JPH0962002A - Radiation sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter excellent in coatability, developability and pattern reproducibility and also to provide a compsn. excellent in dispersion stability of a pigment as a pigment dispersed radiation sensitive compsn. for producing a color filter by photolithography. SOLUTION: This radiation sensitive compsn. contains a graft copolymer having a wt. average mol.wt. of 3×10<-4> -1×10<6> and contg. a monofunctional macromonomer having a wt. average mol.wt. of 1×10<3> -2×10<4> as a copolymerizable component, a radiation sensitive compd. and a pigment. The macromonomer is obtd. by bonding polymerizable double bonds to the terminals of the blocks (B) of an A-B block copolymer consisting of blocks (A) each having an acidic group and the blocks (B) having no acidic group.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method,
Printing, electrodeposition and pigment dispersion methods are known. The dyeing method is a method of producing a color filter by dyeing a dyeing substrate made of a natural resin such as gelatin, glue, casein or the like or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye.

[0003] In the dyeing method, since a dye is used, there are problems in light resistance, heat resistance, moisture resistance, etc. In addition, it is difficult to uniformly control the dyeing and fixing characteristics on a large screen, and color unevenness is likely to occur. In addition, there is a problem that the dyeing requires an anti-staining layer and the steps are complicated. In the electrodeposition method, a color filter is formed by forming a transparent electrode in a predetermined pattern in advance, ionizing a resin containing a pigment dissolved or dispersed in a solvent, and applying a voltage to form a colored image in a pattern. It is a method of manufacturing.

[0004] The electrodeposition method requires a photolithography process including a film formation and an etching process of a transparent electrode for forming a color filter, in addition to a transparent electrode for display. At this time, if there is a short circuit, a line defect occurs and the yield decreases. In addition, there is a problem that it is difficult to apply to a mosaic arrangement other than the stripe arrangement in principle, and it is difficult to manage the transparent electrodes.

[0005] The printing method is a simple method of producing a color filter by printing such as offset printing using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curing resin. However, there is a problem in that defects are likely to occur due to dust, foreign matters, and gelled portions of the ink binder, and there are problems in positional accuracy, line width accuracy, and planar smoothness associated with printing accuracy.

[0006] The pigment dispersion method is a method of producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light and heat due to the use of pigments and is patterned by the photolithographic method, so it has a sufficient positional accuracy and is a method suitable for producing color filters for large screen and high definition color displays. is there.

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

As means for improving the dispersibility of the pigment, JP-A-1-102429 discloses a method of using a processed pigment obtained by treating the pigment with an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate resin, or the like, JP-A-2-181704. Japanese Patent Laid-Open No. 2-199403 discloses a method of using an organic dye derivative as a dispersant, but it is not sufficient.

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

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

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

[0012]

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

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

[0014]

[Means for Solving the Problems] A radiation-sensitive composition containing the following (A), (B), and (C). (A) B- of an AB block copolymer comprising an A-block having an acidic group and a B-block having no acidic group
Weight average molecular weight 3 × containing a monofunctional macromonomer (M) having a polymerizable double bond bonded to a block end in a range of 1 × 10 ³ to 2 × 10 ⁴ as a copolymerization component of the graft copolymer. 10 ⁴ to 1 × 10 ⁶ graft copolymer,
(B) Radiation-sensitive compound, and (C) pigment 2. 1. The acidic group in the A-block of the graft copolymer of is a —H ₂ PO ₃ group, a —SO ₃ H group, a —COOH
Group, phenolic OH group, -P (= O) (R ₀ ) (OH) group [R ₀ represents a hydrocarbon group or -OR (R represents a hydrocarbon group) group] and cyclic acid anhydride 1. At least one acidic group selected from the group The radiation-sensitive composition as described in 1.

3. 1. 1. The B-block of the graft copolymer of 1. contains the polymer component represented by the general formula (I). The radiation-sensitive composition as described in 1.

[0016]

Embedded image

[In the formula (I), d₁And d₂Are hydrogen sources
Child, halogen atom, cyano group, hydrocarbon group, -COO-
R₃₄Or -COO-R via hydrocarbon₃₄Represents (R₃₄
Is a hydrogen atom, alkyl group, alkenyl group, aralkyl
Represents a group, an alicyclic group or an aryl group). X₁Is -C
OO-, -OCO-,-(CH₂)_l1-OCO-,-
(CH ₂)_l2-COO- (l₁, L₂Is an integer from 1 to 3
Fork), -O-, -SO₂-, -CO-, -CON (R
₃₃)-, -SO₂N (R₃₃)-, -CONCHCOO-,
-CONHCONH- or -C₆H_FourRepresents- (where
R₃₃Represents a hydrogen atom or a hydrocarbon group).

R ₃₁ represents a hydrocarbon group. However, X ₁ is −
When representing C ₆ H ₄ —, R ₃₁ represents a hydrogen atom or a hydrocarbon group. ] 4. 1. 1. The graft copolymer of 1. contains at least one monomer represented by the following general formula (II) as a monofunctional monomer that constitutes the graphic copolymer together with the macromonomer (M). The radiation-sensitive composition as described in 1.

[0019]

Embedded image

[In the formula (II), d_Three, D_Four, X₂And R₃₂Is
D in formula (I)₁, D₂, X₁And R ₃₁Same as
Represents the contents of ] 5. The radiation-sensitive compound has (1) at least one addition-polymerizable ethylene group
It has an ethylenic content of 100 ° C or higher under normal pressure.
Compounds with saturated groups (2) Halomethyl oxadiazole compounds, halomethyl
At least one selected from -s-triazine compounds
Active halogen compounds, and 3-aryl substituted coumarins
Compound (3) (1) among at least one type of lophine dimer
And (2) or (1) and (3).
1. The radiation-sensitive composition as described in 1.

6. 1. The pigment has a basic N atom in the pigment molecule. The radiation-sensitive composition as described in 1. 7. 1. The pigment is a processed pigment. The radiation-sensitive composition as described in 1. 8. The processed pigment is 1. ~ 4. 6. The graft copolymer described in 1 above, or a powder, pellets, or paste dispersion in which a pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate resin, ethyl cellulose and nitrocellulose. The radiation-sensitive composition as described in 1.

9. 6. The processed pigment has been subjected to a flushing treatment. The radiation-sensitive composition as described in 1. Ten. A color filter for a liquid crystal display device, wherein a coating film of the radiation-sensitive composition according to claim 1 is formed on the surface of a transparent substrate, exposure and development are repeated, and red, green and blue patterns are formed on the same surface. . 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.
The graft copolymer of the present invention forms an AB block copolymer composed of a monomer having an acidic group as a binder and another monomer, and then a double block is formed at the end of the B block of the block copolymer. It is a graft copolymer obtained by introducing a bond into a macromonomer and copolymerizing another component. Use of this graft copolymer improves the dispersibility of the pigment. The improvement of dispersibility is considered to be that the acidic group of the grafted portion interacts with the pigment, probably an acid-base interaction, but the resin adsorbs to the pigment to enhance the dispersibility.

Although a copolymer containing an acidic group is used in the radiation-sensitive composition, 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. In the present invention, it is considered that the acidic group part is a block copolymer and the whole is forming a graft copolymer, so that it is easily adsorbed to 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.

The monofunctional macromonomer (M) used in the graft copolymer of the present invention will be specifically described.
The acidic groups contained in the components making up the A- block of the macromonomer (M), -H ₂ PO ₃ group, -COO
H group, -SO ₃ H group, a phenolic OH group, -P (= O)
(R ₀ ) (OH) group (R ₀ has the same meaning as R) or a cyclic acid anhydride-containing group, and preferably —COO
H group, -SO ₃ H group, a phenolic OH group, or -P
(= O) (R ₀ ) (OH) group.

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

Examples of the phenolic OH group include methacrylic acid esters or amides containing a hydroxyphenol or hydroxyphenyl group as a substituent. The acidic group-containing copolymerization component of the present invention is, for example, any vinyl compound containing an acidic group that is copolymerizable with the monomer corresponding to the repeating unit represented by the general formula (I) described below. However, it may be described in, for example, "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 form, α-chloro form, α-bromo form, α -Fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form,
α, β-dichloro form), 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), maleic acid, maleic acid half esters,
Maleic acid half amides, vinylbenzene carboxylic acid, vinylbenzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids, and ester derivatives of these carboxylic acids or sulfonic acids, amides Compounds containing the acidic group in the substituent of the derivative are exemplified.

The copolymerization component containing an acidic group will be exemplified. Here, p ₁ represents H or CH ₃ , and p ₂ represents H or C
H ₃ or CH ₂ COOCH ₃ is shown, and R ₄₁ has 1 to 4 carbon atoms.
Indicates an alkyl group, R ₄₂ represents an alkyl group, a benzyl group or a phenyl group having 1 to 6 carbon atoms, i is an integer of 1 to 3, j represents an integer of 2 to 11, k is 1 It shows the integer of 11, l shows the integer of 2-4, and m shows the integer of 2-10.

[0031]

Embedded image

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

[Chemical 12]

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

Two or more kinds of the above-mentioned specific acidic group-containing polymerization components may be contained in the block, and in that case, the two or more kinds of acidic group-containing components are randomly copolymerized in the block. Alternatively, it may be contained in any form of block copolymerization. Further, the component which does not contain the acidic group may be contained in the A block, and examples of the component include a component represented by the general formula (I) described later. The content of the component not containing an acidic group is preferably 0 to 50% by weight in the A block, more preferably 0.
-20% by weight. Most preferably, such acidic group-free components are not included in the A block.

Next, the polymerization component constituting the B block component in the monofunctional macromonomer of the graft copolymer will be described in detail. In the present invention, at least the repeating unit represented by the general formula (I) is contained as a component constituting the B-block. In the general formula (I), X ₁ is —COO—, —OCO—, — (CH ₂ ) ₁₁ —O.
_{CO -, - (CH 2)} l2 -COO- (l 1, l 2 is 1 to 3
Represents an integer of), —O—, —SO ₂ —, —CO—, —
CON (R ₃₃ )-, -SO ₂ N (R ₃₃ )-, -CONH
COO -, - CONHCONH- or -C ₆ H ₄ - represents a.

Here, R ₃₃ is not only a hydrogen atom, but also a preferable hydrocarbon group is a C 1-18 optionally substituted alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). Group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
Methoxyethyl group, 3-bromopropyl group, etc.), alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2
-Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-
Methyl-2-hexenyl group, etc.), aralkyl group having 7 to 12 carbon atoms and which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group) , A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.) and an alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, a cyclohexyl group, 2- Cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or C6
To 12 optionally substituted aromatic groups (eg, 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, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecyloylamidophenyl, etc. ).

R ₃₁ represents a hydrocarbon group, and its preferred specific examples are the same as those described for R ₃₃ . However, when X ₁ in the general formula (I) represents —C ₆ H ₄ —, R ₃₁ represents a hydrogen atom or a hydrocarbon group. X ₁ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group, propoxy group, butoxy group, etc.).

D ₁ and d ₂ may be the same or different from each other, and preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg methyl group). Group, ethyl group, propyl group, butyl group, etc.), —COO—R ₃₄ or hydrocarbon-mediated —C
OO-R ₃₄ (R ₃₄ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically, , And has the same contents as those described for R ₃₃ above).

Examples of the hydrocarbon in -COO-R ₃₄ through the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like. More preferably, in the general formula (I), X ₁ is —COO—, —OCO—, —C.
_{H 2 OCO -, - CH 2} COO -, - O -, - CONH
Represents —, —SO ₂ NH— or —C ₆ H ₄ —, and d ₁ , d ₂
May be the same as or different from each other, and are a hydrogen atom, a methyl group, —COOR ₃₄ or —CH ₂ COOR ₃₄ {R ₃₄ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group. , Butyl group, hexyl group, etc.)
Represents}. Even more preferably, either one of d ₁ and d ₂ represents a hydrogen atom.

In the B block formed separately from the A block consisting of the above-mentioned polymerization component containing a specific acidic group, two or more repeating units represented by the above formula (I) may be contained, and It may contain a polymerization component other than these. When two or more polymerization components are contained in the B block containing no acidic group, the copolymerization component may be contained in the B block in any of random copolymerization and block copolymerization. Is preferably contained at random.

The other polymerization component which may be contained in the other block together with the polymerization component selected from the repeating unit represented by the above formula (I) may be any component which can be copolymerized with these. The polymer component contained in the B-block is, for example, acrylonitrile, methacrylonitrile, or a heteromonomer, which is a monomer corresponding to another repeating unit copolymerizable with the polymer component represented by the formula (I). Examples thereof include cyclic vinyls (for example, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.). These other monomers are used within a range not exceeding 50 parts by weight based on 100 parts by weight of the total polymer component of the B-block. Further, it is preferable that the B-block does not contain a polymer component containing an acidic group which is a constituent of the A-block.

Next, in the macromonomer (M) of the present invention, an A-block consisting of the above-mentioned component containing an acidic group and a B-block consisting of the polymer component represented by the general formula (I) are formed into AB type. And the polymerizable double bond group linked to the other end of the B-block linked to the A-block will be described. Specific examples include a polymerizable double bond group represented by the following general formula (III).

[0051]

Embedded image

In formula (III), X ₃ has the same meaning as X ₁ in formula (I). d ₅ and d ₆ may be different from each other,
It has the same contents as d ₁ and d ₂ in the formula (I). That is, as the polymerizable double bond group represented by the general formula (III), more specifically,

[0053]

Embedded image

And the like. The macromonomer (M) used in the present invention has a polymerizable double bond group represented by the general formula (III) directly bonded to one end of the B-block as described above, or an arbitrary linking group. It has a chemical structure bound by. The linking group includes a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (as a hetero atom, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom-hetero atom. It is composed of any combination of bonding atomic groups.

That is, specifically, a mere bond or -C
(R ₃₅ ) (R ₃₆ )-[R ₃₅ and R ₃₆ 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.)],-(CH =
_{CH) -, - C 6 H} 10 -, - C 6 H 4 -, - O -, - S
-, -C (= O)-, -N ( _R37 )-, -COO-,-
C (= S) -, - SO 2 -, - CON (R 37) -, - S
_{O 2 N (R 37) -} , - NHCOO -, - NHCONH
-, --Si (R ₃₇ ) (R ₃₈ )-[R ₃₇ and R ₃₈ each represent a hydrogen atom, a hydrocarbon group or the like having the same meaning as R ₃₁ in the above formula (I)] and the like. It represents a single linking group selected or a linking group composed of any combination.

When the weight average molecular weight of the macromonomer (M) exceeds 2 × 10 ⁴ , the copolymerizability with other monomers decreases, which is not preferable. On the other hand, when the weight average molecular weight is too small, the improving effect of the present invention becomes small, so 1 × 10 5.
It is preferably ³ or more. The weight average molecular weight of the macromonomer (M) is preferably 1 × 10 ³ to 2 × 10 ⁴ , and more preferably 2 × 10 ³ to 1 × 10 ⁴ .

The macromonomer (M) of the present invention can be produced by a conventionally known synthetic method. For example,
In the monomer corresponding to the polymer component containing the specific acidic group, the acidic group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithiums, lithium diisopropylamides, alkylmagnesium halides, etc.) Alternatively, after synthesizing the AB block copolymer by a known so-called living polymerization reaction such as an ionic polymerization reaction using a hydrogen iodide / iodine system, a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction, Various reagents are reacted with the ends of this living polymer to introduce a polymerizable double bond group.

After that, a method of forming an acidic group by carrying out a deprotection reaction of a functional group having a protected acidic group by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photodecomposition reaction or the like can be mentioned. One example thereof is shown in the following reaction scheme (1).

[0059]

Embedded image

For example, P. Lutz, P. Masson et al, Polym.
Bull. 12, 79 (1984), BCAnderson, GDAndrews et
al, Macromolecules, 14, 1601 (1981), K. Hatada, KU
te, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986),
Koichi Right Hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Transactions on Polymers, 46, 189 (1989), MK
uroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987),
Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985),
DYSogoh, WRHertler et al, Macromolecules, 20,
A living polymer can be synthesized according to the synthetic method described in 1473 (1987) or the like. Further, as a method for introducing a polymerizable double bond group to the terminal of the living polymer, the macromonomer of the present invention can be obtained according to a conventionally known synthesis method of a macromonomer method.

Specifically, P. Dreyfuss & RP Quirk, En
cycl. Polym. Sci. Eng., 7, 551 (1987), PFRempp,
E. Franta, Adu., Polym. Sci. 58, 1 (1984), V. Perce
c. Appl., Polym. Sci., 285, 95 (1984), R. Asami, MT
akaRi, Makromol, Chem. Suppl. 12, 163 (1985), P. Rem
pp. et al, Makromol. Chem. Suppl. 8, 3 (1984), Yusuke Kawakami, Chemical Industry, 38, 56 (1987), Yuya Yamashita, Polymer, 3
1, 988 (1982), Kobayashi Shiro, Polymer, 30, 625 (1981), Toshinobu Higashimura, Japan Adhesion Society Magazine 18,536 (1982), Koichi Ito, Polymer Processing, 35, 262 (1986), Higashi It can be synthesized according to the methods described in the review articles by Kishiro, Takashi Tsuda, Functional Materials, 1987 No. 10, 5 and the references and patents cited therein.

The protecting group for protecting the specific acidic group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above-mentioned references, and further, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" published by Kodansha Co., Ltd. (1977), TWGreene, "Protective Groups in
Organic Synthesis, '' Jon Wiley & Sons (1981), J.
FWMcOmie, `` Protective Groups in Organic Chemist
ry ", Plenum Press, (1973), etc., and the method described in detail in the review can be appropriately selected and performed.

As another method for synthesizing the AB block copolymer [B], it can be synthesized by a photoiniferter polymerization method using a dithiocarbamate compound as an initiator. For example, Takayuki Otsu, Polymer, 37, 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Jap. 37, 3508 (1988
), JP-A 64-111, JP-A 64-26619, etc., and the macromonomer of the present invention can be obtained by utilizing the above-described macromonomer synthesis method. .

Specific examples of the macromonomer (M) of the present invention can include the following compounds. However, the scope of the present invention is not limited to these. Hereinafter, in each example, Q ₁ , Q ₂ and Q ₃ are each −
H, indicates -CH ₃ or -CH ₂ COOCH _3, Q ₄ is -H
Or --CH ₃ and R ₄₃ is --C _n H _{2n + 1} (n is 1 to 18).
An integer _{of), - (CH 2) t} -C 6 H 5 (t is an integer of _{1~3), - C 6 H 4} X (X is -H, -Cl, -B
r, -CH _3, shows a -OCH ₃ or -COCH ₃₎ or _{- (CH 2) p -C 10} H 7 indicates (p is an integer of 0 or 1 to 3), R ₄₄ is C _q H _{2q +} 1 (q is an integer of 1-8) or (CH _{2) t} C ₆ H indicates _5, Y ₁ is -OH, -C
_{OOH, -SO 3 H, -P (} = O) (OH) 2 or -P (=
O) shows the _{(OH) (OCH 3),} Y 2 is -COOH, -SO
₃ H, -P (= O) (OH) ₂ or -P (= O) (OH) (OC
H ₃₎ indicates, r is an integer of 2 to 12, s is 2-6
Indicates an integer. Further, -b- represents a block bond.

[0065]

Embedded image

[0066]

Embedded image

[0067]

[Chemical 21]

[0068]

Embedded image

The monomer copolymerizable with the above-mentioned macromonomer (M) is preferably one represented by the general formula (II). In the formula (II), d ₃ , d ₄ , X ₂ and R ₃₂ have the same contents as d ₁ , d ₂ , X ₁ and R ₃₁ in the formula (I). Particularly preferably d ₃ represents a hydrogen atom, d ₄ represents methyl, X ₂ represents -COO-. In the binder resin of the present invention, the A block / B block ratio is 1 to 80 /
It is preferably 99 to 20, preferably 5 to 60/95 to 40 (weight ratio), and the amount of the acidic group-containing component present in the resin is 0.1 to 60% by weight, particularly 0.5.
It is preferably ˜50% by weight. The composition ratio of the copolymerization component having the macromonomer (M) as a repeating unit and the copolymerization component having the monomer represented by the general formula (II) as a repeating unit is preferably 1 to 80/99 to 20. (Weight composition ratio), more preferably 5 to 60/95 to 40 (weight composition ratio).

The weight average molecular weight of the graft copolymer of the present invention is 2 × 10 ⁴ to 1 × 10 ⁶ , preferably 3 × 10 ^4.
˜5 × 10 ⁵ , more preferably 4 × 10 ^{4 to} 3 × 10 ⁵ . The weight average molecular weight of the graft copolymer is 2 × 10 ⁴
If it is less, the effect of dispersibility is not fully exerted, and
If it is larger than 1 × 10 ⁶ , the solubility is lowered and its use is limited.

In the polymer main chain, --PO ₃ H ₂ group, --PO ₃ H ₂ group,
SO ₃ H group, -COOH group, -OH group, -SH group and -
Those which do not contain a copolymerization component containing an acidic group of PO ₃ RH group are preferable. The binder resin of the present invention can be produced by copolymerizing corresponding monofunctional polymerizable compounds in a desired ratio. As the polymerization method, it can be produced by using a known method such as solution polymerization, suspension polymerization, precipitation polymerization, and emulsion polymerization. For example, in solution polymerization, a monomer can be added at a predetermined ratio in a solvent that dissolves a binder resin produced, and a copolymer solution can be obtained by polymerizing with a azobis compound, a peroxide compound and a radical polymerization initiator. . By drying this or adding it to a poor solvent, a desired copolymer can be obtained. In suspension polymerization, a monomer can be suspended in the presence of a dispersant such as polyvinyl alcohol or polyvinylpyrrolidone and copolymerized in the presence of a radical polymerization initiator to obtain a copolymer.

Binder Resin Synthesis Example 1: [A-1] A mixed solution of 60 g of methyl methacrylate, 40 g of macromonomer (M-1) having the following structure, and 150 g of ethyl 3-ethoxypropionate was heated at a temperature of 85 ° C. under a nitrogen stream. Warmed to. 0.8 g of 1,1-azobis (cyclohexane-1-carbonitrile) (abbreviation: ABCC) was added and 5
Reacts for a time, and B. C. C. 0.5 g was added and reacted for 5 hours.

The Mw (weight average molecular weight) of the obtained copolymer was 1.0 × 10 ⁵ .

[0074]

Embedded image

Synthesis Example 2 of Binder Resin: [A-2] A mixed solution of 50 g of butyl methacrylate, 50 g of macromonomer (M-2) having the following structure and 150 g of propylene glycol monomethyl ether was heated to 70 ° C. under a nitrogen stream.
Was heated. A. I. B. N. 0.5 g was added and the reaction was carried out for 6 hours. I. B. N. 0.3 g was added and reacted for 8 hours.

The Mw of the obtained copolymer was 8.5 × 10 ^4.
Met.

[0077]

Embedded image

Binder Resin Synthesis Examples 3 to 9: [A-3] to
[A-9] Under the same polymerization conditions as in Resin Synthesis Example 2, copolymers shown in Table A below were synthesized. The Mw of the obtained copolymer is 4 × 1 each.
It was 0 ^{4 to} 9 × 10 ⁴ .

[0079]

[Table 1]

[0080]

[Table 2]

Binder Resin Synthesis Examples 10 to 20: [A-1
0] to [A-20] The copolymers shown in Table B below were synthesized under the same polymerization conditions as in Resin Synthesis Example 1. The Mw of the obtained copolymer is 5 × 1 each.
It was 0 ^{4 to} 2 × 10 ⁵ .

[0082]

[Table 3]

[0083]

[Table 4]

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 exceeding 90% does not give favorable results in terms of image strength of the formed image. Preferably 30-85
%.

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

The total amount of the graft copolymer of the present invention and the binder resin used in combination is 5 to 90% by weight based on the total solid components of the radiation-sensitive composition. Preferably 10
It is 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. A diazole compound, at least one active halogen compound selected from halomethyl-s-triazine compounds, and a 3-aryl-substituted coumarin compound, or (1) having at least one addition-polymerizable ethylene group, 100 under normal pressure A compound having an ethylenically unsaturated group having a boiling point of ℃ or higher (3)
It is preferably composed of a combination with at least one lophine dimer.

Here, (2) and (3) are photopolymerization initiators, which have a function of polymerizing the monomer of (1) by light irradiation. Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth). Monofunctional acrylates and methacrylates such as acrylates;
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 After adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane. (Meth) acrylated, JP-B-48-41708
No., JP-B-50-6034, JP-A-51-37193.
Urethane acrylates described in JP-A-48-64183 and JP-B-49-4319.
Examples of the polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B No. 1 and JP-B-52-30490. I can. Further, the Journal of the Adhesion Society of Japan, Vol. 20,
No. 7, pages 300 to 308, photocurable monomers and oligomers can also be used. These radiation-polymerizable monomers or oligomers may be used in any proportion as long as the composition of the present invention can be irradiated with radiation to form a coating film having adhesiveness, as long as the objects and effects of the present invention are not impaired. it can. The amount used is 5 to 90 wt%, preferably 10 to 5 relative to the total solid content of the radiation sensitive composition.
It is 0 wt%.

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

[0090]

Embedded image

Here, W is a substituted or unsubstituted aryl group, X is a hydrogen atom, an alkyl group or an aryl group, Y is a fluorine atom, a chlorine atom or a bromine atom, and n is 1 to 1.
Represents an integer of 3. Specific compounds include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-Trichloromethyl-5- (p-methoxystyryl) -1,3,4
-Oxadiazole and the like. Halomethyl-s-
As a photopolymerization initiator for triazine-based compounds,
JP-A-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.

[0092]

[Chemical formula 26]

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

[0094]

Embedded image

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

[0096]

Embedded image

Here, R ₁ and R ₂ are —H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a general formula.
It is indicated by IVA and IVB.

[0098]

[Chemical 29]

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.

[0101]

Embedded image

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

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

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

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

3-Aryl-substituted coumarin compounds have the general formula
Refers to a compound represented by V. R₈Is hydrogen atom, carbon number 1
~ 8 alkyl group, C6-10 aryl group (preferably
Especially hydrogen atom, methyl group, ethyl group, propyl group,
Chill group) to R₉Is hydrogen atom, alkyl having 1 to 8 carbon atoms
Group, an aryl group having 6 to 10 carbon atoms, represented by the general formula VA
Group (preferably a methyl group, an ethyl group, a propyl group, a group
A chill group, a group represented by the general formula VA, particularly preferably a general group
Represents a group represented by the formula VA). R, R₁₁Is hydrogen
Atoms, alkyl groups having 1 to 8 carbon atoms (eg, methyl group, ether
Cyl group, propyl group, butyl group, octyl group), carbon number
1-8 haloalkyl groups (eg chloromethyl group, fluoro)
(Methyl group, trifluoromethyl group, etc.), carbon number 1-8
Alkoxy groups (eg methoxy, ethoxy, buto
Xy group), optionally substituted aryl having 6 to 10 carbon atoms
Group (for example, phenyl group), amino group, -N (R₁₆)
(R₁₇), Halogen (for example, -Cl, -Br, -F)
Represent. Preferably hydrogen atom, methyl group, ethyl group, metho
Xy group, phenyl group, -N (R₁₆) (R₁₇), -Cl
You. R₁₂Is an optionally substituted aryl having 6 to 16 carbon atoms
Groups (eg phenyl, naphthyl, tolyl, cumyl
Group). As a substituent, an amino group, -N (R₁₆) (R
₁₇), An alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ether group).
Cyl group, propyl group, butyl group, octyl group), carbon number
1-8 haloalkyl groups (eg chloromethyl group, fluoro)
(Methyl group, trifluoromethyl group, etc.), carbon number 1-8
Alkoxy groups (eg methoxy, ethoxy, buto
Xy group), hydroxy group, cyano group, halogen (eg
—Cl, —Br, —F). R₁₃, R₁₄, R
₁₆, R ₁₇Are hydrogen atom and alkyl having 1 to 8 carbon atoms, respectively.
Groups (eg methyl, ethyl, propyl, butyl
Group, octyl group). R₁₃, R₁₄And R₁₆, R₁₇Is
In addition, they are bonded to each other with a nitrogen atom to form a heterocycle (for example, pipette).
Lysine ring, piperazine ring, morpholine ring, pyrazole
Ring, diazole ring, triazole ring, benzotriazo
Ring, etc.) may be formed. R_FifteenIs hydrogen atom, carbon number 1
~ 8 alkyl groups (eg methyl, ethyl, propyl
Group, butyl group, octyl group), C1-C8 alco
Xoxy group (eg methoxy group, ethoxy group, butoxy group
Group), optionally substituted aryl group having 6 to 10 carbon atoms
(Eg phenyl group), amino group, N (R₁₆) (R₁₇),
Represents halogen (for example, -Cl, -Br, -F). Zb
Is = O, = S or = C (R₁₈) (R₁₉). Preferred
Actually = O, = S, = C (CN)₂And 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.

[0108]

[Chemical 31]

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

[0110]

Embedded image

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

In the present invention, other known initiators can be used in addition to the above initiators. US Patent No. 2,36
Bicinal polykettle aldonyl compounds disclosed in US Pat. No. 7,660, US Pat. No. 2,367,661.
.Alpha.-carbonyl compounds disclosed in US Pat. No. 2,367,670 and US Pat. No. 2,448,82.
No. 8, disclosed in U.S. Pat. No. 2,722,512.
-Aromatic acyloin compounds substituted with hydrocarbons, U.S. Pat. Nos. 3,046,127 and 2,951,75
No. 8,491,367, and the combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367, JP-B-51-48516. Disclosed benzothiazole compounds / trihalomethyl-
s-Triazine compounds.

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

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

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

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

[0118]

[Chemical 33]

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

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

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

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

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

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

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

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

Further, by using a powdered processed pigment 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 1,000 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 kinds. Such a dispersant is usually used in the pigment dispersion in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the pigment. In addition to the above, the radiation-sensitive composition of the present invention preferably further contains a thermal polymerization inhibitor. For example, hydroquinone, p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl −
6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

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

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

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

Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc .; Aromatic hydrocarbons such as toluene, 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 combination with each other.
It may be used in combination of more than one kind. The composition of the present invention comprises:
It can be prepared by mixing the above components (A), (B) and (C), and other additives optionally used with a solvent, and mixing and dispersing using various mixers and dispersers. it can. Conventionally known mixers and dispersers can be used. Examples include a sand mill such as a homogenizer, a kneader, a ball mill, a two or three roll mill, a paint shaker, a sand grinder, and a dyno mill.

As a preferred preparation method, first, a solvent is added to the pigment and the binder resin and they are mixed uniformly, and then kneaded by using two or two rolls while heating if necessary to sufficiently mix the pigment and the binder resin. There is a method of blending and obtaining a uniform colored body. Next, a solvent is added to the obtained colored body, and if necessary, a dispersant and various additives are added. Dispersion is performed using a ball mill or various sand mills using glass beads as a dispersion media, for example, a Dyno mill. At this time, a smaller dispersion can be obtained as the diameter of the glass beads is smaller. At this time, a dispersion result with good reproducibility can be obtained by controlling the temperature of the dispersion liquid to be constant.

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

The composition of the present invention is applied to a substrate by a coating method such as spin coating, cast coating, or roll coating to form a radiation-sensitive composition layer, which is exposed through a predetermined mask pattern and developed. By developing with a liquid, a colored pattern is formed. The radiation used at this time
Particularly, ultraviolet rays such as g-line and i-line are preferably used.

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

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

[0148]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Example 1-Example of graft copolymer of the present invention (A-3) 40 wt% 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 Poor ○: 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

[0153]

[Table 5]

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

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

[0156]

[Table 6]

Examples-10, 11 and Comparative Example-4 The radiation-sensitive composition of Example-1 was replaced with the following, 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-3) 40 wt% 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

[0158]

[Table 7]

Example-12 • Graft copolymer (A-12) solution (40 wt%) of the present invention 75 parts • Pentaerythritol tetraacrylate 10 parts • 4- [p-N, N-di (ethoxycarbonylmethyl)] ] -2 parts 2,6-di (trichloromethyl) -s-triazine 7-[{4-chloro-6- (diethylamino) -s-tri 2 parts azin-2-yl} amino] -3-phenylcoumarin Hydroquinone monomethyl ether 0.01 part Propylene glycol monomethyl ether acetate 20 parts The above composition and the following processed pigments were used. 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.

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

Example 13-Graft copolymer (A-3) of the present invention (40 wt%) propylene glycol monomethyl ether acetate solution 25 parts-C.I. I. Pigment Red 155 (10 parts) was kneaded with a two-roll mill to obtain a sheet-like colored material.
Similarly, a sheet-like colored material was obtained in exactly the same manner except that the pigment was changed to 10 parts of CI Pigment Yellow 83.

A radiation-sensitive composition was obtained in the same manner as in Example 1 except that the ratio of the 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.

[0166]

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 (6)

[Claims] 1. A radiation-sensitive composition containing the following (A), (B), and (C). (A) B of an AB block copolymer consisting of an A-block having an acidic group and a B-block having no acidic group
A weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ monofunctional macromonomer (M) having a polymerizable double bond bonded to the block end as a copolymerization component of the graft copolymer, 3 × 10 ⁴ to 1 × 10 ⁶ graft copolymer, (B) radiation-sensitive compound, and (C) pigment 2. The acidic group in the A-block of the graft copolymer according to claim 1, wherein the acidic group is a —H ₂ PO ₃ group, a —SO ₃ H group,
-COOH group, phenolic OH group, -P (= O) ( _R0 )
(OH) group [R ₀ represents a hydrocarbon group or —OR (R represents a hydrocarbon group) group and at least one acidic group selected from cyclic acid anhydride-containing groups. The radiation-sensitive composition according to claim 1. 3. The radiation-sensitive composition according to claim 1, wherein the B-block of the graft copolymer according to claim 1 contains a polymer component represented by the general formula (I). Embedded image Wherein (I), d ₁ and d ₂ are each a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, a -COO-R ₃₄ through -COO-R ₃₄ or a hydrocarbon (R ₃₄ is hydrogen Atom or alkyl group, alkenyl group, aralkyl group, alicyclic group or aryl group). X ₁ is -COO-, -O
_{CO -, - (CH 2)} l1 -OCO -, - (CH 2) l2 -C
OO- (l ₁ , l ₂ represents an integer of 1 to 3), -O-,
_{-SO 2 -, - CO -,} - CON (R 33) -, - SO 2 N
_{(R 33) -, - CONHCOO} -, - CONHCONH
- or -C ₆ H ₄ - represents a (wherein R ₃₃ represents a hydrogen atom or a hydrocarbon group). R ₃₁ represents a hydrocarbon group. However X ₁ is -C ₆ H ₄ - may represent, R ₃₁ represents a hydrogen atom or a hydrocarbon group. ] 4. The graft copolymer according to claim 1, wherein
The graft copolymer is formed together with the macromonomer (M).
As a monofunctional monomer to be formed, it is represented by the following general formula (II).
A contract characterized by containing at least one monomer
The radiation-sensitive composition according to claim 1. [Chemical 2][In the formula (II), d_Three, D_Four, X₂And R₃₂In formula (I)
Kick d₁, D₂, X₁And R ₃₁And the same contents as
I forgot. ] 5. 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 3-aryl-substituted coumarin compound (3) Among at least one lophine dimer, (1)
And (2) or (1) and (3) in combination, The radiation-sensitive composition according to claim 1, characterized in that. 6. The radiation-sensitive composition according to claim 1, wherein the pigment has a basic N atom in the pigment molecule.