JP2000089024A - Photosensitive colored composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive colored composition having high sensitivity and giving a color filter having high transmittance, high contrast, high resolution and uniform superior chromaticity by using a reaction product of a specified polyisocyanate, a mixture of a monohydroxy compound a basic ring forming nitrogen, etc., and a specified compound as a pigment dispersant. SOLUTION: The photosensitive colored composition contains a pigment, a pigment dispersant a radiation sensitive compound and a solvent. The pigment includes a pigment of the formula having 0.01-0.2 μm average particle diameter. The pigment dispersant is a reaction product of (i) at least one polyisocyanate having an average valence of functional groups of 2-5, (ii) a mixture of a monohydroxy compound and a monohydroxymonocarboxylic acid or a monoaminomonocarboxylic acid and (iii) a compound having at least one basic ring forming nitrogen and a group capable of reacting with an isocyanato group or its salt In the formula, R1 and R2 may be the same or different and are each H, alkyl or the like and R3 and R4 may be the same or different and are each alkyl, cycloalkyl or the like.

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. About things.

[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. The dyeing method is a method of 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.

In the dyeing method, there is a problem in light resistance, heat resistance, moisture resistance, etc. due to the use of a dye. In addition, it is difficult to uniformly control the dyeing and fixing characteristics on a large screen, and color unevenness is likely to occur. In addition, there is a problem that the dyeing requires an anti-staining layer and the steps are complicated. In the electrodeposition method, a color filter is formed by forming a transparent electrode in a predetermined pattern in advance, ionizing a resin containing a pigment dissolved or dispersed in a solvent, and applying a voltage to form a colored image in a pattern. It is a method of manufacturing.

In the electrodeposition method, a photolithography process including a film formation and an etching process of a color filter forming transparent electrode is required in addition to a display transparent electrode. 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. 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
JP-A-184482 and JP-A-7-140654 disclose negative photosensitive compositions using a photopolymerizable monomer and a photopolymerization initiator as an alkali-soluble resin.

However, in recent years, there has been a demand for higher definition, lower power consumption and higher brightness of liquid crystal display devices, and further higher transmittance and higher contrast of color filters have been desired. I have. 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 high dispersion stability without pigment sedimentation, and the like. In order to achieve high transmittance of the color filter, there is a method of reducing the content of the pigment component in the photosensitive composition for the color filter or reducing the film thickness. Degrades and becomes whitish overall and loses color vividness.

Conventionally, as a red pigment, JP-A-1-254
As described in JP-A No. 918 and JP-A-2-153353, dianthraquinone pigments (such as CI Pigment Red 177) have been mainly used.
However, this pigment could not meet the above-mentioned demands in recent years, and the transmittance did not increase even if it was finely dispersed. Japanese Patent Application Laid-Open No. 8-6242 discloses a new method that does not require the dispersion of a pigment, which comprises forming an image of a pigment-dispersed pigment precursor, and then performing a chemical method, a thermal method, a photodecomposition method, or the like. (Latent Pigment) is disclosed. 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,
Depending on the heating temperature, a different color tone is produced. Therefore, the heat resistance is not sufficient, and it is not at a stage where it can be practically used.

[0010]

However, the above-mentioned prior art has not sufficiently responded to recent demands for color filters. The present inventors have proposed the above C.I.
I. Pigment Red 177 was used in place of Pigment Red 177, but C.I. I. Pigment Red 254 is difficult to miniaturize, so the resulting photosensitive composition has low transmittance and low contrast, and the photosensitive composition containing the above pigment has poor stability over time, and becomes gel-like over time. Phenomena, such as aggregation of the pigments, were inferior in light transmittance and contrast, and the performance and yield of the color filters were inferior due to the formed gel and the aggregated pigments.

It is an object of the present invention to provide a photosensitive coloring composition which can provide a color filter having high sensitivity, high transmittance, high contrast, high resolving power and a constant and excellent chromaticity. Another object of the present invention is to provide a photosensitive coloring composition for a color filter which has excellent pigment dispersibility over a long period of time and does not cause gelation or aggregation of the pigment.

[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 pigment dispersant, (C) a radiation-sensitive compound, and (D) a solvent, the pigment (A) is an average particle. The following general formula (I) having a diameter of 0.01 to 0.2 μm
And a pigment dispersant (B),
(I) at least one polyisocyanate having an average functionality of 2 to 5, (ii) a mixture of (b1) a monohydroxy compound and (b2) a monohydroxymonocarboxylic acid or a monoaminomonocarboxylic acid, and (iii) A) a photosensitive coloring composition for a color filter, which is a reaction product of at least one basic ring nitrogen and a compound having a group capable of reacting with an isocyanate group, or a salt thereof;

[0013]

Embedded image

In the formula (I), Y represents an oxygen atom or a sulfur atom. R ₁ and R ₂ may be the same or different,
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 alkoxycarbonyl group. R ₃ , R
₄ may be the same or different and represents an alkyl group, a cycloalkyl group, an aralkyl group, or a carbocyclic or heterocyclic aromatic residue. (2) The pigment (A) has an average particle diameter of 0.01 to 0.1.
The photosensitive coloring composition for a color filter according to the above (1), comprising a pigment represented by the following general formula (IA) having a size of 2 μm.

[0015]

Embedded image

In the formula (IA), R is a hydrogen atom, methyl
Group, ethyl group, propyl group, -N (CH _Three)_Two, -N
(C_TwoH_Five)_Two, -CF_Three, Chlorine atom or bromine atom
You.

The photosensitive coloring composition for a color filter of the present invention has the following advantages. (A) Since the use of the above-mentioned specific pigment has a higher transmittance to ultraviolet rays than conventional pigments (for example, the above-mentioned CI Pigment Red 177), unnecessary light by the pigment at the time of exposure by ultraviolet irradiation is used. High absorption efficiency without absorption,
High sensitivity can be obtained by using this in a photosensitive composition.
Therefore, the exposure time is short, and the productivity of the color filter is improved. In particular, the effect becomes remarkable as the size of the substrate becomes larger. (B) Good developability. That is, the change in the image (roughness of the image, change in line width, etc.) obtained by the development conditions such as the development time, the development temperature, and the developer concentration is small (the development latitude is wide). (C) 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. (D) As described above, the pigment represented by the general formula (I) in the present invention has a high transmittance of ultraviolet rays, so that the pigment concentration in the composition can be increased. Thereby, a color filter with high color purity can be obtained. Conventionally, if the pigment concentration is increased, the difference between the exposed part and the unexposed part hardly appears,
I cannot make a satisfactory pattern. (E) Since the composition of the present invention contains a specific pigment dispersant, the dispersibility of the pigment in the composition is good, that is, the pigment can be finely dispersed without much energy or time. The dispersed pigment has good dispersion stability over a long period of time without agglomeration or sedimentation over time.

(F) Since the pigment is finely dispersed as described above, the transmittance of light is high, and scattering by coarse particles is small. Thereby, higher sensitivity is obtained, and the obtained color filter has high resolution and high contrast. In addition, since a stable pigment is used as compared with the above-mentioned latent pigment, a color filter having a constant and excellent chromaticity can be obtained.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) Pigment In the present invention, a pigment represented by the general formula (I) is used as a pigment, and the pigment has an average particle size of 0.01 to 0.2.
μm. In the formula (I), R ₁ ,
The alkyl group for R ₂ , R ₃ and R ₄ may be branched or unbranched.
And more preferably 1 to 12, particularly preferably 1 to 6 carbon atoms. Specific examples include a methyl, ethyl, isopropyl, secondary butyl, tertiary butyl, 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.

As the aryl group for R ₁ and R ₂ ,
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.

In the formula (I), R ₁ , R ₂ , R ₃ and R
_{When 4} represents an aralkyl group, it preferably contains a monocyclic to tricyclic, more preferably a monocyclic or bicyclic aryl residue. Specific examples include benzyl and phenylethyl. In the formula (I), R
_{If 3} and R ₄ represent carbocyclic aromatic residues, preference is given to monocyclic to tetracyclic, especially monocyclic or bicyclic residues, ie phenyl, diphenylyl or naphthyl. Specifically, the following formula,

[0023]

Embedded image

(Wherein T ₁ , T ₂ , and T ₃ have different positions, and each independently represents hydrogen, halogen, carbamoyl, cyano, trifluoromethyl, alkylcarbamoyl having 2 to 13 carbon atoms, 1 to 12 carbon atoms) Alkyl, 1 carbon
~ 12 alkoxy, alkyl mercapto having 1 to 12 carbons, alkoxycarbonyl having 2 to 13 carbons,
Alkanoylamino having 2 to 13 carbon atoms, 1 to 1 carbon atoms
Phenoxy, phenylmercapto, phenoxy substituted by two monoalkylamino, dialkylamino having 2 to 24 carbon atoms, unsubstituted or substituted by halogen, alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons Represents carbonyl, phenylcarbamoyl or benzoylamino. ) Or the following formula:

[0025]

Embedded image

(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:

[0027]

Embedded image

(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 formula (I), when R ₃ and R ₄ represent a heterocyclic aromatic residue, a monocyclic to tricyclic one is preferred. These may be purely heterocyclic,
It may also contain one heterocycle and one or more fused benzene rings, specifically, for example, pyridyl,
Examples include pyrimidyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, coumarinyl, benzofuranyl, benzimidazolyl or benzoxazolyl. Regardless of whether it is a carbocyclic aromatic residue or a heterocyclic aromatic residue, for example, European Patent Application No. 94
It may also represent a conventional water-insoluble solubilizing substituent as described in 911.

In the general formula (I), 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.

In the present invention, the pigment is represented by the general formula (I)
The pigments represented by A) are preferred. Among them, R is more preferably a hydrogen atom, a chlorine atom, a bromine atom or a methyl group, and particularly preferably, R is a chlorine atom. The pigment represented by the general formula (I) is described, for example, in US Pat.
5,685, EP-A-133,156.
Or the method described in JP-A-61-120861.

The pigment represented by the general formula (I) can be used alone or in combination with another pigment for adjusting chromaticity. Specific examples are shown below. Examples of the pigment that can be used in combination include various yellow pigments and red pigments. Examples of the yellow pigment include C.I. I. Pigment Yellow 11, 24,
31, 53, 83, 93, 99, 109, 110, 11
7, 129, 138, 139, 150, 151, 16
7, 185. Examples of the red pigment include C.I. I. Pigment Red 105, 122, 1
49, 150, 155, 171, 175, 177, 20
9, 224 and 255. The amount of the pigment that can be used in combination is preferably 200 parts by weight or less, more preferably 10 parts by weight, based on 100 parts by weight of the pigment according to the present invention.
0 parts by weight or less.

In the present invention, the pigment represented by the general formula (I) has an average particle size of 0.01 to 0.2 μm.
And preferably 0.01 to 0.15 μm, more preferably 0.01 to 0.1 μm.

After the above pigment is synthesized, it is supplied after being dried 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 usually forms an aggregate (secondary particle) in which the 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 of mixing an aqueous dispersion of a pigment and a resin solution dissolved in a water-immiscible solvent, extracting the pigment from an aqueous medium into an organic medium, and treating the pigment with a 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 required 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, and then kneaded using two or two rolls, if necessary, 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 obtained colored body, and if necessary, a dispersant and various additives are added. Dispersion is performed using a ball mill or various sand mills using glass beads as a dispersion media, 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) and provided as a photosensitive composition.

The concentration of the pigment in all the solid components of the photosensitive coloring composition is preferably from 5% by weight 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. Preferably it is from 10% by weight to 60% by weight.

Next, the pigment dispersant (B) blended in the photosensitive coloring composition for a color filter of the present invention will be described. In the present invention, as the pigment dispersant (B), (i)
At least one polyisocyanate having an average functionality of 2 to 5, (ii) a monohydroxy compound (b1) and (b2)
A mixture with a monohydroxymonocarboxylic acid or a monoaminomonocarboxylic acid, and (iii) a reaction product of at least one basic ring nitrogen with a compound having a group capable of reacting with an isocyanate group or a salt thereof is used. .

The average functionality of the polyisocyanate (i) is 2 to 5 as described above. Suitable polyisocyanates are, for example, Desmodur L (trade name) obtained by adding a diisocyanate to a polyol,

[0044]

Embedded image

Death module N (trade name) obtained by the burette reaction,

[0046]

Embedded image

Polyisocyanates having an isocyanurate structure obtained by cyclization of diisocyanate, Desmodur HL (trade name)

[0048]

Embedded image

Death module L (trade name),

[0050]

Embedded image

Poruren KC (trade name),

[0052]

Embedded image

Poruren HR (trade name)

[0054]

Embedded image

Toluylene diisocyanate-isoboron diisocyanate cyanurate

[0056]

Embedded image

Trimeric isophorone diisocyanate (Isocyanurate T from Hemische Welkehus)
1890)

[0058]

Embedded image

And the like.

As already mentioned, these compounds do not have the above formula in pure form, but are commercially available as a mixture of several compounds of similar structure. here,
The average functionality is for isocyanate groups and these commercial products have an average functionality of 2. It is in the range of O-5.

(B1) contained in the mixture of (ii) above
Aliphatic and / or alicyclic hydrocarbons which may contain at least one ether group and / or ester group substituted or unsubstituted with aryl and / or halogen as the monohydroxy compound Monohydroxy compounds can be mentioned. (B1) The monohydroxy compound preferably has a molecular weight of at least 500, particularly preferably 750 to 3500. By using a compound having a molecular weight in this range, a pigment dispersant having excellent dispersibility can be obtained.

(B1) It is preferable that the monohydroxy compound has no substituent other than the hydroxy group which reacts with the isocyanate under the conditions for producing the dispersant.

As the monohydroxy compound (b1), a linear or branched aliphatic compound or an alaliphatic compound may be used, and may be a saturated or unsaturated compound, but a saturated compound is particularly preferable. A part of the hydrogen atoms may be substituted with a halogen, preferably a fluorine atom and / or a chlorine atom. When such a substituted compound is used, it is preferably an aliphatic monoalcohol.
Such products are commercially available and usually do not have a halogen atom attached to the carbon atom close to the hydroxyl group. Specific examples of the fluorinated alcohol include C ₆ F ₁₃ CH ₂ CH ₂
Heptadecafluorodecanol having the structure of OH is mentioned. A commercially available counterpart is a mixture of various fluorinated compounds.

Typical examples of the (b1) monohydroxy compound containing at least one ether group and / or ester group include polyether, polyester and polyether-polyester.
As a specific example of the polyester, a monohydroxy compound having no ester group is used as a starting material, and a lactone such as propiolactone, valerolactone, caprolactone, or a product obtained by polymerizing a ring-opening polymerizable substituted derivative thereof is used. Can be mentioned. Starting materials that can be used include C4-30, preferably C4-14 alkyl monoalcohols, cycloalkyl monoalcohols, phenols such as n-butanol,
Phenol; a relatively long-chain saturated or unsaturated alcohol such as propargyl alcohol, oleyl alcohol, linoleoyl alcohol, oxo alcohol, cyclohexanol, phenylethanol, neopentyl alcohol; and the above-mentioned fluorinated alcohols.

As a specific example of the above-mentioned polyether, there is known a known method in which an alkylene oxide such as ethylene oxide or propylene oxide is addition-polymerized to a starting material of the above-mentioned polyester, that is, to a monoalcohol having 4 to 30 carbon atoms, preferably 4 to 14 carbon atoms. It can be obtained by a method. Specifically, polyoxyalkylene monoalkyl ether,
Examples include polyoxyalkylene monoaryl ether, polyoxyalkylene monoaralkyl ether, and polyoxyalkylene monocycloalkyl ether. Furthermore, these monohydroxy polyethers can be used as starting components for lactone polymerization. In this case, the product is a polyether-polyester.

The molecular weight of these polyesters, polyethers and polyether-polyesters is preferably 300
8000, more preferably 500-5000.

The mixture (ii) further contains (b2) a monohydroxymonocarboxylic acid compound or a monoaminemonocarboxylic acid. The monohydroxymonocarboxylic acid compound in the above (b2) preferably has a carbon chain consisting of at least 8 carbon atoms between the hydroxy group and the carboxylic acid group. Optionally the carbon chain, amides, Koichi ether, ester, may be interrupted by S, S0 ₂ and / or urethane groups. In order to improve the compatibility between the dispersant and other substances, the molecular weight of the monohydroxymonocarboxylic acid compound is at least 500 or more, especially 750 to 4
000 is preferred.

Suitable monohydroxymonocarboxylic acid compounds are obtained by reacting a diol with a dicarboxylic acid or an acid anhydride. For example, it can be obtained by reacting a high molecular weight diol such as polyethylene glycol with a low molecular weight dicarboxylic acid or dicarboxylic anhydride. It can also be obtained by reacting a high molecular weight dicarboxylic acid with a low molecular weight diol. Alternatively, a low-molecular-weight diol and a low-molecular-weight dicarboxylic acid are used in almost stoichiometric proportions, and the reaction is carried out under such conditions that as much as possible monohydroxymonocarboxylic acid is formed and the dihydroxy compound is not substantially formed. Thus, a monohydroxymonocarboxylic acid compound can be obtained. Among them, it is preferable to use a monohydroxymonocarboxylic acid compound obtained by reacting a low molecular weight dicarboxylic acid with a high molecular weight diol such as polyethylene glycol.

As the monoamine monocarboxylic acid in (b2), the above description can be applied by replacing all or a part of the hydroxyl group of the above monohydroxymonocarboxylic acid with an amino group. That is, the same idea as for monohydroxymonocarboxylic acid can be applied to monoaminocarboxylic acid.

The ratio of the amount of the hydroxyl group contained in the monohydroxy compound to the amount of the hydroxyl group contained in the monohydroxymonocarboxylic acid compound is preferably such that the amount of the monohydroxymonocarboxylic acid compound is smaller than that of the (b1) monohydroxy compound. is there. The ratio of the number of hydroxyl groups derived from both compounds (monohydroxy monocarboxylic acid compound / (b1) monohydroxy compound) is preferably 1/1 to 10/1,
More preferably, it is 2/1 to 5/1. When a monoamine monocarboxylic acid is used, the ratio of the number of hydroxyl groups to the number of amino groups (hydroxyl group / amino group) of the (b1) monohydroxy compound is preferably 1/1 to 10/1, more preferably 2/1 to 1/1. 5/1.

(Iii) Specific examples of preferred compounds having a group capable of reacting with an isocyanate group and containing a basic ring nitrogen include N, N-diethyl-1,4-butanediamine,
1- (2-aminoethyl) -piperazine, 2- (1-pyrrolidyl) -ethylamine, 4-amino-2-methoxy-pyrimidine, 2-dimethylaminoethanol, 1-
(2-hydroxyethyl) -piperazine, 4- (2-hydroxyethyl) -morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, N, N-dimethyl-1,3-propanediamine, 4- (2-amino Ethyl) -pyridine, 2-amino-6-methoxybenzothiazole, 4-aminoethyl) -pyridine, N, N-
Diallyl-melamine, 3-amino-1,2,4-triazole, 1- (3-aminopropyl) -imidazole,
4- (2-hydroxyethyl) -pyridine, 1- (2-
(Hydroxyethyl) -imidazole, 3-mercapto-
1,2,4-triazole and the like can be mentioned,
Not limited to these. Particularly preferred are N,
N-dimethyl-1,3-propanediamine, 4- (2-
Aminoethyl) -pyridine, 2-amino-6-methoxybenzothiazole, 4-aminoethyl) -pyridine,
N, N-diallyl-melamine, 3-amino-1,2,4
-Triazole, 1- (3-aminopropyl) -imidazole, 4- (2-hydroxyethyl) -pyridine, 1
-(2-hydroxyethyl) -imidazole, 3-mercapto-1,2,4-triazole and the like can be mentioned.

The characteristics of these compounds are that they contain at least one Zerewitinoff hydrogen atom per molecule, which preferably reacts with isocyanate groups, and that they further react with isocyanate groups to form urea-bonded nitrogen. To have a basic group containing atoms. Such a basic group can also be specified by a pKa value (U.S. Pat. Nos. 3,817,944 and 4,034).
2,698 and 4,070,388). pKa
Compounds having a basic group having a value of 2 to 14, especially a pKa value of 5 to 14 are preferable, and a pKa value of 5 to 14 is most preferable.
It is a compound having 12 basic groups. The pKa value can be determined from the table. Further, the pKa value at 25 ° C. can be measured with a 0.01 molar concentration aqueous solution.
Such a basic group imparts basicity to the reaction product. The reaction product can be converted into a salt due to the basic group. In the present invention, this salt can be used as the pigment dispersant (B).

The above-mentioned salt can be obtained by a method of neutralizing the obtained reaction product with an organic or inorganic acid or a method of quaternization. Salts neutralized with organic monocarboxylic acids are preferred.

In preparing the pigment dispersant (B) of the present invention, a small amount of a dihydroxy compound can be used. However, the amount is small enough to react less than 5%, preferably less than 2.5% of the isocyanate groups.

The above reactions (i), (ii) and (iii) can be carried out by known methods. Generally, the first
Preferably, the step is carried out so that (i) the polyisocyanate reacts with (ii) a mixture of the (b1) monohydroxy compound and the (b2) monohydroxymonocarboxylic acid or monoaminomonocarboxylic acid. The above reaction is usually carried out in an appropriate solvent, for example, a hydrocarbon solvent such as xylene, an ether solvent such as dioxane, an ester solvent such as butyl acetate, or a dimethylformamide solvent in dibutyltin dilaurate, iron acetylacetonate or triacetate. The reaction is performed in the presence or absence of a catalyst such as ethylenediamine. It is also possible to react (i) the polyisocyanate with the (b1) monohydroxy compound first, and further react the resulting product with the (b2) carboxylic acid compound.

After this reaction (generally about 40-80% of the isocyanate groups have been reacted), it is reacted with (iii) a compound having a basic ring nitrogen. In this second stage reaction, 20-60% of the isocyanate groups are reacted. The unreacted isocyanate groups are finally deactivated by reaction with a lower alcohol (particularly preferably butanol is preferably used) or another corresponding compound to obtain (B) a pigment dispersant.

The pigment dispersant (B) 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.

Although not necessary in the present invention, a pigment dispersant other than the above (B) pigment dispersant can be added within a range not to impair the achievement of the object of the present invention. As these dispersants, many types of dispersants are used. For example, phthalocyanine derivatives (commercially available EFKA-
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. 95
(Kyoeisha Yushi Kagaku Kogyo), cationic surfactants such as W001 (Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Nonionic surfactants such as nonylphenyl 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) Manufactured), 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).

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.

[0081]

Embedded image

(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 . )

Any of these radiation-polymerizable monomers or oligomers may be used as long as the composition of the present invention can be irradiated with radiation to form a coating film having adhesiveness, as long as the object and effect 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 compound (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.

[0085]

Embedded image

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.

[0087]

Embedded image

Here, Q represents Br and Cl, and P represents -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-.

[0089]

Embedded image

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.

[0091]

Embedded image

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.

[0093]

Embedded image

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.

[0096]

Embedded image

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-p-N, 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.

[0105]

Embedded image

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

[0107]

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

[0110]

Embedded image

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,

[0112]

Embedded image

The groups represented by are shown below. m is an integer of 1 to 3,
n shows the integer of 1-4.

[0114]

Embedded image

In the formula (J), n is 1 or 2, and Ar is₁
Is a phenyl group, a chlorine atom, a bromine atom,
Droxy group, -SR⁹, -R^Ten, -OR^Ten, -SR^Ten,
-SO_TwoR^Ten, -S-phenyl, -O-phenyl or
Represents a phenyl group substituted with a morpholino group (R^Ten
Represents an alkyl group having 1 to 9 carbon atoms), Ar₁
Is a phenylene-T-phenylene group (T is
-O-, -S- or -CH_TwoRepresents-).
R ⁹Is a hydrogen atom and the number of carbon atoms which may be substituted
An alkyl group having 1 to 12 carbon atoms, an alkyl group having 3 to 6 carbon atoms,
Lucenyl group, cyclohexyl group, phenylalkyl group,
Phenylhydroxyalkyl group, even if it has a substituent
Good phenyl, tolyl, --CH_Two-CH_TwoOH,-
CH_TwoCH_Two-OOC-CH = CH_Two, -CH_Two-CO
OR¹¹(R¹¹Represents an alkyl group having 1 to 9 carbon atoms.
), -CH _TwoCH_Two-COOR¹²(R¹²Is the number of carbon atoms
Represents 1 to 4 alkyl groups),

[0116]

Embedded image

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 photosensitive coloring composition 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, Japanese Patent Application Laid-Open No. 59-44
No. 615, JP-B-54-34327, JP-B-58-1
2577, JP-B-54-25957, JP-A-59-59
No. 53836, JP-A-59-71048, a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a part thereof. There are esterified maleic acid copolymers and the like, as well as acidic cellulose derivatives having a carboxylic acid in the 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) acrylate / (meth)
Acrylic acid copolymer or benzyl (meth) acrylate /
Multicomponent copolymers with (meth) acrylic acid / and other monomers are preferred. In addition, as a water-soluble polymer, 2-
Hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful. 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 described in JP-A-7-140654 Methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Polymers.

As the binder resin and the pigment dispersant, the following graft copolymers described in Japanese Patent Application No. 9-61457 may be used within a range not to impair the achievement of the object of the present invention. Can be. 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). A monofunctional macromonomer having a weight average molecular weight of 3 × 10 ⁴ or less formed by bonding a heavy bond group, a monomer quaternary ammonium salt monomer represented by the following general formula (III), and a monomer represented by the following general formula (IV) And a monomer having at least one unsubstituted or substituted acid amide group in the molecule.

[0123]

Embedded image

[In the formula (A), V ₀ is -COO-, -OC
_{O -, - CH 2 OCO -} , - CH 2 COO -, - O-,
-SO _2- , -CO-, -CONHCOO-, -CON
_{HCONH -, - 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 hydrocarbon group which may be substituted). ]

[0125]

Embedded image

[In the formula (IIa) or (IIb), V ₁ has the same meaning as V ₀ in the formula (A). Q ₁ has 1 to 18 carbon atoms
Represents an aliphatic group 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 represents -CN or -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).]

[0127]

Embedded image

[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). ]

[0129]

Embedded image

[0130] wherein (IV), R _1, R ₂ may be the same or different, each represent a hydrogen atom or a number from 1 to 18 amino optionally substituted hydrocarbon group having a carbon and R ₁ and R ₂ is −
O -, - S -, - NR 3 - ( wherein R ₃ represents a hydrogen atom or a number 1-12 hydrocarbon group having a carbon) may be bonded to each other to form a ring through. ]

Further, as a binder resin, JP-A-10-20
The following polymer described in JP-A-496 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.

[0132]

Embedded image

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 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.

In the composition of the present invention, various additives such as fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anticoagulants 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 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,
-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, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons, such as toluene, xylesi etc. Is mentioned.

Among them, 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, etc. to form a radiation-sensitive composition layer, which is 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.

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 part. 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.

Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and 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.

[0147]

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 it exceeds the gist of the invention. Unless otherwise specified, parts are parts by weight and% is% by weight.

Synthesis Example 1 (Synthesis of caprolactone polyester) 31.92 g of caprolactone, 10.40 g of HD-
Osenol 45/50 (Henkel & Qi, Düsseldorf) is dispersed under an inert gas, 0.0012 g
Of dibutyltin dilaurate was added, and the mixture was heated and stirred at 170 ° C. and reacted for about 8 hours until the solid content became 99%. The product was solid and somewhat yellowish at room temperature.

Synthesis Example 2 (Synthesis of monohydroxy polyether) Polyethylene glycol 60.0 having an average molecular weight of 1000
g was melted under inert gas, and 17.10 g of tetrachlorophthalic anhydride was added with stirring and heated to 150 ° C.
The reaction was stopped when the acid value reached 43.6 (after about 4 hours). The product was waxy and milky at room temperature.

Synthesis Example 3 (Synthesis of monohydroxymonocarboxylic acid) 75.0 polyethylene glycol having an average molecular weight of 1,000
When 0 g was melted under nitrogen introduction and the polyethylene glycol became liquid, 11.10 g of phthalic anhydride was added, and the mixture was heated to 150 ° C. and stirred. The reaction was stopped when the acid value reached 48.87, and a wax-like product was obtained at room temperature.

Synthesis Example 4 (Synthesis of fluorinated monohydroxymonocarboxylic acid) 394 g of pentahydro-perfluorononanediol was melted, and 266.30 g of dodecenyl succinic anhydride was added under an inert gas. Stir until heated. The reaction was stopped when the acid value reached 96 mgKOH / g, and a yellow resin was obtained. This was used as a 70% solution of methoxypropyl acetate.

Synthesis Example 5 (Synthesis of pigment dispersant) Caprolactone polyester 41.06 obtained in Synthesis Example 1
g and Desmodur 1L 63.00 g (51% butyl acetate solution) were dissolved in a mixed solvent of butyl acetate 42.48 g and methoxypropyl acetate 40.99 g while introducing an inert gas while stirring. Next, 12.05 g of the monohydroxycarboxylic acid obtained in Synthesis Example 3 was added, and the mixture was heated to 70 ° C. After 2 hours, an addition reaction occurred, which was confirmed by the NC0 content. 2-amino-4-
32.44 g of a 20% MNP solution of methylpyridine was added, and the mixture was stirred for 1 hour. Thereafter, n-butanol was added to react with unreacted NCO. A viscous yellow product (pigment dispersant) with a solids content of 39.54% was obtained.

Synthesis Example 6 (Synthesis of Pigment Dispersant) Caprolactone polyester obtained in Synthesis Example 1
27 g and 12.00 L of Desmodur (51% butyl acetate solution) were dissolved in 30.62 g of butyl acetate and 36.02 g of methoxypropyl acetate under a nitrogen stream under stirring. Next, 7.68 g of the monohydroxycarboxylic acid obtained in Synthesis Example 2 was added, and the mixture was heated to 70 ° C. After about 2 hours (after completion of the addition reaction), 3-amino-
16.67% NMP solution of 1,2,4-triazole 1
5.11 g was added, and the mixture was further stirred for 1 hour. Then the excess n
-Butanol was added to react with unreacted NCO. The product (pigment dispersant) had a moderate viscosity and was pale yellow.

Synthesis Example 7 (Synthesis of Pigment Dispersant) Caprolactone polyester 4.4 obtained in Synthesis Example 1
2 g and 8.40 g of Desmodur 1L (51% butyl acetate solution) were dissolved in 6.12 g of butyl acetate and 7.20 g of methoxypropyl acetate under a nitrogen stream and stirring. Next, 1.71 g of the monohydroxycarboxylic acid obtained in Synthesis Example 2 was added, and the mixture was heated to 70 ° C. The reaction was allowed to react for 2 hours, resulting in addition. This was confirmed by the NCO content. 1
A mixture of 0.75 g of-(3-aminopropyl) -imidazole and 2.95 g of N-methylpyrrolidone was added, and the mixture was further stirred for 1 hour. Next, excess n-butanol was added to react with unreacted NCO. The product (pigment dispersant) was a pale yellow viscous liquid.

Synthesis 8 (Synthesis of Pigment Dispersant) In a reactor, 25.39 g of the caprolactone polyester obtained in Synthesis Example 1 and 42.00 g of Desmodur 1 L (51% butyl acetate solution) were mixed with butyl acetate 3
8.31 g and 33.32 g of methoxypropyl acetate
Was dissolved under a nitrogen stream and stirring. Next, 6.58 g of the monohydroxycarboxylic acid obtained in Synthesis Example 2 and 1.89 g of the monohydroxycarboxylic acid solution obtained in Synthesis Example 4 were added, and the mixture was heated to 70 ° C. The reaction was allowed to react for 2 hours, resulting in addition. This was confirmed by the NCO content. Butyl acetate 1
4.10 g and 14.10 g of methoxypropyl acetate
Was added thereto, and 21.94 g of a 22.79% NMP solution of 1- (3-aminopropyl) -imidazole was added thereto, followed by further stirring for 1 hour. Next, excess n-butanol was added to react with unreacted NCO. A straw yellow, viscous product (pigment dispersant) was obtained.

Example 1 100 parts of red pigment (pigment of the present invention *) 100 parts of pigment dispersant prepared in Synthesis Example 5 140 parts of cyclohexanone 160 parts of propylene glycol monomethyl ether acetate 160 parts of * In the above general formula (IA), all R's each represent a chlorine atom, which is hereinafter referred to as (IA-1).

After the obtained kneaded material was pulverized, propylene glycol monomethyl ether acetate was added so that the pigment concentration became 15%, and Disperseide 163 (a pigment dispersant manufactured by BYK Chemie) was added to the pigment as a pigment dispersant. % And dispersed by a bead mill (Dynomill: disperser manufactured by Shinmaru Enterprises) for 120 minutes.
The particle size is measured using a centrifugal transmission particle size analyzer, CAPA-7.
0.07μ on average when measured with 00 (Horiba Seisakusho)
m. The following composition was prepared using the obtained dispersion, and applied to a glass substrate for a color filter to a thickness of 1.2 μm. Irradiation was carried out at an exposure of 100 mj / cm ² through a mask using a 2.5 kW ultra-high pressure mercury lamp. 0.25%
And developed at 25 ° C. for 40 seconds. 2
After post-baking at 30 ° C for 30 minutes, colorimeter MCPD
The chromaticity was measured with -1000 (manufactured by Otsuka Electronics).

• 300 parts of the above dispersion (pigment concentration: 14 wt%) • 30 parts of pentaerythritol tetraacrylate • 0.5 parts of 4- {o-bromo-pN, N-di (ethoxycarbonyl) 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 evaluated as follows. (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: when a change in line width of 25 μm is measured and the 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 the image: The roughness of the surface of the image area was evaluated by SEM observation during the development time at which the negative / positive line width of 25 μm was reproduced to 1/1. S: Observation of surface roughness X: Surface roughness Is clearly observed △: Surface roughness is slightly observed ・ Edge profile: SEM observation of a 25 μm line width cross section ○; Forward taper ×; Reverse taper △; Vertical ・ Particle size: Centrifugal transmission type particle size measurement Machine (CAPA
-700 HORIBA, Ltd.)

Comparative Example 1 A photosensitive composition was prepared and evaluated in the same manner as in Example 1, except that no pigment dispersant was used. The results are shown in Table 1.

Examples 2 to 4 The pigment dispersants used in Example 1 were used in Synthesis Example 6 and
Example 1 was repeated except that the pigment dispersant synthesized in Examples 7 and 8 was used.
A photosensitive composition was prepared and evaluated in the same manner as described above. The results are shown in Table 1.

[0163]

[Table 1]

From the results shown in Table 1, the photosensitive compositions of Examples 1 to 4 had a fine particle size, a high brightness, a wide development latitude, a small image roughness, and a forward tapered edge profile. Comparative Example 1, which does not use a pigment dispersant, has a large particle size and is inferior in the above performance. In addition, the photosensitive compositions of Examples 1 to 4 hardly observed precipitation or aggregation of the pigment even when left at room temperature for one month. However, in the case of Comparative Example 1, it was in a gel state.

[0165]

The photosensitive color composition for a color filter of the present invention has high sensitivity, and the obtained color filter has high transmittance, contrast and resolution, and has a constant and excellent chromaticity. In addition, the pigment has excellent dispersibility over a long period, and there is no gelation or aggregation of the pigment.

Claims (2)

[Claims] 1. A pigment (A), a pigment dispersant (B), (C)
In the photosensitive coloring composition for a color filter containing a radiation-sensitive compound and a solvent (D), the pigment (A) has an average particle size of 0.01 to 0.2.
The pigment dispersant (B) contains a pigment represented by the following general formula (I) having an average functionality of 2 to 5:
At least one of the polyisocyanates of (ii) (b
1) a mixture of a monohydroxy compound and (b2) a monohydroxymonocarboxylic acid or a monoaminomonocarboxylic acid, and (iii) at least one basic ring nitrogen.
A photosensitive coloring composition for a color filter, which is a reaction product with a compound having a group capable of reacting with an isocyanate group or a salt thereof. Embedded image In the formula (I), 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 , R
₄ may be the same or different and represents an alkyl group, a cycloalkyl group, an aralkyl group, or a carbocyclic or heterocyclic aromatic residue. 2. The pigment (A) having an average particle size of
In the following general formula (IA) which is 0.01 μm to 0.2 μm,
A pigment according to claim 1, comprising a pigment represented by the formula:
A photosensitive coloring composition for color filters. Embedded imageIn the formula (IA), R represents a hydrogen atom, a methyl group, an ethyl group,
Propyl group, -N (CH _Three)_Two, -N (C_TwoH_Five)_Two,
-CF_Three, A chlorine atom or a bromine atom.