TW201142515A - Positive-type radiation-sensitive composition, interlayer insulating film and method for forming same - Google Patents

Abstract

The present invention provides a positive-type radiation-sensitive composition being able to form interlayer insulating film in which degradation of transmittance, heat-resistant transparency and voltage retention are suppressed, and have excellent light resistance and heat resistance because of keeping radiation sensitivity of radiation-sensitive composition in high level and suppressing generation of radicals and peroxides. The positive-type radiation-sensitive composition comprises [A] polymer which has structure unit containing epoxy groups and structure unit containing groups represented by formula (1) in the same or different polymer compound, [B] photoacid generator and [C] at least one compound selected from the group consisting of compounds containing hindered phenol structure, compounds containing hindered amine structure, compounds containing alkyl phosphite structure and compounds containing thioether structure.

Description

[Technical Field] The present invention relates to a positive radiation sensitive composition, an interlayer insulating film formed of the composition, and a method of forming the interlayer insulating film, the positive type radiation linear composition It is suitable as an interlayer insulating film forming material for a display element such as a liquid crystal display element (LCD) or an organic EL display element (OLED). [Prior Art] In the display element, an interlayer insulating film is generally provided for the purpose of insulating between wirings arranged in a layer. As the material for forming the interlayer insulating film, a positive-type radiation-sensitive composition is widely used because the number of steps for obtaining a necessary pattern shape is small, and it is preferable to have sufficient flatness. The positive-type radiation-sensitive composition used in the formation of such an interlayer insulating film requires good radiation sensitivity and storage stability, and excellent heat resistance, transparency, and the like are required for the interlayer insulating film thus obtained. An acrylic resin is widely used as a component of the positive-type radiation-sensitive linear composition. For example, a positive-type chemically amplified photoresist composition is proposed in Japanese Patent Laid-Open Publication No. Hei 20-4-4669, which is characterized in that it has cross-linking. The agent, the acid generator and a resin 'the resin itself is insoluble or poorly soluble in an aqueous alkali solution' but has a protecting group capable of being cleaved by the action of an acid, and the protecting group is soluble in an aqueous alkali solution after being cleaved. Further, Japanese Laid-Open Patent Publication No. 2004-264623 proposes a radiation sensitive composition comprising a resin and an acid generator containing an acetal and/or ketal structure and an epoxy group. 201142515 However, in the conventional radiation sensitive composition as described above, the bond of the compound contained during the exposure or heating is cleaved, and radicals are generated or peroxide is generated by oxidation. The radical or peroxide causes cracking of the bond of the polymer molecule, whereby the cured film obtained from the composition is inferior in light resistance and heat resistance. In order to solve the problem, a method of adding a hindered phenol compound to a radiation sensitive composition is proposed, for example, in Japanese Laid-Open Patent Publication No. 2002-2292. However, when only such a compound is added, the radiation sensitivity of the radiation-sensitive composition and the light transmittance and voltage holding ratio of the cured film obtained from the radiation-sensitive composition are lowered. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-264623 [Patent Document 3] JP-A-2002-264623 The present invention has been made in view of such problems, and an object thereof is to provide a positive-type radiation-radiating composition capable of maintaining the sensitivities of a radiation-sensitive composition at a high level while simultaneously By suppressing the generation of radicals or peroxides, it is possible to form an interlayer insulating film or the like which has excellent light resistance and heat resistance, and which suppresses light transmittance, heat-resistant transparency, and voltage holding ratio. 201142515 [Means for Solving the Problems] The present invention achieved by solving the above problems is a positive-type radiation-radiating linear composition containing: [A] having the following formula in the same or different polymer molecules ( 1) a polymer having a base structural unit and an epoxy group-containing structural unit; [B] a photoacid generator; and [C] a compound having a hindered phenol structure, a compound having a hindered amine structure, and a sub One or two or more compounds selected from the group consisting of a compound of a phosphate ester structure and a compound containing a thioether structure. R1 - 〇 - C - OR3 (1) R2 (in the formula (1), R1 and R2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the hydrogen atom of the alkyl group, the cycloalkyl group or the aryl group Some or all of them may be substituted by a substituent (wherein, excluding the case where both Ri and R2 are a hydrogen atom). R3 is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group represented by -M(R3m)3. (Μ is Si, Ge or Sn, R3m is an alkyl group), and some or all of these hydrogen atoms may be substituted by a substituent. Ri and R3 may be bonded to form a cyclic ether.) In the positive-type radiation linear composition In addition to the above-mentioned specific structure of [A] polymer and [B] photoacid generator, [C] a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing an alkyl phosphite structure, and A 201142515 or two or more compounds (hereinafter, also referred to as [C] compounds) selected from the group consisting of compounds containing a thioether structure, thereby capturing or causing free radicals generated during heating upon exposure The decomposition of the peroxide formed by oxidation becomes possible, so the free radical can be prevented Cleavage of the peroxide bond of the resulting polymer molecules. As a result, the interlayer insulating film or the like obtained from the composition can exhibit excellent light resistance and heat resistance. Further, the composition [C] having the specific structure described above is used, and therefore, even if these are added, the radiation sensitivity of the composition is maintained at a high level, and the interlayer insulating film obtained from the composition can be prevented. The light transmittance and the voltage retention rate are lowered. The [B] photoacid generator preferably contains a compound including an anthracenesulfonate group represented by the following formula (2). Ο \ I βί ^C=N—〇—S—Rb, (2) Ο (In the formula (2), RB1 represents an alkyl group, a cycloalkyl group or an aryl group, and some or all of the argon atoms of these groups may be substituted. In the composition, the compound having the above-described structure is used as the [B] photoacid generator, and the radiation sensitivity can be further improved, and the interlayer insulating film obtained from the composition can exhibit excellent light transmittance. Heat resistance, transparency and voltage retention. The positive-type radiation-sensitive composition is preferably contained in an amount of 0.1 part by mass or more and 10 parts by mass or less based on 1 part by mass of the [A] polymer '[C] compound. 201142515 The content of the [C] compound with respect to 100 parts by mass of the [A] polymer is within the above range, whereby the interlayer insulating film or the like obtained from the composition is transmitted while maintaining the radiation sensitivity of the composition. The rate, voltage holding ratio, light resistance, and heat resistance can be further improved. Further, the method of forming an interlayer insulating film or the like for a display element of the present invention has the following steps. (1) a step of forming a coating film of the positive-type radiation-sensitive composition 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 in the step ( 2) a step of developing a coating film irradiated with radiation; and (4) a step of heating the coating film developed in the step (3). In this method, the positive-type radiation-sensitive linear composition having excellent sensitivities is used, and the pattern is formed by radiation-sensitive exposure, development, and heating, whereby a fine and delicate pattern can be easily formed. An interlayer insulating film or the like for a display element. Further, the interlayer insulating film or the like thus formed has excellent required properties such as light resistance, heat resistance, light transmittance, heat-resistant transparency, and voltage holding ratio, which are excellent in balance. The radiation described in the present specification refers to a concept including visible rays, ultraviolet rays, far infrared rays, X-rays, charged particle rays, and the like. [Effects of the Invention] As described above, the positive-type radiation-sensitive composition of the present invention can hold the sense of the radiation-sensitive linear composition at a high level by containing the above-mentioned components [A], [B], and [C] by 201142515. The radiation is suppressed while the generation of radicals or peroxides is suppressed, whereby an interlayer insulating film or the like which has excellent light resistance and heat resistance and which suppresses light transmittance and voltage holding ratio can be formed. [Embodiment] The form of the positive radiation sensitive composition of the present invention contains: [A] a specific polymer (hereinafter, simply referred to as "[A] polymer"), [B] light. The acid generator and the [C] compound may further contain other optional components. < [A] Polymer> [A] The polymer has a structural unit containing the group represented by the above formula (1) in the same or different polymer molecules (hereinafter simply referred to as "structural unit (1)") and The structural unit containing an epoxy group may have other structural units as needed. The form of the [A] polymer is not particularly limited, and examples thereof include: (i) having both the structural unit (1) and the epoxy group-containing structural unit in the same polymer molecule 'in the [A] polymer There is a case of a polymer molecule; (ii) having both a structural unit (丨) in one polymer molecule and a structural unit having an epoxy group in a polymer molecule different therefrom, in [A] a case where two polymer molecules are present in a polymer; (iii) having both a structural unit (1) and an epoxy group-containing structural unit in one polymer molecule, and having a structural unit in a polymer molecule different therefrom (1) A case where an epoxy group-containing structure monoterpene 'in the [A] polymer is present in three polymer molecules in a polymer molecule different from them; 201142515 (iv) except (i) to (iii) In the case where the [A] polymer further contains one or two or more kinds of polymer molecules in addition to the predetermined polymer molecule, <Structure unit (1) > Structural unit (1) in the above formula (1) ) the base shown decomposes in the presence of an acid to produce a polarity In the form of a group (hereinafter, simply referred to as "acid-decomposable group"), "the acid generated by the photo-acid generator by irradiation with radiation, and the acid-decomposable group is decomposed" to make the alkali insoluble [A] The polymer becomes alkali soluble. The above acid-decomposable group has an acetal structure or a ketal structure which is relatively stable to a base, and which can be decomposed by the action of an acid. In the above formula (1), the alkyl group represented by R1 and R2 is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and the alkyl chain may have an oxygen atom. Sulfur atom, nitrogen atom. Specific examples of the above alkyl group include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl. a branched alkyl group such as a linear alkyl group such as n-octadecyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a 2-hexyl group or a 3-hexyl group. In the above formula (1), the cycloalkyl group represented by R1 and R2 is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have a polycyclic ring or an oxygen atom in the ring. Specific examples of the above cycloalkyl group include, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decyl group, a decyl group, an adamantyl group and the like. In the above formula (1), 'in the case of the aryl group represented by R1 and R2, preferably the aryl group having 6 to 14 carbon atoms' may be a single ring or a single ring-bonded-10-201142515 structure. It can also be a fused ring. Specific examples of the above aryl group include, for example, a phenyl group, a naphthyl group and the like. Some or all of the hydrogen atoms of the above R1 and R2 may be substituted. Examples of such a substituent include a halogen atom, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (in the case of using the above cycloalkyl group as the cycloalkyl group), and an aryl group (in terms of The aryl group is 'the description of the above aryl group', the alkoxy group (preferably having a carbon number) alkoxy group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a pentyloxy group. Examples of the fluorenyl group having 2 to 20 carbon atoms and a fluorenyl group having 2 to 20 carbon atoms include, for example, an ethyl fluorenyl group, a butyl group, an isobutyl group, etc., and a decyloxy group (for example, an ethyl group, a hexyl group, a heptyl group, and an isobutyl group). Preferred examples of the decyloxy group include an ethoxy group, a propyloxy group, a benzyloxy group, a third pentyloxy group, and the like, and an alkoxycarbonyl group. The alkoxycarbonyl group having 2 to 20 carbon atoms may, for example, be a carbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group, or a haloalkyl group (a part or all of the hydrogen atom of the above cycloalkyl group may be substituted by a halogen atom) Examples of the group include, for example, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a fluorocyclofluorocyclobutyl group, and the like. For the cyclic structure in the aryl group, the cycloalkyl group or the like, the above alkyl group is exemplified as a further substituent. In the above formula (1), the alkyl group, the cycloalkyl group and the aryl group represented by R3 are as defined in R1 and R2. In the above formula (1), the aryl group represented by R3 is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. In the above formula (1), 1 may be a substituted hydroxy group, preferably suitable for the oxime 20, preferably n-butyl fluorene, and the propyl hydrazine is 2 to 10 butyl fluorenyl g (preferably a methoxyalkyl group or a propyl group). For example, the alkyl group may be, for example, a group represented by -M(R3m)3 of R3-11-201142515, and examples thereof include a trimethyldecyl group and a trimethylmethane group. The above-mentioned substituent may be suitably used in place of the aralkyl group represented by r3 or the substituent of -M (a hydrogen atom of the group represented by R3mh). R1 and R3 may be bonded to form a cyclic ether. Examples of such a cyclic ether include, for example, a 2-oxocyclobutane group, a 2-tetrahydrofuranyl group, a 2-tetrahydropiperidyl group, a 2-dialkylalkyl group, etc. The hydrogen atom of the cyclic ether - part or all may be substituted by the above substituents. The structural unit (1) may have the acetal structure or ketal by having a functional group capable of having an acetal structure or a ketal structure by bonding to other carbon atoms. In the above-mentioned functional group capable of having an acetal structure by bonding to other carbon atoms For example, 1-methoxyethoxy, 1-ethoxyethoxy, bupropoxyethoxy, 1-isopropoxyethoxy, 1-n-butoxyethoxy, 1-isobutoxyethoxy, 1-second butoxyethoxy, 1-tert-butoxyethoxy, 1-cyclopentyloxyethoxy, 1-cyclohexyloxyethoxy , 1-norbornoxyethoxy, 1-decyloxyethoxy, phenyloxyethoxy ' 1-(1-naphthyloxy)ethoxy, 1-benzyloxy B Oxyl, 1, phenethyloxyethoxy, (cyclohexyl)(methoxy)methoxy, (cyclohexyl)(ethoxy)methoxy, (cyclohexyl)(n-propoxy) Methoxy, (cyclohexyl)(isopropoxy)methoxy, (cyclohexyl)(cyclohexyloxy)methoxy, (cyclohexyl)(phenoxy)methoxy, (cyclohexyl) ( Benzyloxy)methoxy, (phenyl)(methoxy)methoxy, (phenyl)(ethoxy)methoxy, (phenyl)(n-propoxy)methoxy, Benzene 201142515-based (isopropoxy)methoxy, (phenyl)(cyclohexyloxy)methoxy, (phenyl) (phenoxy) ) methoxy, (phenyl) (benzyloxy) methoxy, (nod) (methoxy) methoxy, (benzyl) (ethoxy) methoxy, (benzyl) ( N-propoxy) methoxy, (benzyl)(isopropoxy)methoxy, (benzyl)(cyclohexyloxy)methoxy, (benzyl)(phenoxy)methoxy, (benzyl)(benzyloxy)methoxy, 2-tetrahydrofuranyloxy, 2-tetrahydropentanyloxy, 1-trimethyldecyloxyethoxy, 1-trimethylmethyl A decyloxyethoxy group, etc. Among them, a preferred series is 1-ethoxyethoxy, 1-cyclohexyloxyethoxy, 2-tetrahydropyranyloxy, 1- The n-propoxyethoxy group. The functional group having a ketal structure by bonding to another carbon atom as described above may, for example, be 1-methyl-1-methoxyethoxy. 1-methyl-1-ethoxyethoxy, 1-methyl-1-n-propoxyethoxy, b-methyl-1-isopropoxyethoxy, 1-methyl-1- n-Butoxyethoxy, 1-methyl-indole-isobutoxyethoxy, 1-methyl-1-butoxyethoxy, 1-methyl -1-t-butoxyethoxy, fluorenyl-methyl-hydrazine-cyclopentyloxyethoxy, 1-methyl-1-cyclohexyloxyethoxy, methyl-hydrazine-norbornyloxy Ethyloxy, 1-methyl-1-indolyloxyethoxy, 1-methyl-buphenyloxyethoxy, 1·methyl-1_(1·naphthyloxy)ethoxy , 1-methyl-1-benzyloxyethoxy, 1-methyl-1-phenylethyloxyethoxy, 1-cyclohexyl-1-methoxyethoxy, 1-ring Hexyl-1-ethoxyethoxy, fluorenyl-cyclohexyl-1-n-propoxyethoxy, 1-cyclohexyl-1-isopropoxyethoxy, fluorene-cyclohexyl-1-cyclohexyl Oxyethoxyethoxy, 1-cyclohexyl-1-phenoxyethoxy, 1-cyclohexyl-1-benzyloxyethoxy, 1-phenyl-1-methoxyethoxy, 1 -Phenyl-1-ethoxyethoxy, 1- 13-201142515 Phenyl-1-n-propoxyethoxy, 1-phenyl-1-isopropoxyethoxy, phenyl- 1-cyclohexyloxyethoxy, 1-phenyl-1-phenyloxyethoxy, 1-phenyl-1-phenyloxyethoxy, 1-pyryl-1_methoxy Ethoxy, 1-pyryl-1-ethoxyethoxy, 1-benzyl-1-n-propoxyethoxy, 1-benzyl-1-isopropoxyethoxy, 1 -benzyl-1-cyclohexyloxyethoxy, 1-benzyl-1-phenyloxyethoxy, 1-benzyl-1-benzyloxyethoxy, 2-(2-A A benzyl-tetrahydrofuranyloxy group, a 2-(2-methyl-tetrahydropyranyl)oxy group, a 1-methoxy-cyclopentyloxy group, a 1-methoxy-cyclohexyloxy group, and the like. Among them, a preferred series is 1-methyl-indole-methoxyethoxy, 1-methyl-1-cyclohexyloxyethoxy. Specific examples of the structural unit (1) having the above acetal or ketal structure include, for example, a structure list represented by the following formulas (1-1) to (1_3).

(In the formulae (1-1) and (1-3), R· is a hydrogen atom or a methyl group. r1, R2 and R3 are the same as those described in the above formula (1).) The above formula (1-1) is provided. The monomer having a radical polymerizable property (hereinafter referred to simply as "a monomer having an acetal structure") of the structural unit (1) represented by (I-3) may, for example, be: -14- 201142515 I-alkoxyalkyl (meth)acrylate, i-(cycloalkyloxy)alkyl (meth)acrylate, 1-(haloalkoxy)alkyl (meth)acrylate, ( Methyl) 1-(aralkyloxy)alkyl acrylate, (meth) acrylate (meth) acrylate-based (meth) acrylate-containing acetal structure-containing monomer; 2,3-di ( 1-(Trialkyldecyloxy)alkoxy)carbonyl)-5-nordecene, 2,3-bis(1-(trialkylcarbinyloxy)alkoxy)carbonyl)- 5-northene, 2,3-bis(1-alkoxyalkoxycarbonyl)-5-nordecene, 2,3-di(1.(cycloalkyloxy)alkoxycarbonyl)- 5-northene, 2,3-bis(1-(aralkyloxy)alkoxycarbonyl)-5-nordecene and the like decene acetal-containing monomer Alkyl styrene, 1-(haloalkoxy)alkoxystyrene, 1-(aralkyloxy)alkoxystyrene, tetrahydropyranyloxystyrene, etc. Monomer of aldehyde structure. Among them, preferred are 1-alkoxyalkyl (meth)acrylate, tetrahydrobenzylidene (meth)acrylate, 1-alkoxyalkoxystyrene, tetrahydropyranyloxyl The styrene is more preferably a 1-alkoxyalkyl (meth)acrylate. + Specific examples of the acetal structure-containing monomer which provides the above structural unit (1) include, for example, 1-ethoxyethyl methacrylate and 1-methoxyethyl methacrylate. Ester, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1-(2-methacrylate) Chloroethoxy)ethyl ester, 1-(2-ethylhexyloxy)ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate Base ester, 1-(2-cyclohexylethoxy)ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2·tetrahydropyranyl methacrylate, -15- 201142515 1-Ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-tert-butoxy acrylate Ethyl ester, 1-(2-chloroethoxy)ethyl acrylate, 1-(2-ethylhexyloxy)ethyl acrylate, hydrazine-n-propoxyethyl acrylate, 1 ring of acrylic acid Hexyloxyethyl ester, propylene 1-(2-cyclohexylethoxy)ethyl ester, 1-benzyloxyethyl acrylate, 2-tetrahydrobenzylidene acrylate, 2,3-bis(1-(trimethyldecyl)alkyl Oxy)ethoxy)carbonyl)-5-nordecene, 2,3-bis(1-(trimethylmethylindenyloxy)ethoxy)carbonyl)_5_norbornene, 2,3 - bis(1-methoxyethoxycarbonyl)-5-nordecene, 2,3-bis(1-(cyclohexyloxy)ethoxycarbonyl)-5-northene, 2,3- Bis(1-(benzyloxy)ethoxycarbonyl)-5-nordecene, p- or m-ethoxyethoxystyrene, p- or m-methoxyethoxybenzene Ethylene, p- or m--1-n-butoxyethoxystyrene, p- or m--1-isobutoxyethoxystyrene, p- or m-(1,1-dimethylethoxyl) Ethyl styrene, p- or m-(2-chloroethoxy)ethoxystyrene, p- or m-(2-ethylhexyloxy)ethoxystyrene, Or m-n-propoxy ethoxystyrene, p- or m-cyclohexyloxyethoxystyrene, p- or m-(_cyclohexylethoxy)ethoxystyrene , p- or m-benzyloxyethoxystyrene, and the like. The above structural unit (1) may be used in combination of two or more kinds. In the acetal-containing monomer which provides the above structural unit (1), 'preferably 1-ethoxyethyl methacrylate, methyl propylene acid b-butoxyethyl-16 - 201142515-based ester , 2-tetrahydropyranyl methacrylate, 丨 节 氧基 ethoxyethyl methacrylate. The acetal structure-containing monomer which provides the structural unit (1) can be used commercially or by a known method. For example, the acetal structure-containing monomer of the structural unit (1) represented by the above formula d"] can be obtained by using (meth)acrylic acid and ethyl phenyl ether in the presence of an acid catalyst as shown below. Reaction synthesis.

Wherein 'R', R1 and R3 correspond to R, and R3 in the above formula (1-1), respectively, and 'R21 and R22 are in the form of -CH(R21)(R22) and in the above formula (1·η R2 corresponds to.) In terms of the content of the structural unit (1) in the [A] polymer, as long as the [a] polymer exhibits alkali solubility by an acid and exhibits desired heat resistance of the cured film, there is no In particular, in the case where both of the structural unit (1) and the epoxy group-containing structural unit are contained in one polymer molecule, the monomer is contained in all the structural units contained in the [A] polymer. The addition ratio is preferably 5% by mass to 70% by mass, more preferably 1 〇 by mass, ～60% by mass, particularly preferably 20% by mass to 50% by mass. On the other hand, it has a polymer molecule Structural unit (1), and in the case of a structural unit containing an epoxy group in another polymer molecule, 'the structural unit in a polymer molecule having the structural unit (1)-17- 201142515 (1) In terms of the content, the total structural unit contained in the polymer molecule is compared with the monomer addition ratio. Preferably, it is 40% by mass to 99% by mass. More preferably, it is 50% by mass to 9.8 % by mass. It is particularly preferably 55% by mass to 9.55% by mass. <The structural unit containing an epoxy group> [A] The polymer has the above structural unit (1) and also has an epoxy group-containing structural unit. The epoxy group-containing structural unit is a structural unit derived from a radical polymerizable epoxy group-containing monomer. The epoxy group may, for example, be an oxiranyl group (1,2-epoxy structure) or an oxycyclobutane group (1,3-epoxy structure). [A] a polymer in a molecule By having a structural unit containing an oxiranyl group or an oxycyclobutane group, the hardness of the hard film obtained from the positive-type radiation-sensitive composition can be improved, and the heat resistance can be further improved. Specific examples of the epoxy group-containing monomer of the structural unit include, for example, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, and methacrylic acid. -3,4-epoxybutyl ester, 3-methyl-3,4-epoxybutyl acrylate, 3-ethyl-3,4-methacrylic acid Oxybutyl acrylate, 5,6-epoxyhexyl acrylate, 5,6-epoxyhexyl methacrylate, 5-methyl-5,6-epoxyhexyl methacrylate, methacrylic acid - 5-ethyl·5,6-epoxyhexyl ester, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate-3,4-epoxy methacrylate Cyclohexyl ester, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexyl propyl methacrylate, A 3,4-epoxycyclohexyl-18- 201142515 butyl acrylate, 3,4-epoxycyclohexyl methacrylate, epoxy cyclohexyl acrylate, 3,4-epoxycyclohexyl acrylate Base ester, epoxy cyclohexylethyl acrylate, 3,4-epoxycyclohexyl propyl acrylate, 3,4-epoxycyclohexyl butyl acid, 3,4-epoxycyclohexyl acrylate, etc. Ethylene oxide-based (meth)acrylic compound; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-ethylene Glycidyl ether, α-methyl-inter-B Vinylbenzyl glycidyl ethers such as benzyl glycidyl ether, benzyl-p-vinylbenzyl glycidyl ether; o-vinylphenyl glycidyl ether, m-vinylphenyl ketal ether, Vinylphenyl condensed ethers such as vinyl phenyl glycidyl ether; 3-(acryloxymethyl)oxycyclobutane, 3-(acryloxymethoxymethyloxybutane, 3-(Allyloxymethyl)-3-ethyloxocyclobutene 3-(acryloxymethyl)-3-phenyloxycyclobutane, 3-(2-propenyloxy)oxy ring Butane, 3-(2-propenyloxyethyl)-3-ethyloxocyclobutene 3-(2-propenyloxyethyl)-3-ethyloxycyclobutane, 3-(2-propene醯ethyl)-3-phenyloxycyclobutane, 3-(methacryloxymethyl)oxycyclobutane, 3-(methylpropionylmethyl)-3-methyloxetane Alkane, 3-(methacryloxymethyl)-3oxycyclobutane, 3-(methacryloxymethyl)-3-phenyloxycyclobutane, methacryloxyloxy Oxycyclobutane, 3-(2-methylpropenyloxy)-3-ethyloxycyclobutane, 3-(2-methylpropenyloxyethyl)-3-ethenebutane , 3-(2 - A Propylene methoxyethyl)-3-phenyloxocyclobutane 3.4- 3.4-propenyl glyceryl benzyl α-methyl oleyl glycyrrhizin I )-3-alkane, ethane ethane, oxy oxime -ethyl 3-(2-ylethyloxy-19- 201142515 2-(acryloxymethyl)oxycyclobutane, 2-(acryloxymethyl)-2-methyloxetane , 2-(acryloxymethyl)-2-ethylcyclobutane, 2-(acryloxymethyl)-2-phenyloxycyclobutane, 2-(2-propenyloxy) Ethyl)oxycyclobutane, 2-(2-propenyloxyethyl)-2-ethylcyclobutane, 2-(2-propenyloxyethyl)-2-ethyloxetane Alkane, 2-(2-propenyloxyethyl)-2-phenyloxycyclobutane, 2-(methacryloxymethyl)oxycyclobutane, 2-(methacryloxyloxy) Methyl)-2-methyloxocyclobutane, 2-(methacryloxymethyl)-2-ethyloxycyclobutane, 2-(methacryloxymethyl)-2- Phenyloxycyclobutane, 2-(2-methylpropenyloxyethyl)oxycyclobutane, .2-(2-methylpropenyloxyethyl)-2-ethyloxycyclobutane , 2-(2-methylpropenyloxyethyl)-2-ethyloxocyclobutane, 2-(2- An (oxy)cycloalkyl group-containing (meth)acrylic compound such as methacryloxyethyl)-2-phenyloxycyclobutane or the like. The above epoxy group-containing structural unit may be used singly or in combination of two or more. Among the above epoxy group-containing monomers, from the viewpoints of copolymerization reactivity with other radical polymerizable monomers and developability of a positive-type radiation-linear composition, methyl propyl sulphonate is preferred. Vinegar, methylpropionic acid-2-methylglycidyl ester, methacrylic acid-3,4-epoxycyclohexyl ester, methyl propionate methyl hexyl epoxy ring

Methyl methoxy allylyl group / (V-methyl methallyl propyl group / IV - 3 , alkane butyl oxymethane butyl epoxide ethoxylate The TQ A rL of the nucleus contained in the ring is 孰 孰 望 望 所 所 所 等 等 等 等 等 等 pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa pa In the case of a structural unit of -20-201142515, the ratio of the monomeric ratio of the monomeric components contained in the [A] polymer is preferably 1 〇 mass% ~ 6 〇 mass% ' More preferably 1 5 mass. ~ 5 5 mass%, particularly preferably 2 〇 mass 5 〇 mass%. On the other hand, having a structural unit in one polymer molecule (1) And in the case where the other structural unit has an epoxy group-containing structural unit, the epoxy group-containing structure of all the structural units contained in one polymer molecule having the epoxy group-containing structural unit In terms of the content of the unit, the addition of the monomer The ratio is preferably 1% by mass or more and 80% by mass or less, more preferably 20% by mass or more, and 70% by mass. More preferably, it is preferably 25% by mass or more and 60% by mass or less. <Other structural units> The radically polymerizable monomer which provides another structural unit may, for example, be a radical polymerizable monomer having a carboxyl group or a derivative thereof, a hydroxyl group, etc. The above-mentioned radical polymerizable single having a carboxyl group or a derivative thereof The main body can be exemplified by acrylic acid, methacrylic acid, crotonic acid, 2-propenylmethoxyethyl succinic acid, 2-methylpropenyloxyethyl succinic acid, 2-propenyl methoxyethyl hexahydro a monocarboxylic acid such as phthalic acid or 2-methylpropenyloxy hexahydrophthalic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; An acid anhydride of a dicarboxylic acid, etc. ' As an example of the above-mentioned radical polymerizable monomer having a hydroxyl group, -21 - 201142515 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate , 4-hydroxybutyl acrylate, 4-hydroxymethylcyclohexyl acrylate Hydroxyalkyl acrylate such as ester; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxy methacrylate a hydroxyalkyl methacrylate such as amyl ester, -6-hydroxyhexyl methacrylate or 4-hydroxymethyl-cyclohexylmethyl methacrylate, etc. Among these radically polymerizable monomers having a hydroxyl group From the viewpoints of copolymerization reactivity with other radical polymerizable monomers and heat resistance of the obtained interlayer insulating film, etc., 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate are preferable. _4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, methacrylic acid-4 -Hydroxymethyl-cyclohexylmethyl ester. Examples of other radical polymerizable monomers include alkyl acrylates such as methyl acrylate and isopropyl acrylate; methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; , alkyl methacrylate such as dibutyl methacrylate or t-butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.02'6]癸-8-yl acrylate, acrylate alicyclic alkyl ester such as 2-(tricyclo[5.2.1.02'6] fluoren-8-yloxy)ethyl acrylate or isodecyl acrylate: methacrylic acid ring Hexyl ester, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.02,0]non-8-yl methacrylate, methacrylic acid-2-(tricyclic-22-201142515 [5.2. 1.02'6] 癸-8-yloxy)ethyl ester, isopropyl methacrylate such as isodecyl methacrylate; aryl acrylate such as phenyl acrylate or benzyl acrylate and acrylic acid Aralkyl ester; aryl ester of methacrylic acid such as phenyl methacrylate or benzyl methacrylate; and aralkyl ester of methacrylic acid; maleic acid a dicarboxylic acid dialkyl ester such as ethyl ester, diethyl fumarate or diethyl itaconate; tetrahydrofurfuryl methacrylate, tetrahydrofuranyl methacrylate, tetrahydropyran methacrylate - a 5-membered heterocyclic methacrylate containing 1 oxygen atom such as 2-methyl ester and an unsaturated 6-membered heterocyclic methacrylate; 4-methylpropenyloxymethyl-2-methyl- 2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxyk-cyclo, 4-methacryl Oxyloxymethyl-2-cyclohexyl-1,3-dioxolan and the like - dimethyl-1,3-dioxolane, 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxymethyl -2,2-diethyl-1,3-dioxolane, 4-propenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-propene醯oxymethyl-2-cyclopentyl-1,3-dioxolan, 4-propenyloxymethyl-2-cyclohexyl-1,3-dioxolan, 4-propene oxy Ethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propane Iridinyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxybutyl-2-methyl-2-ethyl-1,3-di An acrylate having two oxygen atoms and an unsaturated 5-membered heterocyclic ring such as oxylan; -23- 201142515 styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxy a vinyl aromatic compound such as styrene or 4-propenylphenol; Ν-phenyl maleimide, Ν-cyclohexylmaleimide, Ν-benzyl maleimide, Ν-amber Imino-3-maleimide benzoate' Ν-amber quinone imido-4-maleimine butyrate, hydrazine-amber quinone imine-6-maleimide Anthracene-substituted maleimine such as hexanoate, hydrazone-amber quinone imine-3-maleimide propionate, Ν-(9-acridinyl)maleimide; a conjugated diene compound such as 3-butadiene, isoprene or 2,3-dimethyl-1,3-butadiene; acrylonitrile, methacrylonitrile, acrylamide, methacryl Other unsaturated compounds such as decylamine, vinyl chloride, vinylidene chloride, and vinyl acetate. Among these other radically polymerizable monomers, styrene is preferred from the viewpoints of copolymerization reactivity with the radical polymerizable monomer having the above reactive functional group and developability of the positive-type radiation-sensitive composition. 4·isopropenylphenol, tricyclo[5·2·1·02'6]癸_8·yl ester, tetrahydrofurfuryl methacrylate, i,3-butadiene, 4· Propylene methoxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, methyl propylene Acid-based vinegar and so on. The polystyrene-equivalent mass average molecular weight (hereinafter, also referred to as "Mw") obtained by GPC (gel permeation chromatography) of [A] polymer is preferably 2.0 χ 103 〜 l. 〇 xl 〇 5, more preferably 5. 〇xl〇3 to 5·〇χ1〇4° The radiation sensitivity and alkali developability of the positive-type radiation-sensitive composition can be improved by making the Mw of the [A] polymer into the above range. In addition, the polystyrene-equivalent number average molecular weight (hereinafter, also referred to as "Μη") obtained by GPC (gel permeation chromatography) of [A] polymer is preferably 2. 〇xl 〇 3~ L_〇xl〇5' is preferably 5.0Χ103~5.0χ104. By setting the Μη of the copolymer to the above range, the curing reactivity at the time of hardening of the coating film of the positive-type radiation-sensitive composition can be improved. Further, the molecular weight distribution "Mw/Mn" of the [Α] polymer is preferably 3.0 or less', more preferably 2.6 or less. The developability of the obtained interlayer insulating film can be improved by making the Mw/Mn of the [A] polymer 3.0 or less. The positive-type radiation-sensitive composition containing the [A] polymer can be easily formed into a desired pattern shape at the time of development. ΙΑ]Method for Producing Polymer&gt; [Α] The polymer can be produced by radical copolymerization of a monomer having an acetal structure, an epoxy group-containing monomer, and a monomer providing another structural unit. In the case of producing a [Α] polymer comprising both the structural unit (1) and the epoxy group-containing structural unit in the same polymer molecule, a monomer containing at least an acetal structure and an epoxy group-containing polymer are used. The mixture of monomers can be copolymerized. On the other hand, when a [Α] polymer having a structural unit (1) in one polymer molecule and having an epoxy group-containing structural unit in a polymer molecule different therefrom is used, at least a shrinkage-containing polymer is included. Polymerizable solution radical polymerization of a monomer having an aldehyde structure to obtain a polymer molecule having a structural unit (丨), and further radical polymerization of a polymerizable solution containing at least an epoxy group-containing monomer to obtain an epoxy group-containing polymer The polymer molecules of the structural unit are finally mixed to form a polymer. -25- 201142515 The solvent used in the polymerization for producing the [A] polymer is exemplified by, for example, an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether diethylene glycol alkyl ether, a propylene glycol monoalkane. Examples of the solvent include, for example, methanol, ethanol, benzyl alcohol, and 2-benzene. The alcohols are, for example, methanol, ethanol, benzyl alcohol, and 2-benzene. Examples of the ether are, for example, tetrahydrofuran; the glycol ether is, for example, ethylene glycol monomethyl ether, ethylene glycol or the like; and the ethylene glycol alkyl ether acetate is, for example, a Base cellosolve ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethyl ether acetate, etc.; as diethylene glycol alkyl ether is, for example, diethylene glycol monomethyl Alcohol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethylene glycol ethyl methyl ether, etc.; as propylene glycol monoalkyl ether is, for example, propylene glycol monomethyl ether monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, etc. as propylene glycol monoalkyl ether acetate are, for example, propylene glycol monoester, C Glycol monoethyl ether acetate, propylene glycol monopropyl ether propylene glycol monobutyl ether acetate, etc.; as propylene glycol monoalkyl ether propionate, for example, propylene glycol monoester, propylene glycol monoethyl ether propionate, Propylene glycol monopropyl ether propylene glycol monobutyl ether propionate or the like; in terms of, it may be an acetate, a vinyl acetate or the like. Ethanol, 3-monoethyl ether acetate, diol monoethyl ether, diethyl ether, methyl ether acetic acid acetate, methyl ether propyl propionate, -26- 201142515 as aromatic hydrocarbons, for example Toluene, xylene, etc.; 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, Propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, glycolic acid Ester, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxyl Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid Methyl ester, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, propyl acetoxyacetate Ester, methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, Butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, Propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, Esters such as 3-butoxypropionic acid butyl ester. -27- 201142515 Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, methoxyacetate are preferred. Ester, particularly preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl methoxyacetate. As the polymerization initiator used in the polymerization for producing the [A] polymer, those generally known as radical polymerization initiators can be used. The radical polymerization initiator may, for example, be: 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2-methylpropionate), 2,2· -Azo compound such as azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); An organic peroxide such as benzamidine, lauric acid peroxide, tributyl butyl peroxyacetate, 1, bismuth-bis(t-butylperoxy)cyclohexane, and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide and the reducing agent may be combined to form a redox type initiator. In the polymerization for producing a [Α] polymer, a molecular weight regulator can be used to adjust the molecular weight. Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and third (dodecane); Mercaptans such as mercaptan, mercaptoacetic acid; xanthates such as dimethyl xanthate sulfide and diisopropyl xanthate disulfide; -28- 201142515 for capadiene, α- Methylstyrene dimer, and the like. &lt;[Β] Photoacid generator&gt; [Β] The photoacid generator is a compound which generates an acid by irradiation with radiation. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray radiation or the like can be used. The positive-type radiation-radiating composition can exhibit a positive radiation-sensing property by containing a [Β] photo-acid generator. [Β] The photoacid generator is not particularly limited as long as it is a compound which generates an acid (for example, a carboxylic acid, a sulfonic acid, or the like) by irradiation with radiation. The form of the photoacid generator in the composition may be in the form of a photoacid generator (hereinafter also referred to as a [Β] photoacid generator) of a compound described later, or may be [Α] The form of the photoacid generating group combined with a part of the polymer or other polymer may also be the two forms. Examples of the [Β] photoacid generator include an oxime sulfonate compound, a key salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a ruthenium compound, a sulfonate compound, a carboxylic acid ester compound, and the like. Among them, a sulfonate compound is preferred. &lt;Anthracene sulfonate compound&gt; The compound of the above-mentioned formula (2) is preferably a compound containing a sulfonate group represented by the following formula (2). 〇

\ II Ο — Ν — Ο — S — R Βΐ

/ II (2) aryl or aryl, hydroquinone of these groups (in formula (2), RB1 is an alkyl group, a part or all of an atom may be substituted by a substituent) • 29- 201142515 For the alkyl group of RB1 'It is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of RB1 may be an alkoxy group or an alicyclic group having a carbon number of 1 to 10 (including an alicyclic group containing a bridge bond such as a 7,7-dimethyl-2-oxoanthracene group, preferably a system Substituted by a bicycloalkyl group or the like. The aryl group of RB1 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of RB1 may be substituted with an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms. The above compound containing the oxime sulfonate group represented by the above formula (2) is more preferably an oxime sulfonate compound represented by the following formula (3). &lt;X)m

B1 Ο (3) In the above formula (3), the definitions of RB1 and RB1 in the above formula (2) are the same. X is an alkyl group, an alkoxy group or a halogen atom. m is an integer of 0 to 3. When m is 2 or 3, multiple Xs may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group of X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as x is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. Particularly, in the above formula (3), it is preferred that the compound m is 1, X is a methyl group, and the substitution position of X is an ortho-position compound. Specific examples of the oxime sulfonate compound include, for example, a compound (3-i), a compound (3_ii), and a compound (3-iii) represented by the following formulas (3-i) to (3-v), respectively. ), the compound (3_iv) and the compound Ov) and the like. -30- 201142515

S

O N—O—S —n-C3H7 II (3]) o

N-O —— S —— CH2 II o s o

s N—O — S —n-C8Hv (3-ii) II o

(3-iv)

N—-0 — S — n_C8H CH-, CN 〇

II (3-v)

O These may be used singly or in combination of two or more kinds, or may be used in combination with other photoacid generators as a component. The above compound (3_i) [(5_g oxime oxyimino-5H-thiophene-2.subunit)-(2-methylphenyl)acetonitrile], 2 (3-ii)[(5H-octylsulfonate) Oxyiminyl·5η_thiophene. 2_ fenyl)-(2-methyl-acetonitrile), compound (3 - iii) [( camphor sulfonate, oxy-oxygen, hydrazine, 5-H-thiophen-2-yl)-( 2-methylbenzene)acetonitrile], compound (3_iv) p-toluenesulfonyloxy 3 -31- 201142515 yl-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile] and compound (3-v [(5_octylsulfonyloxyimino-(4-methoxyphenyl)acetonitrile] can be obtained by a commercially available product. &lt;Key Salt&gt; As the onium salt, diphenyl can be exemplified a iodine salt, a triphenyl sulfonium salt, a sulfonium salt, a benzothiazolium salt, a tetrahydrothiophene key salt. Examples of the diphenyl iodine salt include diphenyl iodine tetrafluoroborate, and Phenyl iodine hexafluorophosphate, diphenyl iodine hexafluoroarsenate, diphenyl iodine triflate, diphenyl iodine trifluoroacetate, diphenyl iodonium - p-toluene Sulfonate, diphenyl iodide butyl succinate (2,6-difluorophenyl) borate, 4-methoxyphenyl-phenyl iodide tetrafluoroborate Bis(4-tert-butylphenyl) iodine tetrafluoroborate, bis(4-tert-butylphenyl) iodine hexafluoroarsenate, bis(4_t-butylphenyl) iodine gun Triflate, bis(4-t-butylphenyl) iodine trifluoroacetate, bis(4-t-butylphenyl) iodine-p-toluenesulfonate, double (4- Tributylphenyl) iodonium sulfonate, etc. Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, and triphenylsulfonium. Tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylphosphonium butyl (2,6-difluorophenyl) borate, etc. For example, an alkyl sulfonium salt, a benzyl sulfonium salt, a dibenzyl sulfonium salt, a substituted benzyl sulfonium salt, etc. may be mentioned. 'In terms of an alkyl sulfonium salt, for example, 4-ethenyloxyphenyl group Dimethyl sulfonium hexafluoroantimonate, 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate, -32- 201142515 dimethyl-4-(benzyloxycarbonyloxy)phenyl sulfonium hexafluoride Citrate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, two Methyl 4-(benzylideneoxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethenyloxyphenylphosphonium hexafluoroantimonate, etc. Examples of the salt include benzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl shovel hexafluorophosphate, and 4-ethenoxyphenylbenzyl chloride. Methyl hydrazine hexafluoroantimonate, benzyl-4-methoxyphenylmethyl hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate , benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, etc.; For example, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4-ethyloxyphenyldibenzylphosphonium can be cited. Fluoride, dibenzyl-4-methoxyphenylphosphonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl_3_A 4--4-hydroxy-5-t-butylphenylphosphonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, etc.; substituted benzyl For salt, For example, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyl Phenylmethyl hydrazine hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethyl hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenyl Based on hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroantimonate. -33- 201142515 For the benzothiazole salt, for example, 3-benzylbenzothiazole hexafluoroantimonate, 3-benzylbenzothiazole hexafluorophosphate, 3-benzylbenzothiazole Key tetrafluoroborate, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazole hexafluoroantimonate, 3-benzyl - 5-Chlorobenzothiazole key hexafluoroantimonate. The tetrahydrothiophene sulfonium salt may, for example, be 4,7-di-n-butoxy-naphthalene tetrahydrothiophene trifluoromethanesulfonate or 1-(4-n-butoxynaphthalen-1-yl)tetra Hydrothiophene. Key triflate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene hexafluoro-n-butyl sulfonate, 1-(4-n-butoxynaphthalene-1 -yl)tetrahydrothiophene-1,1,2,2-tetrafluoro-2-(nordecen-2-yl)ethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl) Tetrahydrothiophene gun 2-(5-t-butoxycarbonyloxybicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4 -n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(6-t-butoxycarbonyloxybicyclo[2.2.1]hept-2-yl)-1,1,2,2- Tetrafluoroethanesulfonate. &lt;sulfonimide compound&gt; Examples of the sulfonimide compound include fluorene-(trifluoromethylsulfonyloxy) succinimide, hydrazine-(camphorsulfonyloxy) amber Amine, Ν-(4-methylphenylsulfonyloxy) succinimide, Ν-(2-trifluoromethylphenylsulfonyloxy) succinimide, Ν-(4-fluorophenyl Sulfomethoxy) succinimide, Ν-(trifluoromethylsulfonyloxy) phthalimide, Ν-(camphorsulfonyloxy) phthalimide, Ν-( 2-trifluoromethylphenylsulfonyloxy) phthalimide, fluorene-(2-fluorophenylsulfonyloxy) phthalimide, hydrazine-(trifluoromethylsulfonate醯oxy)diphenylmaleimide, Ν-(camphorsulfonyloxy)diphenyl-34- 201142515 carbamazepine, N-(4-methylphenylsulfonyloxy) Phenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenyl醯iimine, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2·2·1]hept-5-ene -2,3-dimethylimine, N-(4_ Phenyl sulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]g-5 -ene-2,3-dimethylimine, N-(nonafluorobutsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-( camphor Sulfomethoxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, Ν·(camphorsulfonyloxy)-7_oxabicyclo[2.2.1]hept-5 -ene-2,3-dimethylimine, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(4-methylphenylsulfonyloxy)bicyclo[2·2·1]hept-5-ene_2,3-dimethylimine, N-(4-methylphenylsulfonyloxy) Alkylheterobicyclic ring I: 2.2·1]hept-5-ene·2,3-dimethylimine, &gt; 1_(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]g -5-ene-2,3-dimethylimine, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2, 3-dimethylimine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, Ν-(4·fluorobenzene Sulfosulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dimethylimine, N-(trifluoromethylsulfonate) Bi) 'bicyclo'[2.2.1]heptane-5,6-oxy-2,3-dimethylimine, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6 -oxy-2,3-dimethylimine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.丨]heptane-5,6-oxy-2,3-di Yttrium, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dimethylimine, N-(4 ·Fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-35- 201142515 alk-5,6-oxy-2,3-dimethylimine, N-(trifluoromethylsulfonyloxy) )naphthyldimethylimine, (camphorsulfonyloxy)naphthyldimethylimine, Ν·(4·methylphenylsulfonyloxy)naphthyldimethylimine, N-(benzene Sulfosulfonyloxy)naphthyldimethylimine, N_(2-trifluoromethylphenylsulfonyloxy)naphthyldimethylimine, N-(4-fluorophenylsulfonyloxy) Naphthyldimethylimine, N-(pentafluoroethylsulfonyloxy)naphthyldimethylimine, N-(heptafluoropropylsulfonyloxy)naphthyldimethylimine, N· (nonafluorobutylsulfonyloxy)naphthyldimethylimine, N_(ethylsulfonyloxy)naphthyldimethylimine, N-(propylsulfonyloxy)naphthalene Dimethylimine, N-(butylsulfonyloxy)naphthyldimethylimine, N-(pentylsulfonyloxy)naphthyldimethylimine, N-(hexylsulfonyloxy) Naphthyldimethylimine, N-(heptylsulfonyloxy)naphthyldimethylimine, N-(octylsulfonyloxy)naphthyldimethylimine, N-(fluorenyl) Sulfomethoxy) naphthyldimethylimine or the like. (Homohalogen-containing compound) The halogen-containing compound may, for example, be a halogenated alkyl group-containing hydrocarbon compound or a haloalkyl group-containing heterocyclic compound. (Diazomethane compound) Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonium)diazomethane, and bis(phenylsulfonyl)diazo Methane, bis(p-sulfonate) diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(p-chlorophenylsulfonyl)diazomethane, methylsulfonium-p-toluene醯Diazomethane, cyclohexylsulfonium (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonate (benzene) Hyperthyroidism, etc. -36- 201142515 (Indole compound) Examples of the ruthenium compound include a β-ketoxime compound, a β-amplifier compound, and a diaryldiamine compound. (Sulphonate Compound) Examples of the sulfonate compound include an alkylsulfonate, an alkylsulfonate, an arylsulfonate, and an imidosulfonate. (Carboxylate Compound) The carboxylate compound may, for example, be an o-nitrobenzyl carboxylate. Among these [Β] photoacid generators, from the viewpoint of radiation sensitivity and solubility, a sulfonate compound is preferable, and a compound containing an oxime sulfonate group represented by the above formula (2) is more preferable. Further preferably, the oxime ester compound represented by the formula (3) is commercially available as [(5-propylsulfonyloxyimino-5-thiophen-2-indenyl)]. (2-methylbenzene)acetonitrile], [(5Η-octylsulfonyloxyimino-5H-thiophene-2-yl)-(2-methylphenyl)acetonitrile], [(5-p-toluene)醯Ominoimido-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], [(camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-A Benzobenzene) acetonitrile], [(5-octylsulfonyloxyimido-(4-methoxyphenyl)acetonitrile]. Further, a key salt is preferred, and a tetrahydrothiophene key salt and a benzyl group are more preferred. Onium salt, 4,7-di-n-butoxy-1-naphthalene tetrahydrothiophene key salt trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate. [B] Photoacid The generating agent may be used singly or in combination of two or more. The content of the [B] photoacid generator in the composition is relative to 1 〇〇. -37- 201142515 parts by mass of [A] polymer, preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass. If the content of the [B] photoacid generator is in the above-mentioned range, the composition can be made. The radiation sensitivity of the object is optimized, and an interlayer insulating film or the like is formed while maintaining the permeability. [C] Compound&gt; In the positive-type radiation-sensitive linear composition, in order to prevent radical oxides, the bond of the compound is caused. Decomposition, and the compound [C] is contained. As the compound, a radical scavenger such as a compound having a hindered phenol structure and a compound having a hindered amine structure, a compound having an alkylene ester structure, and a thioether structure can be exemplified. a compound decomposing agent such as a compound, etc. By containing the above-mentioned [C] compound, the capture of a group which occurs during exposure or heating, or the decomposition of a peroxide generated by oxidation can be prevented, thereby preventing the radical or The decomposition of the polymer molecules by the oxide, and as a result, the interlayer insulating film obtained from the composition can have excellent light resistance and heat resistance. Since a radical scavenger or a peroxide decomposing agent having a fixed structure is used as a compound, even if they are added, it is possible to prevent the transparency of the layer film and the like obtained from the composition while maintaining the radioactivity of the composition at a high level. The rate and the reduction of the voltage holding ratio. For the compound having the above hindered phenol structure, neopentyl quinone [3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionate] , Ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Ten Best, Peripheral or Excessive Free Energy of Phosphoric Oxidation The appliance is [C] sensitive, such as thio-d-octane-38- 201142515-based 3-(3,5-di-t-butyl-4-yl-hydroxyphenyl)propionate, ginseng-(3, 5- Di-tert-butyl-4-hydroxybenzyl)isocyanate, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxybenzyl)benzene, N,N'-hex-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], 3,3',3',5', 5|,5'-hexa-tert-butyl^,&amp;',&amp;|-(mesitylene-2,4,6-triyl)tris-cresol, 4,6-bis(octyl sulphur Methyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4) -hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-para [ (4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-I,3,5·Tri-trap-2,4,6-(111,3^1,51^-three Ketone, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-tri-tac-2-ylamine)phenol. As a compound of the above-mentioned hindered phenol structure, commercially available products include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40 'Adekastab AO-50 ' Adekastab AO-60 ' Adekastab AO-70, produced by ADEKA. ' Adekastab AO-80 ' Adekastab AO-3 3 0 ' Sumitomo Chemical Co., Ltd. produces sumilizerGM, sumilizerGS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80; produced by Ciba Japan IRGANOX 1010, IRGANOX 1 03 5 'IRGANOX 1 076, IRGANOX 1 098, IRGANOX 1135, IRGANOX 1 3 3 0, IRGANOX 1 726, IRGANOX 1 42 5WL, IRGANOX 1 520L 'IRGANOX 245 'IRGANOX 259 'IRGANOX 3114, IRGANOX 565, IRGAMOD 295 ; (share) API Corporation produced by Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, -39- 201142515

Yoshinox 425, Yoshinox 250, Yoshinox 93 0, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314, etc. As the compound having the above hindered amine structure, for example, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetra) Methyl-4-piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octyloxy-2, 2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacic acid Ester, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl- 4-(piperidinyl)2-(3,5-di-t-butyl-4-ylhydroxybenzyl)_2-butylmalonate, bis(1-propenylfluorenyl-2,2,6,6-tetra Methyl-4-piperidinyl) 2,2-bis(3,5-a-second-butyl-4-butanosyl)_2_butylmalonate, bis(1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethyl·4_piperidinyl methacrylate, 4-[3-(3,5-di Tributyl-4-phenylphenyl)propanyloxy]-l-[2-(3-(3,5-di-t-butyl-4-ylhydroxy)propenyloxy]ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperazino)amino-N-(2,2 6, 6-tetramethyl-4(piperidinyl)propanamide, hydrazine (2,2,6,6-tetramethyl-4-piperidinyl) 12,3,4-butane tetracarboxylate, hydrazine (1,2,2,6,6-pentamethyl- 4-piperidinyl oxime", a compound such as 〆-butane tetracarboxylate; N, N', N'', N'''-肆- [4,6-bis-[butyl-(N-methyl-2,2,6,6-tetramethylpiperidinyl-4-yl)amino]-tripper-2·yl]_4,7_ Dioxane oxime, &quot;diamine, monobutylamine and 1,3,5-tri-trap with 1^,;^1_bis(2,2,6,6-tetramethyl_4_piperidine Poly) condensate of 1,6-hexanediamine and ruthenium-(2,2,6,6-tetramethyl-4-piperidyl)butylamine-40- 201142515 Polycondensate of 1,3,5·diindole and ν,Ν1-bis(2,2,6 6 -tetramethylpiperidyl)butylamine, poly[((m3 -tetramethylbutyl)amine) Base-1,3,5-tritrap-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2, 2,6,6-tetramethyl-4-indolyl)imine}], 1,6-hexanediamine-oxime, Ν'-bis(2,2,6,6-tetramethyl-4 -piperidinyl) and polyglycosate of porphyrin-2,4,6-trichloro-1,3,5-three tillage, poly[(6_morpholinyl-average tillage-2,4-diyl) )[(2,2 ,6,6-tetramethyl-4-piperidinyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imido]] a multi-bonded high molecular weight HALS of a piperidine ring by a triterpene skeleton; a copolymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 12,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-methylidene Base)-2,4,8,10-tetraoxaspiro[5,5]~ (----------------------------------------------------------------------------------------------------- As a compound having the above-mentioned hindered amine structure, for example, Adekastab LA-52, Adekastab LA57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63 P 'Adekastab LA-68LD manufactured by ADEKA, for example, are commercially available. 'Adekastab LA-77 'Adekastab LA-82, Adekastab LA-87, sumilizer9A manufactured by Sumitomo Chemical Co., Ltd., CΗ IM ASS ORB 1 1 9FL, CHIMASSORB2020FDL, C Η IM ASSORB 9 4 4 manufactured by Ciba Japan FDL, TINUVIN622LD, TINUVIN144, TIMUVIN7 65, TINUVIN770DF, etc. -41 - 201142515 In the case of a compound having an alkyl phosphite structure, ginylphosphoric acid phosphite, phosphite (p-octylphenyl) ester, and phosphorous acid ginate may be exemplified. 2,4,6-e (α-phenylethyl)]ester, phosphite (p-butenylphenyl) ester, bis(p-nonylphenyl)cyclohexyl phosphite, phosphite (2,4_ di-t-butylphenyl) ester, bis(2,4-di-t-butylphenyl)neopentitol diphosphite, 2,2'-methylene double (4,6 -di-t-butyl-b-phenyloxy)(2-ethylhexyloxy)phosphorus, distearyl neopentyl alcohol diphosphite, 4,4'-isopropylidene-diphenol Phosphite, tetrakis(tridecyl)-4,4'-butylene-bis(3-methyl-6-tert-butylphenol) diphosphite, bismuth (2,4-second third Butylphenyl)-4,4'-extended biphenyl phosphite, 2,6-di-t-butyl-4-methylphenyl.phenyl-neopentitol diphosphite, 2, 6-di-t-pentyl-4-methylphenyl•phenyl.neopentitol diphosphite, 2,6-di-t-butyl-4-ethylphenyl•stearyl • neopenta Tetrahydrin diphosphite (2,6-di-t-butyl-4-methylphenyl)neopentitol diphosphite, 2,6-di-t-pentyl-4-methylphenyl-phenyl-pivala Alcohol diphosphite and the like. For compounds having an alkyl phosphite structure, commercially available, for example, Adekastab PEP-4C 'Adekastab PEP-8 ' Adekastab PEP-8W 'Adekastab PEP-24G 'Adekastab PEP-36 ' Adekastab manufactured by ADEKA HP-10 'Adekastab 2 112, Adekastab 2 6 0, Adekastab 5 2 2 A, Adekastab 117 8, Adekastab 1 5 0 0, Adekastab C, Adekastab 135A 'Adekastab 3010, Adekastab TPP, IGAGAOS168 manufactured by Ciba Japan . -42 - 201142515 For the compound having a thioether structure, for example, dilaurylthiodipropionate, ditridecylthiodipropionate, di(tetradecyl)sulfide may be exemplified. Propionate, distearyl thiodipropionate, neopentyl quinone oxime (3-lauryl thiopropionate), neopentyl quinone oxime (3-octadecyl thiopropionate), neopentyl Tetrapropanol (3-tetradecylthiopropionate), neopentyl pentoxide (3-stearyl thiopropionate), and the like. As the compound of the thioether structure, for example, Adekastab AO-412S manufactured by ADEKA, Adekastab AO-503, sumilizer TPL-R manufactured by Sumitomo Chemical Co., Ltd., sumilizer TPM 'sumilizer TPS, sumilizer TP-D can be exemplified. SUMTP, DSTP, DMTP, DTTP, etc. manufactured by IRGANOXPS800FD, IRG ANOXP S 8 02FD ' (share) API Corporation manufactured by sumilizer MB and Ciba Japan. These compounds may be used alone or in combination of two or more. In the radiation sensitive composition of the present invention, the content of the [C] compound is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 〇·5 by mass based on 1 part by mass of the [A] polymer. More than 5 parts by weight, more preferably 1.5 parts by mass or more and 3 parts by mass or less. When the content of the [C] compound of the [A] polymer is in the above range, the sensitivities of the composition can be maintained, and the interlayer insulating film obtained from the composition can be further improved. Light transmittance, voltage holding ratio, light resistance, and heat resistance. &lt;Other optional components&gt; The composition may contain an interfacial activity -43-201142515 as needed, in addition to the above-mentioned [A] to [C] components, within a range that does not affect the desired effect. Other optional components such as an adhesion aid, a basic compound, a quinonediazide compound, a plasticizer, and the like. The following optional components may be used singly or in combination of two or more. &lt;Interacting Agent&gt; In order to further improve the coating film formability of the positive-type radiation-sensitive composition, it is preferable to add a surfactant. As such a surfactant, for example, a fluorine-based surfactant, a polysiloxane surfactant, and other surfactants may be mentioned. In the case of the fluorine-based surfactant, a compound having a fluoroalkyl group and/or a fluorine-extended alkyl group in at least one of a terminal, a main chain and a side chain is preferred. Examples of the fluorine-based surfactant include, for example, 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, ι, ι, 2, 2-tetrafluoro-n-octyl (n-hexyl)ether, hexaethylene glycol bis(1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octaethylene glycol di(1,1,2 ,2-tetrafluoro-n-butyl)ether, hexapropanediol bis(^,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl Ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10 - decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin (fluoroalkyl polyoxyethylene ether), fluoroalkyl iodide, halothane Betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxide, fluoroalkyl carboxylate, and the like. The commercially available product of the fluorine-based surfactant may, for example, be BM-1000, BM-1100 (above, manufactured by BMCHEMIE), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173 '-44 - 201142515 MEGAFAC F183, MEGAFAC F178, MEGAFAC F19 1, MEGA FA C F471' MEGA FAC F476 (above, manufactured by Otsuka Ink Chemical Industry Co., Ltd.), FLUORADFC-170C, FLUORADFC-171, FLUORADFC-430, FLUORADFC-431 (above, Sumitomo 3M (share) manufacturing ), SurflonS-1 12, SurflonS-1 1 3, SurflonS-13 1 ,

SurflonS-141 'SurflonS -1 45 ' S urf 1 ο n S - 3 8 2 ' S urf 1 ο n SC -1 0 1 ' SurflonS C-1 02 , S urf 1 ο n SC -1 0 3 , SurflonSC- 1 04 ,

Surflon SC-105, Surflon SC-106 (above, manufactured by Asahi Glass Co., Ltd.), EFTOP EF301' EFTOP EF303, EFTOP EF352 (above, manufactured by New Akita Chemicals Co., Ltd.), FTERGENT FT-100, FTERGENT FT-110, FTERGENT FT- 140A, FTERGENT FT-1 50, FTERGENT FT-250 'FTERGENT FT-251 'FTERGENT FT-3 00 'FTERGENT FT-310, FTERGENT FT-400S, FTERGENT FTX-218, FTERGENT FT-251 (above, NEOS) Manufacturing) and so on. Examples of the polyoxo-based surfactant include TORAY SILICONE DC3PA, TORAY SILICONE DC7PA, TORAY SILICONE SH11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH-190, TORAY SILICONE SH- 193, TORAY SILICONE SZ- 6 03 2. TORAY SILICONE SF-8428, TORAY SILICONE DC-57, TORAY SILICONE DC-190, SH 8 4 0 0 FL UID (above, TORAY · DOW CORNING · SILICONE) TSF-4440, TSF-43 00, -45- 201142515 TS F-4445, TSF-4446, TSF-4460, TSF-4452 (above, manufactured by GETOSHIB AS ILI C Ο NE (share)), Organo Siloxane P〇lymerKP341 ( Shin-Etsu Chemical Co., Ltd. manufactures) and so on. These surfactants may be used singly or in combination of two or more. The amount of the surfactant to be used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.05 parts by mass to 1 part by mass, per 100 parts by mass of the component [A]. When the amount of the surfactant used is 0.01 parts by mass to 2 parts by mass, the coating film can be reduced. &lt;Adhesion aid&gt; In the positive-acting radiation-linear composition, an adhesion aid for improving the adhesion of the inorganic material and the insulating film as a substrate, for example, ruthenium, A ruthenium compound such as ruthenium oxide or ruthenium nitride, a glass such as citrate 'quartz, and a metal such as gold, copper or aluminum. It is preferred to use a functional decane coupling agent for such an adhesion aid. Examples of the functional decane coupling agent include reactive substituents such as a carboxyl group, a methacryl group, an isocyanate group, an epoxy group (preferably an oxiran group), and a thiol group. Decane coupling agent, etc. Specific examples of the functional decane coupling agent include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethylene decyl decane, and vinyl trimethyl. Oxydecane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl alkyl dialkoxy decane, γ-chloropropyl Trialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxy-46-201142515 cyclohexyl)ethyltrimethoxydecane, and the like. Among them, preferred are γ-glycidoxypropylalkyl dialkoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and γ-methacryloxyloxy group. Propyltrimethoxydecane. In the positive-type radiation-sensitive linear composition, the adhesion aid is preferably 0.5 parts by mass to 20 parts by mass, more preferably 1 part by mass to 1 part by mass per 100 parts by mass of the [Α] polymer. It is used in an amount of 0 parts by mass. By setting the amount of the adhesion aid to the above range, the adhesion between the formed interlayer insulating film and the substrate can be improved. &lt;Basic compound&gt; As the basic compound, it can be arbitrarily selected from the basic compound used in the chemically amplified photoresist. The basic compound may, for example, be an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide or a quaternary ammonium carboxylic acid salt. By including a basic compound in the positive-type radiation-sensitive composition, the diffusion length of the acid generated by the photo-acid generator during exposure can be appropriately controlled, and good pattern developability can be formed. Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n-pentylamine. Diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like. The aromatic amine may, for example, be aniline, benzylamine, hydrazine, hydrazine-dimethylaniline or diphenylamine. In the case of a heterocyclic amine, it can be exemplified by, for example, a sharp, 2 -methylpyridine ' 4 -methyl oxime ratio, 2 -ethyl oxime Π ' ' 4 -ethyl yttrium, 2 - phenyl D, 4 - -47 - 201142515 Phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzene Imidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid decylamine, quinoline, 8-oxo porphyrin, pyridinium, pyrazole, hydrazine, hydrazine, pyrrolidine , piperidine, pipe trap, porphyrin, 4-methyl morpholine, 1,5-dioxinbicyclo[4,3,0]-5-nonene, 1,8-diguanidine [5,3,0 ]-7-undecene and the like. The quaternary ammonium hydroxide may, for example, be tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide or tetra-n-hexylammonium hydroxide. The carboxylic acid quaternary ammonium salt may, for example, be tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate or tetra-n-butylammonium benzoate. The content of the basic compound in the positive-type radiation-sensitive composition is preferably 1 part by mass or less, more preferably 0.2 part by mass or less based on 100 parts by mass of the [A] polymer. By setting the content of the basic compound to the above range, the pattern developability is good. &lt;Hydrazine diazide compound> The quinonediazide compound is a compound which generates a carboxylic acid by irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic or alcoholic compound (hereinafter referred to as "mother core") and a 1,2-naphthoquinonediazidesulfonium halide can be used. Examples of the above-mentioned mother nucleus include, for example, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, pentahydroxydiphenyl ketone, hexahydroxydiphenyl ketone, (polyhydroxyphenyl) alkane, and other mother nucleus. . -48- 201142515 For these mother cores, there may be mentioned: trihydroxydiphenyl ketone is, for example, 2,3,4-trihydroxydiphenyl ketone, 2,4,6-trihydroxydiphenyl ketone, etc.; Hydroxydiphenyl ketone is, for example, 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3,4,3'-tetrahydroxydiphenyl ketone, 2,3,4,4'-tetra Hydroxydiphenyl ketone, 2,3,4,2'-tetrahydroxy-4'-methyldiphenyl ketone, 2,3,4,4'-tetrahydroxy-3'-methoxydiphenyl ketone Et.; pentahydroxydiphenyl ketone is, for example, 2,3,4,2',6'-pentahydroxydiphenyl ketone or the like; 'hexahydroxydiphenyl ketone is, for example, 2, 4, 6, 3', 4' , 5'-hexahydroxydiphenyl ketone, 3,4,5,3,4|,5'-hexahydroxydiphenyl ketone, etc.; (polyhydroxyphenyl) alkane is, for example, bis(2,4-dihydroxyl) Phenyl)methane, bis(p-hydroxyphenyl)methane, cis (p-hydroxyphenyl)methane, 1,1,1-paraxyl (p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxybenzene) Methane, 2,2·bis(2,3,4-trihydroxyphenyl)propane, 1,1,3·g (2,5-dimethyl-4-hydroxyphenyl)-3-phenyl Propane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5- Methyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiguanidine-5,6,7,5',6 ',7'-hexanol, 2,2,4-trimethyl-7,2',4,trihydroxyflavan, etc.; for other parent cores, for example 2-methyl-2-(2,4 -dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-indole, [1-(3-{1-(4-hydroxyphenyl)-1-methylethyl b 4,6 -dihydroxyphenyl)-1-methylethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl -1-methylethyl)benzene, 4,6-bis U-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxybenzene. -49- 201142515 Among these mother cores, 2,3,4,4'-tetrahydroxydiphenyl ketone, tris(p-hydroxyphenyl)ethane, 4,4'-[1-[4- Π-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol. Further, in the case of the 1,2-naphthoquinonediazidesulfonium halide, 1,2-naphthoquinonediazidesulfonium chloride is preferred. Specific examples of 1,2,naphthoquinonediazide sulfonium chloride include 1,2-naphthoquinone quinone, nitrogen-4-sulfonium chloride, and 1,2-naphthoquinonediazide-5. - sulfonium chloride. Among them, '1,2-naphthoquinonediazide-5-sulfonyl chloride is used. As a suitable example of the condensate of the phenolic compound or the alcohol compound and the 1,2-naphthoquinonediazidesulfonium halide, 1,1,1-tris(p-phenylphenyl)ethane can be exemplified. And condensate of 1,2-naphthoquinonediazide-5-sulfonyl chloride, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1.methylethyl]benzene A condensate of bis]ethylene]bisphenol and 1,2-naphthoquinonediazide-5-open chlorobenzene. In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) and a 1,2-naphthoquinonediazidesulfonium sulfonium halide, the amount of the thiol group in the phenolic compound or the alcoholic compound can be used as Preferably, it is 30 to 85 m〇l%, more preferably 50 to 70 mol% of 1,2-naphthoquinonediazidesulfonium halide. The condensation reaction is carried out by a known method. Further, as the quinonediazide compound, it is also suitable to use 1,2-naphthoquinonediazidesulfonamide which changes the ester bond of the above-exemplified parent core to a guanamine bond, for example, 2, 3, 4 - 3 Aminodiphenyl ketone-1,2-naphthoquinonediazide-4-sulfonamide and the like. These [B] components may be used singly or in combination of two or more. -50- 201142515 &lt;Plasticizer&gt; In the case of a plasticizer, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, polyethylene glycol, glycerin, Dimethyl glycerol phthalate, dibutyl tartrate, dioctyl adipate, triethylene glycerol, and the like. &lt;Solvent&gt;. A solvent which can be used for the preparation of the positive-type radiation-sensitive composition is preferably a solvent which uniformly dissolves or disperses each component and does not react with each component. Examples of such a solvent include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. Classes, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, esters, and the like. Examples of the solvent include alcohols such as benzyl alcohol and diacetone alcohol; and ethers such as tetrahydrofuran and diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, and diisoamyl. a dialkyl ether such as ether or di-n-hexyl ether; and a diethylene glycol alkyl ether such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; ethylene glycol alkyl ether acetates such as methyl fibrin acetate, ethyl fibrin acetate, B Glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; propylene glycol monoalkyl ethers are, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol single Butyl ether and the like; -51- 201142515 Propylene glycol monoalkyl ether acetates are, for example, esters, propylene glycol monoethyl ether acetate, propylene glycol diol monobutyl ether acetate, etc.; propylene glycol monoalkyl ether propionate The class is, for example, an ester, a propylene glycol monoethyl ether propionate, a propylene glycol diol monobutyl ether propionate or the like; an aromatic hydrocarbon is, for example, The benzene or xylone is, for example, methyl ethyl ketone, methyl isoheptanone 4-hydroxy-4-methyl-2-pentanone or the like; the ester is, for example, methyl acetate, ethyl acetate propyl acetate, acetic acid Butyl ester, ethyl 2-hydroxypropionate, ester, ethyl 2-hydroxy-2-methylpropionate, hydroxyethyl ester, butyl glycolate, methyl lactate, butyl lactate, 3-hydroxypropionic acid Ester, 3-hydroxypropyl g-ester, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylate 'methoxyacetate, methoxyethyl butyrate, methyl ethoxyacetate, Ethoxyacetate, butyl ethoxyacetate, propyl propyl propyl acetate, butyl propyl acetate, ethyl oxyacetate, propyl butoxyacetate, butoxy Methyl propionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, and the like. Propylene glycol monomethyl ether acetate monopropyl ether acetate, propylene glycol monomethyl ether propionic acid monopropyl ether propionate, propane, etc.; butyl ketone, cyclohexanone, 2-, propyl acetate, acetic acid Methyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, propyl lactate, ethyl lactate, methyl 3-propylpropionate, propyl methoxyacetate, methoxyacetic acid Ethyl ester, ethoxyacetic acid, ethyl propoxyacetate, methyl butoxyacetate, butyl butoxyacetate, propyl 2-methyl 2-methoxypropionate, 2-ethoxy Ethyl propyl propionate-52-201142515 Among these solvents, ethers such as dialkyl ethers are preferred from the viewpoints of excellent solubility or dispersibility, non-reactivity with each component, and easiness of formation of a coating film. Classes, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters, especially good diethylene glycol Diethyl ether, diethylene glycol ethyl methyl ether, methyl fibrin acetate, ethyl fibrin acetate, propylene glycol monomethyl ether, propylene glycol monoethyl , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy-2- Methyl methacrylate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate, 2-methoxy Ethyl propyl propionate. These solvents may be used singly or in combination. Further, among these solvents, ethers such as dialkyl ethers such as diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisoamyl ether and di-n-hexyl ether are preferred. Diisoamyl ether. By using such a solvent 'when the radiation sensitive composition is coated on a large glass substrate by a slit coating method', the drying step time can be shortened, and the coatability can be further improved (the coating unevenness is suppressed). In addition to the above solvents, 'as needed' can also be combined with benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone Acetone, isophorone, hexanoic acid, citric acid, 1-octanol, 1-decyl alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyl A high boiling point solvent such as lactone, ethyl carbonate, propyl propyl carbonate, phenyl cellosolve acetate, or carboxol acetate is used together. -53- 201142515 &lt;Preparation of positive-type radiation-sensitive composition&gt; The positive-type radiation-sensitive composition of the present invention comprises the above-mentioned [A] polymer, [b] photo-acid generator, [C] compound, and as needed Prepared by mixing arbitrary ingredients. In general, the positive-acting radiation linear composition is preferably prepared and used in a state in which a suitable solvent is dissolved or dispersed. For example, a positive-type radiation-sensitive composition can be prepared by mixing the components [A], [B], and [C] and arbitrary components in a predetermined ratio in a solvent. The solid content concentration of the positive-type radiation-sensitive composition (the ratio of the mass of the polymer contained in the polymer solution to the total weight of the polymer solution) can be arbitrarily set depending on the purpose of use, the desired film thickness, and the like, and is preferably 5 It is 50% by mass, more preferably 10 to 40% by mass, still more preferably 5 to 35% by mass. &lt;Method of Forming Cured Film of Interlayer Insulating Film, etc.&gt; Next, a method of forming a cured film such as an interlayer insulating film on a substrate using the above-described positive-type radiation-sensitive composition will be described. This method includes the following steps described in the following order. (1) a step of forming a coating film of the positive-type radiation-sensitive composition on a substrate, (2) a step of irradiating at least a part of the coating film formed in the step (1), and (3) a step (2) The step of developing the coating film irradiated with radiation, and (4) the step of heating the coating film developed in the step (3). &lt;(1) Step of forming a coating film of the positive-type radiation-sensitive composition on the substrate&gt; In the step (1) above, the solution of the positive-type radiation-sensitive composition is -54-201142515 After the dispersion is applied onto the substrate, it is preferred to remove the solvent by heating (pre-baking) the coated surface to form a coating film. Examples of the base chess that can be used include glass, quartz, enamel, resin, and the like. Specific examples of the resin include a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and polyamidene 'cyclic olefin. And its hydride and the like. The coating method of the composition solution or the dispersion is not particularly limited. For example, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method can be employed. Among these coating methods, a spin coating method or a slit die coating method is preferred, and a slit die coating method is particularly preferred. The pre-baking conditions vary depending on the type of each component, the mixing ratio, etc., and are preferably 70 to 12 (about 1 to 10 minutes under TC.) (2) Step of irradiating at least a part of the coating film with radiation> In the step (2) above, at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it is usually exposed by a mask having a predetermined pattern. Radiation is preferably used for the photoacid generator. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet rays of 3 to 65 nm is particularly preferable. The amount of exposure in this step. The enthalpy obtained by measuring the intensity at a wavelength of 365 nm of the radiation by an illuminometer (OAI Model 356, manufactured by OAI Optical Associates Inc.) is preferably 500 J/m 2 to 6,000 J/m 2 , more preferably 1,500 J/m 2 〜1. 800J/m2 ° -55 - 201142515 &lt;(3) Developing step&gt; In the step (3), the exposed coating film is developed to remove unnecessary portions (irradiated portions of radiation) to form a predetermined Pattern The developing solution used in the step is preferably an alkaline aqueous solution. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia. An inorganic base, a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, etc. Further, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution in an appropriate amount. The concentration of the alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass in view of appropriate developability. For the development method, for example, a suitable method such as a liquid coating method, a dipping method, a vibration dipping method, or a shower method can be used. The development time varies depending on the composition of the positive-type radiation-radiating composition, and is preferably about 1 1 to about 180 seconds. After the development treatment, for example, after 3 to 90 seconds of running water washing, for example, by The compressed air or compressed nitrogen is air-dried to form a desired pattern. &lt;(4) Heating step&gt; In the step (4), heating of the patterned film using a heating means such as a hot plate or an oven can promote Above [A] The hardening reaction of the component [C] is carried out to obtain a cured product. The heating temperature in this step is, for example, 1 2 0 to 250 ° C. The heating time varies depending on the type of the heating device, for example, heating on a hot plate. In the step, it is carried out for 5 to 30 minutes; when the heating step is carried out in an oven, it is '30 to 90 minutes. It is also possible to use a stepwise baking method in which two or more heating steps are performed. Thus, it is possible to form a corresponding surface on the substrate surface. A pattern-like film of the interlayer insulating film is required. -56- 201142515 Further, the above-mentioned cured film is not limited to the interlayer insulating film 'which can be used as a separator or a protective film. &lt;Interlayer insulating film&gt; The film thickness of the interlayer insulating film thus formed is preferably 0.1 to 8', more preferably 0.1 to 6 μm, still more preferably 0.1 to 4 μm, and an interlayer formed by the positive-type radiation-sensitive composition of the present invention. Further, as shown in the following examples, the insulating film can satisfactorily satisfy the generally required properties such as heat resistance, transparency, and voltage holding ratio, and has high flatness without uneven coating. Therefore, the interlayer insulating film is suitable for use as a display element. [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 mass average molecular weight (Mw) and the number average molecular weight (?n) of the polymer were measured by gel permeation chromatography (Gpc) under the following conditions. Device: GPC-101 (manufactured by Showa Denko Co., Ltd.) Column: Combination GPC-KF-801, gpc-KF-802, GPC-KF-803 and GPC-KF-804 Mobile phase: Tetrahydrofuran

Column temperature: 40 ° C Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass -57- 201142515 i Sample injection amount: 1 0 0 μ L Detector: Differential refractometer standard material: monodisperse Synthesis of Polystyrene &lt;(A) Polymer&gt; [Synthesis Example I] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2,-azobis(2,4-dimethyl group) was added. Valeronitrile), 200 parts by mass of diethylene glycol ethyl methyl group. Next, 5 parts by mass of methacrylic acid '40 parts by mass of 1-ethoxyethyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, and 10 parts by mass of methacrylic acid 2 - were added. The hydroxyethyl ester and 3 parts by mass of the α-methylstyrene dimer were slowly stirred after being replaced by nitrogen. The temperature of the solution was raised to 70. (: While maintaining the temperature for 5 hours, a polymer solution containing the copolymer (A-1) was obtained. The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (A-) was 9,000. The solid content concentration of the polymer solution was 32.1% by mass. [Synthesis Example 2] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2,_ azobis (2,4-dimethicone) was added. Base valeronitrile), 200 parts by mass of diethylene glycol ethyl methyl ether, followed by 'addition of 5 parts by mass of methacrylic acid, 40 parts by mass of methyl propyl succinic acid tetrahydro-2H-piperidin-2-yl ester, 5 A part by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate and 3 parts by mass of α-methylstyrene dimer, after nitrogen substitution, started to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-) from 58-201142515. The polystyrene-converted mass of the copolymer (Α·2) The average molecular weight (Mw) is 9, 〇〇〇. In addition, the solid content concentration of the polymer solution obtained here is 31.3. [Synthesis Example 3] In a flask having a condenser and a stirrer, '7 parts by mass of 2,2'-azobis(methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether were added. Acetate. Then, 67 parts by mass of 1-n-butoxyethyl methacrylate, 23 parts by mass of benzyl methacrylate, and 10 parts by mass of methacrylic acid 'nitrogen substitution were added, and stirring was started slowly. The temperature was raised to 80 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (a-1). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (a-fluorene) was Further, the solid content concentration of the polymer solution obtained here was 3 0.3% by mass. [Synthesis Example 4] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2'-azobis (2) was added. -methyl methacrylate), 200 parts by mass of propylene glycol monomethyl ether acetate. Next, 90 parts by mass of 1-benzyloxyethyl methacrylate and 6 parts by mass of 2-hydroxyethyl methacrylate were added. Ester, 4 parts by mass of methacrylic acid, after nitrogen replacement, start slowly stirring to raise the temperature of the solution The temperature was maintained at 80 ° C for 6 hours to obtain a polymer solution containing the copolymer (a-2). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (a-2) was 9, 〇〇〇 Further, the solid content concentration of the polymer solution obtained here was 3 1.2% by mass. -59- 201142515 [Synthesis Example 5] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2'-azo was added. Bis(methyl 2-methylpropionate), 200 parts by mass of propylene glycol monomethyl ether acetate, and then, 85 parts by mass of tetrahydro-2H-pentan-2-yl methacrylate, 7 parts by mass After 2-hydroxyethyl acrylate and 8 parts by mass of methacrylic acid were replaced by nitrogen, stirring was started slowly. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (a-3). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (a-3) was 1,0,000. Further, the solid content concentration of the polymer solution obtained here was 29.2% by mass. [Synthesis Example 6] In a flask having 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. Ether. Next, 52 parts by mass of glycidyl methacrylate and 48 parts by mass of benzyl propyl methacrylate were added, and after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing a copolymer (aa-Ι). The mass average molecular weight (Mw) of the polystyrene of the copolymer (aa-丨) was 10,000. Further, the solid content concentration of the polymer solution obtained here was 32.3% by mass. [Synthesis Example 7] In a flask having a condenser and a stirrer, 7 parts by mass of 2,2,-azobis(2,4-methylpentanenitrile) and 200 parts by mass of diethylene glycol ethyl group were added. Ether. Then, '45 parts by mass of 3,4_epoxycyclohexylmethyl-60-201142515 methacrylate, 45 parts by mass of benzyl methacrylate, and 1 part by mass of methacrylic acid were added, and the mixture was slowly stirred. . The temperature of the solution was raised to 801:, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (aa_2). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (aa-2) was 1,0,000. Further, the solid content concentration of the polymer solution obtained here was 33.3% by mass. [Synthesis Example 8] In a flask having 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. Ether. Then, 35 parts by mass of cesium-n-butoxyethyl methacrylate, 35 parts by mass of benzyl methacrylate, and 30 parts by mass of glycidyl methacrylate were added, and after the replacement with nitrogen, the mixture was slowly stirred. The temperature of the solution was raised to 8 ° C to maintain the temperature for 6 hours to obtain a polymer solution containing the copolymer (aa - 3). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (aa-3) was 1,0,000. Further, the solid content concentration of the polymer solution obtained here was 3 2.3% by mass. &lt;Preparation of Radiation-sensitive Composition&gt; [Example 1] A solution containing the polymer (A-1) obtained in Synthesis Example 1 [corresponding to 1 part by mass (solid content) polymer (A-1) Mixture: 4 parts by mass of [B] component [(camphorsulfonyloxyimido]5H_thiophene-2-ylidene)-(2-methylbenzidine)acetonitrile] (Ciba · Specialty . Chemicals "CGI 1 3 80" manufactured by the company, 1 part by mass of ginseng-(3,5-di-tert-butyl-61-201142515-based 4-hydroxybenzyl)-isocyanate (made by ADEKA) as component [C] "Adekastab AO-20"), 0.20 parts by mass of the organic resin resin surfactant ("SH8400FLUID" manufactured by TORAY DOW CORNING), and 3.0 parts by mass of γ as the component [E] as the component [D] - Glycidylpropyltrimethoxydecane, which was filtered through a membrane filter having a pore size of 0.2 μm, thereby preparing a radiation sensitive composition (S-1). <Examples 2 to 10, Comparative Examples 1 to 4> A positive-type radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of the respective components were as described in Table 1. Further, the components used in the respective examples and comparative examples were as follows. <Photoacid generator [Β] &gt; (Β-1): 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate (Β-2): benzyl-4 -hydroxyphenylmethylphosphonium hexafluorophosphate (Β-3): [(5-propylsulfonyloxyimido-5 Ηthiophen-2-yl)-(2-methylphenyl)acetonitrile] ( "IRGACUREPAG 1 03" (B-4) manufactured by Ciba Specialty Chemicals, Inc. (B-4): [(5-octylsulfonyloxyimido-5H-thiophene-2-ylidene)-(2-methylbenzene) Acetonitrile] ("IRGACUREPAG108", manufactured by Ciba. Specialty Chemicals, Inc.) (B-5): [(5-p-toluenesulfonyloxyimido-5H-thiophene-2-ylidene)-(2-methylbenzene) ) acetonitrile] ("IRGACUREPAG 1 2 1", manufactured by Ciba. Specialty. Chemicals) - 62- 201142515 (Β·6): [( camphorsulfonyloxyimino- 5H-thiophene-2-ylidene)-( 2-methylbenzene)acetonitrile] ("CGI 1 3 80" manufactured by Ciba. Specialty.) (B-7): [(5-octylsulfonyloxyimino-(4-methoxybenzene) ) acetonitrile] (Φ "C G17 2 5" manufactured by Ciba· Specialty · C h em ica 1 s) <Compound [C ] &gt; (Cl): gin-(3,5-di-t-butyl-4 ·Hydroxybenzyl)-isocyanate (ADEKA "AdekastabAO-20" (C-2) manufactured by the company: 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) Benzene ("Adekastab AO-330" produced by ADEKA) (C-3) : 2,2·-methylenebis(4,6·di-t-butyl-1-phenyloxy)(2-ethyl Hexyloxy)phosphorus ("Adekastab HP-1 0" by ADEKA) (C-4): Distearyl neopentyl glycol diphosphite ("AdekastabPEP-8" by ADEKA) (C- 5): Neopentyl alcohol oxime (3_lauryl thiopropionate) ("Adekastab AO-412S" manufactured by ADEKA Corporation) <Interfacial agent [D ] &gt; (D-1): Polyoxonium interface activity Agent ("SH8400FLUID" by DOW CORNING)

(D-2): Fluorine-based surfactant ("FTERGENT FTX-2 1 8" by NE〇S) -63- 201142515 <Adhesion aid [E] &gt; (El) : γ-glycidyloxy Propyltrimethoxydecane (Ε-2): β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (Ε-3): γ-methylpropenyloxypropyltrimethoxy Decane &lt;Basic Compound [F]> (F-1) : 4-Dimethylaminopyridine (F-2) : 1,5-Dioxabicyclo[4,3,0]-5-decene &lt;lt Physical Property Evaluation&gt; Using the various positive-type radiation-sensitive compositions prepared as above, the composition and various properties thereof as a coating film or an interlayer insulating film were evaluated as follows. The evaluation results are shown in Table 1 below. (1) Evaluation of sensitivities hexamethyldioxane (HMDS) was applied to 550 x 650 mm chromium-formed glass and heated at 60 ° C for 1 minute (hereinafter also referred to as "HMDS treatment"). On the HMDS-treated chromium-formed glass, the radiation-sensitive composition prepared as described above was applied by a slit die coater "TR63 2 1 0 5 -CL", and the ultimate pressure was set to 100 Pa under vacuum. Remove the solvent. Thereafter, prebaking was further carried out for 2 minutes in an environment of 90 ° C to form a coating film having a film thickness of 3.0 μm. Next, using a MPA-600FA lithography machine manufactured by CANON, a reticle having a pattern of a line-to-gap ratio (10:1) of 60 μm was used to irradiate the radiation on the coating film with the exposure amount as a variable, and then to Table 1 The tetramethylammonium hydroxide aqueous solution having the stated concentration was developed by a liquid coating method in an environment of 25 t. Here, the development time is as follows, in the case where the concentration of the aqueous solution of tetramethylammonium hydroxide in -64 - 201142515 is 0.4% by mass in the case of τ is 80 seconds, and in the case of using 23.8% by mass of the developer In the case of 5 sec. Next, water washing was performed for 1 minute using ultrapure water, and thereafter, a pattern was formed by drying on a glass substrate formed by chrome plating after HMDS treatment. At this time, in order to completely dissolve the 6 μm gap pattern, the necessary exposure amount was adjusted and evaluated. The case where the 値 is below 500 J / m 2 may be referred to as good sensitivity. (2) Evaluation of light resistance The composition is coated on a ruthenium substrate by a spin coater, and then heated at 90 ° C. The plate was prebaked for 2 minutes to form a coating film having a film thickness of 3.Οηη. The organic tantalum substrate was heated at 220 ° C for 1 hour in a dust-free oven to obtain a cured film. On the cured film, a UV irradiation device ("UVX-02516S1JS01" manufactured by US IO Corporation) was irradiated at 800 00 J/m 2 at an illuminance of 130 mW. When the amount of reduction in film thickness after irradiation is 2% or less as compared with the film thickness before irradiation, it can be said that the film has good light resistance. Further, in the evaluation of the light resistance, the formation pattern of the formed film was not required, so that the development step was omitted, and only the coating film forming step, the light resistance test, and the heating step were carried out, and evaluation was performed. (3) Evaluation of heat resistance A coating film was formed on the ruthenium substrate in the same manner as the above evaluation of light resistance. The tantalum substrate was heated in a dust-free oven at 2 200 t for 1 hour to obtain a cured film. The film thickness (T2) of the obtained cured film was measured. Then, the base material on which the cured film was formed was additionally baked at 240 ° C for 1 hour in a clean oven. Then, the film thickness (t2) of the cured film was measured at -65 to 201142515. Rate {丨t2-T2| /T2}xl〇〇[%]. The evaluation results of heat resistance are shown in Table 1. When the enthalpy is 3% or less, it can be said that the heat resistance is good. (4) Evaluation of light transmittance A coating film was formed on the ruthenium substrate in the same manner as the above evaluation of light resistance. The crucible substrate was heated at 220 ° C for 1 hour in a clean oven to obtain a cured film. The light transmittance at a wavelength of 400 nm was measured by a spectrophotometer ("150-20 type DoubleBeam" manufactured by Hitachi, Ltd.) and evaluated. At this time, less than 90% of the cases are called unacceptable transparency. (5) Evaluation of heat-resistant transparency The substrate measured by the above (4) evaluation of light transmittance was further heated at 250 ° C for 1 hour in a dust-free oven, and the light transmittance before and after heating was as described above (4) After the measurement of the method described in "Evaluation of Light Transmittance", the heat-resistant transparency was calculated according to the following formula. When the enthalpy is 4% or less, it is judged that the heat resistance and transparency are good. Heat-resistant transparency (%) = "(4) Light transmittance (%) - Light transmittance after heating (%) (6) Evaluation of voltage retention rate In preparation of liquid composition On the surface of the object, a Si 02 film for preventing precipitation of sodium ions is formed, and an ITO (indium-tin oxide alloy) electrode is further spin-coated on a soda lime glass substrate having a predetermined shape and then subjected to spin coating at 9 ° C. The film was prebaked in a dust oven for 10 minutes to form a coating film having a film thickness of 2.0 μm. -66- 201142515 Next, the coating film was exposed to an exposure amount of 500 J/m 2 without using a photomask. Thereafter, post-baking was performed at 30 ° C for 30 minutes to cure the coating film to form a permanent cured film. Next, the substrate on which the pixel was formed and the substrate on which only the ITO electrode was vapor-deposited in a predetermined shape were bonded together with a sealant. The sealant was mixed with a glass bead of 0.8 mm, and then injected into a liquid crystal MLC660 manufactured by Merck. 8 (trade name), making liquid crystal cells. Then, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measuring system ("VHR-1A type" manufactured by TOYO Technica Co., Ltd.). At this time, the applied voltage was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is 値 (the potential difference of the liquid crystal cell after 16.7 milliseconds / the voltage applied by 0 milliseconds). When the voltage holding ratio of the liquid crystal cell is less than 90%, 'the liquid crystal cell is in the time of 16.7 milliseconds, and the applied voltage cannot be maintained at a predetermined level, and the liquid crystal cannot be sufficiently oriented to cause burnt of the residual image or the like. The danger of the screen is high. -67- 201142515 i 丨比关4 1 inch 1 i/i 〇*» 〇〇ι^&gt; ο» 丨比纤3 CO 1 Μ 〇cr\ o 8 1〇U-) l£&gt; 丨Comparative example 2 (Μ 1 ω § ίΛ 〇rr, o ΓΛ ΓΛ Ό Ο » 卜 s 1 to 1 1 r*H 1 w O *r 〇mo 8 U-) ΓΛ kD 〇\ 卜 a; I Example 10 ο »- Η 1 00 00 1〇cn fvj — 一〇rn O o 8 — (Ν ι〇Ο 丨Example 9 σ) 1 ΙΟ LO on csj - One moo 8 ι〇&lt;^\ &lt;SJ Example 8 / —V CO 1 00 VwZ LO CsJ —1 — 〇oo - ΟΟ m 3; Example 7 卜 1 t/i Sw&lt;· S — — Ο o ο — CN3 § &lt;S) Example 6 CO 1 CO Sw ^ — — 〇CT) o 8 *— Γ&lt;1 CNJ 丨Example 5 in I lO V__' Another — 〇ΓΛ o 03 No ci Bao Example 4 Inch 1 CO Nw^ 〇rr, 一Ο ΓΤ» &lt;^ 3 inch CVJ &lt;*&lt;*ί &lt;D\ C^J Example 3 /»—N CO 1 in v_/ 8 — 〇ο 〇«Ν (Μ sm 1 Example 2 r—N cs] 1 w 8 一Ο cn oo § 05 ΓΛ S; rr\ 1 Example 1 « •&quot;S rH 1 w 8 — 〇ίΛ o § ΓΛ y〇Oi ms •-H 1 &lt; 03 1 &lt;: J—S 1 03 1 03 C0 1 C3 1 C0 03 1 03 03 y&lt;~&gt; \ 00 1 OT /^~v 1 PQ (M 1 DP 1 (B-3) , 1 m 1 m Ξ 1 CQ 1 DQ 1 o 1 〇1 〇✓ 1 〇&gt;w· 1 〇1 Q 03 1 Q 1 ω Nw^ CM 1 ω CO 1 ω 1 {X4 s 1 tL, developer concentration (mass 簠%) 1 radiation sensitivity U/m2) light resistance (%) 1 heat resistance (%) 1 drunk (%) 1 Heat resistance and transparency (%) 1 Voltage holding ratio (1⁄2) 1 [A ] Structural unit: (mass) S ^ m E $ 〇 □ S [c] Antioxidant (parts by mass) 51 Q靼S—J [E] Adhesive auxiliary (parts by mass) 1 [F] Basic compound: Evaluation of radiation sensitivity composition -89- s 201142515 From the results of Table 1, it can be understood that the implementation of [A], [B], and [C] components is included. The positive-type radiation linear composition of Examples 1 to 10 is not contained in [C] Comparative Example 1 to 4 The positive-type radiation-sensitive linear composition has high light resistance and high heat resistance, and the following interlayer insulating film can be formed, that is, the radiation sensitivity, transparency, heat-resistant transparency, and resistance can be sufficiently satisfied. These general required characteristics of solvent properties. [Industrial Applicability] As described above, the positive-type radiation-sensitive composition of the present invention suppresses the generation of radicals or peroxides while maintaining the radiation sensitivity of the radiation-sensitive linear composition at a high level. This can be suitably used by forming a positive-type radiation-sensitive composition of an interlayer insulating film which has excellent light resistance and heat resistance and which suppresses reduction in light transmittance, heat-resistant transparency, and voltage holding ratio. [Simple description of the diagram] None. [Main component symbol description] No 0 -69-

Claims (1)

201142515 VII. Patent Application Range: 1 · A positive-type radiation-linear composition comprising: [A] a structural unit having a group represented by the following formula (1) and a ring-containing ring in the same or different polymer molecules a polymer of a structural unit of an oxy group; [B] a photoacid generator; and [C] a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing an alkyl phosphite structure, and a thioether-containing structure One or two or more compounds selected from the group consisting of compounds, R1 - 〇 - C - OR3 (1) I Rz In the formula (1), R1 and R2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group Or an aryl group, a part or all of the hydrogen atom of the alkyl group, the cycloalkyl group or the aryl group may be substituted by a substituent, wherein R1 and R2 are both a hydrogen atom, and R3 is an alkyl group or a cycloalkyl group. The arylalkyl group, the aryl group or the group represented by -M(R3m) 3 is Si, Ge or Sn, and R3m is an alkyl group. Some or all of these hydrogen atoms may be substituted by a substituent, and R1 and R3 may be bonded. A cyclic ether is formed. 2. The positive-type radiation-sensitive linear composition according to claim 1, wherein the [B] photo-acid generator contains an oxime sulfonate group represented by the following formula (2), -70-201142515 ο, C= N—〇—s — Rb, (2) / II In the formula (2), RB1 represents an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent. 3. The positive-type radiation-sensitive linear composition according to claim 1 or 2, wherein the content of the [C] compound is 〇·1 part by mass or more and 1 相对 with respect to 1 part by mass of the [A] polymer. Below the mass. 4. A positive-type radiation-sensitive composition as claimed in claim 1 or 2 which is used for forming an interlayer insulating film for a display element. 5. A method of forming an interlayer insulating film for a display element, comprising the steps of: (1) forming a coating film of a positive-type radiation-sensitive composition according to claim 4 of the patent application form 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) a step in the step ( 3) A step of heating the developed coating film. An interlayer insulating film for a display element which is formed of a positive type radiation-sensitive composition as in the fourth aspect of the patent application. -71 - 201142515 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: