JPH11326624A - Polymerization composition for color filter, the color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pixel having high sensitivity and superior surface smoothness by using a composition containing resin having a molecular weight in a certain specific range. SOLUTION: This polymerization composition for color filters contains a resin having polymn. groups in a side chain, a photopolymerizing initiator, a photopolymerizable monomer, pigments and a solvent and the weight average molecular weight of the resin having the polymerizing group at the side chain is >=18,000. In such a case, a resin having the polymerizing group at the side chain is used as the resin. The polymerizing group includes a (meth)acryloyl group, ciannamoyl group, cinnamylidene group, chalconic group, etc., and, the (meth)acryloyl group is more preferable among them. A synthesis means for introducing these polymerizing groups into the resin is to bring a compound having a glycidyl group or epoxycylochexyl group and the (meth)acryloyl group, in combination or chloride acrylate, etc., into reaction with the carboxyl group or hydroxyl group in the resin, by which the resin having the polymerizing groups at the side chain can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer composition for a color filter, a color filter and a liquid crystal display device, and more particularly, to a color filter having excellent surface roughness and a polymer composition for a color filter capable of producing the same. And a liquid crystal display device using a color filter having excellent surface roughness.

[0002]

2. Description of the Related Art A color filter is used in which pixels of red, green, blue, etc. are formed on a glass substrate by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method, or the like. A color filter by a dyeing method is manufactured by forming an image with a photosensitive resin obtained by mixing a dichromate as a photosensitive agent in gelatin, polyvinyl alcohol, or the like, and then dyeing the resultant. In order to form multiple colors on the same substrate, an anti-staining process is indispensable, and there is a problem that the process becomes complicated. Further, the use of dyeing results in poor light fastness. Bichromic acid used as a photosensitive agent is also a problem from the viewpoint of preventing pollution.

A color filter formed by a printing method transfers a thermosetting or photocuring ink to a glass substrate by a method such as screen printing or flexographic printing. Although the process is simple because image formation and dyeing are unnecessary, a high-definition image cannot be obtained and there is a problem in ink smoothness. A color filter by an electrodeposition method is a method in which a glass substrate provided with electrodes is immersed in a bath containing a pigment or a dye, and a color is attached by electrophoresis. Although excellent in smoothness, it is difficult to form a complicated pattern because an electrode is required on the glass substrate in advance. In the pigment dispersion method, an image is formed using a colored resist in which a pigment is dispersed in a photocurable resin. It has advantages such as high heat resistance and no need for dyeing, and is capable of forming images with high precision.

[0004]

In the pigment dispersion method, since an image is formed with a colored resist in which a pigment is dispersed at a high concentration, strong light absorption by the pigment occurs and curing is inhibited by oxygen. In addition, there is a problem in the smoothness of the pixel surface due to film roughness. Although there is a method of forming a protective film for blocking oxygen on a resist in order to prevent curing inhibition by oxygen, it is not preferable because it complicates the process.

As a method for solving the film roughness on the pixel surface, it is conceivable to polish the surface after forming the pixel or to provide an overcoat, but this is also not preferable because it complicates the process. It is also conceivable to lengthen the exposure time, but it is not preferable because workability and image definition deteriorate. An object of the present invention is to solve these problems and to provide a polymer composition for a color filter capable of obtaining a pixel having high sensitivity and excellent surface smoothness.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by using a composition containing a resin having a specific molecular weight within a specific range, the composition has high sensitivity and excellent smoothness on the pixel surface. It became clear that a color filter could be created. That is, the present invention provides a color filter polymerization comprising at least (a) a resin having a polymerizable group in a side chain, (b) a photopolymerization initiator, (c) a photopolymerizable monomer, (d) a pigment, and (e) a solvent. A polymer composition for a color filter, wherein the resin having a polymerizable group in a side chain has a weight average molecular weight of 18,000 or more, and an AFM (atomic force) suitably obtained from the composition. The surface roughness of the pixel measured by a microanalyzer) is 15
It exists in a color filter that is not more than μm. Hereinafter, the present invention will be described specifically. In the present invention, as a resin,
A resin having a polymer group in a side chain is used. Examples of the polymer group include a (meth) acryloyl group, a cinnamoyl group, a cinnamylidene group, and a chalcone group. Among them, a (meth) acryloyl group is preferable. As a synthetic means for introducing these polymer groups into the resin, Japanese Patent Publication No. 50-34
No. 443, Japanese Patent Publication No. 50-34444 and the like are known. Specifically, a compound having a glycidyl group or an epoxycyclohexyl group and a (meth) acryloyl group in combination with a carboxyl group or a hydroxyl group in the resin, or a resin having a polymer group in a side chain by reacting with acrylic acid chloride or the like. Can be obtained. Examples of the compound include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl ether (iso) crotonate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, Compounds such as (meth) acrylic acid chloride and (meth) allylic acid chloride are exemplified.

[0007] As the resin skeleton into which the polymerizable group is introduced, a copolymer containing a certain ratio of a monomer having an acidic group is preferable. Specific examples of such a copolymer include (meth) acrylic acid, (anhydride) maleic acid, crotonic acid, itaconic acid, fumaric acid, iroprenesulfonic acid, styrenesulfonic acid, (o, m, p ,) A monomer having an acidic group such as polyvinylphenol, styrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) ) Butyl acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate,
(Meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N
Copolymers obtained by copolymerizing monomers such as methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminoethylacrylamino. Can be

In particular, monomers having a carboxyl group as an acidic group, such as (meth) acrylic acid, (anhydride) maleic acid, crotonic acid, itaconic acid, and fumaric acid; styrene, α-methylstyrene, benzyl (meth) acrylate A copolymer using a monomer having a phenyl group, such as hydroxyphenyl (meth) acrylic acid, methoxyphenyl (meth) acrylic acid, hydroxyphenyl (meth) acrylamide, or hydroxyphenyl (meth) acrylsulfonamide, is an alkaline developer Is preferred from the viewpoints of developability and pigment dispersibility, and among them, a copolymer using (meth) acrylic acid and styrene which may have a substituent is most preferable.

[0009] The resin of the present invention having a polymer group in the side chain,
The weight average molecular weight measured by GPC is 18,000 or more, preferably 18,000 to 100,000. If the weight average molecular weight is less than 18,000, the surface smoothness of the pixel is poor, and if it exceeds 100,000, the developability is deteriorated, and the pixel tends to become unstable and gel. The molecular weight of the resin having a polymerizable group in the side chain of the present invention is controlled according to a conventional method, for example, by adjusting the amount of a polymerization initiator and the polymerization time. The preferred content of an acidic group such as a carboxyl group is about 5 to 200 in terms of acid value. When the acid value is 5 or less, it becomes insoluble in an alkali developing solution, and when it exceeds 200, the sensitivity may decrease.

The photopolymerization initiator that can be used in the present application includes:
Although there is no particular limitation, for example, an imidazole compound and an aminobenzene derivative, 2-amino-2-benzoyl-1
-A phenylalkane compound, a halomethylated triazine compound or a halomethylated oxadiazole compound. Examples of the imidazole compound include a compound having the following structure in which two imidazoles are connected by one covalent bond.

[0011]

Embedded image

(In the formula, Ar represents an optionally substituted aryl group.) The optionally substituted aryl group is preferably an optionally substituted phenyl group. Examples of the substituent of the aryl group include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a nitro group, a methyl group and a methoxy group. In particular, the ortho position of the phenyl group at the 2-position and the 2'-position is a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom,
Hexaphenylbiimidazole substituted with a nitro group or a methyl group is advantageous from the viewpoints of thermal stability and photoreaction rate characteristics.

Specific examples of hexaarylbiimidazole include 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-bromophenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-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 and 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole. Can be In particular, 2,2'-bis (o-
(Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole is advantageously used.

These hexaarylbiimidazoles are described, for example, in Bull. Chem. Soc. Japan, 3
3,565 (1960) and J.A. Org. Che
m. , 36, 2262 (1971). The aminobenzene derivative is a compound having an aminophenyl group in its structure, and is 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone,
Benzophenone compounds such as 4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, -(P-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,
7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p
-Dimethylaminophenyl) benzothiazole, 2-
(P-diethylaminophenyl) benzothiazole, 2
-(P-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl)
1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline,
-(P-dimethylaminophenyl) pyrimidine, 2-
P- such as (p-diethylaminophenyl) pyrimidine
Examples thereof include dialkylaminophenyl group-containing compounds.

Particularly, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone,
-(P-Dimethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole and 2- (p-diethylaminophenyl) benzimidazole are preferred. In addition, other than the above photopolymerization initiator,
A hydrogen-donating compound such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, or 2-mercaptobenzimidazole can be contained, and the sensitivity and adhesion can be further improved. The 2-amino-2-benzoyl-1-phenylalkane compound is represented by the following general formula.

[0016]

Embedded image

In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
Is a morpholino group or an SR ⁴ group. R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

Specific examples of the 2-amino-2-benzoyl-1-phenylalkane compound are shown below.
There is a compound represented by the formula:

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

2-amino-2- represented by the general formula:
Among the benzoyl-1-phenylalkane compounds, preferred are compounds in which R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 4 carbon atoms and X is a morpholino group. is there. More preferably, R ¹ is
The compound is an alkyl group having 1 to 4 carbon atoms, wherein R ² and R ³ are each independently an alkyl group having 1 to 2 carbon atoms.

The halomethylated triazine compound is represented by the formula
Is represented by the following general formula.

[0029]

Embedded image

In the formula, R ⁵ and R ⁶ are a halomethyl group, and Y is an organic group having 5 or more carbon atoms. Examples of the halomethyl group include a trichloromethyl group, a tribromomethyl group, a dichloromethyl group, a dibromomethyl group, and the like.
Examples of the organic group having 5 or more carbon atoms include a phenyl group, a naphthyl group, a styryl group, a styrylphenyl group, a furylvinyl group, and a quaternized aminoethylamino group which may have a substituent. Specific examples of the halomethylated triazine compound include compounds represented by the following formulas 12 to 33.

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

Among the halomethylated triazine compounds represented by the general formula of Chemical formula 11, preferred ones are as follows.
And compounds represented by the general formulas:

[0054]

Embedded image

In the formula, R ⁵ and R ⁶ are a halomethyl group, R is each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 3 It is.

[0056]

Embedded image

In the formula, R ⁵ and R ⁶ are a halomethyl group, R is each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 3 It is.

[0058]

Embedded image

In the formula, R ⁵ and R ⁶ are a halomethyl group, R is each independently an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 1. Among the compounds represented by the general formulas of Chemical formulas 34 to 36, preferred are R ⁵ and R ⁶
Is a trichloromethyl group, R has 1 to 2 carbon atoms, and in Chemical formulas 34 and 35, n is an integer of 0 to 2;
6 is a compound which is an integer of 0 to 1. The halomethylated oxadiazole compound is represented by the following general formula.

[0060]

Embedded image

In the formula, R ⁷ is a halomethyl group, and Z is a benzofuryl group or a benzofurylvinyl group which may have a substituent. Specific examples of the halomethylated oxadiazole compound include compounds represented by the following formulas 38 to 55.

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

Among the halomethylated oxadiazole compounds represented by the general formula (37), preferred are compounds represented by the following general formula (56).

[0081]

Embedded image

In the formula, R ⁷ is a halomethyl group, R is each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. More preferred are compounds wherein R ⁷ is a trichloromethyl group, R is each independently an alkyl or alkoxy group having 1 to 2 carbon atoms, and n is an integer of 0 to 1.

Examples of the photopolymerizable monomer of the present invention include isobutyl acrylate, t-butyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, isobonyl acrylate, benzyl acrylate, 2-methoxyethyl acrylate, and the like. 3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, tetrahydrofuryl acrylate, phenoxy polyethylene glycol acrylate,
Methoxypropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, Morpholinoethyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorododecyl acrylate, trimethylcyclohexylethyl methacrylate, 1 , 4-pig Diacrylate, 1,
6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, glycerin methacrylate acrylate, bisphenol A, EO adduct Acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane EO added triacrylate, glycerin PO added triacrylate, trisacryloyloxyethyl phosphate, dipentaerythritol hexaacrylate, acrylic acid of novolak epoxy Modified, novolak epoxy acrylic Modified product of and acid anhydride, N-
Vinylpyrrolidone, N-vinylcaprolactam, acrylated isocyanurate, dipentaerythritol monohydroxypentaacrylate, urethane acrylate,
And unsaturated polyester acrylate.

Among these monomers, acrylic monomers having three or more functional groups are particularly preferred. These monomers are used alone or in combination. Examples of the pigment of the present invention include inorganic pigments such as barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, and carbon black, anthraquinone pigments, perylene pigments, azo pigments, phthalocyanine pigments, and isoindoline pigments. Organic pigments such as pigments, dioxazine pigments, quinacridone pigments, perinone pigments, triphenylmethane pigments, thioindigo pigments, and diketopyrrolopyrrole pigments. These can be used alone or in combination. Specifically, for example, pigments represented by the following color index (CI) numbers are exemplified.

[0085]

[Table 1] I. Red; 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254 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, 110, 117, 125, 137, 138, 147, 148, 150, 153, 154, 166, 168, 180 C.I. I. Orange; 36, 43, 51, 55, 59, 61 C.I. I. Violet; 19, 23, 29, 30, 37, 40, 50 C.I. I. Tea; 23, 25, 26

In particular, it is preferable to use at least one selected from anthraquinone pigments, phthaloanine pigments, azo pigments, dioxazine pigments, and diketopyrrolopyrrole pigments as the pigment. The average particle size of these pigments is preferably in the range from 0.005 to 0.5μ. More preferably, it is 0.01 to 0.3 μm. If the average particle size is less than this, thixotropy is likely to occur, and good coating properties cannot be obtained, and if it is more than this, the coating film lacks transparency. To achieve such a particle size, a dispersion treatment such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint shaker, and ultrasonic waves is effective.

As the solvent of the present invention, specifically, diisopropyl ether, mineral spirit, n-pentane,
Amyl ether, ethyl caprylate, n-hexane,
Diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, balsol #
2. Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apco thinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, Socal solvent No1 and No
2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec,
t) -butyl acetate, hexene, shell TS28, solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl ketone, Methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, aluminum formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethyl pentanol , Methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ate , Methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, di Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxypropionic acid methyl ether, 3-methoxypropion Acid methyl, 3-methoxypropio Acid ethyl, 3
-Ethoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether , 3-
Organic solvents such as methyl-3-methoxybutanol, tripropylene glycol methyl ether, and 3-methyl-3-methoxybutyl acetate are exemplified.

It is preferable to select a solvent having a boiling point in the range of 100 ° C. to 200 ° C. More preferably 120
It has a boiling point of 170C to 170C. These solvents are used alone or as a mixture. In particular, propylene glycol methyl ether acetate can be advantageously used. The polymerization composition for a color filter of the present invention comprises 0.05 to 50 parts by weight of a photopolymerization initiator and 5 to 2 parts by weight of a photopolymerizable monomer based on 100 parts by weight of a resin having a polymerizable group in a side chain.
00 parts by weight, pigment 10 to 500 parts by weight, solvent 200 to 5
It is contained in the range of 00 parts by weight. From the viewpoint of expanding color reproducibility, it is desirable that the ratio P / V of the pigment content (P) and the solid content (V) excluding the pigment is 0.5 or more.

When the content of the photopolymerization initiator is less than the above range, sufficient sensitivity cannot be obtained, and when it exceeds the above range, the internal curability deteriorates, and sometimes the initiator recrystallizes and precipitates. Sometimes. If the amount of the monomer is less than the above range, the cross-linking density of the image-exposed image area is insufficient and a good image is hardly obtained, and if it exceeds the above range, the tackiness of the dried resist film becomes large. Workability becomes poor. If the amount of the pigment is less than the above range, it becomes difficult to obtain a color density necessary for preparing a color filter, and if the amount exceeds the above range, light absorption by the pigment becomes too strong, internal light curing does not occur, and an image is lost. . If the amount of the solvent is less than the above range, coating unevenness tends to occur and lacks uniformity of film thickness, and if the amount exceeds the above range, a sufficient film thickness cannot be obtained, and coating defects such as pinholes may occur. It will be easier.

In the present invention, a sensitizer, a pigment dispersing aid, a coating improver, a crosslinker, a development improver, a polymerization inhibitor, a plasticizer, a flame retardant and the like may be added in addition to the above essential components. it can. These can be used alone or in combination of several kinds. The composition of the present invention is applied to a glass substrate by a known method such as a spin coater, a roll coater, a curtain coater, and screen printing. The coating thickness is 0.5 μm
-10 μm is preferred. A convection open or hot plate is used to dry the coating film. The drying temperature is 50 ° C to 150 ° C, and the drying time is 30 seconds to
60 minutes is preferred. A high-pressure mercury lamp is generally used for exposure, and a latent image is formed on a resist film by exposing through a mask. An image is formed by developing with a solvent that dissolves the unexposed portion. Organic solvents such as acetone, toluene, and methyl ethyl ketone can be used as the developing solution, but an alkali developing solution is preferable from the viewpoint of environmental problems. For example, aqueous sodium hydroxide solution,
An aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate, potassium carbonate, aqueous ammonia, an aqueous solution of tetramethylammonium hydroxide, or the like is used. The developing method is not particularly limited, and the paddle property, the dipping method,
It can be performed by a known method such as a spray method. Also, pre-wet may be adopted. After image formation, drying of the developer, post-baking for the purpose of enhancing the curing of the resist film,
After-light curing may be employed.

The color filter of the present invention preferably has a pixel having a surface roughness of 15 μm or less as measured by an AFM (atomic force microanalyzer).
When the surface roughness is larger than 15 μm, it is not preferable to form a liquid crystal display device using the same, since the alignment of the liquid crystal is disturbed. In order to prepare such a color filter having excellent pixel surface smoothness, the polymer composition for a color filter of the present invention is particularly suitable.

[0092]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Synthesis Example 1 20 g of a styrene-acrylic acid resin having an acid value of 240 and a molecular weight of 15,500 (acrylic acid content: 40 mol%), 0.2 g of p-methoxyphenol, 0.2 g of tetraethylammonium chloride, propylene glycol monomethyl ether A flask was charged with 40 g of acetate, and 3,4-
11.4 g of epoxycyclohexylmethyl acrylate
Was added and reacted at 90 ° C. for 33 hours. The weight average molecular weight of the obtained resin measured by GPC was 25,000, and the acid value was 56.

Synthesis Example 2 Synthesis was performed in the same manner as in Synthesis Example 1 except that 11.4 g of 3,4-epoxycyclohexylmethyl acrylate in Synthesis Example 1 was changed to 9.0 g. The weight average molecular weight of the obtained resin measured by GPC was 22,700, and the acid value was 86.

Synthesis Example 3 The styrene-acrylic acid resin of Synthesis Example 1 had a molecular weight of 23,
Synthesis was performed in the same manner as in Synthesis Example 1 except that the number was changed to 500. The weight average molecular weight of the obtained resin measured by GPC was 35,
700 and the acid value was 54.

Synthesis Example 4 Synthesis was performed in the same manner as in Synthesis Example 1 except that 3,4-epoxycyclohexylmethyl acrylate was changed to 9 glycidyl methacrylate. The weight average molecular weight of the obtained resin measured by GPC was 24,300 and the acid value was 8
It was 8.

Comparative Synthesis Example 1 The molecular weight of the styrene-acrylic acid resin of Synthesis Example 1 was 5, 0
The synthesis was performed in the same manner as in Synthesis Example 1 except that 7.6 g of 3,4-epoxycyclohexylmethyl acrylate was changed to 00. The weight average molecular weight of the obtained resin measured by GPC was 8,000, and the acid value was 80.

Reference Example 1 "Preparation of phthalocyanine blue (PB 15: 6) dispersion" 23.3 g of phthalocyanine blue, 21.7 g of a polymer dispersant (43% solids), 2.3 g of a dispersion aid, and propylene as a solvent 52.6 g of glycol monomethyl ether acetate, zirconia beads 35 having a diameter of 0.5 mm
0 g was filled in a stainless steel container and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion.

Reference Example 2 "Preparation of Phthalocyanine Green (PG 36) Dispersion" A green pigment dispersion was prepared using phthalocyanine green instead of phthalocyanine blue of Reference Example 1.

Reference Example 3 "Preparation of Dianthraquinonyl Red (PR177) Dispersion" A red pigment dispersion was prepared by using dianthraquinonyl red in place of phthalocyanine blue of Reference Example 1.

Example 1 39.4 g of the blue pigment dispersion of Reference Example 1 and 20.5 g of the propylene glycol monomethyl ether acetate solution of the resin having a weight average molecular weight of 25,000 obtained in Synthesis Example 1 (solids concentration: 41.5%) 4.3 g of a propylene glycol monomethyl ether acetate solution of a photopolymerizable monomer, dipentaerythritol hexaacrylate (solid content: 50%), and 2,2'-bis (o-chlorophenyl) -4,4 'as a photopolymerization initiator 0.87 g of -5,5'-tetraphenylbiimidazole, 0.61 g of 4,4'-diethylaminobenzophenone, 0.26 g of 2-mercaptobenzothiazole and 34.1 g of propylene glycol monomethyl ether acetate are mixed well and polymerized for a color filter. A composition was prepared.

The prepared polymer composition was applied on a non-alkali glass substrate by a spin coater and dried on a hot plate at 70 ° C. for 150 seconds. Next, through a color filter grid mask, a high pressure mercury lamp was used to 200 mj / cm ^2.
, And shower-developed at 23 ° C. using a 0.2% aqueous potassium carbonate solution containing an alkylene oxide-based surfactant to form blue pixels. The developed sample was cured at 230 ° C. for 30 minutes. The entire surface of the sample for surface roughness measurement by AFM (Atomic Force Microanalyzer) was exposed without using a mask. Observation of the blue pixel of the obtained color filter with an optical microscope revealed that a pixel having good rectangularity was obtained. Also,
AFM (Digital Instruments Nanoscope)
III ad-3000), the surface roughness was measured and found to be 10 μm, indicating excellent smoothness.

Examples 2 to 9 and Comparative Example 1 In the same manner as in Example 1, color filter pixels were formed with the compositions shown in Table 1, and the surface roughness was measured. The results are shown in Table 1.

[0104]

[Table 2]

[0105]

According to the present invention, a color filter which does not disturb the alignment of liquid crystal when incorporated in a liquid crystal display device, and a color filter which can suitably obtain the color filter without complicating the process or deteriorating workability and image definition. The polymer composition for use was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/038 501 G03F 7/038 501

Claims (9)

[Claims] 1. A color filter polymerization comprising at least (a) a resin having a polymerizable group in a side chain, (b) a photopolymerization initiator, (c) a photopolymerizable monomer, (d) a pigment, and (e) a solvent. A polymer composition for a color filter, wherein the resin having a polymerizable group in a side chain has a weight average molecular weight of 18,000 or more. 2. The polymer composition for a color filter according to claim 1, wherein in the resin having a polymer group in a side chain, the polymer group is a (meth) acryloyl group. 3. The resin having a polymer group in a side chain contains at least (meth) acrylic acid and styrene which may have a substituent as a copolymer component.
Or the polymer composition for a color filter according to 2. 4. The method according to claim 1, wherein the polymerization initiator comprises an imidazole compound and an aminobenzene derivative, a 2-amino-2-benzoyl-1-phenylalkane compound, a halomethylated triazine compound, or a halomethylated oxadiazole compound. The polymer composition for a color filter according to claim 1. 5. A pigment comprising an anthraquinone compound, a phthalocyanine compound, an azo compound, a dioxazine compound, a quinophthalone compound, an isoindoline compound,
Benzimidazolone compounds, quinacridone compounds,
It is at least one compound selected from diketopyrrolopyrrole compound systems and perylene compound systems. The ratio of the pigment content (P) expressed by weight to the solid content (V) excluding the pigment content (P / V 5) The polymer composition for a color filter according to any one of claims 1 to 4, wherein 0.5) or more. 6. The polymer composition for a color filter according to claim 1, which is coated on a transparent substrate, exposed, dried,
A color filter obtained by forming pixels by developing. 7. The pixel has a surface roughness of 15 μm or less,
The color filter according to claim 6. 8. A color filter having a pixel whose surface roughness measured by AFM (Atomic Force Microanalyzer) is 15 μm or less. 9. A liquid crystal display device using the color filter according to claim 7.