JP2001343743A - Radiation sensitive resin composition and use of its cured body in element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black radiation sensitive resin composition, which gives a pattern having a forward tapered section and suitable for use as a black cured film for an organic EL element or a black matrix for a liquid crystal display element and imparts necessary resistance against solvent, and to provide an element using the composition. SOLUTION: The radiation sensitive resin composition contains [A] a copolymer, obtained by copolymerizing an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (a1), an epoxy compund (a2) having an olefinically unsaturated bond and an olefinically unsaturated compound (a3) other than the compounds (a1) and (a2), [B] a 1,2-quinonediazido compound and [C] a black colorant. A liquid crystal display element and an organic EL element, each using the composition, are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition and a cured product thereof used for a device. More specifically, it is suitable for producing an interlayer insulating film as a black cured film, a partition material as a black matrix, and a spacer, such as a liquid crystal display device, an integrated circuit device, an organic electroluminescence device (organic EL device), and a solid-state imaging device. The present invention relates to use of a radiation resin composition and a cured product thereof in an element.

[0002]

2. Description of the Related Art Conventionally, when a black cured film which is an interlayer insulating film of an organic EL device or a black matrix of a liquid crystal display device is manufactured using a black radiation-sensitive resin composition, a black colorant is formed on a substrate. Is applied and dried, and then the obtained coating film is irradiated with radiation through a photomask (hereinafter, referred to as "exposure").
Then, by developing, a desired pattern is formed. In particular, recently, as described in JP-A-11-273870, an attempt has been made to provide a light-shielding property to an insulating film and / or a base of an element isolation structure for the purpose of enhancing contrast in an organic EL display. .

However, in the black radiation-sensitive resin composition, it is necessary to use a considerable amount of a black colorant in order to sufficiently enhance the light-shielding properties of the black cured film and the black matrix as described above. Due to the absorption by the colorant, a phenomenon inevitably occurs that the effective intensity of the radiation in the coating gradually decreases from the surface of the coating toward the bottom (that is, near the substrate surface). For this reason, in the conventional material, in order to form the above-mentioned pattern, a black cured film or a black matrix is formed by a design called a negative resist so that an exposed portion becomes insoluble. However, with such a negative resist, the curing reaction inside the coating film tends to become gradually insufficient from the surface toward the bottom,
As a result, there has been a problem that the formed pattern is likely to have an inverted tapered shape, or the pattern adheres to the substrate is deteriorated, and the pattern after development is peeled off, resulting in a drop or a chip. In addition, the conventional black radiation-sensitive resin composition using a negative resist has a problem that residues and background stains are easily generated on the unexposed portion of the substrate.

On the other hand, a positive resist has an absorption in the coating film, and the effective intensity of the radiation in the coating film gradually decreases from the surface of the coating to the bottom (ie, near the substrate surface). Even, as the exposed portion dissolves, as occurs in the negative resist, the shape of the formed pattern is likely to be an inverse tapered shape or the adhesion to the substrate is reduced and the developed pattern is peeled off, missing, Problems such as loss are unlikely to occur.

Nevertheless, nevertheless, the reason why the positive type resist has not been conventionally used for forming a black cured film or a black matrix as described above is mainly due to the following reasons. In other words, the negative resist is exposed to light, the radiation-sensitive resin composition undergoes a curing reaction due to a crosslinking reaction during the exposure, and the solvent resistance is obtained, whereas the positive resist is a portion remaining after development. This is because the unexposed portion is a material which does not change at all from the dried state of the coating film and is originally dissolved in a solvent, and therefore has no solvent resistance at all.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a novel colored radiation-sensitive resin composition. Another object of the present invention is to provide a colored radiation-sensitive resin composition which gives a pattern having a forward tapered cross section by a photolithography method. Still another object of the present invention is to provide a colored radiation-sensitive resin composition which provides a solvent resistance required as a black cured film for an organic EL device or a black matrix for a liquid crystal display device.
Still another object of the present invention is to provide a useful use of the radiation-sensitive resin composition. Still another object of the present invention is to provide an organic EL device using a cured film from the radiation-sensitive resin composition as an interlayer insulating film. Still another object of the present invention is to provide a liquid crystal display device provided with a black matrix from the radiation-sensitive resin composition as, for example, a partition material or a spacer. Still other objects and advantages of the present invention will become apparent from the following description.

[0007]

According to the present invention, the above objects and advantages of the present invention are as follows: [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride;
(A2) an epoxy compound having an olefinically unsaturated bond, and (a3) a copolymer obtained by copolymerizing the olefinically unsaturated compound other than (a1) and (a2), [B] 1,2- This is achieved by a radiation-sensitive resin composition comprising a quinonediazide compound and [C] a colorant.

The above objects and advantages of the present invention are, second,
This is achieved by using the radiation-sensitive resin composition of the present invention for producing a black cured film that is an interlayer insulating film of an organic electroluminescence device. Third, the above objects and advantages of the present invention are achieved by using the radiation-sensitive resin composition of the present invention for producing a black matrix. Fourth, the above objects and advantages of the present invention are achieved by a liquid crystal display device having a patterned black matrix formed from the radiation-sensitive resin composition of the present invention. Fifth, the above objects and advantages of the present invention are as follows.
The present invention is achieved by an organic electroluminescent device including a patterned black cured film formed from the radiation-sensitive resin composition of the present invention as an interlayer insulating film. In the present invention, “radiation” refers to ultraviolet rays, far ultraviolet rays, X rays.
Includes radiation, electron beam, molecular beam, γ-ray, synchrotron radiation, proton beam and the like.

Hereinafter, the radiation-sensitive resin composition of the present invention will be described in detail. The radiation-sensitive resin composition of the present invention,
Copolymer [A], 1,2-quinonediazide compound [B]
And a coloring agent [C].

Copolymer [A] Copolymer [A] is synthesized by radical polymerization of compound (a1), compound (a2) and compound (a3) in a solvent in the presence of a polymerization initiator. be able to.
Compound (a1) is an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride. As the compound (a1),
For example, monocarboxylic acids such as 4-vinylbenzoic acid, acrylic acid, methacrylic acid, crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides and succinic acids of these dicarboxylic acids Mono [2- (meth) acryloyloxyethyl],
Monophthalic acid [2- (meth) acryloyloxyethyl]
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as ω-carboxypolycaprolactone mono (meth) acrylate and the like having a carboxyl group and a hydroxyl group at both terminals. (Meth) acrylates. Of these, 4-
Vinyl benzoic acid, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, solubility in an aqueous alkali solution, and easy availability. These may be used alone or in combination.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a1), preferably 5 units.
-50% by weight, particularly preferably 10-35% by weight. Copolymers containing less than 5% by weight of the structural unit are less likely to be dissolved in an aqueous alkali solution, while copolymers containing more than 50% by weight tend to have too high a solubility in an aqueous alkaline solution. Compound (a2) is an epoxy compound having an olefinically unsaturated bond.

As the compound (a2), for example, 2-vinylbenzyl glycidyl ether, 2-vinylbenzyl-
β-methylglycidyl ether, 2-vinylbenzyl-
β-ethyl glycidyl ether, 2-vinylbenzyl-
β-propyl glycidyl ether, 2-vinylbenzyl-3-methyl-3,4-epoxybutyl, 2-vinylbenzyl-3-ethyl-3,4-epoxybutyl, 2-vinylbenzyl-4-methyl-4,5 -Epoxypentyl, 2-vinylbenzyl-5-methyl-5,6-epoxyhexyl, the following formulas (1) to (3):

[0013]

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3-vinylbenzyl glycidyl ether, 3-vinylbenzyl-β-methyl glycidyl ether, 3-vinylbenzyl-β-ethyl glycidyl ether, 3-vinylbenzyl-β-propyl glycidyl ether, -Vinylbenzyl-3-methyl-3,4-epoxybutyl, 3-vinylbenzyl-3-
Ethyl-3,4-epoxybutyl, 3-vinylbenzyl-4-methyl-4,5-epoxypentyl, 3-vinylbenzyl-5-methyl-5,6-epoxyhexyl, the following formulas (4) to (6) :

[0015]

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4-vinylbenzyl glycidyl ether, 4-vinylbenzyl-β-methyl glycidyl ether, 4-vinylbenzyl-β-ethyl glycidyl ether, 4-vinylbenzyl-β-propyl glycidyl ether, -Vinylbenzyl-3-methyl-3,4-epoxybutyl, 4-vinylbenzyl-3-
Ethyl-3,4-epoxybutyl, 4-vinylbenzyl-4-methyl-4,5-epoxypentyl, 4-vinylbenzyl-5-methyl-5,6-epoxyhexyl, the following formulas (7) to (9) :

[0017]

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Glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α
Glycidyl n-butyl acrylate, acrylic acid-3,
4-epoxybutyl, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, (meth ) -Acrylic acid-β-methylglycidyl, (meth) acrylic acid-β-
Ethyl glycidyl, β-propyl glycidyl (meth) acrylate, β-methyl glycidyl α-ethyl acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, -3- (meth) acrylate Ethyl-3,4
-Epoxybutyl, 4-methyl (meth) acrylate-
4,5-epoxypentyl, (meth) acrylic acid-5
Methyl-5,6-epoxyhexyl, 3-ethyl-3-
Oxetanyl methacrylate, 3-ethyl-3-oxetanyl acrylate, and the like.

Of these, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether, 4-vinylbenzyl glycidyl ether, 4-vinylbenzyl-β-methyl glycidyl ether, (meth)
It is preferably used from the viewpoint of particularly increasing the solvent resistance of the radiation-sensitive resin composition from which acrylate-β-methylglycidyl and the like can be obtained. These may be used alone or in combination. Copolymer [A] used in the present invention
Represents 5 to 60% by weight, particularly preferably 10 to 50% by weight, of a structural unit derived from the compound (a2).
Contains. If the content of this constituent unit is less than 5% by weight, the solvent resistance of the resulting coating film tends to decrease.
If the amount is more than 10% by weight, the storage stability of the copolymer tends to decrease.

The compound (a3) is an olefinically unsaturated compound different from the compounds (a1) and (a2). As the compound (a3), for example, styrene, α
Styrene derivatives such as -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate Alkyl esters; alkyl acrylates such as methyl acrylate and isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.
0 ^2,6 ] decane-8-yl methacrylate (commonly known in the art as "dicyclopentanyl methacrylate"), dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate and other cyclic alkyl methacrylates Esters; cyclohexyl acrylate, 2-methylcyclohexyl acrylate,
Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate (commonly referred to in the art as "dicyclopentanyl acrylate"), dicyclopentanyloxyethyl acrylate, isoboro Cyclic alkyl alkyl esters such as nyl acrylate; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; aryl acrylates such as phenyl acrylate and benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate Hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, N-square; Maleimides such as nimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide And bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene, 5-
Hydroxybicyclo [2.2.1] hept-2-ene, 5-
Carboxycyclo [2.2.1] hept-2-ene, 5-
Hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.
1] Hept-2-ene, 5-methoxybicyclo [2.2.
1] Hept-2-ene, 5-ethoxybicyclo [2.2.
1] Hept-2-ene, 5,6-dihydroxybicyclo
[2.2.1] Hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene,
5,6-di (2'-hydroxyethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-dimethoxybicyclo
[2.2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5
-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-
Ene, 5-carboxy-5-methylbicyclo [2.2.1]
Hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5
-Carboxy-6-methylbicyclo [2.2.1] hept-
2-ene, 5-carboxy-6-ethylbicyclo [2.
2.1] Hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic anhydride), 5-t-butoxycarbonylbicyclo [2.2.
1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (T-butoxycarbonyl) bicyclo
[2.2.1] Hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2
Norbornene-based monomers such as ene and acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, ethylene glycol Diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, glycerol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate,
Glycerol dimethacrylate and the like.

Of these, styrene, p-methoxystyrene, t-butyl methacrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, phenylmaleimide, bicyclo [2.2.1] hept-2-ene, 3-butadiene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, and the like are preferable from the viewpoint of copolymerization reactivity, control of molecular weight distribution, and solubility in an aqueous alkali solution. These may be used alone or in combination.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a3), preferably 1
The content is 0 to 80% by weight, particularly preferably 20 to 70% by weight. If this constituent unit is less than 10% by weight, the storage stability of the copolymer [A] tends to decrease, while if it exceeds 80% by weight, the copolymer [A] is difficult to dissolve in an aqueous alkaline solution. Become.

Examples of the solvent used for polymerizing the compound (a1), the compound (a2) and the compound (a3) include, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran;
Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl Diethylene glycols such as methyl ether; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether,
Propylene glycol monoalkyl ethers such as propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol butyl ether acetate; propylene glycol methyl ether propionate Propylene glycol alkyl ether acetates such as propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, Ketones such as roxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methyl propionate,
Methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate,
Ethyl 3-hydroxypropionate, Protyl 3-hydroxypropionate, Butyl 3-hydroxypropionate, Methyl 2-hydroxy-3-methylbutanoate, Methyl methoxyacetate, Ethyl methoxyacetate, Propyl methoxyacetate, Butyl methoxyacetate, Methyl ethoxyacetate , Ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate,
Methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-
Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxy Ethyl propionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxypropion Methyl acrylate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxyp Acid propyl, 3-propoxy-propionic acid butyl, 3-butoxy-propionic acid methyl 3- butoxy-propionic acid ethyl, 3-butoxy-propionic acid propyl, 3-butoxy-propionic acid butyl, esters such as is.

As the polymerization initiator used for the production of the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2'-azobisisobutyronitrile, Azo compounds such as 2,2'-azobis- (2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t- Organic peroxides such as butylperoxypivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

In the production of the copolymer [A], a molecular weight modifier can be used to regulate the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan;
mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and thioglycolic acid; xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; terpinolene and α-methyl styrene dimer.

As described above, the copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, and has an appropriate solubility in an aqueous alkali solution. It can be easily cured by heating without using a special curing agent. The radiation-sensitive resin composition containing the above-mentioned copolymer [A] can easily form a coating film of a predetermined pattern without developing residue during development and without film thinning.

1,2-quinonediazide compound [B] Examples of the 1,2-quinonediazide compound [B] used in the present invention include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, Preferred are 1,2-benzoquinonediazidosulfonic acid amide, 1,2-naphthoquinonediazidosulfonic acid amide, and the like.

Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide- 5
-Sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester 2,3,4-trihydroxybenzophenone-
1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2
-Naphthoquinonediazide-4-sulfonic acid ester,
2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,
6-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6-trihydroxy 1,2-naphthoquinonediazidosulfonic acid esters of trihydroxybenzophenone such as benzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester; 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-4-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1 , 2-Naphthoquinonediazide-6
Sulfonate 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide
7-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2- Naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1, 2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,3'-
Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,3 '
-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,
4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,
4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,
4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,
4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,
4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,
4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-
Methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3 ,
4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-
Methylbenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3 ,
4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3 '
-Methoxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2
-Naphthoquinonediazide-7-sulfonic acid ester,
1,2-naphthoquinonediazidesulfonic acid ester of tetrahydroxybenzophenone such as 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester;
2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,2', 6'-pentane Hydroxybenzophenone-1,2-naphthoquinonediazide-
1,2-naphthoquinonediazidesulfonic acid ester of pentahydroxybenzophenone, such as 7-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester; 2,4,6,3 ', 4', 5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-
4-sulfonic acid ester, 2,4,6,3 ', 4', 5'-
Hexahydroxybenzophenone-1,2-naphthoquinonediazido-5-sulfonic acid ester, 2,4,6,3 ′,
4 ', 5'-hexahydroxybenzophenone-1,2-
Naphthoquinonediazide-6-sulfonic acid ester, 2,
4,6,3 ', 4', 5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1 , 2-Naphthoquinonediazide-8-
Sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′,
4 ', 5'-hexahydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, 3,
4,5,3 ′, 4 ′, 5′-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-Hexahydroxybenzophenone-1 , 2-Naphthoquinonediazide-7-
1,2-naphthoquinonediazidesulfonic acid ester of hexahydroxybenzophenone such as sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester Bis (2,4-dihydroxyphenyl)
Methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane- 1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-
1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfone Acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-7
-Sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, (P-hydroxyphenyl) methane-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
Tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, tri (p
-Hydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonate, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonate, 1,1,1-tri (p -Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1 , 1-tri (p-
(Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,1-tri (p
-Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (2 , 3,
4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,
3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2
-Naphthoquinonediazide-6-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,
2-naphthoquinonediazide-7-sulfonic acid ester,
Bis (2,3,4-trihydroxyphenyl) methane-
1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis ( 2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,
4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2-
Bis (2,3,4-trihydroxyphenyl) propane-
1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-8-sulfonic acid ester, 1,1,3- Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) ) -3-Phenylpropane-1,2-naphthoquinonediazido-5-sulfonic acid ester, 1,1,
3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4- Hydroxyphenyl) -3-
Phenylpropane-1,2-naphthoquinonediazide-7
-Sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-8-sulfonic acid ester, 4,4 '-[1 -[4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 ′-[1- [4-
[1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, 4,
4 '-[1- [4- [1- [4-hydroxyphenyl]
-1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-6-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl) ] Phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-7-sulfonate, 4,4 '-[1- [4-
[1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-
Naphthoquinonediazide-8-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-
Hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2
-Naphthoquinonediazide-6-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2
-Hydroxyphenylmethane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-8-sulfonic acid ester 3,3,3 ', 3'-tetramethyl-1,
1'-spirobiindene-5,6,7,5 ', 6', 7'-
Hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-
1,1'-spirobiindene-5,6,7,5 ', 6', 7 '
-Hexanol-1,2-naphthoquinonediazide-5
Sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′,
7'-hexanol-1,2-naphthoquinonediazide-
6-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′,
6 ', 7'-hexanol-1,2-naphthoquinonediazide-7-sulfonic acid ester, 3,3,3', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,
5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2
-Naphthoquinonediazide-4-sulfonic acid ester,
2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazido-5-sulfonic acid, 2,2,4-trimethyl-7,2', 4'-trihydroxy Flavan-1,2-naphthoquinonediazide-6
Sulfonic acid ester, 2,2,4-trimethyl-7,2 ',
4'-trihydroxyflavan-1,2-naphthoquinonediazide-7-sulfonic acid, 2,2,4-trimethyl-
1,2-naphthoquinonediazidesulfonic acid esters of (polyhydroxyphenyl) alkanes such as 7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-8-sulfonic acid.

These 1,2-quinonediazide compounds can be used alone or in combination of two or more. The use ratio of the component [B] is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the component [A]. When this ratio is less than 5 parts by weight, the amount of acid generated by irradiation with the radiation is small, so that the difference in solubility between the irradiated part and the unirradiated part in an aqueous alkali solution serving as a developer is small,
Patterning becomes difficult. In addition, since the amount of the acid involved in the reaction of the epoxy group decreases, sufficient heat resistance and solvent resistance cannot be obtained. On the other hand, when this proportion exceeds 100 parts by weight, a large amount of unreacted [B] component remains in a short-time irradiation of radiation, so that the effect of insolubilizing the aqueous alkali solution becomes too high. And it is difficult to develop. Colorant [C] in the present invention
Is preferably composed of a mixture of a coloring pigment and an extender pigment.

The coloring pigment can be appropriately selected according to the use of the radiation-sensitive resin composition. An inorganic pigment or an organic pigment may be used, or one kind of pigment or a mixture of two or more kinds of pigments may be used. As the colorant in the invention, those containing a black pigment are preferable. As the black pigment, a pigment having a high coloring property and a high heat resistance, particularly a pigment having a high thermal decomposition resistance, is preferable, and a combination of carbon black and / or two or more organic pigments is particularly preferable.

As carbon black, for example, SA
F, SAF-HS, ISAF, ISAF-LS, ISA
F-HS, HAF, HAF-LS, HAF-HS, NA
F, FEF, FEF-HS, SRF, SRF-LM, S
RF-LS, GPF, ECF, N-339, N-351
Furnace black; thermal black such as FT and MT; and acetylene black. These carbon blacks can be used alone or in combination of two or more. Examples of the inorganic pigment other than carbon black in the present invention include metal oxides such as titanium black, Cu—Fe—Mn-based oxide, and synthetic iron black. These inorganic pigments can be used alone or in combination of two or more.

Further, the organic pigment in the present invention includes:
For example, the color index (C.I .; The Soc)
iety of Dysers and Colori
(published by Sts)
Compounds classified into t), specifically, compounds having the following color index (CI) numbers can be given. CI Pigment Yellow 1
2, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI
Pigment Yellow 20, CI Pigment Yellow 2
4, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI
Pigment Yellow 93, CI Pigment Yellow 1
09, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 13
9, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154,
CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168;
CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 71;
CI Pigment Red 9 and CI Pigment Red 9
7, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 149, C.I.
Pigment Red 168, CI Pigment Red 17
6, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 209, CI
Pigment Red 215, CI Pigment Red 22
4, CI Pigment Red 242, CI Pigment Red 254; CI Pigment Violet 19,
CI Pigment Violet 23, CI Pigment Violet 29; CI Pigment Blue 15, C.I.
CI Pigment Blue 60, CI Pigment Blue 1
5: 3, CI Pigment Blue 15: 4; CI Pigment Blue 15: 6; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, C CI Pigment Brown 25; CI
Pigment Black 1 and CI Pigment Black 7.

These organic pigments are appropriately selected and used so as to obtain a desired hue as a black resist. The above-mentioned black pigment can be optionally used together with the extender pigment. Examples of the extender include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, satan white, hydrotalcite, and the like. These extenders can be used alone or in combination of two or more. The amount of extender used is black pigment 10
The amount is usually 100 parts by weight or less, preferably 50 parts by weight or less, more preferably 40 parts by weight or less based on 0 parts by weight.

In the present invention, the above-mentioned black pigment and extender pigment may be used after modifying their surface with a polymer, if necessary. Further, the black colorant in the present invention can be optionally used together with a dispersant. Examples of such dispersants include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants.

Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl. Polyoxyethylene alkyl phenyl ethers such as phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Tochem Products Co., Ltd.) Megafac (Dainippon Ink & Chemicals Co., Ltd.), Fluorad (Sumitomo Co., Ltd.
Manufactured by Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), and the like. These surfactants can be used alone or in combination of two or more. The amount of the surfactant used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the black colorant.

<Other Components> The radiation-sensitive resin composition of the present invention contains the above components [A], [B] and [C].
In addition to the components, if necessary, component [D] composed of a heat-sensitive acid-generating compound, component [E] composed of an epoxy resin, component [F] composed of a surfactant, and component [G] composed of an adhesion aid. And an [H] component comprising a low molecular weight carboxylic acid. The heat-sensitive acid-generating compound as the component [D] can be used for improving heat resistance and hardness, and specific examples thereof include antimony fluorides. L80,
Sun-Aid SI-L110, Sun-Aid SI-L150
(Above, manufactured by Sanshin Chemical Industry Co., Ltd.).
The proportion of the component [D] used is preferably 20 parts by weight or less, particularly preferably 5 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin of the component [A]. If this proportion exceeds 20 parts by weight, precipitates are liable to be formed and patterning tends to be difficult.

The epoxy resin as the component (E) is not limited as long as compatibility is not affected, but preferably, for example, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin Resin, cycloaliphatic epoxy resin,
Glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin and resin obtained by (co) polymerizing glycidyl methacrylate can be exemplified. Among these, bisphenol A type epoxy resin, cresol novolak type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.

The proportion of the component [E] is preferably 30 parts by weight or less based on 100 parts by weight of the alkali-soluble resin. When the component [E] is contained at such a ratio, the strength and the like of a coating film obtained from the radiation-sensitive resin composition can be further improved. If this proportion exceeds 30 parts by weight, the compatibility with the alkali-soluble resin will be insufficient, and sufficient film-forming ability will not be obtained.

As the surfactant as the component [F], for example, BM-1000, BM-1100 (BM C
HEMIE), MegaFac F142D, F17
2, F173, F183 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-135, FC-170
C, FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Surflon S-112, S-113, S-131, S-141, S-145, S-38
2, SC-101, SC-102, SC-10
3, SC-104, SC-105, SC-106
(Manufactured by Asahi Glass Co., Ltd.), F-top EF301, 30
3, 352 (manufactured by Shin-Akita Chemical Co., Ltd.), SH-28P
A, SH-190, SH-193, SZ-6032, S
Fluorine- and silicone-based surfactants such as F-8428, DC-57, and DC-190 (manufactured by Toray Dow Corning Silicone); polyoxyethylene lauryl ether;
Polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene dilaurate and polyoxyethylene Nonionic surfactants such as polyoxyethylene dialkyl esters such as distearate; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meta)
Acrylic acid copolymer polyflow Nos. 57 and 95
(Above, manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants are used in an amount of preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant is more than 5 parts by weight, the film tends to be rough at the time of coating.

As the above-mentioned adhesive aid [G] component, a functional silane coupling agent is preferably used, for example, a carboxyl group, a methacryloyl group, an isocyanate group,
Examples include silane coupling agents having a reactive substituent such as an epoxy group. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and γ-isocyanate. Natopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

Examples of the low molecular carboxylic acid as the component [H] include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid. Acids: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethyl Examples thereof include dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, and mesaconic acid; and tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include an aromatic carboxylic acid having a carboxyl group directly bonded to a phenyl group and a carboxylic acid having a carboxyl group bonded to a phenyl group via a carbon chain. Specific examples thereof include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; trimellitic acid and trimesic acid , Aromatic polycarboxylic acids having a valency of 3 or more such as melophanoic acid and pyromellitic acid; and phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid,
Atropic acid, cinnamic acid, cinnamylidenic acid, coumaric acid,
Umberic acid and the like can be mentioned.

Among these organic acids, aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, and phthalic acid are alkali-soluble, This is preferred from the viewpoints of solubility with respect to water, prevention of background contamination in a region other than the portion where the pattern is formed, and the like. The organic acids can be used alone or in combination of two or more.

The amount of the organic acid used is preferably 10% by weight or less, more preferably 0.001 to 10% by weight, and still more preferably 0.0% by weight, based on the whole radiation-sensitive resin composition.
1 to 1% by weight. In this case, the amount of the organic acid used is 10
If the amount exceeds the weight percentage, the adhesion of the formed pattern to the substrate tends to decrease. The radiation-sensitive resin composition of the present invention is prepared by uniformly mixing the copolymer [A], the 1,2-quinonediazide compound [B] and the colorant [C]. Usually, the radiation-sensitive resin composition of the present invention is dissolved in an appropriate solvent and used in the form of a solution. For example, a copolymer [A], a 1,2-quinonediazide compound [B], a coloring agent [C], and other compounding agents are used.
By mixing at a predetermined ratio, a radiation-sensitive resin composition in a solution state can be prepared.

As the solvent used for preparing the radiation-sensitive resin composition of the present invention, the components of the copolymer [A], the 1,2-quinonediazide compound [B] and the colorant [C] are uniformly dissolved. However, those that do not react with each component are used.
Specifically, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetate such as methyl cellosolve acetate and ethyl cellosolve acetate Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; propylene glycol Propylene glycol alkyl ether acetates such as tyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether pro Propylene glycol alkyl ether acetates such as pionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; Methyl acetate,
Ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, Methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3
-Protyl hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate,
Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butylpropoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butoxyacetic acid Propyl, butyl butoxyacetate, 2-
Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2-ethoxy Butyl propionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
Propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3
-Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-
Methyl propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate,
Butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3
Esters such as -propyl butoxypropionate and butyl 3-butoxypropionate.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, esters and the like are preferred in view of solubility, reactivity with each component, and ease of forming a coating film. And diethylene glycols are preferably used. Further, a high boiling point solvent can be used in combination with the above-mentioned solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, carbonic acid Propylene, phenyl cellosolve acetate and the like can be mentioned.

The composition solution prepared as described above can be used after being filtered using a millipore filter having a pore size of about 2 μm. The radiation-sensitive composition of the present invention preferably has a cured film obtained by irradiating the composition with a radiation and having an optical density (OD value) of 0.1 or more at a thickness of 1 μm.

Formation of Patterned Coating Film Next, an organic EL was prepared using the radiation-sensitive resin composition of the present invention.
A method for forming a cured film as an interlayer insulating film of the device will be described. The radiation-sensitive resin composition of the present invention can be applied to the surface of a base substrate, and the solvent can be removed by pre-baking to form a coating film. As a coating method, various methods such as a spray method, a roll coating method, and a spin coating method can be adopted. The conditions of the prebaking vary depending on the type of each component, the mixing ratio, and the like, but the conditions of usually 70 to 90 ° C. for about 1 to 15 minutes are optimal. The radiation-sensitive resin composition of the present invention has a process margin that can sufficiently cope with a pre-bake temperature of about 110 ° C. Next, the prebaked coating film is irradiated with radiation such as ultraviolet rays via a predetermined pattern mask, and further developed with a developer to remove unnecessary portions to form a predetermined pattern. The developing method may be any of a liquid filling method, a dipping method, a shower method and the like, and the developing time is usually 30 to 180 seconds.

Examples of the developer include an aqueous alkali solution, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; and primary amines such as ethylamine and n-propylamine. And diethylamine, di-n
Secondary amines such as -propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; tertiary amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; pyrrole, piperidine and N
-Methylpiperidine, N-methylpyrrolidine, 1,8-
Diazabicyclo [5.4.0] -7-undecene, 1.5
Cyclic tertiary amines such as -diazabicyclo [4.3.0] -5-nonene; aromatic tertiary amines such as pyridine, collidine, lutidine, and quinoline; 4 such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; An aqueous solution of a quaternary ammonium salt can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant to the aqueous alkaline solution can also be used as a developer.

After development, washing with running water is performed for 30 to 90 seconds.
A pattern is formed by removing unnecessary portions and air-drying with compressed air or compressed nitrogen. The formed pattern is irradiated with radiation such as ultraviolet rays, and then the pattern is heated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 130 to 190 ° C., for a predetermined time, for example, 5 to 60 minutes on a hot plate. By performing a heat treatment in an oven for 30 to 90 minutes, a desired patterned coating film of an interlayer insulating film can be obtained.

The pattern of the obtained coating film has a forward tapered cross section, that is, a cross section in the direction perpendicular to the substrate has a trapezoidal shape in which the bottom side is longer than the top side. When forming a black matrix used for a liquid crystal display device using the radiation-sensitive resin composition of the present invention, for example, a normal black matrix and a black matrix used as a diaphragm or a spacer, substantially the same method as described above is employed. Can be.

Production of Organic EL Device The organic EL device of the present invention has a patterned cured film formed as described above. Organic EL of the present invention
The element is manufactured, for example, as follows. A transparent electrode such as ITO is formed on a glass substrate by sputtering, and a positive photoresist is applied thereon as described above,
Prebake. The resist is exposed through a mask and then developed and patterned to form a patterned interlayer insulating film. Next, the ITO film is etched with a hydrochloric acid-based etchant such as ferric chloride, the resist film is stripped, and the transparent electrode is patterned, for example, into a stripe shape. On the substrate having the patterned transparent electrodes, a reverse tapered partition is provided. Thereafter, a hole transport layer, an organic EL medium layer, and a cathode layer are sequentially formed by a vapor deposition method.
As the hole transport layer, for example, a phthalocyanine-based material such as CuPc or H ₂ Pc, or an aromatic amine is used. As the organic EL medium, for example, Alq ₃ , B
A material such as eBq _{3 in which} a base material is doped with quinacridone or coumarin is used. Further, as a cathode material, for example, Mg-Al, Al-Li, Al-Li
₂ O, Al-LiF or the like is used. Next, after sealing the hollow SUS can and the substrate with a sealing material such as epoxy resin, the module is assembled into an organic EL element.

Production of Liquid Crystal Display Element The liquid crystal display element of the present invention has the black matrix formed as described above. The liquid crystal display element of the present invention is manufactured, for example, as follows. A black matrix is formed on a transparent substrate such as glass as described above, and a coating film is formed on the substrate using, for example, a red-colored radiation-sensitive composition. The formed pixels form a pixel array arranged in a predetermined pattern.

Thereafter, if necessary, a color filter is obtained by sequentially forming a pixel array of each color on the same substrate by using each composition of another color (for example, green or blue). After forming a patterned transparent electrode film such as ITO on the color filter, a coating film of a liquid crystal alignment agent is formed. On the other hand, after forming a transparent electrode film (continuous film) on one surface of another transparent substrate, a coating film of a liquid crystal aligning agent is formed in the same manner as described above. Next, a rubbing process is performed on the surface of the coating film on each substrate to form a liquid crystal alignment film.

The substrates on which the liquid crystal alignment films are formed are combined to form a pair, and an adhesive containing a spacer is applied to the outer edges of the two substrates, and then the rubbing of each liquid crystal alignment film is performed. The two substrates are opposed to each other with a gap between them so that the directions intersect, and the two substrates are pressed together so that the outer edges of the substrates come into contact with each other. After filling the liquid crystal into the cell gap defined by the inner surfaces of the two substrates and the cured layer of the adhesive, the injection hole is sealed to form a liquid crystal cell, and a polarizing plate is formed on the outer surface of the liquid crystal cell. A liquid crystal display element can be manufactured by bonding together such that the polarization direction matches the rubbing direction of the liquid crystal alignment film on each substrate.

[0056]

EXAMPLES The present invention will be described more specifically with reference to the following synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples.

Synthesis Example 1 In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and propylene glycol monomethyl ether acetate 220 were added.
The parts by weight were charged. Subsequently, 30 parts by weight of 4-vinylbenzoic acid, 30 parts by weight of styrene, 40 parts by weight of 4-vinylbenzyl glycidyl ether, and α-methylstyrene dimer 1.
Five parts were charged and stirring was begun slowly while replacing with nitrogen. The temperature of the solution was raised to 70 ° C., and the mixture was heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-1].
The solid concentration of the obtained polymer solution was 31.2%,
The weight average molecular weight of the polymer was 12,500 and the molecular weight distribution was 1.8. The weight average molecular weight was measured by GPC (gel permeation chromatography (Tosoh Corporation)
It is an average molecular weight in terms of polystyrene measured using HLC-8020 (manufactured by Co., Ltd.).

Synthesis Example 2 In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and propylene glycol monomethyl ether acetate 220 were added.
The parts by weight were charged. 20 parts by weight of styrene, 4-
30 parts by weight of vinylbenzoic acid, phenylmaleimide 20
, 30 parts by weight of 2-vinylbenzyl glycidyl ether and 1.5 parts of α-methylstyrene dimer were charged and slowly stirred while being replaced with nitrogen. Set the solution temperature to 7
The temperature was raised to 0 ° C., and the mixture was heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-2]. The solid content of the obtained polymer solution was 31.0%, the weight average molecular weight of the polymer was 15,000, and the molecular weight distribution was 2.3.

Example 1 Preparation of Radiation-Sensitive Resin Composition 100 parts by weight (solid content) of the copolymer [A-1] obtained in Synthesis Example 1 and 4,4 '-[1 − [4
-[1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1
Mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol), 30 parts by weight of a condensate, 10 parts by weight of carbon black as the component [C], and
Urethane dispersant (trade name: Disperbyk-18)
2) and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane were mixed, and the solid concentration was 25% by weight.
Was dissolved in propylene glycol monomethyl ether acetate, and then filtered through a 2 μm-pore-size millipore filter to obtain a solution of the radiation-sensitive resin composition (S-1).
Was prepared.

(I) Formation of Black Matrix The composition solution (S-1) was applied on a glass substrate by using a spinner, and then prebaked at 90 ° C. for 3 minutes on a hot plate to form a film having a thickness of 5 μm. A coating was formed.
The coating film obtained above was irradiated with ultraviolet light having an intensity at 365 nm of 10 mW / cm ² for 30 seconds through a mask having a 10 μm square residual pattern. The ultraviolet irradiation at this time was performed in an oxygen atmosphere (in air). Then at 25 ° C. with a 0.1% by weight aqueous solution of tetramethyl ammonium hydroxide
For 90 seconds, and then washed with running pure water for 1 minute. The above-formed partition wall material is placed in an oven at 220 ° C. for 60 minutes.
The mixture was heated and cured for 5 minutes to obtain a black matrix having a thickness of 4.5 μm.

(II) Evaluation of Black Matrix In the black matrix obtained in the above (I), the case where the cross-sectional shape was a forward taper or a rectangle was evaluated as ○, and the case where the cross-sectional shape was an inverse tapered shape was evaluated as ×. Table 1 shows the results. (III) Evaluation of heat resistance The black matrix formed in the above (I) was heated in an oven at 250 ° C for 60 minutes. Table 1 shows the dimensional change rate of the film thickness. When the dimensional change before and after the heating is within 5%, it can be said that the heat-resistant dimensional stability is good. (IV) Evaluation of light-shielding property The thin film having a thickness of 4.5 μm formed by the same process as in the above (I) except that the exposure was not performed, using an optical densitometer (Macbeth TR927 (manufactured by Sakata Inx Co.)). The value was measured. Table 1 shows the results. (V) Evaluation of Adhesion The adhesion of the black matrix obtained in the above (I) was evaluated by a tape peeling test. The results are shown in Table 1. The evaluation results were represented by the number of remaining black matrices in 100 black matrices. (VI) Evaluation of solvent resistance The solvent resistance of the black matrix obtained in the above (I) was evaluated by the swelling ratio after immersion in isopropanol at 50 ° C for 30 minutes. A swelling ratio of 100 to 105% was defined as good, and 100% or less and 105% or more was determined as poor. Table 1 shows the results.

Example 2 A composition solution (S-2) was prepared in the same manner as in Example 1 except that the copolymer [A-2] was used instead of the copolymer [A-1]. ) Was prepared and evaluated. Table 1 shows the results.

Example 3 In Example 1, 4,4 '-[1
-[4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Condensate 30 of bisphenol (1 mol) and 1,2-naphthoquinonediazide-6-sulfonic acid chloride (2 mol) 30 Except for using parts by weight, a composition solution (S-
3) was prepared and evaluated. Table 1 shows the results.

Example 4 In Example 1, 37 parts by weight of CI Pigment Red 177 and 16 parts by weight of CI Pigment Blue 15: 4 as the component [C] were used, and a urethane-based dispersant ( A composition solution (S-4) was prepared and evaluated in the same manner as in Example 2, except that 12 parts by weight of trade name Disperbyk-182) was used. Table 1 shows the results.

[0065]

[Table 1]

[0066]

According to the present invention, it is possible to easily form an interlayer insulating film of an organic EL device or a black matrix of a liquid crystal display device having excellent properties such as a tapered shape, heat resistance and light shielding properties. A resin composition is provided. In addition, a highly reliable interlayer insulating film and black matrix can be obtained from the radiation-sensitive resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/20 101 G02B 5/20 101 5C094 G02F 1/1335 500 G02F 1/1335 500 G03F 7/004 505 G03F 7/004 505 7/022 7/022 G09F 9/30 349 G09F 9/30 349C (72) Inventor Masayuki Endo 2-11-24 Tsukiji 2-chome, Chuo-ku, Tokyo F-term in JSR Corporation (reference) 2H025 AA03 AA10 AA20 AB13 AB20 AC01 AD03 BE01 CB41 CB43 CC12 FA17 2H042 AA09 AA15 AA26 2H048 BA11 BB01 BB42 2H091 FA35Y GA07 LA30 4J002 BC021 BC081 BC091 BC121 BD031 BD101 BF021 BG011 BG041 BG051 BG051 BG051 BG051 BG051 BG051 BG051 BG051 BG051 BG051 AA43 BA27 CA19 DA15 EB02 GB01 GB10

Claims (7)

[Claims] 1. [A] (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, (a2) an epoxy compound having an olefinically unsaturated bond, and (a3)
A copolymer obtained by copolymerizing an olefinically unsaturated compound other than (a1) and (a2), [B] 1,2-
A radiation-sensitive resin composition comprising a quinonediazide compound and [C] a colorant. 2. Use of the radiation-sensitive resin composition according to claim 1 for producing a black cured film which is an interlayer insulating film of an organic electroluminescence device. 3. Use of the radiation-sensitive resin composition according to claim 1 for producing a black matrix of a liquid crystal display device. 4. An organic electroluminescence device comprising a patterned black cured film formed from the radiation-sensitive resin composition according to claim 1 as an interlayer insulating film. 5. The organic electroluminescence device according to claim 4, wherein the pattern of the black cured film has a forward tapered cross section. 6. A liquid crystal display device comprising a patterned black matrix formed from the radiation-sensitive resin composition according to claim 1. 7. The liquid crystal display device according to claim 6, wherein the pattern of the black matrix has a forward tapered cross section.