JP2000249822A - Photopolymerization initiator for color filter, photosensitive coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerization initiator for high-sensitivity color filters by incorporating a sensitizer having a specific absorption wavelength region, a specific organic boron complex and a compound having a thiol group. SOLUTION: The photopolymerization initiator contains the sensitizer having the absorption wavelength region at 300 to 500 nm, the organic boron complex expressed by formula and the compound having the thiol group. In the formula, R1 to R4 respectively independently denote alkyl groups, aryl groups, etc. Z+ denotes ammonium cation, sulfonium cation, etc. The compound having the thiol group is preferably at least one kind selected from 2-mercaptobenzothiazole and pentaerythritol tetrakisthiopropionate. The sensitizer preferably contains benzophenones and/or 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-sensitivity photopolymerization initiator for color filters, a high-quality photosensitive coloring composition for color filters which can be developed with a solvent or an aqueous alkali solution after image exposure with ultraviolet rays, and solid-state imaging. The present invention relates to a color filter used for an element, a liquid crystal display device, and the like, and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, liquid crystal display devices and the like have become thinner and larger, and color filters to be used have been required to be defect-free and thin. Further, in addition to various resistances such as heat resistance and light resistance, high transmittance. Rate and high contrast are required. At the same time, cost reduction of color filters is strongly demanded, and it is necessary to improve the yield in the manufacturing process and shorten the process. The color filter is formed by arranging two or more kinds of fine bands (stripe) of different hues in parallel or intersecting on the surface of a transparent substrate such as glass, or by arranging fine pixels in a fixed arrangement in vertical and horizontal directions. ing. The pixel size has to be a fine shape of several tens to several hundreds of microns, and it is necessary that the pixels be arranged in a predetermined order for each hue. For this reason, various methods have been conventionally proposed for the method of producing a color filter, but from many points such as accuracy and production cost, a pigment is dispersed in a photosensitive composition called a pigment dispersion method. A method using a coloring composition is widely used as a method for producing a color filter.

In this pigment dispersion method, a photosensitive coloring composition containing a resin composed of a pigment, a base material, and a crosslinking agent is applied on a substrate, and each color is formed into a predetermined pattern shape using photolithography. It forms a colored layer. That is,
The photosensitive coloring composition of one filter color is coated on a transparent substrate such as glass, and is subjected to pattern exposure, and the unexposed portion is developed and removed with a solvent or an aqueous alkali solution to form a first color pattern. Subsequently, the same operation is sequentially repeated for all filter colors, whereby a color filter can be manufactured. The photosensitive composition is mainly a negative photosensitive composition because of its physical properties and abundance of materials as a color filter.Also, in the development, a solvent is hardly used due to environmental problems, and the photosensitive composition is used in an aqueous alkaline solution. Development is the mainstream. Regarding the exposure, exposure with ultraviolet rays is usually performed. In this manufacturing process, a chemical reaction is used in which only a predetermined position of the photosensitive resin composition is exposed to ultraviolet rays or the like, and a radical polymerization reaction is caused only in the exposed portion.

In a negative photosensitive composition, a radical polymerization reaction is mainly used, so that the inhibition of the reaction by oxygen in the air also causes a decrease in sensitivity. In this regard, after applying the photosensitive composition, measures such as image exposure after providing an oxygen barrier film such as polyvinyl alcohol thereon have been taken, but recently, from the viewpoint of shortening the process described above, recently, There is a demand for a photoinitiator for a color filter with high sensitivity that does not require treatment such as providing an oxygen barrier film.

For example, JP-A-6-201913 describes a photopolymerization initiator using a triazine compound alone or in combination with a triazine compound and an imidazole compound, and JP-A-10-253513 discloses a polyfunctional thiol compound. And a photoinitiator in combination with at least one compound selected from a biimidazole compound, a titanocene compound, a triazine compound and an oxadiazole compound. However, even with these photopolymerization initiators, red, green, even if it has a certain sensitivity in the blue photopolymerizable composition, black photopolymerizable composition, especially contains a high concentration of black pigment The composition has a disadvantage that the sensitivity of the black pigment due to the light-shielding property at the time of exposure is remarkably reduced, and the exposure time is prolonged and the curing is insufficient.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems and to provide a highly sensitive photopolymerization initiator for a color filter,
It is an object of the present invention to provide a photosensitive coloring composition containing the initiator, a color filter excellent in various resistances, and a method for producing the same.

[0007]

Means for Solving the Problems The present inventors have proposed a method of 300 to 5
A sensitizer (A) having an absorption wavelength region at 00 nm, an organic boron complex (B) and a compound (C) having a thiol group
It has been found that a photopolymerization initiator characterized by containing the above is suitable for use in color filters, and it has been found that the use thereof can solve the above-mentioned problems, thus completing the present invention.
That is, the present invention provides: 1) a sensitizer (A) having an absorption wavelength range of 300 to 500 nm, an organic boron complex (B) represented by the general formula (1), and a compound (C) having a thiol group. Photopolymerization initiator for color filters, characterized by containing
General formula (1);

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a heterocyclic group or an alicyclic group, and Z ⁺ represents an ammonium cation, a sulfonium cation Oxosulfonium cation, pyridinium cation, phosphonium cation, oxonium cation or iodonium cation.) 2) The compound (C) having a thiol group is at least selected from 2-mercaptobenzothiazole and pentaerythritol tetrakisthiopropionate. The photopolymerization initiator according to the above 1), which is one kind. 3) The sensitizer (A) is a benzophenone and / or 2,2′-bis (2-chlorophenyl) -4,4 ′,
The photopolymerization initiator according to the above item 1), which comprises 5,5′-tetraphenyl-1,2′-biimidazole, 4) a transparent polymer polymer soluble in a solvent or an aqueous alkali solution. (D) a compound (E) having an ethylenically unsaturated bond, a pigment (F), and the photopolymerization initiator according to any one of the above 1) to 3). 5) A color filter comprising pixels formed on a transparent substrate using the photosensitive coloring composition for a color filter according to 4) above. 6) A color filter comprising: A method for producing a color filter, comprising: a step of forming the photosensitive coloring composition layer for a color filter described above; and a step of photo-curing the exposed portion of the photosensitive coloring composition layer by exposure.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail. The alkyl group of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) may have a substituent, and specifically, a substituted or unsubstituted linear group having 1 to 12 carbon atoms. Alternatively, a branched alkyl group is preferable, for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, dodecyl group, cyanomethyl group, 4-chlorobutyl group, 2-diethylaminoethyl group, 2-methoxyethyl group And the like.

The aryl group of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) may have a substituent, and is specifically a substituted or unsubstituted aryl group such as phenyl. Group, tolyl group, xylyl group, mesityl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-n-butylphenyl group, 4-tert-butylphenyl group, naphthyl group, anthryl group, phenanthryl group, 4- Nitrophenyl group, 4-trifluoromethylphenyl group, 4
-Fluorophenyl group, 4-chlorophenyl group, 4-dimethylaminophenyl group and the like.

The aralkyl group of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) may have a substituent. Specifically, it is a substituted or unsubstituted aralkyl group such as benzyl. Group, phenethyl group, 1-naphthylmethyl group, 2
-Naphthylmethyl group, 4-methoxybenzyl group and the like.

The alkenyl group of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) may have a substituent, and is specifically a substituted or unsubstituted alkenyl group such as vinyl. Group, propenyl group, butenyl group, octenyl group and the like.

The heterocyclic group represented by R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) may have a substituent. Specifically, the heterocyclic group is a substituted or unsubstituted heterocyclic group. Examples include a pyridyl group, a 4-methylpyridyl group, a quinolyl group, an indolyl group, and the like.

The alicyclic groups of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) may have a substituent. Specifically, they are substituted or unsubstituted alicyclic groups, For example, a cyclohexyl group, a 4-methylcyclohexyl group, a cyclopentyl group, a cycloheptyl group and the like can be mentioned.

In Z ⁺ in the general formula (1), the ammonium cation specifically includes, for example, tetramethylammonium cation, tetraethylammonium cation, tetra-n-propylammonium cation, tetra-n-butylammonium cation, n- Butyltriphenylammonium cation, tetraphenylammonium cation, benzyltriphenylammonium cation and the like. In Z ⁺ in the general formula (1), the sulfonium cation is specifically, for example, triphenylsulfonium cation, tri (4-tolyl)
Examples include a sulfonium cation and a 4-tert-butylphenyldiphenylsulfonium cation. In Z ⁺ in the general formula (1), the oxosulfonium cation specifically includes, for example, a triphenyloxosulfonium cation, a tri (4-tolyl) oxosulfonium cation, a 4-tert-butylphenyldiphenyloxosulfonium cation, and the like. No. In Z ⁺ in the general formula (1), the oxonium cation is specifically, for example, a triphenyloxonium cation, a tri (4-tolyl) oxonium cation, a 4-t
tert-butylphenyldiphenyloxonium cation and the like. In Z ⁺ in the general formula (1), the pyridinium cation specifically includes, for example, N-methylpyridinium cation, Nn-butylpyridinium cation and the like. In Z ⁺ in the general formula (1), the phosphonium cation is specifically, for example, a tetramethylphosphonium cation, a tetra-n-butylphosphonium cation, a tetra-n-octylphosphonium cation, a tetraphenylphosphonium cation, a benzyltriphenylphosphonium cation And the like. In Z ⁺ in the general formula (1), specific examples of the iodonium cation include a diphenyliodonium cation, a di (4-methylphenyl) iodonium cation, and a di (4-tert-butylphenyl) iodonium cation. .

Examples of the organic boron complex represented by the general formula (1) include, for example, tetramethylammonium n-
Butyl triphenyl borate, tetraethyl ammonium isobutyl triphenyl borate, tetra n-butyl ammonium n-butyl tri (4-tert-butyl phenyl) borate, tetra n-butyl ammonium n-
Butyl trinaphthyl borate, tetra n-butyl ammonium methyl tri (4-methylnaphthyl) borate, triphenylsulfonium n-butyl triphenyl borate, triphenyl oxosulfonium n-butyl triphenyl borate, triphenyl oxonium n- Butyltriphenylborate, N-methylpyridium n-butyltriphenylborate, tetraphenylphosphonium n-butyltriphenylborate, diphenyliodonium n-butyltriphenylborate and the like.

The organoboron complex represented by the general formula (1) generally has almost no absorption at 300 nm or more. Therefore, even if used alone, it does not have sensitivity to a light source of an ordinary ultraviolet lamp.
Very high sensitivity can be obtained by combining with a sensitizer. In the present invention, the organic boron complex (B) is generally 1 to 60% by weight, preferably 5 to 30% by weight based on the compound having an ethylenically unsaturated bond.
It is blended so that If the amount of the organic boron complex is too small, the polymerization reaction may not proceed sufficiently. If the amount is too large, the stability of the composition is lowered and the composition is disadvantageous economically.

As the sensitizer (A) having an absorption wavelength in the range of 300 to 500 nm used in the present invention, a photopolymerization initiator, a sensitizer, and a dye having absorption in this wavelength region can be used. Examples of these compounds include compounds such as cationic dyes, benzophenones, acetophenones, benzoins, thioxanthones, imidazoles, bisimidazoles, coumarins, ketocoumarins, triphenylpyryliums, triazines, and benzoic acids. Is exemplified. Further, compounds such as acylphosphine oxide, methylphenylglyoxylate, α-acyloxime ester, benzyl, camphorquinone, and ethylanthraquinone can also be used. These compounds can be used alone or in combination of two or more.

For example, Basic Yellow 1,
11, 13, 21, 28, 36, Basic Oran
cation dyes such as ge21 and 22, benzophenone,
-Methylbenzophenone, 4-dimethylaminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone, 2-methylthioxanthone, N-methylimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (hereinafter abbreviated as HABI), 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetra (ethoxyphenyl) -1,
2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-bromophenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5, 5'-
Tetraphenyl-1,2'-biimidazole, 2,2 '
-Bis (2-chlorophenyl) -4,4 ', 5,5'-
Tetra (3-methoxyphenyl) -1,2′-biimidazole, 2,2′-bis (2-methylphenyl) -4,
4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, coumarin, 7-diethylaminocoumarin, 4-
Ethyl dimethylaminobenzoate or the like can be used alone or in combination of two or more.In view of the stability of the initiator and the composition, the ability to initiate polymerization, etc., benzophenone compounds, benzoic acids, and biimidazole compounds are preferable. Particularly preferred is the above-mentioned HABI. In the present invention, the sensitizer (A) having an absorption wavelength of 300 to 500 nm is used in an amount of generally 1 to 60% by weight, preferably 2 to 30% by weight, based on the compound having an ethylenically unsaturated bond. Mix. If the amount is too small, the sensitizing effect may not be obtained, and if the amount is too large, the light transmission efficiency may be deteriorated due to the light absorption of the sensitizer, and the polymerization initiation efficiency may be reduced.

The compound (C) having a thiol group used in the present invention is a compound having a thiol group in the molecule, for example, 2-mercaptobenzothiazole,
-Mercaptobenzimidazole, 2-mercaptobenzoxazole, 5-chloro-2-mercaptobenzothiazole, 2-mercapto-5-methoxybenzothiazole, 5-methyl-1,3,4-thiadiazole-2-
Thiol, 5-mercapto-1-methyltetrazole,
3-mercapto-4-methyl-4H-1,2,4-triazole, 2-mercapto-1-methylimidazole,
2-mercaptothiazoline, octanethiol, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycol Butanediol bisthiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, etc., and particularly, 2-mercaptobenzothiazole, 2-mercaptobenzo Imidazole,
2-mercaptobenzoxazole, trimethylolpropane tristhioglycolate, and pentaerythritol tetrakisthiopropionate are preferred from the viewpoint of polymerization initiation ability. These compounds having a thiol group can be used alone or in combination of two or more. In the present invention, the compound (C) having a thiol group is generally 1 to the compound having an ethylenically unsaturated bond.
６０60% by weight, preferably 5-30% by weight. If the amount is too small, the polymerization initiation may not proceed efficiently. If the amount is too large, improvement in the polymerization initiation function cannot be expected, and the physical properties of the cured product may be adversely affected. In the present invention, 300 to 500 n
By combining the sensitizer (A) having an absorption wavelength region in the range of m, the organic boron complex (B) represented by the general formula (1) and the compound (C) having a thiol group, the polymerization performance is improved. improves.

The transparent high molecular polymer (D) used in the present invention, which is soluble in a solvent or an aqueous alkali solution, is defined as having high transparency, that is, a film having a thickness of 1 micron and a visible light range of 400-7.
The transmittance is preferably 80 in the entire wavelength region of 00 nm.
% Or more, more preferably 95% or more, and is soluble in a developing solution (solvent or aqueous alkali solution). Examples of such a high-molecular polymer include a thermosetting resin, a thermoplastic resin, and a photosensitive resin, and are used alone or as a mixture of two or more kinds. However, in a subsequent process in the production of a color filter, high-temperature treatment and treatment with various solvents or chemicals are performed, so that the transparent polymer (D) has excellent heat resistance, solvent resistance, and chemical resistance. It is preferred that it is.

As the compound (E) having an ethylenically unsaturated bond used in the present invention, a compound capable of undergoing a radical polymerization (or cross-linking) reaction, which is generally called a monomer or oligomer, is used, and (meth) acrylic acid, Various (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol di ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, styrene, divinylbenzene, (meth) acrylamide, vinyl acetate, N-hydroxymethyl (meth) acrylamide, dipentaerythol hexaacrylate, melamine acrylate, epoxy Chestnut rate prepolymers, and the like. However, it is preferable to use a polyfunctional (meth) acrylic monomer from the viewpoint of exposure sensitivity and various resistances after the effect. In the present invention, “(meth) acryl” means both “methacryl” and “acryl”.

The hues of the color filters are red, green, and blue, which are additive color mixing systems, and cyan, which is a subtractive color mixing system.
Magenta, yellow, and black used for the black matrix portion are mainly used. As the coloring agent, there are a dye and a pigment. As described above, a pigment is used in terms of heat resistance, light resistance and the like. Further, in order to obtain an appropriate spelltle, two or more kinds of pigments are used in combination. For example, blue is a cyan pigment and a violet pigment, green is a green pigment and a yellow pigment, and red is a red pigment and a yellow or orange. An appropriate spectrum is obtained by combining pigments.

The pigment (F) used in the present invention includes:
The following are mentioned. Both are indicated by color index numbers. C. I. Pigment Yellow
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 3
6, 43, 51, 55, 59, 61, C.I. I. Pigm
ent Red 9, 97, 122, 123, 149, 1
68, 177, 180, 192, 215, 216, 21
7, 220, 223, 224, 226, 227, 22
8, 240, C.I. I. Pigment Violet1
9, 23, 29, 30, 37, 40, 50, C.I. I. P
pigmentBlue 15, 15: 1, 15: 4, 1
5: 6, 22, 60, 64, C.I. I. Pigment
Green 7, 36, C.I. I. Pigment Bro
wn23, 25, 26, C.I. I. Pigment Bl
ack7 and titanium black.

In the photosensitive coloring composition of the present invention, since it is necessary to disperse the pigment sufficiently and to apply the composition on a transparent substrate in a film thickness of 1 to 3 μm, it is necessary to provide coating applicability. The viscosity is usually adjusted using a solvent. Examples of the solvent include methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, isoamyl acetate, ethyl lactate, and methyl ethyl ketone. , Acetone, cyclohexanone and the like.
A mixture of more than one species can be used.

The production of the photosensitive coloring composition can be carried out using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, an attritor, a ball mill, a kneader and a paint shaker. For the purpose of preventing gelation due to a polymerization reaction or the like during dispersion, a polymerization inhibitor may be added, and a monomer or a photoinitiator may be blended after the pigment is dispersed. In addition, a dispersing aid can be appropriately added to improve the dispersion of the pigment. Since the dispersing aid has an effect of dispersing the pigment and preventing reaggregation after the dispersion, a color filter having excellent transparency can be obtained.

The color filter of the present invention is generally prepared by coating the photosensitive coloring composition of the present invention on a transparent substrate such as glass.
It is manufactured by light curing by exposure. Generally, a first step; a step of forming a photosensitive colored resin layer on a transparent substrate; a second step; a step of performing pattern exposure on the photosensitive resin layer through a pattern mask having a predetermined pattern; A step of developing the photosensitive resin layer after the pattern exposure, and forming the photosensitive resin layer remaining on the transparent substrate into a pixel layer according to a predetermined pattern; a fourth step; forming a pixel layer after the developing step And baking (post-baking) the transparent substrate. The method for producing a color filter of the present invention is limited to the above method as long as the photosensitive coloring composition of the present invention is used. Not something.

Hereinafter, a preferred process for producing a color filter according to the present invention will be described in detail. In the first step, the photosensitive coloring composition of the present invention is applied on a transparent substrate such as glass by a coating method such as spray coating, spinner coating, roll coating, and screen coating. For the purpose of obtaining appropriate fluidity in these coating machines, the photosensitive coloring composition of the present invention may contain, in addition to the above-mentioned solvent, an extender such as barium sulfate, calcium carbonate, silica, a leveling agent or a dehydrating agent. A small amount of a silicone-based or fluorine-based surfactant may be added as a foaming agent. The applied photosensitive coloring composition is generally treated with a hot air oven or a hot plate for 6 hours.
The solvent may be dried (prebaked) at 0 to 80 ° C. for 10 to 30 minutes. If the temperature at this time is too high or the drying time is too long, partial polymerization or cross-linking occurs, the solubility of the unexposed portion in the developing solution is reduced, and a development defect called so-called seizure may be caused. Is not preferred. In the second step, the photosensitive resin layer obtained in the first step is usually exposed to ultraviolet light through a photomask having a color filter pattern. As a light source, an ultra-high pressure mercury lamp, a metal halide lamp, or the like is generally used. Since ultraviolet light transmitted through a photomask is usually light of 300 nm or more, the emission line spectrum of the ultra-high pressure mercury lamp is i.
Line (365 nm), h line (405 nm), g line (436
(nm) is used for the polymerization reaction or the crosslinking reaction. Therefore, the sensitivity of the photosensitive coloring composition for a color filter to the above three bright line spectra is important. In the third step, the unexposed uncured portion, that is, the photosensitive resin layer other than the pixel region is removed from the exposed photosensitive resin layer obtained in the second step using a weak alkaline developer.
In the fourth step, the transparent substrate on which the pixel layer obtained in the third step is formed is post-baked at 160 to 300 ° C. for about 20 to 30 minutes to obtain a first color pixel layer. The first to fourth steps are repeated for each color to obtain a color filter.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
In the examples, "part" indicates "part by weight" and "%" indicates "% by weight". The prepared photosensitive coloring composition is referred to as a resist for convenience. In this embodiment, an alkali-developing black resist of a pigment dispersion method, which is currently widely used as a method of manufacturing a color filter for a color liquid crystal display, will be described. Prior to the examples, examples of synthesizing a resin soluble in an aqueous alkaline solution will be described.

(Resin Solution Production Example 1) In a 1-liter four-necked flask, 350 parts of cyclohexanone and styrene 2
6 parts, 23 parts of 2-hydroxyethyl acrylate, 35 parts of methacrylic acid, 21 parts of methyl methacrylate, and 70 parts of butyl methacrylate were heated to 90 ° C., and 290 parts of cyclohexanone, 26 parts of styrene, and 2 parts of 2-hydroxyethyl acrylate were prepared in advance. 23 parts, methacrylic acid 35
Part, methyl methacrylate 21 parts, butyl methacrylate 7
A mixture of 0 parts and 1.75 parts of azobisisobutyronitrile was added dropwise over 3 hours, and the mixture was further reacted at 90 ° C. for 3 hours. Furthermore, azobisisobutyronitrile 0.1.
A solution obtained by dissolving 75 parts in 10 parts of cyclohexanone was added, and the reaction was further continued for 1 hour to synthesize a resin solution.
A part of this resin solution was sampled at 180 ° C and 20 ° C.
After heating and drying for a minute, the non-volatile content was measured, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20%, whereby a resin solution 1 was prepared.

(Resin Solution Production Example 2) In a 1-liter four-necked flask, 350 parts of cyclohexanone and styrene 2 were added.
6 parts, 44 parts of 2-hydroxyethyl acrylate, 35 parts of acrylic acid, and 70 parts of butyl methacrylate
290 parts of cyclohexanone, 26 parts of styrene, and 44 parts of 2-hydroxyethyl acrylate.
And 35 parts of acrylic acid, 70 parts of butyl methacrylate, and 1.75 parts of azobisisobutyronitrile were added dropwise over 3 hours, and the mixture was further reacted at 90 ° C. for 3 hours. Further, a solution obtained by dissolving 0.75 part of azobisisobutyronitrile in 10 parts of cyclohexanone was added, and the reaction was further continued for 1 hour to synthesize a resin solution. Then
With the temperature inside the flask at 80 ° C., 24 parts of isocyanateethyl methacrylate and 0.11 part of tin octylate dissolved in 20 parts of cyclohexane were added dropwise in about 10 minutes,
After dropping, the mixture was reacted for 20 minutes to synthesize a resin solution. Next, in the same manner as in the resin solution 1, cyclohexanone was added to prepare a resin solution 2 having a nonvolatile content of 20%.

(Examples 1 to 5) Preparation of black resist Resin solution 1: 55 parts Special Black (manufactured by Degussa):
5.7 parts Dispersant: 0.29 parts Cyclohexanone: 7.8 parts were mixed and dispersed with a paint shaker for 24 hours to prepare a black dispersion. Next, black dispersion: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.85
Part Sensitizer: 0.7 to 1.8 parts Organoboron complex: 0.9 part Thiol compound: 0.9 part Cyclohexanone: 39.0 parts Mix well in a container to form a 1.0 micron filter. Then, a black resist having a nonvolatile component of about 20% was prepared. Table 1 shows combinations of the sensitizer, the organic boron complex, and the thiol compound and the component ratios in the sensitizer.

[0032]

[Table 1]

(Comparative Example) The above black dispersion: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co.): 4.85
Part 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine: 2 parts Cyclohexanone: 39.0 parts are thoroughly mixed in a vessel and filtered through a 1.0 micron filter. Then, a comparative black resist having a nonvolatile component of about 20% was prepared.

In order to measure the spectral sensitivity of the obtained resist, a resist was applied on a 100 mm × 100 mm glass substrate by a spin coater so that the dry film thickness became 1.4 μm, and heated at 70 ° C. for 20 minutes. Dried in the oven,
Irradiation spectrometer (JASCO CT-25CP manufactured by JASCO Corporation)
) And exposed. An ultra-high pressure mercury lamp was used as a light source. The exposed substrate is immersed in a 1% aqueous solution of sodium carbonate for about 60 seconds, developed, and then washed with running water.
Spectrographs were obtained by heating at 20 ° C. for 30 minutes. Table 2 shows i-line (365 nm), h-line (405 nm), and g-line (4
At 36 nm). The relationship between the number of stages and the exposure in this experiment is as follows. That is, the larger the number of stages, the higher the sensitivity.

[0035]

[Table 2]

Table 3 shows the results.

[Table 3]

[0037]

As is evident from the results in Table 3, the present invention provides a photosensitive coloring composition having high sensitivity without forming an oxygen barrier film, so that the process for producing a color filter can be shortened. In addition, it was possible to reduce costs by improving productivity, and at the same time, it was possible to supply a color filter having excellent durability.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H025 AA01 AB13 AC01 AD01 BC13 CA03 CA28 CA30 CA32 CA39 CC12 EA05 FA03 FA17 FA29 2H048 BA45 BA48 BB02 BB42 BB46 4J011 QA02 QA03 QA06 QA08 QA09 QA19 QA23 QA19 SA83B TA03 UA01 VA01 WA01

Claims (6)

[Claims] 1. A sensitizer (A) having an absorption wavelength range of 300 to 500 nm, an organic boron complex (B) represented by the general formula (1), and a compound (C) having a thiol group. A photopolymerization initiator for a color filter, comprising: General formula (1); (Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a heterocyclic group or an alicyclic group, and Z ⁺ represents an ammonium cation, a sulfonium cation Oxosulfonium cation, pyridinium cation, phosphonium cation, oxonium cation or iodonium cation.) 2. The compound (C) having a thiol group is
2. The photopolymerization initiator according to claim 1, wherein the photopolymerization initiator is at least one selected from mercaptobenzothiazole and pentaerythritol tetrakisthiopropionate. 3. The method according to claim 1, wherein the sensitizer (A) is a benzophenone and / or 2,2′-bis (2-chlorophenyl)-.
3. The composition according to claim 1, comprising 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.
The photopolymerization initiator according to the above. 4. The transparent polymer (D) soluble in a solvent or an aqueous alkali solution, a compound (E) having an ethylenically unsaturated bond, a pigment (F), and the pigment according to any one of claims 1 to 3. A photosensitive coloring composition for a color filter, comprising a photopolymerization initiator. 5. A color filter comprising a pixel formed on a transparent substrate using the photosensitive color composition for a color filter according to claim 4. 6. A step of forming a photosensitive color composition layer for a color filter according to claim 4 on a transparent substrate and a step of photo-curing the exposed portion of the photosensitive color composition layer by exposure. A method of manufacturing a color filter.