JP2000338322A - Photopolymerizable composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter having images of smooth surfaces. SOLUTION: This photopolymerizable composition contains (a) a binder resin which is a (meth)acrylic copolymer of a weight average molecular weight of >=10,000 having ethylenically unsaturated double bonds and carboxyl group at its side chain, (b) an epoxy resin, (c) a photopolymerization initiator system, (d) a compound having at least one ethylenically unsaturated double bond in one molecule and (e) a color material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device, a solid-state image pickup device, a red, green, blue color, etc. suitable for the production of color filters used in the production of optical color filters used in cameras and the like. To a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition having excellent surface flatness and image characteristics.

[0002]

2. Description of the Related Art Various methods such as a dyeing method, an electrodeposition method, a printing method and a pigment dispersion method are known as a method for manufacturing a color filter. The pigment dispersion method is the most excellent, and is currently the mainstream color filter production method.

[0003] The pigment dispersion method is a method of producing a color filter by forming a fine colored image on a transparent substrate such as glass by photolithography using a color resist, which is a photosensitive resin in which an organic pigment is dispersed and colored. is there. A color filter needs at least a pattern of three primary colors, and is formed by repeating photolithography using a color resist of these three primary colors. However, since the productivity of the color filter is greatly influenced by the efficiency of photolithography, the material is It is strongly required that color resists have high sensitivity. For this reason, color resists using photosensitive resins of various principles have been proposed, but from the viewpoint of increasing sensitivity, a photo-radical polymerization type using a chain reaction is currently the mainstream.

[0004]

In general, photo-radical polymerization type color resists have the merit of easily increasing the sensitivity, but since they are strongly inhibited from polymerization by oxygen in the air, only the resist surface in contact with the air is cured. However, there is a problem that the surface of the obtained image is roughened by development. Even such fine roughness greatly affects the liquid crystal alignment and degrades the display quality of the liquid crystal display device. Therefore, how to increase the surface flatness of the color filter image has been a major issue.

[0005] Further, in order to prevent the image surface from being roughened (film roughening) due to development, a heat curing treatment may be performed. However, radical polymerization type color resists generally undergo large shrinkage during resin curing due to polymerization. However, there is a problem that the film becomes rough due to shrinkage of the resist coating film due to the heat treatment. Usually, when producing a color filter by a pigment dispersion method, on a glass substrate provided with a black matrix,
Apply a photopolymerizable composition containing a red, green or blue pigment,
After exposing through a mask and developing the non-exposed portions, if necessary, a thermosetting process is performed to form pixels. By repeating this for each color, a color filter is formed. The pixels formed in the first color are subjected to heat treatment many times until the pixels in the third color are formed, and are exposed to the developing solution many times. .

Accordingly, the photopolymerizable composition for a color filter is required to have such characteristics that the coating film has a small shrinkage due to heat and that the obtained pixels are hardly eroded by a developing solution (excellent in chemical resistance). . For example, JP-A-7-325400 describes a photopolymerizable composition for a color filter containing a binder resin having an ethylenically unsaturated double bond and a carboxyl group in a side chain. These are highly sensitive and excellent in chemical resistance, but the resist coating film shrinks due to the heat curing treatment, so that the film is roughened and the surface smoothness of the pixel is considered to be insufficient. Also, JP-A-4-34096
No. 5 discloses a photopolymerizable composition for a color filter containing a compound having an ethylenically unsaturated double bond and an epoxy resin. Since the molecular weight is as low as 8000 or less, the resulting resist coating film has insufficient chemical resistance.

[0007]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have provided a photopolymerizable composition for a color filter having a small roughness of an image surface and a color filter using the same. . That is, the present invention relates to (a) a binder resin which is a (meth) acrylic copolymer having an ethylenically unsaturated double bond and a carboxyl group in a side chain and has a weight average molecular weight of 10,000 or more, (b) an epoxy resin, c) a photopolymerization initiator system, (d) a compound having at least one ethylenically unsaturated double bond in one molecule,
And (e) a photopolymerizable composition for a color filter containing a colorant and a color filter using the same. In the present invention, “image” means “pixel” or “resin black matrix”.

[Detailed Description of the Invention] Hereinafter, the present invention will be described in detail. (A) Binder resin The binder resin in the photopolymerizable composition for a color filter of the present invention has an ethylenically unsaturated double bond and a carboxyl group in a side chain, and has a polymerization average molecular weight of 10,000 or more. It is a polymer. In this specification, “(meth) acryl” indicates “acryl or methacryl”. The same applies to “(meth) acrylate”. Such a copolymer includes, for example, (1) a monomer having at least two ethylenically unsaturated double bonds in one molecule and a monomer having an ethylenically unsaturated double bond and a carboxyl group ( (A part of which is (meth) acrylic acid), or (2) introducing an ethylenically unsaturated double bond group into a trunk resin composed of a (meth) acrylic copolymer. Although it can be obtained, the method (2) is generally preferred from the viewpoint of easy synthesis.

[0009] The base resin comprising the (meth) acrylic copolymer is composed of (meth) acrylic acid and, if necessary, styrene,
Styrene monomers such as α-methyl-styrene and vinyltoluene: unsaturated group-containing carboxylic acids such as cinnamic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid; methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth)
(Meth) such as acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, and methoxyphenyl (meth) acrylate benzyl (meth) acrylate
Esters of acrylic acid; 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2
-(Meth) acryloyloxyethylhexahydrphthalic acid, 2- (meth) acryloyloxyethylmaleic acid,
2- (meth) acryloyloxypropyl succinic acid, 2-
(Meth) acryloyloxypropyl adipic acid, 2-
(Meth) acryloyloxypropylhydrophthalic acid, 2
-(Meth) acryloyloxypropyl phthalic acid, 2-
(Meth) acryloyloxypropylmaleic acid, 2-
(Meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth)
Acryloyloxybutyl hydrophthalic acid, 2- (meth)
Hydroxyalkyl (meth) acrylates such as acryloyloxybutylphthalic acid and 2- (meth) acryloyloxybutylmaleic acid, and acids (such as succinic anhydride, phthalic anhydride, and maleic anhydride) Anhydrous)
A monomer obtained by adding a lactone such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to (meth) acrylic acid; acrylonitrile; acetic acid It can be obtained by polymerizing various monomers such as vinyl, vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl acid such as vinyl pivalate.

Part of the side chain carboxyl group of the obtained trunk resin (preferably 10 to 90 mol%, more preferably 20
To a compound having an ethylenically unsaturated double bond, for example, an ester bond, an acid bond, an ether bond, an imide bond, a urethane bond, etc.
An ethylenically unsaturated double bond can be introduced, and the binder resin of the present invention is obtained.

Above all, the method of introducing via an ester bond is preferable. Specifically, 1) a compound having an ethylenically unsaturated double bond group and an epoxy group in a part of the carboxyl group of a trunk resin having a carboxyl group 2)
Representative examples include a method of half-esterifying a resin having a carboxylic anhydride as a functional group with a compound having an ethylenically unsaturated double bond group and a hydroxyl group, and 3) modifying the resin with an acid anhydride of epoxy acrylate. be able to. Either method may be used. Among them, 1) a method in which a compound having an ethylenically unsaturated double bond group and an epoxy group is reacted with at least a part of the carboxyl group of the trunk resin having a carboxyl group. Most preferred. This will be described in detail below.

Examples of the compound having an ethylenically unsaturated double bond group and an epoxy group include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso)
Crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, (3,
4-epoxycyclohexyl) methyl (meth) acrylate and the compounds listed below.

[0013]

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[0014]

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[0015]

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[In each formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. l shows the integer of 0-10. And the like. In the above, as the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ² , a linear or branched alkylene group such as methylene, ethylene,
Examples include propylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups.
Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene,

[0017]

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And the like. In the present invention, particularly preferred trunk resins of the binder resin include styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, and hydroxy for the purpose of increasing the strength of the coating film. 10 to 98 mol% of a copolymer monomer having a phenyl group such as phenyl (meth) acrylamide and hydroxyphenyl (meth) acrylsulfonamide;
Preferably 20 to 80 mol%, more preferably 30 to 7 mol%.
0 mol%, (meth) acrylic acid, or (meth)
Acrylic acid and 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid, 2-
(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2
A total of at least one monomer selected from (meth) acryloyloxyethylmaleic acid, that is, 2 to 90% by weight, preferably 10 to 70% by weight of a monomer having a carboxyl group; It is a polymerized resin. Particularly preferred binder resin is 2 to 50 mol%, preferably 5 to
A reactant to which an epoxy group-containing unsaturated compound is added at a ratio of ４０40 mol% is desirable.

As a method for reacting a compound having an ethylenically unsaturated double bond group and an epoxy group with the carboxyl group of the trunk resin, a known method can be used. For example, when an ethylenically unsaturated double bond is introduced through an ester bond, the trunk resin having a carboxyl group and a compound having an ethylenically unsaturated double bond group and an epoxy group may be converted into triethylamine and benzylmethylamine. Quaternary ammonium salts such as tertiary amines, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, etc .; By reacting for 10 hours, an epoxy compound can be added to the carboxyl group of the trunk resin.

The molecular weight of the binder resin of the present invention is GP
The weight average molecular weight (Mw) in terms of polystyrene measured by C (gel permeation chromatography) is 1
10,000 or more, preferably 10,000 to 100,0
00, more preferably in the range of 18,000 to 70,000. If the Mw of the binder resin is significantly lower than this range, the image portion tends to be reduced in film thickness during development, and if the Mw is extremely high, the non-image-forming portion tends to have poor removability during development. Further, in order to add a suitable alkali developability, the acid value is 5 to 200 mgK.
OH / g, preferably 10 to 160 mg KO
More preferably, it is H / g.

(B) Epoxy Resin The photopolymerizable composition for a color filter of the present invention contains an epoxy resin for the purpose of improving heat resistance. The epoxy resin in the present invention refers to a low-molecular polymer (prepolymer) having two or more epoxy groups in one molecule and a synthetic resin produced by a ring-opening reaction of the epoxy group, and the molecular weight is not particularly limited. Is usually 150 to 10000, preferably about 300 to 800. More specifically, (1) for example, a glycidyl ether type epoxy resin represented by the following formula,

[0022]

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[0023]

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(2) Crisidyl ester type epoxy resin represented by the following formula:

[0025]

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(3) For example, a cricidylamine type epoxy resin represented by the following formula:

[0027]

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(4) For example, an alicyclic epoxy resin represented by the following formula:

[0029]

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And the like. Among them, those having a polyfunctional epoxy compound having three or more epoxy groups in one molecule as a main component are preferable. In the above (1) to (4),
Those listed as (1) glycidyl ether type epoxy resin and (3) glycidylamine type epoxy resin, in particular,
A glycidyl ether type epoxy resin containing an ethoxy compound having a tetraphenolethane skeleton or a triphenolmethane skeleton as a main component is most preferable.

(C) Photopolymerization initiator system The photopolymerization initiator system used in the present invention is not particularly limited as long as it is a compound capable of polymerizing an ethylenically unsaturated double bond by actinic rays, but is not limited to a biimidazole compound, titanocene Compounds, at least one compound selected from triazine compounds and oxadiazole compounds, and those containing at least one amino group-containing sensitizing dye are preferable, and further selected from thiol compounds or N-phenylglycine and derivatives thereof. Is more preferable.

Specific examples of the biimidazole compound include 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetra (p-carbethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (p-bromophenyl) biimidazole, 2,2'-bis (o-chlorophenyl)-
4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, , 2'-bis (o, p-dichlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole and the like can be mentioned.

The titanocene compound is disclosed in
-152396, JP-A-61-151197, JP-A-63-10602, JP-A-63-41
484, JP-A-2-291, JP-A-3-1
JP-A-2403, JP-A-3-20293, JP-A-3-27393, JP-A-3-52050,
JP-A-4-221958, JP-A-4-21975
No. 6, JP-A-3-27393 and the like can be used. Specifically, di-tanocene compounds can be used.
Cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-
Pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-
Bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-
Ti-bis-2,4-di-fluorophenyl-1-yl,
Di-methylcyclopentadienyl-Ti-bis-2,
3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3
5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti
-Bis-2,6-difluoro-3- (pyrrol-1-yl) -phenyl-1-yl;

As the triazine compound, a triazine compound having a halomethyl group is preferably used. Specifically, 6-phenyl-2,4-bis (trichloromethyl) -s-triazine, 6- (p-methoxyphenyl)
-2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- (p-styrylphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6-p-chlorophenyl-2,4-bis (trichloromethyl) -s-triazine, 6- (p-methylthiophenyl) ) -2,4-Bis (trichloromethyl) -s-
Triazine and the like.

As the oxadiazole compound, an oxadiazole compound having a halomethyl group is preferably used. Specifically, 2-phenyl-5-trichloromethyl-1,3,4-oxadiazole, 2- (p-methylphenyl) -5-trichloromethyl-1,3,4-oxadiazole, (P-methoxyphenyl) -5-
Trichloromethyl-1,3,4-oxadiazole, 2
-Styryl-5-trichloromethyl-1,3,4-oxadiazole, 2- (p-methoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2-
(P-butoxystyryl) -5-trichloromethyl-
1,3,4-oxadiazole and the like.

As the amino group-containing sensitizing dye, for example,
Compounds having a dialkylaminophenyl group described in JP-A-6-19240, JP-A-6-19249 and the like can be mentioned. Specific examples of the compound having a dialkylaminophenyl group include compounds represented by the formula shown in Table 1 below, ethyl p-diethylaminobenzoate, p-diethylaminobenzcarbaldehyde, and 7-julolidylcarbaldehyde. And dialkylaminophenylcarbaldehyde.

[0037]

[Table 1]

[0038]

[Table 2]

Of these, compounds having a dialkylaminophenyl group are preferred because they have higher sensitivity. As the thiol compound, specifically, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate,
Butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakis Aliphatic polyfunctional thiols such as thiopropionate, pentaerythritol tetrakisthioglycolate, and trishydroxyethyltristhiopropionate; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole;
-Mercaptobenzimidazole, 2-mercaptonaphthothiazole, 2-mercaptonaphthoxazole, 2
-Aromatic thiols such as mercaptonaphthoimidazole;

Examples of N-phenylglycine and its derivatives include N-phenylglycine, N-phenylglycine, alkyl group, alkoxyl group, amino group, nitro group,
A cyano group or a substituent substituted by a halogen atom, N-
An alkali metal salt or an alkaline earth metal salt of a carboxylic acid of phenylglycine may, for example, be mentioned.

(D) A compound having at least one ethylenically unsaturated double bond in one minute A compound having at least one ethylenically unsaturated double bond in one molecule (hereinafter referred to as "ethylenic compound") .)
Is a compound in which a polymerization reaction is induced by a radical generated from the photopolymerization initiator system described above. The ethylenic compound may be a monomer or an oligomer having an ethylenically unsaturated double bond in a side chain or a main chain.
The meaning of the monomer in the present invention is a concept corresponding to a so-called polymer substance, and therefore includes not only a monomer in a narrow sense but also a dimer, a trimer, and an oligomer. is there.

Examples of the ethylenic compound include unsaturated carboxylic acids, esters of aliphatic (poly) hydroxy compounds with unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids, and unsaturated carboxylic acids. And polycarboxylic acids and esters obtained from aliphatic polyhydroxy compounds, ethylene oxide of aromatic polyhydroxy compounds, esterification products of propylene oxide adducts and unsaturated carboxylic acids, ethylene oxide of aliphatic polyhydroxy compounds and propylene oxide Esterification reaction product of an adduct and an unsaturated carboxylic acid, ester of caprolactone-modified polyhydric alcohol and unsaturated carboxylic acid, reaction product of polyhydric alcohol and polyisocyanate and unsaturated carboxylic acid, styryl terminal compound, Phosphorus-containing unsaturated compounds, polyepoxy Shi and adducts, and the like with unsaturated carboxylic acids.

Of these, specific examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include:
For example, ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate,
Acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic esters in which the acrylate of these exemplified compounds is replaced with methacrylate; Itaconic acid ester, crotonic acid ester instead of crotonate or maleic acid ester instead of maleate.

Examples of the ester of the aromatic polyhydroxy compound with the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polycarboxylic acid and the polyhydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid and ethylene glycol. Condensate, condensate of acrylic acid, maleic acid and diethylene glycol,
Examples include condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. Examples of the oligomer having an ethylenically unsaturated bond in the main chain include, for example, a polyester obtained by a polycondensation reaction of an unsaturated divalent carboxylic acid and a dihydroxy compound, and a polymerization of an unsaturated divalent carboxylic acid and a diamine. There is a polyamide obtained by a condensation reaction.

The oligomer having an ethylenically unsaturated double bond in the side chain includes a divalent carboxylic acid having an unsaturated bond in the side chain, for example, itaconic acid, propylidene succinic acid, ethylidene malonic acid, etc. There is a condensation polymer with a diamine compound. Further, a polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in a side chain, for example, polyvinyl alcohol, poly (2
-Hydroxyethyl methacrylate), polyepichlorohydrin or the like and a polymer obtained by a polymer reaction of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid can also be suitably used. Among the ethylenic compounds exemplified above, a polyfunctional ethylenic compound containing two or more ethylenically unsaturated double bonds in one molecule is more preferable for the crosslinking reaction of the binder resin by photopolymerization.

(E) Colorant Using the photopolymerizable composition for a color filter of the present invention,
Coloring pigments are preferable as the coloring material used when forming the pixels of the color filter, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based,
Various inorganic pigments and the like can be used in addition to organic pigments such as isoindolinone, dioxazine, indanthrene, and perinone. For example, pigments having the following pigment numbers can be suitably used.

C. I. Red; 9, 97, 122, 123,
149, 168, 177, 180, 192, 215, 2
16, 217, 220, 223, 224, 226, 22
7, 228, 240 C.I. I. Blue; 15, 15; 6, 22, 60, 64 C.I. I. Green; 7, 36 C.I. I. Black; 7 C.I. I. Yellow; 20, 24, 86, 93, 109, 11
0, 117, 125, 137, 138, 139, 14
7, 148, 153, 154, 166, 168 C.I. I. Orange; 36, 43, 51, 55, 59, 6
1 C. I. Violet; 19, 23, 29, 30, 3
7, 40, 50 C.I. I. Tea: 23, 25, 26

The photopolymerizable composition for a color filter of the present invention can also be used for forming a resin black matrix of a color filter. In this case, a black color material is used, and the black color material may be a single color black color material or a plurality of black color materials, or a black color material obtained by mixing red, green, blue and the like. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes.
In the case of inorganic or organic pigments, it is preferable to use them dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

Specific examples of color materials that can be used in combination are Victoria Pure Blue (42595) and Auramine O (4
1000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6 GCP (45160), Rhodamine B (45170), Safranin OK 70: 100
(50240), Erioglaucine X (42080),
No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7
B4401 (15850), Fast Gen Blue TG
RL (74160), Lionol Blue SM (261
50), Lionol Blue ES (Pigment Blue 1)
5: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), and the like (the numbers in parentheses indicate the color index (CI)). Do).

Further, regarding other pigments which can be used in combination, C.I. I. The number is, for example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 11
7, 125, 137, 138, 147, 148, 15
3, 154, 166, C.I. I. Orange pigment 36, 4
3, 51, 55, 59, 61, C.I. I. Red pigment 9, 9
7, 122, 123, 149, 168, 177, 18
0, 192, 215, 216, 217, 220, 22
3, 224, 226, 227, 228, 240, C.I.
I. Violet pigments 19, 23, 29, 30, 37,
40, 50, C.I. I. Blue pigment 15, 15: 1, 15:
4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I.
Brown pigments 23, 25, 26 and the like can be mentioned.

Further, as a black color material that can be used alone,
Carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black,
Cyanine black, titanium black and the like. Among these, carbon black is preferred from the viewpoint of light blocking ratio and image characteristics. Examples of the carbon black include the following carbon blacks.

MA7, MA8, MA1 manufactured by Mitsubishi Chemical Corporation
1, MA100, MA220, MA230, # 52, #
50, # 47, # 45, # 2700, # 2650, # 2
200, # 1000, # 990, # 900 manufactured by Degussa: Printex95, Printex9
0, Printex85, Printex75, Pri
ntex55, Printex45, Printex4
0, Printex30, Printex3, Prin
texA, PrintexG, SpecialBlac
k550, SpecialBlack350, Spec
ialBlack250, SpecialBlack1
00

Monarch 460, manufactured by Cabot Corporation
Monarch 430, Monarch 280, Mon
arch120, Monarch800, Monarc
h4630, REGAL99, REGAL99R, RE
GAL415, REGAL415R, REGAL25
0, REGAL250R, REGAL330, BRAC
K PEARLS480, PEARLS130 manufactured by Colombian Carbon: RAVE11, RAV
EN15, RAVE30, RAVE35, RAVE
N40, RAVEN410, RAVEN420, RAV
EN450, RAVEN500, RAVE780, R
AVEN850, RAVE890H, RAVE10
00, RAVEN1020, RAVEN1040

The above carbon black may be used in combination with other black or colored inorganic or organic pigments. still,
For the production of a resin black matrix having a high optical density and a high surface resistivity, it is particularly preferable to use a resin-coated carbon black.

(F) Phosphoric acid (meth) acrylate compound In addition to the above-mentioned essential components, phosphoric acid (meth) acrylate is compounded to improve the releasability of the non-image area during development during color filter production. It is possible to prevent the occurrence of background stains, improve the adhesiveness of images, and express high image reproducibility. The phosphoric acid (meth) acrylate compound is a phosphoric ester compound having one or more (meth) acryloyl groups, and specific examples thereof include those represented by the following general formula (I).

[0057]

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(Wherein G ¹ represents hydrogen or a methyl group, G ² and G ³ each independently represent an alkylene group which may have a substituent, and a represents an integer of 1-3. , N
Represents an integer of 0 to 10. Among them, G ² and G ³ are each independently preferably a straight-chain or branched alkylene group which may have a substituent having 1 to 15 carbon atoms, and the substituent of the alkylene group is Br. , Cl and an alkyleneoxy group having 1 to 15 carbon atoms are preferred. More specifically, for example,

[0059]

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And the like. In the photopolymerizable composition for a color filter of the present invention, the blending amount of the epoxy resin (b) is 1 to 50% by weight, preferably 5 to 30% by weight based on the total solid. (B) The amount of epoxy resin is 50
If the amount is more than 10% by weight, the sensitivity of the composition to the exposure wavelength at the time of image formation is reduced, so that the image formability tends to be poor. If the amount is less than 1% by weight, the effect of improving the heat resistance of the composition is insufficient, and the resin for forming an image undergoes curing shrinkage in the thermosetting step, so that the film tends to be roughened.

The content of each of the other components of the photopolymerizable composition for a color filter of the present invention is preferably such that the blending amount of the binder resin (a) is 5 to 40% by weight based on the total solid content. Preferably, the compounding amount of (c) the photopolymerization initiator system is 0.1
-20% by weight, in particular 0.5-15% by weight, especially 1-
The content is preferably 12% by weight, and the amount of the (d) ethylenic compound (compound having at least one ethylenically unsaturated double bond) is preferably 5 to 40% by weight. (E) The colorant is 20 to 80% by weight, more preferably 30 to 70% by weight, based on the total solid content.

The amount of (d) the ethylenic compound is
(A) 0.5 to 2. wt.
More preferably, it is 5 times, especially 0.8 to 2.0 times. Further, as a photopolymerization initiator system, at least one compound selected from a biimidazole compound, a titanocene compound, a triazine compound and an oxadiazole compound,
And when it contains an amino group-containing sensitizing dye, a total of 0.01 to 10% by weight based on the total solid content is 0.1 to 10% by weight.
It is preferably in the range of 01 to 10% by weight. When the composition further contains a thiol compound or an N-phenylglycine derivative, the total solid content is 0.01 to 10%.
% By weight, particularly preferably in the range of 0.1 to 4% by weight.

In the present invention, in addition to these essential components, an organic solvent, a pigment dispersant, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant and the like can be appropriately added. In order to improve the adhesion to the substrate, it is preferable to add a silane coupling agent. Types of silane coupling agents include epoxy-based, methacryl-based,
Although various compounds such as amino compounds can be used, epoxy silane coupling agents are particularly preferable.

These components have a solid content of 5 to 50% by weight, preferably 10 to 40% by weight, using an organic solvent.
Is adjusted to be in the range of The organic solvent is not particularly limited as long as it can dissolve and disperse the above-mentioned components and has good handleability. Specifically, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMA
c ". ), Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane, ethyl acetate, methyl lactate, ethyl lactate, methanol, ethanol, propanol, butanol, tetrahydrofuran, etc., with a boiling point in the range of 100 to 200 ° C. And more preferably in the range of 120 to 170 ° C.

The photopolymerizable composition of the present invention is produced according to a conventional method. For example, an ink is prepared by dispersing a coloring material, an organic solvent, a binder resin having a dispersing function, a pigment dispersant, and the like, and further, a binder resin, an ethylenic compound, a photopolymerization initiator system, and the like are blended, mixed, and mixed. It can be obtained by preparing a suitable solution. In the dispersion treatment, it is particularly preferable to use a polymer dispersant as the pigment dispersant because the dispersion stability over time is excellent. Usually, it is preferable that the color material is previously subjected to dispersion treatment using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the color material is finely divided by the dispersion treatment, the coating characteristics of the resist can be improved.

In the case of dispersing with a sand grinder, glass beads or zirconia beads having a diameter of 0.1 to several millimeters are preferably used. The dispersing conditions are usually such that the temperature is from 0 ° C. to 100 ° C., preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (black color material, solvent, dispersant), the size of the sand grinder, and the like. Next, a binder resin, an ethylenic compound, a photopolymerization initiator system, and an organic solvent are blended and mixed into the ink obtained by the dispersion treatment to form a uniform solution. In the manufacturing process, fine dust is often mixed with the photosensitive liquid, and thus the obtained photopolymerizable composition is desirably filtered by a filter or the like. Subsequently, a pixel using the photopolymerizable composition of the present invention,
A method for producing a resin black matrix and a color filter having the same will be described.

First, a photopolymerizable composition containing a coloring material is applied on a transparent substrate by using an applicator such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray, and dried. It is formed by placing a photomask thereon, exposing the image through the photomask, developing, and, if necessary, heat curing or light curing. A pixel can be formed by using a red-green-blue color material as a color material, and a resin black matrix can be formed by using a black color material. By repeating this step, a color filter is formed.
Of course, each pixel may be formed on a transparent substrate having a black matrix formed of chromium, using the photopolymerizable composition of the present invention including a red-green-blue color material.

The transparent substrate used here is a transparent substrate for a color filter, and the material thereof is not particularly limited. Examples thereof include polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, polycarbonate, and polyolefin. Methyl methacrylate, polysulfone thermoplastic sheet,
Examples include thermosetting plastic sheets such as epoxy resin, polyester resin, and poly (meth) acrylic resin, and various glass plates. Particularly, a glass plate and a heat-resistant plastic are preferably used from the viewpoint of heat resistance.

Such a transparent substrate is previously subjected to a corona discharge treatment, an ozone treatment, a thin film treatment of various polymers such as a silane coupling agent and a urethane polymer, etc. in order to improve physical properties such as surface adhesiveness. You can also. For drying, a hot plate, an IR oven, a convection oven, or the like can be used. Preferred drying conditions are 40 to 150 ° C., and the drying time is 10 seconds to 60 minutes. Light sources used for exposure include, for example, xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and the like, argon ion lasers, YAG lasers, excimer lasers, Examples include a laser light source such as a nitrogen laser. When only the wavelength of the specific irradiation light is used, an optical filter can be used.

The developing treatment is not particularly limited as long as it is a solvent capable of dissolving the resist (photopolymerizable composition) film in the unexposed portion, but for example, an organic solvent such as acetone, methylene chloride, trichlene, cyclohexanone, etc. However, the method is not preferable because it involves environmental pollution, harm to the human body, and danger of fire. It is preferable to use an alkali developing solution. As such an alkaline developer, for example,
Sodium carbonate, sodium bicarbonate, potassium carbonate,
Inorganic alkaline agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethylamine, triethanolamine,
An aqueous solution containing an organic alkali agent such as a tetraalkylammonium hydroxide salt and tetramethylammonium hydroxide is exemplified.

If necessary, the alkali developer may contain a surfactant, a water-soluble organic solvent, a wetting agent, a low molecular compound having a hydroxyl group or a carboxylic acid group, or the like. In particular, a surfactant is preferably added because many of them have an effect of improving the developing property, the resolution and the background stain. For example, as a surfactant for a developer, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Surfactants and the like.

The development processing method is not particularly limited, but is usually carried out at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C., by a method such as immersion development, spray development, brush development, or ultrasonic development. . The formed resin black matrix and pixels are preferably subjected to a thermosetting treatment after image formation in order to improve film strength, solvent resistance, alkali resistance and the like. This heat curing treatment is preferably performed at 150 ° C. or more and less than 300 ° C. If the temperature is lower than 150 ° C., the thermosetting is insufficient, so that problems such as film strength, solvent resistance and alkali resistance tend to occur. If the temperature is higher than 300 ° C., excessive volume shrinkage occurs, and problems are likely to occur in the adhesion to the substrate and the accuracy.

When an image is formed by using the photopolymerizable composition for a color filter of the present invention in this way, the surface roughness Ra of the image having a surface roughness of 7 mm or less even after the development step and the heat curing step. Image with few images can be easily obtained. When such an image having a high surface smoothness is used, scattering of light on the image surface is suppressed, and the like.
It is very preferable because it can provide a color filter with clear and bright colors and high contrast.

[0074]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist. (Binder resin)

[0075]

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P-1: In the above structure, Mw = 24000 P-2: In the above structure, Mw = 8000 (Mw: weight average molecular weight in terms of polystyrene measured by GPC) (Epoxy resin) E-1: Triphenol Trifunctional epoxy compound with methane skeleton

[0077]

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E-2: Tetrafunctional epoxy compound having a tetraphenolethane skeleton

[0079]

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(Photopolymerization initiator system) R-1: 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole

[0081]

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Y-1: 4,4'-bis (diethylamino) benzophenone

[0083]

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T-1: 2-mercaptobenzothiazole (2MBT)

[0085]

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(Ethylenic compound) M-1: dipentaerythritol hexaacrylate (DPHA)

[0087]

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(Phosphate acrylate compound) A-1: "PM-21" (manufactured by Nippon Kayaku Co., Ltd.)

[0089]

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Production Example 1: Preparation of Pigment Dispersion Ink 2.6 g of a red pigment "Lionogen Red GD" (manufactured by Toyo Ink Co., Ltd.) and "BYK-16" as a dispersant
1.3 g (manufactured by BYK Chemie KK) and propylene glycol monomethyl ether acetate 11.7
g and mix the mixture by 1.5 times the weight of 0.5 mm
The dispersion was placed in a paint shaker containing zirconia beads having a diameter of 10 hours and dispersed to produce a red pigment-dispersed ink.

Example 1 A binder resin (P-1), an epoxy resin (E-1), a photopolymerization initiator system (R-1, Y-1, T) were added to the red pigment-dispersed ink obtained in Production Example 1. -1), an ethylenic compound (M-1), and a methacrylate phosphate (A-1) as an additive in the proportions shown in Table-2, and propylene glycol monomethyl ether acetate as a solvent, followed by solids concentration. Was adjusted to 25%.

The prepared coating solution was dried to a thickness of 1.2 μm.
m was spin-coated on a chromium substrate (“AN635” manufactured by Asahi Glass Co., Ltd.) and dried at a drying temperature of 70 ° C. for 3 minutes. Next, after exposure with a proper exposure (200 mj / cm ² ) using a 3 kW ultra-high pressure mercury lamp through a photomask, 1% by weight of potassium carbonate and 4% of a nonionic surfactant (“Emulgen A-60” Kao Corporation) )), Using a developer consisting of an aqueous solution containing (a), developing at 23 ° C. with a shower, stopping the development with pure water, and rinsing with a water spray. Thereafter, a heat treatment was performed at 230 ° C. for 30 minutes to form a red image. Table 2 shows the surface roughness of the image after development and after heat treatment. In the obtained red image, deterioration of the surface roughness due to development and heat treatment was small, and the surface roughness was good. The surface roughness of the image was observed using a scanning probe microscope SPA350 (manufactured by Seiko Instruments Inc.) for observing a large sample.

Examples 2 and 3 Images were formed in the same manner as in Example 1 except that the addition amount of the epoxy resin (E-1) was doubled and quadrupled, respectively. Table 2 shows the surface roughness of the obtained image after development and after heat treatment.
Shown in

Example 4 An image was formed in the same manner as in Example 1 except that the epoxy resin was changed to E-2. Table 2 shows the surface roughness of the obtained image after development and after heat treatment.

Comparative Example 1 An image was formed in the same manner as in Example 1 except that the epoxy resin (E-1) was omitted. Table 2 shows the surface roughness of the obtained image after development and after heat treatment. Deterioration of surface roughness due to development was relatively small, but deterioration of surface roughness due to heat treatment was large.

Comparative Example 2 An image was formed in the same manner as in Example 1 except that the binder resin (P-1) was changed to P-2 having a low molecular weight. Table 2 shows the surface roughness of the obtained image after development and after heat treatment. As compared with Example 1, the surface roughness was greatly deteriorated by the development.

Comparative Example 3 An image was formed in the same manner as in Example 1 except that the binder resin (P-1) was changed to P-2 having a low molecular weight and the epoxy resin was omitted. Table 2 shows the surface roughness of the obtained image after development and after heat treatment. The surface roughness was deteriorated by the development and further deteriorated by the heat treatment.

Example 5 An image was formed in the same manner as in Example 1 except that the amount of the binder resin (P-1) was reduced and the amount of the ethylenic compound (M-1) was increased. Table 2 shows the surface roughness of the obtained image after development and after heat treatment. The deterioration of the surface roughness after development was further reduced, and as a result, the surface smoothness of the image was improved.

Examples 6 and 7 An image was formed in the same manner as in Example 5 except that the addition amount of the epoxy resin (E-1) was doubled and quadrupled, respectively. Table 2 shows the surface roughness of the obtained image after development and after heat treatment.
Shown in A pigment-dispersed ink was prepared using blue and green pigments in accordance with Production Example 1, and a coating liquid containing red, blue, and green pigments was prepared. Alternatively, a color filter having an image (pixel) with high surface smoothness can be obtained by forming an image of each color on a glass substrate provided with a resin black matrix.

[0100]

[Table 3]

[0101]

By using the photopolymerizable composition for a color filter of the present invention, the surface of an image (pixel) becomes smooth and light scattering is suppressed. As a result, it is possible to provide a color filter that is bright, clear in color, and excellent in contrast.

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Claims (10)

[Claims] 1. A weight average molecular weight of 100 having (a) an ethylenically unsaturated double bond and a carboxyl group in a side chain.
(B) an epoxy resin, (c) a photopolymerization initiator system,
A photopolymerizable composition for a color filter, comprising (d) a compound having at least one ethylenically unsaturated double bond in one molecule, and (e) a coloring material. 2. The photopolymerizable composition for a color filter according to claim 1, wherein the composition contains (b) an epoxy resin in an amount of 1 to 50% by weight based on all solid molecules of the composition. 3. The photopolymerizable composition for a color filter according to claim 1, wherein (b) the epoxy resin is a compound having three or more epoxy groups in one molecule. 4. The photopolymerizable composition for a color filter according to claim 1, wherein (b) the epoxy resin is a glycidyl ether type epoxy resin and / or a glycidylamine type epoxy resin. 5. The amount of the compound (d) having at least one ethylenically unsaturated double bond in one molecule is 0.5 to 2.5 times by weight the amount of the binder resin (a). The photopolymerizable composition for a color filter according to any one of claims 1 to 4, wherein 6. The photopolymerizable composition for a color filter according to claim 1, wherein (a) the binder resin has an alicyclic (meth) acryloyl group in a side chain. . 7. The photopolymerizable composition for a color filter according to claim 1, further comprising (f) a phosphoric acid (meth) acrylate compound. 8. The photopolymerizable composition for a color filter according to claim 7, wherein (f) the phosphoric acid (meth) acrylate compound is a compound represented by the following general formula (I). Embedded image (In the formula I, G ¹ represents hydrogen or a methyl group, and G ² and G
³ represents an alkylene group which may have a substituent independently,
a shows the integer of 1-3, and n shows the integer of 0-10. ) 9. A color filter having an image formed by using the photopolymerizable composition for a color filter according to claim 1. Description: 10. The color filter according to claim 9, wherein the surface roughness Ra of the image is 7 nm or less.