TW200905383A - Photosensitive insulating resin composition - Google Patents

Abstract

A photosensitive insulating resin composition characterized by containing (A) resin containing a structural unit having a phenolic hydroxyl group, (B) photosensitive acid generating agent, (C) crosslinking agent containing at least one member selected from the group consisting of oxetanylated compound (C1) and epoxidized compound (C2), (D) solvent and (E) crosslinked microparticles so that the total amount of oxetanylated compound (C1) and epoxidized compound (C2) contained in the crosslinking agent (C) is in the range of 70 to 100 mass% based on the whole mass (100 mass%) of the crosslinking agent (C). This composition can provide a crosslinked product excelling in image resolution, electrical insulation, adherence, bonding property, etc. and finds suitable application in uses, such as a surface protective film and interlayer insulating film of semiconductor device.

Description

200905383 IX. The present invention relates to a photosensitive insulating resin used for a surface protective film (Overcoat film) or an interlayer insulating film (Passivation film) of a semiconductor element or the like, a wafer laminating adhesive, and the like. And an insulating hardened material formed by hardening it. More specifically, the photosensitive insulating resin is a cured product excellent in properties such as resolution, electrical insulating properties, adhesion, and adhesion, and a photosensitive insulating resin composition capable of obtaining the cured product. [Prior Art] Conventionally, an interlayer insulating film or a surface protective film used for a semiconductor device of an electronic device has been widely used as a polyimide or a polybenzoxazole-based resin which is excellent in heat resistance and mechanical properties. In addition, in order to improve productivity or to improve the accuracy of film formation, many photosensitive polyimides or photosensitive polybenzoxazole resins have been examined. For example, Patent Document 1 or Patent Document 2 describes a positive photosensitive resin composition formed of a polyimine precursor or a quinonediazide compound. Patent Document 3 and the like describe polybenzoxazole precursors and heavy materials. A positive photosensitive resin composition formed of a hydrazine compound. Further, a negative photosensitive resin composition based on a polyimine precursor introduced by photolinking or an ionic bond is also put into practical use. However, these photosensitive resin compositions have problems such as reduction in the thickness of the cured film (volume shrinkage), multi-stage baking at the time of curing, environmental control, and the like, which are industrially difficult to implement. Further, Patent Document 4 and the like also describe a negative photosensitive insulating resin composition using a polyphenylene ether (-5-200905383 polyphenylene oxide) resin. However, the balance of performance of the photosensitive insulating resin composition such as resolution, electrical insulating properties, thermal shock resistance, and adhesion is still unclear. Therefore, in order to solve the above problems, a photosensitive insulating resin composition having an alkali-soluble resin having a phenolic hydroxyl group such as a phenol resin or a polyhydroxystyrene is proposed (for example, Patent Documents 5 to 9). The alkali-soluble resin used in these resin compositions is a user which can be developed by an aqueous alkali solution. For example, it is described in Patent Documents 5 and 6 that the film formed by using an alkali-soluble resin having a phenolic hydroxyl group has sufficient developability due to the alkali aqueous solution. Further, the molecular weight of the alkali-soluble resin also shows the influence on the resolution, thermal shock resistance and heat resistance of the obtained insulating film. However, in these patent documents, it is not shown that the characteristics other than the above characteristics can be improved by the alkali-soluble resin, and there is no indication about the effect on the kind of the alkali-soluble resin. In particular, it is described that the electrical insulating properties are controlled by the amount of the crosslinking agent, and the addition of the crosslinked fine particles to the thermal shock resistance is improved. Further, Patent Document 10 discloses a radiation sensitive resin composition containing an alkali-soluble resin, an epoxy compound, or a compound containing an oxetane group in the molecule. This patent document discloses that the phenomenon of overheating can be prevented by using an oxetane group-containing compound, but it does not show an additional effect. Further, it is shown that the molecular weight of the alkali-soluble resin affects resolution, developability, and plating resistance, but it is not shown that the ratio of the epoxy group and the oxetane compound to the total crosslinking agent can be improved. In addition to the characteristics of 'in particular electrical insulation, and does not show any efficacy of the type of alkali-soluble resin, and the combination of epoxy compounds and oxetane compounds to the amount of total cross-linking agent . Patent Document 1 1 discloses a photosensitive resin composition containing an adhesive polymer, a photopolymerizable compound having at least one polymerizable cyclic ether group in a molecule, and a photoacid generator, as the above-mentioned gel The viscous polymer is, for example, a styrene resin, and examples of the photopolymerizable compound include an oxetane compound and an epoxy compound. However, this patent document discloses that the sensitivity, the peeling property, and the pattern shape of the photosensitive resin composition by using an oxetane compound or an epoxy compound are increased, but the types and combinations of alkali-soluble resins are not shown. The content of the epoxy group and the oxetane compound to the amount of the total crosslinking agent improves the electrical insulation' and does not show any effect on the kind of the alkali-soluble resin. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. 2000-98. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made to solve the problems associated with the conventional art described above, and to provide a cured product excellent in properties such as resolution, electrical insulating properties, adhesion, and adhesion. In addition, it is intended to provide a photosensitive insulating resin composition which is suitable for the use of an interlayer insulating film or a surface protective film for a semiconductor element. In order to solve the above problems, the inventors of the present invention have intensively studied and found that a cured product excellent in resolution, electrical insulating properties, adhesion, and adhesion can be obtained by using a specific crosslinking agent. Further, it is found to be composed of a photosensitive insulating resin by using an alkali-soluble resin having a phenolic hydroxyl group and using an oxetane group-containing compound and/or an epoxy group-containing compound having a specific ratio or more to the total crosslinking agent. The electrical insulating properties of the cured product, the adhesion to the substrate, and the adhesion to the coated substrate are remarkably increased. Further, by using an oxetane group-containing compound and/or an epoxy group-containing compound having a specific ratio of the total cross-linking agent or more, it has been found that outgas formation at the time of hardening can be reduced, and voids are prevented from occurring. A cured product excellent in adhesion to a substrate and adhesion to a coated substrate can be obtained. The present invention has been completed based on these findings. That is, the photosensitive insulating resin composition of the present invention contains (-8-200905383 A) a resin having a structural unit having a phenolic hydroxyl group, (B) a photo-sensitive acid generator, and (C) at least one selected a cross-linking agent, a (D) solvent, and (E) cross-linked fine particles, which are a group of the oxetane-based compound (C 1 ) and the epoxy group-containing compound (C2), are crosslinked with respect to 100% by mass. The total amount of the agent (C) is characterized in that the total amount of the oxetane compound (C1) and the epoxy group-containing compound (C2) contained in the crosslinking agent (C) is from 7 to 100% by mass. The resin (A) is preferably a structure comprising at least one selected from the group consisting of the structure represented by the following formula (I) and the structure represented by the following formula (Π).

In the formula (I), R is independently ' represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and represents an integer of 1 to 3'. An integer of 3, mi+ni=4.

200905383 In the formula (Π), 'R, Ri and R2 are each independently, and represent a hydrogen atom, a fluorenyl group having 1 to 4 carbon atoms, a decyloxy group having 1 to 4 carbon atoms or a halogen atom, which means 1 to 3; The integer 'n2" represents an integer of 1 to 3, m2+n2=4, the chemical system represents an integer of 〇~3, the n3 represents an integer of 1 to 4, m3+n3=4 〇the above crosslinking agent (C) is It is preferred to contain an oxetane group-containing compound (C1) and an epoxy group-containing compound (C2). The crosslinked fine particles (E) are polymers containing a structural unit derived from a diene compound, a structural unit derived from a hydroxyl group-containing unsaturated compound, and a structural unit derived from a crosslinkable compound having two or more unsaturated polymerizable groups. It is appropriate. Further, the polymer constituting the crosslinked fine particles (E) may further contain a structural unit derived from an aromatic vinyl compound. The photosensitive insulating resin composition may further contain (a) a phenol compound, and may further contain (F) a binder. In the case of using the photosensitive insulating resin composition of the present invention, the semiconductor device of the present invention has a cured insulating film formed using the photosensitive insulating resin composition of the present invention. When the photosensitive insulating resin composition of the present invention is used, the cured product which is excellent in resolution, insulation, adhesion, adhesion, and the like is effectively used as the semiconductor element. The permanent film photoresist of the interlayer insulating film 'surface film and the like. -10-200905383 BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive insulating resin composition and the cured product relating to the present invention will be described in detail below. [Photosensitive insulating resin composition] The photosensitive insulating resin composition of the present invention contains (A) a resin having a structural unit having a phenolic hydroxyl group, and (B) a photoinduced acid generator (C) containing at least one selected A crosslinking agent, a (D) solvent, and (E) crosslinked fine particles in a group of the oxetane group-containing compound (C1) and the epoxy group-containing compound (C2). Further, the photosensitive insulating resin composition may contain other additives such as (a) a phenol compound, (F) a bonding agent, a sensitizer, and a leveling agent, as needed. <Resin (A) > The resin (A) used in the present invention is an alkali-soluble resin containing a structural unit having a phenolic hydroxyl group. Examples of the alkali-soluble resin include polyhydroxystyrene other than a phenol resin, a copolymer, a phenol-benzene dimethanol (phenphenl_xylene glycol) condensation resin, a cresol-benzene dimethanol condensation resin, and a phenol-dicyclopentane pentane. A diene condensation resin, a polybenzoxazole precursor, and the like. Among these, phenolic resin, polyhydroxystyrene, and the copolymer, and polybenzoxazole precursor are preferred. These resins may be used alone or in combination of two or more. The above-mentioned acid resin is obtained by condensing phenols and aldehydes in the presence of a catalyst -11 - 200905383. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylene. Phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, /3-naphthol, bisphenolphthalein and Such derivatives and the like. Further, examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. Specific examples of such a phenol resin include a phenol/formaldehyde condensed phenol resin, a cresol/formaldehyde condensed phenol resin, a phenol-naphthol/formaldehyde condensed phenol resin, and the like, and at least one compound selected from the following formula (I) It is preferable that the structure shown and the structure shown by the following formula (Π) are grouped. [Chemical 3]

In the formula (I), R is independently and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a tooth atom, a mi system representing an integer of 1 to 3, and a ηι system representing 1 to 1. Integer of 3, = -12- (II) (II) 200905383 [Chemical 4]

In the formula (π), R, Ri and R2 are each independently, and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and represent an integer of 1 to 3 '112 The table is not an integer of 1 to 3 'm2+n2=4, and m3 is an integer of 〇~3' n3 means an integer of 1 to 4, and m3+n3=4. It is suitable because it has excellent insulation properties when it has such a structural unit. As the hydroxystyrene and the copolymer, specifically, the viewpoint of the insulating property and the thermal shock resistance of the obtained cured product is suitable for the structural unit (1) represented by the following general formula (1) and the following general formula (2). The copolymer (A1) formed by the structural unit (2) shown. The above copolymer (A1) is a copolymer which can form a monomer of the structural unit (1) and a monomer which can form the structural unit (2). [Chemical 5]

In the formula (1), the Ra system represents an alkyl group, an alkoxy group or an allyl group having 1 to 4 carbon atoms. Rb represents a hydrogen atom or a methyl group. η is an integer of 0 to 3' m is an integer from 1 to 13 to 200905383 to 3. [Chemical 6] CHg-C -

• (2) In the formula (2), Re represents an alkyl group, an alkoxy group or an allyl group having 1 to 4 carbon atoms. Rd represents a hydrogen atom or a methyl group. η 〇 〇 ~ 3 integer. Examples of the monomer capable of forming the above structural unit (1) include basic ethylene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenylhydrazine, m-isopropenylphenol, o-isopropenylphenol, and the like. In this case, it is preferred to use cis-styrene or p-isopropenylphenol. The above structural unit (1) can be obtained by, for example, a monomer which protects a hydroxyl group such as a t-butyl group or an ethyl fluorenyl group. The resulting polymer or copolymer is converted to a hydroxystyrene structural unit by known methods, e.g., by acid catalyst protection. Examples of the monomer capable of forming the above structural unit (2) include styrene, 0; methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and ortho Oxystyrene, m-methoxystyrene, p-methoxystyrene, and the like. In the above-mentioned single system, styrene or p-methoxystyrene may be used alone or in combination of two or more. The above copolymer (A1) is a copolymer of a monomer which can form a structural unit (1) and a monomer which can form a structural unit (2), and is essentially a structural unit (1) and a structural unit which are only composed of -14 to 200905383 (2) It is preferably formed or copolymerized with other monomers. Examples of the other monomer include an unsaturated residual acid or an acid anhydride thereof, an ester of the above unsaturated carboxylic acid, an unsaturated nitrile, an unsaturated guanamine, an unsaturated quinone, and an alicyclic ring. a compound of the skeleton, an unsaturated quinone, N-ethylene _ ε - caprolactam, n - vinyl pyrrolidone, hydrazine - vinyl imidazole, hydrazine - vinyl carbazole, and the like. More specifically, for example, unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride or the like may be mentioned. Such acid anhydrides; methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, n-pentyl ester, n-hexyl ester, ring of the above unsaturated carboxylic acid Hexyl ester, 2-hydroxyethyl ester, 2-hydroxypropyl ester, 3-hydroxypropyl ester, 2,2-dimethyl-3-hydroxypropyl ester, benzyl ester, isophorone, tricyclodecanester , an ester of adamantyl ester, etc.; an unsaturated nitrile of (meth)acrylic acid, maleic nitrile, fumaronitrile, mesocarbonitrile, citracarbonitrile, itacononitrile, etc.; (methyl) propylene Insoluble amides such as decylamine, crotonamide, maleic amine, fumarine, mesaconamine, cimolamide, itaconamide, etc.; maleic imine, hydrazine-phenyl horse Unsaturated quinone imines such as imine, fluorene-cyclohexylmaleimide; bicyclo [2.2.1] hept-2-ene (norbornene), tetracyclo[4.4.0.12'5.17'1 ()] 12-3 -ene 'cyclobutene, cyclohexene, cyclooctene-15 - 200905383, a compound having an alicyclic skeleton such as dicyclopentadiene or tricyclo [5.2.1 · 02, 6] decene; an unsaturated alcohol such as (meth)allyl alcohol; Aniline, vinyl pyridine, quinone-vinyl-e-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole, and the like. These single systems may be used alone or in combination of two or more. In the copolymer (A1), the structural unit amount formed by the other monomer is 1 part by weight or less, and 50 parts by weight based on 100 parts by weight of the structural unit (1) and the structural unit (2). The following is suitable, and it is preferably 25 parts by weight or less. In the above copolymer (A1), the content of the structural unit (1) is 10 to 9 9 mol%, preferably 20 to 9 7 mol%, more preferably 3 to 95 mol%, and structural unit. The content of (2) is 90 to 1 mol%, preferably 80 to 3 mol%, more preferably 70 to 5 mol% (however, the total structural unit constituting the copolymer (A1) is 1 0 0 Moer %). When the content of the structural unit (1) and the structural unit (2) is outside the above range, the pattern property is lowered, and the physical properties such as the thermal shock resistance of the cured product are lowered. When the content of each of the structural units is in the above range, the copolymer (A 1 ) can form a cured product excellent in various properties such as resolution, electrical insulating properties, thermal shock resistance, and adhesion. In particular, it is a cured product excellent in electrical insulation and thermal shock resistance. In the above copolymer (A1), the arrangement of the structural unit formed by the structural unit (1) and the structural unit (2) and the above other monomers is not particularly limited to -16 to 200905383, and the copolymer (A 1 ) is randomly copolymerized. Any one of the substance and the block copolymer may be obtained by obtaining the above copolymer (A 1 ), a compound which can form the structural unit (1) or a compound which protects the hydroxyl group, and a monomer which can form the structural unit (2) And, if necessary, the above-mentioned other monomer' may be polymerized in a solvent in the presence of a starting agent. The polymerization method is not particularly limited, and a radical polymerization or an anionic polymerization can be carried out to obtain a compound having a desired molecular weight. Usually, as the compound which can form the structural unit (1), the monomer whose hydroxyl group is protected is used. After the polymerization of the hydroxy group-protected single system, in a solvent, an acid catalyst such as hydrochloric acid or sulfuric acid, the reaction is carried out at a temperature of 50 to 150 ° C for 1 to 30 hours to carry out deprotection. Form a structural unit containing a phenol ring. The molecular weight of the resin (A) is not particularly limited, but the weight average molecular weight (Mw) in terms of styrene measured by a gel permeation chromatography (GPC) method is, for example, 200,000 or less, preferably 2,000 to 100,000. When the Mw is less than the lower limit, the physical properties such as heat resistance and ductility of the cured product are lowered, and when the upper limit is exceeded, the compatibility with other components is lowered, or the pattern property is lowered. Further, as the resin (A), in order to improve alkali solubility, a mixture of the above copolymer (A 1 ) and a phenol resin can be used. The range of 1 to 200 parts by weight of the phenol resin is preferably in the range of 1 to 15 parts by weight with respect to 100 parts by weight of the above copolymer (A1)', particularly preferably in the range of 1 to 100 parts by weight. . -17- 200905383 <phenol compound (a) > The phenol compound (a) which can be used for the photosensitive insulating resin composition of the present invention is a low molecular weight compound having a phenolic hydroxyl group other than the above resin (A). When the above resin (A) is used, alkali solubility can be improved. Examples of the phenol compound (a) include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, and 1,1 pair. (4-hydroxyphenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1 -(4-hydroxyphenyl)-1-methylethyl]benzene ' 1,4 bis[1 -(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1 -(4-hydroxyphenyl)-1-methylethyl]benzene a 1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, 2,1,2,2-tetrakis(4-hydroxyphenyl)ethane and the like. The phenol compound (a) may be used in an amount of 1 to 200 parts by weight, preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the above resin (A)'. it is good. A composition which produces sufficient alkali solubility can be obtained by containing the phenol compound (a)' in the above range. In the photosensitive insulating resin composition of the present invention, the total amount of the resin (A) and the phenol compound (a) is usually a total of the components other than the solvent (D) in the 00 parts by weight of the composition. 4 0 to 9 parts by weight, preferably 50 to 80 parts by weight. <Photosensitive acid generator (B) > -18- 200905383 The photo-sensitive photoacid generator (hereinafter also referred to as "acid generator (B)") used in the present invention is produced by irradiation of radiation or the like. Acid compound. The oxetane group or the epoxy group in the crosslinking agent (C) described later is reacted with the resin (A) and the ruthenium compound (a) to be cured by an acid generating catalyst, whereby a negative pattern can be formed. The acid generator (B) 'is not particularly limited as long as it is a compound which generates an acid by irradiation with radiation or the like, and examples thereof include a gun salt compound, a halogen-containing compound, a diazoke compound, an anthraquinone compound, and a sulfonic acid. a compound, a thiopurine compound, a diazomethane compound, or the like. The key salt compound may, for example, be an iron iodide salt, a phosphonium salt, a scale salt, a diazo salt or a pyridyl salt. Specific examples of suitable gun salt compounds include, for example, diphenyl iodine triflate, diphenyl iodine p-toluene sulfonate, diphenyl iodonium hexafluoroantimonate, and diphenyl iodine. Key hexafluorophosphate, diphenyl iodine iron tetrafluoroborate, triphenyl sulfonium trifluoromethane sulfonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, 4 - uncle Butyl phenyl diphenyl sulfonium trifluoromethanesulfonate, 4-tert-butylphenyl diphenyl sulfonium p-toluene sulfonate, 4,7-di-n-butoxynaphthalene tetrahydrothiophene Tetrahydro thiophenium), trifluoromethanesulfonate, 4-(phenylthio)benyldiphenylphosphonium tris(pentafluoroethyl)trifluoroacetate, 4-(phenylthio)phenyldiphenylphosphonium (heptafluoropropyl)trifluorophosphate, di-p-tolyl iodide tris(hexafluoroethyl)trifluorophosphate, 4-(phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, and the like. The halogen-containing compound may, for example, be a halogenated alkyl hydrocarbon-containing compound or a halogenated alkyl heterocyclic compound. Specific examples of a suitable halogen-containing compound-19-200905383 include, for example, 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane. Alkane, phenyl-bis(trichloromethyl)_s-triazine, 4-methoxyphenyl-bis(trichloromethyl)_s-triazine, styryl-bis(trichloromethyl)_s- Triazine, naphthyl-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl) _s Triazine or other s-triazine derivative. Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzene quinone, and a diazonaphthoquinone compound. Specific examples thereof include 1,2-weight phenols. Azonaphthoquinone- 4-sulfonate compound. Examples of the ruthenium compound include a ketone oxime compound, an S-sulfonium ruthenium compound, and an α-diazonium compound of such a compound. Specific examples thereof include mesitylphenacyl sulfone. ), bis(phenylsulfonyl)methane, and the like. The sulfonic acid compound may, for example, be an alkylsulfonate, a halogenated alkylsulfonate, an arylsulfonate or an imidosulfonate. Specific examples of suitable examples include benzoin tosylate, pyrogallol tris(trifluoromethanesulfonate), o-nitrobenzyltrifluoromethanesulfonate, and o-nitrobenzoic acid. P-toluenesulfonate and the like. Specific examples of the above thiopurine compound include, for example, N-(di-methanesulfonate)-imide, N-(trifluoromethanesulfonyloxy)phthalimide, and ruthenium- (three Fluoromethanesulfonyloxy)diphenylmaleimide, indole (trifluoromethanesulfonyloxy)bicyclo[2 _2.1]gly-5-ene-2,3-dicarbodiimide, anthracene- (Trifluoromethanesulfonyloxy) naphthoquinone imine and the like. Specific examples of the above diazomethane compound include, for example, bis(3-20-200905383 fluoromethylsulfonium)diazomethane, bis(cyclohexylsulfonium)diazomethane, bis(phenylsulfonate)diazomethane. Wait. The acid generator (B) may be used alone or in combination of two or more. Further, the amount of the acid generator (B) is adjusted to ensure the sensitivity, the resolution, the shape of the pattern of the resin composition of the present invention, and the resin (A) and the phenol compound in an amount of 1 part by weight. The total amount of (a) is preferably 〇.1~ίο parts by weight, preferably 〜5 parts by weight. When the blending amount is within the above range, the composition is sufficiently hardened, and the heat resistance of the cured product is increased, and the transparency is excellent, and the pattern shape is less likely to be deteriorated. <crosslinking agent (C) > The crosslinking agent (c) used in the present invention contains at least one selected from the group consisting of an oxetane group-containing compound (C1) and an epoxy group-containing compound (C2). It acts as a cross-linking component of the above-mentioned resin (A) and the phenol compound (a) required for the reaction. The oxetane group-containing compound (C1) has one or more oxetanyl groups in the molecule. Specifically, for example, the compounds represented by the following formulas (A) to (C) can be mentioned. -21 - 200905383 [7] R7-f°-R67C\"R5)i H2C\ /CH2 o R7-f c-o-r6-c-r5)1 h2c ch2 o

Η O

R7-^-N-C_0-Re-c-R5] A H2C\〇>CH2 1 The alkyl group of the formula (A), (B) and (C), etc., R6 is a methyl group and an ethyl group. R7 is an aryl group such as a methyl group, an ethyl group, a propyl group, a hexyl group or the like; an alkyl group represented by the following formula (i), a methyl group, an exoethyl group, a propyl group, etc. ii)~(vi) The base represented by i is equal to the number. (A) (B) (C), R5 is an alkenyl group such as methyl, ethyl, propyl or propyl, alkyl; phenyl, xylylene dimethyl oxane residue; Phenyl; or the following formula (R7 valence, 1 to 4 of the whole -22- (i) 200905383 [Chemical 8]

(ii) (iii) (v) -h2c, ,ch2- (vi)

CH-CH -h2c〆xch2- where x and y are independent of each other 〇5〇 integer 'z single bond or one CH2—, —C ( C Η 3 ) 2 - ' — C ( CF 3 ) 2 - or -S〇2 - the divalent group represented by . Examples of the compound represented by the above formula (A) to formula (C) include bis[(3-ethyl-3-oxecycloalkylmethoxy)methyl]benzene (trade name "XDO" East Asia). Synthetic company), bis[(3-ethyl-3-oxobutanealkylmethoxy)methyl-phenyl]methane, bis[〇-ethyl-3 oxetanyl methoxy Methyl-phenyl]ether, bis[(3-ethyl-3-oxobutanealkylmethoxy)methyl-phenyl]propane, bis[(3-ethyl-3-oxo) Cyclobutane methoxy)methyl-phenyl]anthracene, bis[(3—ethyl-23-200905383 thio-3-oxetanylmethoxy)methyl-phenyl]one, bis[ (3-ethyl-3-oxetanealkylmethoxy)methyl-phenyl]hexafluoropropane, tris[(3-ethyl-3-oxetanylmethoxy)methyl Benzene, tetrakis[(3-ethyl-3-oxobutanealkylmethoxy)methyl]benzene, and compounds represented by the following formulas (D) to (H).

Ch3ch2c~c

(D) (E) (F) (G) (Η) In addition to these compounds, a high molecular weight compound having a polyvalent oxetane ring can also be used. Specifically, for example, an oxetane oligomer (trade name "Oligo - ΟΧΤ" manufactured by Toagosei Co., Ltd.) and a compound represented by the following formulas (I) to (K) can be mentioned. -24- (I) 200905383 [化10]

(J) (κ) where p, q, and s are independent of 0~1〇, 〇〇〇 integer. In the above, 1,4 pairs of {[(3-ethyloxetan _3_yl)methoxy]methyl}benzene (made by East Asia Synthetic Co., Ltd.) 'trade name: Ο X Τ — 12 1) ' 3 -ethyl- 3 - {[(3-ethyloxyindole)-methoxy)methyl}oxyl trade name: ΟΧΤ - 221) The above-mentioned oxetane Two or more kinds of the epoxy group-containing compounds may be combined, and the phenol resin type epoxy resin epoxy resin, the trisphenol type cyclodimethyl type epoxy resin, the naphthoquinone type epoxy resin, and the phenyl epoxy group may be used. Resin, aromatic ring fine resin, etc. Heterocyclic butane (manufactured by Toagosei Co., Ltd.) is preferred. The alkyl compound (C1) may be used alone. The base compound (C2) is not limited to any molecularly contained ring, but Specific examples thereof include a cresol novolac type epoxy resin, a bisphenol oxime type resin, a tetraphenol type epoxy resin, a phenol mononaphthol-benzoic epoxy resin, and a phenol-phenol-dicyclopentanyl group. Diene type epoxy resin, alicyclic oxygen tree S 曰, S 曰 aliphatic epoxy resin, epoxy cyclohexyl-25- 200905383 As the above phenolic resin type epoxy resin japan epoxy resin (share) Epicoa U52, 154 (The above-mentioned product name) is the EOCN series (trade name) of the cresol-based epoxy resin-based Nippon Kayaku Co., Ltd., and the NC3 000 series (hereinafter referred to as the bisphenol epoxy resin-based Nippon Kayaku Co., Ltd.) The product name) is the EPPN series (trade name) of the above-mentioned trisphenol-based epoxy resin-based Nippon Kayaku Co., Ltd., and the above-mentioned phenol-naphthol type epoxy resin is manufactured by Nippon Chemical Co., Ltd. N C7 0 0 0 Series (trade name) as the above phenol-dicyclopentadiene type Epoxy resin is a XD-1000 series (trade name) manufactured by Sakamoto Chemical Co., Ltd., and is used as the above-mentioned alicyclic A-type epoxy resin Japan Epoxy resin series Epicoat 801 series (trade name). Epoxy resin pentaerythritol glycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENAC0L EX411), trimethyl propylene polyglycidyl ether (manufactured by Nagase ChemteX, trade name: DENACOL EX321, 321L), glycerin Polyglycidyl ether (manufactured by Nagase ChemteX, trade name: DENACOL EX3 13, EX3 14), neopentyl glycol diglycidyl ether (manufactured by Nagase ChemteX (trade name: DENACOL EX211), ethylene/polyethyl Glycol diglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX810, 850 series 歹IJ), propylene/polypropylene glycol diglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX91 1, 941, 920 series) '1,6-hexanediol diglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX212), sorbitol polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX611 , EX612, EX614, -26- 200905383 EX6 14B, EX6 10U), propylene glycol diglycidyl ether (common name: EPOLIGHT 70P manufactured by Kyoeisha Co., Ltd.), trimethylolpropane triglycidyl ether (Kyoeisha) ), the product name: EPOLIGHT 100MF), the above-mentioned aromatic epoxy resin phenyl glycidol awake (Nagase ChemteX (product), trade name: DENACOL EX141), resorcinol diglycidyl ether (Nagase ChemteX ( Co., Ltd., trade name: DENACOL EX201), as the above epoxycyclohexene resin system, 3, 4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate ( DAICEL (stock) system, trade name: CELLOXIDE 2021, 2021A, 2021P), 1,2:8,9 di-epoxy limonene (DAICEL (stock), trade name: CELLOXIDE3000), 2,2 - bis (hydroxymethyl) a 1,2-butoxy-tetra-(2-oxiranyl)cyclohexane adduct of 1,1-butanol, 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate (manufactured by DAICEL Co., Ltd., trade name: EHPE3150CE). In this case, a resin epoxy resin (Epicoat 52, 154 manufactured by Japan epoxy resin), a bisphenol A epoxy resin (Epicoat 801 series manufactured by Japan epoxy resin), and a diphenyl hydrazine dihydrate Glycerol ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX201), pentaerythritol glycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX411), trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX) 'Product name: DENACOL EX321, 321 L), glycerol polyglycidyl ether (manufactured by Nagase ChemteX (trade name: DENACOL EX313, EX314), phenyl glycidic acid (manufactured by Nagase ChemteX), trade name: - 27- 200905383 DENACOL EX141), neopentyl glycol diglycidyl ether (manufactured by Nagase ChemteX, trade name: DENACOL EX211), susceptibility/polyethylene glycol diglycidyl ether (Nagase ChemteX) Name: DENACOL EX810, 850 series), propylene/polypropylene glycol diglycidyl ether (manufactured by Nagase ChemteX (trade name: DENACOL EX91 1, 94 1, 920 series), ι, 6-hexanediol condensate Glycerol ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX212), sorbitol polyglycidyl ether (manufactured by Nagase ChemteX (trade name: DENACOL EX611, EX612, EX614, EX614B, EX610U), propylene glycol condensed water Glycerol ether (trade name: EPOLIGHT 70P manufactured by Kyoeisha Co., Ltd.) and trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Co., Ltd., trade name: EPOLIGHT 100MF) are preferred. The above-mentioned epoxy group-containing compound (C2) may be used alone or in combination of two or more. When the above-mentioned oxetane group-containing compound (C1) and/or the above-mentioned epoxy group-containing compound (C2) is used as a crosslinking agent, since the crosslinking reaction does not accompany the desorption reaction, no outgassing occurs, and therefore insulation is used. The resin and the substrate are excellent in adhesion, and the adhesion between the substrate and the substrate is excellent when laminated. The crosslinking agent (C) may further contain the above oxetane-containing compound (c). 1) and the above-mentioned crosslinking agent other than the epoxy group-containing compound (C2), it is preferred that the crosslinking reaction is not accompanied by the detachment reaction. The total amount of the above-mentioned oxetane group-containing compound (C1) and the above-mentioned epoxy group-containing -28-200905383-based compound (C2) contained in the above-mentioned crosslinking agent (C) is relative to 100% by mass of the crosslinking. The total amount of the agent (C) is 70% to 1% by mass. It is preferably from 80 to 1.0% by mass, and particularly preferably 1% by mass. The total content of the compounds (c 1 ) and (c 2 ) is remarkable because the effects of using the above compounds (C1) and/or (C2) within the above range are remarkable. The amount of the crosslinking agent (c) in the composition of the present invention is preferably 1 to parts by weight based on 100 parts by weight of the above resin (A) and the total amount of the above phenol compound (a) used as needed. , preferably 2 to 70 parts by weight. When the compounding amount is within the above range, the obtained cured film has sufficient chemical resistance and high resolution. &lt;Solvent (D) &gt; The solvent (D) used in the present invention is added for improving the handleability of the resin composition or adjusting the viscosity or preserving stability. The solvent (D) is not particularly limited, and examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether; a propylene glycol monoalkyl ether such as propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether Propylene glycol monoalkyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. Ether acetate; -29- 200905383 Cellulose of ethyl cellosolve, butyl cellosolve, carbitol, etc.; methyl lactate, ethyl lactate, n-propyl lactate, iso-lactic acid lactate An aliphatic carboxy group such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, isobutyl propionate, etc. Acid esters; 3 - methyl methoxypropionate, ethyl 3-methoxypropionate, propyl Other esters such as methyl ester, ethyl 3-ethoxypropionate, methyl ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; 2 - Gengyuan, 3 - Gengyuan, 4 Yi Gengyuan And ketones such as cyclohexanone, N-dimethylformamide, N-methylacetamide, n,N-decylamine, N-methylpyrrolidone, etc.; r-butyrolactone, etc. An organic solvent such as an ester. These organic solvents may be used alone or in combination of one or more kinds. The amount of the solvent (D) in the present invention is appropriately selected depending on the coating method for the composition. 'As long as the composition is uniform, it is not particularly limited, but it is usually 10 to 80 with respect to the composition. 30 to 75% by weight is preferably '40 to 70% by weight. &lt;Crosslinked Fine Particles (E)> The crosslinked fine particles (E) used in the present invention constitute n-butyl ester, propyl ester, propyl 3-ethoxy, pyruvic acid such as carbitol propyl ester; B or mixed 2 uses or a uniform state, % by weight, at least one of the glass transition temperatures (Tg) of the polymer of the microparticles -30-200905383 is preferably 〇t or less. For example, having two or more unsaturated polymerizable groups The crosslinkable monomer (hereinafter referred to as "crosslinkable monomer") may be copolymerized with the crosslinkable monomer, and at least one of the Tg of the copolymer constituting the crosslinked fine particles (E) may be A copolymer of one or more selected monomers (hereinafter also referred to as "other monomer (e)") is preferred. Further, the above-mentioned τ g of the copolymer constituting the crosslinked fine particles (E) is obtained by solidifying and drying the crosslinked fine particle dispersion, and then using a DSC of Seik〇 Instruments SSC/5200H at a temperature of 1 to 15 〇〇c. The range was measured at a heating rate of 10 ° C /miη. Examples of the crosslinkable monomer include divinylbenzene, propylene phthalate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and trimethylolpropane tri(methyl). Acrylic vinegar, pentaerythritol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropanol - (meth) propylene vinegar, etc. having most polymerizable unsaturated groups Compound. Among them, divinylbenzene is preferred. As the other monomer (e), a functional group other than the polymerizable group is preferably a monomer having a functional group such as a mercapto group, an epoxy group, an amine group, an isocyanate group or a perylene group. Specific examples of the other monomer (e) include diene compounds such as butyl bromide, isoprene, dimethylbutadiene, chloropentadiene, and 1,3-pentadiene; Methyl)acrylonitrile, α-chloroacrylonitrile, chloromethylacrylonitrile, “methoxypropenenitrile, α-ethoxy acrylonitrile, nitrile butyrate, meat-31 - 200905383 cinnamic acid nitrile, Yikang An unsaturated nitrile compound such as acid dinitrile, maleic acid dinitrile or fumaric acid dinitrile; (methyl) acrylamide, N, N, -methyl bis(methyl) acrylamide, N, N'-extended ethyl bis(methyl) acrylamide, N, N, - hexyl bis (meth) acrylamide, N - hydroxymethyl (meth) acrylamide, N - (2 - Ethyl (meth) acrylamide, N, N-(2-ethyl) (meth) acrylamide, decyl decanoate, decyl cinnamate, etc.; Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (methyl) (meth) acrylates such as olefin esters, polypropanol (meth) acrylates, etc.; styrene, oxime: methyl benzene benzene, o-methoxy styrene, p- benzene An aromatic vinyl compound such as ethylene or p-isopropenylphenol; a reaction between bisphenol A diglycidyl ether, glycerol diglycidyl ether, and the like (meth)acrylic acid 'hydroxyalkyl (meth)acrylic acid; Epoxy (meth) acrylates; ethyl urethane (meth) acrylates obtained by reacting hydroxyalkyl (meth) acrylates with polyisocyanates; glycidyl (meth) acrylates An epoxy group-containing unsaturated compound such as (meth)allyl glycidyl ether; (meth)acrylic acid, itaconic acid, 1,3-(meth)acryloyloxyethyl succinate, Malay Acid mono/3 - (meth) acryloyloxyethyl ester, phthalic acid - 5 - (meth) acryloyloxyethyl ester, hexahydrophthalic acid - 32 - 200905383 a yS - (methyl) An unsaturated acid compound such as acryloyloxyacetate; dimethylamino (mercapto) acrylate, An amine-based unsaturated compound such as diethylamino (meth) acrylate; an amide-containing unsaturated compound such as (meth) acrylamide or dimethyl (meth) acrylamide; A hydroxyl group-containing unsaturated compound such as a (meth) acrylate, a hydroxypropyl (meth) acrylate or a hydroxybutyl (meth) acrylate. Among these, butadiene, isoprene, (meth)acrylonitrile, alkyl (meth)acrylate, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (A Acrylates, (meth)acrylic acid, hydroxyalkyl (meth)acrylates and the like are preferred, and butadiene is preferred. The suitable form of the polymer constituting the crosslinked fine particles (E) may include, for example, a structural unit derived from a diene compound, a structural unit derived from a hydroxyl group-containing unsaturated compound, and a polymer having two or more unsaturated polymers. A polymer of a structural unit of a cross-linking compound which may further comprise a structural unit derived from an aromatic vinyl compound. The ratio of the crosslinkable monomer constituting the crosslinked fine particles (E) to the other monomer (e) is 1 to 20% by weight based on the total monomer used for the copolymerization, and the amount of the crosslinkable monomer is 1 to 20% by weight. The other monomer (e) is preferably 80 to 99% by weight, preferably 2 to 10% by weight of the crosslinkable monomer and 90 to 98% by weight of the other monomer (e). Further, as the diene compound of the other monomer (e), butadiene is preferably used, and the amount of the total monomer for copolymerization is preferably from 20 to 80% by weight, preferably from 3 to 70. When the weight % is particularly preferable, rubber-like soft crosslinked fine particles can be obtained, and cracks can be prevented from occurring in the obtained cured film (-33-200905383 crack), and a cured film excellent in durability can be obtained. Further, when the styrene and butadiene are used as the other monomer (e), a cured film having a low dielectric constant can be obtained. The average particle diameter of the crosslinked fine particles (E) is usually 30 to 500 nm', preferably 40 to 20 nm. The method of controlling the particle size of the crosslinked microparticles is not particularly limited, and for example, when the crosslinked fine particles are synthesized by emulsion polymerization, the number of colloidal particles in the emulsification polymerization is controlled by the amount of the emulsifier used, and the particle diameter is controlled. Further, the above average particle diameter is measured by using a light scattering flow distribution measuring apparatus LPA-3000 manufactured by Otsuka Electronics, and diluting the dispersion of the crosslinked fine particles according to a usual method. The amount of the crosslinked fine particles (E) is preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the total of the above-mentioned resin (A) and the above-mentioned phenol compound (a). 20 parts by weight is especially preferred. When the compounding amount is in the above range, the obtained cured film has heat-resistant impact resistance, heat resistance, and good compatibility (dispersibility) with other components. &lt;Bindering agent (F)&gt; The adhesive agent (F) which can be used in the present invention is preferably a functional organic sand compound crosslinking agent, and examples thereof include a carboxyl group and a methacrylic acid group. A crosslinking agent of a reactive substituent such as an isocyanate group or an epoxy group. Specifically, for example, trimethoxymethane alkyl benzoic acid, 7-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy hydride, isocyanic acid Salt propyl triethoxy decane, 7-glycidoxypropyl trimethoxy decane, oxime (3,4 -epoxycyclohexyl) -34- 200905383 ethyltrimethoxydecane, 1,3 , 5-N-tris(trimethoxydecanepropyl) trimer isocyanate, and the like. &lt;Other Additives&gt; In the photosensitive insulating resin composition of the present invention, it is also possible to contain a surfactant, a sensitizer, a leveling agent, and another acid generator without impairing the characteristics of the above composition. Various additives. The flattening of the coating film, the flattening of the periphery of the substrate, the streaks, and the like can be improved by the addition of the above-mentioned surfactant. As such a surfactant, for example, a ruthenium-based surfactant, a fluorine-based surfactant, an acrylic surfactant, or the like can be given. &lt;Preparation method&gt; The preparation method of the photosensitive insulating resin composition of the present invention is not particularly limited, and a usual preparation method can be applied. Alternatively, the components may be placed in a sample vial, completely sealed, and conditioned by agitation on a wave rotor. [Cured product] The cured product obtained by curing the photosensitive insulating resin composition according to the present invention is excellent in electrical insulating properties, thermal shock resistance, adhesion, adhesion, and the like. Therefore, the photosensitive insulating resin composition of the present invention is particularly suitably used for a material such as a surface protective film or an interlayer insulating film of a semiconductor element. The cured product (cured film) of the present invention can be formed, for example, as follows. The photosensitive insulating resin composition of the present invention is applied to a support such as a bismuth-35-200905383-tack copper foil, a copper-clad laminate, or a metal-plated film or an alumina substrate, which is dried. The solvent or the like is volatilized to form a coating film. After that, the exposure is performed by the desired mask pattern, and further heat treatment (hereinafter referred to as "PEB" (Post exposure bake)" is used to promote the above resin (A) and the corresponding needs. The above phenol compound (a) and the above crosslinking agent (C) are reacted. Next, development is carried out by an alkali developer, and the desired pattern is obtained by dissolving and removing the unexposed portion. Thereafter, by further heat treatment, a cured film having an insulating film property can be obtained. Here, as a method of applying the resin composition to the support, a coating method such as a dipping method, a spray method, a coating bar method, a roll coating method, or a spin coating method can be used. Further, the coating thickness can be suitably suppressed by adjusting the solid concentration or viscosity of the coating means and the composition. The radiation used for the exposure may, for example, be a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-line optical stepper (g_Hne Stepper), an i-line optical stepper, or the like, or an electron beam or a thunder. Shooting light, etc. The exposure amount is appropriately selected depending on the light source or the thickness of the resin film. For example, when the ultraviolet ray is irradiated by a high pressure mercury lamp, if the resin film thickness is 丨〇~5 〇&quot;m, 'is 1, 〇〇〇~50,000 J/m2. . The post-exposure P E B treatment conditions are usually in the range of from 70 to 150 ° C, depending on the amount of the resin composition or the use of S 旲 thickness #, and from 8 〇 to 120 C, preferably from 1 to 60 minutes. Examples of the development method of the alkaline developer include a shower development method, a spray development method, a immersion development method, a paddle development method, and the like, and the development condition of -36 to 200905383 is usually 20 to 40 ° C, 1 to 10 The degree of minutes. As the alkaline developing solution, for example, an alkaline compound such as sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide or choline is added to water to adjust the concentration to an alkalinity of about 1 to 10% by weight. Aqueous solution. A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution in an appropriate amount. Further, after developing with an alkaline developing solution, the pattern coating film was washed with water to dry. The heat treatment conditions after development are not particularly limited, but may be cured by heat treatment at a temperature of 50 to 200 ° C for 30 minutes to 10 hours in accordance with the use of the cured product. The heat treatment after the development can sufficiently cure the obtained pattern-like coating film, or to prevent the deformation, or to carry out the steps of two or more stages. For example, in the first stage, 50 to 12 (the temperature of TC, heat treatment for 5 minutes to 2 hours, in the second stage at a temperature of 80 to 2000 ° C, heat treatment for 10 minutes to 10 hours, or The pattern-like coating film is hardened. If it is such a hardening condition, a heating plate, an oven, an infrared furnace or the like of a heating device can be used. The cured product of the present invention is excellent in electrical insulation, and the resistance enthalpy after the migration test is 1 Ο 8 Ω or more is preferable, and more preferably 1 〇 9 Ω or more, more preferably 1 〇 1 ° Ω or more. Here, the above-mentioned migration test is specifically carried out as follows. The coating resin composition is shown in Fig. 5 The substrate 1 was evaluated, and a resin coating film having a thickness of 1 〇 &quot;m on a copper foil was prepared by heating on a heating plate for 11 minutes using a heating plate. Thereafter, a convection oven was used to heat at 190 °C. 1 hour, the resin coating film was hardened to obtain a cured film. The evaluation substrate of the cured film was placed in -37-200905383 in the migration evaluation system (TABAI ESPEC (manufacturing), EHS-22 1MD) at a temperature of 121 °C, humidity is 85%, pressure is 1.2 air pressure, and the applied voltage is After the condition of 5 V was treated for 200 hours, the resistance 値 (Ω) of the evaluation substrate was measured. [Semiconductor Element] The related semiconductor element of the present invention has a cured film formed as described above. This cured film is based on a semiconductor element and can be suitably used as a surface. A protective film, an interlayer insulating film, etc. As the semiconductor element, a semiconductor element (with a circuit board) as shown in Figs. 1 and 2 can be exemplified. The circuit board shown in Fig. 1 is first formed with a metal pad 2 on the substrate 1. After the pattern is formed, an insulating film (cured film) 3 is formed into a pattern by using the resin composition described above. Then, the metal circuit 4 is formed into a pattern, and the circuit board shown in Fig. 2 is attached. The resin substrate shown in Fig. 1 is obtained by using the above resin composition to form an insulating film (cured film) 5. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not In addition, any of the following examples and comparative examples are used in the meaning of parts by weight unless otherwise specified. -38-200905383 &lt;Resolving property&gt; Rotating and coating the photosensitive insulating resin composition on a 6-inch wafer using a hot plate and heating at 100 ° C for 5 minutes to produce a uniform thickness of 30 / zm After coating, the Aligner (exposure machine) (manufactured by Suss Microtec Co., Ltd.) was used to expose the ultraviolet light from the high pressure mercury lamp to the 2,000 J/m2 at a wavelength of 350 nm using a pattern mask. Then, it was heated on a hot plate at 1 l ° C for 3 minutes (PEB), and developed using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 2 3 ° C for 1 Torr. The minimum size of the resulting pattern is the resolution. &lt;Adhesiveness&gt; The resin composition was coated on a tantalum wafer or a copper-plated copper wafer, and heated on a hot plate at 120 ° C for 5 minutes to prepare a resin coating film having a uniform thickness of 10 #m. . Thereafter, the exposure machine was used to expose ultraviolet rays from a high pressure mercury lamp so that the exposure amount at a wavelength of 350 nm became 2,000 J/m2. Subsequently, the film was heated at 110 ° C for 3 minutes (PEB) on a hot plate, and heated at 200 ° C for 1 hour using a convection oven (under nitrogen) to harden the resin coating film to obtain a cured film. The cured film was treated for 168 hours under the conditions of a Pressure Cooker test apparatus (manufactured by TABAESPEC Co., Ltd.) at a temperature of 121 ° C and a pressure of 100% 压力 at a pressure of 2.1. The adhesion before and after the test was evaluated according to Π S K 5 400, and the Cross-Cut Test (checker tape method). &lt;Adhesiveness&gt; -39- 200905383 The resin composition was sliced on a lcmx6 cm sand substrate, and heated at 110 °C for 3 minutes using a hot plate to prepare a resin coating film having a uniform thickness of 1 Å. The exposure machine is exposed to ultraviolet light from a high-pressure mercury lamp so that the exposure amount at a wavelength of 350 nm becomes 1, 〇〇〇j/m2. Then, it is heated by π 〇 ° C for 3 minutes (pEB ) on a hot plate, using The convection oven was heated at 150 ° C for 30 hours to semi-harden the resin coating film to obtain a ruthenium substrate slice having a semi-hardened film. The ruthenium substrate having a semi-hardened film was sliced and then sliced with a substrate of 1 cm x 6 cm. Vertically attached as shown in Fig. 6, the upper temperature is 240 °C, the lower temperature is 30 °C / 100kgf / 3 minutes of pressure treatment (APPLIED POWER JAPAN LTD press, model; ENERPAC ESE-924-00 'Production of the evaluation substrate. Using a pressure tester (manufactured by Ikuta Seisakusho Co., Ltd.; model; SDWS-020 1), as shown in Fig. 7, the stress was measured at a speed (5 mm/min.) to confirm the stress of the substrate peeling &lt; Electrical insulation> coating the resin composition on the ruthenium substrate, An insulating film was formed, and a copper box 10 having a pattern as shown in FIG. 5 was formed therein, and a substrate 13 for electrical insulation evaluation was produced. The substrate 1 3 for electrical insulation evaluation was coated with a resin. The product was heated at 110 ° C for 3 minutes using a hot plate to prepare a resin coating film having a thickness of 1 〇 / / m on the copper foil i 。. Then, using Aligner (exposure machine) (Suss Microtec company - 150), exposed to ultraviolet light from a high-pressure mercury lamp, and the exposure amount at a wavelength of 35 〇 nm is 2,000 J/m 2 , and heated at 1 10 ° C for 3 minutes (Peb ) using a hot plate. 40 - 200905383 Next, using a convection type The oven was heated at 2 ° C for 1 hour to harden the resin coating to obtain a substrate having a cured film. The substrate was placed in a migration evaluation system (TABAI ESPEC) to a temperature of 121 ° C. The humidity was 8 5 % 'pressure: 1 · 2 air pressure, and the applied voltage was 5 V for 200 hours. After that, the resistance 値 (Ω ) was measured to confirm the insulation of the cured film of the upper layer. [Synthesis Example 1] Synthesis Resin (Α - 1 ) with 3 L three with mixer, cooling tube and thermometer The separation flask was charged with 840 g of mixed cresol (m-cresol/p-cresol = 60/40 (mole ratio)), 600 g of a 37% by mass aqueous formaldehyde solution, and 3.6 g of oxalic acid. The flask was immersed in an oil bath under stirring, and the internal temperature was maintained at 100 ° C to carry out a reaction for 3 hours. Thereafter, the temperature of the oil bath was raised to 180 ° C, and the inside of the separation flask was depressurized to remove water, unreacted cresol, formaldehyde, and oxalic acid. Next, the molten phenolic resin was recovered and recovered at room temperature to obtain a cresol resin (A-1) having M w 6,500. [Synthesis Example 2] Synthetic Resin (A - 4 ) Dissolving p-tert-butoxystyrene in 150 parts by weight of propylene glycol monomethyl ether in a nitrogen atmosphere, maintaining the reaction temperature at 70 ° C, using 4 parts by weight Diazobisisobutyronitrile was allowed to carry out polymerization for 10 hours. Thereafter, sulfuric acid was added to the reaction solution, the reaction temperature was maintained at 90 ° C, and the reaction was allowed to proceed for 10 hours. The tert-butoxystyrene was deprotected and converted into hydroxystyrene. Ethyl acetate was added to the obtained polymer, and the washing was repeated 5 times, and the ethyl acetate phase -41 - 200905383 was separated, and the solvent was removed to obtain a p-hydroxystyrene alone polymer (A - 4 ) ° as a gel permeation chromatography apparatus. (GPC) When the molecular weight of the polymer (A - 4 ) is measured, the ratio of the weight average molecular weight (Mw) in terms of polystyrene is 10,000' weight average molecular weight (Mw) and number average molecular weight (?η) (Mw/ Mn) is 3.5. [Synthesis Example 3] Synthetic Resin (A-6) Acrylic acid/phenylene methacrylate/styrene = 20/40/40 (weight ratio) was dissolved in 150 parts by weight of ethyl lactate in a nitrogen atmosphere. Next, the reaction temperature was maintained at 7 ° C, and 4 parts by weight of azobisisobutyronitrile was used to carry out polymerization for 1 hour. When the molecular weight of the polymer (A-6) was measured by a gel permeation chromatography (GPC), the weight average molecular weight (Mw) in terms of polystyrene was 10,000, the weight average molecular weight (Mw) and the number average molecular weight (?η). The ratio (Mw/Mn) is 2.5. [Examples 1 to 8] As shown in Table 1, the resin (A), the phenol compound (a), the photoacid generator (B), and the crosslinking agent (C) were dissolved in an amount shown in Table 1, respectively. The photosensitive fine resin composition is prepared by crosslinking the fine particles (E) and the adhesion promoter (F) in the solvent (D). Using this resin composition, a cured film was produced in accordance with the method described in the above evaluation method. The properties of the resin composition and the cured film were measured in accordance with the above evaluation methods. The results are shown in Table 2. -42-200905383 [Comparative Examples 1 to 4] The resin composition and the cured film formed of the components shown in Table 1 were prepared and evaluated in the same manner as in the above examples. The results are shown in Table 2. -43- 200905383 一嗽助密剂(F) Type: Part 1 | Fl:3 F-2:3 Fl:3 Fl:3 Fl:3 j Fl:3 Fl:3 Fl:3 Fl:3 F-2 :3 Fl:3 Fl:3 Crosslinked microparticles (E) Species:parts El:10 El:10 El:10 E-2:10 1 Ε-2Λ0 I E-2:10 E-2:10 Ε-2- Λ0 E-2:10 El:10 El:10 Solvent (D) Type: Part Dl:150 D-2:150 Dl:150 1 Dl:150 Dl:150 Dl:150 Dl:150 Dl:150 丨... Dl: 150 D-1-.110 Dl:140 Dl:150 Crosslinking agent (C) Species: part C3-l:5 C3-l:20 Species: parts C2-l:20 C2-l:20 C2-2:20 C2-l:10 C2-2:20 C2-l:20 C2-l:20 C2-l:20 C2-l:20 Species: parts Cl-1:20 Cl-2:20 Cl-1:20 Cl- l:10 Cl-1:20 Cl-1:20 C2-l:20 C2-l:20 Photoacid generator (B) Type: Part Bl:3 B-2:3 Bl:3 Bl:3 Bl:3 Bl:3 Bl:3 Bl:3 Bl:3 Bl:3 1 Bl:3 Bl:3 Phenol compound (8) Species: part al:10 1 ί al:10 al:10 al:10 al:10 al:10 resin ( A) Type: Part 1_ Al: 100 A-2: 100 A-3: 100 Al: 70, A-5: 20 Al: 70, A-5: 20 Al: 70 &gt; A-5: 20 Al: 70 A-5:20 Al:70 'A-5:20 A-1:70 &gt; A-5:20 Al:100 Al:100 A-6:100 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 - 44 - 200905383 The components described in Table 1 are as follows. &lt;Resin (A) &gt; A-1: a cresol resin formed of m-cresol/p-cresol = 60/40 (mole ratio), Mw = 6,500 A-2: formaldehyde condensation resin of bisphenol A (Daily INK (share) system, trade name; KH-6021), Mw = 3 0 0 0 Α - 3: Resin formed by phenol and 1,4-benzene dimethanol (Mitsui Chemical Co., Ltd., trade name ;XLC—3L) , Mw=2000 A — 4: individual polymer of p-hydroxystyrene, Mw = 10, 〇〇〇, Mw/Mn 2 3.5 A-5: a single polymer of p-hydroxystyrene, Mw = 2,000, Mw / Mn = 3.0 (Kowloon Petrochemical Co., Ltd., trade name; S - 2P) A - 6: Acrylic / phenyl methacrylate / styrene = 20/40/40 (weight Ratio), Mw = 10,000, Mw / Mn = 2.5 &lt; phenolic compound (a) &gt; a - 1: 1,1 - bis(4-hydroxyphenyl)-1 - [4 - {1 - (4 - hydroxyl) Phenyl)-1-methylethyl}phenyl]ethane &lt;photoacid generator (B) &gt; B - 1: 4 -(phenylthio)phenyldiphenylphosphonium tris(pentafluoroethyl) Trifluorophosphate (SAN-APRO (stock), trade name; CPI-210S) B — 2: triarylsulfonium hexafluoroantimonate Chemical system, commodity -45- 200905383 first name; SP-1 72) <crosslinking agent (C 1 ) &gt;

Cl - 1 : 1,4 -bis[[(3-ethyloxyheteroyloxy)methyl]benzene (12 1 by East Asian Synthetic Co., Ltd.) C1—2: 3—Ethyl-3—[[ (3-Ethyl)methoxy]methyl]oxetane (East Asian ϋ product name; ΟΧΤ-221) &lt;crosslinking agent (C 2 ) &gt; C2- 1 : sorbitol polycondensation Glycerol ether), trade name; DENACOLEX 610U) C2 - 2: propylene glycol diglycidyl ether (total | product name; EPOLIGHT 70 Ρ) &lt;crosslinking agent (C 3 ) &gt; C3 - 1: hexamethoxymethyl melamine ( Third, the trade name; CYMEL300) &lt;solvent (D) &gt; D - 1 : ethyl lactate D-2: Ν-methylpyrrolidone butane-3-yl) A 'trade name; 〇X τ - oxygen heterocycle Butane-3 - its company (stock) system, agase ChemteX (I company (share) system, Shangjing Cytec (stock) system -46- 200905383 &lt;crosslinked microparticles (E) &gt; E-1: butadiene /Hydroxybutyl methacrylate / methacrylic acid / divinyl benzene = 60 / 32 / 6 / 2 (% by weight), Tg = - 40. (:, average particle size = 6 5 nm E-2: butadiene /styrene/hydroxybutyl methacrylate/divinylbenzene=6 0/24/14/2 (weight./.), Tg = - 35 ° C, average particle size = 70 nm &lt; adhesion aid (F ) &gt; F-1: 7 _epoxypropoxy Trimethoxy decane (manufactured by Chisso, trade name; S-510) F-2: 1,3,5-N-tris(trimethoxydecanepropyl)trimeric isocyanate (GE Toshiba polydecane) (Stock), trade name; γιΐ 597) Table 2 Resolution Adhesion Insulation Adhesion β m Beryllium Copper Ω N Example 1 10 100/100 100/100 lxl012 30 Example 2 10 100/100 100/100 lxio12 30 Example 3 10 100/100 100/100 1xl012 30 Example 4 10 100/100 100/100 lxio12 30 Example 5 10 100/100 100/100 lxio12 30 Example 6 10 100/100 100/100 lxio12 30 Example 7 10 100/100 100/100 lxio12 30 Example 8 1 0 100/100 100/100 lxio12 3 0 Comparative Example 1 10 100/100 100/100 lxio12 15 Comparative Example 2 Unresolved 0/100 0/100 lxio6 5 Comparative Example 3 10 100/100 100/100 lxio12 20 Comparative Example 4 20 100/100 100/100 lxio6 20 -47- 200905383 [Simplified Schematic] [Fig. 1] A cross-sectional schematic view of a semiconductor element. Fig. 2 is a schematic cross-sectional view showing a semiconductor element. [Fig. 3] A schematic sectional view of a substrate. [Fig. 4] A surface pattern diagram of a substrate. Fig. 5 is a top view of a substrate for evaluation of electrical insulation. Fig. 6 is a schematic view for explaining an evaluation method of adhesion. [Fig. 7] A schematic diagram for explaining an evaluation method of adhesion. Fig. 8 is a schematic view showing an embodiment of the photosensitive insulating resin composition of the present invention. [Main component symbol description] 1 : Substrate 2 : Metal pad 3 : Hardened insulating film 4 : Metal circuit 5 : Hardened insulating film 1 0 : Copper van 1 1 : Copper foil 1 2 : Substrate 13 : Substrate 14 : Substrate 1 5 : Insulating film of metal oxide or metal nitride - 48 - 200905383 1 6 : Hardened insulating film 17 : Conductive electrode 1 8 : Substrate 1 9 : Metal electrode - 49

Claims (1)

200905383 X. Patent application scope 1. A photosensitive insulating resin composition characterized by containing (A) a resin having a structural unit having a phenolic hydroxyl group, (B) a photo-sensitive acid generator, and (c) at least one kind a crosslinking agent selected from the group consisting of an oxetane-containing compound (C1) and an epoxy group-containing compound (C 2 ), (D) a solvent, and (E) a crosslinked fine particle, relative to a mass of 1 〇〇 % of the total amount of the crosslinking agent (C) 'the total amount of the oxetane group-containing compound (C1) and the epoxy group-containing compound (C2) contained in the crosslinking agent (C) is 70 to 00 The photosensitive insulating resin composition of the first aspect of the invention, wherein the resin (A) contains at least one structure selected from the following formula (I) and the following formula (Π) The structure of the group shown in the structure, [Chemical 1] [In the formula (I), 'R is independently, and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, a mi system representing an integer of 1 to 3, and a ηι system representing 1 An integer of ~3, -50- 200905383 [In the formula (π), R, R, and R2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and m2 means 1 to 3; An integer, n2 represents an integer of 1 to 3, m2+n2=4, m3 represents an integer of 0 to 3, and n3 represents an integer of 1 to 4 'm3+n3=4'. 3. The photosensitive insulating resin composition according to claim 1 or 2, wherein the crosslinking agent (C) contains an oxetane group-containing compound (C1) and an epoxy group-containing compound (C2) ). 4. The photosensitive insulating resin composition according to any one of claims 1 to 3, which further comprises (a) a phenol compound. 5. The photosensitive insulating resin composition according to any one of claims 1 to 4, wherein the crosslinked fine particles (E) contain a structural unit derived from a diene compound, and are derived from a hydroxyl group-containing unsaturated compound. A structural unit and a polymer derived from a structural unit containing a crosslinkable compound having two or more unsaturated polymerizable groups. 6. The photosensitive insulating resin composition according to claim 5, wherein the polymer constituting the crosslinked fine particles (E) further contains a structural unit derived from an aromatic vinyl compound. 7. The photosensitive -51 - / 200905383 insulating resin composition according to any one of claims 1 to 6, which further comprises (F) a bonding agent. A cured product obtained by using the photosensitive insulating resin composition according to any one of claims 1 to 7. A semiconductor device characterized by having a cured insulating film formed using the photosensitive insulating resin composition according to any one of items 1 to 7. -52-