decreases, and the viscosity of the vinyl resin [B1] increases, and the viscosity of the photosensitive composition using the same increases, thereby improving the fluidity. May have an effect. From the viewpoint of solvation, n is particularly preferably 1 to 4.

  As the precursor of the structural unit (b2), styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or the general formula (9) is used from the viewpoints of copolymerization with other precursors and chemical resistance. The ethylenically unsaturated monomer shown by these is preferable. These are particularly preferable because a benzene ring can be introduced into the side chain of the vinyl resin [B1]. By introducing a benzene ring into the side chain of the vinyl resin, the side chain benzene ring is oriented to the pigment, so that the resin adsorption to the pigment is promoted and the pigment aggregation is also suppressed. Furthermore, benzyl acrylate and / or benzyl methacrylate are most preferred from the viewpoints of developability and dispersion stability.

[Other structural units]
Vinyl-type resin [B1] may have structural units other than a structural unit (b1) and a structural unit (b2) as another structural unit. However, since the main function of the other structural unit is to provide developability, a small structure is formed with respect to the relatively large ring structure of the side chain of the structural unit (b2) having a chemical resistance function. It is preferable to take. Thereby, it is considered that developability can be imparted while maintaining the characteristics of the structural unit (b2) having a large side chain having chemical resistance.

Examples of other structural unit precursors include:
Methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (Meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate, 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, Alkyl or alkenyl (meth) acrylates such as rohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (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, 1,6-hexanediol diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di Various acrylic and methacrylic esters such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl- 2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2- Examples of monomers and oligomers such as propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate include, but are not limited to, other ethylenically unsaturated monomers. Can be selected, and two or more types can be used in combination. As described above, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferably used from the viewpoint of developability.

Examples of other ethylenically unsaturated monomers include:
(Meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate or 3-methyloxetanyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate; or
(Meth) acrylamide (in the case of “(meth) acrylamide”, it means acrylamide and / or methacrylamide; the same shall apply hereinafter), N, N-dimethyl (meth) acrylamide, N, N -(Meth) acrylamides such as diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine.

Moreover, as a monomer other than the acrylic monomer, for example,
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or
Examples include vinyl acetate, and fatty acid vinyls such as vinyl propionate. The monomer other than the acrylic monomer can be used in combination with the acrylic monomer.

  Moreover, it is preferable that vinyl-type resin [B1] of this invention further contains the structural unit (b3) which has a cyclic structure by the aliphatic cyclic group shown to Formula (4) and Formula (5). The structural unit (b3) has a cyclic structure with an aliphatic ring group represented by the formula (4) and the formula (5), and serves as an affinity site for a pigment or a pigment composition comprising a pigment and a dispersant, and the like. Functions as a hydrophobic site for the alkaline developer.

(Structural unit (b3))
The structural unit (b3) has 2 to 60% by weight from the viewpoint of developing property, dispersion stability, and chemical resistance, based on the weight (100% by weight) of all the structural units of the vinyl resin [B1]. Is preferred. When the content is 2% by weight or more, the affinity site for the pigment or the pigment composition composed of the pigment and the dispersant is sufficient, and a high-quality color filter can be obtained, or the storage stability of the color filter coloring composition can be improved. It is preferable because it becomes good. Further, it is favorable without causing a problem of pattern peeling or chipping in the pixel portion. The amount of 60% by weight or less is preferable because the dissolution rate in an alkali developer is fast, the development time is short, and the productivity of the color filter is improved.

  Examples of the precursor of the structural unit (b3) include an ethylenically unsaturated monomer represented by the general formula (10), an ethylenically unsaturated monomer represented by the general formula (11), and the like.

[一般式（１０）、一般式（１１）中、Ｒ₉は、水素原子、またはメチル基であり、Ｒ₁₀は、炭素数２若しくは３のアルキレン基であり、ｍは、１〜１５の整数である。]

[In General Formula (10) and General Formula (11), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15. It is. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (10) include:
FANCLIL FA-513AS [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R ₁₀ manufactured by Hitachi Chemical Co., Ltd. : None, m = 0] and the like, but not limited thereto, two or more kinds can be used in combination.

As an unsaturated ethylene monomer represented by the general formula (11), for example,
FANCLIL FA-511AS [dicyclopentenyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], FA-512AS [dicyclopentenyloxyethyl acrylate, R ₉ : hydrogen atom, R ₁₀ manufactured by Hitachi Chemical Co., Ltd. : Ethylene group, m = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R _9: methyl group, R _10: an ethylene group, m = 1] and the like but can be exemplified, without limitation, can be used in combination of two or more kinds.

[Introduction of ethylenically unsaturated double bond]
In addition, the vinyl resin [B1] of the present invention is a structural unit having an ethylenically unsaturated double bond in which an ethylenically unsaturated double bond is introduced using an ethylenically unsaturated monomer having an epoxy group ( It is a vinyl resin having b4).
The vinyl resin [B1] has a double bond group and functions as a site that improves the pattern shape. The structural unit (b4) having an ethylenically unsaturated double bond is 2 to 60% by weight from the viewpoint of the pattern shape based on the weight of all the structural units of the vinyl resin [B1] (100% by weight). preferable. When it is 2% by weight or more, the pattern shape is good, and when it is 60% by weight or less, the resolution is good, which is preferable.
As a method for introducing an ethylenically unsaturated double bond using an ethylenically unsaturated monomer having an epoxy group, an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having an epoxy group can be used. Examples thereof include a method in which an ethylenically unsaturated double bond is introduced using a monomer to form a photosensitive resin, and a method (i1) or a method (i2) shown below is exemplified.

[Method (i1)]
Examples of a method for introducing an ethylenically unsaturated double bond using an ethylenically unsaturated monomer having an epoxy group include an ethylenically unsaturated monomer having an epoxy group and one or more other types of ethylene. A carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to the side chain epoxy group of the copolymer obtained by copolymerizing with the polymerizable unsaturated monomer, There is a method (i1) in which a polybasic acid anhydride is reacted with the generated hydroxyl group, an ethylenically unsaturated double bond is introduced to give the function of a photosensitive resin, and a carboxyl group having an alkali-soluble function is introduced. .

  That is, in the present invention, a copolymer (i1-1) was obtained by reacting a precursor of the structural unit (b2) with an ethylenically unsaturated monomer having an epoxy group, and then obtained. A copolymer (i1-2) and an unsaturated monobasic acid are reacted to obtain a copolymer (i1-2). Further, the obtained copolymer (i1-2), a polybasic acid anhydride, A resin obtained by reacting is preferable because the pattern shape is good.

  Moreover, since the carboxyl group of the unsaturated monobasic acid used in this method (i1) forms an ester bond after the addition reaction to the epoxy group, the structural unit (b1) of the vinyl resin [B1] in this specification Since the polybasic acid anhydride forms a carboxyl group after reaction with a hydroxyl group, it corresponds to the structural unit (b1) of the vinyl resin [B1] in this specification.

[Method (i2)]
Alternatively, a part of the side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other ethylenically unsaturated monomers. And the method (i2) of introducing an ethylenically unsaturated double bond and a carboxyl group by addition reaction of an ethylenically unsaturated monomer having an epoxy group.

  That is, in the present invention, the precursor of the structural unit (b1) and the precursor of the structural unit (b2) are reacted to obtain a copolymer (i2-1), and then the copolymer obtained A resin obtained by reacting (i2-1) with an ethylenically unsaturated monomer having an epoxy group is preferable because of excellent heat resistance.

  In this case, only the structural unit corresponding to the carboxyl group that is not used for the addition reaction with the epoxy group corresponds to the structural unit (b1) of the vinyl resin [B1] in the present specification.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step and from the viewpoint of substrate adhesion.

  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. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together. Of these, (meth) acrylic acid is preferred.

Examples of polybasic acid anhydrides 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. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Further, when etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased.
Moreover, it is preferable to use succinic anhydride as the polybasic acid anhydride because it can be excellent in developability.

The weight average molecular weight (Mw) of the vinyl resin [B1] is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, still more preferably 5,000 to 30. , 000. 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.
When the weight average molecular weight (Mw) of the vinyl resin [B1] exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the photosensitive resin composition becomes high, so that the handling tends to be difficult. Further, if the weight average molecular weight (Mw) is less than 5,000, problems may occur in developability and adhesion to a substrate such as glass.

  The weight average molecular weight (Mw) of the vinyl resin [B1] is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. is there. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When the vinyl resin [B1] is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent. The balance between the group and the aromatic group is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The vinyl resin [B1] is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances are insufficient, and if it is more than 500 parts by weight, the concentration of the colorant becomes low and color characteristics cannot be expressed.

(Other resins)
The photosensitive resin composition of the present invention may further contain other resins other than the vinyl resin [B1]. The other resin is preferably a resin having a 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. Other resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and these can be used alone or in admixture of two or more.

  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.

Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (lightness reduction) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  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.

  Energy ray curable resins having an ethylenically unsaturated active double bond include polymers having reactive substituents such as hydroxy groups, carboxyl groups, amino groups, and reactive groups such as isocyanate groups, aldehyde groups, and epoxy groups. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a substituent or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly Ji glycol (meth) acrylate of (meth) acrylates,
Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, vinyl ethers such as isobutyl vinyl ethers, fatty acid vinyls such as vinyl acetate or vinyl propionate Kind.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succin Midyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

  When the binder resin is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and an aromatic group The balance of groups is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The acid value is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K 0070.

  The binder resin is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances are insufficient, and if it is more than 500 parts by weight, the concentration of the colorant becomes low and color characteristics cannot be expressed.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.
Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 diglycy 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-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

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 dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -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-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition 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, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline 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) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  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.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine.
In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like can be mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required. Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition because the brightness and sensitivity are good.

<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.
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).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and 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. Dimethylpolysiloxane having a polyalkylene oxide unit is 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.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
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 the chaotic surfactant that is 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- Til-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 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with 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 with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, 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-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include 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, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention contains a coloring agent in a dye carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a type sand mill, an annular type bead mill, or an attritor. At this time, the specific quinophthalone compound, aluminum phthalocyanine pigment, and other colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition is a mixture of the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, a dispersion aid, and an additive. Can be adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  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. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more. When a pigment derivative is used, one having a quinophthalone skeleton is preferable from the viewpoint of brightness.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  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; 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, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. It is preferable to remove the mixed 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 the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and the filter segment is formed from the colored composition of the present invention. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  The red filter segment can be formed using a normal red coloring composition comprising a red pigment and a colorant carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 280, 281, 282, 283, 284, 285, 286 or 287. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, red coloring compositions include C.I. I. Pigment orange 43, 71, or 73, and / or 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, 82,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. Also, orange dyes and / or yellow dyes such as quinoline, azo, disazo, and methine dyes can be used.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When the dye is used, a triarylmethane dye or a xanthene dye is preferable in terms of lightness.

<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 the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. 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. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  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 a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. 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 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, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet 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. Further, 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.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Resin weight average molecular weight (Mw), number average molecular weight (Mn))
[Weight average molecular weight of acrylic resin]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the acrylic resin used as the binder resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and “TSK-GEL SUPER HZM-N” is connected in series to both packing materials, and the oven temperature is 40 The measurement was performed at a flow rate of 0.35 ml / min using a THF solution as an eluent at ° C. The sample was dissolved in 1 wt% of the above eluent and 20 microliters was injected. All molecular weights are polystyrene equivalent values.

[Average molecular weight of vinyl resin having hindered amine skeleton]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the vinyl resin having a hindered amine skeleton were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, three separation columns are connected in series, and the packing materials are “TSK-GEL SUPER AW-4000”, “AW-3000”, and “Tosoh Corporation” in order. AW-2000 ", an oven temperature of 40 ° C, an eluent of 30 mM triethylamine and 10 mM LiBr in N, N-dimethylformamide solution was used and measurement was performed at a flow rate of 0.6 ml / min. A sample was prepared at a concentration of 1 wt% in a solvent composed of the above eluent, and 50 microliters was injected. All molecular weights are polystyrene equivalent values.

[Average molecular weight of resin type dispersant having phosphoric acid group, sulfuric acid group or sulfonic acid group]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin-type dispersant having a phosphate group, a sulfate group or a sulfonate group were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and “TSK-GEL SUPER HZ-N” is connected in series to both packings. The measurement was carried out at a flow rate of 0.35 ml / min using a THF solution of 100 mM phosphoric acid as an eluent. A sample was prepared at a concentration of 1 wt% in the solvent consisting of the eluent and 10 microliters was injected. All molecular weights are polystyrene equivalent values.

[Average molecular weight of resin-type dispersant having aromatic carboxyl group]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin type dispersant having an aromatic carboxyl group were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and “TSK-GEL SUPER HZM-N” is connected in series to both packing materials, and the oven temperature is 40 The measurement was performed at a flow rate of 0.35 ml / min using a THF solution as an eluent at ° C. The sample was dissolved in 1 wt% of the above eluent and 20 microliters was injected. All molecular weights are polystyrene equivalent values.

(Calculation of glass transition temperature (Tg) (° C.) of resin-type dispersant (C))
The Tg of the polymer site in the resin type dispersant (C) was calculated by the following Fox formula.

1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ... + (Wn / Tgn)

W1 to Wn indicate the weight separation of the monomers used, and Tg1 to Tgn indicate the glass transition temperature (unit is absolute temperature “K”) of the homopolymer of each monomer.
Regarding the Tg of the main homopolymer used for the calculation, the numerical values described in the polymer handbook can be used. The numerical values are exemplified below.
ε-caprolactone: -60 ° C (213K)
Ethyl acrylate: -22 ° C (251K)
t-butyl acrylate: 41 ° C. (314 K)
Methacrylic acid: 130 ° C (403K)
Methyl methacrylate: 105 ° C (378K)
n-butyl acrylate: -54 ° C (219K)
2-methoxyethyl acrylate: -50 ° C (223K)
Diethylaminoethyl methacrylate: 18 ° C (291K)
1-adamantyl methacrylate: 250 ° C. (523 K)

(Resin acid value (mgKOH / g))
[Acid Value of Resin Type Dispersant Having A Phosphoric Acid Group, Sulfate Group, or Sulphonic Acid Group and Acrylic Resin]
The acid value of the resin-type dispersant having a phosphoric acid group, a sulfuric acid group or a sulfonic acid group, and the acrylic resin is based on the potentiometric titration method of JIS K 0070, and the measured acid value (mgKOH / g) is converted into solid content. Value.

(Amine number of resin (mgKOH / g))
The amine value is a value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 into a solid content.

<Method for producing binder resin solution>
[Resin solution (B1-1)]
(Step 1: Polymerization of resin main chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. At the same temperature, 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and azobisisobutyronitrile 3 as a catalyst required for the reaction of the precursor at this stage 0.0 part of the mixture was added dropwise over 2.5 hours to carry out the polymerization reaction.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 17.0 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 12000 (measurement by GPC) was obtained. Since the added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% to obtain a resin solution (B1-1).

  The weight ratio of the structural unit in the resin solution (B1-1) is as follows: tetrahydrophthalic anhydride as the structural unit (b1); 21.7% by weight, styrene as the structural unit (b2); 11.6% by weight, structural unit (b3 ) As dicyclopentanyl methacrylate; 29.3% by weight; as structural unit (b4), the total of glycidyl methacrylate and acrylic acid ester-bonded to the glycidyl terminal; 37.4% by weight, other structural units; 0.0% by weight %.

[Resin solutions (B1-2 to 3, 7 and B2-1)]
Resin solutions (B1-2 to 3, 7) and (B2-1) were obtained in the same manner as the resin solution (B1-1). That is, in the production method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1. The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.
The number of parts of acrylic acid added in Step 2 was equimolar with the glycidyl methacrylate polymerized in Step 1.

[Resin solution (B1-4 to 5)]
Resin solutions (B1-4) to (B1-5) were obtained in the same manner as in steps 1, 2, and 4 of resin solution (B1-1). That is, in the production method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1. The precursor corresponding to MAA (methacrylic acid) in the structural units (b1) to (b3) and the structural unit (b4) is mixed to carry out stage 1 of production, and then GMA (glycidyl methacrylate) is used as the precursor. In addition, stage 2 of the production was carried out and stage 4 was further carried out.
The number of parts of glycidyl methacrylate charged in stage 2 of the resin solution (B1-4) was 38.5 mol% of the methacrylic acid polymerized in stage 1. The number of parts of glycidyl methacrylate charged in stage 2 of the resin solution (B1-5) was 7 mol% of the methacrylic acid polymerized in stage 1.
The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.

[Resin solution (B2-2)]
The resin solution (B2-2) was prepared in the same manner as in Step 1, Step 2, and Step 4 of the resin solution (B1-1). That is, in the production method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1. GMA (glycidyl methacrylate) in the structural unit (b2), the structural unit (b4), and other precursors corresponding to the other structural units are mixed to perform Step 1 of production, and then AA (acrylic acid) is the precursor. In addition, stage 2 of the manufacturing was carried out and stage 4 was further carried out.
The number of parts of acrylic acid added in Step 2 was equimolar with the glycidyl methacrylate polymerized in Step 1.
The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.

  Table 1 shows the compositions and weight ratios of the obtained resin solutions (B1-1 to 5, 7) and resin solutions (B2-1 to 2). The value in parentheses represents the weight ratio (% by weight) of the constituent unit in the resin solid content.

The precursors of the structural units and the abbreviations of the structural units in Table 1 are described below.
AA: acrylic acid MAA: methacrylic acid THPA: tetrahydrophthalic anhydride (4-cyclohexene-1,2-dicarboxylic anhydride)
MMA: Methyl methacrylate BzMA: Benzyl methacrylate St: Styrene DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate GMA-AA: A structural unit GMA added with an acrylic acid MAA-GMA: A structural unit methacrylic acid has GMA BMA: n-butyl methacrylate HEMA: 2-hydroxyethyl methacrylate

[Resin solution (B1-6)]
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 3.0 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin 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 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. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 40 wt% Thus, a resin solution (B1-6) was prepared. The weight average molecular weight (Mw) was 18000.

[Resin solution (B2-3)]
70.0 parts of PGMAC was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. A mixture of 67.2 parts of benzyl methacrylate, 18.4 parts of methacrylic acid, 14.4 parts of dicyclopentanyl methacrylate, and 3.0 parts of 2,2′-azobisisobutyronitrile is added dropwise over 2 hours to polymerize the reaction. Went. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 50% by weight.
After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add PGMAC to the previously synthesized resin solution so that the nonvolatile content is 40 wt% Thus, a resin solution (B2-3) was prepared. The weight average molecular weight was 22000.

[Resin solution (B2-5)]
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add PGMAC to the previously synthesized resin solution so that the nonvolatile content is 40 wt% Thus, a resin solution (B2-5) was prepared. The weight average molecular weight (Mw) was 26000.

<Method for producing colorant>
(Green colorant (PG-1): PG58)
Phthalocyanine green pigment C.I. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. 97 parts of a colorant (PG-1) were obtained. The average primary particle size was 28.2 nm.

(Yellow colorant (PY-1): PY138)
C. I. 100 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of a colorant (PY-1) were obtained. The average primary particle size was 35.5 nm.

(Red colorant (PR-1): PR254)
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by BASF), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 115 parts of red A colorant (PR-1) was obtained. The average primary particle size was 24.8 nm.

(Red colorant (PR-2): PR177)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of 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. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of a red colorant (PR-2) was obtained. The average primary particle size was 27.6 nm.

(Blue colorant (PB-1): PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor “Lionol Blue ES”) 100 parts, ground salt 800 parts, and diethylene glycol 100 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. did. The mixture was added to 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 98 parts of blue A colorant (PB-1) was obtained. The average primary particle size was 28.3 nm.

(Purple colorant (PV-1): PV23)
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 steel 1 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 for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 118 parts of purple A colorant (PV-1) was obtained. The average primary particle size was 26.4 nm.

(Production of pigment derivative (1))
According to the synthesis method described in Japanese Patent No. 4585781, a pigment derivative (1) was obtained.

<Preparation of resin type dispersant (A) having hindered amine structure>
(Production of Resin Type Dispersant (A-1)) Random Copolymer A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of PGMAC, and the temperature was raised to 110 ° C. while purging with nitrogen. Warm up. In a dropping tank, 120 parts of 2,2,6,6-tetramethylpiperidyl methacrylate, 70 parts of methyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAC, and 2,2′-azobis (2,4-dimethylvaleronitrile) ) Was stirred until it became uniform and then dropped into the reaction vessel over 2 hours, and then the reaction was continued at the same temperature for 3 hours. Thus, a vinyl resin type dispersant (A-1) having a hindered amine skeleton having an amine value per solid content of 145 mg KOH / g and a number average molecular weight of 3,500 (Mn) was obtained.
After cooling to room temperature, about 2 g of resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. PGMAC is added so that the non-volatile content is 30% by weight, and a vinyl system having a hindered amine skeleton A resin type dispersant (A-1) solution was prepared.

(Production of Resin Type Dispersant (A-2)) Random Copolymer A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of PGMAC, and the temperature was raised to 110 ° C. while purging with nitrogen. Warm up. In the dropping tank, 177 parts 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts methyl acrylate, 20 parts 2-hydroxyethyl methacrylate, 61 parts PGMAC, and 2,2′-azobis (2,4-dimethyl) 6 parts of valeronitrile) was added and stirred until it was uniform, then dropped into the reaction vessel over 2 hours, and then the reaction was continued at the same temperature for 3 hours. Thus, a vinyl resin type dispersant (A-2) having a hindered amine skeleton having an amine value per solid content of 201 mg KOH / g and a number average molecular weight of 3,800 (Mn) was obtained.
It diluted like (A-1) and prepared the vinyl-type resin type dispersing agent (A-2) solution which has a hindered amine frame | skeleton.

(Production of Resin Type Dispersant (A-3)) Block Copolymer A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 30 parts methyl methacrylate, 30 parts n-butyl methacrylate, hydroxyethyl 20 parts of methacrylate and 13.2 parts of tetramethylethylenediamine were charged and stirred at 50 ° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAC were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion was 98% or more in terms of non-volatile content.
Next, 61 parts of PGMAC and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate as the second block monomer were added to the reactor, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. The reaction was continued. After 2 hours from the introduction of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution is sampled and solid content is measured, and the polymerization conversion rate of the second block is 98% or more in terms of non-volatile content. This was confirmed, and the reaction solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, the polymer had Mw 9200 and Mw / Mn = 1.5, and the reaction conversion rate was 98.5%. In this manner, a block-type resin dispersant (A-3) having a hindered amine structure with an amine value per solid content of 57 mgKOH / g was obtained.
It diluted like (A-1) and prepared the vinyl-type resin type dispersing agent (A-3) solution which has a hindered amine frame | skeleton.

(Production of Resin Type Dispersant (A-4)) Comb Copolymer In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 150 parts of PGMAC, 50 parts of methyl methacrylate, and n-butyl tacrylate 50 parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved in 4 parts of 2-mercaptoethanol was reacted for 10 hours. As a result of solid content measurement, it was confirmed that 95% had reacted, and a reaction product (A-4a) having a number average molecular weight of 3900 and a weight average molecular weight of 8,000 was obtained.

  The above reaction product (A-4a) was charged with 7.8 parts of 2-acryloyloxyethyl isocyanate, 0.05 part of methyldibutyltin dilaurate and 0.05 part of methylhydroquinone, and the reaction vessel was heated to 100 ° C. For 4 hours. Then, it cooled to 40 degreeC and obtained the reactive organism (A-4b).

A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 43 parts of PGMAC and heated to 100 ° C. while purging with nitrogen. In the dropping tank, the reactive organism (A-4b), pentamethylpiperidyl methacrylate (manufactured by ADEKA, Adeka Stub LA-82) 70 parts, methyl acrylate 10 parts, and 2,2′-azobis (2,4-dimethylbutyrate) 4 parts of (nitrile) was added and stirred until it was uniform, then dropped into the reaction vessel over 2 hours, and then the reaction was continued at the same temperature for 3 hours. In this way, a resinous dispersant (A-4) having a hindered amine structure having a comb structure and an amine value per solid content of 57 mgKOH / g and a weight average molecular weight of 22500 (Mw) was obtained.
Dilution was performed in the same manner as (A-1) to prepare a vinyl resin type dispersant (A-4) solution having a hindered amine skeleton having a comb structure.

<Preparation of resin type dispersant (C) having no hindered amine skeleton>
[Acid resin type dispersant]
(Production of resin-type dispersant (C-1))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 80 parts of methyl methacrylate, 20 parts of n-butyl acrylate, and 44 parts of PGMAC, and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 2.2 parts of 3-mercapto-1,2-propanediol, 0.3 part of 2,2′-azobisisobutyronitrile was added to 24 parts of PGMAC. The dissolved product was divided into 20 times and added every 30 minutes. The reaction was continued for 12 hours at 80 ° C., and it was confirmed that 95% of the product was reacted by solid content measurement. Next, 7.4 parts of trimellitic anhydride and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the mixture was added at 120 ° C. for 2 hours and at 80 ° C. for 5 hours. Reacted for hours. A titration confirming that 90% or more of the acid anhydride is half-esterified, and having an acid value per solid content of 40 mg KOH / g, a number average molecular weight (Mn) of 5,200, and a glass transition temperature (Tg) of 57 ° C. Resin-type dispersant (C-1) having a group carboxyl group was obtained.
It diluted like (A-1) and the resin type dispersing agent (C-1) solution which has an aromatic carboxyl group was prepared.

(Production of resin-type dispersant (C-2))
A reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 29.2 parts of 116% polyphosphoric acid (manufactured by Junsei Kagaku) was added thereto and reacted at 120 ° C. for 2 hours to obtain a dispersant. Thus, a resin type dispersant (C-2) having a phosphoric acid group having a number average molecular weight (Mn) of 1,200 per glass and a glass transition temperature (Tg) of −60 ° C. was obtained.
It diluted like (A-1) and the resin type dispersing agent (C-2) solution which has a phosphoric acid group was prepared.

(Production of resin-type dispersant (C-3))
A reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 53.5 parts of sulfur trioxide-pyridine complex was added here, and it was made to react at 50 degreeC for 2 hours. Thereafter, the pyridine was removed by stripping to obtain a dispersant. Thus, a resin type dispersant (C-3) having a sulfate group having a number average molecular weight (Mn) of 1,200 per glass and a glass transition temperature (Tg) of −60 ° C. was obtained.
It diluted like (A-1) and prepared the resin type dispersing agent (C-3) solution which has a sulfate group.

(Production of resin-type dispersant (C-5))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 5.5 parts of 1-dodecanol, 25.0 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 3.0 parts of pyromellitic anhydride was added thereto and reacted at 100 ° C. for 5 hours to obtain a dispersant. Thus, a resin type dispersant (C-5) having a number average molecular weight (Mn) of 2,500 per solid content and a glass transition temperature (Tg) of −60 ° C. was obtained.
To this, 26.0 parts of cyclohexanone and 52.0 parts of PGMAC were added to obtain a resin type dispersant (C-5) solution having an aromatic carboxyl group having a nonvolatile content of 30%.

(Production of resin-type dispersant (C-6))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 60 parts of ethyl acrylate, 40 parts of t-butyl acrylate, 10 parts of methacrylic acid, and 90 parts of methyl methacrylate and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 20 parts of pyromellitic anhydride, 200.0 parts of PGMAC, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed. A resin type dispersant (C-6) as a dispersant was obtained.
568 parts of PGMAC was added thereto to obtain a resin type dispersant (C-6) solution having an aromatic carboxyl group having a nonvolatile content of 30%.

(Production of resin-type dispersant (C-7))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 40 parts of t-butyl acrylate, 10 parts of methacrylic acid, and 150 parts of methyl methacrylate and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 3.0 parts of 3-mercapto-1,2-propanediol was added. Reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. 7.0 parts of pyromellitic anhydride, 200.0 parts of PGMAC and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. . The acid value was measured to confirm that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed. A resinous dispersant (C-7) which is a polyester dispersant was obtained.
500 parts of PGMAC was added thereto to obtain a resin type dispersant (C-7) solution having an aromatic carboxyl group having a nonvolatile content of 30%.

(Production of resin-type dispersant (C-8))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, and 90 parts of 1-adamantyl methacrylate (“ADMA” manufactured by Osaka Organic Chemical Industry Co., Ltd.), and nitrogen gas Replaced with. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 20 parts of pyromellitic anhydride, 200.0 parts of PGMAC, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The acid value was 70 mgKOH / g, the number average molecular weight (Mn) was 5200, and the glass transition temperature (Tg) was 160 ° C. A resinous dispersant (C-8) which is a polyester dispersant was obtained.
568 parts of PGMAC was added here, and the resin type dispersing agent (C-8) solution which has an aromatic carboxyl group of 30% of non volatile matters was obtained.

(Production of resin-type dispersant (C-9))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 75 parts of methyl methacrylate, and 100 parts of 1-adamantyl methacrylate (“ADMA” manufactured by Osaka Organic Chemical Industry Co., Ltd.), and nitrogen gas Replaced with. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 20 parts of pyromellitic anhydride, 200.0 parts of PGMAC, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and the polyester having an acid value of 70 mgKOH / g, a number average molecular weight (Mn) of 5400, and a glass transition temperature (Tg) of 182 ° C. A resin type dispersant (C-9) which is a dispersant was obtained.
568 parts of PGMAC was added here, and the resin type dispersing agent (C-9) solution which has an aromatic carboxyl group of 30% of non volatile matters was obtained.

[Basic resin dispersant]
(Production of resin-type dispersant (C-4))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of PGMAC and heated to 110 ° C. while purging with nitrogen. 200 parts of diethylaminoethyl methacrylate, 61 parts of PGMAC, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were charged into the dropping tank and stirred until uniform, and then dropped into the reaction tank over 2 hours. Then, the reaction was continued for 3 hours at the same temperature. Thus, the vinyl resin type dispersant (C-4) having a hindered amine skeleton having an amine value per solid content of 345 mg KOH / g, a number average molecular weight (Mn) of 3000, and a glass transition temperature (Tg) of 18 ° C. Obtained.
It diluted like (A-1) and the basic resin type dispersing agent (C-4) solution which does not have a hindered amine skeleton was prepared.

<Method for producing colored composition>
[Example 1]
(Green coloring composition (DG-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. It filtered with a 0.0 micrometer filter, and produced green coloring composition (DG-1). At this time, when the coated substrate is used, the green colorant (PG-1) and the yellow colorant (PY-1) are matched with the chromaticity of x = 0.290 and y = 0.600 with the C light source. The ratio was selected.

Green colorant (PG-1) 4.2 parts Yellow colorant (PY-1) 7.8 parts Resin type dispersant (A-2) solution 3.0 parts Resin type dispersant (C-1) solution 9. 0 parts Resin solution (B1-1) 11.0 parts PGMAC 65.0 parts

[Example 2]
(Green coloring composition (DG-2))
A green colored composition (DG-2) is obtained in the same manner as the green colored composition (DG-1) except that the resin type dispersant (C-1) is changed to the resin type dispersant (A-2). It was.

[Examples 3 to 9, 17 and Comparative Examples 1 to 5]
(Green coloring composition (DG-3-9, 17, 23-27))
Except that the resin solution (B1-1) and the resin-type dispersant (A-2) are changed to the resin solution and the dispersant shown in Table 2, the green coloring is performed in the same manner as the green coloring composition (DG-2). Compositions (DG-3 to 9, 17, 23 to 27) were obtained.

[Examples 10 to 16, 18 to 22]
(Green coloring composition (DG-10-16, 18-22))
The same as the green colored composition (DG-1) except that the resin solution (B1-1) and the resin type dispersant (C-1) are changed to the resin solution shown in Table 2 or the resin type dispersant (C). Thus, green colored compositions (DG-10 to 16, 18 to 22) were obtained.

[Example 23]
(Red coloring composition (DR-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. It filtered with a 0.0 micrometer filter, and produced the red coloring composition (DR-1).

Red colorant (PR-1) 9.6 parts Red colorant (PR-2) 2.4 parts Resin type dispersant (A-2) solution 3.0 parts Resin type dispersant (C-1) solution 9. 0 parts Resin solution (B1-1) 11.0 parts PGMAC 65.0 parts

[Example 24]
(Red coloring composition (DR-2))
A red colored composition (DR-2) is obtained in the same manner as the red colored composition (DR-1) except that the resin type dispersant (C-1) is changed to the resin type dispersant (A-2). It was.

[Example 25]
(Blue coloring composition (DB-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. It filtered with a 0.0 micrometer filter, and produced blue coloring composition (DB-1).

Blue colorant (PB-1) 7.2 parts Purple colorant (PV-1) 4.8 parts Resin type dispersant (A-2) solution 3.0 parts Resin type dispersant (C-1) solution 9. 0 parts Resin solution (B1-1) 11.0 parts PGMAC 65.0 parts

[Example 26]
(Blue coloring composition (DB-2))
A blue colored composition (DB-2) is obtained in the same manner as the blue colored composition (DB-1) except that the resin type dispersant (C-1) is changed to the resin type dispersant (A-2). It was.

<Evaluation of coloring composition>
Evaluation of the initial viscosity, storage stability, and heat resistance of the resulting colored compositions (DG-1 to 27, DR-1, 2, DB-1, 2) was performed by the following methods. Table 2 shows the evaluation results.

(Evaluation of initial viscosity)
As for the viscosity of the coloring composition, an initial viscosity at 25 ° C. was measured using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).

(Evaluation of storage stability)
The obtained colored composition was stored in a thermostat at 40 ° C. for 1 week and accelerated over time, and then the viscosity of the colored composition after aging was measured by the same method as the viscosity measurement, and stored at 40 ° C. for 1 week. The change rate of the viscosity before and after the calculation was calculated and evaluated in two stages according to the following criteria.

○: When the viscosity change rate is within ± 20% and no sediment is formed.
X: When the viscosity change rate exceeds ± 20%, or when a precipitate is generated even when the viscosity change rate is within ± 20%.

(Evaluation of heat resistance of coating film)
The obtained colored composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 220 ° C. for 30 minutes and allowed to cool. Thus, a coated substrate was produced. After the heat treatment at 220 ° C., the prepared coated substrate was C = 0.640 for the red coloring composition, y = 0.600 for the green coloring composition, and y = 0.060 for the blue coloring composition. To match the chromaticity of.
The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with 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 and evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 3.0 ○: ΔEab * is 3.0 or more and less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

  As shown in Table 2, each of the colored compositions for color filters of the present invention containing the resin type dispersant (A) having a specific structure and the binder resin [B1] having a specific structure has low viscosity and storage stability. The results were good and the heat resistance was very excellent.

<Method for producing photosensitive coloring composition>
[Example 27]
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (RG-1).

Green coloring composition (DG-1) 37.5 parts Resin solution (B1-1) 9.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd. 3.0 parts Photopolymerization initiator (BASF) "Irgacure 907" manufactured) 1.3 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts PGMAC 49.0 parts

[Examples 28 to 48, Comparative Examples 6 to 10]
(Green photosensitive coloring composition (RG-2 to 27)
The green photosensitive coloring composition was the same as (RG-1) except that the green coloring composition (DG-1) and the resin solution (B1-1) were changed to the green coloring composition and the resin solution shown in Table 3. (RG-2 to 27) were obtained.

[Example 49]
(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 filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).

Red coloring composition (DR-1) 37.5 parts Resin solution (B1-1) 9.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd. 3.0 parts Photopolymerization initiator (BASF) "Irgacure 907" manufactured) 1.3 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts PGMAC 49.0 parts

[Example 50]
(Red photosensitive coloring composition (RR-2)
A red photosensitive coloring composition (RR-2) was obtained in the same manner as (RR-1) except that the red coloring composition (DR-1) was changed to the red coloring composition and resin solution shown in Table 3. .

[Example 51]
(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed 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-1) 37.5 parts Acrylic resin solution (B1-1) 9.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd. 3.0 parts Photopolymerization initiator (BASF "Irgacure 907" manufactured by Co., Ltd.) 1.3 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts PGMAC 49.0 parts

[Example 52]
(Blue photosensitive coloring composition (RB-2)
A blue photosensitive colored composition (RB-2) was obtained in the same manner as (RB-1) except that the blue colored composition (DB-1) was changed to the blue colored composition shown in Table 3.

<Preparation and evaluation of coating film of photosensitive coloring composition>
Evaluation of the developability, heat resistance, resolution, and brightness of the coatings prepared using the photosensitive coloring compositions (RG-1 to 27, RR1-2, RB1-2) was performed by the following methods. Table 3 shows the evaluation results.

(Developability evaluation)
Spin coater with photosensitive coloring composition (RG-1 to 27, RR1, 2, RB1, 2) on a glass substrate of 100 mm × 100 mm, 1.1 mm thickness, with a film thickness after drying of 2 μm The substrate coated with the coating was dried at 70 ° C. for 20 minutes and spray-developed using a 23 ° C. aqueous sodium carbonate solution, and the developability was evaluated in four stages. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The developability evaluation was determined according to the following criteria.

◎: Can be completely removed within 30 seconds ○: Over 30 seconds but completely removed within 33 seconds Δ: Over 33 seconds but completely removed within 36 seconds ×: Over 36 seconds Can not be completely removed

(Evaluation of heat resistance of coating film)
The obtained photosensitive coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and using an ultrahigh pressure mercury lamp, Ultraviolet exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. Subsequently, it was heated at 220 ° C. for 30 minutes and allowed to cool to obtain a coated substrate. After the heat treatment at 220 ° C., the prepared coated substrate was C = 0.640 for the red coloring composition, y = 0.600 for the green coloring composition, and y = 0.060 for the blue coloring composition. To match the chromaticity of.
The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with 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 and evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 3.0 ○: ΔEab * is 3.0 or more and less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

(Resolution evaluation)
After coating the obtained photosensitive coloring composition on a 100 mm × 100 mm, 1.1 mm thick glass substrate, the solvent was removed by heating at 70 ° C. for 20 minutes in a clean oven to obtain a coating film of about 2 μm. Got. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 330 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

The pattern in the 25 μm photomask portion of the filter segment formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The resolution evaluation was determined according to the following criteria.

◎: Good resolution and linearity ○: Slightly inferior in linearity but good resolution △: Partially poor resolution ×: Poor resolution

(Lightness evaluation)
The obtained photosensitive coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and using an ultrahigh pressure mercury lamp, Ultraviolet exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. After heating at 220 ° C. for 30 minutes and cooling, a coated substrate was obtained. After the heat treatment at 220 ° C., the prepared coated substrate was C = 0.640, y = 0.330 for the red colored composition, x = 0.290 for the green colored composition, y = 0. 600, the blue coloring composition was adapted to the chromaticity of x = 0.150 and y = 0.060.
The chromaticity of the obtained coating film with a C light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).

  As shown in Table 3, the coloring composition for a color filter of the present invention containing the resin type dispersant (A) having a specific structure and the binder resin [B1] having a specific structure was evaluated at a high level in all evaluations. Got.

  That is, in the combination with the resin-type dispersant (A) having a specific structure, the development property is improved in the constitution containing a large amount of the structural unit (b1) of the resin [B1], and the heat resistance is obtained in the constitution containing a large amount of the structural unit (b2). In the composition containing a large amount of the structural unit (b3), the effect of imparting high heat resistance and high resolution tends to be recognized, and the colored composition has high performance.

  Further, in combination with the resin type dispersant (A) having a specific structure, the higher the polymer portion Tg of the resin type dispersant (C), the higher the brightness, and the structural unit (b1) of the resin [B1] When it was derived from succinic anhydride, improved developability was observed, and a colored composition having high performance was obtained.

<Production of color filter>
A black matrix is patterned on a glass substrate, and the red photosensitive coloring composition (RR-1) is applied to the substrate with a spin coater in a C light source (hereinafter also used for green and blue) x = 0.640, y = 0.330 was applied to form a colored film. The film was irradiated with ultraviolet rays of 150 mJ / cm ² 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. Using the same method, the blue photosensitive coloring composition (RB-1) of the present invention was used so that x = 0.290 and y = 0.600. A green filter segment and a blue filter segment were formed so that x = 0.150 and y = 0.060, and a color filter was obtained.

  By using the photosensitive coloring composition of the present invention, it was possible to produce a color filter having good heat resistance, and other physical properties could be suitably used without any problem.

Claims (8)

It contains a colorant, a resin type dispersant (A) having a hindered amine skeleton represented by the following general formula (1), and a binder resin, and the binder resin is a vinyl resin into which an ethylenically unsaturated double bond is introduced. A coloring composition for a color filter, which is a vinyl resin [B1] containing the following structural units (b1) and (b2).
General formula (1)

[In the formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. ⁴ and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an acyl group, and R ² and R ³ each independently represents a methyl group, an ethyl group, or a phenyl group. “*” Indicates a bond. ]

(B1); a structural unit having a carboxyl group:
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]
(B2): a structural unit having an aromatic ring group represented by the general formula (2) or the general formula (3):
2 to 80% by weight based on the weight of all structural units of the vinyl resin [B1]

[In General Formulas (2) and (3), R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ] Vinyl resin [B1]
The precursor of the structural unit (b2) is reacted with an ethylenically unsaturated monomer having an epoxy group to obtain a copolymer (i1-1), and then the copolymer (i1-1) obtained ) And an unsaturated monobasic acid to obtain a copolymer (i1-2), and a resin obtained by reacting the obtained copolymer (i1-2) with a polybasic acid anhydride ,
Or
The precursor of the structural unit (b1) and the precursor of the structural unit (b2) are reacted to obtain a copolymer (i2-1), and then the copolymer (i2-1) and epoxy obtained A resin obtained by reacting an ethylenically unsaturated monomer having a group,
The coloring composition for a color filter according to claim 1, wherein The coloring composition for a color filter according to claim 1 or 2, wherein the vinyl resin [B1] further contains the following structural unit (b3).

(B3): a structural unit having an aliphatic cyclic group represented by formula (4) or formula (5):
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]

  The coloring composition for a color filter according to any one of claims 1 to 3, further comprising a resin-type dispersant (C) having no hindered amine structure represented by the formula (1).   The coloring composition for a color filter according to claim 4, wherein the resin-type dispersant (C) having no hindered amine structure has a glass transition temperature of 40 to 170 ° C.   A vinyl resin [B1] is obtained by reacting a precursor of the structural unit (b2) with an ethylenically unsaturated monomer having an epoxy group to obtain a copolymer (i1-1). The copolymer (i1-1) and unsaturated monobasic acid were reacted to obtain a copolymer (i1-2), and the copolymer (i1-2) and succinic anhydride were further obtained. The colored composition for a color filter according to claim 2, which is a resin obtained by reaction.   Furthermore, the coloring composition for color filters in any one of Claims 1-6 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed on the substrate from the colored composition for color filter according to claim 1.