JP2000089025A - Photosensitive colored composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive colored composition for color filter which has a high sensitivity, makes the transmissivity, contrast, resolution of an obtd. color filter high and can obtain a color filter of a constant and excellent chromaticity. SOLUTION: The photosensitive colored composition for color filter incorporates (A) a pigment, (B) a binding resin, (C) a radiation-rensitive compound and (D) a solvent. The (A) pigment containes a combination of (A-1) C.I.Pigment Red 254 and (A-2) at least one kind of Red pigment except C.I. Pigment Red 254, and/or (A-3) Y pigment having a light tansmittance of <=10% at 470 nm and a light transmittance of >=80% at 535 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive coloring composition for a color filter containing a pigment, and more particularly to a photosensitive coloring composition for a color filter suitable for producing a color filter used for a liquid crystal display device or a solid-state imaging device. Composition.

[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 methods, electrodeposition methods and pigment dispersion methods are known.

[0003] The dyeing method is a method for producing a color filter by dyeing a dyeing substrate made of a natural resin such as gelatin, glue, casein or the like or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye. However, in the dyeing method, there is a problem in light resistance, heat resistance, moisture resistance, etc. due to the use of the dye, and it is difficult to uniformly control the dyeing and fixing characteristics on a large screen, and color unevenness is likely to occur. In this case, there is a problem that a dye-proof layer is required and the process is complicated.

In the electrodeposition method, a transparent electrode is formed in a predetermined pattern in advance, a resin containing a pigment dissolved or dispersed in a solvent is ionized, and a voltage is applied to form a colored image in a pattern. This is a method for producing a color filter. However, the electrodeposition method requires a photolithography process including a film formation and an etching process of a transparent electrode for forming a color filter in addition to a transparent electrode for display. At this time, if there is a short circuit, a line defect occurs and the yield decreases.
In addition, there is a problem that it is difficult to apply to a mosaic arrangement other than the stripe arrangement in principle, and it is difficult to manage the transparent electrodes.

[0005] The printing method is a simple method for producing a color filter by printing such as offset printing using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curable resin. It is difficult to perform filtering, and there is a problem in that defects are easily caused by dust, foreign matter, and a gelled portion of the ink binder, and there are problems in positional accuracy, line width accuracy, and planar smoothness associated with printing accuracy.

[0006] The pigment dispersion method is a method of producing a color filter by a photolithography method using a colored radiation-sensitive 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.

In order to produce a color filter by a pigment dispersion method, a radiation-sensitive composition is applied on a glass substrate by a spin coater or a roll coater, and dried to form a coating film. A colored pixel is obtained by developing, and this operation is performed for each color to obtain a color filter. Further, the pigment dispersion method is disclosed in
02469, JP-A-1-152499, JP-A-2-
No. 181704, JP-A-2-199403, JP-A-4
-76062, JP-A-5-273411, JP-A-6-27311
As described in JP-A-184482 and JP-A-7-140654, a negative photosensitive composition using a photopolymerizable monomer and a photopolymerization initiator for an alkali-soluble resin is generally used. .

However, in recent years, there has been a demand for higher definition, lower power consumption, and higher brightness of liquid crystal display devices, and color filters are expected to have higher transmittance and higher contrast. It is rare. From the viewpoint of the production of a color filter, a photosensitive composition for a color filter is required to have a high sensitivity, a wide development latitude, a low pigment sedimentation and a high dispersion stability. In order to achieve high transmittance of the color filter,
There are methods for reducing the content of the pigment component in the photosensitive composition for color filters and reducing the film thickness,
The saturation of the color filter is reduced and the whole becomes whitish, and the color vividness is lost.

Conventionally, as a red pigment, JP-A-1-254
As described in JP-A No. 918 and JP-A-2-153353, mainly a dianthraquinone pigment C.I.
I. Pigment Red 177 has been used. In order to satisfy the above-mentioned recent requirements, pigments have been finely divided and chromaticity has been adjusted in combination with other pigments (Y pigments). However, it is becoming impossible to satisfy the above-mentioned requirements. It is the current situation. In particular, as long as PR-177 is used as the red main pigment, the requirements cannot be satisfied.

Japanese Patent Application Laid-Open No. 8-6242 discloses a new method that does not require pigment dispersion, in which an image of a pigment-dispersed pigment precursor is formed, followed by a chemical method, a thermal method, a photolytic method, or the like. A method for pigmentating a pigment precursor is disclosed (Latent Pigment). With this method, satisfactory results have not been obtained due to insufficient pigmentation performed by a chemical method, a thermal method, a photolytic method, or the like. In particular, since the degree of pigmentation varies depending on the temperature, a different color tone is produced depending on the heating temperature. Therefore, the heat resistance is not sufficient, and it is not at a stage where it can be practically used.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive coloring composition for a color filter, which has a high sensitivity, a high transmittance, a high contrast, a high resolution and a color filter having a constant and excellent chromaticity. It is in.

[0012]

The above object has been attained by the following constitutions. (1) In the photosensitive coloring composition for a color filter containing (A) a pigment, (B) a binder resin, (C) a radiation-sensitive compound, and (D) a solvent, the (A) pigment is (A-
1) CI Pigment Red 254 and (A-2) CIP
A photosensitive coloring composition for a color filter, which is a combination of at least one type of red pigment other than igment Red254. (2) The Red pigment of (A-2) is a CI Pigment.
Red 177 and / or CI Pigment Red 224, wherein the photosensitive coloring composition for a color filter as described in the above item (1). (3) In the photosensitive color composition for a color filter containing (A) a pigment, (B) a binder resin, (C) a radiation-sensitive compound, and (D) a solvent, the (A) pigment is (A-
1) CI Pigment Red 254 and (A-3) 470
light transmittance at 10 nm or less and 535 nm
A photosensitive pigment composition for a color filter, wherein the combination is a combination of Y pigments having a light transmittance of 80% or more. (4) In the photosensitive color composition for a color filter containing (A) a pigment, (B) a binder resin, (C) a radiation-sensitive compound, and (D) a solvent, the (A) pigment is (A-
1) CI Pigment Red 254, (A-2) CI Pigme
At least one type of Red pigment other than nt Red 254 and (A-3) a Y pigment having a light transmittance at 470 nm of 10% or less and a light transmittance at 535 nm of 80% or more. Photosensitive color composition for color filters. (5) The Red pigment of (A-2) is a CI Pigment.
Red 177 and / or CI Pigment Red 224, wherein the photosensitive coloring composition for a color filter as described in (4) above. (6) The (A) pigment has an average particle size of 0.01 to 0.3.
The photosensitive coloring composition for a color filter according to any one of the above (1) to (5), wherein the composition is μm.

The photosensitive coloring composition for a color filter of the present invention has the following various advantages. (A) By using the above specific pigment, compared with a conventional red pigment (for example, CI Pigment Red 177),
High transmission can be achieved by shifting the transmission curve to the short wave side and adjusting the transmission curve to the bright line (610 nm) of the backlight. As a result, the backlight light can be used effectively, so that a color filter with bright light transmission can be produced. In addition, by combining with other various red pigments and yellow pigments, it is possible to create red filters of various chromaticities while maintaining light transmission, and to create a color filter of a new color which has not been available before. it can. (B) Compared to the conventional red pigment, the transmittance of ultraviolet light on the short-wave side is higher, so that unnecessary light absorption by the pigment during exposure by ultraviolet irradiation is eliminated, and the exposure efficiency is high. That is, the sensitivity is high.
Therefore, the exposure time is shortened, and the productivity of the color filter is improved. In particular, the productivity is improved as the size of the substrate increases. (C) Development is stabilized, and the latitude of development is improved.
That is, there is little change in the image (roughness of the image, change in the image density, change in the line width, etc.) obtained by the developing conditions such as the developing time, the developing temperature, and the developer concentration (the developing latitude is wide). (D) The profile of the edge portion (peripheral portion) of the image is a forward taper, that is, the vertical section of the peripheral portion of the image has a gentle slope from the image surface to the substrate contact surface. Thereby, the adhesion to the substrate is improved. In addition, a sharp image with good sharpness is formed with little disturbance of the edge portion. (E) As described above, since the transmittance of ultraviolet rays is high, the pigment concentration in the composition can be increased. Thereby, a color filter with high color purity can be obtained. Conventionally, when the pigment concentration is increased, a difference between an exposed portion and an unexposed portion hardly appears, and a satisfactory pattern cannot be obtained. Since the pigment concentration can be increased, a color filter with high color purity can be created. (F) Since the pigment is finely dispersed, the transmittance of light is high, and scattering by coarse particles is small. Thereby,
Even higher sensitivity is obtained, and the color filter to be produced has high resolution and high contrast. In addition, since a stable pigment is used as compared with the latent pigment, a color filter having a constant and excellent chromaticity can be obtained.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) Pigment In the present invention, the following (I)
To (III). (I) (A-1) CI Pigment Red 254 and (A)
-2) A combination of at least one type of red pigment other than CI Pigment Red 254. (II) (A-1) CI Pigment Red 254 and (A)
-3) A combination of Y pigments having a light transmittance at 470 nm of 10% or less and a light transmittance at 535 nm of 80% or more. (III) (A-1) CI Pigment Red 254, (A-
2) Combination of at least one type of red pigment other than CI Pigment Red 254 and (A-3) a Y pigment having a light transmittance at 470 nm of 10% or less and a light transmittance at 535 nm of 80% or more. . Hereinafter, each pigment is referred to as (A-1) a red pigment, (A-2)
It may be abbreviated as Red pigment or (A-3) Y pigment.

In the above combinations (I) to (III), (A-
1) CI Pigment Red 254 is a pigment having a structure represented by the following formula (1).

[0016]

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(A-2) CI Pigm of the combination (I)
Red pigments other than ent Red 254 are used to improve color purity, and are preferably red pigments having a maximum absorption at 530 nm to 560 nm. As a specific example,
CI Pigment Red 5, 9, 10, 17, 21, 22,
48: 1, 48: 2, 48: 3, 48: 4, 52: 2,
89, 117, 119, 166, 177, 188, 19
0, 216, 224, and 226.
Further, a red pigment represented by the following formula (2) (excluding CI Pigment Red 254 represented by the above formula (1))
However, the present invention is not limited thereto.

[0018]

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In the general formula (2), Y represents an oxygen atom or a sulfur atom. R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, or an alkoxy group. Represents a carbonyl group.
R ₃ and R ₄ may be the same or different and represent an alkyl group, a cycloalkyl group, an aralkyl group, or a carbocyclic or heterocyclic aromatic residue.

In the above general formula (2), R ₁ , R ₂ ,
The alkyl group for R ₃ and R ₄ may be branched or unbranched, preferably 1 to 18, more preferably 1 to 12, particularly preferably 1 to 6.
It should have at least one carbon atom. Specifically, methyl, ethyl, isopropyl, sec-butyl, tert-butyl,
Examples include a tertiary amyl group, octyl, decyl, dodecyl or octadecyl group.

The cycloalkyl group in R ₁ , R ₂ , R ₃ and R ₄ preferably has 3 to 8, more preferably 3 to 6, carbon atoms. Include a cyclopentyl group, a cyclohexyl group and the like. The alkenyl group in R ₁ and R ₂ preferably has 2 to 8, more preferably 2 to 6 carbon atoms. Specific examples include a vinyl group and an allyl group. No. The alkynyl group in R ₁ and R ₂ is preferably 2 to 8, more preferably 2 to 6
It is preferable that the compound has at least two carbon atoms, and specific examples thereof include an ethynyl group.

The aryl group in R ₁ and R ₂ includes
It preferably has 6 to 10 carbon atoms, and specific examples include a phenyl group and a naphthyl group. Examples of the alkyl group of the alkylcarbamoyl group for R ₁ and R ₂ include the same alkyl groups as those described above. Examples of the aryl group of the arylcarbamoyl group for R ₁ and R ₂ include the same aryl groups as those described above. The alkoxy group of the alkoxycarbonyl group in R ₁ and R ₂ has 1 carbon atom.
4 to 4, specifically, methoxy group, ethoxy group, butoxy group and the like.

When R ₁ , R ₂ , R ₃ and R ₄ in the general formula (2) represent an aralkyl group, in particular, a monocyclic to
It may contain a tricyclic, more preferably a monocyclic or bicyclic aryl residue. Specific examples include benzyl and phenylethyl. In the general formula (2), when R ₃ and R ₄ represent a carbocyclic aromatic residue, a monocyclic to tetracyclic, especially a monocyclic or bicyclic residue, ie, phenyl, diphenylyl or naphthyl Is preferred. Specifically, the following formula,

[0024]

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(Wherein T ₁ , T ₂ , and T ₃ are different in position and are the same or different, hydrogen, halogen, carbamoyl, cyano, trifluoromethyl, alkylcarbamoyl having 2 to 13 carbon atoms, carbon number 1-12 alkyls,
Alkoxy having 1 to 12 carbons, alkyl mercapto having 1 to 12 carbons, alkoxycarbonyl having 2 to 13 carbons, alkanoylamino having 2 to 13 carbons, monoalkylamino having 1 to 12 carbons, Dialkylamino having 2 to 24 carbon atoms, unsubstituted or halogen, having 1 to 1 carbon atoms
Represents phenoxy, phenylmercapto, phenoxycarbonyl, phenylcarbamoyl or benzoylamino substituted by 12 alkyl or alkoxy having 1 to 12 carbon atoms. ) Or the following formula:

[0026]

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(Wherein T ₄ and T ₅ are different in position, and each independently represents hydrogen, chlorine, bromine, alkyl having 1 to 4 carbons,
Cyano, phenoxy, carbamoyl, alkylcarbamoyl having 2 to 5 carbon atoms, phenylcarbamoyl unsubstituted or substituted by chlorine, methyl or methoxy Represents ) Or the following formula:

[0028]

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(Wherein T ₆ represents methyl, isobutyl, base, bromine, methoxy, phenoxy or cyano;
T ₇ represents methyl, chlorine or cyano and T ₈ represents methyl or chlorine).

In the general formula (2), when R ₃ and R ₄ represent a heterocyclic aromatic residue, monocyclic to tricyclic ones are preferred. These may be pure heterocyclic, or may contain one heterocycle and one or more fused benzene rings, and specifically include, for example, pyridyl, pyrimidyl, pyrazinyl, Triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, coumarinyl,
Examples include benzofuranyl, benzimidazolyl or benzoxazolyl. Both carbocyclic and heterocyclic aromatic residues may exhibit the usual water-insolubilizing substituents as described, for example, in European Patent Application No. 94911. is there.

In the general formula (2), R₁, R_TwoIs water
An elemental atom is preferred._Three, R _FourAre, independently of each other,
An alkyl group having 1 to 4 carbon atoms, a dialkylamino group,
Having an alkyl group or a halogen atom as a substituent
An optionally substituted phenyl group is preferred.

The pigment represented by the general formula (2) is, for example, US Pat. No. 4,415,685, EP-A-133,156 or JP-A-61-120861.
Can be synthesized by the method described in Japanese Patent Application Laid-Open Publication No. H11-157, 1988.

Among such (A-2) red pigments, CI Pigment Red 177, 224 is preferred.

(A-2) Red pigments may be used alone or in combination of two or more.

(A-3) 470 nm of the combination (II)
Examples of the Y pigments having a light transmittance of 10% or less and a light transmittance at 535 nm of 80% or more include:
CI Pigment Yellow 93, 110, 129, 13
8, 150, 185, etc., but are not limited thereto. It should be noted that CI Pigment Yellow 83, which is a Y pigment conventionally used together with a red pigment,
Nos. 9, 139 etc. do not satisfy the above-mentioned condition of transmittance and are excluded from the present invention. If the Y pigment does not satisfy the required transmittance, the chromaticity as Red cannot be adjusted, and a desired color filter cannot be formed. However, the above conditions may be satisfied by finely dispersing even the above pigment. Therefore, various Y pigments finely dispersed to satisfy the above requirements can be included.

In the combination of the above (I) to (III) of the pigment (A), the preferable mixing ratio of each pigment is as follows. (I) (A-1) Red pigment (CI Pigment Red 254) 20 to 90% by weight, particularly 30 to 80% by weight (A-2) Red pigment 10 to 80% by weight, particularly 20 to 70% by weight % (II) (A-1) Red pigment 70 to 97% by weight, especially 75 to 95% by weight (A-2) Red pigment 10 to 80% by weight, particularly 20 to 70% by weight (III) (A- 1) Red pigment 20 to 80% by weight, particularly 30 to 70% by weight (A-2) Red pigment 10 to 70% by weight, particularly 20 to 50% by weight (A-3) Y pigment 3 to 30% by weight, In particular, 5 to 25% by weight The combination of the above (I) and (III) gives (A-2) Re
When CI Pigment Red 177 and 224 are used together as the d pigment, the weight ratio is preferably as follows. (I) (A-1) Red pigment 20 to 80% by weight, particularly 30 to 70% by weight (A-2) Red pigment CI Pigment Red 177 10 to 60% by weight, particularly 15 to 50% by weight C Pigment Red 224 10 to 60% by weight, especially 15 to 50% by weight (III) (A-1) Red pigment 20 to 80% by weight, especially 30 to 70% by weight (A-2) Red pigment Pigment Red 177 20 to 70% by weight, especially 30 to 60% by weight CI Pigment Red 224 20 to 70% by weight, especially 30 to 60% by weight (A-3) Y pigment 20 to 70% by weight, especially Is 10 to 50% by weight

The size of the pigment particles (A) used in the present invention, that is, the average particle size, is preferably from 0.01 to 0.01.
0.3 μm, more preferably 0.02 to 0.2 μm
m, and particularly preferably 0.03 to 0.1 μm.

After the synthesis of the pigment (A), the pigment is supplied after drying by various methods. Usually, it is dried from an aqueous medium and supplied as a powder, but since water requires a large latent heat of vaporization to dry, a large amount of heat energy is applied to dry it into a powder. Therefore, the pigment (A) generally forms an aggregate (secondary particle) in which primary particles are aggregated.

It is not easy to disperse the pigment forming such an aggregate into fine particles. Therefore, it is preferable that the pigment is previously treated with various resins. These resins include various resins described below. Examples of the treatment method include a flushing treatment and a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, or the like. Among them, a flushing treatment and a kneading method using a two- or three-roll mill are suitable for forming fine particles.

The flushing treatment is generally a method in which an aqueous dispersion of a pigment and a resin solution dissolved in a solvent immiscible with water are mixed, the pigment is extracted from an aqueous medium into an organic medium, and the pigment is treated with the resin. . According to this method, since the pigment does not undergo drying, aggregation of the pigment can be prevented and dispersion becomes easy. In kneading with two or three roll mills, a pigment and a resin or a solution of a resin are mixed, and then the pigment and the resin are kneaded while applying a high shear (shearing force) to coat the pigment surface with the resin. And a method of treating a pigment.

In the present invention, a processed pigment previously treated with an acrylic resin, a vinyl chloride-vinyl acetate resin, a maleic acid resin, an ethylcellulose resin, a nitrocellulose resin or the like can also be conveniently used. The form of the processed pigment treated with the resin is preferably a powder, paste, or pellet in which the resin and the pigment are uniformly dispersed. In addition, a non-uniform lump having a gelled resin is not preferable.

The composition of the present invention is prepared by mixing the above-mentioned component (A) pigment, components (B), (C) and (D) described below, and other additives used as necessary with a solvent. Can be prepared by mixing and dispersing using a mixer or disperser. Conventionally known mixers and dispersers can be used. Examples include a sand mill such as a homogenizer, a kneader, a ball mill, a two or three roll mill, a paint shaker, a sand grinder, and a dyno mill.

As a preferable preparation method, first, a solvent is added to the pigment and the binder resin, and the mixture is uniformly mixed. Then, if necessary, the mixture is kneaded using three or two rolls while heating, so that the pigment and the binder resin are sufficiently mixed. There is a method of blending and obtaining a uniform colored body. Next, a solvent is added to the color mixture obtained by simply mixing the obtained colored body or pigment and the binder resin without being subjected to a roll mill, a dispersant and various additives are added as necessary, and a ball mill or glass beads are used as a dispersion media. Dispersion is performed using various sand mills used, for example, a Dyno mill. At this time, a smaller dispersion can be obtained as the diameter of the glass beads is smaller. At this time, a dispersion result with good reproducibility can be obtained by controlling the temperature of the dispersion liquid to be constant.

From the dispersion obtained here, coarse particles can be removed by centrifugation or decantation, if necessary. The average particle size of the pigment particles of the dispersion liquid thus obtained can be in the above range. The colored dispersions thus obtained are (B), (C),
It is mixed with (D) to provide the photosensitive coloring composition for a color filter of the present invention.

The concentration of the pigment in all solid components of the photosensitive coloring composition (A) for a color filter is preferably from 5 to 80% by weight. If the content is less than 5% by weight, the color purity is not improved unless the film thickness is 10 μm or more, which is a practical problem.
If it exceeds 80% by weight, problems such as scumming of the non-image area and film residue are likely to occur. More preferably, 10 to 60
% By weight.

Next, the binder resin (B) used in the present invention will be described. In the photosensitive coloring composition for a color filter of the present invention, the following alkali-soluble resins and graft copolymers can be used as the binder resin. As these alkali-soluble binder resins, those which are linear organic high molecular polymers, which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution are preferable. As such a linear organic high molecular polymer, a polymer having a carboxylic acid in a side chain,
For example, JP-A-59-44615, JP-B-54-343.
No. 27, JP-B-58-12577, JP-B-54-25
957, JP-A-59-53836 and JP-A-59-7
No. 1048, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers,
There are crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like, and similarly, there is an acidic cellulose derivative having a carboxylic acid in a side chain. In addition, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. Especially among these, benzyl (meth)
Preference is given to acrylate / (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 and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.

Further, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate /
Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer Polymers include 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer.

Further, as a binder resin and a pigment dispersant, the following graft copolymers described in Japanese Patent Application No. 9-61457 can be used. At least one end of the polymer main chain containing at least one of the polymer components represented by the following general formulas (IIa) and (IIb) is a polymerizable polymer represented by the following general formula (A). Weight-average molecular weight of 3 ×, formed by bonding heavy bonding groups
10 ⁴ or less monofunctional macromonomer, monomer quaternary ammonium salt monomer represented by the following general formula (III), and at least one unsubstituted or substituted acid amide group represented by the following general formula (IV) And at least a monomer having the same.

[0049]

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[In the formula (A), V ₀ is -COO-, -OC
_{O -, - CH 2 OCO -} , - CH 2 COO -, - O -, -
SO _2- , -CO-, -CONHCOO-, -CONH
_{CONH -, - CONHSO 2 -,} - CON (P 3)
—, —SO ₂ N (P ₃ ) — or —C ₆ H ₄ — (P ₃
Represents a hydrogen atom or a hydrocarbon group). c ₁ , c
₂ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z 'or -COO-Z' via a hydrocarbon (Z 'is a hydrogen atom or Represents a good hydrocarbon group). ]

[0051]

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[In the formula (IIa) or (IIb), V ₁ has the same meaning as V ₀ in the formula (A). Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms.
d ₁ and d ₂ may be the same or different from each other, and have the same meaning as c ₁ and c ₂ in the formula (A). Q ₀ is -CN or-
Represents a C ₆ H ₄ -T. Here, T is a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, or —COOZ ″ (Z ″).
Represents an alkyl group, an aralkyl group or an aryl group). ]

[0053]

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[In the formula (III), V ₂ is the same as V ₁ in the formula (IIa).
Is synonymous with Q ₂ has the same meaning as Q ₁ in formula (IIa). e ₁ and e ₂ may be the same or different from each other, and have the same meaning as c ₁ and c ₂ in the formula (A). ]

[0055]

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[0056] In [Formula (IV), R _1, R ₂ are each may be the same or different, represent a hydrogen atom or a number from 1 to 18 amino optionally substituted hydrocarbon group having a carbon addition to R ₁ R ₂ is
—O—, —S—, and —NR ₃ — (where R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms) may be bonded to each other to form a ring. ]

Further, as the binder resin (B), Japanese Patent Application Laid-Open
The following polymer described in JP-A-20496 can also be used. The polymer is a polymer obtained by a copolymerization reaction between a monomer represented by the following general formula (K) and a monomer having at least an acidic group.

[0058]

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In the formula (K), R represents a hydrogen atom or a methyl group, and R _{1 to} R ₅ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group.

The binder resin (B) is preferably a polymer having a weight average molecular weight of 1 × 10 ⁴ or more, and more preferably a weight average molecular weight of 2 × 10 ^{4 to} 5 × 10 ⁵ . The amount of the binder resin used in the composition is preferably 0.01 to 60% by weight, more preferably 0.5 to 30% by weight, based on the total solids in the composition.

Next, the radiation-sensitive compound (C) of the present invention will be described. The radiation-sensitive compound (C) of the present invention comprises at least a polymerizable monomer and a photopolymerization initiator. (1) a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or more under normal pressure; and (2) a halomethyloxadiazole compound, halomethyl-s-triazine. At least one active halogen compound selected from compounds and a 3-aryl-substituted coumarin compound (3) at least one lophine dimer

As (1), it has at least one ethylenically unsaturated group capable of addition polymerization and has a boiling point of 100 at normal pressure.
As the compound having a temperature of not less than ° C, monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (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) acrylate, Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, poly (meth) alcohol such as glycerin or trimethylolethane, and ethylene oxide or propylene oxide added to (meth) acrylate, Japanese Patent Publication No. 48-41708
No., JP-B-50-6034, JP-A-51-37193.
Urethane acrylates described in JP-A-48-64183 and JP-B-49-4319.
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid described in JP-A No. 52-30490. I can do it. Further, the Journal of the Adhesion Society of Japan, Vol. 20,
No. 7, pages 300 to 308, photocurable monomers and oligomers can also be used. Also,
A compound represented by the following general formula (B-1) or (B-2) can also be used.

[0063]

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(In the formulas (B-1) and (B-2), B is each independently-(CH ₂ CH ₂ O)-and-(CH ₂ CH
(CH ₃₎ O) - or a represents a; X each independently represents either an acryloyl group, a methacryloyl group and a hydrogen atom, moreover, in formula (B-1), acryloyl group and methacryloyl group The sum is 5 or 6; in formula (B-2) it is 3 or 4; n
Each independently represents an integer of 0 to 6, and the sum of each n is 3 to 24; m represents each independently an integer of 0 to 6, and the sum of each m is 2 to 16 . )

These radiation-polymerizable monomers or oligomers may be used in any form as long as the composition of the present invention can form a coating film having adhesiveness upon irradiation with radiation, as long as the object and effects of the present invention are not impaired. Can be used in proportions. The amount used is 5 to 90% by weight, preferably 10 to 50% by weight, based on the total solids of the radiation-sensitive composition.

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

[0067]

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Here, 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 to
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. Halomethyl-s-
As a photopolymerization initiator for triazine-based compounds,
JP-A-9-1281 discloses a vinyl-halomethyl-s-triazine compound represented by the following general formula II.
-133-428, a 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula III and a 4- (p-amino acid) represented by the following general formula IV Phenyl) -2,6-di-halomethyl-s-triazine compounds.

[0069]

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Here, Q represents Br and Cl, and P is -CQ
_{3, -NH 2, -NHR, -N} (R) 2, -OR ( where R is phenyl or alkyl group), W is represented by optionally substituted aromatic, heterocyclic nucleus or the following general formula IIA Things. Here, Z is -O- or -S-.

[0071]

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In the general formula III, X represents Br or Cl;
m and n are integers of 0 to 3, and R is represented by the general formula IIIA. R ₁ represents H or OR (R is an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ represents a Cl, Br, alkyl, alkenyl, aryl or alkoxy group.

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In the general formula IV, 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 following general formulas IVA and IVB. R ₃ and R ₄ are-
H represents a halogen atom, an alkyl group or an alkoxy group.

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Here, R ₅ , R ₆ and R ₇ each represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Examples of the substituted alkyl group and the substituted aryl group include:
Examples 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. X represents -Cl, -Br, m,
n represents 0, 1 or 2.

When R ₁ and R ₂ form a heterocyclic ring composed of a nonmetallic atom together with the nitrogen atom bonded thereto, examples of the heterocyclic ring include those shown below.

[0078]

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Specific examples of the general formula II include 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 III 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-naphtho-
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 can be mentioned.

As a specific example of the general formula IV, 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-p-
N, N-di (chloroethyl) aminophenyl] -2,6
-Di (trichloromethyl) -s-triazine, 4- [m
-Chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-p-N, 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, 4- (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-ethoxycarbonylmethyl Aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, -(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, etc. And benzothiazole compounds described in JP-A-48516.

The 3-aryl-substituted coumarin compounds are as follows:
Refers to a compound represented by the general formula V. R₈Is hydrogen atom, charcoal
Alkyl having 1 to 8 alkyl groups and 6 to 10 carbon atoms
Group (preferably a hydrogen atom, a methyl group, an ethyl group,
Pill group, butyl group)₉Is a hydrogen atom, having 1 to 8 carbon atoms
Alkyl groups, aryl groups having 6 to 10 carbon atoms,
A group represented by the general formula VA (preferably a methyl group, ethyl
Group, propyl group, butyl group, group represented by general formula VA,
Particularly preferably a group represented by the general formula VA).
R_Ten, R₁₁Represents a hydrogen atom and an alkyl having 1 to 8 carbon atoms, respectively.
Kill groups (eg, methyl, ethyl, propyl,
Octyl group), a haloalkyl group having 1 to 8 carbon atoms
(For example, chloromethyl, fluoromethyl, trifluoromethyl
Methyl group), an alkoxy group having 1 to 8 carbon atoms (for example,
Methoxy, ethoxy, butoxy), even if substituted
An aryl group having a good carbon number of 6 to 10 (eg, phenyl
Group), amino group, -N (R₁₆) (R₁₇), Halogen (for example,
-Cl, -Br, -F). Preferably a hydrogen source
, Methyl, ethyl, methoxy, phenyl,-
N (R ₁₆) (R₁₇), -Cl.

R₁₂Has 6 to 16 carbon atoms which may be substituted
Aryl groups such as phenyl, naphthyl, tolyl
Group, cumyl group). As a substituent, an amino group, -N
(R ₁₆) (R₁₇), An alkyl group having 1 to 8 carbon atoms (for example,
Methyl, ethyl, propyl, butyl, octyl
Group), a haloalkyl group having 1 to 8 carbon atoms (for example, chloro
Methyl, fluoromethyl, trifluoromethyl, etc.),
An alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group,
Toxyl group, butoxy group), hydroxy group, cyano group,
And hydrogen (e.g., -Cl, -Br, -F).
R₁₃, R₁₄, R₁₆, R₁₇Are a hydrogen atom and a carbon atom, respectively.
~ 8 alkyl groups (e.g., methyl, ethyl,
Pill, butyl, octyl). R₁₃And R₁₄Passing
And R₁₆And R₁₇Are also bonded to each other and complex with the nitrogen atom
Ring (eg, piperidine ring, piperazine ring, morpholine
Ring, pyrazole ring, diazole ring, triazole ring,
Azotriazole ring). R_FifteenIs hydrogen
An atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group,
Ethyl, propyl, butyl, octyl), carbon
Number 1 to 8 alkoxy groups (for example, methoxy group, ethoxy group)
Group, butoxy group), optionally having 6 to 10 carbon atoms
Aryl groups (for example, phenyl group), amino group, -N
(R₁₆) (R₁₇), Halogen (eg, -Cl, -Br,-
F). Zb is = 0, = S or = C (R₁₈) (R
₁₉). Preferably = O, = S, = C (CN)_TwoIn
And particularly preferably = 0. R₁₈, R₁₉Each
, A cyano group, -COOR₂₀, -COR_{twenty one}Represents
R₂₀, R_{twenty one}Represents an alkyl group having 1 to 8 carbon atoms (eg,
For example, methyl, ethyl, propyl, butyl, octane
Tyl group), a haloalkyl group having 1 to 8 carbon atoms (for example,
Loromethyl 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 {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula VI.

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The rofin dimer of (3) means a 2,4,5-triphenylimidazolyl dimer consisting of two lophine residues, and its basic structure is shown below.

[0089]

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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, the following general formulas (C) to (H) and (J) can be used as the photopolymerization initiator.

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In the formulas (C) to (H), R₁Are each independently
A hydrogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or
A alkoxy group;_TwoAnd R_ThreeAre independently hydrogen sources
And represents an alkoxy group having 1 to 3 carbon atoms,_Twois there
Iha R_ThreeIs an alkoxy group, and R_FourIs
Hydrogen atom, alkyl group having 1 to 3 carbon atoms or alkoxy
A group represented by R_FiveAnd R₆Each independently has 1 to 3 carbon atoms
Represents an alkyl group; ₇Is hydrogen atom, hydroxyl group, carbon number 1
And represents three to three alkyl groups or alkoxy groups. T is below
Notation,

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And the group represented by m is an integer of 1 to 3,
n shows the integer of 1-4.

[0096]

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In the formula (J), n is 1 or 2, and Ar ₁
Is a phenyl group or a chlorine atom, a bromine atom, a hydroxy group, -SR ⁹ , -R ¹⁰ , -OR ¹⁰ , -SR ¹⁰ , when n is 1
—SO ₂ R ¹⁰ , —S-phenyl, —O-phenyl or a phenyl group substituted with a morpholino group (R ¹⁰
Represents an alkyl group having 1 to 9 carbon atoms), Ar ₁
When n is 2, a phenylene -T- phenylene group (T is -O -, - S- or -CH ₂ - represents a) represents a. R ⁹
Has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkenyl group having 3 to 6 carbon atoms, a cyclohexyl group, a phenylalkyl group, a phenylhydroxyalkyl group, and a substituent. which may be a phenyl group, a tolyl group, -CH ₂ -CH ₂ OH, -CH
₂ CH ₂ -OOC-CH = CH ₂ , -CH ₂ -COOR
¹¹ (R ¹¹ represents an alkyl group having 1 to 9 carbon atoms), —CH ₂ CH ₂ —COOR ¹² (R ¹² represents an alkyl group having 1 to 4 carbon atoms),

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And R¹, R^TwoAre the same or different
Well, -COOR¹²(R¹²Is as defined above)
C 1 -C 8 alkyl, or carbon
Represents a phenylalkyl group having 7 to 9 atoms,
R¹And R^TwoAre together C 4 -C 6 Al
X may represent a kylene group, X is a morpholino group, -N
(R^Four) (R^Five), -OR⁶Or -O-Si (R ⁷)
(R⁸)_TwoAnd R^Four, R^FiveMay be the same or different
And an alkyl group having 1 to 12 carbon atoms, -OR^Tenso
A substituted alkyl group having 2 to 4 carbon atoms, or
R is a group represented by R^FourAnd R^FiveAre together, -O-,
-NH- or -N (R^Ten)-Charcoal which may be intervened
R 4 represents an alkylene group having 4 or 5 atoms;⁶Is water
An atom, an alkyl group having 1 to 12 carbon atoms, allyl
Or a phenylalkyl group having 7 to 9 carbon atoms
And R⁷And R⁸May be the same or different, and
Represents an alkyl group having 1 to 4 atoms or a phenyl group.

In the present invention, other known initiators can be used in addition to the above initiators. 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. 2,448,828 and U.S. Pat. No. 2,448,828.
Ether disclosed in U.S. Pat. No. 2,722,512.
Aromatic acyloin compounds substituted with hydrocarbons; polynuclear quinone compounds disclosed in U.S. Pat. Nos. 3,046,127 and 2,951,758; U.S. Pat. No. 3,549,367 Combinations of triallylimidazole dimer / p-aminophenyl ketone disclosed in JP-B-51-48516 and benzothiazole-based compounds / trihalomethyl-s- disclosed in JP-B-51-48516.
Triazine compounds.

The amount of the initiator used is based on the monomer solid content.
0.01% to 50% by weight, preferably 1% to 2% by weight
0% by weight. If the amount of the initiator is less than 0.01% by weight, the polymerization hardly proceeds, and if it exceeds 50% by weight, the polymerization rate increases but the molecular weight decreases and the film strength decreases.

In the composition of the present invention, various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent and the like may be added, if necessary. Can be blended.

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, the composition of the present invention may contain an organic carboxylic acid, preferably having a molecular weight of 1,000 or less. 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, mesitylene acid; 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.

In the present invention, a dispersant for improving the dispersibility of the pigment can be added, although not necessarily required.
As these dispersants, many types of dispersants are used. For example, phthalocyanine derivatives (commercially available EFK)
A-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, No.
Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo) and W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxy Nonionic surfactants such as ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafax F171, F172, F173 (Dainippon) Ink), Florado FC430, FC431
(Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC-
103, SC-104, SC-105, SC-1068
Fluorosurfactants such as (made by Asahi Glass); W004, W0
05, an anionic surfactant such as W017 (manufactured by Yusho);
EFKA-46, EFKA-47, EFKA-47E
A, 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 and Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 1200
0, 13240, 13940, 17000, 2000
And various Solsperse dispersants (manufactured by Zeneca Corporation) such as 0, 24000, 26000 and 28000; and other isonet S-20 (manufactured by Sanyo Chemical).

These dispersants may be used alone or in combination of two or more. Such a dispersant is usually used in the pigment dispersion in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the pigment. In addition to the above, the radiation-sensitive composition of the present invention preferably further contains a thermal polymerization inhibitor. 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.

As the solvent (D) used in preparing the composition of the present invention, esters such as ethyl acetate,
-N-butyl acetate, 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, oxy Butyl acetate, 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, 3
-Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2- Ethyl methoxypropionate,
Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2
Methyl-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-
Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate,

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, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons, for example, toluene, xylesi etc. Is mentioned.

Among 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.

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 radiation-sensitive composition layer, which is then exposed through a predetermined mask pattern, and developed. By developing with a liquid, a colored pattern is formed. The radiation used at this time
Particularly, ultraviolet rays such as g-line and i-line are 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. These substrates are generally formed with black stripes for isolating each pixel.

As the developer, any developer can be used as long as it dissolves the radiation-sensitive colored composition of the present invention and 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 , An alkaline compound such as choline, pyrrole, piperidine, 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.

[0116]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
Unless otherwise specified, parts are parts by weight and% is% by weight.

Example 1 100 parts of pigment (pigments described in Table 1: CI Pigment Red 254 and 224) 100 parts of benzyl methacrylate / methacrylic acid (70/30 molar ratio) 100 parts Weight average molecular weight; 30,000 cyclohexanone 140 parts-160 parts of propylene glycol monomethyl ether acetate was kneaded with a two-roll mill.

After the obtained kneaded material was pulverized, propylene glycol monomethyl ether acetate was added so that the pigment concentration became 15%, and Disperseid 163 (a pigment dispersant manufactured by BYK Chemie) as a pigment dispersant was added to the pigment for 20 minutes. % And dispersed with a bead mill (Dynomill: disperser manufactured by Shinmaru Enterprises). The particle size of the particles (pigment particles) in the dispersion was measured with a centrifugal transmission type particle size measuring device, CAPA-700 (Horiba, Ltd.) and found to be 0.09 μm on average. The following photosensitive coloring composition was prepared using the obtained dispersion, and was applied to a glass substrate for a color filter to a thickness of 1.1 μm. 2.5kW
100mj / cm2 through a mask using an ultra-high pressure mercury lamp
Irradiation at an exposure of. Development was carried out with a 0.3% aqueous sodium carbonate solution at 25 ° C. for 35 seconds. Further, post-baking was performed at 230 ° C. for 30 minutes.

Photosensitive coloring composition 300 parts of the above dispersion (pigment concentration 14%) 30 parts of pentaerythritol tetraacrylate 30 parts of 4- ｛o-bromo-pN, N-di (ethoxycarbonyl) 0.5 part Aminophenyl｝ 2,6-di (trichloromethyl) -S-triazine ・ Irgacure 907 0.5 part ・ Hydroquinone monomethyl ether 0.01 part ・ Propylene glycol monomethyl ether acetate 100 parts

The chromaticity, development latitude, image roughness, edge profile, and particle size were measured and evaluated as described below. (Evaluation Method and Evaluation Criteria) Chromaticity: Measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics). Y of CIE (International Commission on Illumination) XYZ system
Indication by xy value It shows that lightness is so large (bright) that Y value is large.・ Development latitude: a change in line width of 25 μm is measured, and a development time width that gives a line width variation of ± 10% is 40 seconds or more; ○ 30 to less than 40 seconds; Δ is less than 30 seconds;

Roughness of image: The roughness of the surface of the image portion was evaluated by SEM observation during the development time when the negative / positive line width of 25 μm was reproduced to 1/1. ；: No surface roughness observed ×: Surface roughness observed clearly △: Surface roughness observed slightly ・ Edge profile: SEM observation of 25 μm line width cross section ○: Forward taper ×; Reverse taper △ ; Vertical ・ Particle size: Centrifugal transmission type particle size analyzer (CAPA)
-700 HORIBA, Ltd.)

Comparative Example 1 As shown in Table 1, the C.I.
Pigment Red 254 as C.I. I. A photosensitive colored composition was prepared and evaluated in the same manner except that Pigment Red 177 (the following structure) was used.

[0123]

Embedded image

Examples 2 to 5 As shown in Table 1, the pigments used in Example 1 were C.I. I. Pigment Red 177 and various Y pigments (C.I.
I. Pigment Yellow 138, 150), except that a photosensitive composition was prepared in the same manner as in Example 1 and evaluated by the same method. As described above, the C.I. I. Pigment Yellow 138, 150 satisfies the light transmittance specified in the present invention. Table 2 shows the evaluation results.

Comparative Example 2 C.I. I. Pigment Red 224 is not used, and a C.I. that does not satisfy the light transmittance specified in the present invention as a Y pigment. I. Pigment Yellow 109 was used to prepare a photosensitive colored composition in the same manner as in Example 1, except that the dispersion was performed so that the particle size became 0.33 μm.
Evaluation was performed in the same manner. The evaluation results are shown in Table 2 below.

Comparative Example 3 A photosensitive coloring composition was prepared in the same manner as in Example 4, except that the pigment was dispersed so that the particle size became 0.42 μm, and evaluated by the same method. . The evaluation results are shown in Table 2 below.

Comparative Example 4 In Comparative Example 1, the Y pigment C.I. I. Pigment Yellow15
A photosensitive colored resin composition was prepared and evaluated in the same manner as in Comparative Example 1 except that 0 was used in combination. The evaluation results are shown in Table 2 below.

[0128]

[Table 1]

In Table 1, PR- represents C.I. I. Pigm
ent Red means PY- is C.I. I. Pigment Yellow.

[0130]

[Table 2]

From the results shown in Table 2, the following is clear. In Examples 1 to 5, the brightness is high, the development latitude is wide, the image roughness is small, the edge profile is forward tapered, and excellent performance is obtained. on the other hand,
C. I. Comparative Examples 1 and 4 without Pigment Red 254
Has a narrow developing latitude, a large image roughness, and a vertical to inverse tapered edge profile. C. I.
Pigment Red 254 is used, but no other red pigment is used, and C.I. which does not satisfy the light transmittance specified in the present invention. I. In Comparative Example 2 using Pigment Yellow 109, the chromaticity was satisfied, but the development latitude, image roughness, and edge profile were not satisfactory. P
Comparative Example 3 in which R-254 was not used and the particle size was out of the range of the present invention was similarly unsatisfactory.

The pigment PR-254 to be incorporated in the photosensitive coloring composition for a color filter of the present invention and C.I. I. The transmission spectrum of Pigment Red 177 is shown in FIG. P which is a pigment used in the present invention
R-254 has a high transmittance in the main transmission region of 600 to 610 nm and a high transmittance in the vicinity of 350 to 430 nm. Exposure required for polymerization is effective because unnecessary absorption of ultraviolet rays is small.

[0133]

According to the photosensitive color composition for a color filter of the present invention, a color filter having a high sensitivity, a high light transmittance, a high contrast, a high resolution, and a constant and excellent chromaticity can be obtained.

[Brief description of the drawings]

FIG. 1 shows the composition of C.I. I. Pigment
Red 254 and C.I. I. Pigment Red 1
Fig. 77 is a light transmission spectrum of a sample No. 77.

FIG. 2 shows light transmission spectra of various Y pigments.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Naoki Kato 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref. BB42 BB46

Claims (6)

[Claims] 1. A photosensitive color composition for a color filter comprising (A) a pigment, (B) a binder resin, (C) a radiation-sensitive compound, and (D) a solvent, wherein the (A) pigment comprises (A) A-1) CI Pigment Red 25
And (A-2) a photosensitive coloring composition for a color filter, which is a combination of at least one type of Red pigment other than CI Pigment Red 254. 2. The red pigment of the above (A-2) is a CI pigment.
Pigment Red 177 and / or CI Pigment Red 224
The photosensitive coloring composition for a color filter according to claim 1, wherein 3. The photosensitive coloring composition for a color filter containing (A) a pigment, (B) a binder resin, (C) a radiation-sensitive compound and (D) a solvent, wherein the (A) pigment is (A) A-1) CI Pigment Red 25
4, and (A-3) the light transmittance at 470 nm is 10
% Or less and a combination of Y pigments having a light transmittance at 535 nm of 80% or more. 4. A photosensitive coloring composition for a color filter comprising (A) a pigment, (B) a binder resin, (C) a radiation-sensitive compound and (D) a solvent, wherein the pigment (A) is (A) -1) CI Pigment Red 25
4, (A-2) at least one type of red pigment other than CI Pigment Red 254, and (A-3) a light transmittance at 470 nm of 10% or less and a light transmittance at 535 nm of 80% or more. A photosensitive coloring composition for a color filter, which is a combination of a certain Y pigment. 5. The red pigment according to (A-2), wherein the red pigment is CI.
Pigment Red 177 and / or CI Pigment Red 224
The photosensitive coloring composition for a color filter according to claim 4, wherein 6. The pigment (A) having an average particle size of 0.01
The photosensitive coloring composition for a color filter according to any one of claims 1 to 5, wherein the thickness is from 0.3 to 0.3 µm.