JP3453193B2 - Photosensitive coloring composition for color filter and color filter - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-quality photosensitive coloring composition for color filters, which can be developed with a solvent or an alkaline aqueous solution after imagewise exposure with ultraviolet rays, and a solid-state image pickup device.
The present invention relates to a color filter used in a liquid crystal display device or the like.

[Prior art]

In recent years, liquid crystal display devices and the like have been made thinner and larger, and the color filters used are also required to be thin without defects, and in addition to various resistances such as heat resistance and light resistance, high transmittance is also high. , High contrast is required. At the same time, there is a strong demand for cost reduction of color filters, and it is necessary to improve the yield and shorten the process in the manufacturing process. The color filter is composed of a transparent substrate such as glass having fine bands (stripe) of two or more different hues arranged in parallel or intersecting each other, or fine pixels arranged in a fixed vertical and horizontal arrangement. Has become. The pixel size must be a minute shape of several tens to several hundreds of microns, and moreover, it must be arranged in a predetermined order for each hue. For this reason, various methods have conventionally been proposed for manufacturing color filters.

Since a color filter is required to have smoothness and high dimensional accuracy, a method of forming an image by using photolithography has been the mainstream. Also,
Since high transparency is required for color filters,
A coloring method using a dye, which is generally called a dyeing method, is performed. For example, a dyeable photosensitive material is applied onto a substrate such as a crow, and then pattern exposure of one filter color is performed, an unexposed portion is removed in a developing process, and a remaining pattern portion of the filter color is removed. Stain with dye. A color filter can be manufactured by sequentially repeating this operation for all filter colors. However, when assembling a color liquid crystal display device, the I
It is necessary to form a transparent conductive film such as TO and an alignment film of liquid crystal. Since this process requires very high temperature, the color filter is required to have high heat resistance. The required heat resistance varies depending on the liquid crystal driving method. For example, an active matrix type TFT (thin film transistor) type has a heat resistance of 230 ° C. for 1 hour, and a simple matrix STN (super twist nematic) type has a heat resistance of 260 ° C. for 1 hour. Is required.

Since the color filter produced by the above dyeing method is inferior in heat resistance (usually 200 ° C. or lower), a method of using a pigment having good heat resistance as a dye is predominant at present. Above all, a method called a pigment dispersion method, which uses a colored composition in which a pigment is dispersed in a photosensitive composition, is widely used as a method for producing a color filter. That is, the above-mentioned photosensitive coloring composition of one filter color is applied on a transparent substrate such as glass, pattern exposure is performed, and the unexposed portion is developed and removed with a solvent or an alkaline aqueous solution to form a first color pattern. Then, the same operation is sequentially repeated for all filter colors, whereby a color filter having excellent heat resistance can be manufactured. Incidentally, the photosensitive composition is mainly a negative photosensitive composition because of its physical properties as a color filter and abundance of materials, and in development, a solvent is hardly used because of environmental problems, and an aqueous alkaline solution is used. Development is the mainstream. Regarding exposure, exposure by ultraviolet rays is usually performed.

As described above, since the pigment dispersion method uses a photosensitive composition in which the pigment is dispersed in advance, ultraviolet rays are absorbed by the pigment, and the exposure sensitivity is generally significantly lowered.
Therefore, since the exposure time becomes long, there is a problem in productivity. In addition, since the negative type photosensitive composition mainly utilizes a radical polymerization reaction, the reaction is inhibited by oxygen in the air, which also causes a decrease in sensitivity. In this regard, after the photosensitive composition is applied, a measure of exposing the image after forming an oxygen barrier film of polyvinyl alcohol or the like on it is taken, but since the number of steps increases, the problem of productivity remains. Therefore, a highly sensitive material that does not require an oxygen barrier film is strongly desired. Further, in order to secure the exposure sensitivity, usually a large amount of a photoinitiator is blended, and there is also a problem that it is difficult to obtain the performance of a color filter manufactured by the influence of discoloration due to heat such as a residual, particularly heat resistance. However, it has been desired to develop a photoinitiator that does not affect the heat resistance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly sensitive photosensitive coloring composition for color filters, which solves the above problems, and a color filter excellent in various resistances, particularly in heat resistance.

[Means for solving the problem]

The present invention comprises a transparent high molecular polymer (A) soluble in a solvent or an alkali, a compound (B) having an ethylenically unsaturated bond, a pigment (C) and a sulfonium represented by the following general formula (1). Organic Boron Complex or Oxosulfonium Organic Boron Complex (D) and 300 nm to 400 n
A photosensitive coloring composition for a color filter comprising a triazine compound (E) having a trihalogenomethyl group having absorption in m.

[0008]

[Chemical 2] [In the formula, R ¹ represents a benzyl group, a substituted benzyl group,
Represents a group selected from a phenacyl group, a substituted phenacyl group, an aryloxy group, a substituted aryloxy group, an alkenyl group and a substituted alkenyl group, and R ² and R ³ each independently constitute R ¹ . The same groups as those capable of forming an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, an alicyclic group, or a substituted group. Alicyclic group, alkoxy group, substituted alkoxy group, alkylthio group, substituted alkylthio group, amino group, substituted amino group, or R
² represents a cyclic structure in which R ³ is bonded to each other, R ⁴ represents an oxygen atom or a lone electron pair, and R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or a substituted alkyl group. A group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkenyl group, and a substituted alkenyl group (provided that all of R ⁵ , R ⁶ , R ⁷ and R ⁸ are aryl groups. Or it does not become a substituted aryl group.)]

The sulfonium organic boron complex or oxosulfonium organic boron complex (D) represented by the general formula (1) should be synthesized according to the method described in JP-A-5-213861 and JP-A-5-255347. You can

In the substituents R ¹ , R ² and R ³ on the sulfonium or oxosulfonium cation in the general formula (1), a benzyl group or a substituted benzyl group is a p-cyanobenzyl group or a p-nitrobenzyl group. , P-chlorobenzyl group, p-hydroxybenzyl group, p-methylbenzyl group, p-methoxybenzyl group,
A phenacyl group or a substituted phenacyl group such as a p-dimethylaminobenzyl group or a 1- (or 2-) naphthylmethylene group is a p-cyanophenacyl group, p
-Nitrophenacyl group, p-chlorophenacyl group, p-
Hydroxyphenacyl group, phenacyl group, p-methylphenacyl group, p-dimethylaminophenacyl group, etc.
Examples of the aryloxy group or the substituted aryloxy group include p-cyanophenoxy group, p-nitrophenoxy group, p-chlorophenoxy group, phenoxy group, p-tolyloxy group, p-methoxyphenoxy group, p-dimethylaminophenoxy group. Groups, etc., as an alkenyl group or a substituted alkenyl group, vinyl group, 1-propenyl group, 1-butenyl group, 3,3-dicyano-1-propenyl group, etc., as an alkyl group or a substituted alkyl group Is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group,
tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, allyl group, salicyl group, acetonyl group, cyanomethyl group, chloromethyl group, bromomethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group A group, a menthyl group, a pinanyl group, etc., an aryl group or a substituted aryl group, a phenyl group, a p-tolyl group, a xylyl group, a mesityl group, a cumenyl group, a p-methoxyphenyl group, a biphenylyl group, a naphthyl group, Anthryl group, phenanthryl group, p-cyanophenyl group, p-nitrophenyl group,
2,4-bis (trifluoromethyl) phenyl group, p-
Fluorophenyl group, p-chlorophenyl group, p-dimethylaminophenyl group, p-phenylthiophenyl group and the like are alicyclic groups or substituted alicyclic groups, cyclopentyl group, cyclohexyl group, norbornyl group, bornyl group, A 1-cyclohexenyl group or the like is a methoxy group as an alkoxy group or a substituted alkoxy group,
Ethoxy group, n- (or iso-) propoxy group, n
-(Or sec-, tert-) butoxy group, benzyloxy group, p-cyanobenzyloxy group, p-chlorobenzyloxy group, p-nitrobenzyloxy group, p
-Methylbenzyloxy group, p-methoxybenzyloxy group, etc. are alkylthio groups or substituted alkylthio groups such as methylthio group, ethylthio group, butylthio group, etc., and amino groups or substituted amino groups are amino groups, methyl group Amino groups, dimethylamino groups, diethylamino groups, cyclohexylamino groups, anilino groups, piperidino groups, morpholino groups and the like, and arylthio groups or substituted alkylthio groups, phenylthio groups, p-tolylthio groups, p-cyanophenylthio groups. And R ² and R ³ may have a bonded cyclic structure, for example, a tetramethylene group,
Examples include cyclic structures such as an alkylene group which may have a substituent such as a pentamethylene group and a 1,4-dichlorotetramethylene group, an ethylenedioxy group, a diethylenedioxy group, an adipoyl group and an ethylenedithio group.

In the substituents R ⁵ , R ⁶ , R ⁷ and R ⁸ on the organic boron anion in the general formula (1), an alkyl group or a substituted alkyl group is
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-
A butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an allyl group and a benzyl group are aryl groups or substituted aryl groups such as a phenyl group, a p-tolyl group and a xylyl group. , Mesityl group, cumenyl group, p-methoxyphenyl group, naphthyl group, 2,4-bis (trifluoromethyl) phenyl group, p-fluorophenyl group, p-chlorophenyl group,
Examples of the alkenyl group or substituted alkenyl group such as p-bromophenyl group include vinyl group, 1-propenyl group, 1-butenyl group, and the like, and alkenyl group which may have a substituent include ethenyl group. , 2-tert-butylethenyl group, 2-phenylethenyl group and the like.

An example of such a sulfonium organic boron complex or oxosulfonium organic boron complex (D) is dimethyl-tert-butylsulfonium-ter.
t-Butyltriethylborate, dimethylbenzylsulfonium phenyltriethylborate, dimethyl (p-
Chlorobenzyl) sulfonium methyltriphenylborate, dibutyl (p-bromobenzyl) sulfonium isopropyltriphenylborate, dimethyl (p-cyanobenzyl) sulfoniumbutyltriphenylborate, dimethylphenacylsulfoniumbutyltriphenylborate, dimethylphenacylsulfonium-sec
-Butyltriphenylborate, di-tert-butylphenacylsulfonium-sec-butyltriphenylborate, dimethyl (p-chlorophenacyl) sulfonium-tert-butyltriphenylborate, dimethyl (p-bromophenacyl) sulfoniumbenzyltriphenylborate , Dimethyl (2-phenyl-3,3-
Dicyanoprop-2-enyl) sulfonium butyl tri (p-methoxyphenyl) borate, dibutylethoxysulfonium butyl tri (p-fluorophenyl) borate, dimethylphenoxysulfonium butyl tri (p)
-Chlorophenyl) borate, methyl (dimethylamino) (p-tolyl) sulfoniumbutyl tri (p-bromophenyl) borate, dimethyl (methylthio) sulfoniumbutyl tris [3,5-bis (trifluoromethyl) phenyl] borate, dimethylphenyl Thiosulfonium-sec-butyltri (p-methoxyphenyl)
Borate, methylphenyl (p-cyanobenzyl) sulfonium-sec-butyltri (p-fluorophenyl) borate, methylphenylphenacylsulfonium, methylphenyl (2-phenyl-3,3-dicyanoprop-2-enyl) sulfonium-tert- Butyltri (p-bromophenyl) borate, methylphenylethoxysulfonium butyltriphenylborate, butylphenylphenoxysulfonium butyltriphenylborate, dimethylaminobis (p-tolyl) sulfonium-sec-butyltri (p-bromophenyl) borate, tetramethylene Phenacylsulfonium-se
c-Butyltriphenylborate, dimethylallylsulfonium butyltriphenylborate, dimethylcyanomethylsulfoniumbutyltriphenylborate, dimethylacetonylsulfoniumbutyltriphenylborate, dimethylethoxycarbonylmethylsulfonium-
tert-butyltri (p-chlorophenyl) borate, dimethyl (methylthiomethyl) sulfoniumbutyltriphenylborate, tetramethylene-p-cyanobenzylsulfonium-sec-butyltri-p-fluorophenylborate, dimethylbenzyloxosulfoniumbutyltriphenylborate, dimethyl Phenacyloxosulfonium-sec-butyltri (p-chlorophenyl) borate, methylphenylbenzyloxosulfonium-tert-butyltri (p-methoxyphenyl) borate, methylphenylphenacyloxosulfonium-tert-butyltri (p-fluorophenyl) borate, Diphenylbenzyl sulfonium butyl triphenyl borate, diphenyl (p-chlorobenzyl) sulfonium acetate Lutris (p-methoxyphenyl) borate, diphenyl (p-bromobenzyl) sulfoniumbutyl tris (p-fluorophenyl) borate, diphenyl (p-cyanobenzyl) sulfoniumbutyltriphenylborate, bis (p-tert-butylphenyl) benzyl Sulfonium butyl tris (p-
Bromophenyl) borate, bis (p-chlorophenyl) (p-cyanobenzyl) sulfoniumbutyltriphenylborate, diphenyl (p-cyanobenzyl) sulfoniumphenyltributylborate, diphenyl (p-cyanobenzyl) sulfoniumdibutyldiphenylborate, diphenyl (p -Cyanobenzyl) sulfonium vinyltriphenylborate, diphenyl (p-
Cyanobenzyl) sulfonium-sec-butyltriphenylborate, diphenyl (p-cyanobenzyl) sulfoniumcyclohexyltriphenylborate, diphenylphenacylsulfoniumbutyltriphenylborate, diphenyl (p-chlorophenacyl) sulfoniumbutyltriphenylborate, diphenyl ( p-Bromophenacyl) sulfonium butyltriphenylborate, diphenyl (p-methoxyphenacyl) sulfoniumbutyltriphenylborate, diphenyl (p-cyanophenacyl) sulfoniumcyclohexyltris (p
-Methoxyphenyl) borate, bis (p-tert-)
Butylphenyl) phenacylsulfonium-sec-butyltris (p-fluorophenyl) borate, bis (p-methoxyphenyl) (p-chlorophenacyl) sulfoniumdibutyldiphenylborate, bis (p-chlorophenyl) (p-bromophenacyl) sulfoniumbenzyl Triphenylborate, bis (p-methylphenyl) (p-methoxyphenacyl) sulfonium-te
rt-butyltriphenylborate, bis (p-ter
t-Butylphenyl) (p-cyanophenacyl) sulfonium benzyltributylborate, diphenylallylsulfoniumbutyltriphenylborate, diphenyl (2-methyl-3,3-dicyano-2-propenyl) sulfonium-2-phenylethynyltriphenylborate, diphenyl (2-phenyl-3,3-dicyano-2
-Propenyl) sulfonium butyl triphenylborate, diphenyl [2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl] sulfonium-se
c-Butyltriphenylborate, bis (p-chlorophenyl) allylsulfoniumphenyltriethylborate, bis (p-tert-butylphenyl) (2-methyl-3,3-dicyano-2-propenyl) sulfonium di (sec-butyl) Diphenyl borate, bis (p-
Methylphenyl) (2-phenyl-3,3-dicyano-
2-propenyl) sulfonium butyl triphenyl borate, diphenyl acetonyl sulfonium butyl triphenyl borate, diphenyl cyanomethyl sulfonium butyl triphenyl borate, diphenyl methoxycarbonylmethyl sulfonium butyl triphenyl borate, diphenyl sulfomethyl sulfonium methyl tris (p-fluorophenyl) Borate, diphenyl-p-
Toluenesulfonyl methyl sulfonium dicyclohexyl diphenyl borate, diphenyl (trimethylammoniumylmethyl) sulfonium bis (butyl triphenyl borate), diphenyl (triphenylphenacyl phosphonium umilumyl methyl) sulfonium bis (butyl triphenyl borate), diphenyl (phenyliodonium mil) Ethynyl) sulfonium bis (butyltriphenylborate), diphenylbenzyloxosulfoniumbutyltriphenylborate, diphenyl (p-cyanobenzyl) oxosulfoniumbutyltriphenylborate, diphenyl (p-cyanobenzyl) oxosulfonium-sec-butyltriphenylborate , Diphenyl (p-cyanobenzyl) oxosulfonium cyclohexyl tris (p- Luorophenyl) borate, diphenylphenacyloxosulfonium butyltriphenylborate, diphenyl (p-chlorophenacyl) oxosulfonium-sec-butyltris (p-fluorophenyl) borate, bis (p-tert-butylphenyl) phenacyloxosulfonium octyl Tris (p-fluorophenyl) borate, diphenylallyloxosulfonium butyltriphenylborate, diphenyl (2-phenyl-3,3-dicyano-2-propenyl) oxosulfonium-tert-butyltriphenylborate, diphenylmethoxycarbonylmethyloxosulfonium Butyltriphenylborate, diphenyl (trimethylammoniumylmethyl) oxosulfonium bis (butyltriphenylborate) ), Diphenyl (triphenyl phenacyl oxo phosphonium Niu mill methyl) oxosulfonium bis (butyl triphenyl borate), and the like. Representative compounds (a) to (l) are shown below.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

[0023]

[Chemical 13]

[0024]

[Chemical 14]

Since the sulfonium organoboron complex represented by the general formula (1) or the oxosulfonium organoboron complex (D) usually has almost no absorption of 300 nm or more, even if used alone, it is sensitive to a light source of a usual ultraviolet lamp. However, it is possible to obtain very high sensitivity by combining with a triazine compound (E) having a trihalogenomethyl group having an absorption at 300 nm to 400 nm. The photosensitive coloring composition of the present invention further comprises another 30
A compound having absorption at 0 nm to 400 nm can be contained. As the other compound having absorption at 300 nm to 400 nm, a photoinitiator or a sensitizer having sensitivity in this wavelength region can be used. Examples of these compounds include acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, carbazole-based, imidazole-based, coumarin-based, ketocoumarin-based, triphenylpyrylium-based, triazine compounds other than triazine compounds (E) having a trihalogenomethyl group. There are compounds such as systems. Further, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-Tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-
Compounds such as diethylaminobenzophenone can also be used. Each of these compounds is a single substance or 2
A combination of two or more species can be used.

Particularly, the combined use of the sulfonium organoboron complex represented by the general formula (1) or the oxosulfonium organoboron complex (D) with a triazine compound having a trihalogenomethyl group and a chromophore group in the molecule is highly effective. It gives a photosensitive composition of sensitivity.

As the triazine compound having a trihalogenomethyl group in the molecule, first, 2-phenyl-4,6-
Bis (trichloromethyl) -s-triazine, 2- (p
-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-
Bis (trichloromethyl) -s-triazine, 2- (p
-Chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine and their tribromomethyl compounds. Further, a triazine compound having improved absorption characteristics in the ultraviolet to visible region by extending the conjugated system of the chromophore group is more preferably used in the present invention. As an example, first, Japanese Patent Laid-Open No. 48
General formula (2) described in JP-A-36281.

[0028]

[Chemical 15] [In the formula, X is bromine or chlorine, and Y is -CX ₃ ,-.
NH ₂ , -NHR, -NR ₂ or -OR (where R
Is phenyl or lower alkyl having 1 to 6 carbon atoms,
n is an integer of 1 to 3, W represents a substituted or unsubstituted aromatic ring or heterocycle. ]

An s-triazine compound having at least one chromophore moiety conjugated to the triazine ring by at least one trihalomethyl group and an ethylenically unsaturated group represented by, for example, vinyl-halomethyl-s-triazine. And methyl-halomethyl-s-triazine,
For example, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine,
2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-
Triazine, 2,4-bis (trichloromethyl) -6
(N-ethyl-2 (3H) -benzoxazolidine)
-Ethylidene s-triazine, 2-trichloromethyl-
4-amino-6-p-methoxystyryl-s-triazine, 2,4-bis (tribromomethyl) -6-styryl-s-triazine, 2,4-bis (tribromomethyl)
-6-p-methoxystyryl-s-triazine, 2,4
-Bis (tribromomethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2,4-bis (tribromomethyl) -6 (N-ethyl-2 (3H ) -Benzoxazolidine) -ethylidene-s-triazine, 2-tribromomethyl-4-amino-6-p-methoxystyryl-s-triazine,
2,4-bis (trichloromethyl) -6-methyl-s-
Triazine, 2,4-bis (tribromomethyl) -6-
Methyl-s-triazine etc. can be mentioned. Compounds (1) to (6) are shown below as typical compounds.

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

[0033]

[Chemical 19]

[0034]

[Chemical 20]

[0035]

[Chemical 21]

Next, the general formula (3) described in JP-A-53-133428 is described.

[Chemical formula 22] [In the formula, X represents bromine or chlorine, and Z represents a substituted or unsubstituted dinuclear or trinuclear aromatic ring or heterocycle. ]
An s-triazine compound having one substituted or unsubstituted dinuclear or trinuclear aromatic group or heterocyclic aromatic ring group and two trihalogenomethyl groups, for example, 2
-(Naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-butoxy-naphth-1-yl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
[4- (2-Methoxyethyl) -naphth-1-yl]-
4,6-bis (trichloromethyl) -s-triazine,
2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2-butoxyethyl) -naphth-1
-Yl] -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxy-naphth-1-yl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (6-methoxy-5-methyl-naphth-2-yl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (6-methoxynaphth-2-yl) -4,6-
Bis (trichloromethyl) -s-triazine, 2- (5
-Methoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4,7-dimethoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (6-methoxynaphtho-
2-yl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (4,5-dimethoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (acenaphth-5-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (naphth-2-yl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (phenanthryl-9-yl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (dibenzothien-2-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (benzopyran-3-yl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (4-methoxyanthracene-1)
-Yl) -4,6-bis (trichloromethyl) -s-triazine and tribromomethyl-substituted derivatives thereof and the like. Compounds (7) to (10) are shown below as typical compounds.

[0037]

[Chemical formula 23]

[0038]

[Chemical formula 24]

[0039]

[Chemical 25]

[0040]

[Chemical formula 26]

Next, the following general formula (4) described in JP-A-60-105667 is used.

[Chemical 27] [In the formula, Ar represents a substituted or unsubstituted mononuclear to trinuclear aromatic group, R ⁹ and R ¹⁰ represent a hydrogen atom or an alkyl group, and R ¹¹ and R ¹³ are different from each other,
Each represents a hydrogen atom or a 4,6-bis-trichloromethyl-s-triazin-2-yl group, R ¹² , R ¹⁴ and R ¹⁵ are the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted Represents an alkyl, alkenyl or alkoxy group. ] The aryl vinyl phenyl-bis-trihalogenomethyl-s-triazine compound represented by these. Specific examples include compounds (11) to (13).

[0042]

[Chemical 28]

[0043]

[Chemical 29]

[0044]

[Chemical 30]

Further, as the triazine compound having a trihalogenomethyl group which is preferably used in the present invention, a carbonylmethylene heterocyclic compound containing a trihalogenomethyl group described in JP-A-60-89473,
Specifically, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-benzothiazole, 2- (p-
Trichloromethylbenzoylmethylene) -3-ethyl-
5-methylbenzothiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-benzylbenzothiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-methylbenzothiazoline, 2- (trichloroacetylmethylene) -3- Methylbenzothiazoline, 2
-(P-Trichloromethylbenzoylmethylene) -3-
(2-Methoxyethyl) -benzothiazoline, 2- (p
-Trichloromethylbenzoylmethylene) -3-n-hexylbenzothiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-methyl-naphtho [1,2-
d] thiazoline, 2- [3,5-bis (trichloromethyl) benzoylmethylene] -3-methyl-naphtho [1,
2-d] thiazoline, 2-trichloroacetylmethylene-3-methyl-naphtho [1,2-d] thiazoline, 2-
(P-Trichloromethylbenzoylmethylene) -3-ethyl-5-methylbenzoselenazoline, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-5
Methoxybenzoselenazoline, 2-trichloroacetylmethylene-3-ethylbenzoselenazoline, 2- (p-
Trichloromethylbenzoylmethylene) -1,3,3-
Triethyl-5-chloroindoline, 2- (m-trichloromethylbenzoylmethylene) -1,3,3-trimethylindoline, 2-trichloroacetylmethylene-
1,3,3-trimethylindoline, 2-trichloroacetylmethylene-1,3,3-trimethyl-5-chloroindoline, 2- [3,5-bis (trichloromethyl)
-Benzomethylene] -1,3,3, -trimethylindoline, 2- [bis (p-trichloromethylbenzoyl)
-Methylene] -3-ethylbenzothiazoline, 2-trichloroacetylmethylene-3-ethylbenzothiazoline, 2-trichloroacetylmethylene-3-ethyl-5
-Methylbenzothiazoline, 2-trichloroacetylmethylene-3-benzylbenzothiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-4
-Methyl-5-ethoxycarbonylthiazoline, 2-trichloroacetylmethylene-3-ethyl-4-methyl-
5-ethoxycarbonylthiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-4,5
-Diphenylthiazoline, 2-trichloroacetylmethylene-3-ethyl-4,5-diphenylthiazoline, 2
-Trichloroacetylmethylene-3-ethyl-5-phenylthiazoline, 2-trichloroacetylmethylene-1
-Methyl-1,2-dihydroquinoline, 2-bis (trichloroacetylmethylene) -1-methyl-1,2-dihydroquinoline and the like, and further JP-A-2-3686,
The triazine compounds described in JP-A-2-4782, JP-A-2-4787 and JP-A-2-292278 can be mentioned.

In addition to the triazine compound (E) having a trihalogenomethyl group, 300 nm to 400 nm
You may use together the photoinitiating auxiliary agent which does not have absorption. Examples of such compounds include amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, and polymerizable tertiary amines, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Examples thereof include ester compounds such as isoamyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate.

In the present invention, the sulfonium organoboron complex or oxosulfonium organoboron complex (D) and the trihalogenomethyl group-containing triazine compound (E) are each 1 relative to the compound (B) having an ethylenically unsaturated bond. -60% by weight, preferably 5-30
It is blended so as to be a weight%.

The transparent high molecular polymer (A) used in the present invention has a film thickness of 1 micron and a visible light region of 400 nm.
It is a high molecular weight polymer having a transmittance of 80% or more, preferably 95% or more in the entire wavelength region of up to 700 nm, and is soluble in a developing solution (solvent or alkaline aqueous solution).
Examples of such high molecular weight polymers include thermosetting resins, thermoplastic resins, and photosensitive resins, which may be used alone or in admixture of two or more. However, since high temperature treatment and treatment with various solvents or chemicals are performed in the post-process in the production of the color filter, the transparent polymer (A) has heat resistance, solvent resistance and chemical resistance. It is necessary to use an excellent one.

Examples of the thermosetting resin and thermoplastic resin include butyral resin, styrene-maleic acid copolymer, maleic acid resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. Coalesce, polyvinyl acetate, polyurethane resin, phenol resin, polyester resin, polyamide, acrylic resin, alkyd resin, polystyrene, rubber resin,
Examples thereof include cyclized rubber, epoxy resin, celluloses, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin and urea resin.

As the photosensitive resin, a linear polymer having a hydroxyl group, a carboxyl group, an amino group or the like is photocrosslinked with a (meth) acrylic compound, a cinnamic acid compound or the like via an isocyanate group, an aldehyde group, an epoxy group or the like. A resin in which a functional group is introduced is used. Hydroxyalkyl (meth), a linear polymer containing an acid anhydride such as a styrene-maleic acid copolymer or an α-olefin-maleic anhydride copolymer
A half ester of a (meth) acrylic compound having a hydroxyl group such as acrylate may also be used.

As the compound (B) having an ethylenically unsaturated bond used in the present invention, a compound which is generally called a monomer or an oligomer and which can undergo a radical polymerization (or crosslinking) reaction is used. Acrylic acid, methacrylic acid,
Various (meth) s such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate
Acrylic ester, ethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, styrene, divinylbenzene, (meth) acrylamide, vinyl acetate, N-hydroxymethyl (meth)
Examples thereof include acrylamide, dipentaerythritol hexaacrylate, melamine acrylate, and epoxy acrylate prepolymer. However, it is preferable to use a polyfunctional (meth) acrylic monomer from the viewpoint of exposure sensitivity and resistance after curing.

The hues of the color filters include red, green and blue of additive color mixture system and cyan of subtractive color mixture system,
Magenta, yellow, and black used for the black matrix portion are mainly used. Although there are dyes and pigments as colorants, pigments are used in terms of various resistances such as heat resistance and light resistance as described above. Further, in order to obtain an appropriate spectrum, two or more kinds of pigments are used in combination, for example, blue is a cyan pigment and violet pigment, green is a green pigment and yellow pigment, red is a red pigment and yellow or orange. The proper spectrum is obtained by combining pigments.

The pigment (C) used in the present invention includes
The following are listed. All are indicated by color index numbers. C. I. Pigment Yell
ow12, 13, 14, 17, 20, 24, 55, 8
3, 86, 93, 109, 110, 117, 125, 1
37, 139, 147, 148, 153, 154, 16
6, 168, C.I. I. Pigment Orange
36, 43, 51, 55, 59, 61, C.I. I. Pig
ment Red 9, 97, 122, 123, 14
9, 168, 177, 180, 192, 215, 21
6, 217, 220, 223, 224, 226, 22
7, 228, 240, C.I. I. PigmentVile
t 19, 23, 29, 30, 37, 40, 50, C.I.
I. Pigment Blue 15, 15: 1, 1
5: 4, 15: 6, 22, 60, 64, C.I. I. Pig
ment Green 7, 36, C.I. I. Pigme
nt Brown 23, 25, 26, C.I. I. Pig
Mental Black 7 and titanium black can be exemplified.

In the photosensitive coloring composition of the present invention, it is necessary to sufficiently disperse the pigment and to coat the transparent substrate with a film thickness of 1 to 3 μm. Usually, the viscosity is adjusted using a solvent. Examples of the solvent include cyclohexanone, isophorone,
Cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, ethyl cellosolve, butyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether, isoamyl acetate, ethyl lactate, etc. may be mentioned alone or in admixture of two or more. Can be used.

The photosensitive coloring composition can be produced using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, an attritor, a ball mill and a kneader. A polymerization inhibitor may be added for the purpose of preventing gelation due to a polymerization reaction or the like at the time of dispersion, and a monomer and a photoinitiator may be added after the pigment is dispersed. Also,
A dispersion aid can be added as appropriate to improve the dispersion of the pigment. As such a dispersion aid, various surfactants, pigment derivatives and the like can be used. Since the dispersion aid has an effect of helping the dispersion of the pigment and preventing re-aggregation after the dispersion, a color filter having excellent transparency can be obtained.

The photosensitive coloring composition of the present invention is applied onto a transparent substrate such as glass by a coating method such as spray coating, spinner coating, roll coating or screen coating. For the purpose of obtaining proper fluidity in these coating machines, the photosensitive coloring composition of the present invention, in addition to the solvent described above, barium sulfate, calcium carbonate, extender pigments such as silica,
A small amount of silicon-based or fluorine-based surfactant may be added as a leveling agent or an antifoaming agent. The applied photosensitive coloring composition is dried in a hot air oven, a hot plate or the like at 60 ° C. to 80 ° C. for 10 minutes to 30 minutes to remove the solvent. If the temperature at this time is too high or if the drying time is too long, partial polymerization or crosslinking occurs, the solubility of the unexposed area in the developing solution is reduced, and the so-called "burning" causes poor development. .

The dried coating film is usually exposed to ultraviolet light through a photomask having a color filter pattern.
Although an ultra-high pressure mercury lamp is generally used as a light source, since ultraviolet rays passing through a photomask are usually light of 300 nm or more, the i-line (36) of the emission line spectrum of the ultra-high pressure mercury lamp is used.
5 nm), h line (405 nm) and g line (436n)
Light of a wavelength called m) is used for the polymerization reaction or the crosslinking reaction. Therefore, the sensitivity of the photosensitive coloring composition for the color filter to the above three bright line spectra is important.

After the exposure, the coating film on the unexposed area is dissolved and removed by a developing solution, leaving the pattern on the exposed area. This step is generally called development, but the photosensitive coloring composition of the present invention can be developed with a solvent or an aqueous alkali solution, depending on the solubility of the transparent polymer (A) used. However, as described above, alkaline development has become the mainstream due to environmental problems. As the alkaline developing solution, an inorganic alkaline aqueous solution such as sodium carbonate or sodium hydroxide, or an organic alkaline aqueous solution such as dimethylbenzylamine, triethanolamine or tetramethylammonium hydroxide can be used. After development, if necessary, further irradiation with ultraviolet rays or heating may be carried out to further promote the reaction, whereby various resistances as a color filter can be improved.

[0059]

EXAMPLES The present invention will be described below based on examples.
In the examples, “part” means “part by weight” and “%” means “% by weight”. Moreover, the prepared photosensitive coloring composition is called a resist for convenience. In this example, the alkali-developing red, green, and blue colored resists of the pigment dispersion method, which are currently widely used as a method for manufacturing a color filter for a color liquid crystal display, will be described. Prior to the examples, synthetic examples of alkali-soluble resins will be shown. (Resin solution production example a) In a 1-liter four-necked flask,
Cyclohexanone 350.0 parts, styrene 26.2 parts,
23.3 parts of 2-hydroxy acrylate, 35.0 parts of methacrylic acid, 20.5 parts of methyl methacrylate and 70.0 parts of butyl methacrylate were charged and heated to 90 ° C., and 290.0 parts of cyclohexanone and 26.2 of styrene were previously prepared. Part, 2
-Hydroxy acrylate 23.3 parts, acrylic acid 3
5.0 parts, methyl methacrylate 20.5 parts, butyl methacrylate 70.0 parts and azobisisobutyronitrile 1.
What mixed and melt | dissolved 75 parts was dripped in 3 hours, and it was made to react at 90 degreeC for 3 hours. Further, 0.70 part of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was continued for another hour to synthesize a resin solution. Sampling a part of the resin solution, 180 ℃, 2
Non-volatile content was measured by heating and drying for 0 minutes, and cyclohexanone was added to the resin solution (non-volatile content 30 to 35%) synthesized above so that the non-volatile content was 20% to prepare a resin solution a.

(Resin Solution Production Example b) In a 1 liter four-necked flask, 350.0 parts of cyclohexanone, 26.2 parts of styrene, 43.8 parts of 2-hydroxy acrylate,
Charge 35.0 parts of acrylic acid and 70.0 parts of butyl methacrylate and heat to 90 ° C. to prepare cyclohexanone 29 in advance.
0.0 parts, styrene 26.3 parts, 2-hydroxy acrylate 43.8 parts, acrylic acid 35.0 parts, butyl methacrylate 70.0 parts and azobisisobutyronitrile 1.
What mixed and melt | dissolved 75 parts was dripped in 3 hours, and it was made to react at 90 degreeC for 3 hours. Further, 0.70 part of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was continued for 1 hour. Next, the temperature inside the flask was set to 80 ° C., 23.5 parts of isocyanate ethyl methacrylate and 0.11 part of tin octylate dissolved in 20 parts of cyclohexanone were added dropwise in about 10 minutes, and after the addition, the reaction was continued for 2 hours to obtain a resin solution. Was synthesized. Next, in the same manner as the resin solution a, cyclohexanone was added to prepare a resin solution b having a nonvolatile content of 20%.

Comparative Examples 1 to 9 Preparation of Green Resist Resin solution a 42.48 parts Lionol Green 6YK (manufactured by Toyo Ink Mfg. Co., Ltd.) 6.07 parts Pariotor Yellow D-1819 (manufactured by BASF) 1. 82 parts Dispersant 0.46 part Cyclohexanone 19.68 parts were mixed and dispersed in a sand mill for 60 minutes to prepare a green dispersion. Next, 56.16 parts of green dispersion NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.15 parts Compound A 0.80 parts 4,4'-diethylaminobenzophenone 0.80 parts Cyclohexanone 38.09 parts in a container The mixture was mixed and filtered with a 1.0 μm filter to prepare a green resist 1 having a nonvolatile content of about 20%.

As the compound A, the following sulfonium organoboron complex or oxosulfonium organoboron complex was used. (Comparative Example 1) Dimethylphenacylsulfonium butyltriphenylborate (Comparative Example 2) Dimethylphenacylsulfonium-sec
-Butyltriphenylborate (Comparative Example 3) Dimethylphenacylsulfonium-ter
t-Butyltriphenylborate (Comparative Example 4) Dimethyl-p-cyanobenzylsulfonium butyltriphenylborate (Comparative Example 5) Dimethylphenacylsulfonium-sec
-Butyltri (p-fluorophenyl) borate (Comparative Example 6) Dimethylphenacylsulfonium-sec
-Butyltri (p-methoxyphenyl) borate (Comparative Example 7) Dimethyl-p-chlorophenacylsulfonium butyltriphenylborate (Comparative Example 8) Dimethylbenzyloxosulfoniumbutyl triphenylborate (Comparative Example 9) Dimethylphenacyloxosulfoniumbutyl Triphenyl borate

In order to measure the spectral sensitivity of the obtained resist, a resist was coated on a 100 mm × 100 mm glass substrate with a spin coater so that the dry film thickness was 1.6 μ, and the hot air oven was heated at 70 ° C. for 20 minutes. Dry with an irradiation spectroscope (JASCO CT-25CP type manufactured by JASCO Corporation)
Exposure was performed. An ultra-high pressure mercury lamp was used as the light source. The exposed substrate is immersed in a 2% sodium carbonate aqueous solution for about 20 seconds to develop, and then washed with running water,
It was heated at 220 ° C. for 30 minutes to obtain a spectrophotograph. Table 1 shows i-line (365 nm), h-line (405 nm) and g-line (43 nm).
6 nm) shows the number of steps remaining after development. The relationship between the number of steps and the exposure amount in this experiment is as follows. That is, the larger the number of stages, the higher the sensitivity. 13 steps 1.00 mJ / cm ² 12 steps 1.78 mJ / cm ² 11 steps 3.16 mJ / cm ² 10 steps 5.62 mJ / cm ² 9 steps 10.0 mJ / cm ² 8 steps 17.8 mJ / cm ² 7 steps 31.6 mJ / cm ² 6 steps 56.2 mJ / cm ² 5 steps 100 mJ / cm ² 4 steps 177 mJ / cm ² 3 steps 316 mJ / cm ² 2 steps 562 mJ / cm ² 1 step 1000 mJ / cm ²

[Comparative Example 10] Using the green dispersions used in Comparative Examples 1 to 9, resists having the following compositions were similarly prepared. Green dispersion 56.16 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.15 parts Dimethylphenacyloxosulfonium butyl-triphenylborate 1.60 parts Cyclohexanone 38.09 parts Spectral sensitivity of the obtained resist is shown in Example. It measured by the method similar to 1-9.

Comparative Example 11 Using the green dispersions used in Comparative Examples 1 to 9, resists having the following compositions were similarly prepared. Green dispersion 56.16 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.15 parts 4,4'-diethylaminobenzophenone 1.60 parts Cyclohexanone 38.09 parts Spectral sensitivity of the obtained resists was evaluated as Examples 1 to 9. It measured by the method similar to.

[Comparative Example 12] Using the green dispersions used in Comparative Examples 1 to 9, resists having the following compositions were similarly prepared. Green dispersion 56.16 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.15 parts 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 0.80 parts 4,4 '-Diethylaminobenzophenone 0.80 parts Cyclohexanone 38.09 parts The spectral sensitivity of the obtained resist was measured by the same method as in Examples 1-9.

[Comparative Example 13] Further, for the purpose of confirming the effect of the present invention, the resist obtained in Comparative Example 10 was applied onto a glass substrate by the same method, dried and then further applied onto the coating film. A 6% aqueous solution of polyvinyl alcohol (# 500, manufactured by Kokusan Kagaku Co., Ltd.) was applied by a spin coater to a dry film thickness of 1.2 to 1.3 μm, and dried in a hot air oven at 70 ° C. for 20 minutes to block oxygen. After forming the film, the spectral sensitivity was measured by the same method as in Comparative Examples 1 to 9.

[0068]

[Table 1]

[0069]

[Examples 1 and 2, Comparative Examples 14 to 17] (1) Preparation of green resist Resin solution b 42.48 parts Lionol Green 6YK (manufactured by Toyo Ink Mfg. Co., Ltd.) 6.07 parts Pariotor Yellow D- 1819 (manufactured by BASF) 1.82 parts Dispersant 0.46 parts Cyclohexanone 19.68 parts were mixed and dispersed for 60 minutes by a sand mill to prepare a green dispersion. Next, green dispersion 56.16 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.15 parts Dimethylphenacyloxosulfonium butyl triphenylborate 0.80 parts Compound B 0.80 parts Cyclohexanone 38.09 parts in a container. The mixture was thoroughly mixed and filtered with a 1.0 μm filter to prepare a green resist having a nonvolatile content of about 20%. The following compound was used as the compound B. (Comparative Example 14) 2-Benzyl-2-dimethylamino-1
-(4-morpholinophenyl) -butanone-1 (Comparative Example 15) Isopropylthioxanthone (Comparative Example 16) 2,4-Diethylthioxanthone (Comparative Example 17) 1-Chloro-4-propoxythioxanthone (Example 1) 2, 4-Trichloromethyl (4′-methoxystyryl) -6-triazine (Example 2) 2,4-trichloromethyl (4′-methoxynaphthyl) -6-triazine The spectral sensitivity of the obtained green resist was compared with Comparative Examples 1 to 1. Measurement was carried out in the same manner as in No. 9, and the results shown in Table 2 were obtained.

[0071]

[Table 2]

[Examples 3 to 8] Preparation of green resist Resin solution b 42.48 parts Lionol green 6YK (manufactured by Toyo Ink Mfg. Co.) 6.07 parts Pariotor Yellow D-1819 (manufactured by BASF) 1.82 Parts Dispersant 0.46 parts Cyclohexanone 19.68 parts were mixed and dispersed in a sand mill for 60 minutes to prepare a green dispersion. Next, green dispersion 56.16 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.15 parts Dimethylphenacyloxosulfonium butyl triphenylborate 0.80 parts 2,4-trichloromethyl (4'-methoxystyryl) -6 -Triazine 0.40 part Compound C 0.40 part Cyclohexanone 38.09 parts were thoroughly mixed in a container and filtered with a 1.0 μm filter to prepare a green resist having a nonvolatile content of about 20%. The following compound was used as the compound C. (Example 3) 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone-1 (Example 4) isopropylthioxanthone (Example 5) 2,4-diethylthioxanthone (Example 6) 1-chloro-4-propoxythioxanthone (Example 7) 3,3 ′, 4,4′-Tetra (tert-
(Butyl peroxycarphenone) (Example 8) (η ⁵ -2,4-cyclopentadiene-1
-Yl-) [(1,26-η)-(1-methylethyl)
Benzene] -Iron (1+) Lophosphate (1
+) The spectral sensitivity of the obtained green resist was measured by the same method as in Comparative Examples 1 to 9, and the results in Table 3 were obtained.

[0073]

[Table 3]

Example 9 (1) Preparation of Green Resist Resin solution b 42.48 parts Rionol Green 6YK (manufactured by Toyo Ink Mfg. Co., Ltd.) 6.07 parts Pariotor Yellow D-1819 (manufactured by BASF) 1. 82 parts Dispersant 0.46 part Cyclohexanone 19.68 parts were mixed and dispersed in a sand mill for 60 minutes to prepare a green dispersion. Green dispersion 56.16 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.15 parts Dimethylphenacyloxosulfonium butyl triphenylborate 0.80 parts 2,4-Trichloromethyl (4'-methoxystyryl) -6- Triazine 0.40 part 4,4 'Diethylaminobenzophenone 0.40 part Cyclohexanone 38.09 parts were mixed thoroughly in a container and filtered through a 1.0 μm filter to prepare a green resist having a nonvolatile content of about 20%. The spectral sensitivity was measured by the same method as in Comparative Examples 1 to 9. Next, in the same manner, the present resist was applied to a thickness of 1.6 μm and the entire surface of the dried film was subjected to an integrated light amount of 15 using an ultra-high pressure mercury lamp.
A sample for heat resistance evaluation was prepared by irradiating with ultraviolet rays to 0 mJ / cm ² , immersing in an aqueous solution of 2% sodium carbonate for 20 seconds, and washing with water.

[Comparative Example 18] In the same manner as in Example 9, except that dimethylphenacyloxosulfoniumbutyltriphenylborate and 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine were replaced with the following compounds, a green color was obtained. A resist was prepared and the spectral sensitivity was measured by the same method as in Comparative Examples 1-9. 2,4-Trichloromethyl (4'-methoxynaphthyl) -6-triazine 0.80 part 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Imidazole 0.40 part

Example 10 Preparation of Red Resist Resin solution b 43.92 parts Chromophtal red A3B (manufactured by Ciba Geigy) 7.68 parts Dispersant 0.38 parts Cyclohexanone 15.41 parts were mixed and mixed in a sand mill. And dispersed for 60 minutes to prepare a red dispersion. Next, red dispersion 56.16 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.05 parts dimethylphenacyloxosulfonium butyl triphenylborate 0.80 parts 2,4-trichloromethyl (4'-methoxystyryl) -6 -Triazine 0.40 part 4,4 'Diethylaminobenzophenone 0.40 part Cyclohexanone 37.99 parts were thoroughly mixed in a container and filtered through a 1.0 μm filter to prepare a red resist having a nonvolatile content of about 20%. Then, the spectral sensitivity was measured by the same method as in Comparative Examples 1 to 9. Next, a sample for heat resistance evaluation was prepared in the same manner as in Example 9.

[Comparative Example 19] In the same manner as in Example 10, except that dimethylphenacyloxosulfonium butyltriphenylborate and 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine were replaced with the following compounds, a red color was obtained. A resist was prepared and the spectral sensitivity was measured by the same method as in Comparative Examples 1-9. 2,4-Trichloromethyl (4'-methoxynaphthyl) -6-triazine 0.80 part 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Imidazole 0.40 part

Example 11 Blue resist resin solution b 54.42 parts Lionol blue E (manufactured by Toyo Ink Mfg. Co., Ltd.) 5.68 parts Dispersant 0.29 parts Cyclohexanone 7.01 parts were mixed and mixed in a sand mill. And dispersed for 60 minutes to prepare a blue dispersion. Blue dispersion 56.16 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.23 parts Dimethylphenacyloxosulfonium butyl triphenylborate 0.80 parts 2,4-trichloromethyl (4'-methoxystyryl) -6 -Triazine 0.40 part 4,4 'Diethylaminobenzophenone 0.40 part Cyclohexanone 37.81 parts were thoroughly mixed in a container and filtered through a 1.0 μm filter to prepare a blue resist having a nonvolatile content of about 20%. Then, the spectral sensitivity was measured by the same method as in Comparative Examples 1 to 9.

Comparative Example 20 In the same manner as in Example 11, except that dimethylphenacyloxosulfoniumbutyltriphenylborate and 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine were replaced with the following compounds, red color was obtained. A resist was prepared and the spectral sensitivity was measured by the same method as in Comparative Examples 1-9. 2,4-Trichloromethyl (4'-methoxynaphthyl) -6-triazine 0.80 part 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Imidazole 0.40 part

Table 4 shows the measurement results of the spectral sensitivities of Examples 9 to 11 and Comparative Examples 18 to 20.

[Table 4]

Further, when the samples for heat resistance evaluation prepared in Example 9 and Comparative Example 18 were heated in a hot air oven at 260 ° C. for 1 hour, the transmittance at a peak wavelength near 440 nm before and after heating was measured by spectrophotometry. Table 5 shows the results measured by the meter.

[Table 5]

[0082]

According to the present invention, since a highly sensitive photosensitive coloring composition can be obtained without forming an oxygen barrier film, it is possible to shorten the steps in manufacturing a color filter and to reduce costs by improving productivity. At the same time, a color filter having excellent heat resistance can be supplied.

Continued front page    (72) Inventor Kaoru Nakajima               2-3-13, Kyobashi, Chuo-ku, Tokyo Toyo               Nki Manufacturing Co., Ltd.                (56) Reference JP-A-1-152449 (JP, A)                 JP-A-6-157623 (JP, A)

Claims (2)

(57) [Claims] 1. A transparent high molecular polymer (A) soluble in a solvent or an alkali, a compound (B) having an ethylenically unsaturated bond, a pigment (C), and a sulfonium organic boron represented by the following general formula (1). A photosensitive coloring composition for a color filter, comprising a complex or an oxosulfonium organic boron complex (D) and a triazine compound (E) having a trihalogenomethyl group having an absorption at 300 nm to 400 nm. [Chemical 1] [Wherein R 1 is a benzyl group, a substituted benzyl group,
Represents a group selected from a phenacyl group, a substituted phenacyl group, an aryloxy group, a substituted aryloxy group, an alkenyl group, and a substituted alkenyl group, and R2 and R3 are each independently a group capable of forming R1. Same group or alkyl group, substituted alkyl group, aryl group, substituted aryl group, aralkyl group, substituted aralkyl group, alkynyl group, substituted alkynyl group, alicyclic group, substituted alicyclic group Group, alkoxy group, substituted alkoxy group, alkylthio group, substituted alkylthio group, amino group, substituted amino group, or R
2 and R3 each represent a cyclic structure in which R4 represents an oxygen atom or a lone electron pair, R5, R6, R7 and R8 each independently represent an alkyl group, a substituted alkyl group, an aryl group or a substituted group. Represents an aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, or a substituted alkynyl group (provided that all of R5, R6, R7 and R8 are an aryl group or a substituted aryl group. Absent.)] 2. A color filter comprising a transparent substrate on which pixels are formed by using the photosensitive coloring composition for color filters according to claim 1.