TW201122728A - Positive rediation-sensitive resin composition, interlayer insulation film and method for forming the same - Google Patents

Abstract

An object of the present invention is to provide a positive radiation-sensitive resin composition which is capable of forming an interlayer insulation film having high radiation sensitivity and development margin while having excellent thermoresistance, solvent resistance, low dielectric constant, light transmittance, light resistance and dry-etching resistance. The present invention is a positive radiation-sensitive resin composition comprising [A] alkali-soluable resin with hindered amin structure and/or hindered phenol and [B] 1, 2-quinone amide compound. Preferably, the component [A] is a copolymer obtained from (a1) a monomer containing at least one selected from unsaturated carboxylic acid or unsaturated carboxylic anhydride and (a2) a monomer containing at least one compound selected from compounds represented by formula (1), formula (2) or formula (3). The [A] component may be a copolymer of compound (a1), (a2) and (a3) a monomer containing unsaturated compound having epoxy group.

Description

[Technical Field] The present invention relates to a positive-type radiation-sensitive resin composition, an interlayer insulating film formed from the composition, and a method of forming the interlayer insulating film, the positive-type radiation The resin composition is suitable as a material for forming an interlayer insulating film of a liquid crystal display element (LCD) or the like. [Prior Art] In an electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, and an image sensor, an interlayer insulating film is generally provided so as to be layered. Insulation between wirings. As a material for forming the interlayer insulating film, it is preferable to use a positive-type radiation-sensitive resin composition (see Patent Document 1) because the number of steps for obtaining a necessary pattern shape is small and the flatness is sufficient. Among the above electronic members, for example, a TFT-type liquid crystal display element is produced by forming a transparent electrode film on an interlayer insulating film and forming a liquid crystal alignment film thereon. When such a TFT type liquid crystal display element is manufactured, the interlayer insulating film is exposed to high temperature conditions in the step of forming the transparent electrode film, or exposed to the photoresist stripping liquid used for forming the pattern of the electrode, or exposed to light of various wavelengths. Medium, so it must have sufficient heat resistance, solvent resistance and light resistance. In addition, since it is also possible to carry out the dry etching step of the interlayer insulating film, it is necessary to sufficiently withstand dry etching (refer to Patent Document 2 and Patent Document 3). -4- 201122728 In addition, in recent years, TFT-type liquid crystal display devices have a tendency to increase in size, brightness, accuracy, speed response, and thickness. Therefore, as a radiation sensitive composition for forming an interlayer insulating film used in a TFT type liquid crystal display element, high sensitivity to radiation is required, and a low dielectric constant and a high light transmittance are required as an interlayer insulating film. These are excellent performances that are gradually increasing compared to the present. Further, in the developing step in forming the interlayer insulating film, even if the development time is only slightly longer than the optimum time, the developer penetrates between the pattern and the substrate, and the pattern is easily peeled off from the substrate. Therefore, in the developing step at the time of forming the interlayer insulating film, it is necessary to strictly control the developing time, which is problematic in terms of the yield of the article. When the interlayer insulating film is formed of the radiation sensitive resin composition, the composition is required to have high sensitivity to radiation, and in the development step when the interlayer insulating film is formed, when the development time is excessive than the predetermined time, the pattern is displayed. The interlayer adhesive film to be formed is required to have excellent heat resistance, solvent resistance, low dielectric property, light transmittance, light resistance, dry etching resistance, and the like. However, it is not known at present that there is a radiation sensitive resin composition that fully satisfies such requirements. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PRIOR ART SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above problems, and has a positive-type radiation-sensitive resin composition which is resistant to peeling of a pattern from a substrate in a developing step of the composition, and is resistant to heat. An interlayer insulating film excellent in properties, solvent resistance, low dielectric property, and light transmittance dry etching property; and a method of forming the interlayer insulating film and the interlayer insulating film. The invention proposed to solve the above problems is a positive resin composition comprising: [A] having a hindered amine structure and/or a hindered oxime structure I fat, and [B] 1,2-quinonediazide compound. Since the positive-type radiation-sensitive resin composition has an alkali-soluble resin and a nitrogen compound which are composed of an amine structure and/or a hindered phenol structure, the radiation sensitivity and the allowable range (development margin) of the development time which is peeled off in the development step are high, and heat resistance An interlayer insulating film excellent in properties, solvent resistance, low dielectric property, and light transmittance and dry etching property. In addition, the "alkali-soluble resin of the hindered amine structure" herein means an "alkali-soluble resin having a hindered phenol structure" having a hydroxyl group in which one carbon atom of the amine group is less than one carbon atom. The at least one benzene ring carbon atom of the linking moiety is bonded to the alkali-soluble resin of the phenol structure, and provides a layer-type radiation-sensitive β-alkali-soluble tree having a radiation sensitivity and which can be formed, light-resistant, and resistant to the product. Blocked [B]l, 2-醌 in the second stack of patterns from the substrate and can be formed, light fastness and resistance to "have been atomically contiguous to soluble resin: refers to the phenolic tertiary group containing -6- 201122728 In the positive-type radiation-sensitive resin composition, the [A] alkali-soluble resin preferably contains one or more monomers selected from the group consisting of unsaturated carboxylic acids or unsaturated carboxylic anhydrides, and (a2) contains A copolymer obtained from a compound represented by the following formula (1), a compound represented by the following formula (2), or a monomer of one or more compounds represented by the following formula (3). R1

R9^%j^\R8

OH 201122728

In the formula (1), R1 is a hydrogen atom or a group having 1 to 4 carbon atoms, and R2 to R5 are each independently an alkyl group having 1 to 6 carbon atoms, and R6 is a hydrogen atom or has 1 carbon atom. ~6 alkyl, Βι is a single bond, -C00_ or -CONH-, and m is an integer from 〇~3. In the formula (2), R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R7 to R1() are each independently a hydrogen atom or an alkyl group having a carbon number of 6 and at least R8 and R9. One is a tertiary butyl or a tertiary pentyl group, Βι is a single bond, -COO: or -CONH-, and η is an integer of 0 to 3. In the formula (3), R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R11 is each independently a hydrogen atom or an alkyl group having a carbon number, and t is an integer of 1 to 4'. The ground is a hydrogen atom or a group of 1 to 6 carbon atoms. At least one of R15 and R16 is a tertiary butyl or a tertiary pentyl group. Βι is a single bond, -COO- or -CONH-, B2 is a single The key, -CO-, -S-, _CH2-, -CH(CH3)- or -C(CH3)2-, k is an integer of 〇~3. As a constituent component of the copolymer of the [A] alkali-soluble resin, by using these compounds having a hindered structure, the heat resistance of the interlayer insulating film formed of the positive-acting -8 - 201122728 radiation-linear resin composition can be further improved. Light fastness and dry etching resistance. In the positive-type radiation-sensitive resin composition, the [A] alkali-soluble resin preferably contains (a3) an epoxy group-containing unsaturated compound in addition to the compounds represented by the above (al) and (a2). The monomer obtained copolymer. As a constituent component of the copolymer of the [A] alkali-soluble resin, by using an epoxy group-containing unsaturated compound, the heat resistance and solvent resistance of the interlayer insulating film formed of the positive radiation sensitive resin composition can be further improved. Sex. Further, the method for forming an interlayer insulating film of the present invention comprises: (1) a step of forming a coating film of the positive-type radiation-sensitive resin composition on a substrate, and (2) a coating film formed in the step (1). a step of irradiating at least a part of the radiation, (3) a step of developing the coating film irradiated with the radiation in the step (2), and (4) a step of heating the coating film developed in the step (3). In this method, by using the above-described positive-type radiation-sensitive resin composition having excellent radiation sensitivity, a pattern is formed by radiation-sensitive exposure, development, and heating, whereby a fine and delicate pattern can be easily formed. Interlayer insulating film. The interlayer insulating film thus formed is excellent in heat resistance, solvent resistance, low dielectric property, light transmittance, light resistance, and dry etching resistance. Further, such an interlayer insulating film can be widely used for electronic components such as a magnetic head element, an integrated circuit element, and a solid-state imaging element typified by a TFT type liquid crystal display element. -9- 201122728 The positive-type radiation-sensitive resin composition of the present invention has high radiation sensitivity and has a development margin (developing a good pattern shape even in the case of ultra-optimal development time) in the developing step (development) High adhesion in the step). Further, the positive-type radiation-sensitive resin composition ' can form an interlayer insulating film of an electronic member excellent in heat resistance, solvent resistance, low dielectric property, light transmittance, light resistance, and dry etching resistance. [Embodiment] The positive radiation sensitive resin composition of the present invention comprises [A] an alkali-soluble resin having a hindered amine structure and/or a hindered phenol structure, [B] 1,2-quinonediazide compound And other optional components ([C] a thermosensitive acid generating compound or a thermosensitive base generating compound, [D] a polymerizable compound having at least one ethylenically unsaturated double bond, etc.). [A] an alkali-soluble resin having a hindered amine structure and/or a hindered phenol structure. The alkali-soluble resin of the component [A] used in the positive-type radiation-sensitive resin composition contains a hindered amine structure and/or a hindered phenol structure. Further, the positive-type radiation-sensitive resin composition containing the component is not particularly limited as long as it is soluble in the alkali developer used in the development treatment step. The alkali-soluble resin as the component [A] is preferably an alkali-soluble resin having a hindered amine structure and/or a hindered phenol structure and having a carboxyl group or a carboxylic anhydride group. Further, the alkali-soluble resin as the component [A] is particularly preferably one selected from the group consisting of an unsaturated carboxylic acid or an unsaturated carboxylic anhydride (hereinafter sometimes referred to as "compound (al)"). The above monomer and (a2) include one or more selected from the group consisting of a compound represented by the above formula-10-201122728 (1), a compound represented by the above formula (2), or a compound represented by the above formula (). A copolymer obtained by a monomer which is sometimes referred to as "compound (a2)"). Such an alkali-soluble resin (hereinafter sometimes referred to as a copolymer [A]) can be obtained by using a monomer containing the compounds (al) and (a2) in the presence of a polymerization initiator in a solvent, a radical Manufactured by polymerization. In addition, as the alkali-soluble resin [A], an (a3) epoxy group-containing unsaturated compound (hereinafter sometimes referred to as "compound" may be used in addition to the above compounds (al) and (a2). The copolymer [A] obtained from the monomer of a3)"). Further, as the alkali-soluble resin [A], a copolymer [A] obtained by combining the compounds (al), (a2) and (a3) with the compound (a4), wherein the compound (a4) is contained Unsaturated compound other than compound @ monomer. The compound (al) used to obtain the copolymer [A] is an unsaturated carboxylic acid having a radical polymerizable property or an unsaturated carboxylic anhydride. Specific examples of the compound (a) include a monocarboxylic acid, a dicarboxylic acid, an anhydride of a dicarboxylic acid, and a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid, in two A mono(meth)acrylate having a polymer having a mercapto group and a hydroxyl group at the terminal, a polycyclic compound having a carboxyl group, an anhydride thereof, and the like. Specific examples of these compounds (a 1 ) can be exemplified as: monodecanoic acid is an alkenoic acid 'methyl propylene citrate, crotonic acid, etc.; as a diterpene carboxylic acid is maleic acid, fumaric acid, and lemon Anhydrous acid, mesaconic acid, itaconic acid, etc.; -11- 201122728 An anhydride of a dicarboxylic acid is an anhydride of a compound exemplified as the above dicarboxylic acid; and a mono[(meth)acryl hydrazine as a polyvalent carboxylic acid; The oxyalkyl]ester is succinic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, phthalic acid mono [2_(methyl) propylene oxiranyl ethyl ester], etc.; The mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at the terminal is ω-carboxypolycaprolactone mono(meth)acrylate or the like; and the polycyclic compound having a carboxyl group and an anhydride thereof are 5-carboxybicyclo[ 2.2.1] Hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]heptan-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-ethyl Bicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like. Among these compounds (al), it is preferred to use an anhydride of a monocarboxylic acid or a dicarboxylic acid. From the viewpoints of copolymerization reactivity, solubility to an aqueous alkaline solution, and ease of availability, it is particularly preferred to use acrylic acid, methyl acrylate, and maleic anhydride. These compounds (a 1) may be used alone or in combination of two or more. The copolymer [A] is preferably a repeating unit derived from the compound (al) in an amount of 5 to 40% by mass, particularly preferably 5 to 25% by mass, based on the total of the repeating units constituting the copolymer [A]. By allowing the repeating unit derived from the compound (ai) in the copolymer [A] to be in the range of 5 to 40% by mass, the solubility of the copolymer in the aqueous alkaline solution can be optimized during the development step. The compound (a2) for obtaining the copolymer [A] is at least one selected from the group consisting of the compound represented by the above formula (1), the compound represented by the above formula (2) or the compound represented by the above formula (3). 201122728 A preferred specific example of the compound represented by the above formula (1) is exemplified by (meth)acrylic acid, 2,2,6,6-tetramethyl-4-piperidinyl vinegar, (methyl Acetone acid (1,2,2,6,6-pentamethylindole D-butyl) vinegar, (methyl) propyl-provenic acid (1-ethyl-2,2,6,6-tetramethylpiperate) () vinegar '(methyl)propionic acid (丨·n-propyl-2,2,6,6-tetramethylpiperidin-4-yl) ester, (meth)acrylic acid (1-isopropyl) Base-2,2,6,6-tetramethylpiperazinyl ester, (meth)acrylic acid (1-n-butyl-2,2,6,6-tetramethylpiperidyl) vinegar, (methyl)acrylic acid (1-isobutyl-2,2,6,6-tetramethylpiperidine-4-yl) vinegar, (methyl) propyl acid tert-butyl-2,2, 6,6-Tetramethylpiperazole_4_yl) vinegar, methyl propyl phenyl propyl)-2,2,6,6-tetramethylpiperidin-4-yl] ester and the like. Among these, 'excellent is (meth)acrylic acid-2,2,6,6-tetramethyl-4-piperidyl vinegar, (meth)acrylic acid (1,2,2,6) , 6-pentamethylpiperidine _4_yl) ester. Preferable specific examples of the compound represented by the above formula (2) include 2-tris-butyl-5-methyl·4·vinylphenol and 2·3 pentyl-5-methyl-4. _Ethyl phenyl hydrazine, 2 - butyl butyl-5-ethyl-4-ethyl basal hydrazine, 2,5-di-tertiary butyl-4-vinyl phenylhydrazine, 2 _ tertiary butyl 5-5-methyl-indole benzophenone, 2-3-tert-butyl-5-ethyl-4-isopropenylphenol, 2,5-di-tertiary butyl-4-isopropyl Benzoic acid, 2_2-butyl-5-methyl-4-(methyl)propancanoxybenzoquinone, 2-3-tert-butyl-5-ethyl-4-(methyl)propenyloxy Phenol, 25-di-secondary butyl-4.-(.methyl)propane oxime oxybenzoquinone, and the like. Preferable specific examples of the compound represented by the above formula (3) include 2-tertiary butyl-6-(>tris-butyl-2-indan-5-methylbenzyl)-4 -Methylphenyl (meth) decenoate, transmethyl-3,5-di-tert-butylbenzene 201122728-based ethyl]-4,6·di-triamylphenyl (methyl) Acrylate, benzyl- 3,5-di-tri-pentylphenyl)ethyl]- 4,6-di-tri-pentylphenyl (meth)propionate, and the like. The compounds represented by the formulae (1) to (3) specifically exemplified herein are preferably improved from the copolymerization reactivity with other compounds and the light resistance of the obtained cured film. As the compound (a2), the compounds represented by the above formulas (1) to (3) may be used alone or in combination of two or more. The copolymer [A] is preferably contained in an amount of from 1 to 60% by mass, particularly preferably from 5 to 50% by weight, based on the total amount of the repeating unit constituting the copolymer [A], from the repeating unit derived from the compound (a2). In the copolymer [A], the light resistance of the obtained interlayer insulating film can be sufficiently ensured by making the repeating unit derived from the compound (a2) 1% by mass or more. On the other hand, when the repeating unit is 60% by mass or less, the transparency and heat resistance of the obtained interlayer insulating film can be prevented from being lowered. The compound (a3) used to obtain the copolymer [A] is an unsaturated compound containing an epoxy group having a radical polymerizability. The epoxy group here may, for example, be an oxiranyl group (1,2-epoxy structure) or an propylene oxide group (1,3-epoxy structure). Specific examples of the unsaturated compound having an oxirane group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-n-propyl acrylate glycidyl ester. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, A 6,7-epoxyheptyl acrylate, α-ethyl acrylate·6,7-epoxyheptyl ester, -14- 201122728 o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidol Ethyl ether 'p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like. Among these unsaturated compounds having an oxiranyl group, it is preferred to use glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, ortho-ethylene from the viewpoint of improving copolymerization reactivity. Alkyl benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like. Further, 'specific examples of the unsaturated compound having an oxypropylene group' may be exemplified by 3-(acryloxymethyl) propylene oxide and 3-(acryloxymethyl)-2-methyl ring, respectively. Oxypropane, 3-(propylene methoxymethyl)-3-ethyl propylene oxide, 3-(acryloxymethyl)-2-phenyl propylene oxide, 3-(2-propenyloxyl) Ethyl) propylene oxide, 3-(2-propenyloxyethyl)-2-ethyl propylene oxide, 3-(2-propyleneoxyethyl)-3-ethyl propylene oxide, 3 -(2-propenyloxyethyl)-2-phenyl propylene oxide, 3-(methacryloxymethyl) propylene oxide, 3-(methacryloxymethyl)-2 -methyl propylene oxide, 3_(methacryloxymethyl)-3-ethyl propylene oxide, 3-(methacryloxymethyl)-2-phenyl propylene oxide, 3- (2-methacryloxyethyl) propylene oxide, 3-(2-methylpropenyloxyethyl)-2-ethyl propylene oxide, 3-(2-methylpropenyloxyl) Ethyl)-3-ethyl propylene oxide, 3-(2-methylpropenyloxyethyl)-2-phenyl propylene oxide, and the like. These compounds (a3) can be used singly or in combination. The copolymer [A] is preferably contained in an amount of from 1 to 80% by mass, particularly preferably from 30 to 80% by mass, based on the total amount of the repeating unit constituting the copolymer [A], from the compound (a3) derived repeating single 201122728 yuan. . In the copolymer [A], the heat resistance and solvent resistance of the obtained interlayer insulating film can be further improved by making the repeating unit 10 to 80% by mass. The compound (a4) is not particularly limited as long as it is an unsaturated compound having a radical polymerizable property other than the above compounds (al), (a2) and (a3). Examples of the compound (a4) include a chain alkyl methacrylate, a cyclic alkyl methacrylate, a methacrylate having a hydroxyl group, a cyclic alkyl acrylate, and an aryl methacrylate. , aryl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran a skeleton, a pyran skeleton, an unsaturated compound of a skeleton represented by the following formula (4), or a phenolic hydroxyl group-containing unsaturated compound represented by the following formula (5) (however, in addition to the above formulas (2) and (3) Other than the compounds shown), as well as other unsaturated compounds.

In the formula (4), R19 is a hydrogen atom or a methyl group, and p is an integer of 2 to 1 Å. R20 / H2C=C\

B

• 16-201122728 In the formula (5), R2G is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R21 to R25 are the same or different and are a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. B is a single bond, -COO- or -CONH-, q is an integer of 〇~3' wherein at least one of R21 to R25 is a hydroxyl group, and the substituent adjacent to the hydroxyl group is not a tertiary butyl group as a compound (a4) Specific examples of the methacrylic acid chain alkyl ester are methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, and methyl group. Tributyl acrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, methacrylate n-octadecane a cyclic alkyl ester of methacrylic acid is cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0''6] fluoren-8-yl methacrylate, Tricyclo [0.4.1.02'6]癸-8·yloxyethyl methacrylate, isophorone methacrylate The methacrylate having a hydroxyl group is hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4·hydroxybutyl methacrylate, and Ethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methylpropenyloxyethyl glycoside, 4-hydroxyphenyl methacrylate, etc.; The alkyl ester is cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.02'6]non-8-yl acrylate, tricyclo[5 ·2.1.02,6]癸_8 _ ethoxyethyl ester 'isophorone acrylate, etc.; 201122728 aryl methacrylate is phenyl methacrylate, benzyl methacrylate, etc.; as aryl acrylate is phenyl acrylate Benzyl acrylate or the like; as the unsaturated dicarboxylic acid diester is diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; as a bicyclic unsaturated compound is a bicyclic ring [2.2 .1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo [2.2.1] Geng-2- 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-tris-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tertiarybutoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5, 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, 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-ethylbicyclo[2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; as a maleimide compound is N-phenylmaleimide, N- Cyclohexylmaleimide, N-benzylmaleimide, Ν-(4.hydroxyphenyl)maleimine, Ν-(4.hydroxybenzyl)maleimide, hydrazine- Amber 醯imino-3-maleimide benzoate, Ν-amber 醯imino-4_马醯iminobutyrate, Ν-瑭 醯 醯 胺 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 醯 醯 醯 醯 -3- ( ( ( ( - aridinyl) maleimine, etc.; 201122728 As unsaturated aromatic compounds are styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy Styrene or the like; conjugated diene is 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.; as an unsaturated compound containing a tetrahydrofuran skeleton ( Methyl)tetrahydrofurfuryl acrylate, 2-methylpropenyloxy-tetrahydrofurfuryl propionate, 3-(meth) propylene decyloxytetrahydrofuran-2-one, etc.; as an unsaturated group containing a furan skeleton The compound is 2-methyl-5-(3-furyl)-1-penten-3-one, decyl (meth)acrylate, 1-furan-2-but-3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)-2-methyl-1.hexen-3-one, 6-furan- 2-yl-hex-1-en-3-one, 2-furan-2-yl.-1-methyl-ethyl acrylate, 6-(2-carboyl)-6-methyl-1 -hepten-3-one, etc. As an unsaturated compound containing a tetrahydropyran skeleton, it is methyl (tetrahydropyran-2-yl)methylpropanoate, 2,6-dimethyl-8-(tetrahydropyrene-pyran-2_氧基oxy)-oct-1-ene-3·one, 2-hydropyran-2-yl methacrylate, 1-(tetrahydropyran-2-oxy)-butyl-3-ene 2-ketone or the like; as an unsaturated compound containing a pyran skeleton, 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyran, 4 -(1,5-dioxa-6-oxo-7-octyl)-6-methyl-2-3⁄4 aryl; etc.; as an unsaturated compound containing a skeleton represented by the above formula (4), it is a poly Ethylene glycol (n=2 to 10) mono(meth)acrylate, polypropylene glycol (n=2~l) mono(meth)acrylate, and the like. In addition, as the unsaturated compound containing a phenol skeleton, the compound represented by the above formula (5) is represented by the following formulas (6) to (10), based on the definitions of B and q. Compounds, etc. R20

(6) In the formula (6), r is an integer of 1 to 3, and the definitions of R2G, R21, R22, R23, R24 and R2 5 are the same as defined in the above formula (5).

In the formula (7), the definitions of R2G, R21, R22, R23, R24 and R25 are the same as defined in the above formula (5). -20- 201122728 R20

Ο

In the formula (8), 's is an integer of 1 to 3, and the definitions of R20, R21, R22, R23, R24 and R25 are the same as defined in the above formula (5).

The definitions of 'R2G, R21, R22, R23, R24 and R25 in the formula (9) are the same as defined in the above formula (5).

-2 1- 201122728 In equation (10), R2. The definitions of 'R21, R22, R23, R24 and R25 are the same as defined in the above formula (5). Examples of the other unsaturated compound include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate. In the examples of the compound (a4), a chain alkyl ester of methacrylic acid, a cyclic alkyl methacrylate, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, or the like is preferable. The pyran skeleton, the unsaturated compound of the skeleton represented by the above formula (4), the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (5), the unsaturated aromatic compound, and the cyclic alkyl acrylate. Among these, from the viewpoints of copolymerization reactivity and solubility in an aqueous alkaline solution, styrene, butyl methacrylate, and trimethyl methacrylate [5.2.1.02'6] oxime are particularly preferred. -8-yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydroanthracene (meth)acrylate Base ester, polyethylene glycol (η = 2~10) mono(meth)acrylate, 3-(meth)acryloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene. Preferable specific examples of the respective constituent components of the copolymer [Α] include methacrylic acid/trimethyl methacrylate [5.2.1.02'6] fluoren-8-yl ester/2-methylcyclohexyl acrylate. /glycidyl methacrylate / 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate, methacrylic acid / glycidyl methacrylate / Ν-cyclohexylmalay醯imino/3-(2-methylpropenyloxyethyl)-22- 201122728 • Propylene oxide/2,5-di-tert-butyl-4-isopropenylphenol, styrene/methyl Acrylic acid/glycidyl methacrylate/tricyclomethacrylate [5.2.1.02'6] 癸-8-yl ester/2-tertiary butyl _6_(3_tri-butyl-2.hydroxy-5- Methylbenzyl)-4-methylphenyl (meth) acrylate, methacrylic acid/trimethyl methacrylate [5.2.1. 02'6] 癸-8-yl ester / tetrahydroanthracene methacrylate Glycol/glycidyl methacrylate/(meth)acrylic acid 2,2,6,6-tetramethyl-4-piperidyl ester, methacrylic acid/methacrylic acid tricyclic [5.2.1.02,6 ]癸-8-yl ester/tetrahydrofurfuryl methacrylate/glycidyl methacrylate/2,5-di-tertiary butyl-4-iso Alkenylphenol, methacrylic acid/trimethyl methacrylate [5.2.1.0''6] fluoren-8-yl ester / tetrahydrofurfuryl methacrylate / methyl propyl oxalate / 2 - tributyl -6-(3-tris-pentyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl (meth) acrylate, methacrylic acid/methacrylic acid tricyclo[5.2.1.02 '6] 癸-8-yl ester / tetrahydrofurfuryl methacrylate / methyl propyl. Polyglycidyl acrylate / 2-tert-butyl - 6-(3-tert-butyl-2-hydroxy- 5-methylbenzyl)-4-methylphenyl (meth) acrylate. These compounds (a4) can be used individually or in combination of 2 or more types. The copolymer [A] is preferably a derivative repeating unit derived from the compound (a4) in an amount of 0 to 60% by mass, particularly preferably 5 to 50% by mass based on the total of the repeating units constituting the copolymer [A]. In the copolymer [A], by reducing the amount of the repeating unit to 60% by mass or less, deterioration of developability of the positive-type radiation-sensitive resin composition can be suppressed. 6 Copolymer [A] by GPC (gel) The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the permeation chromatography method is preferably -23 to 201122728 2x10 3 to 1 x 10 5 ' more preferably 5 x 10 3 to 5 χ 104 β by making the Mw of the copolymer [A] When the ratio is 2x10 or more, the development margin of the positive-type radiation-sensitive resin composition can be improved to suppress the decrease in heat resistance of the obtained interlayer insulating film. On the other hand, by making the Mw of the copolymer [A] 1x10 or less, excellent radiation sensitivity and developability can be obtained. Further, the molecular weight distribution of the copolymer [A] (hereinafter referred to as "Mw/Mn") is preferably 5.0 or less, more preferably 3.0 or less. By setting the M w/M η of the copolymer [A] to 5.0 or less, it is possible to ensure good developability of the obtained interlayer insulating film. Examples of the solvent used in the polymerization reaction for producing the copolymer [Α] include diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate. , propylene glycol monoalkyl ether propionate, ketones, other esters, and the like. Examples of the solvent include, as the diethylene glycol dialkyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and the like; The dipropylene glycol dialkyl ether is, for example, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether or the like; as the propylene glycol monoalkyl ether is, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.: as propylene glycol monoalkyl ether acetate is, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Ester and the like: as the propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc. ; -24- 201122728 As a ketone, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.; as other esters, for example, methyl acetate, ethyl acetate, acetic acid Propyl ester, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3 -methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-propyl propyl propionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methoxyacetate Ester, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate , methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, Butyl butyloxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-B Methyl oxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butyl Ethyl oxypropionate, propyl 2-butoxypropionate, dibutyl 2-butoxypropionate Ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-methoxypropionic acid Ester, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxypropionic acid Ester, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Ester, butyl 3-butoxypropionate, and the like. -25- 201122728 Among these solvents, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, diol diol monoalkyl ether acetate, and other esters are preferred. To use diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 3-methoxypropionic acid Methyl ester. As the polymerization initiator used for the production of the copolymer [A], those known as general radical polymerization initiators can be used. Specific examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2,2'-couple. An azo compound such as nitrogen di-(4-methoxy-2,4-dimethylvaleronitrile). In the production of the copolymer [A], a molecular weight regulator for adjusting the molecular weight can be used. Specific examples of the molecular weight modifier include mercaptan such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl mercaptan, and mercaptoacetic acid; and dimethyl sulfide; Xanthate such as xanthate or diisopropyl xanthate; tertylene, α-methylstyrene dimer, and the like. [B] 1,2-quinonediazide compound The [Β] component used in the positive radiation sensitive resin composition is a 1,2-quinonediazide compound which generates a carboxylic acid by irradiation with radiation. As the 1,2-anthracene azide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and a 1,2-naphthoquinonediazidesulfonium halide can be used. Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other mother nucleus. -26- 201122728 As such a mother nucleus, as the trihydroxybenzophenone, for example, 2,3,4-trihydroxydibenzopyrene, 2,4,6-trihydroxybenzophenone, etc.; Tetrahydroxybenzophenone is, for example, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'- Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybiphenyl a ketone or the like; as the pentahydroxybenzophenone, for example, 2,3,4,2',6'-pentahydroxybenzophenone or the like; as the hexahydroxybenzophenone is, for example, 2, 4, 6, 3', 4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; as (polyhydroxyphenyl)alkane is, for example, two (2, 4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, di(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_ Methyl ethyl]phenyl]ethylidene]biphenyl fluorene, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'- Tetramethyl-1,1'-spirobifluorene-5,6,7,5',6,7,-hexanol, 2,2,4-trimethyl-7,2,,4'-three Hydroxyflavan, etc.; as other parent cores are, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 2-[di{ (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-27- 201122728 'yl)-1-methylethyl}- 4,6-Dihydroxyphenyl)-1-methylethyl)benzene, 4,6-di{1-(4-hydroxyphenyl)-1-methylethyl 1,3-dihydroxybenzene. Among these cores, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl)ethane, 4,4'-[1- [4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]biphenol. Further, as the 1,2-naphthoquinonediazidesulfonium halide, 1,2-naphthoquinonediazidesulfonium chloride is preferred. Specific examples of the 1,2-naphthoquinonediazidesulfonium chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonate. chlorine. Among these, it is particularly preferred to use 1,2-naphthoquinonediazide-5-sulfonyl chloride. In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) and a 1,2-naphthoquinonediazidesulfonium halide, the equivalent amount of the OH group in the phenolic compound or the alcoholic compound can be used. Preferably, it is 3 0 to 8 5 mol %, more preferably 50 to 70 m 〇 1% of 1,2-naphthoquinonediazide sulfonium halide. The condensation reaction can be carried out by a known method. Further, as the 1,2?-quinonediazide compound, it is also suitable to use 1,2-naphthoquinonediazidesulfonate oxime which converts the ester bond of the above-exemplified parent core to a guanamine bond, for example, 2, 3 4-trihydroxydibenzopyrene-1,2.naphthoquinonediazide-4-sulfonic acid decylamine, etc. These [Β] components may be used singly or in combination of two or more. The proportion of the [Β] component in the positive-acting radiation-linear resin composition is preferably from 5 to 100 parts by mass, more preferably from 1 to 50 parts by mass, per 100 parts by mass of the copolymer [Α]. By using the ratio of the [Β] component in the range of 5 to 100 parts by mass, the difference between the solubility of the portion irradiated with the radiation -28-201122728 and the portion of the unirradiated portion to the alkaline aqueous solution as the developer is large, and the developability is good, and The obtained interlayer insulating film was also excellent in heat resistance and solvent resistance. Other optional components The positive-type radiation-sensitive resin composition may contain a [C] sensible acid-generating compound or may be contained as needed, in addition to the above-mentioned [A] and [B] components, within a range not impairing the intended effect. A thermosensitive base generating compound, [D] a polymerizable compound having at least one ethylenically unsaturated double bond, [E] a surfactant, and [F] an adhesion aid. The thermosensitive acid generating compound or the thermosensitive base generating compound of the component [C] is defined as a compound which can release an acidic active material or an alkaline active material by heating. Such a heat-sensitive acid generating compound or a heat-sensitive base generating compound is added to the positive-type radiation-sensitive resin composition in order to improve the heat resistance or solvent resistance of the obtained interlayer insulating film. Examples of the thermosensitive acid-producing compound as the component [C] include a diphenylsulfonium salt, a triphenylsulfonium salt, and a key such as a phosphonium salt, a benzothiazole salt, an ammonium salt, a phosphonium salt, or a tetrahydrothiophene key salt. salt. Examples of the diphenylphosphonium salt include diphenyl-terminated tetrafluoroantimonate, diphenylsulfonium hexafluorophosphate, diphenylsulfonium hexafluoroarsenate, and diphenylsulfonium trifluoromethanesulfonic acid. Salt, diphenylphosphonium trifluoroacetate, diphenylphosphonium-p-toluenesulfonate, diphenylphosphonium butyl tris(2,6-difluorophenyl)borate, 4-methoxybenzene Base-phenylindole tetrafluoroborate, bis(4-tributylphenyl)phosphonium tetrafluoroborate, bis(4-tributylphenyl)iodohexafluoroarsenate, di(4_3) Ding-29- 201122728 'Phenylphenyl) fluorene triflate, bis(4-tributylphenyl)phosphonium trifluoride, bis(4-tributylphenyl) fluorene- P-toluenesulfonate, bis(4-tributylphenyl) camphorsulfonate, and the like. Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, triphenylsulfonium tetrafluoroborate, and triphenylsulfonium trifluoroacetate. Triphenylphosphonium-p-toluenesulfonate, triphenylsulfonylbutyltris(2,6-difluorophenyl)borate, and the like. Examples of the onium salt include an alkyl phosphonium salt, a benzyl phosphonium salt, a dibenzyl phosphonium salt, a substituted benzyl phosphonium salt, and the like. As these onium salts, they can be exemplified as follows: as a base vegetable salt, for example, 4-ethoxyphenyloxy-methyl vegetable hexafluoroantimonate, 4-ethyloxyphenyl dimethyl sulfonium hexafluoride Arsenate, dimethyl-4-(benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzhydryloxy)phenylphosphonium hexafluoroantimony Acid salt, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethyloxyphenylphosphonium hexafluoroantimonate And the benzyl sulfonium salt is, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, 4-ethylhydrazineoxy Phenylbenzyl methyl hydrazine hexafluoroantimonate, benzyl-4-methoxyphenylmethyl hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hydrazine Hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate Et al; -30- 201122728 as a guanidine sulfonium salt is, for example, dibenzyl _4· citrate, ylanggan, hexafluoro-indenyl-4-hydroxyphenyl Hexafluorophosphate phenyl dihydrazide "gasoline acid salt, bis... methyl group: ethoxylated acid salt, Μ 甘 Gan & 】 hexafluoroanthryl-3-chloro 4-Hydroxyphenylphosphonium hexafluoroarsenic acid pro, diyl-3-methyl-l-yl-5-t-butyl benzyl fluorene, fluoroanthracene 4-methoxy sigh 4-hydroxyphenylphosphonium hexafluorophosphate, etc.: as a substituted fluorenyl mirror salt is, for example, a p-chlorobenzyl group-methyl hexafluoroantimonate salt, and a sulfonate group. , prepared with methyl hydrazine /, fluoro-substituted henyl-4-pyridyl phenylmethyl hexafluoro-p-nitrophenyl-3-methyl 4p lys ran, and thiol-4-hydroxy Methyl hydrazine octafluoro decanoate, 3, 5 _ chloroindenyl _ 4 hydroxy phenyl methyl hexafluoro decanoate, o-chlorobenzyl-3-chloro-4-yl Phenylmethyl hydrazine hexafluoroantimonate, etc. As an example of the benzothiazole gun salt, 3 _ benzyl benzothiazepine hexahydroepide salt, 3-benzyl benzothiazole key 6 Fluorophosphate, 3_mercaptobenzothiazole gun tetrafluoroborate, 3 _(p-methoxybenzyl)benzothiazole key hexafluoroantimonic acid , 3-benzyl-2-methylthiobenzothiazole, hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazole, hexafluoroantimonate, etc. as tetrahydrothiophene salt As an example, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl). Hydrothienyl hexafluoro-n-butyl sulfonate, 1-(4-n-butoxynaphthalene-buyl). Tetrahydrothiophene-1,1,2,2-tetrafluoro-2-(norbornane) 2-yl)ethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(5-tris-butoxy ortho-oxybicyclo[2.2.1 ]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1_(4_ -31 - 201122728 n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(6 - Tert-butyloxycarbonyloxybicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4,7-dibutoxy- 1-naphthyl)tetrahydrothiophene trifluoromethanesulfonate and the like. Examples of such a sensible acid generating compound include SUNAID SI-L85, the same SI-L 1 1 0, the same SI - L 1 4 5, the same s ! _ L i 5 〇, and the same SI-L160 (three New chemical industry (stock) manufacturing) and so on. Among these heat-sensitive acid generating compounds, from the viewpoint of improving the heat resistance of the obtained interlayer insulating film, a triphenylsulfonium salt, a phosphonium salt, a benzothiazole salt and a tetrahydrothiophene key salt are preferably used. Among these, it is particularly preferred to use triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl _ 4-hydroxyphenylmethylphosphonium hexafluoroantimonate, 4-ethoxyethoxyphenylbenzylmethylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate Salt, 4_acetoxyphenylbenzylmethyl hexafluoroantimonate, 3-benzylbenzothiazole hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl hexafluorophosphate Phosphate, dibutoxy-naphthyl) tetrahydrothiophene trifluoromethanesulfonate. Examples of the thermosensitive base-forming compound as the component [C] include 2-nitrobenzylcyclohexylamino group. Formate, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, bis[[(2-nitrobenzyl) Alkyloxy]carbonyl]hexane-1,6-diamine, triphenylmethanol, hydrazino-aminomethylhydrazine hydroxy decylamine, 0-aminomethylhydrazine hydrazine, 4-(methylthiobenzene) Mercapto)-1-methyl-1-morpholinoethane' (4_picolinylbenzimidyl)·; _benzyl 4-dimethylaminopropane, 2-benzyl 2-dimethylamino-1- (4-substituted phenyl mirin) - -32-201122728 butanone, hexamine cobalt (ΠΙ) tris (phenylmethyl borate) and the like. Among the thermosensitive alkali generating compounds of the component [c], 2-nitrobenzylcyclohexyl carbazate and hydrazine-amine-based group are particularly preferable from the viewpoint of improving the heat resistance of the obtained interlayer insulating film. Mercaptohydroxyamine. The thermosensitive acid generating compound or the thermosensitive base generating compound of the component [C] may be used singly or in combination of two or more. The amount when the [C] component is used in the positive-type radiation-sensitive resin composition is preferably 〇.1 to 1 〇 by mass, more preferably 0.5 to 5 by mass based on 100 parts by mass of the copolymer [A]'. Share. By using the component [C] in a ratio of 〇.1 to 1 Å by mass, an interlayer insulating film having excellent heat resistance and solvent resistance can be formed. As the polymerizable compound having at least one ethylenically unsaturated double bond as the component [D], for example, a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) is preferably used. Acrylate and the like. Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth)acrylate, carbitol (meth)acrylate, isophorone (meth)acrylate, and (methyl). 3 - methoxybutyl acrylate, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate, and the like. As a commercial product of these monofunctional (meth)acrylate, for example, ARONIX ARONIX Mm, ARONIX M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-1 1 OS, KAYARAD TC-1 20S (above) , manufactured by Nippon Kayaku Co., Ltd.) VISCOAT158, VISCOAT2311 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.). -33- 201122728 Examples of the bifunctional (meth) acrylate include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-fluorene. Alcohol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, diphenoxyethanol quinone di(meth)acrylate, diphenoxyethanol Bis(di)(meth)acrylate and the like. As a commercial product of these bifunctional (meth)acrylate, for example, ARON IX M-210, ARONIXM-240, ARONIXM-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above, manufactured by Sakamoto Chemical Co., Ltd.), VISCOAT 260, VISCOAT 312, VISCOAT 3 3 5 HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tri(meth)acrylate, neopentyltriol tri(meth)acrylate, and tris((meth)acrylofluorene oxide. Ethyl ethyl) phosphate, neopentyltetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Examples of such a trifunctional or higher (meth) acrylate include ARONIXM-309, ARONIXM-400, ARONIX M-405, ARONIX M-450, ARONIX M-7 100, ARONIX M-803 0, and ARONIX. M-8060 (above, manufactured by East Asia Synthetic Co., Ltd.) 'KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30 'KAYARAD DPCA-60,

KAYARAD DPCA-120 (above, manufactured by Sakamoto Chemical Co., Ltd.), VISCOAT 295, VISCOAT 300, VISCOAT 360, VISCOAT GPT, VISCOAT 3PA, VISCOAT 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.). -34- 201122728 Among these (meth) acrylates, a trifunctional or higher (meth) acrylate is preferably used. Among these, trimethylolpropane tri(meth)acrylate, neopentyltetrakis(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are particularly preferable. These monofunctional, bifunctional or trifunctional or higher (meth) acrylates may be used singly or in combination. In the positive-type radiation-sensitive resin composition, the amount of the component [D] is preferably from 1 to 50 parts by mass, more preferably from 3 to 30% by mass based on 100 parts by mass of the copolymer [A]. Share. By using the ratio of the component [D] in an amount of from 1 to 50 parts by mass, the heat resistance and solvent resistance of the obtained interlayer insulating film can be further improved. In the positive-type radiation-sensitive resin composition, a surfactant as the component [E] can be used to further improve the coatability at the time of formation of a coating film. As a surfactant which is suitably used, a fluorine-containing surfactant, a polyoxyn surfactant, and a nonionic surfactant are mentioned. Examples of the fluorine-containing surfactant include 1,1,i,2-tetrafluorooctyl (1,1,2,2·tetrafluoropropyl)ether, 1,1,2,2- Tetrafluorooctylhexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro Fluoride such as pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether Ethylene ether; sodium perfluorododecylsulfonate; 1,1,2,2,8,8,9,9,1〇,1〇_decafluorododecane, 1,1,2, a fluoroalkane such as 2,3,3-hexafluorodecane; a sodium fluoro-based benzene sulfonate; a fluoroalkyl oxyalkyl ether; a iodinated fluorocarbon; a fluoroalkyl group; Polyoxyethylene ethers; perfluoroalkyl polyoxyl alcohols; perfluoroalkyl alkoxides; fluorine-containing alkyl esters. -35- 201122728 As a commercial product of these fluorine-containing surfactants, BM-1000, BM-1100 (above, BM Chemie), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183, MEGAFAC F 1 7 8 ' MEGAFAC F191, MEGAFAC F471 (above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), FLUORAD FC-170C, FC-171, FC-430, FC-43 1 (above, Sumitomo 3M (share) manufacturing), SURFLON S -112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145, SURFLON S- 3 82, SURFLON SC-101 'SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (manufactured by Asahi Glass Co., Ltd.), EFTOPEF301, EFTOP 303, EFTOP 352 (manufactured by Shinki Ueda Chemical Co., Ltd.), etc. As a specific example of a polyoxonated surfactant, it is commercially available. The trade name indicates that you can cite the DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray-Dow Corning) -Polyoxygen (manufactured by polyoxyl), TSF-4440 ' TSF-4300 ' TSF-4445 , TS F-4446, TSF-4460, TSF-4452 (above, GE Toshiba Polyoxane (manufactured by GE)). Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octylbenzene; Polyoxyethylene aryl ethers such as alkyl ethers and polyoxyethylene nonylphenyl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (methyl) Acrylic total -36- 201122728 Polymers, etc. As a representative product of the nonionic surfactant, POLYFLOW No. 57, 95 (manufactured by Seiko Chemical Co., Ltd.) can be cited. The surfactant of the component [E] may be used singly or in combination of two or more. The amount of the [E] component to be used in the positive-type radiation-sensitive resin composition is preferably 0.01 to 3 parts by mass, more preferably 〇.〇5, based on 1 part by mass of the copolymer [A]. ~ 2 parts by mass. By using the ratio of the component [E] in an amount of 0.01 to 3 parts by mass, it is possible to suppress uneven coating from occurring when a coating film is formed on a substrate. In the positive-type radiation-sensitive resin composition, an adhesion aid as the component [F] can be used to improve the adhesion between the obtained interlayer insulating film and the substrate. As such an adhesion aid, a functional decane coupling agent is preferably used. Examples of the functional decane coupling agent include a decane coupling agent having a reactive substituent such as a carboxyl group, a methyl propylene group, an isocyanate group or an epoxy group. Specific examples of the functional decane coupling agent include trimethoxymethyl sulfonyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethylene decyl decane, and ethylene. Trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. The adhesion aid of the component [F] may be used singly or in combination of two or more. The amount of the [F] component to be used in the positive-type radiation-sensitive resin composition is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, per 100 parts by mass of the copolymer [Α]. . When the amount of the adhesion aid of the component [F] is from 0.01 to 20 parts by mass, the adhesion between the interlayer insulating film and the substrate can be optimized. -37- 201122728 'Positive-type radiation-sensitive resin composition The positive-type radiation-sensitive resin composition of the present invention comprises the above-mentioned [A] and [B] components, and optional components ([C] to [F] The ingredients are prepared by uniformly mixing. Usually, the positive-type radiation-sensitive resin composition is preferably dissolved in a suitable solvent and stored and used in a solution state. For example, a positive-type radiation-sensitive resin composition in a solution state can be prepared by mixing the components [A] and [B] and optional components in a predetermined ratio in a solvent. The solvent used for preparing the positive-type radiation-sensitive resin composition is a compound which can uniformly dissolve the above-mentioned [A] and [B] components and optional components ([C] to [F] components), and does not There is no particular limitation on the reaction with each component. As such a solvent, the same solvent as the solvent exemplified for producing the solvent used for the copolymer [A] can be mentioned. In such a solvent, it is preferred to use an alcohol, a glycol ether, or an ethylene glycol monoalkyl ether B from the viewpoints of solubility of each component, non-reactivity of each component, easiness of formation of a coating film, and the like. Acid esters, esters, diethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate. Among these solvents, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred. , diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , 2_ or 3-methoxypropionic acid methyl ester, 2- or 3-ethoxypropionic acid ethyl ester. Further, in order to improve the in-plane uniformity of the formed coating film, a high boiling point solvent may be used together with the above solvent. Examples of the high-boiling solvent that can be used include N-methylformamide, N,N-dimethylformamide, N-methylformamide, and N-methylacetamide. n,N-Dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, citric acid, 1- Octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl fumed fiber Agent acetate and the like. Among these high boiling solvents, decyl-methylpyrrolidone, γ-butyrolactone, hydrazine, hydrazine-dimethylacetamide are preferred. When the high-boiling solvent is used as the solvent of the positive-type radioactive resin composition, the amount of the high-boiling solvent is 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass based on the total amount of the solvent. % the following. When the use ratio of the high boiling point solvent is 50% by mass or less, it is possible to suppress the decrease in the radiation sensitivity while improving the film thickness uniformity of the coating film. When the positive-type radiation-sensitive resin composition is prepared in a solution state, the ratio of the components other than the solvent in the solution (that is, the total amount of the above [Α] and [Β] components, and other optional components) may be It is arbitrarily set to be preferably from 5. to 50% by mass, more preferably from 10 to 40% by mass, even more preferably from 15 to 35% by mass, depending on the purpose of use and the desired film thickness. The solution of the positive-type radiation-sensitive resin composition thus prepared can be filtered using a micropore filter having a pore diameter of about 0.2 μm, etc., using -39-201122728' formation of an interlayer insulating film, followed by using the positive-type radiation linearity. The resin composition 'described method of forming the interlayer insulating film of the present invention will be described. The method includes the following steps described in the following order. (1) a step of forming a coating film of the positive-sensitive radiation-sensitive resin composition of the present invention on a substrate, (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation, and (3) The step of developing the coating film irradiated with radiation in the step (2), and (4) the step of heating the coating film developed in the step (3). (1) Step of Forming Coating Film of Positive Radiation-Sensitive Resin Composition on Substrate In the step (1) above, after applying a solution of the positive-type radiation-sensitive resin composition of the present invention to the surface of the substrate, It is preferred to remove the solvent by prebaking to form a coating film of the positive radiation sensitive resin composition. Examples of the type of the substrate that can be used include a glass substrate, a tantalum wafer, and a substrate on which various metals are formed on the surface. The coating method of the composition solution is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet method can be employed. Among these coating methods, a spin coating method or a slit die coating method is preferred. The prebaking conditions may vary depending on the type of the various components, the ratio of use, and the like, and may be, for example, from 60 to 110 - 40 to 201122728 ° C for about 30 seconds to 15 minutes. The film thickness of the formed coating film is not preferably 2 to 5 μm, for example, after baking. (2) Step of irradiating at least a part of the coating film with radiation In the step (2), the formed coating film is irradiated with radiation by a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like. Examples of the ultraviolet light include a g line (wavelength of 4 6 nm), an i line (wavelength of 3 65 nm), and the like. Examples of the far ultraviolet rays include a KrF excimer laser or the like. Examples of the X-rays include radiation of a synchrotron and the like. Examples of the charged particle beam include an electron beam and the like. Among these radiations, ultraviolet rays, particularly preferably ultraviolet rays, and radiation containing g-line and/or i-line are preferable as the exposure amount, preferably 50 to 1, 50 (U/m2). (3) The development step is (3) In the developing step, the coating film irradiated with radiation in the step (2) is developed to remove a portion irradiated with radiation, and a desired pattern can be formed. As the developing solution used in the developing treatment, sodium hydroxide or hydrogen can be used. Potassium oxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine 'triethylamine, methyldiethyl An aqueous solution of an alkali (basic compound) such as an amine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide or hydroxyhydrogen: tetraethylammonium. Further, methanol or ethanol may be appropriately added to the above alkaline aqueous solution. An aqueous solution formed by a water-soluble organic solvent or a surfactant, or a small amount of an aqueous alkaline solution containing various organic solvents containing a radiation-sensitive radiation-sensitive resin composition is used as a developing solution for the 201122728. Further, as a developing method, it can be utilized. For example, a suitable method such as a liquid-filling method, a dipping method, a shaking dipping method, a shower method, etc. The development time varies depending on the composition of the radiation-sensitive resin composition, and may be, for example, 30 to 120 seconds. When the development time exceeds the optimum 値20 to 25 seconds, the formed pattern is peeled off, so the development time must be strictly controlled. On the other hand, the positive-type radiation-sensitive resin composition of the present invention Since the development margin is high, even if the optimum development time is exceeded for more than 30 seconds, a good pattern can be formed, which has a great advantage in manufacturing yield. (4) Heating step followed by 'in (4) heating step In the developing step (3), it is preferred that the patterned film is subjected to a rinsing treatment by running water washing, and then preferably, the entire surface is irradiated with radiation (post exposure) by a high pressure mercury lamp or the like. The 1,2-quinonediazide compound remaining in the film is subjected to decomposition treatment. Then, the film is subjected to heat treatment using a heating device such as a hot plate or an oven (after The baking treatment is performed to cure the film. The exposure amount of the post-exposure is preferably about 2,000 to 5, 〇〇〇j/m2, and the firing temperature in the curing treatment is, for example, 12 Å to 250 °C. The heating time varies depending on the type of the heating device, for example, 5 to 30 minutes when heat treatment is performed on a hot plate, and 30 to 90 minutes when heat treatment is performed in an oven. In this case, it may be used twice or more. The step-by-step baking method of the heating step, etc., can form a pattern-like film corresponding to the target interlayer insulating film on the surface of the substrate. -42- 201122728 _ The interlayer insulating film formed as described above is heat resistant and resistant as shown in the later-described embodiment. Solvent, low dielectric, light transmittance, light resistance, and dry etching resistance are excellent. When an electronic component such as a liquid crystal display element is produced using such an interlayer insulating film, dry etching can be performed as needed. Examples of the etching gas used in the dry etching step include ruthenium 2, N2, CF4, SiF6 and the like. As the etching method, there are two types of reactive dry etching of an ion impact substrate and plasma dry etching of a radical impact substrate by applying a voltage between a substrate on which an interlayer insulating film pattern is formed and an electrode. The kind of these gases and the dry etching method are appropriately selected depending on the type of the underlying metal of the interlayer insulating film. As described above, the interlayer insulating thickness formed by the positive-type radiation-sensitive resin composition of the present invention is excellent in resistance to dry etching. EXAMPLES Hereinafter, the present invention will be specifically described by way of Synthesis Examples and Examples, but the present invention is not limited by the following examples. Hereinafter, the weight average molecular weight (Mw) and the number average molecular weight (?η) of the copolymer were measured by gel permeation chromatography (GPC) under the following conditions. Measuring device: "HLC8220 System" (manufactured by Tosoh Co., Ltd.) Separation column: 4 TSKgel GMHhr-N (manufactured by Tosoh Corporation) series connection

Column temperature: 40 °C Elution solvent: tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 m L /min -43 - 201122728 'Sample concentration: 1.0% by mass Sample injection amount: ΙΟΟμπι Device: Differential Refractometer Standard Material: Synthesis Example and Comparative Synthesis Example of Monodisperse Polystyrene Copolymer [Synthesis Example 7 In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azo was added. Di(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Then, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo[5·2·1.02'6]non-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, and 45 parts by mass of methyl group were added. Glycidyl acrylate, 5 parts by mass of 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 3 parts by mass of α-methylstyrene dimer, which started slowly after nitrogen replacement Stir. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [Α-1]. The copolymer [A-1] had a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 and a molecular weight distribution (Mw/Mn) of 2 to 3. Further, the solid content concentration of the obtained polymer solution (the ratio of the quality of the copolymer contained in the polymer solution to the total mass of the polymer solution, the same applies hereinafter) was 33.3% by mass. [Synthesis Example 2] In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2,·azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol B were added. Methyl ether. Then, 18 parts by mass of methacrylic acid, 2 parts by mass of methacrylic acid-44-201122728 acid tricyclo[5.2.1.02,6]non-8-yl ester, 12 parts by mass of tetrahydrofurfuryl methacrylate, 45 were added. Parts by mass of glycidyl methacrylate, 5 parts by mass of 2,5-di-tert-butyl-4-isopropenylphenol and 3 parts by mass of ct-methylstyrene dimer, nitrogen, after replacement, start slowly The temperature of the solution was raised to 7 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The copolymer [A-2] had a polystyrene-equivalent weight average molecular weight (Mw) of 10,200 and a molecular weight distribution (Mw/Mn) of 2.2. Further, the solid content concentration of the obtained polymer solution was 33.5% by mass. [Synthesis Example 3] In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl group were added. Methyl ether. Then, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo[5.2.1.〇2'6]癸-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, and 45 parts by mass are added. Methyl propylene: acid glycidyl ester, 5 parts by mass of 2-tert-butyl- 6-(3-tert-amyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate After 3 parts by mass of the α-methylstyrene dimer, after nitrogen substitution, slow stirring was started. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A·3]. The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer [A-3] was 9,900, and the molecular weight distribution (Mw/Mn) was 2.2. Further, the solid content concentration of the obtained polymer solution was 33.1% by mass. -45- 201122728 ' [Synthesis Example 4] Adding 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass in a flask equipped with a condenser and a stirrer Ethylene glycol ethyl methyl ether. Then, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo[5.2.1.02,6]non-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, and 45 parts by mass of methacrylic acid shrinkage were added. Glyceride, 2 parts by mass of 2-tris-butyl-6-(3-tert-pentyl-2-hydroxy-5-methylbenzyl)-4.methylphenyl acrylate, 3 parts by mass of methacrylic acid - 2,2,6,6-tetramethyl-4·piperidinyl ester and 3 parts by mass of α-methylstyrene dimer' after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 °, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-4]. The copolymer [A-4] had a polystyrene-equivalent weight average molecular weight (Mw) of 9,900 and a molecular weight distribution (Mw/Mn) of 2.2. Further, the obtained polymer solution had a solid content concentration of 32.8% by mass. [Comparative Synthesis Example 1] In a flask equipped with a condenser and a stirrer, '7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol B were added. Methyl ether. Then, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo [5.2.1.Ό2,6]癸-8-yl methacrylate, 12 parts by mass of tetrahydrofurfuryl methacrylate, and 45 parts by mass of methyl group were added. Glycidyl acrylate, 5 parts by mass of methyl methacrylate and 3 parts by mass of α-methylstyrene dimer. After nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [a-1]. The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer [a-1] was 9,900, and the molecular weight distribution -46 to 201122728 (Μ w/Mn) was 2.2. Further, the solid content concentration of the obtained polymer solution was 33.3% by mass. Preparation of a positive-type radiation-sensitive resin composition [Example 1] 100 parts by mass (solid content) of the copolymer [A-1] obtained in Synthesis Example 1 as the component [A], and 25 parts by mass as the component [B] 4,4'-[1-[4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]biphenol (1.0 mol) and 1,2-naphthalene a condensate (B-1) of quinonediazide-5-sulfonyl chloride (2.0 mol), and a mass ratio of 0" by mass of a polyoxonated surfactant as an [E] component (Toray-Dow Corning-Polyoxime ( "SH-28PA" manufactured by the company) and 0.1 parts by mass of γ-glycidoxypropyltrimethoxydecane as the component [F], dissolved in diethylene glycol ethyl methyl ether, and solid After the component concentration was 30% by mass, the solution (S-1) of the positive radiation sensitive resin composition was prepared by filtration through a membrane filter having a diameter of 0.2 μm. [Examples 2 to 4 and Comparative Example 1] Positive radiation was prepared in the same manner as in Example 1 except that the components and the components described in Table i were used as the [Α] component, the [Β] component, and other components. Solutions (S-2) to (S-4) and (s-1) of the resin composition. [Example 5] In addition to dissolving into diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate (quality ratio of 6 / 4) and solid content concentration of 20% by mass, and as [B] component a condensate of 20 parts by mass of ι, ι, ΐ-tris(p-hydroxyphenyl) ethene (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2_0 mol) -47- 201122728 A solution (S-5) of a positive radiation sensitive resin composition was prepared in the same manner as in Example 1 except for (B-2) [Examples 6 to 10 and Comparative Example 2] except as the [A] component, [B In the same manner as in Example 5, the solutions (S-6) to (S-10) and (s) of the positive radiation sensitive resin composition were prepared in the same manner as in Example 5 except for the components and other components described in Table 1. -2). In Table 1, the abbreviation of the component means the following compound. B-1 : 4,4'-[1-[4-[1-[4.hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]biphenol (1.0 mol) and 1, a condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol) Β·2: 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthalene Condensate of quinonediazide-5-sulfonyl chloride (2.0 mol) C-1: benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate D-1: trimethylolpropane triacrylate D -2: Dipentaerythritol hexaacrylate E-1: Polyoxonated surfactant ("SH-28PA" manufactured by Toray-Dow Corning-Polyoxime) F-1: γ-glycidol Evaluation of Properties of oxypropyltrimethoxydecane as Interlayer Insulation The positive-type radiation-sensitive resin composition prepared as above was used, and the properties of each of the interlayer insulating films were evaluated as follows. -48- 201122728 [radiation sensitivity of the positive-type radiation-sensitive resin composition, the above-mentioned compositions (S1) to (S-4) and (s-1) coated on the ruthenium substrate with respect to Examples 1 to 4 and Comparative Example 1 After prebaking for 2 minutes, a coating film 5 to 10 having a film thickness of 3. Ομηη, and a comparative example 2 were used, and a slot die applicator was used, and the coating (S-5) to (S-10), (s -2), pre-baked on a hot plate for 2 minutes under vacuum drying at 0.5 Torr to form a film having a film thickness of 3. Ομηη using a PLA-501F exposure 3 silver lamp manufactured by CANON Co., Ltd., having a size of 3.0 μm The line and the gap (1 〇: 1) cover, change the exposure time, after exposure, in a 4% by mass aqueous ammonium solution, by developing at 25 °C by liquid method 80, washing with ultrapure water for 1 minute. When dry, on a wafer, measure the amount of exposure of the line and gap (10: 1) that completely dissolves 3.0 μm. When the enthalpy is used as the radiation sensitivity, it is considered to be radiation sensitive when the enthalpy is 1,000 J / m 2 or less [the development margin S of the positive-type radiation-sensitive resin composition and the above [the positive-type radiation-sensitive resin composition] Evaluation] Similarly, a coating film was formed on the ruthenium substrate. Exposure of the radiation measured by the above-mentioned [Evaluation of Radiation Sensitivity] in the mask of the pattern of the line and the gap (1 〇: 1) of the PLA-501F exposure machine (Ultra-high pressure mercury lamp) manufactured by the user. The amount of exposure was measured in '0.4% by mass of hydric acid tetrachloride, and the developing time was changed at 25 ° C, and it was evaluated by a liquid-filling method.] Using a spin coater, a hot plate at 90 ° C. Regarding the examples, the above composition t was applied at 90 ° C. The resulting motor (the pattern of the ultra-high pressure water pattern is masked with tetramethyl hydroxy hydroxide for a second. Then, a pattern is formed. This gap pattern is shown in Table 1. The degree is good. The price] The radiation sensitivity is CANON. The film has a linear sensitivity of 値methylammonium solution on a 3 Ομιη t film. Then, it is washed with ultrapure water for 1 minute by -49-201122728, and dried. When formed on a wafer, the line width is 3. Ομιη The necessary development time is shown as optimum in Table 1. In addition, when the image is reimaged from the optimum development time, the time until the line pattern of 3.0 μm is peeled off, as the allowable range of the shadow time, is shown in Table 1. . The 値 is 30 and the development margin is good. [Evaluation of Solvent Resistance of Interlayer Insulating Film] A coating film was formed on the crucible substrate in the same manner as in the above [Evaluation of Discharge of the Positive Radiation Resin Composition]. Using the manufactured PLA-501F exposure machine (ultra-high pressure mercury lamp), the exposure was such that the cumulative irradiation amount was 3,000 J / m 2 , and the curing oven was heated at 2 2 ° C for 1 hour to obtain a cured curing. Film thickness (T 1 ) of the film. Then, the film thickness (t1) of the cured film was immersed in dimethyl sulfonium having a temperature controlled at 7 ° C for 20 minutes, and the alcohol {|tl-Tl|/Tl}xl00 caused by the immersion was calculated. %]. When the evaluation of the solvent resistance is 5% or less, it is considered that the solvent resistance is good. In addition, in the evaluation, since the patterning of the film which does not need to be formed is performed, only the coating film forming step is performed. A radiation exposure step for evaluation. [Evaluation of heat resistance of interlayer insulating film] and [Evaluation of solvent resistance of interlayer insulating film] The film was as defined, and the film thickness (T2) of the obtained cured film was measured. Then, form a pattern. At this development time, the visible film margin (the sensitization of the ray sensitivity CANON) is carried out, and the ruthenium substrate is cleaned. After the 矽 substrate clock of the film is measured, the I thickness change rate I 1 is measured. In the solvent resistance, the ruthenium substrate which forms the solid film of the solid-50-201122728 is formed in a cleaning oven by omitting the appearance and the heating step, and after baking for another hour at 240 ° C, the measurement is performed. The film thickness (t2) of the cured film was calculated as the film thickness change rate {|t2-T2|/T2}x100 [%] due to the additional baking. The evaluation results of the heat resistance are shown in Table! When the 値 is 1% or less [Evaluation of heat resistance is good. [Evaluation of light resistance of interlayer insulating film] In the same manner as in the above [Evaluation of solvent resistance of interlayer insulating film], a cured film is formed, and a light mask is not inserted, and 200 J is exposed by light at 310 nm. /m2. The cured film thus exposed is analyzed by headspace gas chromatography/mass analysis (Head Spacer Sampler: manufactured by Nippon Analytical Industries Co., Ltd., model "JHS-100A"; headspace gas chromatography/mass spectrometer·· Japan Analytical Industry Co., Ltd., "JE OL JMS-AX5 05 W-type mass spectrometer"). The purification conditions were l〇〇°C /min, and the peak area generated from the volatile component of the photopolymerization initiator was determined. 使用»Use n-octane (specific gravity: 0.701) The amount of the volatile component derived from the photopolymerization initiator in terms of n-octane is determined from the following formula, and the amount of the volatile component is 2 pg or less. The sublimation material from the cured film was small, and the light resistance was considered to be good. The evaluation results of the light resistance were shown in Table 1. The calculation formula of the amount of volatile components in terms of n-octane conversion The amount of volatile components (μ§) = Αχ (n-octane) (pg) / (peak area of n-octane) [Evaluation of dry etching resistance of interlayer insulating film] A cured film is formed in the same manner as in the above [Evaluation of Solvent Resistance of Interlayer Insulating Film], and the obtained cured film is obtained. Dry etching apparatus "CDE-8 0N" (manufactured by Shiga-51 - 201122728 Pu MechatrOniCS Co., Ltd.) was dried under conditions of CF450 ml/min, O210 ml/min, output of 400 mW, and etching time of 90 seconds as a dry etching gas. Etching, measuring the film before and after treatment The evaluation result of the dry etching resistance is shown in Table 1. When the film thickness reduction is less than 〇.7 〇μηη, it is considered that the dry etching resistance is good. [Evaluation of transparency of interlayer insulating film] In addition to the above [interlayer insulating film] In the evaluation of the solvent resistance, a glass substrate "CORNING 7 05 9" (manufactured by CORNING Co., Ltd.) was used instead of the ruthenium substrate, and a cured film was formed on the glass substrate in the same manner. The light transmittance of the glass substrate on which the cured film was formed was used. A spectrophotometer "1 5 0-2 0-beam dual-beam spectrophotometer" (manufactured by Hitachi, Ltd.) was measured at a wavelength in the range of 400 to 800 nm. The 光线 of the lowest light transmittance at this time is shown in Table 1. When the enthalpy is 90% or more, transparency is considered to be good. [Evaluation of Relative Dielectric Constant of Interlayer Insulating Film] The compositions of Examples 1 to 4 and Comparative Example 1 were coated on each of the honed SUS304 substrates by using a spin coater. The film was prebaked on a hot plate at 90 ° C for 2 minutes to form a film having a film thickness of 3.Ομηη. With respect to the compositions of Examples 5 to 10 and Comparative Example 2, each composition was applied by a slit extrusion applicator, dried under vacuum at 0.5 Torr, and prebaked on a hot plate at 90 ° C. 2 minutes, a coating film having a film thickness of 3.0 μm was formed. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J /m 2 using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by CANON Co., Ltd., and then fired at 220 ° C for 1 hour in a cleaning oven to obtain Cured film. A Pt/Pb electrode pattern was formed on the cured film by a vapor deposition method of -52 - 201122728 to prepare a sample for measuring a relative dielectric constant. The obtained sample was subjected to a relative dielectric constant at a frequency of 10 kHz by a CV method using an HP16451B electrode manufactured by Yokogawa Hewlett-Packard Co., Ltd. and an HP4284 APrecision LCR meter. The evaluation results of the relative dielectric constant are shown in Table 1. When the enthalpy is 3.9 or less, the relative dielectric constant is considered to be good. Further, in the evaluation of the relative dielectric constant, since the patterning of the film to be formed was not required, the development step was omitted, and only the coating film forming step, the radiation irradiation step, and the heating step were used for evaluation. [Table 1] Example Comparative Example I 2 3 4 5 6 7 8 9 10 1 2 [A] component Α·1 (parts by mass) 100 100 Α-2 (parts by mass) 100 100 Α·3 (parts by mass) 100 100 Α-4 (parts by mass) 100 100 100 100 a-Ι (parts by mass) 100 100 [B Cheng B-1 (mass) 25 25 25 25 8 8 25 B-2 (mass) 20 20 20 20 6 6 20 [C] component C-1 (parts by mass) 1 1 1 1 1 P] component D-1 (parts by mass) 10 D-2 (parts by mass) 5 5 5 [E Cheng E-1 (mass) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 [F Cheng Cheng F-1 (parts by mass) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Radiation sensitivity developer concentration (% by mass) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Radiation sensitivity_2) 700 700 700 700 700 700 700 700 700 700 700 700 700 Development margin Optimal development time (seconds) 80 80 80 80 80 80 80 80 80 80 80 80 Development margin ( Second) 40 40 40 40 40 40 40 40 40 40 40 40 Solvent Resistance (%) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Resistance Heat (%) 0.5 0.6 0.5 0.4 0.5 0.5 0.5 0.5 0.5 0.5 0.6 0.6 Light transmittance (%) 94 94 94 94 94 94 94 94 97 97 94 94 Light resistance (4) 0.9 0.9 1.1 0.6 0.9 0.6 0.8 0.6 0.7 0.7 3.4 3.5 Resistance to dryness _J (4) 0.45 0.54 0.56 0.49 0.45 0.5 0.48 0.48 0.52 0.53 0.99 1.02 Relative dielectric constant 3.5 3.5 3.5 3.5 3.5 3,5 3.5 3.5 3.5 3.5 3.5 3.5 From the results of Table 1, we can know the positive of Example 1 ~ 1 The radiation-sensitive linear composition has high radiation sensitivity and development margin, and the interlayer insulating film formed of the composition has good heat resistance, solvent resistance, and low dielectric properties and light transmittance. Further, compared with the compositions of Comparative Examples 1 and 2, the light resistance and the dry etching resistance were more excellent. INDUSTRIAL APPLICABILITY The interlayer insulating film formed of the positive-type radiation-sensitive resin composition of the present invention is excellent in various properties described above, and is therefore suitable as a magnetic head element, an integrated circuit element, and a solid body typified by a TFT-type liquid crystal display element. An electronic component such as a photographic element. [Simple description of the diagram] None. [Main component symbol description] None. -54-

Claims (1)

201122728 VII. Patent application scope: 1. A positive-type radiation-sensitive resin composition containing: [A] a soluble resin having a hindered amine structure and/or a hindered phenol structure, and [B] l, 2 - 醌Azide compound. 2. The positive-type radiation-sensitive resin composition as claimed in claim 1 wherein [A] the alkali-soluble resin is one or more monomers selected from (a) selected from the group consisting of unsaturated carboxylic acids or unsaturated carboxylic anhydrides. And (a2) a copolymer obtained by including one or more monomers selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), or a compound represented by the following formula (3); 'R1 -55- 201122728 In the formula (1), R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 to R5 are each independently an alkyl group having 1 to 6 carbon atoms, and R6 is a hydrogen atom or carbon. An alkyl group having 1 to 6 atoms, 8! is a single bond, -COO- or -CONH., and a claw is an integer of 〇~3. In the formula (2), R1 is a hydrogen atom or the number of carbon atoms is 4 The alkyl group, R7~R1<} are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least one of R8 and R9 is a tertiary butyl group or a tertiary pentyl group, which is a single bond, -COO - or - CONH-, η is an integer of 0 to 3, and in the formula (3), R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each of R11 is independently a hydrogen atom or an alkane having a carbon number And t is an integer, R15 to R18 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least one of R15 and R16 is a tertiary butyl group or a tertiary pentyl group, and Βι is a single bond. , -C 0.0- or - CON Η-, B2 is a single bond, -CO-, -S-, -CH2-, -CH(CH3)- or -C(CH3)2-, k is an integer from 0 to 3 . 3. The positive-type radiation-sensitive resin composition according to claim 2, wherein the [A] oxime-soluble resin further comprises (a3) a ring-containing compound in addition to the compounds represented by the above (al) and (a2) A copolymer obtained from a monomer of an oxy unsaturated compound. 4. A positive-type radiation-sensitive resin composition as claimed in claim 1, 2 or 3, which is used for forming an interlayer insulating film. An interlayer insulating film formed of a positive-type radiation-sensitive resin composition as disclosed in claim 4 of the patent application. -56- 201122728 ' 6. - A method for forming an interlayer insulating film, comprising: (1) a step of forming a coating film of a positive-type radiation-sensitive resin composition as in claim 4 of the patent application on a substrate, (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation, (3) a step of developing the coating film irradiated with radiation in the step (2), and (4) heating in the step (3) The step of developing the coated film. -57- 201122728 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. -3-