JP2003255121A - Method for manufacturing color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter with excellent productivity, which utilizes a photosensitive coloring composition with excellent storage stability and high sensitivity and the color filter. <P>SOLUTION: In the method, the photosensitive coloring composition is utilized. The composition comprises a transparent polymer (A) soluble in a solvent or in an aqueous alkali solution, a radical polymerizable compound (B) with an ethylenic unsaturated bond, a colorant (C), a dispersant (D), a solvent (E), a sensitizer (F) with an absorption wavelength region in 300-500 nm, an organic boron complex compound (G) expressed by the general formula (1) and a photopolymerization initiator (I) composed of a compound (H) which is a compound with a plurality of thiol groups in one molecule and with branched structures on α and/or β positions with respect to the thiol groups in major proportions. Coloring patterns with arbitrary colors are formed on an identical substrate. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color filter used in a liquid crystal display device, a solid-state image pickup device and the like with high productivity and a color filter.

[0002]

2. Description of the Related Art In recent years, liquid crystal display devices, etc. have become large in size, high in performance and low in price, and the color filters used have no defect, heat resistance, light resistance, chemical resistance, etc. High performance such as transmittance and high contrast is demanded, and at the same time, cost reduction of color filters is also strongly demanded, and it is necessary to improve the yield and shorten the process in the manufacturing process.

A color filter for a liquid crystal display device is composed of a transparent base material such as glass having fine pixels or bands (stripe) of a plurality of hues arranged in a fixed arrangement on the surface thereof. The width of the band is extremely small, that is, several tens to several hundreds of μm. For this reason, various methods have been conventionally proposed as a method for manufacturing a color filter, but in many points such as various characteristics and productivity, it is called a pigment dispersion method, which is a photosensitive coloring in which a pigment is dispersed in a photosensitive resin. A method of forming a pattern (pixel or band) by photolithography using a composition has been widely adopted as a method of manufacturing a color filter for a liquid crystal display device.

In this pigment dispersion method, a photosensitive coloring composition containing a resin consisting of a pigment, a matrix and a cross-linking agent is applied onto a substrate, and photolithography is used to form a colored layer of each color in a predetermined pattern shape. Is formed. That is, a photosensitive coloring composition containing a pigment of one filter color is applied onto a substrate such as glass, and pattern exposure and development are performed to form a first color pattern. Further, the photosensitive coloring composition is mainly a negative photosensitive composition from the viewpoints of physical properties as a color filter, abundance of materials, and productivity, and development is a point of influence on environment. Therefore, almost no solvent is used, and development with an alkaline aqueous solution has become the mainstream. Regarding exposure, usually, exposure using ultraviolet rays is performed. In this manufacturing process, only a predetermined position of the photosensitive composition is irradiated with ultraviolet rays or the like through a photomask or the like, and in the irradiated portion, the photoinitiator in the coating film is cleaved to generate radicals to cause radical polymerization. It uses the reaction of causing it.

However, in the pigment dispersion method, the photosensitive composition itself contains a pigment as a colorant, but in order to obtain a desired spectral characteristic with an appropriate film thickness for use as a color filter, the pigment concentration Needs to be quite high. Therefore, most of the ultraviolet light irradiated in the coating film is absorbed by the pigment, and the efficiency of radical polymerization decreases in the depth direction of the coating film. If the exposure dose required for the photoreaction cannot be obtained, the curing failure inside the coating film occurs, and the pattern failure occurs during development. That is, it is necessary to increase the exposure amount in order to sufficiently cure the inside of the coating film and not to cause a defective pattern shape during development. As a result, the exposure time becomes long and the productivity decreases. Occur.

Further, in the negative type photosensitive composition,
Since the radical polymerization reaction is mainly used, inhibition of the polymerization reaction by oxygen in the air is one of the causes of the decrease in sensitivity. With respect to this, measures such as exposure after applying a photosensitive composition and then providing an oxygen barrier film such as polyvinyl alcohol have been taken, but from the viewpoint of shortening the above-mentioned steps and improving productivity, Therefore, there is a demand for a highly sensitive coloring composition for a color filter which does not require treatment such as providing an oxygen barrier film.

Japanese Patent Application Laid-Open No. 2000-249822 discloses a coloring composition containing such a highly sensitive photoinitiator.
Although a photosensitive coloring composition containing a sensitizer having an absorption wavelength region of 00 to 500 nm and an organic boron complex and a compound having a thiol group is described, the photosensitive coloring composition described is used. When a color filter is prepared, the sensitivity is high when the photosensitive coloring composition immediately after preparation is used, but there is a defect that the sensitivity is lost with time if the photosensitive coloring composition is left to stand.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and uses a photosensitive coloring composition having high sensitivity and excellent storability, and a color having excellent productivity. An object of the present invention is to provide a method for manufacturing a filter. It is another object of the present invention to provide a color filter having excellent productivity by the color filter manufacturing method.

[0009]

The present invention comprises a transparent polymer (A) soluble in a solvent or an aqueous alkali solution, a radically polymerizable compound (B) having an ethylenically unsaturated bond, and a colorant (C). , Dispersant (D), solvent (E), 3
A sensitizer (F) having an absorption wavelength range from 00 to 500 nm, an organoboron complex (G) represented by the general formula (1), and a compound having a plurality of thiol groups in one molecule, Using a photosensitive coloring composition containing a photopolymerization initiator (I) composed of a compound (H) having a branched structure at the α-position and / or β-position with respect to the group as a main component A method of manufacturing a color filter, which comprises forming a colored pattern.

[0010]

[Chemical 3]

Further, in the present invention, in the method for producing a color filter according to the above invention, the compound (H) comprises at least one compound represented by the general formula (2), the general formula (3) or the general formula (4). The method for producing a color filter is characterized by including one or more.

[0012]

[Chemical 4]

In the method for producing a color filter according to the present invention, the compound (H) is ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), trimethylolpropane. Tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3 -Mercaptoisobutyrate) and pentaerythritol tetrakis (3-mercaptoisobutyrate) at least one compound is contained.

Further, the present invention provides the method for producing a color filter according to the above invention, wherein the sensitizer (F) contains at least one benzophenone and / or anthraquinone. Is the way.

Further, the present invention is a color filter manufactured by using the method for manufacturing a color filter according to the above invention.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. R ¹ , R ² , R ³ in the general formula (1),
And the alkyl group of R ⁴ may have a substituent, specifically, a C 1-12 substituted or unsubstituted straight chain,
Alternatively, a branched alkyl group is preferable, for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group,
Normal butyl group, isobutyl group, sec-butyl group,
Examples thereof include tert-butyl group, n-pentyl group, n-hexyl group, n-hexyl group, n-octyl group, dodecyl group, cyanomethyl group, 4-chlorobutyl group, 2-diethylaminophenyl group, and the like. It is not limited.

The aryl group of R ¹ , R ² , R ³ and R ^{4 in} the above general formula (1) may have a substituent, and specifically, it may be a substituted or unsubstituted aryl group. , For example, phenyl group, tolyl group, xylyl group, mesityl group,
4-methoxyphenyl group, 2-methoxyphenyl group, 4
-N-butylphenyl group, 4-tert-butylphenyl group, naphthyl group, 4-methylnaphthyl group, anthryl group, phenanthryl group, 4-nitrophenyl group, 4-trifluoromethylphenyl group, 4-fluorophenyl group, Examples thereof include 4-chlorophenyl group and 4-dimethylaminophenyl group, but are not limited thereto.

The aralkyl group of R ¹ , R ² , R ³ and R ^{4 in} the above general formula (1) may have a substituent,
Specific examples of the substituted or unsubstituted aralkyl group include, but are not limited to, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, and 4-methoxybenzyl group. Not something.

The alkenyl group represented by R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) may have a substituent,
Specific examples of the substituted or unsubstituted alkenyl group include, but are not limited to, a vinyl group, a propenyl group, a butenyl group, and an octenyl group.

The heterocyclic group represented by R ¹ , R ² , R ³ and R ^{4 in} the above general formula (1) may have a substituent, specifically, a substituted or unsubstituted heterocyclic group. Examples of the group include, but are not limited to, a pyridyl group, a 4-methylpyridyl group, a quinolyl group, and an indolyl group.

The alicyclic group represented by R ¹ , R ² , R ³ and R ^{4 in} the above general formula (1) may have a substituent, specifically, a substituted or unsubstituted alicyclic group. Examples of the group include, but are not limited to, a cyclohexyl group, a 4-methylcyclohexyl group, a cyclopentyl group, a cycloheptyl group, and the like.

In Z ⁺ in the above general formula (1), the ammonium cation is specifically, for example, tetramethylammonium cation, tetraethylammonium cation, tetra-n-propylammonium cation,
Examples thereof include tetra-n-butylammonium cation, n-butyltriphenylammonium cation, tetraphenylammonium cation, and benzyltriphenylammonium cation, but are not limited thereto.

In Z ⁺ in the above general formula (1), the sulfonium cation is specifically, for example, triphenylsulfonium cation, tri (4-tolyl) sulfonium cation, 4-tert-butylphenyldiphenylsulfonium cation, etc. However, the present invention is not limited to these.

In Z ⁺ in the above general formula (1), the oxosulfonium cation is specifically, for example, triphenyloxosulfonium cation, tri (4-tolyl) oxosulfonium cation, 4-tert-butylphenyldiphenyl. Examples thereof include, but are not limited to, an oxosulfonium cation.

In Z ⁺ in the above general formula (1), the oxonium cations are specifically, for example, triphenyloxonium cation, tri (4-tolyl) oxonium cation, 4-tert-butylphenyldiphenyl. Examples thereof include, but are not limited to, oxonium cations.

Specific examples of the pyridinium cation in Z ⁺ in the above general formula (1) include, but are not limited to, N-methylpyridinium cation and N-n-butylpyridinium cation. Absent.

In Z ⁺ in the above general formula (1), the phosphonium cation is specifically, for example, tetramethylphosphonium cation, tetra-n-butylphosphonium cation, tetra-n-octylphosphonium cation or tetraphenylphosphonium. Examples thereof include cations and benzyltriphenylphosphonium cations, but are not limited thereto.

In Z ⁺ in the above general formula (1), the iodonium cations are specifically, for example, diphenyliodonium cation, di (4-methylphenyl) iodonium cation, di (4-tert-butylphenyl).
Examples thereof include iodonium cations, but are not limited thereto.

Examples of the organic boron complex (G) represented by the general formula (1) include, for example, tetramethylammonium-n-butyltriphenylborate, tetra-n-ethylammoniumisobutyltriphenylborate, tetra- n-butylammonium-n-butyltri (4-
tert-butylphenyl) borate, tetra-n-butylammoniummethyltri (4-methylnaphthyl) borate, triphenylsulfonium-n-butyltriphenylborate, triphenyloxosulfonium-n
-Butyltriphenylborate, triphenyloxonium-n-butyltriphenylborate, N-methylpyridinium-n-butyltriphenylborate, tetraphenylphosphonium-n-butyltriphenylborate, diphenyliodonium-n- Butyl triphenyl borate and the like can be mentioned, but the present invention is not limited thereto.

Since the organoboron complex (G) represented by the general formula (1) does not usually absorb much above 300 nm,
When used alone, it has no sensitivity to the light source of an ordinary ultraviolet lamp, but when combined with a sensitizer, very high sensitivity can be obtained.

In the present invention, the organoboron complex (G) is generally added in an amount of 1 to 100% by weight, preferably 5 to 80% by weight, based on the compound having an ethylenically unsaturated compound. If the amount of the organoboron complex is too small, the polymerization reaction may not proceed sufficiently, and if it is too large, the stability of the composition may be reduced and it may be economically disadvantageous.

As the sensitizer (F) having an absorption wavelength in the range of 300 to 500 nm used in the present invention, a photopolymerization initiator having an absorption in this wavelength range, a sensitizer, a dye or the like can be used. These compounds include cationic dyes, benzophenones, acetophenones, benzoins, thioxanthones, anthraquinones, imidazoles,
Examples thereof include compounds such as biimidazoles, coumarins, ketocoumarins, triphenylpyrriniums, triazines and benzoic acids. Further, compounds such as acylphosphine oxide, methylphenylglyoxylate, α-acyloxime ester, benzyl and camphorquinone can also be used. These compounds can be used alone or in combination of two or more. For example, Basic Yellow1, 11, 1
3, 21, 28, 36, Basic Orange2
1, 22 and other cationic dyes, benzophenone, 4-methylbenzophenone, 4-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2,4
-Diethylthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, ethylanthraquinone, 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-chlorophenyl) -4,
4 ', 5,5'-tetra (2-methylphenyl) -1,
2′-biimidazole, coumarin, 7-diethylaminocoumarin, 4-dimethylaminobenzoic acid and the like can be used alone or in combination of two or more, but are not limited thereto. Further, in consideration of the stability of the initiator and the composition, the ability to initiate polymerization, and the like, benzophenone compounds, anthraquinones, benzoic acids, and biimidazole compounds are preferable.

In the present invention, the sensitizer (F) having an absorption wavelength in the range of 300 to 500 nm is generally 1 for the radically polymerizable compound (B) having an ethylenically unsaturated bond.
It is blended so as to be -60% by weight, preferably 2-30% by weight. If the amount is too small, the sensitizing effect may not be obtained. If the amount is too large, the light absorption efficiency of the sensitizer may be deteriorated, and the polymerization initiation efficiency may be decreased.

A compound having a plurality of thiol groups in one molecule used in the present invention, wherein α is
The compound (H) having a branched structure at the β-position and / or the β-position is
For example, 2,5-hexanedithiol, 2,9-decanedithiol, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), tri Methylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis ( 2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), ethylene glycol bis (2-mercaptoisobutyrate) G), butane diol bis (2-
Mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), ethylene glycol bis (3-mercapto) Valerate), butanediol bis (3-mercapto valerate), octane diol bis (3-mercapto valerate), trimethylolpropane tris (3-mercapto valerate), pentaerythritol tetrakis (3-mercapto valerate) 1, 4-bis (1-mercaptoethyl) benzene, (2-mercaptoethyl) benzene, phthalic acid di (2-mercaptoethyl ester), phthalic acid di (2-mercaptopropyl ester), phthalic acid di (2-mercapa) Preparative butyl ester) and the like, but not limited thereto.

Further, preferably ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate). ), Pentaerythritol tetrakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), tri Methylolpropane tris (2-mercaptoisobutyrate) and pentaerythritol tetrakis (2-mercaptoisobutyrate), more preferably ethylene glycol bis (3-mercaptobutyrate), butanedi Bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), and pentaerythritol tetrakis (3-mercaptobutyrate) have excellent polymerization initiation ability and storage stability. It is preferable from the aspect. These compounds having a thiol group can be used alone or in combination of two or more kinds.

In the present invention, the compound (H) having a plurality of thiol groups in one molecule and having a branched structure at the α-position and / or β-position with respect to the thiol group is an ethylenically unsaturated bond. Radically polymerizable compound (B) having
On the other hand, generally 1 to 200% by weight, preferably 10 to
It is mixed so as to be 100% by weight. If the amount is too small, the polymerization initiation may not proceed efficiently. If the amount is too large, the polymerization initiation function cannot be expected to be improved, and the physical properties of the cured product may be adversely affected.

The sensitizer (F) having an absorption wavelength region in the range of 300 to 500 nm, the organoboron complex (G) represented by the general formula (1), and a plurality of thiol groups in one molecule are used in the present invention. The order of adding the compound (H) which has a branched structure in the molecule to the resist is not particularly limited.

In the present invention, a sensitizer (F) having an absorption wavelength region in the range of 300 to 500 nm, an organoboron complex (G) represented by the general formula (1), and a plurality of thiol groups in one molecule are contained. A compound having α to the thiol group
The photosensitive coloring composition containing a compound (H) having a branched structure at the position and / or β-position is a highly sensitive and highly stable (storable) photosensitive coloring composition. By using the composition, it becomes possible to efficiently produce a color filter.

The transparent high molecular weight polymer (A) soluble in the solvent or the alkaline aqueous solution used in the present invention has a film thickness of 1 μm.
In the visible light range of 400 to 700 nm, the transmittance is preferably 80% or more, more preferably 9%.
It is a polymer of 5% or more and is soluble in a developing solution such as a solvent or an alkaline aqueous solution. However, considering the influence on the environment, it is preferable to use an alkaline aqueous solution as the developing solution. Such a transparent high molecular weight polymer is generally a hydrophilic monomer represented by (meth) acrylic acid, 2-hydroxyethyl, acrylamide, a monomer having N-vinylpyrrolidone or an ammonium salt, and (meth) acrylic. There is known a polymer conjugate in which an acid ester, vinyl acetate, styrene, a lipophilic monomer typified by N-vinylcarbazole, and the like are copolymerized by a known method at an appropriate mixing ratio.

Such a transparent high molecular polymer can be used as a negative type resist, that is, a type in which a light-shielded portion is removed by development, by combining it with a radically polymerizable monomer having an ethylenically unsaturated group. .
In addition, since heat treatment and treatment with various solvents and chemicals are performed in the post-process in the production of the color filter and in the process of incorporating into the liquid crystal display device, heat resistance as a transparent high molecular polymer (A), It is preferable that it has excellent chemical resistance, and that it may be exposed to strong light depending on the environment in which the color filter is used, so that it is preferable that it has light resistance. In addition, "(meth) acry" in the present invention means both "methacryl" and "acry".

As the hue of the color filter, red, green and blue of additive color mixture system and cyan, magenta, yellow of subtractive color mixture system and black used in the black matrix portion are mainly used. As the coloring agent (C), there are dyes and pigments, but it is preferable to use pigments from the viewpoint of heat resistance and light resistance as described above. Also, two or more kinds of colorants may be used in order to obtain an appropriate spectrum. For example, blue may be combined with a cyan pigment and violet pigment, green may be combined with green pigment and yellow pigment, and red may be combined with red pigment and yellow or orange pigment to obtain an appropriate spectrum.

As the colorant (C) used in the present invention,
Examples of dyes include Acid Red 52, 87,
92, 122, Solvent Red 8, 83, 1
09, 125, 132, Disperse Red 6
0, 72, 88, 206, Basic Red 12,
27, Acid Blue 9, 40, 83, 129,
249, Solvent Blue 25, 35, 3
6, 55, 67, 70, Disperse Blue
56, 60, 81, 87, 149, 197, 211, 2
14, Basic Blue 1, 7, 26, 77, A
cid Green 18, Solvent Green
n 3, Basic Green 1, Acid Ye
low 38, 99, Solvent Yellow
25, 88, 89, 146, Disperse Ye
low 42, 60, 87, 198, Basic Y
Examples thereof include, but are not limited to, ELLOW 21.

As a specific example of the pigment, Pigme
nt Red 9, 19, 38, 43, 97, 122,
123, 144, 149, 166, 168, 177, 1
79, 180, 192, 215, 216, 217, 22
0,223,224,226,227,228,24
0, Pigment Blue 15, 15: 6, 1
6, 22, 29, 60, 64, Pigment Gre
en 7, 36, Pigment Yellow 2
0, 24, 81, 83, 86, 93, 108, 109,
110, 117, 125, 137, 138, 139, 1
47, 148, 153, 154, 166, 168, 18
5, Pigment Orange 36, Pigme
nt Violet 23, Pigment Brow
n 23, 25, 26, Pigment Black
7 and titanium black, but not limited thereto. Further, two or more kinds may be mixed in order to obtain a desired hue.

As the radically polymerizable 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. Various (meth) acrylic acid esters such as acrylic acid, 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,
Trimethylolpropane tri (meth) acrylate, styrene, divinylbenzene, (meth) acrylamide,
Examples thereof include, but are not limited to, vinyl acetate, N-hydroxymethyl (meth) acrylamide, dipentaerythritol hexa (meth) acrylate, melamine acrylate, and epoxy acrylate prepolymer. However, it is preferable to use a polyfunctional (meth) acrylic monomer in view of exposure sensitivity and various properties after curing.

In the photosensitive coloring composition used in the present invention, the pigment is sufficiently dispersed, and 1 to 3 μm on the transparent substrate.
Since it is necessary to apply a coating film having a film thickness of, the viscosity is usually adjusted using the solvent (E) in order to impart coating suitability.
Examples of the solvent include alcohols, ketones, esters and the like. For example, methanol, ethanol, propanol, isopropyl alcohol, n-butanol, tert-butanol, 2-methylpropyl alcohol, toluene, xylene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, isoamyl acetate, ethyl acetate, ethyl lactate, methyl ethyl ketone,
Acetone, cyclohexanone, chloroform, dichloromethane, tetrachloromethane, 1,4-dioxane, tetrahydrofuran, n-pentane, n-hexane, n-
Heptane, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl ether,
2- (2-ethoxy) ethoxyethanol, 2- (2-
Butoxy) ethoxy ethanol, 2- (2-ethoxy)
Examples thereof include ethoxyethyl acetate, 2- (2-butoxy) ethoxyethyl acetate, and 2-phenoxyethanol, but are not limited thereto. If necessary, two or more kinds of solvents may be mixed and used.

The photosensitive coloring composition used in the present invention can be produced by using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, an attrider, a ball mill, a kneader and a paint shaker. A polymerization inhibitor may be added for the purpose of preventing gelation due to the initiation of polymerization during dispersion, and the monomer and the photoinitiator may be added after the pigment is dispersed. In addition, a dispersion aid can be added as appropriate to improve the dispersion of the pigment. Since the dispersion aid has an effect of helping the dispersion of the pigment and preventing re-aggregation after dispersion, a color filter having excellent transparency can be provided.

As the compound (H) having a thiol group used in the present invention, it is preferable to use the compounds represented by the general formulas (2), (3) and (4).
If the molecular weight of the compound having a thiol group is too small, it will volatilize with the solvent during drying and will not function as an initiator, and the odor of volatile matter will also be a problem. Further, when the molecular weight is too large, there arises a problem that the developability is lowered.

Examples of the compound (H) having a thiol group used in the present invention include ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate). Rate), pentaerythritol tetrakis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate) It is preferable to use at least one compound represented by pentaerythritol tetrakis (3-mercaptoisobutyrate) in terms of sensitivity and storage stability.

As the sensitizer (F) having an absorption wavelength in the range of 300 to 500 nm used in the present invention, a photopolymerization initiator, a sensitizer, a dye or the like having absorption in this wavelength range can be used. These compounds include cationic dyes,
Penzophenones, acetophenones, penzoins,
Thioxanthones, anthraquinones, imidazoles, biimidazoles, coumarins, ketocoumarins,
Examples thereof include compounds such as triphenylpyrriniums, triazines and benzoic acids. Further, compounds such as acylphosphine oxide, methylphenylglyoxylate, α-acyloxime ester, penzyl, and camphorquinone can also be used.

Each of these compounds may be used alone or 2
A combination of two or more species can be used. For example, B
asicYellow1, 11, 13, 21, 28, 3
6, cationic dyes such as Basic Orange 21 and 22, benzophenone, 4-methylbenzophenone, 4-
Dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2,4-diethylthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, ethylanthraquinone, N-methylimidazole, 2,2'-bis (2-chlorophenyl) -4,
4 ', 5,5'-tetraphenyl 1,2'-biimidazole (hereinafter abbreviated as HABI), 2,2'-his (2-chlorophenyl) -4,4', 5,5'-tetra (ethoxyphenyl) -1,2'-biimidazole, 2,2'-
Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-flomophenyl) -1,2'-biimidazole, 2,2'-his (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-chlorophenyl) -4,4 ', 5,5'-tetra (2-methylphenyl) -1,2'-biimidazole, coumarin, 7 -Fuethylaminocoumarin, 4-dimethylaminobenzoic acid and the like can be used alone or in combination of two or more kinds. Further, considering the stability of the initiator and the composition, the ability to initiate polymerization, etc., penzophenone compounds, anthraquinones, benzoic acids, and biimidazole compounds are preferable, and at least one or more benzophenone compounds and / or anthraquinones are used. It is particularly preferable to include it from the viewpoint of polymerization initiation ability and spectral characteristics of the cured coating film.

The color filter of the present invention is manufactured by a method including at least the following steps. First step: a step of forming a photosensitive colored layer on a transparent substrate. Second step: a step of performing pattern exposure on the photosensitive colored layer through a pattern mask having a predetermined pattern.
Third step: a step of developing the photosensitive colored layer after the pattern exposure, removing the light-shielding portion other than the cured portion of the photosensitive colored layer on the transparent substrate to form a pixel layer. Fourth step: a step of baking the pixel layer to fix it on the transparent substrate after the developing step (post-baking).

In the first step, the photosensitive coloring composition can be coated on a transparent substrate by a coating method such as spray coating, spinner coating, roll coating or screen coating. Any material can be used for the transparent substrate as long as it has a certain level of strength and resistance and is not attacked by a coloring solution, a developing solution or the like. For example, a polycarbonate plate, a polymethylmethacrylate plate, a polyester film and the like can be used in addition to the glass plate, but the glass plate is not limited to these. Further, when applying the photosensitive coloring composition, proper fluidity in a coating liquid,
In addition, a leveling agent or an antifoaming agent can be added in addition to the above-mentioned solvent in order to impart smoothness to the coating film. The applied photosensitive coloring composition can be dried (pre-baked) on a hot plate or an oven, but if the temperature at this time is too high or the drying time is too long, partial polymerization or crosslinking will occur in the coating film. In addition, the solubility of the unexposed area in the developing solution is lowered, and defective development occurs, which is not preferable.

In the second step, the photosensitive colored layer obtained in the first step is usually exposed to ultraviolet light through a photomask having a predetermined color filter pattern. As a light source, an ultra-high pressure mercury lamp, a metal halide lamp, etc. are generally used, but the ultraviolet ray passing through the photomask is usually 3
Since it is light of 00 nm or more, i-line (365 nm), h-line (405 nm), g-line (4
Light having a wavelength of 36 nm) is used for the polymerization reaction or the crosslinking reaction. Therefore, the sensitivity of the photosensitive colored layer to the three bright lines is important.

In the third step, a weak alkaline developing solution is used for the exposed photosensitive colored layer obtained in the second step to remove the unexposed uncured portion, that is, the photosensitive colored layer other than the pixel region.
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 60 minutes to obtain the pixel layer of the first color. First for each color
The fourth step is repeated to obtain a color filter.

[0055]

The present invention will be described in detail below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. Further, the photosensitive coloring composition is referred to as a resist for convenience. In the examples, a method using an alkali-developing resist of a pigment dispersion method, which is widely used at present as a method for manufacturing a color filter for a color liquid crystal display, is described, but the present invention is not limited to this.

<Example 1> [Synthesis of alkali-soluble resin] Cyclohexanone (350 parts) and styrene (26) were placed in a 1-liter four-necked flask.
Parts, 23 parts of 2-hydroxyethyl acrylate, 35 parts of methacrylic acid, 21 parts of methyl methacrylate, 70 parts of butyl methacrylate, were heated to 90 ° C. and 290 parts of cyclohexanone, 26 parts of styrene, and 2-hydroxyethyl acrylate were previously prepared. A mixture of 23 parts, 35 parts of methacrylic acid, 21 parts of methyl methacrylate, 70 parts of butyl methacrylate, and 1.75 parts of azobisisobutyronitrile was added dropwise over 3 hours and further reacted at 90 ° C. for 3 hours. It was Further, a solution prepared by dissolving 0.75 parts of azobisisobutyronitrile 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 and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution previously synthesized so that the non-volatile content was 20%.

[Preparation of Blue Resist] The above resin solution 1:
55 parts, Lionol Blue E (Toyo Ink Mfg. Co., Ltd.)
(Manufactured): 5.7 parts, dispersant: 0.29 part, and cyclohexanone: 7.8 parts were mixed and dispersed for 24 hours with a paint shaker to prepare a blue dispersion. Next, the blue dispersion: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts Ethyl Michler's ketone 0.3 parts Ethyl anthraquinone 0.3 parts Tetrabutylammonium methyltri (4-methylnaphthylborate) 0.8 parts Trimethylolpropane tris (3-mercaptobutyrate) 1.0 parts Cyclohexanone 39.0 parts were thoroughly mixed in a container and filtered through a 1.0-micron filter to prepare a blue resist having a nonvolatile content of 20%.

<Example 2> [Preparation of red resist] 1:55 parts of the above resin solution, Pi
gment Red 168: 4.0 parts, Pigmen
t Orange 36: 1.7 parts, dispersant: 0.29
Parts and cyclohexanone: 7.8 parts were mixed and dispersed with a paint shaker for 24 hours to prepare a red dispersion.
Then, the red dispersion: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts Ethyl Michler's ketone 0.3 parts Ethyl anthraquinone 0.3 parts Tetrabutylammonium methyltri (4-methylnaphthylborate) 0.8 parts Trimethylolpropane tris (3-mercaptobutyrate) 1.0 parts Cyclohexanone 39.0 parts were thoroughly mixed in a container and filtered through a 1.0-micron filter to prepare a red resist having a nonvolatile content of 20%.

<Example 3> [Preparation of green resist] 1:55 parts of the above resin solution, Pi
gment Green 36: 4.0, Pigme
nt Yellow 154: 1.7 parts, dispersant: 0.
29 parts and cyclohexanone: 7.8 parts were mixed and dispersed with a paint shaker for 24 hours to prepare a green dispersion. Then, the green dispersion: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts Ethyl Michler's ketone 0.3 parts Ethyl anthraquinone 0.3 parts Tetrabutylammonium methyltri (4-methylnaphthylborate) 0.8 parts Trimethylolpropane tris (3-mercaptobutyrate) 1.0 parts Cyclohexanone 39.0 parts were thoroughly mixed in a container and filtered with a 1.0-micron filter to prepare a 20% non-volatile green resist.

Comparative Example 1 [Preparation of Blue Resist] 1:55 parts of the above resin solution, Lionol Blue E (manufactured by Toyo Ink Mfg. Co., Ltd.): 5.7
Parts, a dispersant: 0.29 parts, and cyclohexanone: 7.8 parts were mixed and dispersed with a paint shaker for 24 hours to prepare a blue dispersion. Next, the blue dispersion: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts Ethyl Michler's ketone 0.3 parts Ethyl anthraquinone 0.3 parts Tetrabutylammonium methyltri (4-methylnaphthylborate) 0.8 parts Trimethylolpropane tris (3-mercaptopropionate) 1.0 parts 39.0 parts of cyclohexanone were thoroughly mixed in a container and filtered with a 1.0-micron filter to prepare a blue resist having a nonvolatile content of 20%.

<Comparative Example 2> [Preparation of blue resist] Blue dispersion in Comparative Example 1: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine: 2 parts Cyclohexanone: 39.0 parts were thoroughly mixed in a container and filtered with a 1.0 micron filter. Filtered, nonvolatile 2
A 0% blue resist was prepared.

<Comparative Example 3> [Preparation of red resist] 1:55 parts of the above resin solution, Pi
gment Red 168: 4.0 parts, Pigmen
t Orange 36: 1.7 parts, dispersant: 0.29
Parts and cyclohexanone: 7.8 parts were mixed and dispersed with a paint shaker for 24 hours to prepare a red dispersion.
Then, the red dispersion: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts Ethyl Michler's ketone 0.3 parts Ethyl anthraquinone 0.3 parts Tetrabutylammonium methyltri (4-methylnaphthylborate) 0.8 parts Trimethylolpropane tris (3-mercaptopropionate) 1.0 parts 39.0 parts of cyclohexanone were thoroughly mixed in a container and filtered with a 1.0-micron filter to prepare a red resist having a nonvolatile content of 20%.

<Comparative Example 4> [Preparation of red resist] Red dispersion in Comparative Example 3: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine: 2 parts Cyclohexanone: 39.0 parts were thoroughly mixed in a container and filtered with a 1.0 micron filter. Filtered, nonvolatile 2
A 0% red resist was prepared.

<Comparative Example 5> [Preparation of green resist] 1:55 parts of the above resin solution, Pi
gment Green 36: 4.0, Pigme
nt Yellow 154: 1.7 parts, dispersant: 0.
29 parts and cyclohexanone: 7.8 parts were mixed and dispersed with a paint shaker for 24 hours to prepare a green dispersion. Then, the green dispersion: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts Ethyl Michler's ketone 0.3 parts Ethyl anthraquinone 0.3 parts Tetrabutylammonium methyltri (4-methylnaphthylborate) 0.8 parts Trimethylolpropane tris (3-mercaptopropionate) 1.0 parts 39.0 parts of cyclohexanone were sufficiently mixed in a container and filtered with a 1.0-micron filter to prepare a 20% non-volatile green resist.

<Comparative Example 6> [Preparation of green resist] Green dispersion in Comparative Example 5: 54.15 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8
5 parts 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine: 2 parts Cyclohexanone: 39.0 parts were thoroughly mixed in a container and filtered with a 1.0 micron filter. A green resist having a nonvolatile content of 20% was prepared by filtration.

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 film thickness was about 2 μm, and dried in a hot air oven at 70 ° C. for 20 minutes. , Irradiation spectroscope (manufactured by JASCO Corporation: JASCO CT-25CP type)
Exposure was performed. An ultra-high pressure mercury lamp was used as the light source. The exposed substrate was immersed in a 0.5% sodium carbonate aqueous solution for about 40 seconds to develop it, and then washed with running water.
It heated at 20 degreeC for 30 minutes, and obtained the spectrogram. Sensitivity is measured on the day the resist is prepared and at room temperature (22-24 ° C).
The results are shown in Table 1 after being stored for a week (28 days).

[0067]

[Table 1]

[0068]

[Table 2] Spectral sensitivity means i-line (365nm), h-line (405n)
m) and g-line (436 nm). In Table 1, the larger the value, the higher the sensitivity. The sensitivity was determined by whether or not the resist film remained after development at each exposure amount shown in Table 2, and this numerical value represents the exposure amount by the number of steps. As shown in Table 1, Examples 1 to 3 are photosensitive coloring compositions which are highly sensitive and have excellent storage stability.

[0069]

INDUSTRIAL APPLICABILITY The present invention provides a transparent polymer (A), a radically polymerizable compound (B), a colorant (C), a dispersant (D), a solvent (E), a sensitizer (F), Photosensitization containing a photopolymerization initiator (I) composed of an organic boron complex (G) represented by the general formula (1) and a compound (H) as a main component and having high sensitivity but excellent storage stability. Since this is a method for producing a color filter which forms a colored pattern using a colorant-coloring composition, it is a method for producing a color filter having excellent productivity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/004 503 G03F 7/004 503Z 505 505 7/029 7/029 F term (reference) 2H025 AA01 AA06 AA10 AA11 AB13 AC01 AD01 BC13 BC42 CA03 CA31 CA39 CA48 CB42 CC04 CC11 CC20 FA17 2H048 BA02 BA48 BB02 BB42 2H091 FA02Y FB04 FB11 FC10 LA12 4J011 AA03 AA05 AC04 PA02 PA22 PA43 PA48 PA63 PA65 PA68 PA69 PB25 PC02 PC08 QA03 QA09 QA13 QA23 QA24 QA25 UA01 WA02 4J026 AA17 AA38 AA45 AA48 AA55 AA60 BA05 BA20 BA25 BA27 BA28 BA29 BA32

Claims (5)

[Claims] 1. A transparent polymer (A) soluble in a solvent or an aqueous alkaline solution, a radically polymerizable compound (B) having an ethylenically unsaturated bond, a colorant (C), a dispersant (D), and a solvent. (E), a sensitizer (F) having an absorption wavelength range of 300 to 500 nm, an organoboron complex (G) represented by the general formula (1), and a compound having a plurality of thiol groups in one molecule. Then, a photosensitive coloring composition containing a photopolymerization initiator (I) composed of a compound (H) having a branched structure at the α-position and / or β-position with respect to a thiol group as a main component is used, and the same substrate is used. A method for producing a color filter, which comprises forming an arbitrary colored pattern on the top. [Chemical 1] 2. The compound (H) comprises at least one compound represented by the general formula (2), the general formula (3) or the general formula (4).
The method of manufacturing a color filter according to claim 1, wherein the method comprises one or more. [Chemical 2] 3. The compound (H) is ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3). -Mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercapto) 3. A method for producing a color filter according to claim 1, further comprising at least one compound represented by (isobutyrate). 4. The production of a color filter according to claim 1, wherein the sensitizer (F) contains at least one benzophenone and / or anthraquinone. Method. 5. A color filter manufactured by using the method for manufacturing a color filter according to claim 1. Description: