KR100976031B1 - Radiation Sensitive Resin Composition, Insulating Interlayer and Microlens, and Process for Preparing the Same - Google Patents

Abstract

The present invention has a (A) acetal structure and / or a ketal structure, and an epoxy structure, a high molecular weight polystyrene equivalent weight average molecular weight of 2,000 or more measured by gel permeation chromatography, and (B) irradiation with pKa. The radiation sensitive resin composition containing the compound which produces | generates the acid whose number is 4.0 or less is provided. This composition has a high radiation sensitivity, good storage stability, a developing margin capable of forming a good pattern shape even when exceeding an optimum developing time in the developing step, and easily a patterned thin film excellent in adhesion. It can be formed so as to form an interlayer insulating film having a high transmittance and a low dielectric constant, and a microlens having a high transmittance and a good melt shape.

Radiation-sensitive resin composition, radiation sensitivity, interlayer insulation film, micro lens, acetal structure, ketal structure, epoxy structure

Description

Radiation Sensitive Resin Composition, Insulating Interlayer and Microlens, and Process for Preparing the Same}

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram of the cross-sectional shape of a micro lens.

TECHNICAL FIELD This invention relates to a radiation sensitive resin composition, an interlayer insulation film and a micro lens, and their manufacturing method.

In an electronic component such as a thin film transistor (hereinafter referred to as a "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state image sensor, an interlayer insulating film is generally provided to insulate between wirings arranged in layers. do. As the material for forming the interlayer insulating film, it is preferable that the number of steps for obtaining the required pattern shape is small and the flatness is sufficient, and the radiation-sensitive resin composition is widely used (Japanese Patent Laid-Open No. 2001-354822 and Japanese Patent). See Publication 2001-343743.

Since the TFT type liquid crystal display element is manufactured through the process of forming a transparent electrode film on said interlayer insulation film, and forming a liquid crystal aligning film on it, among these electronic components, an interlayer insulation film is a formation process of a transparent electrode film, for example. Sufficient resistance to them is required because they are exposed to high temperature conditions at or exposed to the stripping solution of the resist used for pattern formation of the electrode.

In recent years, in the TFT type liquid crystal display device, there are trends such as large screen, high brightness, high precision, high speed response, and thinning, and the composition for forming an interlayer insulating film used therein is required to have high sensitivity and good storage stability. As a result, the formed interlayer insulating film is required to have higher performance than conventional ones in terms of low dielectric constant, high transmittance, and the like.

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

To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is as a lens or by dry etching using a melt-flown lens pattern as a mask. The method of transferring a lens shape to this is known. The radiation sensitive resin composition is widely used for formation of the said lens pattern (refer Unexamined-Japanese-Patent No. 6-18702 and 6-136239).

By the way, the element in which the microlens or microlens array as described above is formed is then coated with a flattening film and an etching resist film in order to remove various insulating films on the bonding pads, which are wiring forming portions, and exposed using a desired mask. And developing to remove the etching resist of the bonding pad portion, and subsequently removing the planarization film and various insulating films by etching to expose the bonding pad portion. Therefore, in the microlens or the microlens array, solvent resistance and heat resistance are required in the coating film forming step and the etching step of the planarization film and the etching resist.

The radiation sensitive resin composition used to form such a microlens is required to have high sensitivity and good storage stability, and the microlenses formed therefrom have a desired radius of curvature, have high heat resistance, high transmittance, and the like. Required.

In the developing step of forming the interlayer insulating film or the microlens obtained in this way, if the developing time exceeds even a little more than the optimum time, the developing solution penetrates easily between the pattern and the substrate, and peeling easily occurs. Therefore, it is necessary to strictly control the developing time. There was a problem in terms of yield of the product.

Thus, when forming an interlayer insulation film and a microlens from a radiation sensitive resin composition, it is calculated | required that a composition has high sensitivity and favorable storage stability. In addition, even when the developing time exceeds a predetermined time in the developing step during the forming step, no peeling of the pattern occurs and good adhesion, and the interlayer insulating film formed therefrom requires high heat resistance, high solvent resistance, low dielectric constant, high transmittance, and the like. do. On the other hand, in the case of forming a microlens, a microlens requires good melt shape (desirable curvature radius), high heat resistance, high solvent resistance, and high transmittance, but a radiation sensitive resin composition that satisfies such a requirement is known in the art. There was not.

The present invention has been made on the basis of the above circumstances, and an object thereof is to have a high radiation sensitivity, good storage stability, and to form a good pattern shape even when the optimum developing time is exceeded in the developing step. It is providing the radiation sensitive resin composition which has image development margin and can easily form the patterned thin film which is excellent in adhesiveness. Another object of the present invention is to form an interlayer insulating film having a high transmittance and a low dielectric constant when used for forming an interlayer insulating film, and a micro lens having a high transmittance and a good melt shape when used for forming a microlens. It is providing the radiation sensitive resin composition which can form a.

Still another object of the present invention is to provide a method for forming an interlayer insulating film and a micro lens using the above-described radiation-sensitive resin composition, and an interlayer insulating film and a micro lens formed by the method.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above object of the present invention firstly,

(A) High molecular weight body which has acetal ester structure of carboxylic acid and / or ketal ester structure of carboxylic acid, and epoxy structure, and polystyrene conversion weight average molecular weight measured by gel permeation chromatography is 2,000 or more (hereinafter, "polymer And (B) radiation-sensitive resin composition containing a compound that generates an acid having a pKa of 4.0 or less by irradiation with radiation.

The above object of the present invention is secondly achieved by a method for forming an interlayer insulating film, which comprises at least the following steps.

(1) process of forming the coating film of said radiation sensitive resin composition on a board | substrate,

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

(3) developing process,

(4) heating step.

The above object of the present invention is thirdly achieved by a method for forming a microlens comprising at least the following steps.

(1) process of forming the coating film of said radiation sensitive resin composition on a board | substrate,

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

(3) developing process,

(4) heating step.

Moreover, the said subject of this invention is 4th achieved by the interlayer insulation film or microlens formed from the said radiation sensitive composition.

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

High molecular weight (A)

The high molecular weight (A) used in the present invention has acetal ester structure of carboxylic acid and / or ketal ester structure of carboxylic acid and epoxy structure, and the polystyrene reduced weight average molecular weight measured by gel permeation chromatography 2,000 or more high molecular weight body.

The high molecular weight (A) can be produced by bonding an acetal structure or a ketal structure to another carbon atom to form a functional group which should have such a structure.

As a group which couple | bonds with a carboxyl group and forms the acetal ester structure of carboxylic acid, it is a 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-, for example. Propoxyethoxy group, 1-n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyl Oxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) Ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (cyclohexyl) (methoxy) methoxy group, (cyclohexyl) (ethoxy) methoxy group, (cyclohexyl) (n-pro Foxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) Methoxy group, (phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) methoxy group, (pe ) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group, (phenyl) (phenoxy) methoxy group, (phenyl) (benzyloxy ) Methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, (benzyl) (i-propoxy) methoxy group, (benzyl (Cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, etc. are mentioned. .

Among these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydrofuranyloxy group, 1-n-propoxyoxy group, and 2-tetrahydropyranyloxy group are mentioned as a preferable thing. have.

As a group which couple | bonds with a carboxyl group and forms the ketal ester structure of a carboxylic acid, it is a 1-methyl-1- methoxyethoxy group, 1-methyl-1- ethoxyethoxy group, 1-methyl-1-, for example. n-propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1-sec-butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxy Ethoxy group, 1-methyl-1-norbornyloxyethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- ( 1-naphthyloxy) ethoxy group, 1-methyl-1-benzyloxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclo Hexyl-1-ethoxyethoxy group, 1-cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxy Ethoxy group, 1-cyclo Sil-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl -1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl-1-phenyloxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxyethoxy group , 2- (2-methyl-tetrahydrofuranyl) oxy group, 2- (2-methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclohexyloxy group Etc. can be mentioned.                     

Among these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group are mentioned as a preferable thing.

The high molecular weight (A) has a polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography, but is preferably 2,000 or more, preferably 2,000 to 100,000, and more preferably 4,000 to 50,000. . In this case, when Mw is less than 2,000, a developing margin may become inadequate, the residual film ratio etc. of a film obtained may fall, or a pattern shape, heat resistance, etc. may fall. On the other hand, when Mw exceeds 100,000, a sensitivity may fall or a pattern shape may fall. The radiation-sensitive resin composition containing the high molecular weight (A) as described above can easily form a desired pattern shape without developing residue when developing and without reducing the film.

The high molecular weight (A) is not particularly limited as long as it satisfies the above conditions, but for example, (a1) an unsaturated compound having an acetal ester structure of carboxylic acid or a ketal ester structure of carboxylic acid (hereinafter, Olefinic unsaturated compounds other than "monomer (a1)", (a2) unsaturated compounds having an epoxy group (hereinafter also referred to as "monomer (a2)"), and (a3) (a1) and (a2) (Hereinafter also referred to as "monomer (a3)") may be a copolymer (hereinafter also referred to as "copolymer (A)").

As a monomer (a1), the norbornene compound which has acetal ester structure of carboxylic acid or the ketal ester structure of carboxylic acid, the (meth) acrylic acid ester compound which has acetal ester structure of carboxylic acid or a ketal ester structure, for example Can be mentioned. Specific examples thereof include 2,3-di-tetrahydropyran-2-yloxycarbonyl-5-norbornene, for example, as a norbornene compound having the acetal ester structure or the ketal ester structure,

2,3-di-trimethylsilanyloxycarbonyl-5-norbornene, 2,3-ditriethylsilanyloxycarbonyl-5-norbornene, 2,3-di-t-butyldimethylsilanyl Oxycarbonyl-5-norbornene, 2,3-di-trimethylgelmiloxycarbonyl-5-norbornene, 2,3-di-triethylgelmiloxycarbonyl-5-norbornene, 2,3 -Di-t-butyldimethylgelmiloxycarbonyl-5-norbornene, 2,3-di-t-butyloxycarbonyl-5-norbornene, 2,3-di-benzyloxycarbonyl-5- Norbornene, 2,3-di-tetrahydrofuran-2-yloxycarbonyl-5-norbornene, 2,3-di-tetrahydropyran-2-yloxycarbonyl-5-norbornene, 2,3-di-cyclobutyloxycarbonyl-5-norbornene, 2,3-di-cyclopentyloxycarbonyl-5-norbornene, 2,3-di-cyclohexyloxycarbonyl-5 -Norbornene, 2,3-di-cycloheptyloxycarbonyl-5-norbornene, 2,3-di-1-methoxyethoxycarbonyl-5-norbornene, 2,3-di- 1-t-butoxyethoxycar Bonyl-5-norbornene, 2,3-di-1-benzyloxyethoxycarbonyl-5-norbornene, 2,3-di- (cyclohexyl) (ethoxy) methoxycarbonyl-5- Norbornene, 2,3-di-1-methyl-1-methoxyethoxycarbonyl-5-norbornene, 2,3-di-1-methyl-1-i-butoxyethoxycarbonyl- 5-norbornene, 2,3-di- (benzyl) (ethoxy) methoxycarbonyl-5-norbornene and the like;

As the (meth) acrylic acid ester compound having the acetal ester structure or the ketal ester structure, 1-ethoxyethyl (meth) acrylate, tetrahydro-2H-pyran-2-yl (meth) acrylate, 1- (cyclohexhexane) Siloxy) ethyl (meth) acrylate, 1- (2-methylpropoxy) ethyl (meth) acrylate, 1- (1,1-dimethyl-ethoxy) ethyl (meth) acrylate, 1- (cyclohex) Siloxy) ethyl (meth) acrylate, and the like.                     

Among these, the (meth) acrylic acid ester compound which has the acetal ester structure or the ketal ester structure of carboxylic acid is preferable, and especially 1-ethoxyethyl (meth) acrylate and tetrahydro-2H-pyran-2-yl (meth) ) Acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate, 1- (2-methylpropoxy) ethyl (meth) acrylate, 1- (1,1-dimethyl-ethoxy) ethyl (meth ) Acrylate and 1- (cyclohexyloxy) ethyl (meth) acrylate are preferred.

These are used individually or in combination.

As a monomer (a2), for example, glycidyl acrylate, glycidyl methacrylate, glycidyl (alpha)-ethyl acrylate, glycidyl (alpha)-n-propyl acrylate, glycidyl (alpha)-n-butyl acrylate, 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 in terms of increasing the reactivity and the heat resistance and surface hardness of the obtained microlens or interlayer insulating film.

These are used individually or in combination.

As the monomer (a3), for example, methacrylic acid alkyl ester, acrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester and bicyclo Unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, and other unsaturated compounds.

As specific examples thereof, for example, as methacrylic acid alkyl ester, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, di Ethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl Methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl Methacrylate and the like;

As alkyl acrylate, methyl acrylate, isopropyl acrylate, etc .;

As methacrylic acid cyclic alkyl esters, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isoboroyl methacrylate, and the like;

As acrylic acid cyclic alkylester, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.O ^2,6 ] decane -8-yloxyethyl acrylate, isoboroyl acrylate, and the like;

As methacrylic acid aryl ester, Phenyl methacrylate, benzyl methacrylate, etc .;

As acrylic acid aryl ester, Phenyl acrylate, Benzyl acrylate, etc .;

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like;

As the bicyclo unsaturated compounds, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2- N, 5-methoxybicyclo [2.2.l] hept-2-ene, 5-ethoxybicyclo [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- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di Hydroxybicyclo [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-ethylbicyclo [2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like;

As maleimide compounds, phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl -6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As an unsaturated aromatic compound, Styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc .;

As a conjugated diene type compound, 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene, etc .;

As unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, etc .;

As unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;

As unsaturated dicarboxylic anhydride, each anhydride of the said unsaturated dicarboxylic acid;

As another unsaturated compound, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc. are mentioned.

Among them, styrene, t-butyl methacrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-ylmethacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3 -Butadiene, bicyclo [2.2.1] hept-2-ene and the like are preferable in terms of copolymerization reactivity and the like.

These are used alone or in combination.

The copolymer (A) contains a structural unit derived from the monomer (a1), preferably 5 to 60% by weight, more preferably 10 to 50% by weight. In this range, good patterning characteristics can be realized.

The copolymer (A) preferably contains 10 to 70% by weight, more preferably 20 to 60% by weight of the structural unit derived from the monomer (a2). If this value is less than 10 weight%, the heat resistance and surface hardness of the obtained interlayer insulation film and microlens may be insufficient. On the other hand, when this value exceeds 70 weight%, there exists a tendency for the storage stability of a radiation sensitive resin composition to fall.

Although content of the structural unit derived from the monomer (a3) in a copolymer (A) is represented as the amount which subtracted content of the structural unit derived from the said monomer (a1) and (a2) from 100 weight%, monomer (a3) When unsaturated monocarboxylic acid, unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride is used as the sum, the sum of the contents of the structural units derived from the unsaturated monocarboxylic acid, the unsaturated dicarboxylic acid and the unsaturated dicarboxylic acid anhydride When it exceeds 40 weight%, since the stability of the composition obtained may be impaired, it is preferable not to exceed this value.

Preferred specific examples of the copolymer (A) include, for example, 1- (cyclohexyloxy) ethyl methacrylate / tricyclo [5.2.1.O ^2,6 ] decane-8-ylmethacrylate / methacryl Shanglycidyl copolymer, 1- (cyclohexyloxy) ethyl methacrylate / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / glycidyl methacrylate / p- Vinylbenzyl glycidyl ether copolymer, 1- (cyclohexyloxy) ethyl methacrylate / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate / glymethacrylate Dyl / 2-hydroxyethyl methacrylate copolymer, 1- (cyclohexyloxy) ethyl methacrylate / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / methacrylic acid And glycidyl / n-lauryl methacrylate copolymers.

Such a copolymer (A) can synthesize | combine the said monomer (a1), (a2), and (a3) by a well-known method, for example, radical polymerization, in presence of a suitable solvent and a suitable polymerization initiator.

(B) A compound that generates an acid having a pKa of 4.0 or less by irradiation with radiation

Compounds which generate an acid having a pKa of 4.0 or less by irradiation of (B) radiation used in the present invention (hereinafter also referred to as "(B) component") are radiation such as ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like. Is a compound capable of generating an acid having a pKa of 4.0 or less. The value of pKa of the acid generated by irradiation of radiation is preferably 3.5 or less, and more preferably 3.0 or less.

Examples of such a compound include trichloromethyl-s-triazines, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts, and sulfonic acid esters. Among these, diaryl iodonium salts and triarylsulfonium salts are preferable.

Specific examples thereof include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine and 2- (4-methoxy, for example, as trichloromethyl-s-triazines. Phenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4- Methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-piperonylbis (4,6-trichloromethyl) -s-triazine, 2- [2 -(Furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4 , 6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine or 2 -(4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine and the like;                     

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxy Phenylphenyl iodonium trifluoroacetate, phenyl, 4- (2'-hydroxy-1'- tetradecaoxy) phenyl iodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1 ' -Tetradecaoxy) phenyl iodonium hexafluoro antimonate, phenyl, 4- (2'-hydroxy-1'- tetradecaoxy) phenyl iodonium-p-toluenesulfonate, etc .;

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, and the like;

As quaternary ammonium salts, tetramethylammoniumbutyltris (2,6-difluorophenyl) borate, tetramethylammoniumhexyltris (p-chlorophenyl) borate, tetramethylammoniumhexyltris (3-trifluoromethylphenyl) Borate, benzyldimethylphenylammoniumbutyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammoniumhexyltris (p-chlorophenyl) borate, benzyldimethylphenylammoniumhexyltris (3-trifluoromethylphenyl) borate ;

As sulfonic acid ester, 2, 6- dinitro benzyl- p-toluene sulfonic acid ester, 2, 6- dinitro benzyl- trifluoromethane sulfonic acid ester, N-hydroxy naphthalimide-p-toluene sulfonic acid ester, N -Hydroxy naphthalimide- trifluoromethanesulfonic acid ester, respectively is mentioned.                     

In this invention, the usage-amount of (B) component becomes like this. Preferably it is 1-40 weight part with respect to 100 weight part of high molecular weight (A), More preferably, it is 2-20 weight part. When this amount is less than 1 weight part, patterning may become difficult and also the heat resistance and solvent resistance of the interlayer insulation film or microlens obtained may become inadequate. On the other hand, when this amount exceeds 40 weight part, patterning may become difficult. Other ingredients

Although the radiation sensitive resin composition of this invention contains the above-mentioned high molecular weight (A) and (B) component as an essential component, it can contain another component as needed.

As another component which the radiation sensitive resin composition of this invention may contain, it is (C) 1,2-quinonediazide compound, (D) thermosensitive acid generator, (E) at least 1 ethylenic, for example. The compound which has an unsaturated double bond, (F) epoxy resin, (G) surfactant, (H) adhesion | attachment adjuvant, etc. are mentioned.

(C) 1,2-quinonediazide compound

Said (C) 1,2-quinone diazide compound is a 1, 2- quinone diazide compound which generate | occur | produces a carboxylic acid by irradiation of a radiation, and is a phenolic compound or an alcoholic compound (henceforth "mother nucleus"). And condensates of 1,2-naphthoquinone diazide sulfonic acid halide can be used.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cores.                     

As specific examples of these, for example, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc. as trihydroxybenzophenone;

As tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As pentahydroxy benzophenone, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc .;

2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone etc. as hexahydroxy benzophenone;

As (polyhydroxyphenyl) alkane, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri ( p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris ( 2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'spirobiindene-5,6,7 , 5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxypropane and the like;

As another parent nucleus, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxycycloman, 2- [bis {(5-isopropyl- 4-hydroxy-2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1 -Methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6 -Bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.                     

Moreover, the 1, 2- naphthoquinone diazide sulfonic acid amides which changed the ester bond of the above-mentioned mother core to an amide bond, for example, 2,3, 4- trihydroxy benzophenone- 1, 2- naphthoquinone Diazido-4-sulfonic acid amide and the like are also preferably used.

Of these mother cores, 2,3,4,4'-tetrahydroxybenzophenone, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene ] Bisphenol is preferred.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinone diazido-4-sulfonic acid chloride and 1, 2-naphthoquinone diazido-5-sulfonic acid chloride is mentioned. Among them, it is preferable to use 1,2-naphthoquinone diazido-5-sulfonic acid chloride.

The amount of the mother nucleus and 1,2-naphthoquinone diazide sulfonic acid halide to be used for the condensation reaction is preferably 1.0 to 4.0 mol, more preferably 1,2-naphthoquinone diazide sulfonic acid halide per 1 mol of the mother nucleus. Is 1.5 to 3.0 mol.

Condensation reaction can be performed by a well-known method.

The use ratio of (C) 1,2-naphthoquinone diazide is preferably 100 parts by weight or less, and more preferably 40 parts by weight or less based on 100 parts by weight of the high molecular weight (A). When this ratio exceeds 100 weight part, formation of a pattern may become difficult.

(D) thermosensitive acid generator

The said (D) thermosensitive acid generator can be used in order to improve heat resistance and hardness. Specific examples thereof include antimony fluoride, and commercially available products include Sunaid SI-L80, Sunaid SI-L110, Sunaid SI-L150 (manufactured by Sanshin Kagaku Kogyo Co., Ltd.), and the like.

(D) The thermosensitive acid generator is preferably 20 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the high molecular weight (A). When this ratio exceeds 20 weight part, precipitates may arise and patterning may become difficult.

(E) a compound having at least one ethylenically unsaturated double bond

As the compound (E) having at least one ethylenically unsaturated double bond, for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or higher (meth) acrylate can be preferably used. .

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth), for example Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned. As these commercial items, for example, Alonics M-101, M-111, M-114 (manufactured by Toa Kosei Co., Ltd.), KAYARAD TC-110 S, and TC-120 S (Nippon Kayaku Co., Ltd.) And Biscoat 158, Copper 2311 (manufactured by Osaka Yuki Chemical Co., Ltd.).

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, and the like. As these commercial items, for example, Alonics M-210, M-240, M-6200 (manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.) ), Biscoat 260, copper 312, copper 335 HP (manufactured by Osaka Yuki Chemical Co., Ltd.), and the like.

As said trifunctional or more than (meth) acrylate, a trimethol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a tri ((meth) acryloyloxyethyl) phosphate, a pentaerytate, for example Lithol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. As the commercial item, for example, Alonics M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.) , KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3 PA, copper 400 (the Osaka Yuki Kagaku Kogyo KK) etc. are mentioned.

These (E) compounds having at least one ethylenically unsaturated double bond are used alone or in combination. (E) The use ratio of the compound which has at least 1 ethylenically unsaturated double bond becomes like this. Preferably it is 50 weight part or less, More preferably, it is 30 weight part or less with respect to 100 weight part of high molecular weight (A).

By containing the compound which has (E) at least 1 ethylenically unsaturated double bond 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, film roughness may arise at the time of coating of a composition.                     

(F) epoxy resin

The said (F) epoxy resin is not limited as long as it does not affect compatibility with the other component of the radiation sensitive resin composition of this invention. Preferably, bisphenol-A epoxy resin, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, glyc The resin etc. which co-polymerized the cydyl methacrylate can be used. Among these, bisphenol-A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester-type epoxy resin, etc. are preferable.

The use ratio of the (F) epoxy resin is preferably 30 parts by weight or less based on 100 parts by weight of the high molecular weight (A). By containing (F) epoxy resin in such a ratio, the heat resistance and surface hardness of the interlayer insulation film or microlens obtained from the radiation sensitive resin composition of this invention can be improved further. When this use ratio exceeds 30 weight part per 100 weight part of high molecular weight bodies (A), sufficient coating film formation ability may not be obtained.

Moreover, although high molecular weight (A) can also be called "epoxy resin", since high molecular weight (A) has an acetal ester structure of carboxylic acid or a ketal ester structure of carboxylic acid, it does not have these structures (F ) It is different from epoxy resin.

(G) surfactant

The radiation sensitive resin composition of this invention can also contain surfactant (G) in order to improve applicability | paintability. As an example of (G) surfactant, a fluorine-type surfactant, a silicone type surfactant, and a nonionic surfactant can be used preferably.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1, 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2 Sodium fluoroalkylbenzenesulfonates in addition to 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodines; Fluoroalkyl polyoxyethylene ethers; Perfluoroalkyl polyoxyethanols; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like.

As these commercial items, BM-1000, BM-1100 (above, BM Chemie Co., Ltd.), Megapack F 142D, Copper F 172, Copper F 173, Copper F 183, Copper F 178, Copper F 191, Copper F 471 ( Dai Nippon Ink Chemical Co., Ltd.), Florard FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Supron S-112, Copper S-113, S-131, S-141, S-145, S-382, SSC-101, SSC-102, SSC-103, SSC-104, SSC-105, S SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF 301, copper 303, copper 352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032 , SF-8428, DC-57, DC-190 (manufactured by Toray Dow Corning Silicon Co., Ltd.), and the like.                     

As said silicone type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper FS-1265-300 (above, Toray Dow Corning Silicone Co., Ltd. product) And TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, the Toshiba Silicone Co., Ltd. product) etc. are mentioned.

As said nonionic surfactant, For example, 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;

Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate;

(Meth) acrylic acid copolymer polyflow Nos. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be used.

These surfactant can be used individually or in combination of 2 or more types.

Such a surfactant (G) is preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the high molecular weight (A). When this amount exceeds 5 weight part, film roughness may arise easily at the time of application | coating of a composition.

(H) Adhesion Preparation

The radiation sensitive resin composition of this invention may also contain the (H) adhesion | attachment adjuvant in order to improve the adhesiveness with a base | substrate. As such an adhesion aid, a functional silane coupling agent is preferably used. As the example, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group, is mentioned. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned. These adhesion aids are used with respect to 100 weight part of high molecular weight bodies (A), Preferably it is 20 weight part or less, More preferably, it is used in the quantity of 10 weight part or less. When the amount of the adhesion assistant exceeds 20 parts by weight, the development residue may easily occur.

Radiation-sensitive resin composition

The radiation sensitive resin composition of this invention is manufactured by mixing uniformly the above-mentioned high molecular weight (A) and (B) component, and the other components added arbitrarily as mentioned above. The radiation-sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state.

As a solvent which can be used for manufacture of the radiation sensitive resin composition of this invention, although each component of a high molecular weight (A), (B) component, and the other component mix | blended arbitrarily is melt | dissolved uniformly, it does not react with each component Is preferably used.

Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, and propylene glycol alkyl ether propionates. And aromatic hydrocarbons, ketones and esters.

As these specific examples, For example, as alcohols, methanol, ethanol, etc .;

Tetrahydrofuran etc. as ethers;

As glycol ether, Ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetates, methyl cellosolve acetate, ethyl cellosolve acetate, etc .;

As diethylene glycol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ethers, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;

As propylene glycol alkyl ether acetates, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;

As propylene glycol alkyl ether propionates, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

As aromatic hydrocarbons, toluene, xylene, etc .;                     

As ketones, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanane, etc .;

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and methyl hydroxyacetate, Ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl hydroxypropionate, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, methyl ethoxyacetate, ethoxyacetic acid, ethoxyacetic acid propyl, ethoxyacetic acid Butyl, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, butoxy Ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-meth Methyl oxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy Butyl propionate, 3-propoxy propionate, 3-propoxy propionate, 3-propoxy propionate, 3-propoxy propionate, 3-butoxypropionate, 3-butoxypropionate, 3-part Propyl oxypropionate, butyl 3-butoxy propionate, etc. are mentioned.                     

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycols are preferably used in view of solubility, reactivity with each component, and ease of coating film formation. In addition, these solvents can be used independently and can also use 2 or more types together.

When the solvent is used in the radiation-sensitive resin composition of the present invention, the amount of the solid used in the composition (that is, the amount of the portion excluding the solvent from the total amount of the composition) is preferably 5 to 50% by weight of the whole composition, more preferably. For example, it may be used in an amount of 10 to 40% by weight.

In addition, the composition solution prepared as described above may be used after filtering using a Millipore filter having a pore size of about 0.2 μm or the like.

Interlayer insulating film, formation of micro lens

The method of forming the interlayer insulation film and microlens of this invention using the radiation sensitive resin composition of this invention is demonstrated. The method for forming an interlayer insulating film or microlens of the present invention includes at least the following steps.

(1) forming the coating film of the radiation sensitive composition of the present invention on a substrate;

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

(3) developing process,

(4) heating step.

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

In the process of said (1), a solvent is removed by apply | coating the composition solution of this invention to the board | substrate surface, and prebaking, and the coating film of a radiation sensitive resin composition is formed.

As a kind of board | substrate which can be used for this invention, the glass substrate, a silicon wafer, and the board | substrate with which various metal layers were formed in this surface are mentioned, for example.

The coating method of a composition solution is not specifically limited, For example, the appropriate method, such as the spray method, the roll coat method, the rotation coating method, the bar coating method, can be employ | adopted. The conditions of prebaking differ according to the kind, usage ratio, etc. of each component. For example, it is about 30 to 15 minutes at 60-110 degreeC.

The film thickness of the coating film formed is a value after prebaking, and when forming an interlayer insulation film, 3-6 micrometers is preferable, and when forming a microlens, 0.5-3 micrometers is preferable.

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

In the process of (2), after irradiating radiation to the formed coating film through the mask which has a predetermined | prescribed 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, far ultraviolet rays, X-rays, charged particle beams, and the like.

As said ultraviolet-ray, g line | wire (wavelength 436 nm), i line | wire (wavelength 365 nm), etc. are mentioned, for example. As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. As X-ray, a synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example.                     

Among these, ultraviolet rays are preferable, and radiation including g rays and / or i rays is particularly preferable.

The exposure dose is preferably 500 to 5,000 J / m ² , and more preferably 750 to 3,000 J / m ² . In addition, using a radiation sensitive resin composition known in the art requires an exposure amount exceeding 1,50O J / m ² when forming an interlayer insulating film, and ² , OO J / m when forming a microlens. ^Although an exposure amount exceeding ² is required, in the case of the radiation-sensitive resin composition of the present invention, an exposure dose of 1,50OO J / m ² or less when forming an interlayer insulating film, and 2,00OJ when forming a microlens By employing an exposure dose of / m ² or less, there is an advantage that desired patterning can be achieved.

(3) developing process

As a developing solution used for image development treatment, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propyl Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] Aqueous solutions of alkalis, such as -7-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 amount in the said aqueous solution of alkalis, or various organic solvents which melt | dissolve the composition of this invention can be used as a developing solution. As the developing method, a suitable method such as a paddle method, a dipping method, a rocking dipping method or a shower method can be used. The development time at this time depends on the composition of the composition, but is, for example, between 30 and 120 seconds.

In addition, since the peeling will generate | occur | produce in the pattern formed when the developing time exceeds about 20-25 second from the optimal value, the radiation-sensitive resin composition of this invention was known conventionally. In this case, even if the excess time from the optimum developing time is 30 seconds or more, good pattern formation is possible, and there is an advantage in product yield.

(4) heating process

After the (3) developing step carried out as described above, the patterned thin film is preferably rinsed by, for example, running water washing, and preferably irradiated with radiation on the entire surface by a high pressure mercury lamp or the like (post exposure). By doing so, the decomposition treatment of the 1,2-quinonediazide compound remaining in the thin film is performed. Then, this thin film is heat-processed (postbaked process) with heating apparatuses, such as a hotplate and oven, and hardening process of this thin film is performed. The exposure amount in the said postexposure process becomes like this. Preferably it is about 2,000-5,00O / m <^2> . In addition, the heating temperature in this postbaking process is 120-250 degreeC, for example. Preferable heating temperature is 150-250 degreeC.

Although heating time changes with kinds of a heating apparatus, it can be set as 5 to 30 minutes, for example, when heat processing on a hotplate, and 30 to 90 minutes when heat processing in an oven. At this time, the step baking method etc. which perform two or more heating processes can be used.

In this way, a patterned thin film corresponding to the target interlayer insulating film or micro lens can be formed on the surface of the substrate.

The interlayer insulating film and the 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.

Interlayer insulation film

The interlayer insulating film of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, high transmittance and low dielectric constant, and can be suitably used as an interlayer insulating film for electronic components. .

Micro lens

The microlens of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, and has high transmittance and good melt shape, and is preferably used as a microlens of a solid-state imaging device. Can be.

In addition, the shape of the microlens of this invention becomes a semi-convex lens shape, as shown to FIG. 1 (a).

<Examples>

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

Synthesis Example of High Molecular Weight (A)

Synthesis Example 1

To the flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 40 parts by weight of 1- (cyclohexyloxy) ethyl methacrylate, 5 parts by weight of styrene, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate and 2 parts of α-methylstyrene After adding 3 parts by weight of a sieve and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-1). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-1) was 11,000. In addition, the solid content concentration of the polymer solution obtained here was 31.6 weight%.

Synthesis Example 2

To the flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. 4 parts by weight of 1-ethoxyethyl methacrylate, 5 parts by weight of styrene, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate and 3 parts by weight of α-methylstyrene dimer After nitrogen was substituted and gently stirred, the stirring was started. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-2). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-2) was 11,000. In addition, the solid content concentration of the polymer solution obtained here was 31.7 weight%.

&Lt; Synthesis Example 3 &

To the flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 40 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 5 parts by weight of styrene, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate and α-methylstyrene After adding 3 parts by weight of dimer and replacing with nitrogen, stirring was started gently. 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). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-3) was 11,000. In addition, the solid content concentration of the polymer solution obtained here was 31.6 weight%.

&Lt; Synthesis Example 4 &

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were added to the flask equipped with a cooling tube and a stirrer. Subsequently, 5 parts by weight of styrene, 22 parts by weight of 1- (cyclohexyloxy) ethyl methacrylate, 28 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and glycerin methacrylate 45 parts by weight of dill and 5 parts by weight of α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing a copolymer (A-4). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-4) was 8,000. In addition, the solid content concentration of the polymer solution obtained here was 29.9 weight%.

&Lt; Synthesis Example 5 &

To the flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 40 parts by weight of 1- (cyclohexyloxy) ethyl methacrylate, 27 parts by weight of glycidyl methacrylate, 29 parts by weight of p-vinylbenzyl glycidyl ether, and 12 parts by weight of 2-hydroxyethyl methacrylate Part and 3 parts by weight of α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4.5 hours to obtain a polymer solution containing a copolymer (A-5). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-5) was 13,000. In addition, the solid content concentration of the polymer solution obtained here was 32.7 weight%.

Comparative Synthesis Example 1

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were added to the flask equipped with a cooling tube and a stirrer. 5 parts by weight of styrene, 22 parts by weight of methacrylic acid, 28 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 45 parts by weight of glycidyl methacrylate and α-methylstyrene After adding 5 parts by weight of dimer and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer (a-1). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (a-1) was 8,000. In addition, the solid content concentration of the polymer solution obtained here was 29.8 weight%.

[Adjustment of radiation sensitive resin composition]

&Lt; Example 1 >                     

The solution containing the polymer (A-1) as the component (A) synthesized in Synthesis Example 1 in an amount equivalent to 100 parts by weight (solid content) of the copolymer (A-1), and 4, as the component (B) 5 parts by weight of 7-di-n-butoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate (B-1) was dissolved in diethylene glycol methylethyl ether so that the solid content concentration was 30% by weight. It filtered by the membrane filter of 0.2 micrometer of calibers, and prepared the solution (S-1) of a radiation sensitive resin composition.

<Examples 2 to 12>

In Example 1, it carried out similarly to Example 1 except having used the kind and quantity as Table 1 as a high molecular weight (A) and (B) component, and the solution of a radiation sensitive resin composition (S-2 ) To (S-12).

In addition, description of (C) component in Examples 7-12 shows that the 1, 2- quinonediazide compound was added.

Comparative Example 1

The solution containing the copolymer (a-1) synthesized in Comparative Synthesis Example 1 was used in an amount equivalent to 100 parts by weight (solid content) of the copolymer (a-1) and 4 as 1,2-quinonediazide compound. , 4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mole) and 1,2-naphthoquinone diazido-5-sulfonic acid 30 parts by weight of a condensate of chloride (2.0 mol) was dissolved in diethylene glycol methylethyl ether so that the solid content concentration was 30% by weight, and then filtered through a membrane filter having a diameter of 0.2 µm to obtain a solution of the radiation-sensitive resin composition (s -1) was prepared.                     

In addition, in Table 1, the abbreviation of a component shows the next compound.

(B-1): 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

(B-2): 2- (4-methoxy-β-styryl) -4,6-bis (trichloroethyl) -s-triazine

(B-3): 4,7-di-hydroxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate

(C-1): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho Condensate of quinonediazido-5-sulfonic acid chloride (1.0 mole)

(C-2): 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinone diazido-5-sulfonic acid ester (2.44 mol)

(C-3): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho Condensate of quinonediazido-5-sulfonic acid chloride (2.0 mol)

(C-4): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho Condensate of quinonediazido-4-sulfonic acid chloride (2.0 mol)                     

[Performance Evaluation as an Interlayer Insulation Film]

<Examples 13-24, Comparative Examples 2-4>

The various characteristics as an interlayer insulation film were evaluated as follows using the radiation sensitive resin composition manufactured as mentioned above. In addition, the composition used by the comparative examples 2 and 3 is a commercial item (made by Tokyo Oka Corporation) of the composition of m / p-cresol novolak and 1,2-naphthoquinone diazido-5-sulfonic acid ester.

[Evaluation of sensitivity]

After applying the composition shown in Table 3 using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. After exposing while changing exposure time with the PLA-501F exposure machine (ultra high pressure mercury lamp) of Canon Corporation through the pattern mask which has a predetermined | prescribed pattern in the obtained coating film, the tetramethylammonium hydroxide of the density shown in Table 2 was carried out. It developed by the paddle method for 90 second at 25 degreeC as aqueous solution of a lock seed. Flowing water was washed for 1 minute with ultrapure water, dried and a pattern was formed on the wafer. The exposure amount required for complete dissolution of the space pattern of the line and space (10 to 1) of 3.0 mu m was measured. This value is shown in Table 2 as a sensitivity. When this value is 1,500 J / m <^2> or less, it can be said that a sensitivity is favorable.

[Evaluation of Development Margin]

After applying the composition shown in Table 2 using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. Through the mask which has a pattern of a line-and-space (10 to 1) of 3.0 micrometers in the obtained coating film, using the Canon-made PLA-501F exposure machine (ultra high pressure mercury lamp) said "[evaluation of sensitivity]" It exposed at the exposure amount corresponded to the value of the sensitivity measured by this, and it developed by the paddle method at 25 degreeC as the aqueous tetramethylammonium hydroxide solution of the density | concentration shown in Table 2. Subsequently, flowing water wash | cleaned for 1 minute of ultrapure water, it dried, and the pattern was formed on the wafer. At this time, the developing time required for the line width to be 3 m is shown in Table 2 as the optimum developing time. In addition, the time from the optimum development time to the time when the development was continued and the line pattern of 3.0 µm was peeled off was measured and shown in Table 3 as the development margin. When this value is 30 seconds or more, the development margin can be said to be good.                     

[Evaluation of Preservation Stability]

In the evaluation of the sensitivity for each of the compositions stored at room temperature (23 ° C.) for 15 days after production, the exposure dose required for dissolving the space pattern of the line and space (10 to 1) of 3.0 µm completely was dissolved. It measured and computed the increase rate of the required exposure amount at this time. The results are shown in Table 2. When this value is 5%, it can be said that storage stability is favorable.

[Evaluation of solvent resistance]

After applying the base composition shown in Table 2 using a spinner on a silicon substrate, it was prebaked at 90 ° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. The obtained coating film was exposed so that the accumulated irradiation amount might be 3,000 J / m ² with a Canon PLA-501 F exposure machine (ultra high pressure mercury lamp), and the silicon substrate was heated at 220 ° C. in a clean oven for 1 hour to obtain a cured film. . The film thickness (T1) of the obtained 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 to determine the film thickness change rate due to the immersion {│t1-T1│ / T1 } X 100 [%] was calculated. The results are shown in Table 3. When this value is 5% or less, it can be said that solvent resistance is favorable.

In the evaluation of solvent resistance, since the patterning of the film to be formed is unnecessary, the radiation irradiation step and the developing step were omitted, and only the coating film forming step, the postbaking step and the heating step were evaluated.                     

[Evaluation of Heat Resistance]

The cured film was formed like the evaluation of said solvent resistance, 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 the 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} × 100 [%] was calculated. The results are shown in Table 3. When this value is 5% or less, it can be said that heat resistance is favorable.

[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 at the wavelength of 400-800 nm using the spectrophotometer "150-20 type double beam (made by Hitachi, Ltd.)." Table 3 shows the minimum light transmittance values at this time. When this value is 95% or more, it can be said that transparency is favorable.                     

[Performance Evaluation as a Micro Lens]

<Examples 25-36, Comparative Examples 5-7>

Each characteristic as a micro lens was evaluated as follows using the radiation sensitive resin composition manufactured as mentioned above. In addition, evaluation of heat resistance and transparency refer to the performance evaluation result as the said interlayer insulation film.

In addition, the composition used by Comparative Examples 6 and 7 is a commercial item (made by Tokyo Oka Co., Ltd.) of the composition of all m- / p-cresol novolak and a 1, 2- naphthoquinone diazido-5-sulfonic acid ester. .

[Evaluation of sensitivity]

After applying the composition shown in Table 4 using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. The obtained coating film was exposed to light with varying exposure time with a Nikon Corporation NSR1755i7A reduced projection exposure machine (NA = 0.50, λ = 365 nm) through a pattern mask having a predetermined pattern, and tetramethylammonium at the concentrations shown in Table 4 It developed by the paddle method for 1 minute at 25 degreeC as aqueous hydroxide solution. Rinsed with water and dried to form a pattern on the wafer. The exposure time required for the space line width of the 0.8 mu m line and space pattern (1 to 1) to be 0.8 mu m was measured. This value is shown in Table 4 as the sensitivity. When this value is 2,000 J / m <^2> or less, it can be said that a sensitivity is favorable.

[Evaluation of Development Margin]

After applying the composition shown in Table 4 using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. Sensitivity measured in the "[evaluation of sensitivity]" with the Nikon Corporation NSR 1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a 4.0 micrometer dot and a 2.0 micrometer space pattern to the obtained coating film. The exposure was performed at an exposure amount corresponding to the value of, and developed by a paddle method for 1 minute at 25 ° C. with an aqueous tetramethylammonium hydroxide solution having a concentration shown in Table 4. Rinsed with water and dried to form a pattern on the wafer. Table 4 shows the development time required for the space line width of the 0.8 µm line and space pattern (1 to 1) to be 0.8 µm. In addition, the time (development margin) from the optimum image development time until the pattern of 0.8 micrometers in width | variety was peeled off when developing continued, was shown in Table 4 as image development margin. When this value is 30 seconds or more, the development margin can be said to be good.

[Evaluation of Preservation Stability]

In the evaluation of the sensitivity described above for each composition stored at room temperature (23 ° C.) for 15 days after production, the exposure dose required for complete dissolution of the 4.0 μm dot 2.0 μm space pattern was measured. The increase rate was calculated. The results are shown in Table 4. When this value is 5% or less, it can be said that storage stability is favorable.

[Evaluation of solvent resistance]

After applying the composition shown in Table 4 using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. It exposed to the obtained coating film so that accumulated irradiation amount might be 3,000 J / m <^2> by Canon's PLA-501F exposure machine (super high pressure mercury lamp), and this silicon substrate was heated at 220 degreeC in the clean oven for 1 hour, and the cured film was obtained. The film thickness (T3) of the obtained cured film was measured. After the silicon substrate on which the cured film was formed was immersed in isopropyl alcohol temperature controlled at 50 ° C. for 10 minutes, the film thickness t3 of the cured film was measured, and the film thickness change rate due to immersion {| t3-T3 | / T3} x100 [%] was calculated. The results are shown in Table 4.

In the evaluation of solvent resistance, since the patterning of the film to be formed is unnecessary, the irradiation step and the developing step were omitted, and only the coating film forming step, the postbaking process and the heating step were evaluated.

[Evaluation of Shape of Micro Lens]

After applying the composition shown in Table 4 using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. The sensitivity of the sensitivity measured in the "[evaluation of sensitivity]" was measured by the Nikon Co., Ltd. NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a 4.0 micrometer dot and a 2.0 micrometer space pattern in the obtained coating film. It exposed at the exposure amount corresponding to a value, and it developed by the paddle method for 1 minute at 25 degreeC as the aqueous tetramethylammonium hydroxide solution of the density | concentration described as the developer concentration in evaluation of the sensitivity of Table 4. Rinsed with water and dried to form a pattern on the wafer. Then, it exposed by the Canon Co., Ltd. make PLA-501F exposure machine (ultra high pressure mercury lamp) so that accumulated irradiation amount might be 3,00 J / m <^2> . Thereafter, the plate was heated at 160 ° C. for 10 minutes and further heated at 230 ° C. for 10 minutes to melt-flow the pattern to form a microlens.

Table 4 shows the dimensions (diameter) and the cross-sectional shape of the bottom (surface in contact with the substrate) of the formed microlenses. The dimension of the microlens bottom may be said to be good when it is more than 4.0 micrometers and less than 5.0 micrometers. Moreover, when this dimension is 5.0 micrometers or more, it will be in the state which the adjacent lenses contact, and it is not preferable. In addition, in the schematic diagram shown in FIG. 1, a cross-sectional shape is favorable when it is a semi-convex lens shape like (a), and is bad when it is a substantially trapezoidal shape like (b).                     

According to the present invention, a patterned thin film having high radiation sensitivity, good storage stability, 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 can be easily formed, and when used for the formation of the interlayer insulating film, it is possible to form an interlayer insulating film of high transmittance and low dielectric constant, and when used for the formation of the microlens, a microlens having high transmittance and good melt shape. There is provided a radiation-sensitive resin composition capable of forming.

According to the present invention, there is also provided a method of forming an interlayer insulating film and a micro lens using the radiation-sensitive resin composition, and an interlayer insulating film and a micro lens formed by the method.

Claims (10)

(A) (a1) a norbornene compound having an acetal structure or a ketal structure, or a (meth) acrylic acid ester compound having an acetal structure or a ketal structure, (a2) selected from glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether At least one, and (a3) Olefinically unsaturated compounds other than (a1) and (a2) Copolymerization, the copolymer having a polystyrene reduced weight average molecular weight of 2,000 or more, as measured by gel permeation chromatography, and (B) A compound that generates an acid having a pKa of 4.0 or less by irradiation with radiation A radiation sensitive resin composition for forming an interlayer insulating film containing a film. An olefinically unsaturated compound other than (a1) and (a2) of (a3) is styrene, t-butyl methacrylate, tricyclo [5.2.1.O ^2,6 ] decane-8- Interlayer insulating film formation, characterized in that it is at least one selected from one methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene and bicyclo [2.2.1] hept-2-ene. Radiation-sensitive resin composition for. The radiation sensitive resin composition for interlayer insulation film formation of Claim 1 which further contains (C) 1,2-quinonediazide compound. At least (1) Process of forming the coating film of the radiation sensitive resin composition for interlayer insulation film formation of Claim 3 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, (4) heating process Method for forming an interlayer insulating film, characterized in that it comprises a. The interlayer insulation film formed from the radiation sensitive resin composition for interlayer insulation film formation in any one of Claims 1-3. A) (a1) a norbornene compound having an acetal structure or a ketal structure, or a (meth) acrylic acid ester compound having an acetal structure or a ketal structure, (a2) selected from glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether At least one, and (a3) Olefinically unsaturated compounds other than (a1) and (a2) Copolymerization, the copolymer having a polystyrene reduced weight average molecular weight of 2,000 or more, as measured by gel permeation chromatography, and (B) A compound that generates an acid having a pKa of 4.0 or less by irradiation with radiation The radiation sensitive resin composition for microlens formation containing the above. The olefinically unsaturated compounds other than (a1) and (a2) of (a3) are styrene, t-butyl methacrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-. Micro lens formation, characterized in that it is at least one selected from one methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene and bicyclo [2.2.1] hept-2-ene Radiation-sensitive resin composition for. The radiation sensitive resin composition for microlens formation of Claim 6 or 7 which further contains (C) 1,2-quinonediazide compound. At least (1) Process of forming the coating film of the radiation sensitive resin composition for microlens formation of Claim 6 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, (4) heating process Forming a micro lens, characterized in that it comprises a. The microlens formed from the radiation sensitive resin composition for microlens formation of Claim 6.

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