JP2001330953A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition having a wide process margin and shelf stability and capable of forming an interlayer insulation film and microlenses excellent in heat and solvent resistances and transparency, and to provide an interlayer insulation film and microlenses obtained from the composition. SOLUTION: The radiation sensitive resin composition contains [A] a copolymer of (a1) an unsaturated carboxylic acid and/or its anhydride, (a2) a specified monomer containing an oxetanyl group and (a3) an olefinically unsaturated compound other than the components (a) and (a2) and [B] a 1,2-quinonediazido compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition. Specifically, a positive-type radiation-sensitive resin composition suitable for producing an interlayer insulating film or a microlens using radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, and proton beams. About.
More specifically, materials for forming an interlayer insulating film, particularly, an interlayer insulating film such as a liquid crystal display element, an integrated circuit element, a magnetic head element, and a solid-state imaging element, and a minute optical lens body are regularly arranged. The present invention relates to a radiation-sensitive resin composition suitable for producing a lens array or the like.

[0002]

2. Description of the Related Art Generally, a thin film transistor (hereinafter referred to as "T
FT ". 2. Description of the Related Art Electronic components such as a liquid crystal display device, a magnetic head device, an integrated circuit device, and a solid-state imaging device are provided with an interlayer insulating film for insulating between wirings arranged in layers. As a material for forming an interlayer insulating film, a radiation-sensitive resin composition having a feature that the number of steps for obtaining an interlayer insulating film having a required pattern shape is small and an interlayer insulating film having sufficient flatness can be obtained. Things are widely used. In general, a facsimile, an electronic copier, a microlens having a lens diameter of about 5 to 100 μm as an optical system material for an on-chip color filter such as a solid-state image sensor or an optical fiber connector, or a microlens thereof. A regularly arranged microlens array is used. To form a microlens or microlens array, after forming a lens pattern, the pattern is melt-flowed by heating and then used as it is as a lens, or by dry etching using the melt-flowed lens pattern as a mask A method of transferring a lens shape to a base is known. For the formation of the lens pattern, a radiation-sensitive resin composition having a feature that a microlens having a desired radius of curvature is obtained is widely used. These interlayer insulating films and microlenses or microlens arrays are required to have various properties such as high heat resistance, high solvent resistance, high transparency, and adhesion to a base. Therefore, it is necessary that the radiation-sensitive composition can provide a cured product excellent in the above various properties. In addition, it is desired to have good storage stability and to have a wide process margin that enables pattern formation under various process conditions according to the purpose of use. However, a radiation-sensitive composition that can provide a cured product having high heat resistance and high solvent resistance, has good storage stability, and has a wide process margin has not been proposed.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
It has a sufficient process margin and good storage stability, and has the heat resistance required as an interlayer insulating film and microlens,
An object of the present invention is to provide a radiation-sensitive resin composition that can provide a cured product having solvent resistance, transparency, and adhesion to a substrate. Still other objects and advantages of the present invention will become apparent from the following description.

[0004]

Means for Solving the Problems The object of the present invention is to provide [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (hereinafter also referred to as "compound (a1)") according to the present invention. (A2) a compound represented by the general formula (I) or (II) (hereinafter, also referred to as “compound (a2)”);

[0005]

Embedded image

[Where R is a hydrogen atom or a carbon atom having 1 to
R ¹ is a hydrogen atom or a carbon atom 1
And R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoro group having 1 to 4 carbon atoms. An alkyl group, and n is an integer from 1 to 6. And (a3) the above (a1)
And a copolymer obtained by copolymerizing an olefinically unsaturated compound other than (a2) (hereinafter, also referred to as “compound (a3)”) (hereinafter, also referred to as “copolymer [A]”).
And [B] a radiation-sensitive resin composition characterized by containing a radiation-sensitive resin composition characterized by containing a 1,2-quinonediazide compound.

Hereinafter, the radiation-sensitive resin composition of the present invention will be described in detail. The radiation-sensitive resin composition of the present invention comprises a copolymer [A] and a 1,2-quinonediazide compound [B].

Copolymer [A] The copolymer [A] comprises a compound (a1), a compound (a2),
The compound (a3) can be synthesized by radical polymerization of a compound (a3) in a solvent in the presence of a polymerization initiator.

The copolymer [A] used in the present invention comprises a structural unit derived from compound (a1), preferably 5 units.
-40% by weight, particularly preferably 10-35% by weight. Copolymers having less than 5% by weight of the structural unit are less likely to be dissolved in an aqueous alkaline solution, while copolymers exceeding 40% by weight tend to have too high a solubility in an aqueous alkaline solution. Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;
And anhydrides of these dicarboxylic acids; monosuccinic acid [2
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as-(meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalate; Carboxypolycaprolactone mono (meth) acrylate and the like, and polymer mono (meth) acrylates having a carboxyl group and a hydroxyl group at both ends, and the like can be mentioned. Among them, 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 (a2), preferably 5 units.
To 60% by weight, particularly preferably 10 to 50% by weight. If this constituent unit is less than 5% by weight, the heat resistance of the resulting coating film tends to decrease, while if it exceeds 60% by weight, the storage stability of the copolymer tends to decrease.

As the compound (a2) represented by the general formula (I), for example, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-
Ethyl oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3-
(Methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl)
-2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,
2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3
-(Methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl)
-2-pentafluoroethyloxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,
2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,
Methacrylic acid esters such as 2,4-trifluorooxetane and 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;

3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-
Methyl oxetane, 3- (acryloyloxymethyl)
-2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,
2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl ) Oxetane, 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl ) -2-Pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4 -Trifluorooxetane, 3-
And acrylates such as (acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane.

As the compound (a2) represented by the general formula (II), for example, 2- (methacryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, 3-methyl-2- (methacryloyloxy) Methyl) oxetane, 4-methyl-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoromethyloxetane, 2- ( (Methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -3-
Pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -4-pentafluoroethyl oxetane,
2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) -3-
Phenyloxetane, 2- (methacryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2
-(Methacryloyloxymethyl) oxetane, 2,4
-Difluoro-2- (methacryloyloxymethyl) oxetane, 3,3-difluoro-2- (methacryloyloxymethyl) oxetane, 3,4-difluoro-2- (methacryloyloxymethyl) oxetane, 4,4-difluoro-2- (Methacryloyloxymethyl) oxetane,
2- (methacryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,3,4 4-tetrafluorooxetane,

2- (methacryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (methacryloyloxyethyl)- 2-methyloxetane, 2- (methacryloyloxyethyl) -4-methyloxetane, 2-
(Methacryloyloxyethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxyethyl)-
3-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -4-trifluoromethyloxetane,
2- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (methacryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxyethyl) -4-pentafluoroethyloxetane, 2- (methacryloyloxy Ethyl) -2-
Phenyloxetane, 2- (methacryloyloxyethyl) -3-phenyloxetane, 2- (methacryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro-2- (methacryloyloxyethyl) oxetane, 2,4-difluoro- 2- (methacryloyloxyethyl) oxetane, 3,3-difluoro-2- (methacryloyloxyethyl) oxetane, 3,4-difluoro-
2- (methacryloyloxyethyl) oxetane, 4,
4-difluoro-2- (methacryloyloxyethyl) oxetane, 2- (methacryloyloxyethyl) -3,
3,4-trifluorooxetane, 2- (methacryloyloxyethyl) -3,4,4-trifluorooxetane,
2- (methacryloyloxyethyl) -3,3,4,4
-Methacrylates such as tetrafluorooxetane;

2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acryloyloxymethyl)
Oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) -3-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 2- (acryloyloxymethyl) -3-pentafluoro Ethyloxetane, 2- (acryloyloxymethyl) -4-pentafluoroethyloxetane, 2- (acryloyloxymethyl) -2-phenyloxetane, 2- (acryloyloxymethyl) -3-phenyloxetane, 2- (acryloyloxy Chill) -4-phenyl oxetane,
2,3-difluoro-2- (acryloyloxymethyl)
Oxetane, 2,4-difluoro-2- (acryloyloxymethyl) oxetane, 3,3-difluoro-2- (acryloyloxymethyl) oxetane, 3,4-difluoro-2- (acryloyloxymethyl) oxetane,
4,4-difluoro-2- (acryloyloxymethyl)
Oxetane, 2- (acryloyloxymethyl) -3,
3,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane, 2
-(Acryloyloxymethyl) -3,3,4,4-tetrafluorooxetane,

2- (acryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl)- 2-methyloxetane, 2- (acryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxyethyl) -2-trifluoromethyloxetane, 2- (acryloyloxyethyl) -3-trifluoromethyloxetane, 2- (Acryloyloxyethyl) -4-trifluoromethyloxetane, 2- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -4-penta Rollo ethyl oxetane, 2- (acryloyloxyethyl) -2-phenyl oxetane,
2- (acryloyloxyethyl) -3-phenyloxetane, 2- (acryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro-2- (acryloyloxyethyl) oxetane, 2,4-difluoro-2-
(Acryloyloxyethyl) oxetane, 3,3-difluoro-2- (acryloyloxyethyl) oxetane, 3,4-difluoro-2- (acryloyloxyethyl) oxetane, 4,4-difluoro-2- (acryloyloxyethyl) Oxetane, 2- (acryloyloxyethyl) -3,3,4-trifluorooxetane, 2-
(Acryloyloxyethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxyethyl)-
Acrylic esters such as 3,3,4,4-tetrafluorooxetane are exemplified.

Of these, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane,
2- (methacryloyloxymethyl) oxetane, 2-
(Methacryloyloxymethyl) -4-trifluoromethyloxetane is preferably used because the process margin of the photosensitive resin composition from which the obtained resin composition is obtained is wide, and the obtained interlayer insulating film and microlens increase the chemical resistance. 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 compound (a3) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; 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 referred to in the art as dicyclopentanyl methacrylate), Cyclic alkyl esters of methacrylic acid such as cyclopentanyloxyethyl methacrylate and isobornyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate Over door, tricyclo [5.2.1.0
^2,6 ] decane-8-yl acrylate (commonly referred to in the art as dicyclopentanyl acrylate), dicyclopentanyloxyethyl acrylate, and cyclic alkyl esters of acrylic acid such as isobornyl acrylate; Aryl acrylates 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; 2-hydroxyethyl methacrylate; -Hydroxyalkyl esters such as hydroxypropyl methacrylate;

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
-Carboxybicyclo [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- En, 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 acid 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-
Bicyclo unsaturated compounds such as di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Kind;

Phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-
3-maleimidobenzoate, N-succinimidyl-
4-maleimidobutyrate, N-succinimidyl-6
Maleimide caproate, N-succinimidyl-3
Dicarbonylimide derivatives such as -maleimidopropionate, N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p
-Methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, methacrylic acid Glycidyl,
Glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6, acrylic acid 7-
Epoxyheptyl, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethylacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like. .

Of these, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-
Methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, glycidyl methacrylate, o
-Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, phenylmaleimide, cyclohexylmaleimide, bicyclo [2.2.1] hept-2-ene, etc. are copolymerizable and soluble in alkaline aqueous solution It is preferable from the viewpoint of properties. These may be used alone or in combination.

As described above, the copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic acid anhydride group and an epoxy group, and has a proper solubility in an aqueous alkali solution. In addition to having a special curing agent, it can be easily cured by heating. 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.

Examples of the solvent used in the synthesis of the copolymer [A] include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; and ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Glycol ethers; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol methyl ether; Propylene glycol ethyl ether, professional 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 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy- Ethyl 2-methylpropionate, 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, butoxyacetic acid Ethyl, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate,
Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2
-Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2-
Butyl ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxypropion Ethyl acid, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, 3-butoxy Propionic acid butyl, esters such as is.

As the polymerization initiator used for producing the copolymer [A], those generally known as a radical polymerization initiator can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-
Azo compounds such as methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-
Organic peroxides such as 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.

The copolymer [A] used in the present invention has a polystyrene equivalent weight average molecular weight (hereinafter, referred to as “Mw”) of usually 2 × 10 3 to 5 × 10 5, preferably 5 × 10 5.
It is desirable that it be 10 3 to 1 × 10 5. Mw is 2 × 1
If it is less than 03, the residual film ratio after development tends to be low.

1,2-quinonediazide compound [B] As the 1,2-quinonediazide compound [B] used in the present invention, as the 1,2-quinonediazide compound, 1,2-benzoquinonediazidesulfonic acid ester, 2-naphthoquinonediazidosulfonic acid ester, 1,2-benzoquinonediazidosulfonic acid amide,
1,2-naphthoquinonediazidosulfonic acid amide and the like can be mentioned.

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-trihydroxybenzophenone-1,2-
1,2-naphthoquinonediazidosulfonic acid esters of trihydroxybenzophenone such as naphthoquinonediazide-8-sulfonic acid ester;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-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-sulfonic acid ester, 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′-tetrahydroxy ester Benzophenone-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
Sulfonate, 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-naphtho Quinonediazide-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, 2,3,4,4'-tetrahydroxy-3'-
1,2-naphthoquinonediazidesulfonic acid esters of tetrahydroxybenzophenone such as 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-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2',
6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3
4,2 ', 6'-pentahydroxybenzophenone-
1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester and other pentahydroxybenzophenone 1,2 -Naphthoquinonediazidosulfonic acid esters;

2,4,6,3 ′, 4 ′, 5′-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′,
4 ', 5'-hexahydroxybenzophenone-1,2
-Naphthoquinonediazide-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-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone 1,2-naphthoquinonediazidosulfonic acid esters of hexahydroxybenzophenone such as -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-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

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-naphthoquinonediazido-5-sulfonic acid ester, bis (2
3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonate, 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-naphthoquinonediazide-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-sulfonic acid ester, 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-naphthoquinonediazide-5-sulfonic acid, 2,2,4-trimethyl-7,
2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2,4
-Trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-7-sulfonic acid,
1,2-naphthoquinonediazidesulfonic acid esters of (polyhydroxyphenyl) alkanes such as 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-8-sulfonic acid No. These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

The proportion of the component [B] used is that of the copolymer [A]
5 to 100 parts by weight, preferably 1 to 100 parts by weight
0 to 50 parts by weight. When this ratio is less than 5 parts by weight, the amount of acid generated by irradiation with 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, and patterning is difficult. It tends to be. In addition, since the amount of the acid involved in the reaction with the copolymer [A] decreases, sufficient heat resistance and solvent resistance may not be obtained. On the other hand, when this ratio exceeds 100 parts by weight, a large amount of unreacted [B] component remains in the short-time irradiation of radiation,
The effect of insolubilization in the aqueous alkali solution tends to be too high to make development difficult.

Other Components In the radiation-sensitive resin composition of the present invention, in addition to the above-mentioned copolymers [A] and [B], if necessary, at least a heat-sensitive acid-generating compound [C], A polymerizable compound [D] having one ethylenically unsaturated double bond, an epoxy resin [E], a melamine resin [F], a surfactant [G],
And each component of the adhesion aid [H] can be contained.

The heat-sensitive acid-generating compound as the component (C) can be used to improve heat resistance and hardness. Specific examples thereof include antimony fluorides. San-Aid SI-L80, San-Aid SI-L110, and San-Aid SI-L150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

The proportion of the component [C] used is that of the copolymer [A]
It is preferably 20 parts by weight or less, particularly preferably 5 parts by weight or less based on 100 parts by weight. When this proportion exceeds 20 parts by weight, a precipitate is generated, and patterning tends to be difficult.

The polymerizable compound having at least one ethylenically unsaturated double bond as the component [D] includes a monofunctional (meth) acrylate, a difunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate. Acrylates can be suitably used. Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl -2-hydroxypropyl phthalate and the like, and commercially available products thereof include, for example, Aronix M-
101, M-111, M-114 (Toagosei Co., Ltd.)
KAYARAD TC-110S, TC-12
OSS (manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 158, 231
1 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the above bifunctional (meth) acrylate include ethylene glycol (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange acrylate, and the like are listed as commercial products. For example, Aronix M-2
10, M-240, M-6200 (Toagosei Co., Ltd.)
KAYARADHDDA, HX-220, R
-604 (manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 260, 3
12, 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

The above trifunctional or higher functional (meth) acrylates include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra ( Examples thereof include (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, and commercially available products thereof include, for example, Aronix M-309, M-400, and M-40.
5, the same M-450, the same M-7100, the same M-8030,
M-8060 (Toagosei Co., Ltd.), KAYARAD
TMPTA, DPHA, DPCA-20, DPC
A-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 295, 300, 36
0, the same GPT, the same 3PA, the same 400 (Osaka Organic Chemical Industry)
Co., Ltd.). These monofunctional, difunctional or trifunctional or higher (meth) acrylates can be used alone or in combination.

The proportion of the component [D] used is that of the copolymer [A]
It is preferably 50 parts by weight or less, especially 30 parts by weight or less based on 100 parts by weight. By containing the component [D] at such a ratio, the heat resistance, strength, and the like of the patterned thin film obtained from the radiation-sensitive resin composition can be improved. If this proportion exceeds 50 parts by weight, the compatibility with the copolymer [A] becomes insufficient,
Roughness may occur during coating.

The epoxy resin as the component [E] is not limited as long as compatibility is not affected, but is preferably a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, Examples thereof include a cycloaliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a heterocyclic epoxy resin, and a resin obtained by (co) polymerizing glycidyl methacrylate.
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] used is that of the copolymer [A]
It is preferably 30 parts by weight or less for 100 parts by weight. When the component [E] is contained at such a ratio, the heat resistance, strength, and the like of the patterned coating film obtained from the radiation-sensitive resin composition of the present invention 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. When an unsaturated compound having an epoxy group is used as the compound (a3) when synthesizing the copolymer [A], the copolymer [A] can also be referred to as an “epoxy resin”. [A] is different from the epoxy resin as the component [E] in that it has alkali solubility and is required to have a relatively high molecular weight.

The melamine resin as the component (F) is represented by the following formula (III):

[0050]

Embedded image

[In the formula, R ⁶ represents an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms or a hydrogen atom. A compound having preferably two or more monovalent organic groups in one molecule, preferably a compound in which the monovalent organic group is bonded to a nitrogen atom, that is, an N-methylol group and / or an N-alkoxymethyl group And the like. When two or more organic groups of the general formula (III) are present in one molecule, R ⁶ of those groups may be the same or different. When the component [F] is used in the radiation-sensitive resin composition of the present invention, the organic group represented by the general formula (III)
It reacts with the carboxyl group of the copolymer of component (A) to form a crosslinked structure.

As an example of the component [F], for example, the following formula (I)
V)

[0053]

Embedded image

Wherein each R ⁷ is the same or different and is an alkyl group having 1 to 4 carbon atoms. N, N, N, N, N,
Alkoxymethylated melamine such as N- (hexaalkoxymethyl) melamine, and the following formula (V)

[0055]

Embedded image

Wherein each R ⁸ is the same or different and is an alkyl group having 1 to 4 carbon atoms. N, N, N, N-
And alkoxymethylated glycoluril such as (tetraalkoxymethyl) glycoluril. Further, as the component [F], a urea-formaldehyde resin,
It is also possible to use a thiourea-formaldehyde resin, a melamine-formaldehyde resin, a guanamine-formaldehyde resin, a benzoguanamine-formaldehyde resin, a glycoluril-formaldehyde resin, and a compound in which a group represented by the general formula (III) is introduced into polyvinylphenols. it can.

The proportion of the component [F] used is that of the copolymer [A].
It is usually at most 10 parts by weight, preferably at most 7 parts by weight, per 100 parts by weight. When the component [F] is contained at such a ratio, the heat resistance, strength, and the like of the patterned coating film obtained from the radiation-sensitive resin composition of the present invention can be further improved.

In the radiation-sensitive resin composition of the present invention, a surfactant, which is the component (G), can be used to improve coatability. Commercially available products include, for example, BM-1
000, BM-1100 (above, manufactured by BM CHEMIE), MegaFac F142D, F172, F17
3. F183 (above, Dainippon Ink and Chemicals, Inc.)
FC-135, FC-170C, FC-430, FC-431 (Sumitomo 3M)
Co., Ltd.), 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
(The above are manufactured by Asahi Glass Co., Ltd.), F-Top EF301, 3
03, 352 (all manufactured by Shin-Akita Chemical Co., Ltd.), SH-
28PA, SH-190, SH-193, SZ-603
2, fluorine-based and silicone-based surfactants such as SF-8428, DC-57, and DC-190 (both manufactured by Dow Corning Toray Silicone Co., Ltd.).

In addition, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; Ethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.)
Co., Ltd.), (meth) acrylic acid copolymer polyflow No. 5
7, 95 (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

The surfactant [G] is 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 [G] is more than 5 parts by weight, the film tends to be roughened at the time of coating.

Further, in order to improve the adhesion to the substrate, an adhesion aid can be used as the component [H]. As such an adhesion aid, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group. Include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

[0062] Such an adhesion assistant is a copolymer [A] 1
It is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less based on 00 parts by weight. When the amount of the adhesion aid exceeds 20 parts by weight, development residue tends to occur.

The radiation-sensitive resin composition of the present invention is prepared by uniformly mixing the above-mentioned copolymer [A], 1,2-quinonediazide compound [B], and other optional additives. Prepared by 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 radiation-sensitive resin composition in a solution state is prepared by mixing the copolymer [A], 1,2-quinonediazide [B], and other additives optionally added at a predetermined ratio. be able to.

As the solvent used for preparing the radiation-sensitive resin composition of the present invention, the components of the copolymer [A] and the 1,2-quinonediazide compound [B] are uniformly dissolved and reacted with each component. Those that do not 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;

And 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, 3-
Ethyl 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 acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropionic acid Butyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate Butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxypropionate Methyl ester, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropion Esters such as butyl acid, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, esters, And diethylene glycols are preferably used.

Further, a high boiling point solvent can be used together 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,
Examples include ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

The composition solution prepared as described above can be used after being filtered using a millipore filter having a pore size of about 0.5 μm.

Formation of Patterned Coating Film The radiation-sensitive resin composition of the present invention can be formed into a coating film by applying it to the surface of an underlying substrate and removing the solvent by pre-baking. Various methods such as a spray method, a roll coating method, a spin coating method, and a bar coating method can be employed as the coating method. The conditions of the prebaking vary depending on the type of each component, the mixing ratio, and the like. In the conventional radiation-sensitive composition, the prebaking temperature is generally assumed to be in the range of 70 to 80 ° C. If the prebaking temperature exceeds this range, the resolution may be hindered. However, the radiation-sensitive composition of the present invention can be suitably used in such a wide temperature range. 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 developing solution include aqueous alkali solutions, 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,
Cyclic tertiary amines such as 5-diazabicyclo [4.3.0] -5-nonene; aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of a quaternary ammonium salt can be used. Also, methanol,
An aqueous solution to which an appropriate amount of a water-soluble organic solvent such as ethanol and / or a surfactant has been added can also be used as a developer.

After development, running water washing 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, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on a hot plate. By performing a heat treatment in an oven for 30 to 90 minutes, a patterned coating film corresponding to the intended interlayer insulating film or microlens can be obtained.

[0072]

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. Followed by 22 parts by weight of methacrylic acid,
38 parts of dicyclopentanyl methacrylate, 3- (methacryloyloxymethyl) -2-phenyloxetane 4
0 parts by weight and 1.5 parts of α-methylstyrene dimer were charged, and stirring was started 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 content concentration of the obtained polymer solution was 31.2%, the weight average molecular weight of the polymer was 18,500, and the molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) was 1.8. The weight average molecular weight and the number average molecular weight were measured by GPC (gel permeation chromatography (HLC-Tosoh Corporation).
8020) as measured in terms of polystyrene.

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. Subsequently, 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts of phenylmaleimide,
35 parts by weight of (methacryloyloxymethyl) -3-ethyloxetane and 1.5 parts of α-methylstyrene dimer were charged, and the mixture was slowly stirred while being replaced 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-2]. The solid content concentration of the obtained polymer solution was 31.0%, the weight average molecular weight of the polymer was 21,000, and the molecular weight distribution was 2.1.

Synthesis Example 3 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 150 were added.
The parts by weight were charged. Subsequently, 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts of phenylmaleimide, 3
35 parts by weight of-(methacryloyloxymethyl) -2-trifluoromethyloxetane and 1.5 parts of α-methylstyrene dimer were charged, and the mixture was slowly stirred while being replaced with nitrogen. The temperature of the solution was raised to 70 ° C., and the mixture was heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The solid content concentration of the obtained polymer solution was 39.8%, the weight average molecular weight of the polymer was 23,000, and the molecular weight distribution was 2.4.

Synthesis Example 4 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, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 50 parts by weight of 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, α
-2.0 parts of methylstyrene dimer was charged, and stirring was started slowly while replacing with nitrogen. The temperature of the solution was raised to 70 ° C., and the solution was heated at this temperature for 5 hours to obtain the copolymer [A-
4] was obtained. The solid content concentration of the obtained polymer solution was 31.0%, the weight average molecular weight of the polymer was 19000, and the molecular weight distribution was 1.7.

Comparative Synthesis Example 1 A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 23 parts by weight of methacrylic acid, 47 parts by weight of dicyclopentanyl methacrylate, 20 parts by weight of glycidyl methacrylate, and 2.0 parts of α-methylstyrene dimer were charged and slowly stirred while being replaced with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-1R]. The solid content of the obtained polymer solution was 32.8%, the weight average molecular weight of the polymer was 24,000, and the molecular weight distribution was 2.3.

Comparative Synthesis Example 2 A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 25 parts by weight of methacrylic acid, 35 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 2-hydroxyethyl methacrylate, and 2.0 parts of α-methylstyrene dimer were charged, and gentle stirring was started while replacing with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-2R]. The solid content of the obtained polymer solution was 32.8%, the weight average molecular weight of the polymer was 25,000, and the molecular weight distribution was 2.4.

Example 1 Preparation of Radiation-Sensitive Resin Composition A polymer solution containing the copolymer [A-1] obtained in Synthesis Example 1 (100 parts by weight (solid content) of the copolymer [A-1]) Equivalent to)
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) with a condensate (4,4 ′-[1- [4- [1- [4
-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate) and 30 parts by weight of γ-methacryloxypropyltrimethoxysilane, After dissolving in propylene glycol monomethyl ether acetate so as to have a concentration of 30% by weight, the solution was filtered through a millipore filter having a pore size of 0.5 μm to prepare a solution (S-1) of the radiation-sensitive resin composition.

Evaluation of Interlayer Insulating Film (I) Formation of Patterned Thin Film The above composition solution (S-1) was applied on a glass substrate using a spinner, and then prebaked on a hot plate at 80 ° C. for 3 minutes. To form a coating film. The coating film obtained above was irradiated with ultraviolet light having an intensity at 365 nm of 10 mW / cm ² for 15 seconds using a predetermined pattern mask. Then tetramethylammonium hydroxide 0.1.
After developing with a 5% by weight aqueous solution at 25 ° C. for 1 minute, adding
Rinse for a minute. Unnecessary portions were removed by these operations. The pattern formed above was irradiated with ultraviolet light having an intensity at 365 nm of 10 mW / cm ² for 30 seconds, and then heated and cured in an oven at 200 ° C. for 60 minutes to obtain a patterned thin film having a thickness of 3 μm. The same operation as described above was performed except that the pre-bake temperatures were 90 ° C. and 100 ° C., to form three types of patterned thin films having different pre-bake temperatures.

(II) Evaluation of Resolution In the patterned thin film obtained in the above (I), the case where the punched pattern (5 μm × 5 μm hole) was resolved was evaluated as ○, and the case where it was not resolved was evaluated as ×. Table 1 shows the results.

(III) Evaluation of Heat Resistance Dimensional Stability In the above (I), the thin film pattern formed at a prebake temperature of 80 ° C. was heated in an oven at 200 ° C. for 60 minutes. Table 2 shows the change rate of the film thickness before and after heating. When the dimensional change rate at this time is within 5% before and after heating, the heat resistant dimensional stability is good, and when the dimensional change rate exceeds 5%, it can be regarded as poor.

(IV) Evaluation of Transparency In the above (I), the transmittance at 400 nm of the patterned thin film formed at a pre-bake temperature of 80 ° C. was measured using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.) ))
Was used to evaluate the transparency. Table 2 shows the results. At this time, when the transmittance is 90% or more, the transparency is good, and when the transmittance is less than 90%, the transparency is bad.

(V) Evaluation of heat discoloration resistance In the above (I), a substrate having a patterned thin film formed at a pre-bake temperature of 80 ° C. was heated in an oven at 250 ° C. for 1 hour, and the transmission of the patterned thin film before and after heating was performed. The heat discoloration resistance was evaluated based on the change in rate. Table 2 shows the evaluation results at this time. When the rate of change is less than 5%, the heat discoloration resistance is good, and when it exceeds 5%, it can be said that it is bad. The transmittance was determined in the same manner as in (VI) Evaluation of transparency.

(VI) Evaluation of Adhesion In the above (I), the adhesion of the patterned thin film formed at a prebake temperature of 80 ° C. was evaluated by cross-cutting after a pressure cooker test (120 ° C., 100% humidity, 4 hours). It was evaluated by a test. Table 2 shows the evaluation results at this time.
The evaluation result was represented by the number of remaining crosscuts in 100 crosscuts.

(VII) Evaluation of Storage Stability The composition solution was heated in an oven at 40 ° C. for one week, and the storage stability was evaluated by a change in viscosity before and after heating. Table 1 shows the viscosity change rate at this time. 5% change rate
If it is less than 5, storage stability is good, and if it is 5% or more, storage stability is poor.

Evaluation of Microlens (I) Formation of Microlens The above composition solution (S-1) was spin-coated on a 6-inch silicon substrate to a thickness of 2.5 μm and placed on a hot plate at 70 ° C. for 3 minutes. To form a coating film. The coating film obtained above was irradiated with ultraviolet light having an intensity at 436 nm of 10 mW / cm ² using a predetermined pattern mask. Next, the film was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, and then rinsed with pure water for 1 minute. By these operations, unnecessary portions were removed and a pattern was formed. The pattern formed above has an intensity at 436 nm of 10 mW / cm ^2.
After irradiation of 200 mJ / cm ^{2 of} UV light,
After heating at 10 ° C. for 10 minutes, the pattern was melt-flowed by heating at 230 ° C. for 10 minutes to form microlenses.

(II) Evaluation of Sensitivity The microlens pattern after the melt flow obtained in the above (I) was resolved by a 0.8 μm line and space pattern (10 to 1) space line width. Table 3 shows the lowest possible dose. When this value is 100 mJ / cm ² or less, the resolution is good, and when the sensitivity exceeds 100 mJ / cm ² , the resolution is poor.

(III) Evaluation of Transparency A patterned thin film was formed on a glass substrate in the same manner as in (I) above. For the glass substrate on which the microlens pattern after melt flow was formed, the transmittance at 400 nm was measured using a spectrophotometer (150-20 type double beam (Hitachi, Ltd.)
)) To evaluate the transparency. Table 3 shows the transmittance at 400 nm at this time. When the transmittance is 90 to 100%, the transmittance is good, and when the transmittance is less than 90%, the transmittance is poor.

(IV) Evaluation of Thermal Discoloration Resistance The glass substrate having the patterned thin film formed in the above (III) was heated in an oven at 250 ° C. for 1 hour, and the heat discoloration due to the change in transmittance of the patterned thin film before and after heating. The sex was evaluated. Table 3 shows the change rate of the transmittance at this time. When the rate of change is less than 5%, the heat discoloration resistance is good,
If it exceeds 5%, it can be said that it is defective. The transmittance is (II
I) It was determined in the same manner as the evaluation of transparency.

(V) Evaluation of Adhesion The adhesion of the patterned thin film formed in the above (I) was evaluated by a pressure cooker test (120 ° C., 100% humidity,
After 4 hours), it was evaluated by a cross-cut peel test. Table 3 shows the evaluation results at this time. The evaluation result was represented by the number of remaining crosscuts in 100 crosscuts.

(VII) Evaluation of Solvent Resistance A glass substrate having a patterned thin film formed in the same manner as in (III) above was immersed in isopropyl alcohol at 50 ° C. for 10 minutes, and the change in film thickness was evaluated. Table 3 shows the rate of change at this time. When the rate of change is 0 to 5%, the solvent resistance is good. When the rate exceeds 5%, and when the film thickness is reduced by dissolution, it can be said that the solvent resistance is poor.

Example 2 In Example 1, except that a solution containing the copolymer [A-2] was used instead of the solution containing the copolymer [A-1],
A composition solution (S-2) was prepared in the same manner as in Example 1,
evaluated. The results are shown in Tables 1 to 3.

Example 3 In Example 1, except that the solution containing the copolymer [A-3] was used instead of the solution containing the copolymer [A-1],
A composition solution (S-3) was prepared in the same manner as in Example 1,
evaluated. The results are shown in Tables 1 to 3.

Example 4 The procedure of Example 1 was repeated, except that the solution containing the copolymer [A-4] was used instead of the solution containing the copolymer [A-1].
A composition solution (S-4) was prepared in the same manner as in Example 1,
evaluated. The results are shown in Tables 1 to 3.

Comparative Example 1 The composition was changed in the same manner as in Example 1 except that the solution containing the copolymer [A-1R] was used instead of the solution containing the copolymer [A-1]. A product solution (S-1R) was prepared and evaluated. The results are shown in Tables 1 to 3.

Comparative Example 2 A solution containing the copolymer [A-2R] obtained in Comparative Synthesis Example 2 (corresponding to 100 parts by weight (solid content) of copolymer @ A-2R) and component [B] 4,4 ′-[1- [4- [1
-[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,
Condensation product with 2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) (4,4 '-[1- [4- [1-
[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester) 30 parts by weight,
After mixing 25 parts by weight of hexamethylol melamine and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane and dissolving the same in propylene glycol monomethyl ether acetate so as to have a solid concentration of 30% by weight, a mixture having a pore size of 0.5 μm was obtained. The solution (S-2R) of the radiation-sensitive resin composition was prepared by filtration with a Millipore filter. In Example 1, an interlayer insulating film was formed using the above (S-2R) instead of the resin composition solution (S-1), and the evaluation was performed. The results are shown in Tables 1 and 2.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

According to the present invention, a sufficient process margin and storage stability can be obtained, and the heat resistance, solvent resistance, transparency, and adhesion to a base required for an interlayer insulating film and a microlens can be obtained. It is possible to obtain a radiation-sensitive resin composition capable of providing the provided patterned thin film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 222/04 C08F 222/04 C08K 5/28 C08K 5/28 C08L 33/00 C08L 33/00 35/00 35/00 C09D 4/02 C09D 4/02 5/00 5/00 Z 133/04 133/04 201/06 201/06 G02B 1/04 G02B 1/04 3/00 3/00 A G03F 7/022 G03F 7/022 // C09D 5/25 C09D 5/25 (72) Inventor Kazuaki Niwa 2-11 Tsukiji 2-chome, Chuo-ku, Tokyo FSR-term (reference) 2H025 AA06 AA10 AA14 AA20 AB14 AB20 AC01 AD03 BE01 CB08 CB14 CB41 CB43 CB51 CC17 FA29 4J002 BC041 BG011 BG041 BG051 BG061 BG071 BG101 BG131 BH021 BK001 BL011 BL021 CC185 CD005 CD191 EQ036 EV246 FD200 FD310 GH01 GP01 GQ01 CF011CG011CG011J011CA02 GA02 GA06 JB15 NA04 NA12 NA14 NA21 PA17 PB08 PB09 PB11 4J100 AB02R AB03R AB04R AB07R AC03R AC04R AG04R AJ01P AJ02P AJ08P AJ09P AK31P AK32P AL03R AL08P AL08Q AL08R AL09R AL10R AL34R AL44R AM02R AM15R AM47R AM48R AS01R AS02R AS03R AS15R BA03R BA04R BA05R BA06R BA15R BA16P BA16R BA20R BA21P BB07Q BB18Q BC04R BC12R BC28R BC43P BC43Q BC43R BC53Q BC54R BC55R BC66R CA05 DA01 DA04 JA01 JA33 JA44

Claims (1)

[Claims] [1] [A] (a1) an unsaturated carboxylic acid and / or
Or an unsaturated carboxylic anhydride, (a2) a compound represented by the general formula (I)
Or a compound represented by the general formula (II): [Where R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each Independently, it is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6. And (A3) a copolymer obtained by copolymerizing an olefinically unsaturated compound other than (a1) and (a2), and [B] a 1,2-quinonediazide compound. A radiation-sensitive resin composition.