KR100795290B1 - Radiation-sensitive Resin Composition, Method for Forming Insulating Interlayers and Microlens, and Insulating Interlayers and Microlens - Google Patents

Abstract

TECHNICAL FIELD This invention relates to a radiation sensitive resin composition. Specifically, It is related with the positive radiation sensitive resin composition suitable for manufacture of an interlayer insulation film or microlens by photolithography.

Moreover, this invention relates to the formation method of the said interlayer insulation film and a micro lens of the said radiation sensitive composition.

The present invention also relates to an interlayer insulating film and microlens formed from the radiation sensitive composition.

Radiation-sensitive resin composition, interlayer insulating film, microlens

Description

Radiation-sensitive Resin Composition, Method for Forming Insulating Interlayers and Microlens, and Insulating Interlayers and Microlens}

TECHNICAL FIELD This invention relates to a radiation sensitive resin composition. Specifically, It is related with the positive radiation sensitive resin composition suitable for manufacture of an interlayer insulation film or microlens by photolithography.

Moreover, this invention relates to the formation method of the said interlayer insulation film and a micro lens of the said radiation sensitive composition.

The present invention also relates to an interlayer insulating film and microlens formed from the radiation sensitive composition.

In general, an electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, magnetic head element, integrated circuit element, solid-state image sensor, or the like, has an interlayer insulating film in order to insulate between wirings arranged in layers. Installed. As a material for forming the interlayer insulating film, a radiation-sensitive resin composition having a feature of obtaining an interlayer insulating film having a low number of processes for obtaining a required patterned interlayer insulating film and having sufficient flatness is widely used.

A TFT type liquid crystal display element is manufactured through the process of forming a transparent electrode film on the said interlayer insulation film, and forming a liquid crystal aligning film on it.

On the other hand, a microlens having a lens diameter of about 3 to 100 µm or an array of these microlenses is regularly arranged as an imaging optical system of an on-chip color filter such as a facsimile, an electronic copier, a solid-state imaging device, or an optical system material of an optical fiber connector. Micro lens arrays are used.

To form a microlens or microlens array, a lens pattern is formed and then heat-treated to melt the pattern to be used as a lens as it is, or to transfer the lens shape by dry etching using a meltflowed lens pattern as a mask. Known methods are known. The radiation sensitive resin composition which has the characteristic that the microlens which has a desired curvature radius is obtained for formation of the said lens pattern is used widely.

In the microlens or the interlayer insulating film, it is necessary to control the developing time strictly because the developing solution easily penetrates between the pattern and the substrate when the developing time becomes excessively shorter than the optimum time in the developing step when forming them. There is a problem in terms of yield of the product. Also, in the formation of peripheral devices such as wiring, the resistance of the resist used for forming the wiring, etc., is insufficient, and the phenomenon that the peeling liquid penetrates at the interface between the substrate and the microlens or the interlayer insulating film may occur. In some cases, it may be a problem to be peeled off or peeled off on the substrate.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to have a high radiation sensitivity, a developing margin capable of forming a good pattern shape even when exceeding an optimum developing time in a developing step, and having excellent adhesion. It is providing the radiation sensitive resin composition suitable for formation of an interlayer insulation film and a micro lens which can form a patterned thin film easily.

Moreover, another object of this invention is to use for formation of the interlayer insulation film and micro lens of the said radiation sensitive resin composition.

Still another object of the present invention is to provide an interlayer insulating film and a micro lens formed from the radiation-sensitive resin composition.

According to the present invention, the above objects and advantages of the present invention,

[A] a copolymer of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (a3) hydroxyl group-containing unsaturated compound, and (a4) other olefinically unsaturated compound, And

[B] 1,2-quinonediazide compound

It is achieved by the radiation sensitive resin composition characterized by the above-mentioned.

The object and advantages of the present invention are secondly achieved by a method of forming an interlayer insulating film and a microlens using the radiation-sensitive composition.                     

The object and advantages of the present invention are thirdly achieved by an interlayer insulating film and microlens formed from the radiation sensitive composition.

Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.

The radiation sensitive resin composition of this invention is characterized by including a copolymer [A] and a 1, 2- quinonediazide compound [B].

Copolymer [A]

Copolymer [A] can be produced by radical polymerization of compound (a1), compound (a2), compound (a3) and compound (a4) in the presence of a polymerization initiator in a solvent.

The copolymer [A] used in the present invention is preferably based on the sum of the repeating units derived from the compounds (a1), (a2), (a3) and (a4) of the structural units derived from the compound (a1). Preferably it is 5 to 40 weight%, Especially preferably, it is 10 to 30 weight%. The copolymer whose structural unit is less than 5 weight% becomes difficult to melt | dissolve in aqueous alkali solution, On the other hand, the copolymer exceeding 40 weight% tends to become too soluble in aqueous alkali solution too much. As a compound (a1), For example, 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; Mono [(meth) acryloyloxyalkyl] of bivalent or more polyvalent carboxylic acids, such as succinic acid mono [2- (meth) acryloyloxyethyl] and monophthalic acid [2- (meth) acryloyloxyethyl] Esters; Mono (meth) acrylates of the polymer which has a carboxyl group and a hydroxyl group at the sock end, such as (omega) -carboxypolycaprolactone mono (meth) acrylate, etc. are mentioned. Among these, 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 are used alone or in combination.

The copolymer [A] used in the present invention is based on the sum of the repeating units derived from the compounds (a1), (a2), (a3) and (a4) of the structural units derived from the compound (a2). Preferably it is 10 to 70 weight%, Especially preferably, it contains 20 to 60 weight%. When this structural unit is less than 10 weight%, the heat resistance and surface hardness of a protective film or insulating film obtained tend to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a copolymer to fall.

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-propyl acrylate, glycidyl α-butyl acrylate, and acrylic acid. -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like. Among these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like are copolymerized. It is preferably used from the point of improving the reactivity, the heat resistance and surface hardness of the protective film or insulating film obtained. These are used alone or in combination.

The copolymer [A] used in the present invention is based on the sum of the repeating units derived from the compounds (a1), (a2), (a3) and (a4) of the structural units derived from the compound (a3). Preferably, it is 2-50 weight%, Especially preferably, it contains 5-40 weight%. When this structural unit is less than 5 weight%, adhesiveness tends to fall, and when it exceeds 50 weight%, there exists a tendency for the film-forming property of a coating film to fall.

As the compound (a3), hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2, 3-dihydroxypropylmethacrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenylmethacrylate, 5- (2'-hydroxyethyl) bicyclo [2,2,1] hept-2 -Ene, 5,6-dihydroxybicyclo [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-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5- Ethyl bicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methyl bicyclo [2.2.1] hept-2-ene, etc. are mentioned. These can be used individually or in combination of 2 or more types.

The copolymer [A] used in the present invention is based on the sum of the repeating units derived from the compounds (a1), (a2), (a3) and (a4) of the structural units derived from the compound (a4). It is preferably 10 to 70% by weight, particularly preferably 15 to 50% by weight. When this structural unit is less than 10 weight%, there exists a tendency for the storage stability of copolymer [A] to fall, and when it exceeds 70 weight%, there exists a tendency for copolymer [A] to be insoluble in aqueous alkali solution. .                     

Examples of the compound (a4) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yloxy Methacrylic acid cyclic alkyl esters such as ethyl methacrylate and isoboroyl methacrylate; Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethylacrylate Acrylic cyclic alkyl esters such as isoboroyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-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-hydroxybi Cyclo [2,2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5-methoxy ratio Cyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2,2.1] hept-2-ene, 5,6-dicarboxybicyclo [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-carboxy-5-methylbicyclo [2.2.1] hept 2-ene, 5-carboxy-5-ethylbicyclo [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, 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 unsaturated compounds, such as) bicyclo [2.2.1] hept-2-ene and 5, 6- di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

Phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide capro Maleimide compounds such as eight, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

And 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, and the like.

Among them, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxy styrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2- Yen and the like are preferred in view of copolymerization reactivity and solubility in aqueous alkali solution. These are used alone or in combination.

Preferred specific examples of the copolymer [A] used in the present invention include, for example, styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] Decan-8-ylmethacrylate copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / t-butyl methacrylate copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / p-methoxystyrene copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 2-methylcyclohexylacrylate copolymer ,

Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2,1.0 ^2,6 ] decane-8-ylmethacrylate / 1,3-butadiene copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / bicyclo [2.2.1] hept- 2-ene copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropylmethacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / t-butylmethacrylate Copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / p-methoxystyrene aerial coalescence,

Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 2-methylcyclohexylacrylic Latex copolymer,

Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropylmethacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 1,3-butadiene aerial coalescence,

Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropylmethacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / bicyclo [2.2.1 ] Hept-2-ene copolymer, etc. are mentioned.

As for the copolymer [A] used by this invention, the polystyrene conversion weight average molecular weight (henceforth "Mw") is 2x10 <^3> -1x10 <^5> normally, Preferably it is 5x10 <^3> -5x10 It is preferable that it is ^four . If the Mw is less than 2 × 10 ^{3, the} development margin may drop, the remaining film ratio of the resulting film may decrease, or the pattern shape, heat resistance, etc. may fall, while if it exceeds 1 × 10 ⁵ , the sensitivity may decrease. The pattern shape may be inferior.

The radiation sensitive resin composition containing the said copolymer [A] does not generate | occur | produce a developing residue, and does not reduce film | membrane at the time of image development, and can form a predetermined pattern shape easily.

As a solvent used for manufacture of copolymer [A], For example, Alcohol, 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 glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl 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 alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate 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, and Ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate, butyl 3-hydroxypropionate, 2 Methyl hydroxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl butyl acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate Methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy 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, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxypropionic acid Methyl, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, butyl 3-ethoxypropionate , 3-propoxy propionate, 3-propoxy propionate, 3-propoxy propionate, 3-propoxy propionate, 3-butoxypropionate, 3-butoxy ethyl propionate, 3-butoxypropion Esters such as propyl acid and butyl 3-butoxypropionate.

As a polymerization initiator used for manufacture of copolymer [A], what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile and 2,2'- azobis- Azo compounds such as (2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, a peroxide may be used with a reducing agent and may be used as a redox type initiator.

1,2-quinonediazide compound [B]

As a 1, 2- quinone diazide compound [B] used by this invention, a 1, 2- benzoquinone diazide sulfonic acid ester, a 1, 2- naphthoquinone diazide sulfonic acid ester, a 1, 2- benzoquinone, for example. Diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, and the like.

Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinoneazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonedia Zide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2- 1,2-naphthoquinone diazide sulfonic acid ester of trihydroxy benzophenone, such as naphthoquinone diazide-5-sulfonic acid ester; 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2 Naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,3 ' Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-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, 2,3,4,2'-tetrahydroxy-4'-methylbenzo Phenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy -3'-methoxybenzophenone-1,2-na Diazide-5-sulfonic acid ester, such as tetra-hydroxy-benzophenone 1,2-naphthoquinonediazide sulfonic acid ester;

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxy benzophenone, such as -1, 2- naphthoquinone diazide-5- sulfonic acid ester; 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6,3 ', 4', 5 ' Hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone Hexahydroxy benzophene, such as a diazide-4- sulfonic acid ester and a 3,4,5,3 ', 4', 5'-hexahydroxy benzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester Discussion 1,2-naphthoquinone diazide 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 (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide -5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide -5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl Ethane-1,2-naphthoquinonediazide-5-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, 2,2-bis (2,3,4-trihydroxy Nil) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5- 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,

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinone diazide-4-sulfonic acid ester, 4 , 4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis ( 2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl)- 2-hydroxyphenylmethane-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-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, 2,2,4-trimethyl-7,2 ', 4'-trihydrate Oxyflavane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavane-1,2-naphthoquinonediazide 1,2-naphthoquinone diazide sulfonic acid ester of (polyhydroxyphenyl) alkane, such as -5-sulfonic acid ester, is mentioned.

Moreover, the 1,2-naphthoquinone diazide sulfonic-acid amides which changed the ester bond of the above-mentioned 1,2-naphthoquinone diazide sulfonic-acid ester into an amide bond, for example, 2,3,4- trihydride Roxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide etc. are also used suitably.

Among them, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinoneazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-4-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) Methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol -1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonedia Zide-4-sulfonic acid ester etc. are used preferably, and 2,3, 4- trihydroxy benzophenone- 1, 2- naphthoquinone azide- 4-sulfonic acid ester, 2, 3, 4, 4'- tetrahydrate Hydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene ]ratio Phenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone Diazide-4-sulfonic acid ester is especially preferable.

These 1,2-quinonediazide compounds can be used individually or in combination of 2 or more types.

The use ratio of the component [B] is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the component [A].

When this ratio is less than 5 parts by weight, since the amount of acid generated by irradiation of the radiation is small, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution serving as the developing solution becomes small, and patterning becomes difficult. In addition, since the amount of 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 ratio exceeds 100 weight part, since unreacted [B] component remains in large quantities by irradiation of radiation for a short time, the insolubilizing effect to the said aqueous alkali solution will become high too much, and it will become difficult to develop.

<Other ingredients>

In the radiation sensitive resin composition of the present invention, in addition to the component [A] and the component [B], a polymerizable polymer having a [C] thermosensitive acid generating compound and [D] at least one ethylenically unsaturated double bond, if necessary. A compound, [E] epoxy resin, [F] adhesion adjuvant, and [G] surfactant can be contained.

The said (C) thermosensitive acid generating compound can be used in order to improve heat resistance and hardness. Specific examples thereof include antimony fluoride, and examples of commercially available products include Sun Aid SI-L80, Sun Aid SI-Ll10, Sun Aid SI-L150 (above, manufactured by Sanshin Kagaku Kogyo Co., Ltd.) and the like.

The use ratio of the component [C] is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the copolymer [A].

When this ratio exceeds 20 weight part, precipitates may arise and patterning may become difficult.

[D] As the polymerizable compound having at least one ethylenically unsaturated double bond, for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or higher (meth) acrylate can be suitably used. have.

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth) acryl And 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate.

As these commercial items, for example, Aronix M-101, M-111, M-114 (manufactured by Toa Kosei Co., Ltd.), KAYARAD TC-110S, and TC-120 S (manufactured by Nihon Kayaku Co., Ltd.) , Biscoat 158, copper 2311 (manufactured by Osaka Organic Chemical Industries, Ltd.), and the like.

As said bifunctional (meth) acrylate, for example, 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 fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, etc. are mentioned.

As these commercial items, for example, Aronix M-210, M-240, M-6200 (manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nihon Kayaku Co., Ltd.) And biscoat 260, copper 312 and copper 335 HP (manufactured by Osaka Organic Chemical Industries, Ltd.).                     

As said trifunctional or more than (meth) acrylate, a trimethol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, a tri ((meth) acrylyloxyethyl) phosphate, pentaerythritol tetra, for example (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned, As a commercial item, it is Aronix M-309, copper M-400, East M-405, East M-450, East M-7100, East M-8030, East M-8060 (manufactured by Toa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (manufactured by Nihon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (manufactured by Osaka Organic Chemical Industries, Ltd.) Can be.

These monofunctional, bifunctional or trifunctional or more (meth) acrylates are used alone or in combination.

The use ratio of the component [D] is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less based on 100 parts by weight of the copolymer [A].

By containing [D] component in such a ratio, the heat resistance, surface hardness, etc. of the protective film or insulating film obtained from the radiation sensitive resin composition of this invention can be improved. When this ratio exceeds 50 weight part, compatibility with alkali-soluble resin which is a copolymer [A] will become inadequate, and film | membrane roughness may arise at the time of application | coating.

The epoxy resin [E] is not limited as long as it does not affect compatibility, but is preferably a bisphenol A epoxy resin, a phenol novolak epoxy resin, a cresol novolak epoxy resin, a cyclic aliphatic epoxy resin, or glycidyl ester. The epoxy resin, the glycidyl amine epoxy resin, the heterocyclic epoxy resin, the resin which co-polymerized glycidyl methacrylate, etc. are mentioned.

Among these, bisphenol-A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester-type epoxy resin, etc. are preferable.

The use ratio of the component [E] is preferably 30 parts by weight or less based on 100 parts by weight of the copolymer [A].

By containing [E] component in such a ratio, the heat resistance, surface hardness, etc. of a protective film or insulating film obtained from the radiation sensitive resin composition of this invention can be improved further.

When this ratio exceeds 30 weight part, compatibility with alkali-soluble resin which is a copolymer [A] may become inadequate, and sufficient coating film formation ability may not be obtained.

Moreover, although copolymer [A] can also be called "epoxy resin", it differs from [E] component by the point which has alkali solubility.

[F] surfactant can be used in order to improve applicability. As the commercial item, for example, BM-1000, BM-1100 (manufactured by BM CHEMIE Co., Ltd.), Megapack F142D, Copper F172, Copper F173, Copper F183 (manufactured by Dainippon Ink Chemical Industries, Ltd.), Flora FC-135 , FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Supron S-112, Copper S-113, Copper S-131, Copper S-141, Copper S- 145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF 301 , 303, 352 (manufactured by Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (Toray Silicon Co., Ltd.) Fluorine-type and silicone type surfactant etc. are mentioned.

In addition, as [F] component, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based copolymer polyflow No. 57,95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be used.

These surfactant is used with respect to 100 weight part of copolymers [A], Preferably it is 5 weight part or less, More preferably, it is used in 2 weight part or less. When the amount of the surfactant exceeds 5 parts by weight, film roughness may easily occur at the time of coating.

Moreover, in order to improve adhesiveness with a base, [G] adhesion | attachment adjuvant can also be used. As this adhesion | attachment adjuvant, a functional silane coupling agent is used preferably, For example, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned.                     

Such adhesion aid is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion assistant exceeds 20 parts by weight, development residual may easily occur.

The radiation sensitive resin composition of this invention is prepared by uniformly mixing the said copolymer [A], a 1, 2- quinonediazide compound [B], and the other compounding agent added arbitrarily as mentioned above. Usually, the radiation sensitive resin composition of this invention is melt | dissolved in a suitable solvent, and is used in a solution state. For example, the radiation sensitive resin composition of a solution state can be prepared by mixing a copolymer [A], 1, 2- quinonediazide [B], and the other compounding agent added arbitrarily at a predetermined ratio.

As a solvent used for preparation of the radiation sensitive resin composition of this invention, each component of a copolymer [A], a 1, 2- quinonediazide compound [B], and the other compounding agent mix | blended arbitrarily is melt | dissolved uniformly, Those that do not react with each component are used.

Specifically, For example, alcohol, 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 glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl 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 alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate 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, hydroxyacetic acid Ethyl, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3-hydroxypropionate butyl, 2-hydroxy Methyl oxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, pro Methyl acetate, ethyl propoxy acetate, propyl acetate, propoxy acetate, butyl acetate, methyl butoxy acetate, ethyl butoxy acetate, Propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ethyl, 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-methoxy propionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxypropionic acid Butyl, 3-propoxypropionate, 3-propoxypropionate, 3-propoxypropionate, 3-butyl propionate, 3-butoxypropionate, 3-butoxypropionate, 3-butoxypropion Esters such as propyl acid and butyl 3-butoxypropionate.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycols are preferably used because of their solubility, reactivity with each component, and ease of forming a coating film.

Moreover, a high boiling point solvent can also be used together with the said solvent. As a high boiling point solvent which can be used together, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrroli Don, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, capuronic acid, capuryl acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, Diethyl maleate, gamma -butylolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

In addition, the composition solution prepared as mentioned above can be used for use, after filtering using a Millipore filter of about 0.2 micrometer of pore diameters, etc.

Formation of microlens, interlayer insulating film

Next, the method of forming the interlayer insulation film and microlens of this invention using the radiation sensitive resin composition of this invention is stated.

The method for forming an interlayer insulating film or microlens of the present invention includes at least the following steps.

(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate.

(2) Irradiating at least a part of said coating film with radiation.

(3) Developing process.

(4) Post Bake Process.

Hereinafter, each process mentioned above is demonstrated.

(1) Process of forming the coating film of radiation sensitive composition of this invention on board | substrate

In the process of said (1), a solvent is removed and the coating film of a radiation sensitive resin composition is formed by apply | coating the composition solution of this invention to the board | substrate surface, and prebaking. It does not specifically limit as a coating method of a composition solution, For example, various methods, such as a spray method, a roll coat method, a rotary coating method, and a bar coating method, can be employ | adopted.

As the conditions of prebaking, although it changes also with the kind, usage ratio, etc. of each component, it is about 30 to 15 minutes normally at 60-110 degreeC.

(2) irradiating at least a part of the coating film with radiation

In the process of said (2), after irradiating radiation to the formed coating film through the mask of a predetermined pattern, patterning is performed by developing using a developing solution and removing the irradiation part of radiation. Examples of the radiation used at this time include ultraviolet rays such as g rays (wavelength 436 nm), i rays (wavelength 365 nm), far ultraviolet rays such as KrF excimer lasers, X rays such as synchrotron radiation, and charged particle beams such as electron beams. Among these, g line | wire and i line | wire are mentioned as a preferable thing.

(3) developing process

Examples of the developer used for the developing treatment include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium merosilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine and triethyl Amine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7 Aqueous solutions of alkalis such as -undecene and 1,5-diazabicyclo [4,3,0] -5-nonane can be used.

Moreover, the aqueous solution which added water-soluble organic solvents, such as methanol and ethanol, and surfactant in an appropriate quantity to the aqueous solution of the said alkalis, or the various organic solvent which melt | dissolves the composition of this invention can be used as a developing solution.

As the developing method, an adhesion method, a dipping method, a rocking dipping method, or the like can be used.

Although the developing time at this time changes with composition of a composition, it is normally performed for 30 to 120 second. Moreover, as a composition for conventional interlayer insulation films and microlenses, the development margin (excess time allowed for the optimal development time) is less than 15 seconds, but the development margin of the composition of the present invention is preferably 15 seconds or more, more preferably. It is more than 30 seconds.                     

(4) post-baking process

After the development treatment carried out as described above, the patterned thin film is usually rinsed by running water washing, for example, and preferably 1,2-quinonedia remaining in the thin film by irradiating the entire surface with radiation by a high pressure mercury lamp or the like. After carrying out the decomposition | disassembly process of a zide compound, this thin film is baked by heating apparatus, such as a hotplate and oven, and hardening process of this thin film is performed.

The firing temperature in this curing treatment is, for example, 150 to 250 ° C, and the firing time is, for example, 5 to 90 minutes (when baking is carried out in an oven for 5 to 30 minutes when baking on a hot plate, 30 to 90 minutes).

In this manner, an excellent patterned thin film corresponding to the target interlayer insulating film or microlens can be formed on the surface of the substrate.

The interlayer insulating film and microlens formed as described above are excellent in adhesion, heat resistance, solvent resistance, transparency, and the like, as will be apparent from the examples described later.

Although a synthesis example and an Example are shown to the following and this invention is concretely demonstrated to it, this invention is not limited to a following example.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 20 parts by weight of 2-hydroxyethyl methacrylate were added to replace the nitrogen, and then stirring was slowly started. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 30.6 weight%.

Synthesis Example 2

Polymer containing copolymer [A-2] by the same operation except having used 20 weight part of 2, 3- dihydroxy propyl methacrylate instead of 20 weight part of 2-hydroxyethyl methacrylates of the synthesis example 1. A solution was obtained. Solid content concentration of the obtained polymer solution was 31.0 weight%.

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added. 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate and 2,3-dihydroxypropylmetha After adding 20 parts by weight of acrylate to replace the nitrogen, stirring was gradually started. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer [A-3]. Solid content concentration of the obtained polymer solution was 31.0 weight%.

<Example 1>                     

[Preparation of radiation sensitive resin composition]

Polymer solution obtained in Synthesis Example 1 (equivalent to 100 parts by weight of copolymer [A-1]), 2,3,4,4'-tetrahydroxybenzophenone (1 mol) and 1,2 as component [B]. Condensates with naphthoquinonediazide-5-sulfonic acid chloride (2 mol) (2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester) 30 weight part was mixed, it dissolved in diethylene glycol ethyl methyl ether so that solid content concentration might be 30 weight%, and it filtered with the Millipore filter of 0.2 micrometer of pore diameters, and prepared the solution (S-1) of a radiation sensitive resin composition. .

[Evaluation of a radiation sensitive resin composition]

About the said composition (S-1), radiation sensitivity was evaluated as follows, and the solvent resistance, heat resistance, and transparency of the pattern type thin film formed in (S-1) were evaluated.

[Evaluation of Radiation Radiation]

After apply | coating the said composition (S-1) using a spinner on a silicon substrate, it prebaked at 90 degreeC on a hotplate for 5 minutes, and formed the coating film of 3.0 micrometers in film thicknesses. A predetermined amount of ultraviolet light was irradiated to the obtained coating film by the mercury lamp through the pattern mask which has a pattern of width 3micrometer. Subsequently, after developing 90 degreeC at 25 degreeC using the developing solution which consists of a 0.3 weight% aqueous solution of tetramethylammonium hydroxide, the flowing water wash | cleaned with ultrapure water for 1 minute.

At this time, the minimum ultraviolet irradiation amount (henceforth "pattern formation minimum exposure amount") required in order for the 3 micrometer width pattern to melt | dissolve completely in a developing solution was measured. The results are shown in Table 1. The radiation-sensitivity is excellent when the pattern-forming minimum exposure amount is less than 80 mJ / cm ² , the radiation sensitivity is good when 80 to 100 mJ / cm ² , and the radiation sensitivity is poor when it exceeds 10 mJ / cm ² . .

[Evaluation of Development Margin]

After apply | coating the said composition (S-1) using a spinner on a silicon substrate, it prebaked on the hotplate for 2 minutes at 90 degreeC, and formed the coating film of 3.0 micrometers in film thicknesses. 80 mJ / cm <^2> of ultraviolet-rays were irradiated to the obtained coating film with the mercury lamp through the pattern mask which has a pattern of width 3micrometer. Subsequently, the image development process was performed at 25 degreeC using the developing solution which consists of a 0.3 weight% aqueous solution of tetramethylammonium hydroxide, and it washed with water for 1 minute with ultrapure water. At this time, the optimum development time and the time (development margin) from the optimum development time until the pattern of 3 micrometers in width | variety were peeled off when continuing development were measured. The results are shown in Table 1. When the time until peeling is 30 second or more, the developing margin is excellent, and when the developing margin is 15 or less and less than 30 seconds, the developing margin is good, and when the developing margin is less than 15 seconds, the developing margin is evaluated as poor.

[Evaluation of solvent resistance]

After apply | coating the said composition (S-1) using a spinner on a silicon substrate, it prebaked on the hotplate for 2 minutes at 90 degreeC, and formed the coating film of 3.0 micrometers in film thicknesses. The coating film was cured by irradiating ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 30 mJ / cm ² , and then firing the silicon substrate at 220 ° C. in a clean oven for 1 hour. The film thickness (T1) of the cured film was measured. After the silicon substrate on which the cured film was formed was immersed in dimethyl sulfoxide for 20 minutes at a temperature controlled at 70 ° C., the film thickness t1 of the cured film was measured and the film thickness change rate by immersion {(t1-T1) / T1} × 100 [%] was calculated.

When the absolute value of this value is less than 5%, solvent resistance is excellent, when 5-10%, solvent resistance is good, and when it exceeds 10%, solvent resistance can be said to be bad. The results are shown in Table 1.

[Evaluation of Heat Resistance]

In the same manner as the above evaluation of the solvent resistance, a cured film was formed, and the film thickness (T2) of the obtained cured film was measured. Subsequently, after further baking this cured film board | substrate at 240 degreeC in a clean oven for 1 hour, the film thickness (t2) of this cured film was measured, and the film thickness change rate by further baking {(t2-T2) / T2} x100 [%] Was calculated. When the absolute value of this value is less than 5%, heat resistance is excellent, heat resistance is good when it is 5 to 10%, and when it exceeds 10%, it can be said that heat resistance is bad. The results are shown in Table 1.

[Evaluation of transparency]

In evaluation of said solvent resistance, the cured film was formed on the glass substrate similarly except having used the glass substrate "Corning 7059 (made by Corning Corporation)" instead of the silicon substrate. The light transmittance of the glass substrate which has this cured film was measured with the wavelength of the range of 400-800 nm using the spectrophotometer "150-20 type double beam (made by Hitachi, Ltd.)." In the case where the minimum transmittance at this time is 90% or more, the transparency is excellent, 85% or more and less than 90%, the transparency is good, and when it is less than 85%, the transparency can be said to be poor. The results are shown in Table 1.

<Example 2>

In Example 1, it carried out similarly to Example 1 except having used the polymer solution containing copolymer [A-2] instead of the polymer solution containing copolymer [A-1], and the composition solution (S- 2) was prepared and evaluated. The results are shown in Table 1.

<Example 3>

In Example 1, it carried out similarly to Example 1 except having used the polymer solution containing copolymer [A-3] instead of the polymer solution containing copolymer [A-1], and the composition solution (S- 3) was prepared and evaluated. The results are shown in Table 1.

<Example 4>

In Example 1, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl-3-phenyl) propane (1 mol) and 1,2-naphthoquinonediazide as component [B] Condensate with -5-sulfonic acid chloride (1.9 mol) (1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide- A composition solution (S-4) was prepared and evaluated in the same manner as in Example 1 except that 30 parts by weight of 5-sulfonic acid ester) was used. The results are shown in Table 1.

Radiation Development margin                                              Solvent resistance Heat resistance Transparency Pattern exposure minimum exposure (mJ / cm ² ) Best time (seconds) Development margin (seconds) Film thickness change rate (%) Film thickness change rate (%) Lowest transmittance (%) between 400 and 800 nm Example 1 70 80 35 +3.0 -3.5 90 Example 2 65 75 30 +3.0 -3.0 90 Example 3 75 85 40 +2.5 -3.0 92 Example 4 70 80 35 +3.0 -3.5 90

The radiation sensitive resin composition of this invention can obtain a high radiation sensitivity and can easily form the microlens and interlayer insulation film which are excellent in adhesiveness, solvent resistance, transparency, and heat resistance.

Moreover, the interlayer insulation film of this invention is suitable as an interlayer insulation film provided in a TFT type liquid crystal display element or an integrated circuit element.

The microlens of the present invention is also suitable as an optical material of an imaging optical system of an on-chip color filter or an optical fiber connector.

Claims (8)

[A] a copolymer of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (a3) hydroxyl group-containing unsaturated compound, and (a4) other olefinically unsaturated compound, And [B] 1,2-quinonediazide compound The radiation sensitive resin composition characterized by the above-mentioned. The component (A) according to claim 1, wherein the component [A] is styrene / methacrylic acid / glycidyl glycidyl / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmeth Acrylate copolymer, Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / t-butyl methacrylate copolymer, Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / p-methoxystyrene copolymer, Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 2-methylcyclohexylacrylate copolymer , Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 1,3-butadiene copolymer, Styrene / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / bicyclo [2.2.1] hept- 2-ene copolymer, Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate copolymer, Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropylmethacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / t-butylmethacrylate Copolymer, Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / p-methoxystyrene aerial coalescence, Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 2-methylcyclohexylacrylic Latex copolymer, Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropylmethacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 1,3-butadiene aerial Coalescing, and Styrene / methacrylic acid / glycidyl methacrylate / 2,3-dihydroxypropylmethacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / bicyclo [2.2.1 ] The radiation sensitive composition which is at least 1 sort (s) chosen from a hept-2-ene copolymer. The radiation sensitive composition according to claim 1 or 2, wherein the radiation sensitive composition is for forming an interlayer insulating film. At least (1) forming a coating film of the radiation sensitive composition according to claim 3 on a substrate; (2) irradiating at least a part of said coating film with radiation, (3) developing process, (4) post-baking process Forming method of an interlayer insulating film comprising a. The interlayer insulating film formed from the radiation sensitive composition of Claim 3. The radiation sensitive composition according to claim 1 or 2, wherein the radiation sensitive composition is for forming a microlens. Forming at least the coating film of the radiation sensitive composition of Claim (1) on a board | substrate, (2) irradiating at least a part of said coating film with radiation, (3) developing process, (4) post-baking process Formation method of a micro lens comprising a. The microlens formed from the radiation sensitive composition of Claim 6.