JPH09171253A - Radiation sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. contg. a pigment dispersible as fine particles and having improved dispersion stability by incorporating a resin made of a specified graft copolymer, a radiation sensitive compd. and a pigment. SOLUTION: This compsn. contains a resin made of a graft copolymer having a wt. average mol.wt. of 3×10<4> -1×10<6> and contg. at least one of polyester type macromonomers each having a wt. average mol.wt. of 1×10<3> -1.5×10<4> represented by formula I, II as a polymer component, a radiation sensitive compd. and a pigment. In the formulae, each of f1 -f4 is H, halogen, etc., X1 and X2 is a single bond,-COO-,-OCO-, etc., Y1 and Y2 are groups combining X1 and X2 with Z1 and Z2 , respectively, each of Z1 and Z2 is -CH2 -, -O- or -NH-, each of W1 -W3 is a divalent aliphatic group, a divalent arom. group, etc., and R61 is H, hydrocarbon or -COR63 (R63 is hydrocarbon).

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 and a color filter which are good and have excellent coatability.

[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 of using a processed pigment obtained by treating the pigment with an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate resin, or the like, JP-A-2-181704. Japanese Patent Laid-Open No. 2-199403 discloses a method of using an organic dye derivative as a dispersant, but it 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.

To prepare a color filter, a radiation-sensitive composition is coated on a glass substrate with a spin coater, a roll coater or the like, dried to form a coating film, exposed and developed to obtain a colored pixel. This operation is performed for each color to obtain a color filter. Pixels formed by the conventional radiation-sensitive composition are easily peeled off from the substrate during development or washing with water to cause defects in the color filter, while improving the pixel adhesion. If so, there is a problem that the solubility of the non-image area is lowered at the time of development and scumming of the non-image area is likely to occur.

[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 containing a pigment capable of dispersing fine particles and having improved dispersion stability.

Still another object of the present invention is to provide a color filter which is excellent in coatability, hardly causes background stain after development, and has excellent adhesion of formed pixels and good pattern reproducibility. It is in.

[0014]

The above objects of the present invention can be achieved by the following constitutions (1) to (4), and further (5) to (8). (1) A radiation-sensitive composition containing the following (A), (B), and (C). (A) Binder resin: the following general formula (Ia) and general formula (I)
b), weight average molecular weight 1 × 10 ^{3 to} 1.5 ×
A resin comprising a graft copolymer having a weight average molecular weight of 3 × 10 ⁴ to 1 × 10 ^{6 and} containing at least one of 10 ⁴ polyester type macromonomers (MB) as a polymer component.

(B) Radiation-sensitive compound, and (C) pigment

[0016]

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In formulas (Ia) and (Ib), [] represents a repeating unit. f ₁ and f 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 having 1 to 8 carbon atoms, —COO—V ₁ or a hydrocarbon group having 1 to 8 carbon atoms. Via --COO-V ₂ (V ₁ and V ₂ each represent a hydrocarbon group having 1 to 18 carbon atoms)
Represents

X ₁ is a single bond or --COO--, --O.
_{CO -, - (CH 2)} u1 -COO -, - (CH 2) u2 -OC
O- (u ₁ and u ₂ represent an integer of 1 to 3), -CON
(D ₁ )-(d ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), -CONHCONH-, -CONHC
OO -, - O -, - C 6 H 4 - or -SO ₂ - represent.

Y ₁ represents a group connecting X ₁ and Z ₁ . Z ₁ is -CH ₂ -, - O- or represent -NH-. W
₁ and W ₂ may be the same as or different from each other, and each is a divalent aliphatic group, a divalent aromatic group {-O-, -S-,-in the bond of each divalent organic residue. N (d ₂ )-(d ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), -SO
_2- , -COO-, -OCO-, -CONHCO-,-
_{NHCONH -, - CON (d 3} ) - (d 3 represents the same content as _{d 2), - SO 2 N} (d 4) - (d 4 represents the same content as d ₂₎ and -Si ( d ₃ ) (d ₄ )-may be intervened with at least one bonding group} or an organic residue constituted by a combination of these residues.

R ₆₁ is a hydrogen atom, a hydrocarbon group or --COR
_{It represents 63} groups (R ₆₃ represents a hydrocarbon group). W ₃ represents a divalent aliphatic group. f ₃ and f ₄ are f ₁ and f _2, and X
₂ , Y ₂ and Z ₂ have the same meanings as X ₁ , Y ₁ and Z ₁ , and R ₆₂ has the same meaning as R ₆₁ . (2) The resin has a —PO ₃ H ₂ group, a —SO ₂ H group, a —CO
OH group, -OH group, -P (= O) (OH) (R) group [R is a hydrocarbon group or -OR 'group (R' represents a hydrocarbon group)
And a cyclic acid anhydride-containing group. The radiation-sensitive resin according to (1), which is a resin obtained by bonding at least one polar group selected from the group containing a cyclic acid anhydride to the end of the main chain of the polymer of the copolymer. Composition. (3) The radiation-sensitive compound is (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) halomethyloxadi At least one active halogen compound selected from an azole compound and a halomethyl-s-triazine compound, and / or a 3-aryl-substituted coumarin compound (3) Among at least one lophine dimer, (1)
And (2), (1) and (3) or (1) and (2) and (3)
The radiation-sensitive composition according to claim 1, which is a combination thereof. (4) The radiation-sensitive composition as described in (1), wherein the pigment has a basic N atom in the pigment molecule.

(5) The radiation-sensitive composition as described in (1), wherein the pigment is a processed pigment. (6) The processed pigment is a graft copolymer described in (1) to (4) above, or a powder in which a pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate resin, ethyl cellulose and nitrocellulose, 7. Pellet or paste-like dispersion The radiation-sensitive composition as described in 1. (7) The radiation-sensitive composition as described in (7), wherein the processed pigment is subjected to a flushing treatment. (8) A liquid crystal in which a coating film of the radiation-sensitive composition according to (1) to (7) is formed on the surface of a transparent substrate, exposure and development are repeated, and red, green and blue patterns are formed on the same surface. Color filter for display device.

The present invention will be described in detail below. In the present invention, in the radiation-sensitive composition containing a pigment,
By containing the graft copolymer (binder resin) (A) obtained by polymerizing the polyester type macromonomer (MB) having a specific structure, the radiation-sensitive compound (B) and the pigment (C), dispersibility is improved. It is possible to provide a color filter that is remarkably improved, has excellent coating properties, and has no pattern dropout after development and no image residue in non-image areas and excellent pattern reproducibility.
Further, by making the above (A) to (C) specific, it is possible to obtain a better effect.

Copolymers containing acidic groups are often used in radiation-sensitive compositions, but improvement in dispersibility cannot be expected. Although these have acidic groups, they are generally random copolymers and adsorb at multiple points with the pigment, so that dispersibility is not improved. Rather, aggregation is promoted by using such a random copolymer. In the case of a graft copolymer having a main chain and a graft part in one copolymer, the dispersibility is improved because either the main chain or the graft part is oriented and adsorbed on the pigment. Further, it is considered that the pigment having a basic N atom is likely to cause an acid-base interaction and the dispersibility is specifically improved.

Further, in the radiation-sensitive composition of the present invention, 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 unclear, that this was caused by the combination of the above graft copolymer with a properly selected radiation sensitive compound. Next, the resin used in the present invention will be described.

The weight average molecular weight of the resin is 3 × 10 ^4.
˜1 × 10 ⁶ , preferably 8 × 10 ^{4 to} 5 × 10 ⁵ . The proportion of the macromonomer represented by formula (Ia) and / or (Ib) in the polymer is preferably 0.5 to 80% by weight, more preferably 1 to 40% by weight.
It is.

The glass transition point of the resin is preferably from 0 ° C to
110 degreeC, More preferably, it is 20 degreeC-90 degreeC. or,
If the molecular weight of the binder resin is smaller than 3 × 10 ⁴ , the effects of the present invention, particularly the effect of dispersibility, will not be sufficiently exerted, while if the molecular weight is larger than 10 ⁶ , the solubility will decrease and the use will be restricted. .

If the content of the macromonomer in the binder resin is less than 0.5% 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 composition of the macromonomer serving as the graft portion becomes small, resulting in almost the same composition as the conventional homopolymer or random copolymer. On the other hand, when the content of the macromonomer exceeds 80%, the copolymerizability of the monomer corresponding to the other copolymerization component and the macromonomer according to the present invention becomes insufficient, and the effect of the present invention cannot be obtained. I will end up.

The resins of the present invention have the formulas (Ia) and (Ib)
Weight average molecular weight of 1 × 10 ^{3 to} 1.5 × 10 ⁴
Of at least one of the macromonomer contain a copolymer, more preferably the polymer main polar at one end of the chain groups {-PO ₃ H ₂ group, -SO ₃ H group, -COOH group,
-OH group, -P (= O) (OH) R group [R represents a hydrocarbon group or a -OR 'group (R' represents a hydrocarbon group)], or a cyclic acid anhydride-containing group} It is a high molecular weight resin composed of a graft copolymer having a weight average molecular weight of 3 × 10 ⁴ to 1 × 10 ⁶ .

The macromonomer having a polyester structure, which is used as a copolymerization component of the graft copolymer resin used in the resin of the present invention, will be described in more detail. In the general formulas (Ia) and (Ib),
The inside of [] represents a repeating unit sufficient to make the weight average molecular weight of the macromonomer of the formula (Ia) and / or (Ib) 1 × 10 ^{3 to} 1.5 × 10 ⁴ .

In the macromonomer of the general formula (Ia)
And preferably f₁And f_TwoAre the same or different from each other
May be a hydrogen atom or a halogen atom (for example, chlorine source).
Child, bromine atom, fluorine atom), cyano group, carbon number 1-3
Alkyl groups (eg methyl, ethyl, propyl)
Etc.), -COOZ₁Or -CH_TwoCOOZ_Two{Z₁And Z
_TwoAre each an alkyl group having 1 to 8 carbon atoms (for example, a methyl group,
Ethyl, propyl, butyl, pentyl, hexyl
Group, octyl group, etc.), aralkyl group having 7 to 9 carbon atoms
(For example, benzyl group, phenethyl group, 3-phenylpro group
Pill group) or an optionally substituted phenyl group (eg, phenyl group).
Phenyl group, tolyl group, xylyl group, methoxyphenyl group
And the like).

More preferably, _one of f ₁ and f ₂ represents a hydrogen atom. X ₁ is preferably a single bond, —COO—, —OCO—, —CH ₂ COO—, —.
_{CH 2 OCO -, - CONH -} , - CONHCONH
-, - CONHCOO- or -C ₆ H ₄ - represents a. Further, d ₁ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group,
Hexyl, octyl, decyl, dodecyl, 2-
Methoxyethyl, 2-chloroethyl, 2-cyanoethyl, benzyl, methylbenzyl, chlorobenzyl, methoxybenzyl, phenethyl, phenyl, tolyl, chlorophenyl, methoxyphenyl, butylphenyl, etc. Represents

Y ₁ represents a group connecting X ₁ and Z _1, and represents a single bond or a group connecting them. Specifically as linking radicals - _{[C (e 1) (e 2} ) ] _{-, - C 6 H 10 -} , -
C ₆ H ₄ -, - _{[C (e 3) = C (} e 4) ] -, - COO
-, - OCO -, - O -, - S -, - SO 2 -, - N
_{(E 5) -, - CON} (e 6) -, - SO 2 N (e 7) -,
-NHCOO-, -NHCONH-, or -C (= O)
Represents a linking group selected from-or a linking group formed by a combination of these linking groups. Here, e _{1 to} e ₄ may be the same or different and each is a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or a hydrocarbon group having 1 to 7 carbon atoms (preferably Is, for example, methyl group, ethyl group, propyl group, butyl group, 2
-Chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, benzyl group, methoxybenzyl group, phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, etc., and e _{5 to} e ₇ are the above d ₁ Represents the same as the content of.

W ₁ and W _{2, which} may be the same or different, each represents a divalent organic residue, and are --O--, --S--,-.
_{N (d 2) -, -} SO -, - SO 2 -, - COO -, - O
CO-, -CONHCO-, -NHCONH, -CON
_{(D 3) -, - SO} 2 N (d 4) - and _{-Si (d 3) (d 4} )
A bonding group selected from-may be interposed. It represents an organic residue composed of a divalent aliphatic group or a divalent aromatic group, or a combination of these divalent residues. here,
d _{2 to} d ₄ represent the same contents as d ₁ .

As the divalent aliphatic group, for example,-[C (e
₈ ) (e ₉ )]-,-[(e ₈ ) C = C (e ₉ )]-,-(C
_{≡C) -, - C 6 H} 10 -,

[0035]

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And the like. Here, e ₈ and e ₉ may be the same as or different from each other, and each is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or an alkyl group having 1 to 12 carbon atoms (for example, a methyl group). , Ethyl group, propyl group, chloromethyl group, bromomethyl group,
Butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Q is -O -, - S- or -NR ₆₄ - represents, R ₆₄ is an alkyl group having 1 to 4 carbon atoms, -CH ₂ C
l or represents a -CH ₂ Br.

Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, selected from an oxygen atom, a sulfur atom and a nitrogen atom). Containing at least one hetero atom). These aromatic groups may have a substituent, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group). Examples thereof include a group, a butyl group, a hexyl group, an octyl group) and an alkoxy group having 1 to 6 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group).

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-oxazoline ring and the like. W ₃ is
Represents a divalent aliphatic residue, for example, - (CH _{2) m1} -
(M ₁ represents an integer of _{2~18), - C (CH 3} ) 2 -
_{(CH 2) 2 -, -} CH 2 -C (r 1) (r 2) - (r 1 and r ₂
May be the same or different, and each is a hydrogen atom, a methyl group,
It represents an alkyl group having 1 to 12 carbon atoms such as ethyl group, propyl group, butyl group, hexyl group, octyl group and decyl group. However, r ₁ and r ₂ do not represent hydrogen atoms at the same time), —CH (r ₃ ) — (CH ₂ ) _{m 2} — (r ₃ has 1 to 10 carbon atoms).
12 represents an alkyl group, and specific examples thereof include the same alkyl groups as r ₁ and r ₂ . m ₂ represents an integer of 3 to 18) and the like.

R ₆₁ is preferably a hydrogen atom, having 1 to 4 carbon atoms.
Alkyl group (eg, methyl group, ethyl group, propyl group, butyl group) or —COR ₆₃ group (R ₆₃ is preferably R
And an alkyl group similar to ₆₁ is shown). In formula (Ib), preferred c ₃ , c ₄ , X ₂ , Y ₂ and R ₆₂ are respectively those described as preferred in c ₁ , c ₂ , X ₁ , Y ₁ and R ₆₁ of formula (Ia). Represent the same content.

In the macromonomer (MB) in the general formula (Ia) and the general formula (Ib)

[0041]

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Specific examples of the portion represented by are the followings, but are not limited to these. However, in each of the following examples, Q ₁ is —H, —CH ₃ ,
-CH ₂ COOCH _3, -Cl, shows -Br or -CN, Q ₂ represents -H or -CH _3, X is -Cl or -B
r, n is an integer of 2 to 12, and m is an integer of 1 to 4.

[0043]

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[0044]

[Chemical 6]

[0045]

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[0046]

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Specific examples of W ₁ and W ₂ include the following organic residues, but the present invention is not limited thereto. However, in each of the following examples, R ₄₁ is an alkyl group having 1 to 4 carbon atoms, —CH ₂ Cl or —CH ₂ Br.
R ₄₂ is an alkyl group having 1 to 8 carbon atoms, — (CH ₂ ).
_u3- OR ₄₁ (R ₄₁ represents the above meaning, u ₃ represents 2 to 8)
Represents an integer of 4), —CH ₂ Cl or —CH ₂ Br, R ₄₃ represents —H or —CH ₃ , and R ₄₄ represents 1 to 4 carbon atoms.
4 is an alkyl group, and Q is -O-, -S-, or -N.
R ₄₁ - shows the (R ₄₁ represents the above meaning), p is 1
26 represents an integer, q represents 0 or an integer of 1 to 4, and r
Represents an integer of 1 to 10, j represents an integer of 0 or 1 to 4, and k represents an integer of 2 to 6.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The macromonomer (MB) represented by the general formula (Ia) is a diol and a dicarboxylic acid, which are exemplified in "Polymer Data Handbook [Basic Edition]" (1986), Baifukan, etc., edited by The Society of Polymer Science, Japan. A polyester oligomer having a weight average molecular weight of 1 × 10 ^{3 to} 1.5 × 10 ⁴ synthesized by a polycondensation reaction with a dicarboxylic acid anhydride or a dicarboxylic acid ester has a polymer reaction only at a carboxyl group at one end. It can be easily produced by a method of introducing a polymerizable double bond group.

The polyester is synthesized by a conventionally known polycondensation reaction. Specifically, specifically, Eiichiro Takiyama "Polyester Resin Handbook", Nikkan Kogyo Shimbun (19
1986), "Polycondensation and Polyaddition" edited by The Society of Polymer Science, Kyoritsu Publishing (1980), I. Goodman "Encyclopedia of Polymer"
Science and Engineering '' Vol. 12, p1, John Wiley & S
It can be synthesized according to the method described in ons (1985).

As a method for introducing a polymerizable dipolymerizable group into only one carboxyl group of the polyester oligomer, a reaction of esterifying a carboxylic acid or an acid amidation of a carboxylic acid in a conventionally known low molecular weight compound is used. Can be synthesized with. That is, a functional group containing a polymerizable double bond group in the molecule and chemically reacting with a carboxyl group (for example,

[0057]

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Halogen (chloride, bromide, iodide), --NH ₂ , --COOR ₆₂ (R ₆₂ is a methyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, etc.) The macromonomer is synthesized by polymer-reacting the contained compound with the polyester oligomer.
Specifically, the Chemical Society of Japan "New Experimental Chemistry Course 14, Synthesis and Reactions of Organic Compounds (II)", Chapter 5, Maruzen Co., Ltd. (19
1977), Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" Kodansha (1977) and the like.

The macromonomer represented by the general formula (Ib) is the same as in the macromonomer synthesis of the general formula (Ia) after synthesizing a polyester oligomer by a self-polycondensation reaction of carboxylic acids having a hydroxyl group in the molecule. It can be produced by a method of synthesizing a macromonomer by a polymer reaction. Further, specific examples of the macromonomer (MB) represented by the formula (Ia) or (Ib) are shown below. However, the scope of the present invention is not limited to these.

However, in each of the following examples, the weight average molecular weight of the macromonomer (MB) in the brackets [] is from 1 × 10 ³ to
Exhibits sufficient repeating units and 1.5 × 10 ^4, Q ₃
Represents —H or —CH ₃ , R ₆₅ and R _{66, which} may be the same or different, each represent —CH ₃ or —C ₂ H ₅ , and R ₆₇
Represents a _{-CH 3, -C 2 H 5,} -C 3 H 7 or -C ₄ H _9,
Y shows -Cl or -Br, W shows -O- or -S-, s shows the integer of 2-12, t shows the integer of 1-25, u shows the integer of 2-12. , X is an integer of 2 to 16, y is an integer of 1 to 4, z is 0, 1 or 2
Is shown.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The resin used in the binder resin of the present invention is a graft copolymer containing at least one macromonomer selected from the above general formulas (Ia) and (Ib) as at least a copolymerization component, and The copolymerization component may be any monomer as long as it satisfies the physical properties of the binder resin and is radically copolymerizable with the macromonomer.

Preferred are repeating units of the formula (II).

[0069]

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[In the formula (II), T is -COO-,-
_{OCO -, - (CH 2)} c -OCO -, - (CH 2) d -C
OO -, - O -, - SO 2 -, - CON (R 7) -, - S
_{O 2 N (R 7) -} , - CONHCOO -, - CONHCO
Represents NH- or -C (= O)-. (However, c, d
Each represent an integer of 1 to 2, and R ₇ represents the same content as R ₁ . ). R ₁ represents a hydrocarbon group. In the repeating unit represented by the general formula (II), the hydrocarbon group of R ₁ may be substituted.

R ₁ preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than a polar group bonded to one end of the polymer main chain, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), —O—
_{R 2, -COO-R 2,} -OCO-R 2 (R 2 is a carbon number 1
To 22 alkyl groups, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.) and the like. The preferred hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
Methoxyethyl group, 3-bromopropyl group, etc.), alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 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, 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) , A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), and an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, 2- A cyclohexyl group, a 2-cyclopentylethyl group, etc.) or a carbon number of 6 to 1
2 optionally substituted aromatic groups (eg, phenyl groups,
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.).

B ₁ and b ₂ may be the same or different and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—R ₈ or 1 to 8 carbon atoms.
-COO-R ₈ (R ₈ is a carbon number of 1 to
18 hydrocarbon groups are represented). More preferably, b ₁ and b ₂ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), —COO—R ₈ or -CH ₂ C
OO-R ₈ (where R ₈ is more preferably C 1-18)
Represents an alkyl group or an alkenyl group of, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
Examples include an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a pentenyl group, a hexenyl group, an octenyl group and a decenyl group.
_It may have a substituent similar to that shown in ₁ ).

Further, other monomers constituting repeating units other than these include, for example, styrenes (for example, styrene, vinylstyrene, chlorostyrene, bromostyrene, dichlorostyrene, vinylphenol, methoxystyrene, chloromethylstyrene). , Methoxymethylstyrene, acetoxystyrene, methoxycarbonylstyrene, methylcarbamoylstyrene, etc.), acrylonitrile, methacrylonitrile, acrolein, methacrolein, vinyl group-containing heterocyclic compounds (eg N-vinylpyrrolidone, vinylpyridine, vinylimidazole, vinyl) Thiophene), acryloamide, methacryloamide and the like. However, the other copolymerization components are not limited to these.

A monomer corresponding to the repeating unit represented by the general formula (II) is contained as a copolymerization component in an amount of 30% by weight to 99% by weight in the copolymer. For resins, these formulas (Ia)
And / or a polyester type macromonomer represented by (Ib) and a monomer corresponding to the repeating unit represented by the general formula (II), and a monomer other than these as a copolymerization component. Good.

For example, in addition to methacrylic acid esters, acrylic acid esters, crotonic acid esters containing substituents other than those described in the general formula (II), α-olefins, vinyl carboxylates or allyl esters ( For example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, Methacrylamides, styrenes (eg styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene,
Methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (eg, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene,
Vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

It is preferable that these other monomers do not exceed 30% by weight in the copolymer in the resin.
Further, the resin of the present invention is preferably a resin obtained by further bonding the polar group to one end of the polymer main chain.
Polar group attached to the polymer backbone, -PO ₃ H ₂ group, -S
O ₃ H group, -COOH group, -P (= O) (R ) (OH) group {R represents a hydrocarbon group or -OR 'group (R' represents a hydrocarbon group)}, and cyclic acid anhydride It is at least one selected from the substance-containing groups.

Further, -P (= O) in "an acidic group bonded to one end of the polymer main chain" contained in the resin of the present invention
In the (R) (OH) group, R is a hydrocarbon group or -O.
Represents an R'group (R 'represents a hydrocarbon group), and R and R'are preferably an aliphatic group having 1 to 22 carbon atoms (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 aryl group which may be substituted (eg, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group) Group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group and the like).

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride contained include aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring, and a cyclopentane-
1,2-dicarboxylic anhydride ring, cyclohexane-1,
2-dicarboxylic anhydride ring, cyclohexene-1,2-
Dicarboxylic anhydride ring, 2,3-bicyclo [2,2
2] octanedicarboxylic anhydride rings and the like, and these rings are substituted with, for example, halogen atoms such as chlorine atom and bromine atom, and alkyl groups such as methyl group, ethyl group, butyl group and hexyl group. Is also good.

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.

The specific acidic group bonded to only one end of the polymer main chain has a chemical structure which is directly bonded to one end of the polymer main chain or is bonded via 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-[C
(R ₂₁ ) (R ₂₂ )]-[R ₂₁ and R ₂₂ are a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
A cyano group, a hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.) and the like],-(CH
_{= CH) -, - C 6} H 10 -, - C 6 H 4 -, - O -, - S
-, - C (= O) -, - N (R 23) -, - COO -, -
_{SO 2 -, - CON (R} 23) -, - SO 2 N (R 23) -,
-NHCOO -, - NHCONH -, - Si (R 23) (R
₂₄ )-[wherein R ₂₃ and R ₂₄ are each a hydrogen atom or a carbon number of 1 to
8 hydrocarbon groups (eg methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, benzyl group,
Phenethyl group, phenyl group, tolyl group, etc.) or —OR ₂₅
(R ₂₅ represents the same content as the hydrocarbon group of R ₂₃ )] and the like.

The resin of the present invention in which a specific polar group is bonded only to at least one terminal of the polymer main chain has various known reagents at the terminal of the living polymer obtained by conventionally known anionic polymerization or cationic polymerization. Method of reacting (method of ionic polymerization method) Method of radical polymerization using polymerization initiator and / or chain transfer agent containing specific polar group in molecule (method of radical polymerization method), or ionic weight as above It can be easily produced by a synthetic method such as a method of converting a polymer having a reactive group at the terminal obtained by a legal method or a radical polymerization method into a specific polar group of the present invention by a polymer reaction.

Specifically, P. Dreyfuss, RPQuirk, Enc
ycl. Polym. Sci. Eng, 7: 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Pharmaceuticals", 30, 232 (1985), Akira Ueda, Susumu Nagai "Science and Industry" 60, 57 (1986), etc. Can be produced by the methods described in the review article and references cited therein. However, in the method of introducing the polar group by a high molecular reaction, since the resin is a high molecular weight compound, the reaction progresses slowly and becomes a long time reaction, and the quantitative reaction is difficult to proceed. It is preferable to synthesize by a polymerization reaction with the contained polymerization initiator and / or chain transfer agent.

Synthesis example of polyester type macromonomer (MB) 1: 90.1 g of MB-11,4-butanediol, 10 succinic anhydride
A mixture of 5.1 g, 1.6 g of p-toluenesulfonic acid monohydrate and 200 g of toluene was heated under reflux for 4 hours with stirring in a flask equipped with a Dean-Star® reflux device. The amount of water distilled off azeotropically with the toluene solvent was 17.5 g.

Next, after adding a mixed solution of 21.2 g of 2-hydroxyethyl methacrylate and 150 g of toluene and 1.0 g of t-butylhydroquinone to the above reaction product,
Dicyclohexylcarbodiimide (D.C.C.) 3
A mixed solution of 3.5 g, 1.0 g of 4- (N, N-dimethylamino) pyridine and 100 g of methylene chloride was added dropwise to the above mixture under stirring for 1 hour. Furthermore, 4 as it is
Stirred for hours.

The reaction mixture was passed through a nylon cloth of 200 mesh to remove insoluble matter by filtration. The filtrate was reprecipitated in 3 liters of methanol, and the powder was collected by filtration. 200 g of methylene chloride
, And reprecipitated again in 3 liters of methanol. The powder is collected by filtration, dried under reduced pressure, and weight-average molecular weight (hereinafter Mw).
103 g of 6.3 × 10 ³ macromonomers were obtained.

[0086]

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Macromonomer (MB) Synthesis Example 2: MB
-120 g of 1,6-hexanediol, glutaric anhydride 1
14.1 g, p-toluenesulfonic acid monohydrate 3.0 g
And a mixture of 250 g of toluene were reacted under the same conditions as in Synthesis Example 1. The amount of water distilled off azeotropically was 17.5 g. After cooling to room temperature, reprecipitation in 2 liters of n-hexane,
The liquid was decanted, collected, and dried under reduced pressure.

The above reaction product was dissolved in toluene to give
The carboxyl group content was measured by the method of neutralization titration with 1N potassium hydroxide in methanol to obtain 500 μmol / g.
It became. 100 g of the above solid, 10.7 g of glycidyl methacrylate, 1.0 g of t-butyl hydroquinone,
A mixture of 1.0 g of N, N-dimethyldodecylamine and 200 g of xylene was stirred at a temperature of 140 ° C. for 5 hours.

After cooling, the reaction solution was reprecipitated in 3 liters of n-hexane, the liquid was decanted, collected, and dried under reduced pressure. This macromonomer was titrated by the above-mentioned neutralization titration method to measure the residual carboxyl group content.
It was 1 / g, and the reaction rate was 99.8%. The yield of the obtained macromonomer was 63 g and the weight average molecular weight was 7.6 ×.
It was 10 ^3.

[0090]

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Macromonomer (MB) Synthesis Example 3: MB
-3 100 g of the polyester oligomer obtained in Synthesis Example 2,
To a mixture of 200 g of methylene chloride and 1 cc of dimethylformamide, 15 g of thionyl chloride was added dropwise with stirring at a temperature of 25 to 30 ° C. After completion of dropping, the mixture was stirred for 2 hours as it was.
Next, methylene chloride and excess thionyl chloride were distilled off under reduced pressure with an aspirator, and tetrahydrofuran 2 was added to the residue.
00 g and 11.9 g of pyridine were added and dissolved, and 8.7 g of allyl alcohol was added dropwise with stirring at a temperature of 25 to 30 ° C. After the dropping, the mixture was stirred as it was for 3 hours, and then the reaction mixture was put into 1 liter of water and stirred for 1 hour. After standing, the precipitated liquid was separated by decanting. 1 liter of water was added to this liquid material, the mixture was stirred again for 30 minutes, and allowed to stand, and the liquid material precipitated was collected by decanting. This operation was repeated until the supernatant solution became neutral. Next, add 500 ml of diethyl ether to this liquid and stir,
It was solidified.

The solid matter was collected by filtration and dried under reduced pressure to obtain 59 g of a macromonomer having a weight average molecular weight of 7.7 × 10 ³ . (MB-3) CH ₂ = CH-CH ₂ -O- [COCH ₂ CH ₂ CH ₂ COO (CH ₂ ) _h -O] -H

Macromonomer (MB) Synthesis Example 4: MB
-4 12-hydroxystearic acid 500g, outside temperature 150
The mixture was stirred in an oil bath at 0 ° C for 10 hours while distilling off water produced under reduced pressure of 10 to 15 mmHg. The carboxyl group content of the obtained liquid was 600 μmol / g. 100 g of the above liquid, 13.9 2-hydroxyethyl acrylate
g, t-butylhydroquinone 1.5 g and methylene chloride 200 g in a mixed solution of dicyclohexylcarbodiimide (abbreviation: D.C.C.) 24.8 g, 4- (N, N-
Dimethyl) aminopyridine 0.8 g and methylene chloride 1
00 g of the mixed solution was added dropwise to the above mixture under stirring at room temperature for 1 hour. The mixture was further stirred for 4 hours. The reaction mixture was filtered through a 200-mesh nylon cloth to remove insoluble materials.

The filtrate was concentrated under reduced pressure, 300 g of n-hexane was added to the residue and the mixture was stirred, and the insoluble matter was filtered off with a filter paper. After the filtrate was concentrated, 100 g of tetrahydrofuran was added to the residue to dissolve it. This mixture was reprecipitated in 1 liter of methanol, and the precipitated liquid material was dispersed by decanting.
After drying under reduced pressure, the yield was 50 g and the weight average molecular weight was 6.7 × 10.
³ macromonomers were obtained.

[0095]

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Resin Synthesis Example 1: [A-1] A mixture of 80 g of ethyl methacrylate, 20 g of the compound (MB-1) of Synthesis Example 1 of macromonomer and 150 g of toluene was heated to a temperature of 70 ° C. under a nitrogen stream. 4,4 '
-Azobis (4-cyanovaleric acid) (abbreviation A.C.V.)
0.8 g was added and stirred for 6 hours. Further, A. C. V.
0.1 g was added for 2 hours and then A. C. V. 0.
1 g was added and stirred for 3 hours. The weight average molecular weight of the obtained copolymer was 9.2 × 10 ⁴ .

[0097]

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Resin Synthesis Examples 2 to 17: [A-2] to [A
-17] Each resin in Table-A was synthesized by the same polymerization method as in Resin Synthesis Example 1. The weight average molecular weight of each resin is 8.5 × 10 ⁴ ~
It was 1.0 × 10 ³ .

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

Resin Synthesis Example 18: [A-18] A mixed solution of 80 g of ethyl methacrylate, 20 g of macromonomer (MB-5) having the following structure, 0.8 g of thioglycolic acid and 150 g of toluene was heated at 80 ° C. under a nitrogen stream.
Was heated. 1,1'-azobis (cyclohexane-1
-Carbonitrile) (abbreviation A.C.C.) 0.5 g was added and stirred for 5 hours.

Furthermore, A. C. C. Add 0.3g for 4 hours,
Further, A. C. C. 0.3 g was added and stirred for 5 hours. The weight average molecular weight of the obtained copolymer was 1.8 × 10 ⁵ .

[0104]

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Resin Synthesis Examples 19 to 29: [A-19] to
[A-29] Under the same polymerization conditions as in Resin Synthesis Example 18, the respective monomers and the mercapto compound were replaced and reacted to synthesize the resins shown in Table-B. The weight average molecular weight of each resin thus obtained was 9.0 ×.
It was in the range of 10 ^{4 to} 2.0 × 10 ⁵ .

[0106]

[Table 4]

[0107]

[Table 5]

Resin Synthesis Examples 30 to 35: [A-30] to
[A-35] A mixed solution of monomers and macromonomers corresponding to the following Table-C and 150 g of toluene was heated under a nitrogen stream at a temperature of 80 ° C.
Was heated. 1,1'-azobis (cyclohexane-1
-Carbonitrile) (abbreviation ABCCC) 0.8 g
Was added and stirred for 5 hours. B. C. C. 0.5 g
Add 3 hours, then A. B. C. C. 0.5 g was added and the temperature was raised to 90 ° C., followed by stirring for 4 hours. The weight average molecular weight of each of the obtained copolymers was 8 × 10 ^{4 to} 1.2 × 10 ⁵ .

[0109]

[Table 6]

As the binder resin of the radiation-sensitive composition of the present invention, in addition to the above graft copolymer, known binder resins conventionally used in the pigment dispersion method can be used in combination. As the binder resin, a linear organic high molecular polymer, which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution, is preferable. Examples of such a linear organic high molecular polymer include a polymer having a carboxylic acid in a side chain, for example, JP-A-59-44615 and JP-B-54-3432.
No. 7, JP-B-58-12577, JP-B-54-259
57, JP-A-59-53836, JP-A-59-71.
No. 048, 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. Especially among these, benzyl (meth)
Preference is given to acrylate / (meth) acrylic acid copolymers and multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers. Other useful water-soluble polymers include 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol. In 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 binder resin of the present invention and the resins that can be used in combination, it is in view of the image strength and the like to be formed. 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 binder resin used in combination therewith is from 5 to 90% by weight based on the total solid components of the radiation-sensitive composition. Preferably 10
60 wt%. If the total amount of the binder resin is less than 5 wt%, the film strength will be reduced, and if it is more than 90 wt%, the acid content will be large, and it will be difficult to control the solubility. Image density cannot be obtained.

Next, the radiation-sensitive compound of the present invention will be described. The radiation-sensitive compound of the present invention comprises (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) halomethyloxa. A diazole compound, at least one active halogen compound selected from halomethyl-s-triazine compounds, and / or a 3-aryl-substituted coumarin compound, (1) having at least one addition-polymerizable ethylene group, and under normal pressure A compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher and (3) at least one lophine dimer, or (1) at least one addition-polymerizable ethylene group, at 100 ° C. or higher under normal pressure (2) halomethyl-oxadiazole compound, halomethyl-s-triazinated compound having ethylenically unsaturated group with boiling point of At least one active halogen compound selected from the object, and a and / or 3-aryl-substituted coumarin compound, (3) at least one lophine dimer, it is preferred that a combination of a.

Here, (2) and (3) are photopolymerization initiators, which have a function of polymerizing the monomer of (1) by light irradiation. It has at least one addition-polymerizable ethylenically unsaturated group (1) and has a boiling point of 10 at atmospheric pressure.
Examples of the compound at 0 ° C. or higher include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, triglyceride Methylolethane tri (meth) acrylate,
Neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, to which ethylene oxide and propylene oxide are added and then (meth) acrylated, JP-B-48-41
No. 708, Japanese Patent Publication No. 50-6034, and Japanese Patent Laid-Open No. 51-37.
Urethane acrylates as described in JP-A No. 193, JP-A-48-64183 and JP-B-49-4.
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, described in JP 3191 and JP-B-52-30490 may be mentioned. I can. Further, the Journal of the Adhesion Society of Japan, Vol. 2
0, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers 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 10 based on the total solid content of the radiation-sensitive composition.
˜50 wt%.

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

[0116]

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Here, W is a substituted or unsubstituted aryl group, X is a hydrogen atom, an alkyl group or an aryl group, Y is a fluorine atom, a chlorine atom or a bromine atom, and n is 1 to 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-9-1281 discloses a vinyl-halomethyl-s-triazine compound represented by the following general formula II.
-133-428, a 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula III and a 4- (p-amino acid) represented by the following general formula IV Phenyl) -2,6-di-halomethyl-s-triazine compounds.

[0118]

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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 IIA -O- Or, it is -S-.

[0120]

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Here, X represents --Br, --Cl, and m, n
Is an integer of 0 to 3 and R is represented by the general formula IIIA, 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.

[0122]

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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.
It is indicated by IVA and IVB.

[0124]

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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.

[0127]

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Specific examples of the general formula II include 2,4-
Bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl)
-6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like.

Specific examples of the general formula III include 2-
(Naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1
-Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2
-(4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2
-Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4-
(2-ethoxyethyl) -naphth-1-yl] -4,6
-Bis-trichloromethyl-s-triazine, 2- [4
-(2-butoxyethyl) -naphth-1-yl] -4,
6-bis-trichloromethyl-s-triazine, 2-
(2-methoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-
1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-ethoxy-naphth-2-yl) -4,6
-Bis-trichloromethyl-s-triazine, 2-
(4,5-dimethoxy-naphth-1-yl) -4,6-
Bis-trichloromethyl-s-triazine and the like can be mentioned.

Specific examples of the general formula IV 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 a compound represented by V. R₈Is hydrogen atom, carbon number 1
~ 8 alkyl group, C6-10 aryl group (preferably
Especially hydrogen atom, methyl group, ethyl group, propyl group,
Chill group) to R₉Is hydrogen atom, alkyl having 1 to 8 carbon atoms
Group, an aryl group having 6 to 10 carbon atoms, represented by the general formula VA
Group (preferably a methyl group, an ethyl group, a propyl group, a group
A chill group, a group represented by the general formula VA, particularly preferably a general group
Represents a group represented by the formula VA). R, R₁₁Is hydrogen
Atoms, alkyl groups having 1 to 8 carbon atoms (eg, methyl group, ether
Cyl group, propyl group, butyl group, octyl group), carbon number
1-8 haloalkyl groups (eg chloromethyl group, fluoro)
(Methyl group, trifluoromethyl group, etc.), carbon number 1-8
Alkoxy groups (eg methoxy, ethoxy, buto
Xy group), optionally substituted aryl having 6 to 10 carbon atoms
Group (for example, phenyl group), amino group, -N (R₁₆)
(R₁₇), Halogen (for example, -Cl, -Br, -F)
Represent. Preferably hydrogen atom, methyl group, ethyl group, metho
Xy group, phenyl group, -N (R₁₆) (R₁₇), -Cl
You. R₁₂Is an optionally substituted aryl having 6 to 16 carbon atoms
Groups (eg phenyl, naphthyl, tolyl, cumyl
Group). As a substituent, an amino group, -N (R₁₆) (R
₁₇), An alkyl group having 1 to 8 carbon atoms (for example, a methyl group, 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.), carbon number 1-8
Alkoxy groups (eg methoxy, ethoxy, buto
Xy group), hydroxy group, cyano group, halogen (eg
—Cl, —Br, —F). R₁₃, R₁₄, R
₁₆, R ₁₇Are hydrogen atom and alkyl having 1 to 8 carbon atoms, respectively.
Groups (eg methyl, ethyl, propyl, butyl
Group, octyl group). R₁₃, R₁₄And R₁₆, R₁₇Is
In addition, they are bonded to each other with a nitrogen atom to form a heterocycle (for example, pipette).
Lysine ring, piperazine ring, morpholine ring, pyrazole
Ring, diazole ring, triazole ring, benzotriazo
Ring, etc.) may be formed. R_FifteenIs hydrogen atom, carbon number 1
~ 8 alkyl groups (eg methyl, ethyl, propyl
Group, butyl group, octyl group), C1-C8 alco
Xoxy group (eg methoxy group, ethoxy group, butoxy group
Group), optionally substituted aryl group having 6 to 10 carbon atoms
(Eg phenyl group), amino group, N (R₁₆) (R₁₇),
Represents halogen (for example, -Cl, -Br, -F). Zb
Is = O, = S or = C (R₁₈) (R₁₉). Like
Actually = O, = S, = C (CN)_TwoAnd particularly preferred
Is = O. R₁₈, R₁₉Is a cyano group, -C
OOR₂₀, -COR_{twenty one}Represents R₂₀, R_{twenty one}Each is charcoal
Alkyl groups having a prime number of 1 to 8 (eg, methyl group, ethyl group,
Propyl group, butyl group, octyl group), having 1 to 8 carbon atoms
Haloalkyl group (eg chloromethyl group, fluoromethyl group
Group, trifluoromethyl group, etc.), optionally substituted carbon
It represents an aryl group of the formulas 6 to 10 (for example, a phenyl group).

A particularly preferred 3-aryl-substituted coumarin compound (B) is represented by the general formula VI {(s-triazine-
2-yl) amino} -3-arylcoumarin compounds.

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

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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, 109, 110, 138, 139, 151, 154, 167 CIPigment Orange 36, 38, 43 CIPigment Red 105 , 122, 149, 150, 155, 171, 175, 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 and the like.

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 A-block portion of the AB block portion forming the graft copolymer and the basic component of the pigment specifically interact with each other.

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

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

In the present invention, a processed pigment previously treated with an acrylic resin, a vinyl chloride-vinyl acetate resin, a maleic acid resin, an ethyl cellulose resin, a nitrocellulose resin or the like can also be conveniently used. 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 type pigment alone or a mixture with a dioxazine type 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. Below 100: 41, there was a problem in dispersion stability.

Further, the pigment concentration in the total solid components of the radiation-sensitive composition of the pigment of each color is from 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.

Further, in order to promote the alkali solubility in the unirradiated area and 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 necessary 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 and the like. 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 they are mixed uniformly, and then kneaded by using two rolls or two rolls while heating if necessary to sufficiently mix the pigment and the binder resin. 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 to 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.

Examples of the substrate include soda glass, Pyrex glass, quartz glass used for liquid crystal display devices and the like, those having a transparent conductive film adhered thereto, and photoelectric conversion device substrates used for solid-state image pickup devices such as silicon. Examples include substrates. These substrates are generally formed with black stripes for isolating each pixel.

Any developer 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 kinds of organic solvents and 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 alkalinity, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Alkaline compounds such as choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene are added at a concentration of 0.001-
An alkaline aqueous solution dissolved to be 10% by weight, preferably 0.01 to 1% by weight is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0175]

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. Example 1-Example of the graft copolymer of the present invention (A-5) 40 wt% toluene solution 50 parts-Methyl methacrylate / methacrylic acid copolymer (80/20 wt ratio) 40 parts-Dipentaerythritol pentaacrylate 40 parts-C. 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, whereby a red uniform coating film was obtained. 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-
Without using 5), a methyl methacrylate / methacrylic acid copolymer alone was dispersed in the same manner to prepare a radiation-sensitive composition. 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-D 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 D. As a result, the invention is all good.

Evaluation and Evaluation Criteria ×: 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 μ 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

[0180]

[Table 7]

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. -Example of graft copolymer of the present invention (A-2) 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 E. As a result, it is understood that the present invention is good.

[0183]

[Table 8]

Examples-10, 11 and Comparative Example-4 The radiation-sensitive composition of Example-1 was replaced with the following ones, and dispersion, coating, exposure and development were carried out in the same manner as in Example 1 to obtain a color filter pattern. Was produced. As shown in Table-F, with 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 parts ・ Propylene glycol monomethyl ether acetate 250 parts ・ Ethyl 3-ethoxypropionate 250 parts

[0185]

[Table 9]

Example-12 -Graft copolymer (A-12) of the present invention (40 wt% toluene solution) 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 so that the solid content was 25 wt%, and the mixture was dispersed with 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 above 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, coating, exposure and development were sequentially repeated on a glass substrate on which a black matrix had been patterned 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.

[0193]

INDUSTRIAL APPLICABILITY In the radiation-sensitive composition in which the pigment of the present invention is dispersed, the binder resin described above can be used to obtain a composition having excellent pigment dispersibility. By using this composition, a color filter having excellent coatability, high quality image quality and high reliability can be produced.

Claims (4)

[Claims] 1. A radiation-sensitive composition containing the following (A), (B), and (C). (A) Binder resin: the following general formula (Ia) and general formula (I)
b), weight average molecular weight 1 × 10 ^{3 to} 1.5 ×
A resin comprising a graft copolymer having a weight average molecular weight of 3 × 10 ⁴ to 1 × 10 ^{6 and} containing at least one of 10 ⁴ polyester type macromonomers (MB) as a polymer component. (B) radiation-sensitive compound, and (C) pigment In formulas (Ia) and (Ib), [] represents a repeating unit. f ₁ and f ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, or a carbon number of 1.
~ 8 hydrocarbon group, -COO-V ₁ or -COO-V ₂ via a hydrocarbon group having 1 to 8 carbon atoms (V ₁ and V ₂ each represent a hydrocarbon group having 1 to 18 carbon atoms) Represents X
₁ is a single bond or -COO-, -OCO-,-(C
_{H 2) u1 -COO -, -} (CH 2) u2 -OCO- (u 1, u 2
Represents an integer of 1 to 3), -CON (d ₁ )-(d ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms),
-CONHCONH-, -CONHCOO-, -O-,
-C ₆ H ₄ - or -SO ₂ - represent. Y ₁ represents a group connecting X ₁ and Z ₁ . Z ₁ is —CH ₂ —, —O— or —
Represents NH-. W ₁ and W ₂ may be the same or different from each other, and each is a divalent aliphatic group, a divalent aromatic group {-O-, -S-, in the bond of each divalent organic residue, -N (d
₂₎ - (d ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon _{atoms), - SO 2 -, -} COO -, - OCO -, -
CONHCO -, - NHCONH -, - CON (d 3)
- (d ₃ represents the same content as d _2), - SO ₂ N
(D ₄₎ - (d ₄ represents the same content as d ₂₎ and -Si
(d ₃ ) (d ₄ )-may be interposed with at least one bonding group} or an organic residue constituted by a combination of these residues. R ₆₁ represents a hydrogen atom, a hydrocarbon group or a —COR ₆₃ group (R ₆₃ represents a hydrocarbon group).
W ₃ represents a divalent aliphatic group. f ₃ and f ₄ are f ₁ and f
₂ , ₂ , X ₂ , Y ₂ and Z ₂ are the same as X ₁ , Y ₁ and Z ₁ , and R ₆₂ is the same as R ₆₁ . 2. The resin comprises a —PO ₃ H ₂ group, a —SO ₂ H group.
Group, -COOH group, -OH group, -P (= O) (OH) (R)
Group (R represents a hydrocarbon group or an —OR ′ group (R ′ represents a hydrocarbon group)) and at least one polar group selected from a cyclic acid anhydride-containing group, a polymer of the copolymer The radiation-sensitive composition according to claim 1, which is a resin formed by bonding to an end of a main chain portion. 3. The radiation-sensitive compound is (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) 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) and (2) and (3)
The radiation-sensitive composition according to claim 1, which is a combination thereof. 4. The radiation-sensitive composition according to claim 1, wherein the pigment has a basic N atom in the pigment molecule.