JPH11326606A - Photosensitive composition for black matrix - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which has superior developability and image reproducibility, has high resolving power and has improved insulatability, coloring power and hiding power by making the solubility of a coating resin in a solvent lower than the solubility of a binder resin in the solvent. SOLUTION: The solubility of the coating resin in the solvent used in a composition is made lower than that of the binder resin used in the composition. As a measure, the resin having the solubility of 10 g resin/100 g solvent or above, more preferably 20 g resin/100 g solvent or above is preferably used as the binder resin and the resin, having a solubility of 10 g resin/100 g solvent or below, more preferably 5 g resin/100 g solvent or below is preferably used as the coating resin. The acid value of the coating resin is 0 to 200 and the acid value of the binder resin is 50 to 150, and the acid value of the binder resin is preferably higher or lower than the acid value of the coating resin. Furthermore, the average particle size of the carbon black coated with the coating resin is in the range of 0.005 to 0.5 μm and preferably, in the range of 0.005 to 0.3 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition suitable for producing a black matrix of a color filter used for a liquid crystal display device or a solid-state imaging device, and a color filter formed using the same.

[0002]

2. Description of the Related Art As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method,
Printing, electrodeposition and pigment dispersion methods are known. Pigment dispersion method (for example, JP-A-57-16407, JP-A-5
7-16408, JP-A-60-237403, JP-A-60-129707, JP-A-61-267004
JP-A-1-152449, JP-A-2-18170
4, JP-A-2-153353, JP-A-2-1994
No. 03, JP-A-2-199404, etc.) are methods for producing a color filter by a photolithography method using a colored radiation-sensitive colored composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light and heat due to the use of pigments and is patterned by the photolithographic method, so it has a sufficient positional accuracy and is a method suitable for producing color filters for large screen and high definition color displays. is there.

[0003] To prepare a color filter using a pigment dispersion method, a radiation-sensitive composition is applied to a glass substrate by a spin coater or a roll coater and dried to form a coating film, which is then exposed and developed. A colored image was obtained, and this operation was performed for each color to obtain a color filter.However, the image formed by the conventional radiation-sensitive composition containing a pigment peeled off from the substrate during development or washing, causing defects in the color filter. On the other hand, when the adhesion of the image is improved, the solubility of the non-image portion is reduced at the time of development, and the background of the non-image portion tends to be stained. Further, the image pattern obtained by development has a large dependency on the conditions of the development time and the development temperature, and it is difficult to always obtain a constant pattern. This is because the development latitude is narrow.

[0004] A grid-like black pattern called a black matrix is generally arranged between the red, blue and green colored images of the color filter for the purpose of improving the contrast. The black matrix is generally formed by depositing chromium on the entire glass substrate and forming a pattern by etching.However, since chromium is used, the cost is high and the reflectance is high. I have. For this reason, studies for producing a black matrix by a pigment dispersion method capable of fine processing have been earnestly studied.

[0005] A photosensitive composition for forming a black matrix is a photosensitive composition which is made black by mixing different color pigments or several kinds of pigments. Since this photosensitive composition is intended to shield light, it is a composition containing a large amount of a pigment insoluble in a developer. For this reason, this photosensitive composition has problems such as poor developability, necessity of long-term development, and a required resolution cannot be obtained. Therefore, there is room for improvement in the developability of the photosensitive composition for producing a color filter including each color including the black matrix.

Further, a filter for fine color separation using a black matrix is mounted on a thin film transistor (hereinafter, referred to as a thin film transistor).
When provided on a liquid crystal display panel (referred to as TFT), there is a problem that the aperture ratio of the TFT liquid crystal display panel is low and power consumption is large.

Therefore, in order to improve the aperture ratio of the TFT liquid crystal display panel and reduce the power consumption, there has been proposed a liquid crystal display panel provided with a black matrix on the TFT side as shown in FIG.

A liquid crystal panel 1 shown in FIG. 1 is provided from a pair of glass substrates 2 and 3 with a liquid crystal material 4 interposed therebetween. A surface of the glass substrate 2 facing the glass substrate 3 has a plurality of pixel electrodes. 5 are formed, and each pixel electrode 5 has
The TFT 6 is connected. On the surface of the glass substrate 2 facing the glass substrate 3, a black matrix 7 is provided between the pixel electrodes 5 and on the TFT 6 so as to avoid over the pixel electrodes 5. Glass substrate 2 of glass substrate 3
A plurality of red (R), green (G), and blue (B) color filters 8 are provided so as not to contact with each other on the surface facing the glass substrate 3. The common electrode 9 is formed on the entire surface facing the glass substrate 2 of FIG.
Are formed.

As described above, in the liquid crystal panel 1 in which the black matrix 7 is provided on the TFT 6 side, since the black matrix 7 directly contacts the pixel electrode 5 and the TFT 6, the black matrix 7 is required to have a high insulating property. Is done.

As a composition for a liquid crystal panel, a composition colored black with a coloring pigment other than carbon black has been studied. However, in order to sufficiently color black with a coloring pigment other than carbon black, the concealing power of the coloring pigment is weak, so that the blending amount must be extremely large, and as a result, the viscosity of the composition increases. In addition, there is a problem that handling becomes difficult, and the strength of the formed film and the adhesion to the substrate are significantly reduced.

As described above, in particular, a photosensitive composition for a black matrix, which has not only developability but also a large coloring power and hiding power, excellent insulating properties, and which can be suitably used for a liquid crystal panel such as a liquid crystal display, has not yet been obtained. The fact is that it has not been developed, and development of such a composition has been awaited.

Japanese Patent Application Laid-Open No. 9-26571 describes a composition for a liquid crystal panel in which carbon black coated with a resin is dispersed in a dispersion medium. JP-A-9-7173
No. 3 describes carbon black for a black matrix, which is coated with a resin and has a total content of Na and Ca of 100 ppm or less. JP-A-9-9562
No. 5 describes a carbon black for an insulating black matrix obtained by coating a carbon black having a specified total oxygen content with a resin. JP-A-9-12
Japanese Patent No. 4969 describes a carbon black for an insulating black matrix obtained by coating carbon black with a polyfunctional epoxy resin. JP-A-10-10
No. 311 discloses a black resist composition for a color filter containing carbon black having a specific resin adsorption amount.

The carbon black coated with the resin described in each of the above publications is insulative because it is coated with the resin. However, there have been cases where the resin is decoated from the carbon black and its insulation is reduced. Further, the resin contained in the composition needs to have alkali developability. When the above resin-coated carbon black is used, there is room for improvement in alkali developability.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in order to improve the above-mentioned drawbacks of the prior art, and has as its object to have excellent developability, excellent image reproducibility, high resolution, and An object of the present invention is to provide a photosensitive composition for a black matrix from which a black matrix having excellent insulating properties, coloring power and hiding power can be obtained. Another object of the present invention is to provide a color filter having a black matrix having excellent insulating properties, coloring power and hiding power.

[0015]

The object of the present invention has been attained by the following constitutions. (1) In a photosensitive composition for a black matrix containing an insulating carbon black coated with a coating resin, a binder resin, a dispersant, a radiation-sensitive compound, and a solvent, the solubility of the coating resin in the solvent is determined by the binder resin. A photosensitive composition for a black matrix, which has a lower solubility than the solvent for the resin to be coated. (2) The photosensitive composition for a black matrix according to the above (1), wherein the coating resin has an acid value of 0 to 200 and the binding resin has an acid value of 50 to 150. (3) The photosensitive composition for black matrix as described in (1) or (2) above, wherein the acid value of the binder resin is higher than the acid value of the coating resin. (4) The photosensitive composition for a black matrix according to the above (1) or (2), wherein the acid value of the binder resin is lower than the acid value of the coating resin. (5) The photosensitive material for black matrix as described in any of (1) to (5) above, wherein the average particle size of the insulating carbon black coated with the coating resin is 0.003 to 0.5 μm. Composition. (6) A color filter comprising a black matrix formed using the photosensitive composition for a black matrix according to any one of (1) to (6).

In the photosensitive composition for a black matrix of the present invention, carbon black coated with a coating resin is used, and the solubility of the coating resin in a solvent in the composition is determined by the solubility in a binder resin of the composition. By using a low one, the decoating of the coating resin from the carbon black is reduced, a black matrix having high insulation properties is obtained, and excellent developability (wide development latitude, little development residue) is obtained, high resolution, A high-quality color filter can be obtained. In the present invention, the coating resin and the binder resin preferably have a specific acid value. More preferably, the coating resin has an acid value lower or higher than that of the binder resin. As a result, at the time of development, the carbon black remains wrapped in the coating resin, or the coating resin dissolves earlier than the binder resin. Is reduced. Further, the cutting of the edge pattern is good, and high resolution and high image quality are obtained. Further, the image portion is hardly affected by the developing solution, is stable, has less roughness on the surface of the image, and has a smooth surface.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the solubility of the coating resin in the solvent used in the composition is lower than that of the binder resin used in the composition of the present invention. In the present invention, any resin combination can be used as long as the solubility of the coating resin is smaller than that of the binder resin as described above.
100 g solvent or more, more preferably 20 g resin / 100
A resin having a solubility of at least g solvent is used as the binder resin, and less than 10 g resin / 100 g solvent, more preferably less than 5 g resin.
It is preferable to use a resin having a solubility of not more than g resin / 100 g solvent as the coating resin.

The difference between the solubility of the coating resin and the solubility of the binder resin is preferably 5 g resin / 100 g solvent or more, more preferably 10 g resin / 100 g solvent or more. Here, the solubility of the resin in the solvent means the amount of the resin dissolved in 100 g of the solvent at 25 ° C., and can be measured by a gravimetric method, a UV absorption method, a GPC measurement method, or the like. Further, the solvent of the composition,
It is a single or mixed solvent constituting the photosensitive composition. .

In the present invention, the coating resin has an acid value of 0 to 0.
200, the binder resin preferably has an acid value of 50 to 150. Further, it is preferable that the acid value of the binder resin is higher or lower than the acid value of the coating resin. Here, the acid value of the resin means the number of mg of KOH required to neutralize 1 g of the resin. The acid value of the above coating resin is from 0 to 20.
0 mgKOH / g is preferred, and more preferably 0-18 KOH / g.
0 mgKOH / g. The acid value of the binder resin is preferably from 50 to 150 mgKOH / g, more preferably from 70 to 130 mgKOH / g. The difference in acid value between the coating resin and the binder resin is preferably from 10 to 150, more preferably from 20 to 120. The combination of the coating resin and the binder resin as described above can be variously selected so as to satisfy the above-mentioned properties (difference in solubility and difference in acid value). Specifically, it can be selected from the following examples of resins.

1) Polyolefin-based polymer Polyethylene, polypropylene, polyisobutylene, etc. 2) Diene-based polymer Polybutadiene, polyisoprene, etc. 3) Polymer having a conjugated polyene structure Polyacetylene-based polymer, polyphenylene-based polymer, etc. 4) Vinyl polymer polyvinyl chloride, polystyrene , Vinyl acetate, polyvinyl alcohol, poly (meth) acrylic acid, poly (meth)
Acrylic acid ester, polyacrylamide, polyacrylonitrile, polyvinylphenol, etc. 5) polyether polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyetherketone,
6) Phenol resin novolak resin, resol resin, etc. 7) Polyester polyethylene terephthalate, polyphenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc. 8) Polyamide nylon-6, nylon 66, water-soluble Nylon, polyphenylene amide, etc. 9) Polypeptide gelatin, casein, etc. 10) Epoxy resin and modified products thereof Novolak epoxy resin, bisphenol epoxy resin, modified resin with novolak epoxy acrylate and acid anhydride, etc. 11) Other polyurethane, polyimide, melamine resin, Urea resin,
Polyimidazole, polyoxazole, polypyrrole,
Polyaniline, polysulfide, polysulfone, celluloses, etc.

More specifically, the acrylic resin containing a carboxyl group includes, for example, (meth) acrylic acid, (anhydride) maleic acid, crotonic acid, itaconic acid, fumaric acid,
Monomers having a carboxyl group such as styrene, α
-Methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonate, (meth) acrylic chloride Benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethylacrylamide And the like. Among them, preferred is an acrylic resin containing at least (meth) acrylic acid or alkyl (meth) acrylate as a constituent monomer, and more preferred is an acrylic resin containing (meth) acrylic acid and styrene.

These resins can also have an ethylenic double bond added to the resin side chain. By imparting a double bond to the resin side chain, the photocurability is enhanced, so that the resolution and adhesion can be further improved, which is preferable. As a synthetic means for introducing an ethylenic double bond, for example,
The methods described in JP-B-50-34443, JP-B-50-34444 and the like can be mentioned. Specific examples include a method of reacting a compound having a glycidyl group, an epoxycyclohexyl group, and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, acrylic acid chloride, or the like. For example, glycidyl (meth) acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate,
Using compounds such as crotonyl glycidyl ether, glycidyl ether (iso) crotonate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic acid chloride, and (meth) allyl chloride, a carboxyl group or a hydroxyl group The resin having a polymerizable group in the side chain can be obtained by reacting with a resin having Particularly, a resin obtained by reacting (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable.

In the present invention, as the coating resin or the binder resin, at least a monomer represented by the following general formula [I] and a monomer having at least an acidic group (the above-mentioned copolymer component can be mentioned). A polymer obtained by a copolymerization reaction can also be used.

[0024]

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(Wherein R represents a hydrogen atom or a methyl group, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group and an aryl group. Here, specific examples of the halogen atom include Cl, Br,
I and the like. The alkyl group may be linear, branched, or cyclic, and includes a methyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, and the like, and preferably has 1 to 7 carbon atoms. Examples of the aryl group include a phenyl group, a furyl group, and a naphthyl group.

The following resins can also be used. A linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable. As such a linear organic high molecular polymer, those having an acidic group such as a carboxy group or a phenolic hydroxyl group on the side chain or main chain of the resin are preferable from the viewpoint of preventing pollution since they can be alkali-developed. In particular, a resin having a carboxyl group, for example, an acrylic acid (co) polymer, a styrene / maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, and the like are preferable because of high alkali developability. Examples of the polymer having a carboxylic acid in the side chain include, for example, those described in
Nos. 9-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. There are methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is an acidic cellulose derivative having the formula: In addition, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. Among these, benzyl (meth) acrylate /
Also suitable are (meth) acrylic acid copolymers and multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers. Other useful water-soluble polymers include 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol. In order to increase the strength of the cured film, alcohol-soluble nylon or 2,2-bis-
Polyethers of (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These polymers can be mixed in any amount.

The following epoxy resins can also be used. Glycidylamine epoxy resin Triphenylglycidylmethane epoxy resin Tetraphenylglycidylmethane epoxy resin Aminophenol epoxy resin Diamidediphenylmethane epoxy resin Phenol novolak epoxy resin Orthocresol epoxy resin Bisphenol A novolak epoxy resin

In the above, various monomers are selected as the coating resin and the binder resin, and the solubility and the acid value can be controlled. Therefore, the copolymer of (meth) acrylic acid and (meth) acrylate Polymers are preferred.

The preferred range of the weight average molecular weight of these coating resin and binder resin measured by GPC is from 1000 to 3
000, more preferably 3000 to 15
It is 0000. If it exceeds 300,000, developability tends to decrease.

The carbon black used in the present invention includes the following. Specifically, carbon blacks # 2400, # 2350, and # 2 manufactured by Mitsubishi Chemical Corporation
2300, # 2200, # 1000, # 980, # 97
0, # 960, # 950, # 900, # 850, MCF
88, # 650, MA600, MA7, MA8, MA1
1, MA100, MA220, IL30B, IL31
B, IL7B, IL11B, IL52B, # 4000,
# 4010, # 55, # 52, # 50, # 47, # 4
5, # 44, # 40, # 33, # 32, # 30, # 2
0, # 10, # 5, CF9, # 3050, # 3150,
# 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N23
4, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E,
Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP. Carbon black THERMAX N990, N991, N
907, N908, N990, N991, N908. Asahi Carbon Co., Ltd. carbon black Asahi # 80, Asahi # 70,
Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN,
Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 5
0H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa carbon black ColorBlack Fw200, ColorBl
ack Fw2, ColorBlack Fw2V, C
colorBlack Fw1, ColorBlack
Fw18, ColorBlackS170, Color
Black S160, SpecialBlack6,
SpecialBlack5, SpecialBlac
k4, SpecialBlack4A, Printex
U, PrintexV, Printex140U, Pr
index 140V and the like. 1

In order to coat the above coating resin with these carbon blacks, a coating base and a solvent are added to the carbon black to prepare a mill base, which is then subjected to a flushing treatment, a kneader, a ball mill, a sand mill, a bead mill,
Dispersion treatment is performed by a method using a book or 3-roll mill, extruder, paint shaker, ultrasonic wave, homogenizer, or the like. Two or more of these processing methods can be combined. If necessary, a dispersant can be used to uniformly disperse the carbon black. As the dispersant, the above-mentioned coating resin can be used as it is, or a dispersant as described later can be used in combination. These dispersants can be used alone or in combination. By the dispersion treatment, the resin is adsorbed on the carbon black surface, and at the same time, the aggregation of the carbon black particles is destroyed and the particle size is reduced.

In the present invention, examples of the form of the carbon black coated with the coating resin include powder, paste, pellet, paste, and sheet.

The preferred average particle size of the carbon black coated with the coating resin is in the range of 0.003 to 0.5 μm, and more preferably in the range of 0.005 to 0.3 μm. , In particular, developability and image reproducibility are further improved.

The dispersant which can be used in combination with the above is BYK
Anti-Terra-U, Disperbyk
-160, 161, 162, 163, Solspers 20000, 24000GR, 26 manufactured by ZENECA
000, 28000, DA-703-5 manufactured by Kusumoto Kasei Co., Ltd.
0, NDC-8194L, NDC-8203L, ND
C-8257L, KS-860, Kao's homogenal L-18, L-1820, L-95, L-100, Nippon Paint's VP5000, Goodrich's E
5703P, VAGH manufactured by Union Carbide, UR8200 manufactured by Toyobo, MR113 manufactured by Zeon Corporation,
And other known dispersing resins.

Further, phthalocyanine derivatives (commercially available EF)
KA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, N
o.95 (manufactured by Kyoeisha Yushi Kagaku Kogyo), W001 (manufactured by Yusho)
Cationic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; F-Top EF301, EF303, EF352 Akita Kasei), MegaFac F171, F172, F173
(Dainippon Ink), Florado FC430, FC43
1 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC
-103, SC-104, SC-105, SC-106
8 (manufactured by Asahi Glass) or the like; W004, W
Anionic surfactants such as 005, W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47
EA, EFKA polymer 100, EFKA polymer 40
0, EFKA polymer 401, EFKA polymer 450
Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 1200
0, 13240, 13940, 17000, 2400
Various Solsperse dispersants such as 0, 26000 and 28000 (manufactured by Zeneca Corporation); Adecapluronic L3
1, F38, L42, L44, L61, L64, F6
8, L72, P95, F77, P84, F87, P9
4, L101, P103, F108, L121, P-1
23 (manufactured by Asahi Denka) and Isonet S-20 (manufactured by Sanyo Chemical).

Next, the photosensitive composition of the present invention contains a radiation-sensitive compound. The radiation-sensitive compound can be used in combination with various conventionally known photopolymerizable monomers and a polymerization initiator. Examples of the photopolymerizable monomer include those having at least one addition-polymerizable ethylene group. Compounds having an ethylenically unsaturated group having a boiling point of 100 ° C. or more under pressure are mentioned. Examples of the photopolymerization initiator include a halomethyloxadiazole compound and a halomethyl-
Examples include an active halogen compound such as an s-triazine compound, a 3-aryl-substituted coumarin compound, and at least one kind of lophine dimer.

As the photopolymerizable monomer, a compound having at least one ethylenically unsaturated group capable of addition polymerization and having a boiling point of 100 ° C. or more at normal pressure includes polyethylene glycol mono (meth) acrylate and polypropylene glycol mono Monofunctional acrylates and methacrylates such as (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth)
Acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) After adding ethylene oxide or propylene oxide to polyfunctional alcohols such as acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane, and then (meth) acrylated Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193. Polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490, epoxy acrylates which are reaction products of epoxy resins with (meth) acrylic acid, etc. And polyfunctional acrylates and methacrylates. Furthermore, the Journal of the Adhesion Society of Japan Vol. 20, No. 7, pages 300 to 308 as photocurable monomers and oligomers. These radiation-polymerizable monomers or oligomers may be used in any proportion as long as the composition of the present invention can form a coating film having adhesiveness by receiving irradiation with radiation, as long as the object and effects of the present invention are not impaired. it can. The amount used is 5 to 90% by weight, preferably 10 to 50% by weight, based on the total solid content of the photosensitive composition.

Examples of active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine include 2-halomethyl-5-vinyl-1,3 represented by the following general formula IV described in JP-B-57-6096. , 4-oxadiazole compounds.

[0039]

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In the formula (IV), W is a substituted or unsubstituted aryl group, X is a hydrogen atom, an alkyl group or an aryl group, Y is a fluorine atom, a chlorine atom or a bromine atom, and n is 1 Represents an integer of ~ 3. Specific compounds include 2-
Trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p -Methoxystyryl) -1,
3,4-oxadiazole and the like. Examples of the photopolymerization initiator of the halomethyl-s-triazine-based compound include vinyl-halomethyl-s-triazine compounds represented by the following general formula V described in JP-B-59-1281 and JP-A-53-133428. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula VI and 4- (p-aminophenyl) -2,2 represented by the following general formula VII 6-di-halomethyl-s-triazine compounds.

[0041]

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In the formula (V), Q ₃ is Br, Cl, and P is -C
Q ₃ , —NH ₂ , —NHR, —N (R) ₂ , —OR (where R is a phenyl or alkyl group), W is an optionally substituted aromatic, heterocyclic nucleus or general formula VA. In the formula VA, Z is -O- or -S-, and R is as defined above.

[0043]

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In the formula (VI), X represents -Br, -Cl;
m and n are integers of 0 to 3, R ′ is represented by the general formula VIA,
R ₁ is H or OR _c (R _c is an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ is —Cl, —Br
Or an alkyl, alkenyl, aryl, or alkoxy group.

[0045]

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In the formula (VII), R ₁ and R ₂ are represented by —H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or the general formulas VIIA and VIIB. R ₃ and R ₄ are -H,
Represents a halogen atom, an alkyl group, or an alkoxy group. X,
Y represents -Cl, -Br, and m and n represent 0, 1 or 2.

[0047]

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In the formulas VII A and VII B, R ₅ , R ₆ and R ₇ represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Examples of the substituent in the substituted alkyl group and the substituted aryl group include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, a carboaryloxy group, an acyl group, a nitro group, a dialkylamino group, and a sulfonyl derivative. Is mentioned.

In the formula (VII), R ₁ and R ₂ may form a heterocyclic ring composed of a nonmetallic atom together with the nitrogen atom bonded thereto, in which case the heterocyclic ring may be one of the following: No.

[0050]

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As a specific example of the general formula V, 2,4-
Bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl)
-6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like.

Specific examples of the general formula VI include 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-methoxy-naphth-2-yl) -4,6- Bis-trichloromethyl-s-
Triazine, 2- (5-methoxy-naphth-1-yl)
-4,6-bis-trichloromethyl-s-triazine,
2- (4,7-dimethoxy-naphth-1-yl) -4,
6-bis-trichloromethyl-s-triazine, 2-
(6-ethoxy-naphth-2-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine and the like.

Specific examples of the general formula VII include 4- [p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o -Methyl-
p-N, N-di (chloroethyl) aminophenyl]-
2,6-di (trichloromethyl) -s-triazine, 4
-(P-N-chloroethylaminophenyl) -2,6-
Di (trichloromethyl) -s-triazine, 4- (p-
N-ethoxycarbonylmethylaminophenyl) -2,
6-di (trichloromethyl) -s-triazine, 4-
[P-N, N-di (phenyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
(P-N-chloroethylcarbonylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, 4
-[PN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- [m-bromo-p-N,
N-di (ethoxycarbonylmethyl) aminophenyl]
-2,6-di (trichloromethyl) -s-triazine,
4- [m-chloro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-p
-N, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-p
-N, N-di (chloroethyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
[O-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN,
N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo -P-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, (O-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo -P-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-p-N
-Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p
-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- (o-chloro-p-N-chloroethylaminophenyl) -2,6
-Di (trichloromethyl) -s-triazine, 4- (o
-Fluoro-p-N-chloroethylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, and the like.

The following sensitizers can be used in combination with these initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone,
2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10- Anthraquinone, 2-
t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (Dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p-
(Diethylamino) benzophenone, benzoanthrone and the like and benzothiazole compounds described in JP-B-51-48516 are exemplified.

The 3-aryl-substituted coumarin compound is as follows:
Refers to a compound represented by the general formula VIII. R₈Is a hydrogen atom,
C1-C8 alkyl group, C6-C10 aryl
Group (preferably a hydrogen atom, a methyl group, an ethyl group,
Butyl group), R₉Is a hydrogen atom, having 1 to 8 carbon atoms
Alkyl group, aryl group having 6 to 10 carbon atoms, the following general formula
A group represented by VIIIA (preferably a methyl group, an ethyl group,
A propyl group, a butyl group, a group represented by the general formula VIIIA,
Preferably a group represented by the general formula VIIIA).
R_Ten, R₁₁Represents a hydrogen atom and an alkyl having 1 to 8 carbon atoms, respectively.
(Such as methyl, ethyl, propyl, butyl
Group, octyl group), haloalkyl group having 1 to 8 carbon atoms (eg,
For example, chloromethyl group, fluoromethyl group, trifluoromethy
And an alkoxy group having 1 to 8 carbon atoms (for example,
Xy, ethoxy, butoxy), which may be substituted
An aryl group having 6 to 10 carbon atoms (for example, a phenyl group);
Amino group, -N (R₁₆) (R₁₇), Halogen (eg, -C
1, -Br, -F). Preferably a hydrogen atom, methyl
Group, ethyl group, methoxy group, phenyl group, -N
(R₁₆) (R₁₇), -Cl. R₁₂May be replaced
Aryl groups having 6 to 16 carbon atoms (e.g., phenyl,
Phenyl, tolyl, cumyl). As a substituent
Is an amino group, -N (R₁₆) (R₁₇), Al having 1 to 8 carbon atoms
Kill groups (eg, methyl, ethyl, propyl,
Octyl group), a haloalkyl group having 1 to 8 carbon atoms
(For example, chloromethyl, fluoromethyl, trifluoromethyl
A methyl group), an alkoxy group having 1 to 8 carbon atoms (for example,
Methoxy, ethoxy, butoxy), hydroxy
Group, cyano group, halogen (for example, -Cl, -Br,-
F). R₁₃, R₁₄, R₁₆, R₁₇Are each
A hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, methyl
Group, ethyl group, propyl group, butyl group, octyl group)
Represent. R₁₃And R ₁₄And R₁₆And R₁₇Are also bonded to each other
Heterocycle (eg piperidine ring, piperazine
Ring, morpholine ring, pyrazole ring, diazole ring,
(Riazole ring, benzotriazole ring, etc.)
Good. R_FifteenIs a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg,
For example, methyl, ethyl, propyl, butyl, octane
Tyl group), an alkoxy group having 1 to 8 carbon atoms (for example,
Group, ethoxy group, butoxy group), optionally substituted charcoal
Aryl groups having a prime number of 6 to 10 (for example, phenyl group),
Group, N (R₁₆) (R₁₇), Halogen (eg, -Cl,-
Br, -F). Zb is = O, = S or = C
(R₁₈) (R₁₉). Preferably = O, = S, = C
(CN)_TwoAnd particularly preferably 好 ま し く O. R₁₈, R
₁₉Is a cyano group, -COOR₂₀, -COR_{twenty one}To
Represent. R₂₀, R_{twenty one}Is an alkyl group having 1 to 8 carbon atoms
(E.g., methyl, ethyl, propyl, butyl,
Octyl group), a haloalkyl group having 1 to 8 carbon atoms (for example,
Chloromethyl group, fluoromethyl group, trifluoromethyl group
Etc.), an aryl group having 6 to 10 carbon atoms which may be substituted
(For example, a phenyl group).

Particularly preferred 3-aryl-substituted coumarin compounds are the {(s-triazin-2-yl) amino} -3-arylcoumarin compounds of the general formula IX.

[0057]

Embedded image

The lophine dimer means a 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and its basic structure is shown below.

[0059]

Embedded image

Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer,
-(O-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,
5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2 , 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2
-(P-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer and the like.

In the present invention, other than the above initiators, other known initiators can be used. US Patent No. 2,36
Bicinal polykettle aldonyl compounds disclosed in US Pat. No. 7,660, US Pat. No. 2,367,661.
-Carbonyl compounds disclosed in U.S. Pat. No. 2,448,82 and U.S. Pat. No. 2,448,82.
No. 8, disclosed in U.S. Pat. No. 2,722,512.
-Aromatic acyloin compounds substituted with hydrocarbons, U.S. Pat. Nos. 3,046,127 and 2,951,75
No. 8,491,367, and the combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367, JP-B-51-48516. Disclosed benzothiazole-based compounds / trihalomethylol-s-triazine-based compounds.

The amount of the initiator used is based on the monomer solid content.
0.01 wt% to 100 wt%, preferably 1 wt% to
50 wt%. If the amount of the initiator is less than 0.01% by weight, the polymerization hardly proceeds. If the amount exceeds 100% by weight, the polymerization rate increases but the molecular weight decreases and the film strength decreases.

The composition of the present invention may contain various additives, if necessary, such as a filler, a polymer compound other than the resin of the present invention, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, An inhibitor or the like can be added.

Specific examples of these additives include fillers such as glass and alumina; and high molecular compounds other than the binder polymer (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. Surfactants such as nonionic, cationic and anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane ,
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3
-Glycidoxypropylmethyldimethoxysilane, 2-
Adhesion promoters such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane ; 2,2
-Antioxidants such as -thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5- UV absorbers such as chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

In order to promote the alkali solubility of the non-irradiated portion to further improve the developability of the composition of the present invention, an organic carboxylic acid, preferably having a molecular weight of 1,000 or less, is added to the composition of the present invention. Can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; oxalic acid, malonic acid, succinic acid, and glutaric acid Aliphatic dicarboxylic acids such as acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, melophanic acid and pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

It is preferred that the radiation-sensitive composition of the present invention further comprises a thermal polymerization inhibitor in addition to the above.
For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 '
-Methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

Solvents used in preparing the composition of the present invention include esters such as ethyl acetate and acetic acid-n.
-Butyl, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, ethyl oxyacetate, Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate,

Alkyl 3-oxypropionates such as methyl 3-hydroxypropionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate;
Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-
Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, methyl 2-oxy-2-methylpropionate, 2-
Ethyl oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-
Ethyl methyl propionate,

Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether; Ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,

Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons, such as toluene, xylesi etc. Is mentioned.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl Carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.

These solvents may be used alone or
It may be used in combination of more than one kind. The composition of the present invention comprises:
Prepared by mixing the carbon black dispersion coated with the above coating resin, the radiation-sensitive compound, and other additives used as necessary with a solvent, and mixing and dispersing using various mixers and dispersers. can do.

The composition of the present invention is applied to a substrate by a coating method such as spin coating, casting coating, roll coating or the like to form a photosensitive composition layer (film thickness 0.5 to 2 μm) and a predetermined mask A colored pattern is formed by exposing through a pattern and developing with a developing solution. As the radiation used at this time, ultraviolet rays such as g-rays, h-rays, and i-rays are particularly preferably used.

As the substrate, for example, soda glass, Pyrex glass, quartz glass used for a liquid crystal display device or the like and a transparent conductive film adhered thereto, or a photoelectric conversion device substrate used for a solid-state imaging device or the like, for example, silicon Substrates and the like can be mentioned.

Any developer can be used as long as it dissolves the photosensitive composition of the present invention but does not dissolve the irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned solvents used when preparing the composition of the present invention.

As the alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , Choline, pyrrole, piperidine, an alkaline compound such as 1,8-diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001 to 0.001.
An alkaline aqueous solution dissolved to be 10% by weight, preferably 0.01 to 1% by weight is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development. After the formation of the black matrix, red, blue and green colored images can be formed by a known method. Further, a black matrix may be formed with a configuration as shown in FIG.

[0077]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Example-1 (Carbon black coating-1) Carbon black # 40 (manufactured by Mitsubishi Chemical Corporation) 80 parts Styrene / methacrylic acid copolymer (coating resin) 20 parts (acid value 30 mgKOH / g, weight average molecular weight 45,000) ) 100 parts of cyclohexanone was mixed and kneaded with a three-mill at 80 ° C for 20 minutes. The obtained sheet-like kneaded material was pulverized into small pieces of about 1 mm square.

(Composition for Black Matrix-1) 100 parts of the above carbon black coating material-1 100 parts Benzyl methacrylate / methacrylic acid copolymer (binder resin) 60 parts (acid value 105 mgKOH / g, weight average molecular weight 30,000) propylene glycol After mixing a mixture of 350 parts of monomethyl ether acetate with a dissolver, a bead mill dispersing machine (DCP mill: DCP-SF12, manufactured by Eirich Japan)
For 1 hour.

(Photosensitive Composition for Black Matrix-1) 100 parts of Composition for Black Matrix 100 parts Dipentaerythritol hexaacrylate 30 parts 2- (p-methoxyphenyl) -4,6-bis (trischloromethyl)- s-Triazine 2 parts 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane 2 parts p-methoxyphenol 0.01 parts Propylene glycol monomethyl ether acetate 500 parts Photosensitivity for the above black matrix Composition-1 was applied to a glass substrate (Corning Co., No. 7059) using a spin coater, and then dried on a hot plate at 100 ° C. for 60 seconds (thickness: 1.3 μm). Exposure was performed by irradiating 400 mj / cm ² with a high-pressure mercury lamp through a black matrix mask. Next, it was developed (25 ° C.) with 5% by weight of a developing solution CD-2000 (manufactured by FUJIFILM Aulin Co., Ltd.), and then washed with spray water to obtain a black matrix pattern.

Comparative Example-1 As a comparison of Example-1, carbon black coating-1
The composition 1 for a black matrix was prepared in exactly the same composition except that no coating resin was used to obtain a photosensitive composition for a black matrix. A black matrix pattern was obtained in the same manner as in Example-1. Comparative Example-2 As a comparison with Example-1, carbon black coating-1
A coating material and a composition for a black matrix were prepared with exactly the same composition except that the same coating resin as the binder resin was used to obtain a photosensitive composition for a black matrix. A black matrix pattern was obtained in the same manner as in Example-1. Comparative Example-3 As a comparison of Example-1, a carbon black coating and a composition for a black matrix were prepared with exactly the same composition except that no binder resin was used, to obtain a photosensitive composition for a black matrix. Evaluation was performed in the same manner as in Example-1. In this case, the black matrix pattern could not be formed due to poor developability. Comparative Example-4 As a comparison with Example-1, the composition was completely the same except that a coating resin and a binder resin (a combination in which the solubility of the coating resin was larger than that of the binder resin) as shown in Table 1 below were used. A carbon black coating and a composition for a black matrix were prepared to obtain a photosensitive composition for a black matrix. Evaluation was performed in the same manner as in Example-1. A black matrix pattern was obtained in the same manner as in Example-1.

Table 1 shows the materials of Example-1 and Comparative Examples-1 to 3, and the solubility of each resin in a solvent (propylene glycol monomethyl ether acetate) was measured by a gravimetric method. Table 2 shows the evaluation results by the following evaluation method.

(Evaluation Method and Evaluation Criteria) Particle Size (Particle Size of Carbon Black Coated with Coating Resin): Centrifugal Transmission Measuring Instrument (CAP manufactured by Horiba, Ltd.)
A-700) average size measured. Specific resistance value (Ω · cm): The photosensitive composition of the present invention was coated on a chromium-deposited glass substrate, dried, and measured with a high-resistance resistivity meter Hiresta UP (manufactured by Mitsubishi Chemical Corporation). . Development latitude: The width of the development time at which the line width change rate of 25 μm is ± 10% is: o: 40 seconds or more Δ: 20 seconds to less than 40 seconds ×: less than 20 seconds Edge shape: 25 μm line edge shape ○: Edge shape is smooth and there is no jagging. △: Edge shape is between ○ and ×. ×: Edge shape is jagged. Optical density: OD value per 1 μm film thickness Resolution: ○: 10 μm resolution ×: when 10 μm is not resolved

[0083]

[Table 1]

[0084]

[Table 2]

As shown in Table 2, Example 1 using the composition of the present invention had a high specific resistance value, a wide development latitude, and was excellent in edge shape and resolution. Comparative Example-
All of the samples Nos. 1 to 3 were inferior in performance to Example 1 in spite of using the same carbon black.

Examples 2 to 5 Photosensitive compositions were prepared in the same manner as in Example 1 except that a coating resin, a binder resin, carbon black and a solvent as shown in Table 3 were used. evaluated. Table 3 shows the composition.
4 shows the results.

[0087]

[Table 3]

[0088]

[Table 4]

In all of Examples 2 to 5 of the present invention, black matrices having high resistance, wide developing latitude, and good image quality were obtained.

[0090]

According to the present invention, there is provided a photosensitive composition for a black matrix, which is excellent in developability and image reproducibility, has a high resolution, and is capable of obtaining a black matrix excellent in insulation, coloring and hiding power. it can. Further, a black matrix having excellent insulating properties, coloring power and hiding power can be provided.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a liquid crystal panel in which a black matrix is provided on a TFT side.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Liquid crystal panel 2, 3 Glass substrate 4 Liquid crystal material 5 Pixel electrode 6 TFT 7 Black matrix 8 Color filter 9 Common electrode

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 5/22 G02B 5/22 G03F 7/004 501 G03F 7/004 501 505 505 7/032 7/032 // C09D 5/00 C09D 5/00 C 5/32 5/32 7/12 7/12 Z 133/00 133/00

Claims (6)

[Claims] 1. A photosensitive composition for a black matrix comprising an insulating carbon black coated with a coating resin, a binder resin, a dispersant, a radiation-sensitive compound and a solvent, wherein the solubility of the coating resin in the solvent is: A photosensitive composition for a black matrix, which has a lower solubility than the binder resin in the solvent. 2. An acid value of the coating resin is 0 to 200, and an acid value of the binder resin is 50 to 150.
3. The photosensitive composition for black matrix according to item 1. 3. The photosensitive composition for a black matrix according to claim 1, wherein the acid value of the binder resin is higher than the acid value of the coating resin. 4. The photosensitive composition for a black matrix according to claim 1, wherein the acid value of the binder resin is lower than the acid value of the coating resin. 5. The photosensitive material for a black matrix according to claim 1, wherein the average particle size of the insulating carbon black coated with the coating resin is 0.003 to 0.5 μm. Composition. 6. A color filter comprising a black matrix formed using the photosensitive composition for a black matrix according to claim 1.