JPH09146272A - Radiatopm sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation sensitive compsn. capable of dispersing fine particles and having improved dispersion stability of a pigment by incorporating a specified copolymer, a radiation sensitive compd. and a pigment. SOLUTION: This compsn. contains a copolymer having a wt. average mol.wt. of 5×10<4> -1×10<6> , a radiation sensitive compd. and a pigment. The copolymer consists of a monofunctional macromonomer having a wt. average mol.wt. of <=2×10<4> obtd. by bonding a polymerizable double bond group represented by formula III to only one terminal of the principal chain of a polymer contg. at least one of polymer components represented by formulae I, II and at least one polymer component having an acidic group such as -COOH or -PO3 H and a monomer represented by formula IV. In the formulae, each of X0 -X2 is -COO-, -OCO-, etc., Q0 is -CN, -CONH2 , etc., each of Q1 and Q2 is a 1-18C aliphatic group or a 6-12C arom. group and each of c1 , c2 d1 , d2 , e1 and e2 is H, halogen, cyano, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive composition in which a pigment suitable for producing a color filter used for a liquid crystal display device or a solid-state image pickup device is dispersed, and more specifically, it has a pigment dispersibility. The present invention relates to a radiation-sensitive composition capable of producing a good color filter having excellent coating properties.

[0002]

2. Description of the Related Art As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method,
Printing, electrodeposition and pigment dispersion methods are known. 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.

[0003] In the dyeing method, since a dye is used, there are problems in light resistance, heat resistance, moisture resistance, etc. 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.

[0004] 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 of 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 curing resin. However, there is a problem in that defects are likely to occur due to dust, foreign matters, and gelled portions 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.

Japanese Patent Application Laid-Open No. 60-237403 discloses a photosensitive polyimide resin in which a pigment is dispersed. In the case of a polyimide resin, when the thickness exceeds 1.0 μm, absorption occurs in a visible light region to cause color reproduction. Cause problems in sex.
If the dispersibility of the pigment is insufficient, the color filter produced by the pigment dispersion method causes a problem in color purity and dimensional accuracy, and the display contrast ratio is significantly deteriorated due to depolarization. Further, the radiation-sensitive composition in which the pigment is dispersed causes agglomeration over time, which causes problems in coating properties and causes the above-mentioned problems in the color filter.

As means for improving the dispersibility of the pigment, JP-A-1-102429 discloses a method using a processed pigment obtained by treating a pigment with an acrylic resin, a maleic resin, a vinyl chloride-vinyl acetate resin, and the like. And JP-A-2-199403 disclose a method using an organic dye derivative as a dispersant, but this method is not sufficient.

Although a dispersion method using a surfactant is also known, this method has problems such as a reaction between the surfactant and a pigment or a resin, and precipitation of the surfactant during use of a color filter. is there. Japanese Patent Application Laid-Open No. 4-76062 discloses a pigment dispersion method using a combination of an ionic surfactant and an ionic resin having the same polarity. However, in fact, satisfactory results have not been obtained.

Japanese Patent Publication No. 4-39041 discloses a method for producing a color filter using a pigment of a specific size. However, the pigment is centrifuged to obtain pigment particles of a specific size, and then filtered through a glass filter or a membrane filter. ing. According to this method, particles having a target particle size can be obtained, but the process is complicated and the efficiency is poor. JP 7
JP-A-140654 proposes a radiation-sensitive composition containing a resin composed of an alkali-soluble monomer, a monomer having an alcoholic hydroxyl group and a macromonomer of styrene or methyl methacrylate, but the dispersibility of the pigment by the resin is satisfactory. I couldn't do it.

In order to produce a color filter,
A radiation-sensitive composition is applied onto a glass substrate by a spin coater, a roll coater or the like, dried to form a coating film, exposed and developed to obtain colored pixels, and this operation is performed for each color to obtain a color filter. . Pixels formed by the conventional radiation-sensitive composition are liable to peel off from the substrate during development or washing with water to cause defects in the color filter. On the other hand, when the adhesion of the pixels is improved, the solubility of the non-image area is reduced during development, There is a problem that the image area is easily stained.

[0012]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and an object thereof is to provide a novel radiation-sensitive composition having a pigment dispersed therein. . Another object of the present invention is to provide a radiation-sensitive composition capable of dispersing fine particles and having improved pigment dispersion stability.

Still another object of the present invention is a feeling that a color filter having excellent coating properties, hardly causing background stain after development, excellent adhesion of formed pixels and good pattern reproducibility can be prepared. It is to provide a radioactive composition.

[0014]

[Means for Solving the Problems] A radiation-sensitive composition containing the following (A) copolymer, (B) radiation-sensitive compound and (C) pigment.
(A) copolymer; at least one of the polymer components represented by the following general formulas (Ia) and (Ib),

[0015]

Embedded image

A component containing at least one acidic group selected from the group {R ₀ represents a hydrocarbon group or a --OR ₀ 'group (R ₀ ' represents a hydrocarbon group)} group and a cyclic acid anhydride-containing group. Containing at least one of the polymer components containing at least one of the following general formula (I
Monofunctional macromonomer (M) having a weight average molecular weight of 2 × 10 ⁴ or less formed by binding a polymerizable double bond group represented by I)
And a monomer represented by the following general formula (III), having a weight average molecular weight of 5 × 10 ⁴ to 1 × 10 ⁶ .

General formula (II)

[0018]

Embedded image

(Here, R ₃₁ represents a hydrogen atom or a hydrocarbon group.) C ₁ and c ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, COO-Z ₁ or —COO-Z ₁ (Z ₁ each represents a hydrogen atom or a hydrocarbon group which may be substituted) via a hydrocarbon is represented.

[0020]

Embedded image

In the formula (Ia) or (Ib), X ₁ is the formula (II)
Represents the same content as X _{0 in} . Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. d _1, d
₂ may be the same as or different from each other, and c in formula (II)
₁ represents a c ₂ same content as.

[0022]

Embedded image

Y represents a hydrogen atom, a halogen atom, an alkoxy group or --COOZ ₂ (Z ₂ represents an alkyl group, an aralkyl group or an aryl group).

[0024]

Embedded image

In formula (III), X ₂ has the same content as X ₁ in formula (Ia), and Q ₂ has the same content as Q _{1 in} (Ia). e ₁ and e ₂ may be the same or different from each other and are represented by the formula (II)
Represents the same content as c ₁ and c _{2 in} . 2. The copolymer is

[0026]

Embedded image

At least one acidic group selected from {R ₀ represents a hydrocarbon group or a --OR ₀ 'group (R ₀ ' represents a hydrocarbon group)} and a cyclic acid anhydride-containing group, The above 1. which is a copolymer formed by bonding to the end of the main chain of the united polymer. The radiation-sensitive composition as described in 1. 3. The radiation-sensitive compound has (1) a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure (2) halomethyloxadiazole compound , At least one active halogen compound selected from halomethyl-s-triazine compounds, and / or 3-aryl-substituted coumarin compound (3) (1) among at least one lophine dimer
And (2), (1) and (3) or (1) and (2) and (3)
1. A combination of the above 1. Or 2. The radiation-sensitive composition as described in 1. 4. 1. The above-mentioned 1., wherein the pigment has a basic N atom in the pigment molecule. The radiation-sensitive composition as described in 1.
Achieved by

Hereinafter, the present invention will be described in detail. In the present invention, in the radiation-sensitive composition containing a pigment,
By containing (A) a graft copolymer having a specific acidic group and a specific structure, (B) a radiation-sensitive compound and (C) a pigment, the dispersibility is remarkably improved and the coating property is excellent,
It has become possible to provide a color filter with excellent pattern reproducibility, with no loss of pixels after development and no image residue in non-image areas. Further, by the above (A) to (C), a better effect can be obtained.

Although it is not clear why the effects of the present invention are exerted, the present inventors consider as follows.
The copolymer as the binder resin of the present invention is a graft copolymer composed of a macromonomer having an acidic group and another monomer. Use of this graft copolymer improves the dispersibility of the pigment. The improvement in dispersibility is considered to be that the acidic group in the graft portion interacts with the pigment, probably an acid-base interaction, but the resin is adsorbed on the pigment to enhance the dispersibility.

A copolymer containing an acidic group is often used in the radiation-sensitive composition, but improvement in dispersibility cannot be expected. Although these have acidic groups, they are generally random copolymers and do not improve the dispersibility because they adsorb at multiple points with the pigment. In the present invention, since the acidic group exists in the graft portion of the graft copolymer, it is considered that the acidic group is easily adsorbed to the pigment. Further, it is considered that the pigment having a basic nitrogen atom is likely to cause an acid-base interaction and the dispersibility is specifically improved.

Further, the radiation-sensitive composition of the present invention is characterized in that the pixels do not fall off and there is no residue in the non-image area. In other words, the adhesion of the image area is excellent and the solubility of the non-image area is excellent. It is believed, though uncertain, that this was the result of the combination of the above graft copolymer with a properly selected radiation sensitive composition.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) graft copolymer used in the present invention will be described. The weight average molecular weight of the (A) graft copolymer is 5 × 10 ⁴ to
It is 1 × 10 ⁶ , preferably 8 × 10 ^{4 to} 5 × 10 ⁵ . If the molecular weight of the (A) graft copolymer is smaller than 5 × 10 ⁴ , the effects of the present invention, particularly the effect of dispersibility, will not be sufficiently exerted, and if it is larger than 1 × 10 ⁶ , the solubility will decrease and the use will be poor. Limited.

The proportion of the monofunctional macromonomer present in the copolymer is preferably 1 to 70% by weight, and the monomer represented by the general formula (III) is present in the copolymer. The abundance ratio is preferably 30 to 99% by weight. When the content of the monofunctional macromonomer in the graft copolymer (A) is less than 1.0% by weight, the effect of dispersing the pigment is lowered and the effect of the present invention is not exhibited. It is considered that this is because the macromonomer which becomes the graft portion becomes fine, resulting in almost the same composition as the conventional homopolymer or random copolymer.

On the other hand, if the content of monofunctional macromonomer is
When it exceeds 70%, the copolymerizability with a monomer corresponding to another copolymerization component becomes insufficient, and the effect of the present invention cannot be obtained. In the (A) graft copolymer of the present invention, the monofunctional macromonomer (M), which is provided as a copolymerization component of the graft copolymer, will be described more specifically.

The monofunctional macromonomer (M) comprises a polymerizable double bond group represented by the general formula (II) and at least one polymer component represented by the general formulas (Ia) and (Ib). And certain acidic groups

[0036]

Embedded image

And / or an acid anhydride-containing group), the weight-average molecular weight of 2 ×, which is formed by bonding only to one end of the polymer main chain containing at least one of the polymer components containing
10 ⁴ or less. Formulas (II), (Ia) and (I
In b), the hydrocarbon groups contained in c ₁ , c ₂ , X ₀ , d ₁ , d ₂ , X ₁ , Q ₁ and Q ₀ are each the carbon number (unsubstituted hydrocarbon However, these hydrocarbon groups may have a substituent.

In the general formula (II), X ₀ is -COO-, -OC
O-, -CH ₂ OCO-, -CH ₂ COO-, -O-, -SO _2- , -CO-,

[0039]

Embedded image

Represents Here, in addition to a hydrogen atom, R ₃₁ is preferably a hydrocarbon group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group). Base,
Octyl, decyl, dodecyl, hexadecyl,
Octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), which may be substituted with 4 to 18 carbon atoms. Alkenyl group (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4- Methyl-2-hexenyl group), carbon number 7
To 12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group) , A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or An optionally substituted aromatic group having 6 to 12 carbon atoms (for example,
Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.). X ₀

[0041]

Embedded image

When represented by, the benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group,
Ethoxy group, propioxy group, butoxy group, etc.) and the like.

C ₁ and c ₂ may be the same or different from each other, and preferably a hydrogen atom or a halogen atom (for example,
Chlorine atom, bromine atom, etc.), cyano group, alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group,
Butyl group), -COO-Z ₁ or -COO-Z ₁ via a hydrocarbon
(Z ₁ is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically, It represents the same contents as those described for R ₃₁ ).

Examples of the hydrocarbon in the -COO-Z ₁ group through the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like. More preferably, in the general formula (II), X ₀ is —COO—, —OCO—, —CH ₂ OCO—, —CH ₂ COO.
-, -O-, -CONHCOO-, -CONHCONH-, -CONH-,-
SO ₂ NH −

[0045]

Embedded image

And c ₁ and c ₂ may be the same or different from each other, and each is a hydrogen atom, a methyl group, —COOZ ₃ or —CH ₂ COOZ ₃ {Z ₃ is more preferably a hydrogen atom or a carbon number. 1 to 6 alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.) are shown. Represents｝. Even more preferably, either c ₁ or c ₂ represents a hydrogen atom.

That is, as the polymerizable double bond group represented by the general formula (II), specifically,

[0048]

Embedded image

And the like. Formula (Ia) or (Ib)
In, X ₁ has the same meaning as X ₀ in formula (II).
d ₁ and d ₂ may be the same as or different from each other, and in the formula (II),
Represents the same content as c ₁ and c ₂ . Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. Specifically, an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, Hexadecyl group, octadecyl group,
2-chloroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (trimethoxysilyl) ethyl group, 2 -Tetrahydrofuryl group, 2-thienylethyl group, 2-N, N-dimethylaminoethyl group, 2-N, N-diethylaminoethyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms (for example, cycloheptyl group, cyclohexyl) Group, cyclooctyl group, etc.), aralkyl group having 7 to 12 carbon atoms and which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group,
Chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro-methyl-benzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, etc.) and further substituted with 6 to 12 carbon atoms Aryl group which may be (for example, phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, naphthyl group, chloronaphthyl group And the like).

In the formula (Ia), X ₁ is preferably --COO.
-, - OCO -, - CH 2 COO -, - CH 2 OCO -, - O -, -C
O -, - CONHCOO -, - CONHCONH -, - CONH -, - SO 2 NH
−

[0051]

Embedded image

Represents the following. Preferred examples of d ₁ and d ₂ represent the same contents as those of c ₁ and c ₂ described above. In the general formula (Ib), Q ₀ is -CN, -CONH ₂ or

[0053]

Embedded image

Represents Y, a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) or --COOZ ₂ (Z ₂ is preferably Represents an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an aryl group). The macromonomer (M) has the formula (Ia)
And / or 2 or more types of polymer components shown by (Ib) may be contained.

When Q ₁ is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms is preferably used within a range not exceeding 20% by weight based on all polymer components in the macromonomer (M). . Further, in the case where X ₁ in the general formula (Ia) is —COO—, it can be represented by the formula (I) in all polymer components in the macromonomer (M).
It is preferable that the polymer component represented by a) is contained in an amount of at least 30% by weight or more.

Further, in the macromonomer (M), the formula
The component containing an acidic group in the present invention, which is copolymerized as the third component together with the copolymer component represented by (Ia) and / or (Ib), has the formula (Ia) and / or (I
Any vinyl compound containing the above-mentioned acidic group that can be copolymerized with the monomer corresponding to the copolymer component represented by b) can be used. For example, "Polymer Data Handbook (Basic)" edited by The Society of Polymer Science, Baifukan (1986
Published) etc. Specifically, acrylic acid, α
-And / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α-fluoro form,
α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, β-fluoro compound, β-mesoxy compound,
α, β-dichloro form), methacrylic acid, itaconic acid,
Itaconic acid half esters, itaconic acid semiamides, crotonic acid, 2-alkenyl carboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid), maleic acid, maleic acid half esters,
Maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids, half-ester derivatives of vinyl or allyl groups of alcohols, and ester derivatives of these carboxylic acids or sulfonic acids , Compounds containing the acidic group in the substituent of the amide derivative, and the like.

[0057]

Embedded image

In R, R ₀ preferably has 1 to 22 carbon atoms.
Aliphatic groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-
Methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc. ) Or an optionally substituted aryl group (eg, phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl, fluorophenyl, bromophenyl, chloro-methyl-phenyl, dichlorophenyl, methoxyphenyl) Group,
Cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

Examples of R ₀ 'include the same as R ₀ . Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride to be contained include an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride. To be Examples of the aliphatic dicarboxylic acid anhydride ring include succinic acid anhydride ring, glutaconic acid anhydride ring, maleic acid anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid. Anhydrous ring, cyclohexene-
1,2-dicarboxylic anhydride ring, 2,3-bicyclo [2,
2,2] octane dicarboxylic acid anhydride ring and the like, and these rings are substituted with, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group. May be.

Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic acid anhydride ring, pyridine-dicarboxylic acid anhydride ring, thiophene-
Dicarboxylic acid anhydride ring and the like, these rings, for example, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group,
A hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (such as a methoxy group and an ethoxy group as the alkoxy group) may be substituted.

As the —OH group, alcohols containing vinyl group or allyl group (eg allyl alcohol, methacrylic acid ester, ester substituent such as acrylamide, N
-Compounds containing a -OH group in the substituents), and methacrylic acid esters or amides containing a hydroxyphenol or hydroxyphenyl group as a substituent.

Examples of the vinyl compound having an acidic group which can be copolymerized with the monomer corresponding to the copolymer component represented by the formula (Ia) and / or (Ib) include, for example, the following monomers: However, the scope of the present invention is not limited to these. Here, in each of the following examples, Q ₁ is -H,
-CH _3, -Cl, shows -Br, -CN, a -CH ₂ COOCH ₃ or -CH ₂ COOH, Q ₂ represents -H or -CH _3, j represents an integer of 2 to 18, k Represents an integer of 2 to 5, l represents an integer of 1 to 4, and m represents an integer of 1 to 12.

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

Among all polymer components in the macromonomer (M),
The amount of the acidic group-containing copolymer component contained is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of all the polymer components. When the monofunctional macromonomer composed of these acidic group-containing random copolymers is contained in the copolymer (A) as a copolymerization component, it is contained in all graft parts in the copolymer (A). The total amount of the acidic group-containing components is preferably 0.1 to 10 parts by weight based on 100 parts by weight of all the polymer components in the copolymer (A).

More preferably, --COOH group, --SO ₃ H group and --P
When the copolymer (A) contains an acidic group selected from O ₃ H ₂ groups, the total amount present in the graft portion is 0.1 to 5% by weight. As a polymer component in the macromonomer (M),
It may contain a polymer component other than these, for example, as a monomer corresponding to another repeating unit that can be polymerized,
Acrylonitrile, methacrylonitrile, acrylamides, methacrylamides, styrene and its derivatives (for example vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxymethylstyrene,
N, N-dimethylaminomethylstyrene, etc.), heterocyclic vinyls (for example, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole,
Vinyl dioxane, vinyl oxazine, etc.) and the like.

When these other monomers are contained,
1-2 per 100 parts by weight of all polymer components of macromonomer (M)
It is preferably 0 parts by weight. The macromonomer provided in the present invention has the general formula (Ia) and / or
Alternatively, the polymerizable double bond group represented by the general formula (II) is present only at one end of the random polymer main chain comprising at least a repeating unit represented by (Ib) and a repeating unit containing a specific acidic group. , Those having a chemical structure which is directly bonded or is bonded by an arbitrary linking group.

The linking group for linking the component of formula (II) and the component of formula (Ia) or (Ib) or the component containing an acidic group includes a carbon-carbon bond (single bond or double bond), carbon-heteroatom bond. (As the hetero atom, for example, an oxygen atom,
Sulfur atom, nitrogen atom, silicon atom, etc.), hetero atom-
It is composed of any combination of heteroatom-bonded atomic groups.

[0080]

Embedded image

[R ₃₄ and R ₃₅ are a hydrogen atom, or a compound of the above formula (Ia)
A hydrocarbon group or the like having the same meaning as Q _{1 in}
Represents a single linking group selected from the following atomic groups or two or more linking groups composed of any combination. When the weight average molecular weight of the macromonomer (M) exceeds 2 × 10 ⁴ , the formula (II
It is not preferable because the copolymerizability with the monomer represented by I) is lowered. On the other hand, when the weight average molecular weight is too small, the effect of improving the dispersibility becomes small, so that it is preferably 1 × 10 ³ or more.

The macromonomer (M) used in the present invention is
It can be produced by a conventionally known synthesis method. Specifically, radical polymerization is performed using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a carboxy halide group, a hydroxyl group, an amino group, a halogen atom, or an epoxy group in a molecule. The oligomer having a terminal reactive group bonded thereto is reacted with various reagents to produce a macromer by a radical polymerization method or the like.

Specifically, P. Dreyfuss & RPQuirk, En
cycl. Polym.Sci.Eng., 7 , 551 (1987), PFRempp, &
E.Franta, Adv. Polym. Sci., 58 , 1 (1984), Yusuke Kawakami "Chemical Industry" 38 , 56 (1987), Yuya Yamashita "Polymer" 3
1 , 988 (1982), Shiro Kobayashi "Polymer" 30 , 625 (1981),
Koichi Ito "Polymer Processing" 35 , 262 (1986), Kishiro Higashi, Takashi Tsuda "Functional Materials" 1987 No. 10, 5 etc. and the methods described in the literature and patents cited therein. it can.

However, since the macromonomer (M) of the present invention contains the acidic group as a component of its repeating unit, it is synthesized in consideration of, for example, the following. As one of the methods, for example, as shown in the following reaction formula (I), radical polymerization and terminal reactive groups are carried out using a monomer containing a functional group in which the acidic group is protected by the above method. Is introduced.

[0085]

Embedded image

[0086]

Embedded image

The acidic group (randomly contained in the macromonomer (M) used in the present invention (

[0088]

Embedded image

The protective group introduction reaction and deprotection reaction (for example, hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, etc.) of the group, the cyclic acid anhydride-containing group) can be carried out by a conventionally known method. Specifically, JFW McOmie,
"Protective Gvoups in Organic Chemistry", Plenum Pr
ess (1973), TWGreene, “Protective Gvoups in
Organic Synthesis ", John Wiley & Sons (1981),
Ryohei Oda "Polymer Fine Chemicals" Kodansha (1976)
, Yoshio Iwakura, Keisuke Kurita "Reactive Polymer" Kodansha (1977
Y.), G. Berner et al, J. Radiation Curing, 1986,
No. 10, p10, JP-A-62-212669, JP-A-62-286064
No. 62-210475, No. 62-195684, No. 62-195684
62-258476, JP-A-63-260439, Japanese Patent Application No. 62-220510
And Japanese Patent Application No. 62-226692.

As another method, for example, as shown in the following reaction formula (II), after synthesizing an oligomer as described above, a "specific reactive group" bonded to one end of the oligomer is used. It is a method of synthesizing by reacting with a reagent containing a polymerizable double bond group which reacts only with "specific reactivity", by utilizing the difference in reactivity with the acidic group contained in the oligomer.

Reaction formula (II)

[0092]

Embedded image

As shown in the reaction formula (II), specific examples of combinations of specific functional groups are shown in Table-A as follows. However, the present invention is not limited to these, and what is important is that macromonomerization can be achieved without protecting the acidic group in the oligomer by utilizing the selectivity of the reaction in a normal organic chemical reaction. That should be done.

[0094]

[Table 1]

[0095]

[Table 2]

As chain transfer agents that can be used,
For example, the acidic group or a mercapto compound containing a substituent capable of being subsequently induced to the acidic group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N -(2-Mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N
-(2-Mercaptoethyl) amino] propionic acid, N
-(3-Mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto -2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mecarpurimidazole, 2
-Mercapto-3-pyridinol or the like) or a disulfide compound which is an oxidized form of these mercapto compounds, or an iodinated alkyl compound having the above-mentioned acidic group or substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodo). Ethanesulfonic acid, 3-iodopropanesulfonic acid, etc.) and the like. Preferably, a mercapto compound is used.

Specific examples of the reactive group-containing polymerization initiator that can be used include 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 4 , 4'-Azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) Propane], 2,2'-azobis [2- (2-imidazolin-2-yl)
Propane], 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2,2'-azobis {2- [1- (2-hydroxyethyl)- 2-Imidazoline-2-
Ile] propane}, 2,2'-azobis [2-methyl-N- (2-
Hydroxyethyl) -propionamide] and derivatives thereof.

These chain transfer agents or polymerization initiators are
The amount is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on 100 parts by weight of all the monomers. Specific examples of the macromonomer (M) of the present invention include the following compounds. However, the scope of the present invention is not limited to these. In each of the following examples,
Q ₂ represents -H or -CH ₃ , Q ₃ represents -H, -CH ₃ or -CH ₂ COOCH ₃ , R ₄₁ represents -C _n H _{2n + 1} (n represents an integer of 1 to 18). ),

[0099]

Embedded image

W ₁ is -CN, -OCOCH ₃ , -CONH ₂ or -C ₆ H ₅
And W ₂ represents -Cl, -Br, -CN or -OCH ₃ , and r
Represents an integer of 2 to 18, s represents an integer of 2 to 12, and t represents an integer of 2 to 4.

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

On the other hand, the monomer copolymerizable with the above-mentioned macromonomer (M) is represented by the general formula (III). In formula (III), e ₁ and e ₂ may be the same or different from each other, and
It has the same contents as c ₁ and c _{2 in} I). X ₂ is X in formula (Ia)
₁ and Q ₂ have the same contents as Q ₁ in formula (Ia).

In the copolymer of the present invention, the copolymerization component having the macromonomer (M) as a repeating unit and the general formula (II
The composition ratio of the copolymerization component having a monomer represented by I) as a repeating unit is preferably 1 to 90/99 to 10 (weight composition ratio), more preferably 5 to 60/95 to 40 (weight composition ratio). ). Further, the copolymer (A) of the present invention may contain a monomer other than the above-mentioned macromonomer (M) and the monomer of the general formula (III) as a further copolymerization component.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides,
Methacrylamides, styrenes, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline,
Vinyl thiazole, vinyl oxazine, etc.) and the like.

However, the macromonomer (M) and the formula (III)
Other than these monomers, these other monomers do not exceed 20% by weight in the copolymer. Further, the copolymer (A) contains only at least one repeating unit represented by the general formula (III) and at least one repeating unit represented by the macromonomer (M) at only one end of the main chain of the polymer. , A copolymer formed by bonding at least one of the acidic groups (hereinafter,
In particular, it may be a copolymer (A '). Further, the copolymers (A) and (A ') may be used in combination.

Here, the acidic group has a chemical structure which is directly bonded to one end of the polymer main chain or bonded through an arbitrary linking group. Examples of the bonding group include a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom), and a heteroatom-heteroatom bond. It is composed of any combination of atomic groups. For example,

[0115]

Embedded image

(R _{32 to} R ₃₅ each have the same content as R _{32 to} R ₃₅ ) and the like, or a linking group composed of a single atomic group or a combination of two or more atomic groups. In the copolymer (A) used in the present invention, at least the above-mentioned macromonomer (M) can be used for synthesizing the copolymer (A ') in which the acidic group is bonded to the terminal of the polymer main chain. Achieved by the combined use of a polymerization initiator or a chain transfer agent containing in the molecule the acidic group or a specific reactive group that can be induced in the acidic group during the polymerization reaction of the monomer represented by the general formula (III) It

Specifically, it can be obtained in the same manner as in the synthesis of macromonomers as described above for the method of the oligomer having a reactive group bonded at one end. In the present invention, in addition to the copolymer (A) (including (A ')) according to the present invention, known resins conventionally used in the pigment dispersion method can be used in combination. As these 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 its side chain, for example, JP-A-59-44615 and JP-B-54-34327.
No. 58-12577 / 54-2595
7, JP-A-59-53836, JP-A-59-710.
Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is also an acidic cellulose derivative 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. Among these, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are particularly preferable. Other useful water-soluble polymers include 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol. In addition, alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful for increasing the strength of the cured film. These polymers can be mixed in arbitrary amounts, but if the amount exceeds 90% with respect to the total amount of the (A) graft copolymer of the present invention and the resin used in combination, the image strength to be formed, etc. Does not give favorable results. It is preferably 30 to 85%.

Further, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl. 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 Examples thereof include polymers.

The total amount of the graft copolymer of the present invention and the resin used in combination is 5 to 90 wt% with respect to the total solid components of the radiation-sensitive composition. Preferably 10-60
wt%. If the total amount is less than 5 wt%, the film strength will decrease, and if it is more than 90 wt%, the acid content will increase, which makes it difficult to control the solubility. I can't get it.

Next, the radiation-sensitive compound of the present invention will be described. The radiation-sensitive compound (B) includes (1) a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure, and (2) halomethyl. Oxadiazole compound, at least one active halogen compound selected from halomethyl-s-triazine compound, and / or 3-aryl-substituted coumarin compound (3) At least one lophine dimer, (1)
And (2), (1) and (3) or (1), (2) and (3).

Here, (2) and (3) are photopolymerization initiators, which have a function of polymerizing the monomer of (1) by light irradiation. Examples of the compound (1) having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as 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) (Meth) acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as isocyanurate, glycerin and trimethylolethane, JP-B-48-4
1708, Japanese Examined Patent Publication No. 50-6034, JP-A-51-3
Urethane acrylates as described in JP-A-7193, JP-A-48-64183 and JP-B-49-
And polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-43191 and JP-B-52-30490, and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid. I can do it. Further, the Journal of the Adhesion Society of Japan, Vol.
The materials introduced as photocurable monomers and oligomers on page 20, No. 7, pages 300 to 308 can also be used.
These radiation-polymerizable monomers or oligomers may be used in any proportion 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 objects and effects of the present invention are not impaired. it can. The amount used is 5 to 90 wt%, preferably 1 based on the total solid content of the radiation-sensitive composition.
0 to 50 wt%.

As the active halogen compound such as halomethyloxadiazole and (2) halomethyl-s-triazine, the following general formula described in JP-B-57-6096 can be used.
2-halomethyl-5-vinyl-1,3,4 represented by IV
-Oxadiazole compounds.

[0123]

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 1.
Represents an integer of 3. Specific compounds include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-Trichloromethyl-5- (p-methoxystyryl) -1,3,4
-Oxadiazole and the like. Halomethyl-s-
As a photopolymerization initiator for triazine-based compounds,
JP-A No. 9-1281, vinyl-halomethyl-s-triazine compound represented by the following general formula V: JP-A-53-53
-(Naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula VI described in JP-A-133428 and 4- (p-amino represented by the following general formula VII. Phenyl) -2,6-di-halomethyl-s-triazine compounds.

[0125]

Embedded image

Here, Q is Br, Cl, P is -CQ ₃ ,-.
_{NH 2, -NHR, -NR 2,} -OR ( where R is phenyl or alkyl group), an aromatic W is an optionally substituted, and Z in those represented by the heterocyclic nucleus or formula VA -O- Or, it is -S-.

[0127]

Embedded image

Here, X represents --Br, --Cl, and m, n
Is an integer of 0 to 3 and R is represented by the general formula VIA, R ₁ is H or OR (R is an alkyl, cycloalkyl, alkenyl, aryl group) R ₂ is —Cl, —Br or alkyl, alkenyl, aryl, alkoxy. Represents a group.

[0129]

Embedded image

Here, R ₁ and R ₂ are —H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a general formula.
VII A and VII B.

[0131]

Embedded image

Here, R ₅ , R ₆ and R ₇ represent an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Examples of the substituted alkyl group and the substituted aryl group include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, a carboaryloxy group, an acyl group,
Examples thereof include a nitro group, a dialkylamino group and a sulfonyl derivative. R _3, R ₄ represents -H, a halogen atom, an alkyl group, an alkoxy group. X and Y represent -Cl and -Br, and m and n represent 0, 1 or 2.

When R ₁ and R ₂ form a heterocyclic ring composed of a non-metal atom together with the nitrogen atom to which it is bonded, the heterocyclic ring includes those shown below.

[0134]

Embedded image

Specific examples of the general formula V 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.

A specific example of the general formula VI is 2- (naphth-1-yl) -4,6-bis-trichloromethyl-
s-Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6
-Bis-trichloromethyl-s-triazine, 2- (4
-Butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl -S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-
Trichloromethyl-s-triazine, 2- [4- (2-
Butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine , 2- (6-Methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6- Bis-trichloromethyl-s-
Triazine, 2- (5-methoxy-naphth-1-yl)
-4,6-bis-trichloromethyl-s-triazine,
2- (4,7-dimethoxy-naphth-1-yl) -4,
6-bis-trichloromethyl-s-triazine, 2-
(6-Ethoxy-naphth-2-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine and the like can be mentioned.

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

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

3-Aryl-substituted coumarin compounds have the general formula
Refers to the compound represented by VIII. R₈Is hydrogen atom, carbon number
An alkyl group having 1 to 8 and an aryl group having 6 to 10 carbon atoms (preferred
More preferably, hydrogen atom, methyl group, ethyl group, propyl group,
Butyl group), R₉Is a hydrogen atom, an alkyl having 1 to 8 carbon atoms
Group, an aryl group having 6 to 10 carbon atoms, represented by the general formula VIIIA
Group (preferably methyl group, ethyl group, propyl group
Groups, butyl groups, groups of general formula VIIIA, particularly preferred
Represents a group represented by the general formula VIIIA). R, R ₁₁Haso
A hydrogen atom and an alkyl group having 1 to 8 carbon atoms (for example,
Cyl, ethyl, propyl, butyl, octyl
Group), a haloalkyl group having 1 to 8 carbon atoms (for example, chloroform
Chill group, fluoromethyl group, trifluoromethyl group, etc.),
An alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, et
Xy group, butoxy group), optionally substituted carbon number 6 to 1
0 aryl group (eg phenyl group), amino group, -N
(R₁₆) (R₁₇), Halogen (for example, -Cl, -Br,-)
F) is represented. Preferably hydrogen atom, methyl group, ethyl
Group, methoxy group, phenyl group, -N (R₁₆) (R₁₇),-
It is Cl. R₁₂Is an optionally substituted C6-16
Aryl groups (eg phenyl, naphthyl, tolyl)
Group, cumyl group). As a substituent, an amino group, -N
(R₁₆) (R₁₇), An alkyl group having 1 to 8 carbon atoms (for example,
Cyl, ethyl, propyl, butyl, octyl
Group), a haloalkyl group having 1 to 8 carbon atoms (for example, chloroform
Chill group, fluoromethyl group, trifluoromethyl group, etc.),
An alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, et
Xy group, butoxy group), hydroxy group, cyano group, halo
Gen (for example, -Cl, -Br, -F) may be mentioned. R
₁₃, R₁₄, R₁₆, R₁₇Are each hydrogen atom, carbon number 1 to
8 alkyl groups (eg methyl, ethyl, propyl
Group, butyl group, octyl group). R₁₃, R₁₄And R
₁₆, R₁₇Are also bound to each other and the heterocycle with the nitrogen atom
(For example, piperidine ring, piperazine ring, morpholine ring,
Pyrazole ring, diazole ring, triazole ring, benzo
A triazole ring, etc.) may be formed. R_FifteenIs hydrogen field
Child, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group)
Group, propyl group, butyl group, octyl group), carbon number 1
8 alkoxy groups (eg methoxy, ethoxy,
Butoxy group), optionally substituted ant having 6 to 10 carbon atoms
Group (eg phenyl group), amino group, N (R₁₆) (R
₁₇), Halogen (eg, -Cl, -Br, -F).
You. Zb is = O, = S or = C (R₁₈) (R₁₉)
You. Preferably = O, = S, = C (CN)_TwoAnd especially
Preferably it is = O. R₁₈, R₁₉Are each cyano
Group, -COOR₂₀, -COR_{twenty one}Represents R₂₀, R_{twenty one}Haso
Each is an alkyl group having 1 to 8 carbon atoms (for example, a methyl group or an ether group).
Cyl group, propyl group, butyl group, octyl group), carbon number
1-8 haloalkyl groups (eg chloromethyl group, fluoro)
(Methyl group, trifluoromethyl group, etc.), even if substituted
Good aryl group having 6 to 10 carbon atoms (eg phenyl group)
Represents

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

[0141]

Embedded image

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

[0143]

Embedded image

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

In the present invention, other 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.
.Alpha.-carbonyl compounds disclosed in US Pat. No. 2,367,670 and US Pat. No. 2,448,82.
No. 8, disclosed in U.S. Pat. No. 2,722,512.
-Aromatic acyloin compounds substituted with hydrocarbons, U.S. Pat. Nos. 3,046,127 and 2,951,75
No. 8,491,367, and the combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367, JP-B-51-48516. Disclosed benzothiazole compounds / trihalomethyl-
s-Triazine compounds.

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

As the pigment (C) of the present invention, various conventionally known inorganic pigments or organic pigments can be used.
The inorganic pigment is a metal oxide, a metal compound represented by a metal complex salt, and specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony. , And complex oxides of the above metals.

As the organic pigment, CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 10
9, 110, 138, 139, 151, 154, 167 CIPigment Orange 36, 38, 43 CIPigment Red 105, 122, 149, 150, 155, 171, 1
75, 176, 177, 209 CIPigment Violet 19, 23, 32, 39 CIPigment Blue 1, 2, 15, 16, 22, 60, 66 CIPigment Green 7, 36, 37 CIPigment Brown 25, 28 CIPigment Black 1, 7 etc. Can be mentioned.

In the present invention, pigments having a basic N atom in the structural formula can be preferably used. These basic N atom-containing pigments show good dispersibility in the radiation-sensitive composition of the present invention. Although the cause has not been fully clarified, it is presumed that the good affinity between the graft copolymer of the present invention and the pigment has an influence. It is considered that the acidic group in the graft copolymer and the basic component of the pigment interact specifically.

Examples of these pigments include, but are not limited to, the followings.

[0151]

Embedded image

[0152]

Embedded image

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image

These pigments are supplied after being dried by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder body, 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 pigments forming such aggregates into fine particles. Therefore, it is preferable that the pigment is previously treated with various resins. These resins include the graft copolymer of the present invention. 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 usually 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 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, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be used conveniently. As the form of the graft copolymer of the present invention or the processed pigment treated with the above-described various resins, powder, paste, pellet, and paste in which the resin and the pigment are uniformly dispersed are preferable. In addition, a non-uniform lump having a gelled resin is not preferable.

These organic pigments are used alone or in various combinations for increasing the color purity. Specific examples are shown below.
As the red pigment, an anthraquinone pigment, a perylene pigment alone, or a mixture of at least one of them and a disazo yellow pigment or an isoindoline yellow pigment is used. For example, as anthraquinone pigments, C.I.
I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155, and C.I. I. Pigment Yellow 83 or C.I.
I. Pigment Yellow 139 was mixed well. The weight ratio of the red pigment to the yellow pigment is from 100: 5 to 1
00:50 was good. 400 below 100: 4
The light transmittance from nm to 500 nm could not be suppressed and the color purity could not be increased. When the ratio is 100: 51 or more, the dominant wavelength becomes shorter and the deviation from the NTSC target hue becomes large. Especially from 100: 10 to 100: 30
Range was optimal.

As the green pigment, a halogenated phthalocyanine type pigment alone or a mixture with a disazo type yellow pigment or an isoindoline type yellow pigment may be used. I.
Pigment Green 7, 36, 37 and C.I. I. Pigment Yellow 83 or C.I. I. Pigment Yellow 13
Mixing with 9 was good. The weight ratio of the green pigment and the yellow pigment was 100: 40, which was better than 100: 5. 10
Below 0: 4, the light transmittance from 400 nm to 450 nm could not be suppressed and the color purity could not be increased. If the ratio is 100: 41 or more, the dominant wavelength becomes longer and NT
The deviation from the SC target hue became large. Especially 100:
The range of 100: 20 was optimal from 5.

As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment Blue 15: 3 and C.I.
I. Pigment Violet 23 was good. The weight ratio of blue pigment to purple pigment is 1 from 100: 5.
00:50 was good. 400 below 100: 4
The light transmittance from nm to 420 nm could not be suppressed, and the color purity could not be increased. When it was 100: 51 or more, the dominant wavelength was longer and the deviation from the NTSC target hue was large. In particular, the range of 100: 5 to 100: 20 was optimal.

Further, by using a powdered processed pigment obtained by finely dispersing the above pigment in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, etc., a pigment having good dispersibility and dispersion stability. A photosensitive resin containing was obtained. As the pigment for the black matrix, carbon, titanium carbon, iron oxide alone or a mixture was used, and carbon and titanium carbon were good. The weight ratio was good in the range of 100: 5 to 100: 40. When the ratio was 100: 4 or less, the long-wavelength light transmittance increased. If the ratio is 100: 41 or more, there is a problem in dispersion stability.

Further, the pigment concentration in the total solid component of the radiation-sensitive composition of the pigment of each color is 5 wt% (wt%) to 80 w.
t%. If the content is 5 wt% or less, the color purity does not increase unless the film thickness is 10 μm or more, which poses a practical problem. 80
When the content is not less than wt%, problems such as scumming of the non-image portion and film residue are likely to occur. Preferably 10wt% to 60w
t%.

In the composition of the present invention, if necessary, various additives such as fillers, polymer compounds other than the binder resin of the present invention, surfactants, adhesion promoters, antioxidants, and ultraviolet absorbers. Alternatively, an anti-aggregation agent or the like may be added.

Specific examples of these additives include fillers such as glass and alumina; polymer compounds other than the binder polymer (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. Nonionic, cationic, anionic and other 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 in the unirradiated area and to further improve the developability of the composition of the present invention, the composition of the present invention may be added with an organic carboxylic acid, preferably a molecular weight of 1,000 or less. The low molecular weight organic carboxylic acid 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 and citraconic acid; Aliphatic tricarboxylic acids such as carballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, melophanic acid and pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

Although not necessarily required in the present invention, a dispersant for improving the dispersibility of the pigment can be added.
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; EFTOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), MegaFac 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, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 1200
0, 13240, 13940, 17000, 2000
Various Solsperse dispersants such as 0, 24000, 26000, and 28000 (manufactured by Zeneca Corporation); other examples include ISONET S-20 (manufactured by Sanyo Kasei).

These dispersants may be used alone or in combination of two or more kinds. 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.

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

3-Oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate
Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-
Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, methyl 2-oxy-2-methylpropionate, 2-
Ethyl oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-
Ethyl methyl propionate,

Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; 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 and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylesi etc. Is mentioned.

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

These solvents may be used alone or in a mixture of 2
It may be used in combination of more than one kind. The composition of the present invention comprises:
It can be prepared by mixing the above components (A), (B) and (C), and other additives optionally used with a solvent, and mixing and dispersing using various mixers and dispersers. it can. 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 preferred preparation method, first, a solvent is added to the pigment and the binder resin, and the mixture is uniformly mixed. Then, the pigment and the binder resin are sufficiently kneaded by using two or two rolls while heating if necessary. 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.

Coarse particles can be removed from the obtained dispersion by centrifugation or decantation, if necessary. The size of the pigment particles in the dispersion thus obtained is preferably 1 μm or less. More preferably, it is more preferably 0.02 μm to 0.3 μm. The colored dispersion thus obtained is mixed with the radiation-sensitive compound (B) to provide a radiation-sensitive composition.

The composition of the present invention is applied onto a substrate by a coating method such as spin coating, cast coating, or roll coating 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 liquid crystal display elements or the like and those obtained by attaching a transparent conductive film to them, or photoelectric conversion element substrates used for solid-state image pickup elements, such as silicon, are used. Examples include substrates. These substrates are generally formed with black stripes for isolating each pixel.

As the developing solution, any composition can be used as long as it is a composition that dissolves the radiation-sensitive composition of the present invention but does not dissolve the radiation-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, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline. , Pyrrole, piperidine, 1,8-
An alkaline compound such as diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001 to 10% by weight,
It is preferable to use an alkaline aqueous solution which is dissolved so as to be 0.01 to 1% by weight. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0182]

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. Production Example of Macromonomer 1: 90 g of MM-1 ethyl methacrylate, 10 g of 2-hydroxyethyl methacrylate, 5 g of thioglycolic acid and toluene 2
While stirring the mixed solution of 00g under nitrogen stream, the temperature is 75 ℃.
Was heated. 2,2'-azobisisobutyronitrile (abbreviation
AIBN) 1.0 g was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of n-hexane to give a white powder.
82 g was obtained. The weight average molecular weight of the polymer was 3.8 × 10 ³ .

[0183]

Embedded image

Production Example 2 of Macromonomer: MM-2 butyl methacrylate 90 g, methacrylic acid 10 g, 2-
Mercaptoethanol 4g, tetrahydrofuran 200g
The mixed solution of was heated to 70 ° C. under a nitrogen stream. AIBN
1.2 g was added and reacted for 8 hours. Then, the reaction solution was cooled in a water bath to a temperature of 20 ° C., and 10.2 g of triethylamine was added.
Then, 14.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature of 25 ° C or lower. After the addition, the mixture was further stirred for 1 hour. Then add 0.5 g of t-butyl hydroquinone and
The mixture was heated to 60 ° C and stirred for 4 hours. After cooling, the mixture was dropped into 1 liter of water with stirring (for about 10 minutes), stirred for 1 hour as it was, and allowed to stand, and then water was removed by decantation. After washing with water twice more, tetrahydrofuran 1
It was dissolved in 00 ml and reprecipitated in 2 liters of petroleum ether.
The precipitate was collected by decantation and dried under reduced pressure. The obtained viscous product had a yield of 65 g and a weight average molecular weight of 5.6.
× was 10 ^3.

[0185]

Embedded image

Production Example 3 of Macromonomer: MM-3 A mixture of 95 g of benzyl methacrylate, 5 g of 2-phosphonoethyl methacrylate, 4 g of 2-aminoethyl mercaptan and 200 g of tetrahydrofuran was heated to 70 ° C. under stirring under a nitrogen stream. did. AIBN (1.5 g) was added and reacted for 4 hours, and AIBN (0.5 g) was added and reacted for 4 hours. Next, this reaction solution was cooled to a temperature of 20 ° C., 10 g of acrylic acid anhydride was added, and the mixture was stirred at a temperature of 20 to 25 ° C. for 1 hour. Next, 1.0 g of t-butyl hydroquinone was added and the temperature was adjusted to 50.
Stir at ~ 60 ° C for 4 hours. After cooling, the reaction mixture was added dropwise to about 1 liter of water with stirring for about 10 minutes, and the mixture was stirred for 1 hour and then allowed to stand to remove water by decantation. After washing with water twice more, it was dissolved in 100 ml of tetrahydrofuran and reprecipitated in 2 l of petroleum ether. The precipitate is collected by decantation,
Dry under reduced pressure. The obtained viscous product had a yield of 70 g and a weight average molecular weight of 7.4 × 10 ³ .

[0187]

Embedded image

Production Example 4 of Macromonomer: MM-4 2-chlorophenyl methacrylate 95 g, monomer (I) 5 g having the following structure, thioglycolic acid 4 g and toluene 2
00 g of the mixed solution was heated to a temperature of 70 ° C. under a nitrogen stream. A.
Add 1.5 g of IBN and react for 5 hours, then add 0.5 g of AIBN
The reaction was performed for 4 hours. Next, glycidyl methacrylate 1
2.4 g, N, N-dimethyldodecylamine 1.0 g and t-butylhydroquinone 1.5 g were added and the reaction was carried out at a temperature of 110 ° C. for 8 hours. After cooling, this reaction mixture was added to 3 g of p-toluenesulfonic acid and 100 ml of a 90 vol% tetrahydrofuran aqueous solution, and the mixture was stirred at a temperature of 30 to 35 ° C for 1 hour. The above mixture was reprecipitated in 2 liters of a mixed solution of water / ethanol [(1/3) volume ratio], and the precipitate was collected by decantation.
This precipitate was dissolved in 200 ml of tetrahydrofuran and reprecipitated in 2 liters of n-hexane to obtain 58 g of powder. The weight average molecular weight was 7.6 × 10 ³ .

Monomer (I)

[0190]

Embedded image

Production Example 5 of Macromonomer: MM-5 2,6-dichlorophenyl methacrylate 95 g, 3- (2'-
Nitrobenzyloxysulfonyl) propyl methacrylate 5g, toluene 150g and isopropyl alcohol
50 g of the mixed solution was heated to a temperature of 80 ° C. under a nitrogen stream. 2,
5.0 g of 2'-azobis (2-cyanovaleric acid) (abbreviation: ACV)
Was added and reacted for 5 hours, 1.0 g of ACV was further added and reacted for 4 hours. After cooling, the reaction product was reprecipitated in 2 liters of methanol, the powder was collected by filtration, and dried under reduced pressure.

50 g of the above powder, glycidyl methacrylate
A mixture of 14 g, N, N-dimethyldosylamine 0.6 g, t-butylhydroquinone 1.0 g and toluene 100 g was added at a temperature of 110 ° C.
It was stirred for 10 hours. After cooling to room temperature, this mixture was irradiated with light with an 80 W high pressure mercury lamp for 1 hour with stirring. Then, the reaction mixture was reprecipitated in 1 liter of methanol, and the powder was collected by filtration and dried under reduced pressure. Yield 34g, weight average molecular weight 7.3 × 10
^{Was 3} .

[0193]

Embedded image

Production Example 1 of (A) Graft Copolymer: [A
-1] A mixed solution of 80 g of benzyl methacrylate, 20 g of the compound (MM-2) of Synthesis Example 2 of macromonomer and 100 g of toluene,
The mixture was heated to a temperature of 75 ° C. under a stream of nitrogen. 1,1'-azobis (cyclohexane-1-carbocyanide) (abbreviation ABCC)
0.8 g was added and reacted for 4 hours, and 0.5 g of AIBN was further added and reacted for 3 hours.

Weight average molecular weight (Mw) of the obtained copolymer
Was 1.0 × 10 ⁵ .

[0196]

Embedded image

Production Example 2 of (A) Graft Copolymer: [A
-2] 70 g of 2-chlorophenyl methacrylate, 30 g of the compound (MM-1) of Synthesis Example 1 of macromonomer, thioglycolic acid
A mixed solution of 7 g and 150 g of toluene was heated under a nitrogen stream at a temperature of 80 ° C.
Was heated. Add 0.5 g of ABCC and react for 5 hours.
Add 0.3 g of ABCC and react for 3 hours.
0.2 g was added and reacted for 3 hours.

The Mw of the obtained copolymer was 9.2 × 10 ⁴ .

[0199]

Embedded image

Production Example 3 of (A) Graft Copolymer: [A
-3] Synthesis example 4 of 60 g of ethyl methacrylate and macromonomer
Compound: MM-4 (25 g), methyl acrylate (15 g) and toluene (150 g) were mixed and heated to a temperature of 75 ° C. under a nitrogen stream. ACV 0.5g was added and reacted for 5 hours, and then ACV 0.3g was added and reacted for 4 hours. The Mw of the obtained copolymer was 1.1 × 10
It was ^five .

[0201]

Embedded image

Production Examples 4 to 11 of (A) Graft Copolymer:
(A-4) to (A-11) In the same manner as in the production example of the graft copolymer [A-1], each resin was synthesized using the methacrylate and macromonomer corresponding to the following Table-B. Mw of each resin is 9.5 × 10 ⁴ ~
The range was 1.2 × 10 ⁵ .

[0203]

[Table 3]

[0204]

[Table 4]

Production Examples 12 to 19 of (A) Graft Copolymer:
(A-12) to (A-19) In the same manner as in the production example of the graft copolymer [A-2], the methacrylate and the macromonomer mercapto compound were each replaced, and the resins of the following Table-C were respectively synthesized. Mw of each resin
Was in the range of 9 × 10 ^{4 to} 1.1 × 10 ⁵ .

[0206]

[Table 5]

[0207]

[Table 6]

Production Examples 20-27 of (A) Graft Copolymer:
(A-20) to (A-27) In the same manner as in Production Example 3 of the graft copolymer [A], the methacrylate, the macromonomer and the azobis compound were each replaced, and the resins shown in Table D below were respectively synthesized. . Of each resin
Mw was in the range of 9.5 × 10 ^{4 to} 1.5 × 10 ⁵ .

[0209]

[Table 7]

[0210]

[Table 8]

Example 1-Example of graft copolymer of the present invention (A-1) (40 wt%) toluene solution 50 parts-Methyl methacrylate / methacrylic acid copolymer (80/20 wt ratio) 40 parts-Dipentaerythritol pentaacrylate 40 copies C.I. I. Pigment Red 155 30 parts C.I. I. Pigment Yellow 83 10 parts. 4- [o-bromo-p-N, N-di (ethoxycarbonyl) 3 parts aminophenyl] -2,6-di (trichloromethyl) -s-triazine.7-[{4- Chloro-6- (diethylamino) -s-triazine 2 parts-2-yl} amino] -3-phenylcoumarin-hydroquinone monomethyl ether 0.01 part-propylene glycol monomethyl ether acetate 250 parts-ethyl 3-ethoxypropionate 250 parts Was dispersed all day and night with a sand mill. After dispersion, pore size 5μm
Then, the radiation-sensitive composition of the present invention was obtained. The resulting composition was a uniform dispersion without any sedimentation of the pigment, no precipitation of the polymer and no change in the viscosity even after standing for 2 weeks. Further, when the pigment was left standing for one week, a slight settling of the pigment was observed. However, the pigment was easily redispersed by gently shaking the container.

This composition was applied on a glass substrate for a color filter by a spin coater so that the dry film thickness was 1.5 μm, and dried at 100 ° C. for 2 minutes to obtain a red uniform coating film. It was An exposure amount of 200 mj / cm ² was applied through a mask using a 2.5 kW ultra-high pressure mercury lamp. It was immersed in a 0.5% aqueous sodium carbonate solution and developed. The resulting images are pinholes, film roughening, pixel loss,
There was no development residue or the like in the non-image area, a thin line pattern of 10 to 200 μm was reproduced, and a sharp edge pattern was obtained.

Comparative Example-1 The graft copolymer (A-
A radiation-sensitive composition was prepared in the same manner without using 1) but with a methyl methacrylate / methacrylic acid copolymer alone. When the dispersion thus obtained was allowed to stand for 2 weeks, the pigment settled and the viscosity was lowered. Example-1
When the coating, exposure and development were carried out in the same manner as in Example 1, roughness of the fine line edge and pigment residue were observed in the non-image area.

Examples-2 to 4 and Comparative Example-2 In the same manner as in Example-1, the radiation-sensitive composition using the graft copolymer of the present invention shown in Table-E was prepared and dispersed to give Examples. A color filter pattern was prepared in the same manner as in -1. The results are shown in Table-E. As a result, the invention is all good.

Evaluation and Evaluation Criteria x: Poor Δ: Slightly Bad ○: Good ◎: Excellent Dispersibility: Presence or absence of sedimentation of pigments etc. after standing for 2 weeks Image loss: Relative comparison of defects due to loss of 20 μm line width pixels Development residue: Relative comparison of pigment residue in non-image area Pattern reproducibility: Grain degree at edge of pixel with 20 μm line width

[0216]

[Table 9]

Example-5 In the same manner as in Example 1, except that the radiation-sensitive composition of Example-1 was replaced by the following, dispersion, coating, exposure and development were carried out to prepare a color filter pattern. The same results as in Example 1 were obtained. -Graft copolymer example (A-2) of the present invention (40 wt%) toluene solution 50 parts-Benzyl methacrylate / methacrylic acid copolymer (80/20 wt ratio) 40 parts-Dipentaerythritol hexaacrylate 40 parts-C. I. Pigment Red 177 30 parts I. Pigment Yellow 139 10 parts 2- (2-chlorophenyl) -4,5-diphenyl imidazolyl dimer 2 parts Michler's ketone 1 part 2-mercapto-5-methylthio-1,3,4-thiazole 1 part Hydroquinone monomethyl ether 0.01 parts ・ Propylene glycol monomethyl ether acetate 250 parts ・ Ethyl 3-ethoxypropionate 250 parts

Examples 6 to 9 and Comparative Example-3 A radiation sensitive composition was prepared in the same manner as in Example 5 except that the graft copolymer was changed to another, and a color filter pattern was prepared. Table 5 shows the results together with Example 5.
Shown in F. As a result, it is understood that the present invention is good.

[0219]

[Table 10]

Examples-10, 11 and Comparative Example-4 The radiation-sensitive composition of Example-1 was replaced with the following one, as shown in Table-G, and dispersed and coated in the same manner as in Example-1. ,
It was exposed and developed to prepare a color filter pattern. As shown in Table-G, in the case of the present invention, the same results as in Example 1 were obtained.

-Example of graft copolymer of the present invention (A-3) (40 wt%) toluene solution 50 parts-Benzyl methacrylate / methacrylic acid copolymer (80/20 wt ratio) 40 parts-Dipentaerythritol hexaacrylate 40 parts- C. I. Pigment Green 36 30 parts C.I. I. Pigment Yellow 139 10 parts 2- (2-chlorophenyl) -4,5-diphenyl imidazolyl dimer 2 parts-Michler's ketone 1 part 2-mercapto-5-methylthio-1,3,4-thiazole 1 part- Hydroquinone monomethyl ether 0.01 part-Propylene glycol monomethyl ether acetate 250 parts-Ethyl 3-ethoxypropionate 250 parts

[0222]

[Table 11]

Example-12-Graft copolymer (A-12) (40 wt%) toluene solution of the present invention 75 parts-Pentaerythritol tetraacrylate 10 parts-4- [p-N, N-di (ethoxycarbonylmethyl) )]-2 parts 2,6-di (trichloromethyl) -s-triazine. 7-[{4-chloro-6- (diethylamino) -s-tri 2 parts azin-2-yl} amino] -3-phenyl. Coumarin-hydroquinone monomethyl ether 0.01 part-propylene glycol monomethyl ether acetate 20 parts C.I. I. Pigment Red 177 Acrylic resin processed pigment (Colortex Red U38N, Sanyo Pigment) 8 parts I. Pigment Yellow 83 Ethylcellulose resin Processed pigment (Colortex Yellow E119, manufactured by Sanyo Pigment Co., Ltd.) 2 parts Kneaded with a three-roll mill to prepare a colored paste.

Then, propylene glycol monomethyl ether acetate was added to the obtained colored paste material so that the solid content was 25 wt%, and the mixture was dispersed by Dynomill using glass beads having a diameter of 1 mm to obtain a radiation-sensitive composition. It was This composition did not settle at all for 2 weeks. Using this composition, a color filter pattern was prepared in the same manner as in Example 1.
Both the development residue and the pattern reproducibility were satisfactory.

EXAMPLE-13 Graft Copolymer (A-3) of the Present Invention (40 wt%) Propylene Glycol Monomethyl Ether Acetate Solution 25 parts C.I. I. Pigment Red 155 (10 parts) was kneaded with a two-roll mill to obtain a sheet-like colored material.
Similarly, a sheet-like colored material was obtained in exactly the same manner except that the pigment was changed to 10 parts of CI Pigment Yellow 83.

A radiation-sensitive composition was obtained in the same manner as in Example 1 except that the ratio of the Red and Yellow colored materials was set to 8: 2 (weight ratio). The resulting composition was left for 4 weeks, but no sedimentation of the pigment was observed. A color filter pattern was prepared in the same manner as in Example 1. However, the dropout of pixels, the development residue, and the pattern reproducibility were all satisfactory.

Example-14 The pigment of Example-13 was mixed with C.I. I. Pigment Blue 15 30 parts C.I. I. Pigment Violet 198 parts, and dispersion, coating, exposure and development were carried out in the same manner as in Example 1 to produce a color filter pattern.

The same results as in Example 1 were obtained.

Example-15 Using the radiation-sensitive compositions of Examples-5, 10, and 14, a glass substrate on which a black matrix had been previously patterned was sequentially coated, exposed, and developed to prepare a color filter. did. The color filter obtained without any peeling of the film or the undeveloped residue of each color pixel had a small depolarizing effect and a high contrast.

[0230]

According to the present invention, a radiation-sensitive composition having excellent pigment dispersibility can be obtained by using the graft copolymer. Therefore, according to the radiation-sensitive composition of the present invention, it is possible to produce a color filter having excellent coating properties, high image quality, and high reliability.

Claims (4)

[Claims] 1. A radiation-sensitive composition containing the following (A) copolymer, (B) radiation-sensitive compound and (C) pigment. (A) copolymer; the following general formulas (Ia) and (Ib)
At least one of the polymer components represented by At least one component containing at least one acidic group selected from the group {R ₀ represents a hydrocarbon group or a -OR ₀ 'group (R ₀ ' represents a hydrocarbon group)} group and a cyclic acid anhydride-containing group.
A polymer having at least one kind of a polymer component containing a seed, the weight average molecular weight of the polymer main chain containing the polymerizable double bond group represented by the following general formula (II) 2 ×
10 ⁴ or less monofunctional macromonomer (M) and the following general formula
A copolymer having a weight average molecular weight of 5 × 10 ⁴ to 1 × 10 ^{6 and} containing at least the monomer represented by the formula (III). General formula (II) (Here, R ₃₁ represents a hydrogen atom or a hydrocarbon group.)
c _1, c _2, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ₁ or -COO-Z ₁ via a hydrocarbon (Z ₁ each Represents a hydrogen atom or an optionally substituted hydrocarbon group). Embedded image In formula (Ia) or (Ib), X ₁ has the same meaning as X ₀ in formula (II). 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 as or different from each other, and have the same contents as c ₁ and c ₂ in the formula (II). Embedded image Y is a hydrogen atom, a halogen atom, an alkoxy group or -COOZ
₂ (Z ₂ represents an alkyl group, an aralkyl group or an aryl group). Embedded image In formula (III), X ₂ has the same content as X ₁ in formula (Ia), and Q ₂ has the same content as Q _{1 in} (Ia). 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 (II). 2. The copolymer is: {R ₀ represents a hydrocarbon group or a --OR ₀ 'group (R ₀ ' represents a hydrocarbon group)}, and at least one acidic group selected from a cyclic acid anhydride-containing group, The radiation-sensitive composition according to claim 1, which is a copolymer formed by binding to the ends of chain portions. 3. The radiation-sensitive compound comprises (1) a compound having at least one addition-polymerizable ethylene group and an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure (2) halo At least one active halogen compound selected from a methyloxadiazole compound and a halomethyl-s-triazine compound, and / or a 3-aryl-substituted coumarin compound (3) Among the at least one lophine dimer, (1)
And (2), (1) and (3) or (1) and (2) and (3)
It is a combination with and
The radiation-sensitive composition as described in 1. 4. The radiation-sensitive composition according to claim 1, wherein the pigment has a basic N atom in the pigment molecule.