JPH09179295A - Radiation sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve dispersibility, properties of a coating film and pattern reproducibility by incorporating a graft copolymer (bonding resin) having specific acidic groups and a specified structure, a radiation sensitive compd. and a pigment. SOLUTION: This compsn. contains a bonding resin made of a copolymer of a monofunctional macromonomer having a wt. average mol.wt. of <=2×10<4> obtd. by bonding a polymerizable double bond group represented by formula I to only one terminal of a polymeric principal chain including at least one of polymer components represented by formulae II, III with a monomer represented by formula IV, a radiation sensitive compd. and a pigment. In the formula I, V0 is -COO-, -OCO-, etc., and each of c1 and c2 is H, halogen, etc. In the formulae II, III, V1 , d1 and d2 have the same meanings as V0 , c1 and c2 in the formula I, respectively, Q1 is a 6-12C arom. group, etc., and Q0 is -CN, -CONH2 , etc. In the formula IV, V2 and Q2 have the same meanings as V1 and Q2 in the formula II, respectively, and e1 and e2 have the same meanings as c1 and c2 in the formula I, respectively.

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 obtained by dispersing a pigment in a thermosetting resin or an ultraviolet curable resin. Filtering is difficult, and there is a problem in that defects are likely to occur due to dust, foreign matter, 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.

[0009] A dispersion method using a surfactant is also known, but this method has problems such as a reaction between the surfactant and a pigment or a resin, and a problem that the surfactant is protruded 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]

[Means for Solving the Problems] The following (A) is represented by the following general formula (I) only at one end of the polymer main chain containing at least one of the polymer components represented by the following general formulas (IIa) and (IIb). Weight average molecular weight 2 formed by combining polymerizable double bond groups
A monofunctional macromonomer of 10 ⁴ or less and the following general formula (II
A binder resin which is a copolymer comprising at least the monomer represented by I), (B) a radiation-sensitive compound, and (C)
A radiation-sensitive composition containing a pigment.

[0015]

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

[0017]

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[In the formula (IIa) or (IIb), V ₁ is a formula
It has the same contents as V _{0 in} (I). Q ₁ has 1 to 1 carbon atoms
It represents an aliphatic group having 18 or an aromatic group having 6 to 12 carbon atoms. d ₁ and d ₂ may be the same as or different from each other and represent the same contents as c ₁ and c ₂ in the formula (I). Q ₀ is -C
N, represents a -CONH ₂ or -C ₆ H ₄ T.

Here, T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or -COOZ "(Z" represents an alkyl group, an aralkyl group or an aryl group). ]

[0020]

[Chemical 6]

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

2. 1. The copolymer in the resin (A) of (1) further contains —H ₂ PO ₃ group, —SO ₃ H group, —COOH.
Group, a phenolic OH group, and -P (= O) ( _R0 ) (O
H) group (R ₀ represents a hydrocarbon group or —OR (R represents a hydrocarbon group) group), and at least one acidic group selected from these groups is bonded to one end of the main chain of the copolymer. The radiation-sensitive compound according to 1.

3. The radiation-sensitive compound is (1) a compound having at least one addition-polymerizable ethylene group and an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure (2) a halomethyloxadiazole compound, At least one active halogen compound selected from halomethyl-s-triazine compounds, and / or 3-aryl-substituted coumarin compound (3) Among at least one lophine dimer, (1)
And (2), (1) and (3), or (1) and (3). The radiation-sensitive composition as described in 1.

4. 1. The pigment has a basic N atom in the pigment molecule. The radiation-sensitive composition as described in 1. 5. 1. The pigment is a processed pigment. The radiation-sensitive composition as described in 1. 6. The processed pigment is 1. ~ 2. 4. The graft copolymer described in 1 above, or a powder, pellets, or paste-like agent obtained by finely dispersing a pigment in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate resin, ethyl cellulose and nitrocellulose. The radiation-sensitive composition as described in 1.

[7] 4. The processed pigment has been subjected to a flushing treatment. The radiation-sensitive composition as described in 1. 8. 1. On the transparent substrate surface ~ 7. A color filter for a liquid crystal display device, which comprises forming a coating film of the radiation-sensitive composition as described in 1 above and repeating exposure and development to form red, green and blue patterns on the same surface. It was achieved by

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), the radiation-sensitive compound (B) and the pigment (C) having a specific acidic group and a specific structure, the dispersibility is remarkably improved,
It has become possible to provide a color filter which has excellent coating properties and has no pattern drop-off 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.

Although it is not clear why the effect of the present invention is exerted, the present inventors consider as follows.
A copolymer containing an acidic group is often used in the radiation-sensitive composition, but improvement in dispersibility cannot be expected. Although these have acidic groups, they are generally random copolymers and 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 portion in one copolymer, the dispersibility is improved because either the main chain or the graft portion 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.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The resin [A] used in the present invention will be described below. The resin [A] satisfies the above-mentioned physical properties and has the same general formula (I) as the monofunctional macromonomer (MB)
The resin is composed of a graft-type copolymer containing at least the monomer represented by II).

The resin [A] is preferably a graft type copolymer resin having a weight average molecular weight of 3 × 10 ⁴ or more.
More preferably, the weight average molecular weight is 5 × 10 ^{4 to} 3 × 10 ^5.
It is. When the molecular weight is smaller than 3 × 10 ⁴ , the effects of the present invention, particularly the effect of dispersibility, cannot be sufficiently exerted, and 3 × 10
^{When it is 5} or more, the solubility tends to decrease.

The glass transition point of the resin [A] is preferably 0.
The temperature is in the range of ℃ to 120 ℃, more preferably 10 ℃ to 90 ℃.

The monofunctional macromonomer (MB) has a polymerizable double bond group represented by the general formula (I) and a polymerizable double bond group represented by the general formula (II).
a) or at least one polymer component represented by (IIb)
A polymer having a weight average molecular weight of 2 × 10 ⁴ or less, which is formed by bonding to only one end of a polymer main chain containing a seed. In the general formulas (I), (IIa) and (IIb), c ₁ , c ₂ and
The hydrocarbon groups contained in V ₀ , d ₁ , d ₂ , V ₁ , Q ₁ and Q ₂ respectively have the indicated carbon number (as an unsubstituted hydrocarbon group).
However, these hydrocarbon groups may have a substituent.

In the general formula (I) showing the macromonomer (MB), V ₀ is --COO--, --OCO--, --C.
_{H 2 OCO -, - CH 2} COO -, - O -, - SO 2 -,
-CO-, -CONHCOO-, -CONHCONH
_{-, - CONHSO 2 -, -} CON (P 3) -, - SO 2
(P ₃₎ - or -C ₆ H ₄ - represents a. Here, P ₃ is a hydrogen atom, and a preferable hydrocarbon group has 1 to 1 carbon atoms.
18 optionally substituted alkyl groups (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-
A bromoethyl group, a 2-cyanoethyl group, a 2-methoxycarbonylethyl group, a 2-methoxyethyl group, a 3-bromopropyl group, and the like, an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1 A 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.), and optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2- Naphthylethyl group,
Chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), having 5 to 8 carbon atoms
An optionally substituted alicyclic group (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, a phenyl group , Naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromo And a phenyl group, a cyanophenyl group, an acetylphenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, a butoxycarbonylphenyl group, an acetamidophenyl group, a propioamidophenyl group, a dodecyloylamidophenyl group and the like).

[0035] V ₀ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group,
Chloromethyl group, methoxymethyl group, etc.) and alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.).

C ₁ and c ₂ may be the same or different from each other, preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, a carbon number of 1 to 4
Alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, etc.), -COO-Z 'or -COO-Z' through a hydrocarbon (Z 'is a hydrogen atom or a carbon number of 1 to 1).
8 represents an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, each of which may be substituted, and specifically has the same meanings as those described for P ₃ ). Represent.

Examples of the hydrocarbon in the -COO-Z 'group via the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (I),
V ₀ is -COO -, - OCO -, - CH 2 OCO -, - C
_{H 2 COO -, - O -} , - CONHCOO -, - CON
HCONH -, - CONH -, - SO 2 NH- or -C ₆
H ₄ —, wherein c ₁ and c ₂ may be the same or different and each represents a hydrogen atom, a methyl group, —COO-Z ′ or —CH
₂ COO-Z ′ (Z ′ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group,
Butyl group, hexyl group, etc.)). Even more preferably, one of c ₁ and c ₂ represents a necessary hydrogen atom. That is, as the polymerizable double bond group represented by the general formula (I), specifically,

[0039]

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And the like. In the general formula (IIa), V ₁ has the same content as V ₀ in the formula (I).
d ₁ and d ₂ may be the same as or different from each other, and have the same contents as c ₁ and c ₂ in the formula (I). Q ₁ has 1 to 1 carbon atoms
It represents an aliphatic group having 18 or an aromatic group having 6 to 12 carbon atoms.

Specifically, 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, Tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxylethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (Trimethoxysilyl) ethyl group, 2-tetrahydrofuryl group, 2-thienylethyl group, 2-N, N-dimethylaminoethyl group, 2
-N, N-diethylaminoethyl group), carbon number 5-8
A cycloalkyl group (for example, a cycloheptyl group, a cyclohexyl group, a cyclooctyl group, etc.), and an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a phenethyl group, a 3-phenylpropyl group, a naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group,
Chloro-methyl-benzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, etc.) and the like.

Further, an optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl group, tolyl group, xylyl group,
Aromatic groups such as chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, naphthyl group, chloronaphthyl group and the like. Formula (II
In a), preferably V ₁ is -COO-, -OCO.
_{-, - CH 2 COO -,} - CH 2 OCO -, - O -, - C
O-, -CONHCOO-, -CONHCONH-,-
CONH -, - SO ₂ NH-, or -C ₆ H ₄ - represents a.

Preferred examples of d ₁ and d ₂ are the above-mentioned c ₁ and
Represents the same contents as c ₂ . In formula (IIb), Q ₀ represents —CN, —CONH ₂ or —C ₆ H ₄ T, and T represents a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a hydrocarbon group (eg, methyl group, Ethyl group, propyl group, butyl group, chloromethyl group, phenyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.) or-
COO-Z "(Z is preferably an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an aryl group).

The macromonomer (MB) may contain two or more kinds of polymer components represented by the formula (IIa) or (IIb). In the formula (IIa), when Q ₁ is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms is a macromonomer (M
It is preferably used within a range not exceeding 20% by weight based on the total polymer components in B). Further, when V ₁ in the general formula (IIa) is —COO—, at least 30% by weight or more of the polymer component represented by the formula (IIa) in all the polymer components in the macromonomer (MB). It is preferable to be contained.

In the macromonomer (MB), acrylonitrile, methacrylonitrile, acrylamide may be used as a monomer corresponding to a repeating unit which can be copolymerized with the polymer component represented by the formula (IIa) and / or (IIb). , Methacrylamides, styrene and derivatives thereof (eg vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxymethylstyrene, N, N-dimethylaminomethylstyrene, etc.), heterocyclic vinyls (eg vinylpyridine, vinylimidazole) , Vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.) and the like.

The macromonomer (MB) provided in the resin [A] of the present invention is one of the polymer main chains composed of repeating units represented by the general formulas (IIa) and / or (IIb) as described above. The polymerizable double bond group represented by the general formula (I) is directly bonded only to the terminal or has a chemical structure in which it is bonded by an arbitrary linking group. The group connecting the component of formula (I) and the component of formula (IIa) or (IIb) includes carbon-carbon (single bond or double bond),
It is composed of any combination of carbon-heteroatom bonds (for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.) and heteroatom-heteroatom bonds.

Preferred among the macromonomers (MB) of the present invention are those represented by the formula (IIa) or (IIb).

[0048]

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In the formula (IIa) or (IIb), c ₁ , c ₂ and d
₁ , d ₂ , V ₀ , V ₁ , Q ₁ , and Q ₀ are represented by the formulas (I) and (II), respectively.
It has the same contents as those described in a) and (IIb). W ₀ is a mere bond or-[C (h ₁ ).
(h ₂ )]-[h ₁ and h ₂ are hydrogen atom, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (eg, methyl group, ethyl group, propyl). Group etc.) etc.],

[0050]

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[H ₃ and h ₄ are each a hydrogen atom, the above formula (II
a) represents a hydrocarbon group having the same meaning as Q ₁ in a)] or a single linking group selected from atomic groups or a linking group composed of any combination. When the weight average molecular weight of the macromonomer (MB) exceeds 2 × 10 ⁴ , the formula becomes
The copolymerizability with the monomer represented by (III) decreases. On the other hand, if the molecular weight is too small, the effect of improving the dispersibility of the pigment will be small, so that it is preferably 1 × 10 ³ or more.

The macromonomer (MB) used for the resin [A] in the present invention can be produced by a conventionally known synthesis method. For example, a method by an ionic polymerization method in which various reagents are reacted with the ends of a living polymer obtained by anionic polymerization or cationic polymerization to form a macromer, and a reactive group such as a carboxyl group, a hydroxyl group or an amino group is contained in the molecule. Polymerization initiator and /
Or, by using a chain transfer agent, a radical polymerization method obtained by reacting an oligomer having a terminal reactive group bond obtained by radical polymerization with various reagents to form a macromer, or an oligomer obtained by a polyaddition or polycondensation reaction In the same manner as the above radical polymerization method, a method by a polyaddition condensation method of introducing a polymerizable double bond group and the like can be mentioned.

Specifically, P. Dreyfuss & RPQuirk, En
cycl. Polym. Sci. Eng., 7 , 551 (1987), PFRempp,
E. Franta, Adv. Polym. Sci., 58 , 1 (1984), V. Percec,
Appl. Polym. Sci., 285 , 95 (1984), R. Asami, M. Tak
aRi, Makromol. Chem. Suppl., 12 , 163 (1985), P.Remp
p et al., Makromol. Chem. Suppl., 8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 3
1 , (1982), Kobayashi Shiro, Polymer, 30 , 625 (1981), Higashimura Toshinobu, Japan Adhesion Society Journal 18 , 536 (1982), Ito Koichi, Polymer Processing, 35 , 262 (1986), Toki It can be synthesized according to the methods described in Shiro, Takashi Tsuda, Functional Materials, 1987 No. 10, 5 etc. and the references and patents cited therein.

More specifically, the macromonomer (MB) of the present invention can be exemplified by the following compounds. However, the scope of the present invention is not limited to these.

However, in each of the following examples, c ₁ represents —H or —CH ₃ , d ₁ represents —H or —CH ₃ , and d ₂ represents —H, —CH ₃ or —CH ₂ COOCH ₃ are shown, R ₁₁ is _{-C d H 2d + 1, -CH} 2 C 6 H 5, -C 6 H 5 or -C ₆ H ₄ -
CH ₃ , R ₁₂ is —C _d H _{2 d + 1} , — (CH ₂ ) ₄ —C ₆
H ₅ or —C ₆ H ₄ —T ₁ , wherein R ₁₃ is —C _d H _{2d + 1} ,
CH ₂ C ₆ H ₅ or -C indicates ₆ H _5, R ₁₄ is -C _d H _{2d + 1} or indicates _{-CH 2 C 6 H 5, R} 15 is _{-C d H 2d + 1, -CH} 2
C ₆ H ₅ or —CH ₂ —C ₆ H ₄ —T ₁ , wherein R ₁₆ is —C _d
Indicates H _{2d + 1,} R ₁₇ represents a _{-C d H 2d + 1, -CH} 2 C 6 H 5 or _{-C 6 H 4 -T 2, R} 18 is -C _d H _2d + 1, -CH ₂ C ₆
H ₅ or indicates _{-C 6 H 4 -T 3, V} 1 is -COOCH _3, -
C ₆ H ₅ or —CN, and V ₂ is —OC _d H _{2d + 1} , —OC
_{OC d H 2d + 1, -COOCH} 3, -C 6 H 5 or indicates -CN, V ₃ is _{-COOCH 3, -C 6 H 5,} -C 6 H 4 -T 4 or indicates -CN, V ₄ is -OCOC _d H _{2d + 1} , -CN,-
CONH ₂ or -C indicates ₆ H _5, V ₅ is -CN, -CON
H ₂ or -C indicates ₆ H _5, V ₆ is -COOCH _3, -C ₆ H
₅ or -C ₆ H ₄ shows a -T _1, T ₁ is -CH _3, -Cl, -
Br or indicates -OCH _3, T ₂ is -CH _3, shows a -Cl or -Br, T ₃ is -H, -Cl, -Br, -CH _3,
Indicates -CN or -COOCH _3, T ₄ is -CH _3, -C
shows the l or -Br, T ₅ is -Cl, -Br, -F, -
OH or shows a -CN, T ₆ is -H, -CH _3, -Cl,
Represents —Br, —OCH ₃ or —COOCH ₃ , and d is 1 to
18 is an integer, e is an integer of 1 to 3, and f is 2 to
Indicates an integer of 4.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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The monomer copolymerizable with the above-mentioned macromonomer (MB) is represented by the general formula (III). In the formula (III), e ₁ and e ₂ may be the same as or different from each other, and have the same contents as c ₁ and c _{2 in} the formula (I). V ₂ is the formula (II
V ₁ and Q _{2 in} a) have the same contents as Q _{1 in} formula (IIa). Further, the resin [A] of the present invention may contain, in addition to the above-mentioned macromonomer (MB) and the monomer of the general formula (III), another monomer other than these as a copolymerization component.

For example, vinyl compounds containing an acid group, α-olefins, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, vinyl group-containing naphthalene compounds (eg vinyl-naphthalene, 1-isopropenylnaphthalene, etc.). And vinyl group-containing heterocyclic compounds (for example, vinylpyridine, vinylpyrrolidone, vinylthiophene, vinyl-tetrahydrofuran, vinyl-1,3-dioxolane, vinylimidazole, vinylthiazole, vinyloxazoline, etc.).

In the resin [A], the macromonomer (M
A copolymerization component having B) as a repeating unit and a general formula (III)
The compositional ratio of the copolymerization component having the monomer represented by (1) as a repeating unit is 1 to 80/99 to 20 (weight composition ratio),
It is preferably 5 to 60/95 to 40 weight composition ratio. The vinyl compound containing an acidic group is described, for example, in "Polymer Data Handbook [Basic Edition]", edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form,
α- (2-amino) methyl, α-chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, α-chloro- β
-Methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl- 2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4
-Ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzene carboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl group or allyl of dicarboxylic acids Half-ester derivatives of these groups, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing an acidic group in the substituent of the amide derivative.

When the "vinyl compound containing an acidic group" is contained as a repeating unit as another copolymerization component, the acidic group-containing copolymerization component preferably does not exceed 10% of the copolymer. Further, the resin [A ′] that can be used as a preferred embodiment of the present invention contains at least one repeating unit represented by the general formula (III) and at least one repeating unit represented by the macromonomer (MB). at one end of the polymer main chain only, -PO ₃ H ₂ group, -
SO ₃ H group, -COOH group, -OH group, -SH group and _{-P (= O) (R 0} ) (OH) group {R ₀ is a hydrocarbon group or -O
R ₀ ′ (R ₀ ′ represents a hydrocarbon group) is a polymer formed by bonding at least one acidic group selected from the following.

Here, the hydrocarbon group represented by R ₀ and R ₀ ′ is an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group). Group, octyl group, decyl group, dodecyl group,
Tetradecyl group, octadecyl group, 2-methoxyethyl group, 3-methoxyethyl group, 2-cyanoethyl group, 2-
An ethoxyethyl group or the like, an optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3
-Phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms (eg cyclopentyl group, cyclohexyl group, etc.), substitution having 6 to 12 carbon atoms Aromatic group which may be (for example, phenyl group, tolyl group, xylyl group, naphthyl group, chlorophenyl group, bromophenyl group, alkoxyphenyl group (as an alkyl group,
Methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.), acetoxyphenyl group, methyl-chloro-phenyl group, propylphenyl group, butylphenyl group, decylphenyl Groups, etc.) and the like.

When the above acidic group is bonded to one end of the polymer main chain, a copolymerization component containing a polar group such as carboxyl group, sulfo group, hydroxyl group and phosphono group in the polymer main chain is used. It is preferable not to contain it. Resin [A ']
In the above, the acidic group has a chemical structure which is directly bonded to one end of the polymer main chain or bonded through an arbitrary linking group.

As the bonding group, carbon-carbon bond (single bond or double bond), carbon-hetero atom bond (as the hetero atom, for example, oxygen atom, sulfur atom, nitrogen atom,
Silicon atom) and any combination of heteroatom-heteroatom bond atomic groups. For example-[C
(H ₅ ) (h ₆ )]-[h ₅ and h ₆ represent the same contents as the above h ₁ and h ₂ ]

[0068]

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(Wherein h ₇ and h ₈ represent the same contents as the above h ₃ and h ₄ ) and the like, a single linking group selected from atomic groups or a linking group composed of an arbitrary combination thereof, etc. Can be mentioned.
The content of the acidic group bonded to only one end of the polymer main chain in the resin [A '] is preferably 0.1 to 15% by weight, more preferably 0.1% by weight per 100 parts by weight of the resin [A'].
5 to 10% by weight. If it is less than 0.1% by weight, the effect of improving the dispersibility becomes small, and if it is 15% by weight or more, the solubility is lowered or the compatibility with the binder resin used in combination is lowered, so that a uniform coating film cannot be formed.

The resin [A '] of the present invention in which a specific acidic group is bonded only to one end of the main chain of the polymer has various reagents at the end of the living polymer obtained by conventionally known anionic or cationic polymerization. Or a radical polymerization method using a polymerization initiator and / or a chain transfer agent containing a specific acidic group in the molecule, or a method described above. It can be easily produced by a synthetic method such as a method of converting a polymer having a reactive group at a terminal obtained by an ionic polymerization method or a radical polymerization method into a specific acidic 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 Chemicals" 30 , 232 (1985), Akira Ueda, Susumu Nagai "Science and Industry" 60 , 57 (1986) Etc. and the literature cited therein.

(Production Example of Macromonomer Used for Resin [A]) Production Example of Macromonomer 1: (M-1) A mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was stirred under a nitrogen stream while stirring. The temperature was raised to 75 ° C. 1.0 g of 2,2'-azobis (cyanovaleric acid) (abbreviated as ACV) was added, and 8
Reacted for hours. Next, 8 g of glycidyl methacrylate and 1.0 g of N, N-dimethyldodecylamine were added to the reaction solution.
And 0.5 g of t-butyl hydroquinone,
The mixture was stirred at 00 ° C for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder.
The number average molecular weight of the polymer (M-1) was 6,500. Production Example of Macromonomer: (M-2) A mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C while stirring under a nitrogen stream. 1.5 g of 2,2'-azobis (isobutyronitrile) (abbreviated as AIBN) was added and reacted for 8 hours. Next, 7.5 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.8 g of t-butylhydroquinone were added to the reaction solution.
Was added and stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 85 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (M-2) was 2,400.

Production Example 3 of Macromonomer: (M-3) A mixed solution of 94 g of propyl methacrylate, 6 g of 2-mercaptoethanol and 200 g of toluene was heated to a temperature of 70 ° C. under a nitrogen stream. A. I. B. N. 1.2 g was added and reacted for 8 hours. Next, the reaction solution was cooled to a temperature of 20 ° C. in a water bath, 10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was added at a temperature of 25 ° C.
The mixture was stirred and dripped below. After the addition, the mixture was further stirred for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added, the mixture was heated to a temperature of 60 ° C, and stirred for 4 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol to obtain 79 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (M-3) was 4,500. Production Example 4 of Macromonomer: (M-4) A mixed solution of 95 g of ethyl methacrylate and 200 g of toluene was heated to 70 ° C under a nitrogen stream. 2,2 '
5 g of -azobis (cyanoheptanol) was added and reacted for 8 hours.

After cooling, the reaction solution was cooled to 20 ° C. in a water bath.
1.0 g of triethylamine and 21 g of methacrylic anhydride were added, and the mixture was stirred for 1 hour, and then stirred at a temperature of 60 ° C. for 6 hours. The obtained reaction product was cooled and then reprecipitated in 2 liters of methanol to obtain 75 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (M-4) was 6,200.

Preparation Example 5 of Macromonomer: (M-5) 93 g of benzyl methacrylate, 7 g of 6-mercaptopropionic acid, 170 g of toluene and 3 of isopropanol
0 g of the mixture was heated to a temperature of 70 ° C. under a nitrogen stream to obtain a homogeneous solution. A. I. B. N. 2.0 g was added and reacted for 8 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol and heated to 50 ° C. under reduced pressure to distill off the solvent. The obtained viscous material was dissolved in 200 g of toluene, 16 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecyl methacrylate and 1.0 g of t-butylhydroquinone were added to the mixed solution, and the mixture was stirred at a temperature of 110 ° C. for 10 hours. This reaction solution was reprecipitated again in 2 liters of methanol. The number average molecular weight of the obtained pale yellow viscous substance (M-5) was 3,400. Production Example 6 of Macromonomer: (M-6) 95 g of propyl methacrylate, 5 g of thioglycolic acid
And a mixed solution of 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. A. I. B. N. 1.0g
Was added and reacted for 8 hours. Next, 13 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 1.0 g of t-butylhydroquinone were added to the reaction solution, and the mixture was stirred at a temperature of 110 ° C. for 10 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol,
6 g were obtained. The number average molecular weight of the polymer (M-6) was 3,50.
It was 0.

Production Example 7 of Macromonomer: (M-7) 40 g of methyl methacrylate, 5 of ethyl methacrylate
4 g, 2-mercaptoethylamine 6 g, toluene 15
A mixture of 0 g and 50 g of tetrahydrofuran was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. A. I. B.
N. 2.0 g was added and reacted for 8 hours. Next, this reaction solution was brought to a temperature of 20 ° C. in a water bath, and 23 g of methacrylic anhydride was added dropwise thereto so that the temperature did not exceed 25 ° C., followed by further stirring for 1 hour. 0.5 g of 2,2'-methylenebis (6-t-butyl-p-cresol) was added, and the mixture was stirred at a temperature of 40 ° C for 3 hours. After cooling, this solution was reprecipitated in 2 liters of methanol to obtain 83 g of a viscous substance. The number average molecular weight of the polymer (M-7) was 2,200. Production Example 8 of Macromonomer: (M-8) 95 g of 2-chlorophenyl methacrylate, 1 toluene
A mixed solution of 50 g and ethanol 150 g was heated to a temperature of 75 ° C. under a nitrogen stream. A. C. V. Add 5g,
The reaction was performed for 8 hours. Next, glycidyl acrylate 15
g, 1.0 g of N, N-dimethyldodecylamine and 2,
1.0 g of 2'-methylenebis- (6-t-butyl-p-cresol) was added, and the mixture was stirred at a temperature of 100 ° C for 15 hours.
After cooling, this reaction solution was reprecipitated in 2 liters of methanol to obtain 83 g of a transparent viscous material. The number average molecular weight of the polymer (M-8) was 3,600.

Production Examples 9 to 17 of Macromonomer: (M-
9) to (M-17) In Production Example 2 of macromonomer, the same procedure as in Production Example 2 was performed except that the monomers shown in Table 1 below were used instead of methyl methacrylate. 9) ~
(M-17) was produced.

[0078]

[Table 1]

(Production Example of Resin [A]) Production Example of Resin [A] 1: Resin [A-1] 70 g of ethyl methacrylate, macromonomer (M-
1) A mixed solution of 30 g and 150 g of toluene was heated to a temperature of 70 ° C. under a nitrogen stream. Next, A. I. B. N. 0.5
g, and reacted for 4 hours. I. B. N.
0.3g was added and it was made to react for 6 hours. The weight average molecular weight of the obtained copolymer [A-1] was 9.8 × 10 ⁴ , and the glass transition point was 72 ° C.

[0080]

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Production Examples 2 to 15 of Resin [A]: Resin [A-
2] to [A-15] Under the same polymerization conditions as in Production Example 1 of Resin [A], the following Table-2 was used.
Resin [A] was produced. Mw of each resin is 8 × 10 ⁴ ~
The range was 1.5 × 10 ⁵ .

[0082]

[Table 2]

[0083]

[Table 3]

[0084]

[Table 4]

Production Example 16 of Resin [A]: Resin [A-1
6] 70 g of ethyl methacrylate, macromonomer (M-
2) A mixed solution of 30 g, toluene 150 g, and isopropanol 50 g was heated to a temperature of 70 ° C. under a nitrogen stream.
Next, 4,4'-azobis (4-cyanovaleric acid) 0.8
g was added and reacted for 10 hours. The weight average molecular weight (Mw) of the obtained copolymer was 9.8 × 10 ⁴ and the glass transition point was 72 ° C.

[0086]

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Production Examples 17 to 21 of Resin [A]: Resin [A
-17] to [A-21] In Production Example 16 of Resin [A], the macromonomer (M
-2), the same procedure as in Production Example 16 was repeated except that the macromonomers shown in Table 3 below were used, and each resin [A] was used.
Was manufactured. Mw of each resin is 9 × 10 ^{4 to} 1.2 × 10 ⁵
Met.

[0088]

[Table 5]

Production Examples 22 to 24 of Resin [A]: Resin [A
-22] to [A-24 ] in Production Example 16 of Resin [A], the procedure of A. C. V. Polymer was produced in the same manner as in Production Example 16 except that the azobis compounds shown in Table 4 below were used instead of.

[0090]

[Table 6]

Production Example 25 of Resin [A]: Resin [A-2
5] 80 g of butyl methacrylate, macromonomer (M-
8) 20 g, thioglycolic acid 1.0 g, toluene 10
A mixed solution of 0 g and 50 g of isopropanol was heated to a temperature of 80 ° C. under a nitrogen stream. 1,1'-azobis (cyclohexane-1-carbonitrile) (abbreviation ACH.
N. ) 0.5 g, and stirred for 4 hours. C. H.
N. 0.3 g was added and stirred for 4 hours. The obtained polymer Mw was 8.0 × 10 ⁴ , and the glass transition point was 41 ° C.

[0092]

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Production Examples 26 to 32 of Resin [A]: Resin [A
-26] to [A-32] In Production Example 25 of Resin [A], the compounds of Table 5 below were used instead of thioglycolic acid.
A polymer was produced in the same manner as in.

[0094]

[Table 7]

Production Examples 33 to 36 of Resin [A]: Resin [A
-33] to [A-36] The following Table 6 was used under the same polymerization conditions as in Production Example 26 of Resin [A].
Was produced. Mw of each resin is 9.5 × 10 ⁴
The range was up to 1.2 × 10 ⁵ .

[0096]

[Table 8]

Production Examples 37 to 44 of Resin [A]: Resin [A
-37] to [A-44] Under the same polymerization conditions as in Production Example 16 of Resin [A],
Each resin shown in Table 7 below was produced. Each resin obtained [A]
Mw was 9.5 × 10 ^{4 to} 1.1 × 10 ⁵ .

[0098]

[Table 9]

[0099]

[Table 10]

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 graft copolymer (A) of the present invention and the resin used in combination, the image strength to be formed, etc. Does not give favorable results. It is preferably 30 to 85%.

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

The total amount of the graft copolymer of the present invention and the binder resin used together 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 composition 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. At least one active halogen compound selected from a diazole compound and a halomethyl-s-triazine compound, and a 3-aryl-substituted coumarin compound (3) Among the at least one lophine dimer, (1)
And (2), (1) and (3), or (1), (2) and (3).

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

As the active halogen compound such as halomethyl oxadiazole 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.

[0106]

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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.

[0108]

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Here, Q ₃ is Br, Cl, P is -CQ ₃ ,
—NH ₂ , —NHR, —NR ₂ , —OR (where R is a phenyl or alkyl group), W is an optionally substituted aromatic,
Heterocyclic nuclei or those of general formula IIA where Z is -O-
Or, it is -S-.

[0110]

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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.

[0112]

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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.

[0114]

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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, examples of the heterocyclic ring include those shown below.

[0117]

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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 (R)
(R₁₇), An alkyl group having 1 to 8 carbon atoms (for example, methyl
Group, ethyl group, propyl group, butyl group, octyl group),
C1-C8 haloalkyl groups (eg chloromethyl
Group, fluoromethyl group, trifluoromethyl group, etc.), carbon
Alkoxy groups of the numbers 1 to 8 (eg, methoxy group, ethoxy group
Group, butoxy group), hydroxy group, cyano group, halogen
(For example, -Cl, -Br, -F). R₁₃,
R₁₄, R₁₆, R ₁₇Are hydrogen atom and C1-8, respectively.
Alkyl group (eg, methyl group, ethyl group, propyl group,
Butyl group, octyl group). R₁₃, R₁₄And R₁₆,
R₁₇Are also bonded to each other with a nitrogen atom and a heterocycle (eg
For example, piperidine ring, piperazine ring, morpholine ring, pyrazo
Ring, diazole ring, triazole ring, benzotria
Sol ring, etc.) may be formed. R_FifteenIs a hydrogen atom, carbon
Alkyl groups of numbers 1 to 8 (for example, methyl group, ethyl group,
Ropyl group, butyl group, octyl group),
Lucoxy 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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The lophine dimer means a 2,4,5-triphenylimidazolyl dimer consisting of two lophine residues, and its basic structure is shown below.

[0126]

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

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

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

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[0135]

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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.

Further, 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 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 pigment alone or a mixture with a dioxazine purple pigment is used. For example, C.I. 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 in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin or the like, a pigment having good dispersibility and dispersion stability can be obtained. 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.

In order to promote the alkali solubility in the unirradiated area and further improve the developability of the composition of the present invention, an organic carboxylic acid, preferably a molecular weight of 1000 or less is added to the composition of the present invention. The low molecular weight organic carboxylic acid can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; oxalic acid, malonic acid, succinic acid, and glutaric acid Aliphatic dicarboxylic acids such as acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid and citraconic acid; Aliphatic tricarboxylic acids such as carballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, melophanic acid and pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

Although not necessarily required in the present invention, a dispersant which improves 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. Such a dispersant is usually used in the pigment dispersion in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the pigment. In addition to the above, the radiation-sensitive composition of the present invention preferably further contains a thermal polymerization inhibitor. For example, hydroquinone, p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl −
6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

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

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

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

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

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

These solvents may be used alone or in the form 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 preferable 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 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.

If necessary, coarse particles can be removed from the dispersion obtained here by centrifugation or decantation. 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.

As the substrate, for example, soda glass, Pyrex glass, quartz glass used for liquid crystal display elements or the like and those obtained by attaching a transparent conductive film to these, or photoelectric conversion element substrates used for solid-state image pickup elements or the like, for example, silicon are used. Examples include substrates. These substrates are generally formed with black stripes for isolating each pixel.

As the developing solution, any composition can be used as long as it is a composition that dissolves the radiation-sensitive composition of the present invention but does not dissolve the radiation-irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned solvents used when preparing the composition of the present invention.

Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene and other alkaline compounds 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.

[0165]

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 graft copolymer of the present invention (A-3) 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 3), 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-C was prepared and dispersed to prepare Examples. A color filter pattern was prepared in the same manner as in -1. The results are shown in Table-C. As a result, the invention is all good.

Evaluation and Evaluation Criteria x: Poor Δ: Slightly Bad ○: Good ◎: Excellent Dispersibility: Presence or absence of sedimentation of pigments etc. after standing for 2 weeks Image dropout: Relative comparison of defects due to dropout 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

[0170]

[Table 11]

Example-5 In the same manner as in Example 1, except that the radiation-sensitive composition of Example-1 was replaced with the following, the color filter pattern was prepared by dispersing, coating, exposing and developing. The same results as in Example 1 were obtained. -Example of graft copolymer of the present invention (A-2) 50 parts by weight of a 40 wt% toluene solution-40 parts of benzyl methacrylate / methacrylic acid copolymer (80/20 wt ratio)-40 parts of dipentaerythritol hexaacrylate-C.I. 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 to prepare a color filter pattern. Table 5 shows the results together with Example 5.
D. As a result, it is understood that the present invention is good.

[0173]

[Table 12]

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-E, the same results as in Example 1 were obtained with the present invention. -Example of graft copolymer of the present invention (A-8) 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

[0175]

[Table 13]

Example-12-Graft copolymer of the present invention (A-16) 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-phenylcoumarin. Hydroquinone monomethyl ether 0.01 part Propylene glycol monomethyl ether acetate 20 parts The above composition and the following processed pigments: I. Pigment Red 177 Acrylic resin processed pigment (Colortex Red U38N, Sanyo Pigment) 8 parts I. Pigment Yellow 83 Ethylcellulose resin Processed pigment (Colortex Yellow E119, manufactured by Sanyo Pigment Co., Ltd.) 2 parts Kneaded with a three-roll mill to prepare a colored paste.

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

Example-13 Graft Copolymer (A-16) (40 wt%) Propylene Glycol Monomethyl Ether Acetate Solution 25 Parts of the Present Invention 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.

[0183]

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] (A) The following general formulas (IIa) and (IIb)
The weight average molecular weight of the polymer main chain containing at least one of the polymer components represented by the formula (I) and having a polymerizable double bond group represented by the following general formula (I) bonded to only one end thereof. A monofunctional macromonomer of 10 ⁴ or less and the following general formula
A radiation-sensitive composition comprising a binder resin which is a copolymer containing at least the monomer represented by (III), (B) a radiation-sensitive compound, and (C) a pigment. Embedded image [In formula (I), V ₀ is -COO-, -OCO-, -CH _{2
OCO -, - CH 2 COO -} , - O -, - SO 2 -, - C
O-, -CONHCOO-, -CONHCONH-,-
_{CONHSO 2 -, - CON (P} 3) -, - SO 2 N
(P ₃₎ - or -C ₆ H ₄ - represents a (P ₃ represents a hydrogen atom or a hydrocarbon group). c ₁ and c ₂ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a cyano group,
Hydrocarbon group, -COO-Z 'or -C via hydrocarbon
OO-Z '(Z' represents a hydrogen atom or a hydrocarbon group which may be substituted) is represented. [Chemical formula 2] [In the formula (IIa) or (IIb), V ₁ represents the same content as V ₀ in the formula (I). Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. d ₁ , d
₂ may be the same as or different from each other and represent the same contents as c ₁ and c ₂ in the formula (I). Q ₀ is -CN, -CO
NH represents ₂ or -C ₆ H ₄ T. Where T is a hydrogen atom,
Halogen atom, hydrocarbon group, alkoxy group or -COO
Z "(Z" represents an alkyl group, an aralkyl group or an aryl group). ] [Chemical 3] [In the formula (III), V ₂ represents the same content as V ₁ in the formula (IIa). Q ₂ has the same meaning as Q ₁ in formula (IIa). e ₁ and e ₂ may be the same as or different from each other, and have the same contents as c ₁ and c ₂ in the formula (I). ] 2. The copolymer of the resin (A) further comprises a —H ₂ PO ₃ group, a —SO ₃ H group, a —COOH group, a phenolic OH group, and a —P (═O) (R ₀ ). (OH) group (R ₀ represents a hydrocarbon group or —OR (R represents a hydrocarbon group) group) and at least one acidic group selected from the group bonded to one end of the main chain of the copolymer. The radiation-sensitive compound according to claim 1, wherein the radiation-sensitive compound is formed. 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) Among at least one lophine dimer, (1)
And (2), (1) and (3), or (1), (2) and (3) in combination.
The radiation-sensitive composition as described in 1. 4. The radiation-sensitive composition according to claim 1, wherein the pigment has a basic N atom in the pigment molecule.