JP5035240B2 - Radiation-sensitive insulating resin composition - Google Patents

Description

  The present invention relates to a radiation-sensitive insulating resin composition. More specifically, the present invention relates to a radiation-sensitive insulating resin composition comprising a compound having a disulfide structure, a resin, and a radiation-sensitive compound.

  Conventionally, various photosensitive resin compositions have been used to form an interlayer insulating film (passivation film) or a surface protective film (overcoat film) in a semiconductor element of an electronic device. For example, the negative photosensitive resin composition includes a resin composition containing a polyimide precursor into which a photocrosslinking group is introduced by an ester bond or an ionic bond, and the positive photosensitive resin composition includes a polyimide Examples include a composition composed of a precursor and a quinonediazide compound (see Patent Document 1 and Patent Document 2), and a composition composed of a polybenzoxazole precursor and a quinonediazide compound (see Patent Document 3).

  However, in the case of the negative type, the above-mentioned resin composition has problems in resolution and film formation, and in the case of the positive type, there are problems in heat resistance, electrical insulation, adhesion to the substrate, and the like. It was.

  On the other hand, in Patent Document 4, a curing formed using a positive photosensitive resin composition containing an alkali-soluble resin having a phenolic hydroxyl group, a compound having a quinonediazide group, crosslinked fine particles, a curing agent and a solvent. Attempts have been made to improve various properties such as resolution, electrical insulation, and adhesion.

  However, each characteristic of the cured product formed from the resin composition has room for improvement. For this reason, there has been a demand for a resin composition capable of forming a cured product having a good balance between resolution and thermal shock resistance as well as electrical insulation and adhesion.

Patent Document 5 discloses a curable resin composition containing an epoxy resin, a curing agent, and a disulfide compound having a disulfide structure as a modifier in order to improve low hygroscopicity, heat resistance, and adhesion. ing.
JP-A-5-5996 JP 2000-98601 A Japanese Patent Laid-Open No. 11-237736 JP 2003-215789 A Japanese Patent Laid-Open No. 2005-2221

  An object of the present invention is to provide a radiation-sensitive insulating resin composition capable of obtaining a cured product having improved electrical insulation, resolution, adhesion, and thermal shock resistance in a well-balanced manner.

  As a result of intensive studies to solve the above problems, the present inventors have found that a cured product excellent in electrical insulation, resolution, adhesion and crack resistance can be obtained by using a compound having a disulfide structure. The headline and the present invention were completed.

  That is, the radiation-sensitive insulating resin composition according to the present invention includes a compound (A) having a disulfide structure, a resin (B), and a radiation-sensitive compound (D).

  The resin (B) is preferably an alkali-soluble resin (B1).

  The alkali-soluble resin (B1) is preferably an alkali-soluble resin (B2) having a phenolic hydroxyl group.

  The radiation-sensitive insulating resin composition preferably further includes a compound (C) having a functional group capable of reacting with the alkali-soluble resin (B1).

  The radiation sensitive compound (D) is preferably a quinonediazide compound (D1).

  The radiation sensitive compound (D) is preferably a light sensitive acid generator (D2).

  The radiation-sensitive insulating resin composition preferably further includes crosslinked fine particles (E) having an average particle size of 30 to 500 nm.

  The compound (A) having a disulfide structure is preferably represented by the following general formula (A1).

(In the above formula, A ′ represents a monovalent organic group which may have a substituent, and A represents a divalent organic group which may have a substituent. When there are a plurality of A, (It may be the same or different. N represents an integer of 1 to 10.)
The compound (A) having a disulfide structure preferably has a reactive group.

  The radiation-sensitive insulating resin composition preferably further contains 50 to 1000 ppm of a surfactant (H).

  The cured product according to the present invention is obtained using the radiation-sensitive insulating resin composition.

  The semiconductor element according to the present invention has a cured film formed using the radiation-sensitive insulating resin composition.

  According to the radiation-sensitive insulating resin composition of the present invention, a cured product having improved electrical insulation, resolution, adhesion and thermal shock resistance in a well-balanced manner can be obtained. Moreover, the said hardened | cured material is used suitably as interlayer insulation films (passivation film | membrane) and surface protective films (overcoat film | membrane), such as a semiconductor element.

FIG. 1 is a cross-sectional view showing an example of a semiconductor device according to the present invention. FIG. 2 is a cross-sectional view showing an example of a semiconductor element according to the present invention. FIG. 3 is a cross-sectional view of the base material for thermal shock evaluation. FIG. 4 is a top view of the base material for thermal shock evaluation. FIG. 5 is a top view of the electrically insulating substrate.

Explanation of symbols

1 Substrate 2 Metal pad 3, 6 Insulating film (cured film)
4 Metal wiring 5 Semiconductor element material 10 Copper foil 11 Copper foil having gold on the surface 12 Substrate 13 Base material

  Hereinafter, the present invention will be specifically described.

  The radiation-sensitive insulating resin composition according to the present invention includes a compound (A) having a disulfide structure, a resin (B), and a radiation-sensitive compound (D). When the resin (B) is an alkali-soluble resin (B1), the radiation-sensitive insulating resin composition is a compound (C) having a functional group capable of reacting with the alkali-soluble resin (B1) as necessary. It is preferable to further contain crosslinked fine particles (E) having an average particle diameter of 30 to 500 nm.

<Compound (A) having disulfide structure>
The compound (A) having a disulfide structure used in the present invention (also referred to as “disulfide compound (A)” in the present specification) is not particularly limited as long as it has a disulfide structure (—S—S—). However, a compound represented by the following general formula (A1) is preferably used.

  In the above formula, A ′ represents a monovalent organic group which may have a substituent.

  Examples of the monovalent organic group include an aryl group, an alkyl group, and derivatives thereof, and an aryl group and an alkyl group are preferable.

  The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and specific examples include a phenyl group and a naphthyl group.

  The alkyl group may be linear or branched, and an alkyl group having 1 to 9 carbon atoms is preferably used. Specific examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert-butyl group, cyclobutyl group, pentyl group, Examples include isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, nonyl group and the like.

  In the above formula, A represents a divalent organic group which may have a substituent.

  Examples of the divalent organic group include an arylene group and an alkylene group. When there are a plurality of A, they may be the same or different.

  The arylene group is preferably an arylene group having 6 to 20 carbon atoms, and specific examples include a p-phenylene group, an m-phenylene group, an o-phenylene group, and a 2,6-naphthalene group.

  The alkylene group may be linear or branched, and a methylene group or an alkylene group having 2 to 9 carbon atoms is preferably used. Specific examples of the alkylene group having 2 to 9 carbon atoms include an ethylene group, a trimethylene group, and a propylene group.

  A ′ and A may each have at least one substituent, and examples of the substituent include an aryl group, an alkyl group, an alkoxy group, and an aralkyl group. Specific examples of the aryl group and alkyl group include the same groups as described above. Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

  The disulfide compound (A) preferably has a reactive group. As a result, the compound (C) having a functional group capable of reacting with the disulfide compound (A), the alkali-soluble resin (B1), and the alkali-soluble resin (B1) reacted, and was excellent in adhesion, resolution, and thermal shock resistance. A cured product is obtained.

  Specifically, in the above formula (A1), it is preferable that at least one of the substituents A ′ and / or A has is a reactive group. Examples of the reactive group include a hydroxyl group, a carboxyl group, a vinyl group, a mercapto group, an amino group, and an aldehyde group. Among these, a hydroxyl group and a carboxyl group are more preferable.

  The compound represented by the formula (A1) may have a repeating structure, and n represents an integer of 1 to 10, preferably 1 to 4. Of these, compounds in which n is 1 are particularly preferably used. According to the compound in which n is 1, a cured product having excellent insulating properties can be obtained even when it is miniaturized or used under severe conditions while maintaining adhesion and resolution.

  Of the above, dithiobisphenol and 2-hydroxyethyl disulfide are preferably used as the disulfide compound (A).

  The disulfide compound (A) may be in a crystalline state or an amorphous state at room temperature. Further, it may be a liquid or solid resinous material. The molecular weight of the disulfide compound (A) is not particularly limited, and may be a low molecule or a polymer, but is preferably 150 to 10,000, more preferably 200 to 3000, particularly preferably 200 to 1000. is there.

  A disulfide compound (A) may be used independently or may be used in combination of 2 or more type.

  In the resin composition according to the present invention, the amount of the disulfide compound (A) is determined from the viewpoint of the insulating properties, adhesion, resolution, and thermal shock resistance of the cured product obtained by alkali-soluble resin (B1) (phenol compound (B ′ ) Is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of the alkali-soluble resin (B1) and the phenol compound (B ′). is there.

<Resin (B)>
As resin (B) used for this invention, alkali-soluble resin (B1) is preferable.

  The alkali-soluble resin (B1) is not particularly limited as long as it is alkali-soluble, but an alkali-soluble resin (B2) having a phenolic hydroxyl group (also referred to as “phenol resin (B2)” in this specification), a polyimide precursor. The body is preferred.

  As phenol resin (B2), in addition to novolak resin, polyhydroxystyrene and its copolymer, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, polybenzoxazole precursor Examples include the body. Of these, novolak resins, polyhydroxystyrene and copolymers thereof, and polybenzoxazole precursors are preferred. These resins may be used alone or in combination of two or more.

  The novolak resin is obtained by condensing phenols and aldehydes in the presence of a catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 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- Examples thereof include trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

  Specific examples of such novolak resins include phenol / formaldehyde condensed novolak resins, cresol / formaldehyde condensed novolak resins, phenol-naphthol / formaldehyde condensed novolak resins, and the like.

  Specific examples of the polyhydroxystyrene and the copolymer thereof include the structural unit (b1) represented by the following general formula (1) and the following general formula from the viewpoint of insulation and thermal shock resistance of the resulting cured product. A copolymer (B3) composed of the structural unit (b2) represented by (2) is preferably used. The copolymer (B3) comprises a monomer that can form the structural unit (b1) represented by the following general formula (1) and a monomer that can form the structural unit (b2) represented by the following general formula (2). It is a copolymer.

(Ra represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an allyl group. Rb represents a hydrogen atom or a methyl group. N represents an integer of 0 to 3, and m represents an integer of 1 to 3. )
Examples of the monomer that can form the structural unit (b1) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol, and the like. Of these, p-hydroxystyrene and p-isopropenylphenol are preferable.

  The structural unit (b1) may be obtained, for example, by polymerizing a monomer whose hydroxyl group is protected with a t-butyl group, an acetyl group or the like. The obtained polymer or copolymer is converted into a hydroxystyrene-based structural unit by a known method, for example, deprotection under an acid catalyst.

(Rc represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group or an allyl group. Rd represents a hydrogen atom or a methyl group. N is an integer of 0 to 3.)
Examples of the monomer that can form the structural unit (b2) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, and p-methoxy. Examples include styrene. Among these, styrene and p-methoxystyrene are preferable, and styrene is more preferable.

  These monomers may be used alone or in combination of two or more.

  The copolymer (B3) is a copolymer of a monomer that can form the structural unit (b1) and a monomer that can form the structural unit (b2). Essentially, the copolymer (B1) and the structural unit ( Although it is preferable to consist only of b2), other monomers may be copolymerized.

  Examples of the other monomers include unsaturated carboxylic acids or their anhydrides, esters of the unsaturated carboxylic acids, unsaturated nitriles, unsaturated amides, unsaturated imides, and alicyclic skeletons. Compounds, unsaturated alcohols, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole 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 acid anhydrides thereof;
Methyl ester, ethyl ester, n-propyl ester, i-propyl ester, n-butyl ester, i-butyl ester, sec-butyl ester, t-butyl ester, n-amyl ester, n-hexyl of the above unsaturated carboxylic acid Ester, cyclohexyl ester, 2-hydroxyethyl ester, 2-hydroxypropyl ester, 3-hydroxypropyl ester, 2,2-dimethyl-3-hydroxypropyl ester, benzyl ester, isobornyl ester, tricyclodecanyl ester, 1 -Esters such as adamantyl ester;
Unsaturated nitriles such as (meth) acrylonitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconnitrile;
Unsaturated amides such as (meth) acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide, citraconamide, itaconamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Bicyclo [2.2.1] hept-2-ene (norbornene), tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, cyclobutene, cyclopentene, cyclooctene, dicyclopentadiene, tricyclo [5.2. 1.0 ^2,6 ] a compound having an alicyclic skeleton such as decene;
Unsaturated alcohols such as (meth) allyl alcohol;
N-vinylaniline, vinylpyridines, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole and the like can be mentioned.

  These monomers may be used alone or in combination of two or more.

  In the copolymer (B3), the amount of structural units formed from other monomers is 100 parts by weight or less with respect to a total of 100 parts by weight of the structural unit (b1) and the structural unit (b2), preferably It is 50 parts by weight or less, more preferably 25 parts by weight or less.

  In the copolymer (B3), the content of the structural unit (b1) is 10 to 99 mol%, preferably 20 to 97 mol%, more preferably 30 to 95 mol%, and the structural unit (b2) Content is 90-1 mol%, Preferably it is 80-3 mol%, More preferably, it is 70-5 mol% (Here, the total amount of the structural unit which comprises a copolymer (B3) is 100 mol%. And). When the content of the structural unit (b1) and the structural unit (b2) is out of the above range, patterning characteristics may be deteriorated, and physical properties such as thermal shock properties of the cured product may be deteriorated.

  When the copolymer (B3) is composed of the above structural units and the content of each structural unit is in the above range, a cured product excellent in various properties such as resolution, electrical insulation, thermal shock, adhesion, In particular, a cured product having excellent electrical insulation and thermal shock properties can be formed.

  In the copolymer (B3), the arrangement of the structural unit (b1), the structural unit (b2), and the structural unit formed from the other monomers is not particularly limited, and the copolymer (B3) is a random copolymer. Either a polymer or a block copolymer may be used.

  In order to obtain the copolymer (B3), a compound capable of forming the structural unit (b1) or a compound in which the hydroxyl group thereof is protected, a monomer capable of forming the structural unit (b2), and the other monomers described above are started. The polymerization may be carried out in a solvent in the presence of an agent. The polymerization method is not particularly limited, and may be performed by radical polymerization or anionic polymerization in order to obtain a compound having a desired molecular weight.

  Usually, as the monomer capable of forming the structural unit represented by the structural unit (b1), a monomer in which the hydroxyl group is protected is used. Monomers with protected hydroxyl groups are deprotected by polymerization at a temperature of 50 to 150 ° C. for 1 to 30 hours under an acid catalyst such as hydrochloric acid or sulfuric acid after polymerization, and converted to a phenol ring-containing structural unit. Is done.

  Although the molecular weight of alkali-soluble resin (B1) is not specifically limited, The weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC) method is 200,000 or less, Preferably it is 2,000-100. , 000. When Mw is less than 2,000, physical properties such as heat resistance and elongation of the cured product may be deteriorated, and when it exceeds 200,000, compatibility with other components is reduced and patterning characteristics are deteriorated. Sometimes.

  In addition, in order to improve alkali solubility as a phenol resin (B2), you may use the mixture of a copolymer (B3) and a novolak resin. The novolak resin is preferably in the range of 1 to 200 parts by weight, more preferably in the range of 1 to 150 parts by weight, and still more preferably in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the copolymer (B3). Used in

  In the resin composition according to the present invention, an alkali-soluble resin (B1) and a phenolic low molecular compound (also referred to as “phenol compound (B ′)” in this specification) may be used in combination.

  Examples of the phenol compound (B ′) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (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] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4 -{1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane and the like.

  When the phenol compound (B ′) is blended, the resin composition is blended to such an extent that sufficient alkali solubility can be expressed. Specifically, with respect to 100 parts by weight of the alkali-soluble resin (B1), The amount is preferably in the range of 1 to 200 parts by weight, more preferably in the range of 1 to 150 parts by weight, and still more preferably in the range of 1 to 100 parts by weight.

  In the resin composition according to the present invention, the amount of the alkali-soluble resin (B1) (when using the phenol compound (B ′), the total content of the alkali-soluble resin (B1) and the phenol compound (B ′)) is: The amount is usually 40 to 95 parts by weight, preferably 50 to 80 parts by weight per 100 parts by weight of the resin composition (excluding the solvent).

<Compound (C) having functional group capable of reacting with alkali-soluble resin (B1)>
The compound (C) having a functional group capable of reacting with the alkali-soluble resin (B1) used in the present invention (also referred to as “cross-linking agent (C)” in this specification) is composed of an alkali-soluble resin (B1) and phenol. It is a crosslinking component that reacts with the compound (B ′).

  Examples of the crosslinking agent (C) include, for example, a methylol group and / or alkoxymethyl group-containing aromatic compound (excluding an aromatic compound containing an amino group) (c1), an aromatic aldehyde compound (c2), a fat And at least one compound selected from the group consisting of group aldehyde compounds (c3), alkyl etherified amino group-containing compounds (c4), and epoxy group-containing compounds (c5). Among these, a methylol group and / or alkoxymethyl group-containing aromatic compound (excluding an aromatic compound containing an amino group) (c1), an aromatic aldehyde compound (c2), and an aliphatic aldehyde compound ( at least one compound (C1) selected from the group consisting of c3), or at least one compound (C2) selected from the group consisting of an alkyl etherified amino group-containing compound (c4) and an epoxy group-containing compound (c5) ) Is preferred.

  The methylol group and / or alkoxymethyl group-containing aromatic compound (excluding the aromatic compound containing an amino group) (c1) has a methylol group and / or an alkoxymethyl group in the molecule, and If it does not have a group, it is not particularly limited. For example, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 2,6-bis (hydroxymethyl) -p- Cresol, 2,6-bis (hydroxymethyl) -4-methylphenol, 5- [1,1-dimethyl-ethyl] 2-hydroxy-1,3-benzenedimethanol, 2-hydroxy-1,3,5- Benzene trimethanol, 2,6-dimethoxymethyl-4-methylphenol, 2,6-dimethoxymethyl-4- (1,1-dimethylethyl) phenol, 3,3′-methylenebis (2-hydroxy-5-me Ru-benzenemethanol), 4,4 ′-(1-methylethylidene) bis (2-methyl-6-methoxymethylphenol), 4,4 ′-(1-phenylethylidene) bis (2-hydroxyethoxyphenol), 3,3 ', 5,5'-tetramethylol-2,2-bis (4-hydroxyphenylpropane), 3,3', 5,5'-tetramethoxymethyl-2,2-bis (4-hydroxyphenyl) Propane), 1,2,4,5-tetramethylolbenzene, 1,2,4,5-tetramethoxymethylbenzene and the like.

  The aromatic aldehyde compound (c2) and the aliphatic aldehyde compound (c3) are not particularly limited as long as they contain an aldehyde group in the molecule. For example, formaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α- Phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, Examples include isophthalaldehyde.

  Examples of the alkyl etherified amino group-containing compound (c4) include active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea. And nitrogen-containing compounds obtained by alkyl etherifying all or part of the above. Here, the alkyl group constituting the alkyl ether is a methyl group, an ethyl group, or a butyl group, and may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like are preferably used.

  The epoxy group-containing compound (c5) is not particularly limited as long as it contains an oxirane ring in the molecule. For example, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol epoxy resin, a trisphenol epoxy resin , Tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. It is done.

  Compound (c1) to compound (c5) may be used alone or in combination of two or more.

  In the resin composition according to the present invention, the amount of the crosslinking agent (C) may be selected from the alkali-soluble resin (B1) (when the phenol compound (B ′) is used, the alkali-soluble resin (B1) and the phenol compound (B ′). The total amount is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight with respect to 100 parts by weight. When the amount is less than 1 part by weight, the chemical resistance of the resulting cured film may be lowered, and when the amount exceeds 100 parts by weight, the resolution may be lowered.

<Radiation sensitive compound (D)>
Examples of the radiation sensitive compound (D) used in the present invention include a quinonediazide compound (D1) and a photosensitive acid generator (D2).

  The quinonediazide compound (D1) includes, for example, a compound having a quinonediazide group and having one or more phenolic hydroxyl groups, 1,2-naphthoquinonediazide-4-sulfonic acid, or 1,2-naphthoquinonediazide-5-sulfonic acid, The ester compound. According to this compound, a positive pattern can be formed by irradiation with radiation or the like.

  The compound having one or more phenolic hydroxyl groups is not particularly limited, but compounds having the following structures are preferred.

(In General Formula (3), X _{1 to} X ₁₀ may be the same as or different from each other, and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or At least one of X _{1 to} X ₅ is a hydroxyl group, and A is a single bond, O, S, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C═O, Or SO _2. )

(In the general formula (4), X _{11 to} X ₂₃ may be the same as or different from each other, and are the same as in the case of X _{1 to} X _{10. In} the combination of X _{11 to} X ₁₅ , at least One is a hydroxyl group, and R _{1 to} R ₄ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(In the general formula (5), X _{25 to} X ₃₉ may be the same as or different from each other, and are the same as in the case of X _{1 to} X _10. X _{25 to} X ₂₉ and X ₃₀ to (In each combination of X ₃₄ , at least one is a hydroxyl group, and R ₅ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(In the general formula (6), X _{40 to} X ₅₈ may be the same as or different from each other, and are the same as in the case of X _{1 to} X _10. X _{40 to} X ₄₄ , X ₄₅ to In each combination of X ₄₉ and X _{50 to} X ₅₄ , at least one is a hydroxyl group, and R _{6 to} R ₈ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(In the general formula (7), X _{59 to} X ₇₂ may be the same as or different from each other, and are the same as in the case of X _{1 to} X _10. X _{59 to} X ₆₂ and X ₆₃ to In each combination of X ₆₇ , at least one is a hydroxyl group.)
Examples of the quinonediazide compound (D1) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 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] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl)- 1-methyl ester Le} phenyl] 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds such as ethane or 1,2-naphthoquinonediazide-5-sulfonic acid ester compounds, and the like.

  These quinonediazide compounds (D1) may be used alone or in combination of two or more.

  In the resin composition according to the present invention, the amount of the quinonediazide compound (D1) is the amount of the alkali-soluble resin (B1) (when using the phenol compound (B ′), the alkali-soluble resin (B1) and the phenol compound (B ′). The total amount is preferably 10 to 50 parts by weight, more preferably 15 to 30 parts by weight with respect to 100 parts by weight. If the amount is less than 10 parts by weight, the remaining film ratio of the unexposed part may be reduced, or an image faithful to the mask pattern may not be obtained. On the other hand, when the amount exceeds 50 parts by weight, the pattern shape may be deteriorated or foamed during curing.

The photosensitive acid generator used in the present invention (also referred to as “acid generator (D2)” in the present specification) is a compound that generates an acid upon irradiation with radiation or the like. When the alkyl ether group is contained in the cross-linking agent (C), a negative pattern can be formed such that the alkyl ether group reacts with the phenol resin (B2) with dealcoholization by the catalytic action of this acid.
The acid generator (D2) is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation or the like. For example, an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound And diazomethane compounds.

  Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluorochlorosulfonate, Phenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n- Butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate And the like.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, and phenyl-bis (trichloromethyl) -s-triazine. S-triazine derivatives such as 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and the like.

  Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like, and specific examples include 1,2-naphthoquinonediazide-4-sulfone of phenols. Examples include acid ester compounds.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphenacylsulfone. And bis (phenacylsulfonyl) methane.

  Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred specific examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate and the like.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

  These acid generators (D2) may be used alone or in combination of two or more.

  Further, in the resin composition according to the present invention, the amount of the acid generator (D2) is selected from the viewpoints of ensuring the sensitivity, resolution, pattern shape, etc. of the resin composition, the alkali-soluble resin (B1) (phenol compound (B When ') is used, it is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the total of the alkali-soluble resin (B1) and the phenol compound (B'). It is. If the amount is less than 0.1 parts by weight, curing may be insufficient and heat resistance may be reduced. If the amount exceeds 10 parts by weight, the transparency to radiation is reduced, and the pattern shape is reduced. May cause deterioration.

<Crosslinked fine particles (E)>
The crosslinked fine particle (E) used in the present invention is not particularly limited as long as the glass transition temperature (T _g ) of the polymer constituting the crosslinked fine particle is 100 ° C. or lower, and has two or more unsaturated polymerizable groups. crosslinking monomer (also referred to herein as "crosslinking monomer (e1)".) and one or more other selected such that at least one T _g of the crosslinked fine particles (E) is 0 ℃ or less A copolymer with a monomer (also referred to as “other monomer (e2)” in the present specification) is preferable. The other monomer (e2) is preferably a monomer having a functional group other than a polymerizable group, for example, a functional group such as a carboxyl group, an epoxy group, an amino group, an isocyanate group, or a hydroxyl group.

In the present specification, the T _g of the crosslinked fine particles (E) means a range of −100 ° C. to 150 ° C. using a DSC of Seiko Instruments SSC / 5200H after solidifying and drying the dispersion of the crosslinked fine particles. The value measured at a temperature elevation rate of 10 ° C./min.

  Examples of the crosslinkable monomer (e1) include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples thereof include compounds having a plurality of polymerizable unsaturated groups such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. Of these, divinylbenzene is preferred.

  The ratio of the crosslinkable monomer (e1) constituting the crosslinked fine particles (E) is preferably in the range of 1 to 20% by weight, more preferably 2 to 10% by weight, based on the total monomers used for the copolymerization. It is a range.

As other monomer (e2), for example,
Diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene, 1,3-pentadiene;
Unsaturation such as (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumarate dinitrile, etc. Nitrile compounds;
(Meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, N, N′-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, Unsaturated amides such as N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene (Meth) acrylic acid esters such as glycol (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, o-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol;
Epoxy (meth) acrylate, hydroxyalkyl (meth) acrylate and polyisocyanate obtained by reaction of diglycidyl ether of bisphenol A, diglycidyl ether of glycol and the like with (meth) acrylic acid, hydroxyalkyl (meth) acrylate, etc. Epoxy group-containing unsaturated compounds such as urethane (meth) acrylates, glycidyl (meth) acrylate and (meth) allyl glycidyl ether obtained by the reaction of
(Meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β- (meth) acryloxyethyl, hexahydrophthalic acid- unsaturated acid compounds such as β- (meth) acryloxyethyl;
Amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate;
Amide group-containing unsaturated compounds such as (meth) acrylamide and dimethyl (meth) acrylamide;
Examples thereof include hydroxyl group-containing unsaturated compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

  Among these, butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, (meth) acrylic acid, hydroxyalkyl (Meth) acrylates and the like are preferably used.

  As such other monomer (e2), it is preferable to use at least one diene compound, specifically, butadiene. Such a diene compound is desirably used in an amount of 20 to 80% by weight, preferably 30 to 70% by weight, based on all monomers used for copolymerization. The crosslinked fine particles (E) used in the present invention, when the diene compound is copolymerized in the above amount as the other monomer (e2), become rubbery soft fine particles, and in the obtained cured film, cracks ( A cured film having excellent durability can be obtained. Moreover, it is preferable to use styrene and butadiene together as the other monomer (e2) in that a cured film having a low dielectric constant can be obtained.

  The average particle size of the crosslinked fine particles (E) is 30 to 500 nm, preferably 40 to 200 nm, and more preferably 50 to 120 nm. The method for controlling the particle size is not particularly limited. For example, if the crosslinked fine particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization can be controlled by controlling the number of micelles by the amount of emulsifier used. .

  In the present specification, the average particle diameter of the crosslinked fine particles (E) was measured by diluting a dispersion of crosslinked fine particles according to a conventional method using a light scattering flow distribution measuring device LPA-3000 manufactured by Otsuka Electronics. Value.

  These crosslinked fine particles (E) may be used alone or in combination of two or more.

  In the resin composition according to the present invention, the amount of the crosslinked fine particles (E) may be selected from alkali-soluble resin (B1) (when phenol compound (B ′) is used, alkali-soluble resin (B1) and phenol compound (B ′). ) Is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, based on 100 parts by weight. If the amount is less than 0.1 parts by weight, the thermal shock resistance of the resulting cured film may be reduced. If the amount is more than 50 parts by weight, the heat resistance may be reduced or the compatibility with other components may be reduced. (Dispersibility) may decrease.

<Others>
The resin composition according to the present invention may further contain a solvent (F), an adhesion assistant (G), a surfactant (H), other additives, and the like as necessary.

[Solvent (F)]
The solvent (F) used for this invention is added in order to improve the handleability of a resin composition, or to adjust a viscosity or storage stability.

Such a solvent (F) 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 monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butylcellosolve, and carbitols such as butylcarbitol;
Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate;
Other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolacun. These solvents (F) may be used alone or in combination of two or more.

  In the resin composition according to the present invention, the amount of the solvent (F) is usually 40 to 900 parts by weight with respect to 100 parts by weight of the total components other than the solvent (F) in the resin composition, preferably 60 to 400 parts by weight.

[Adhesion aid (G)]
As the adhesion assistant (G) used in the present invention, a functional silane coupling agent is preferable, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. It is done. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate and the like. These adhesion assistants (G) may be used alone or in combination of two or more.

  In the resin composition according to the present invention, the amount of the adhesion assistant (G) is alkali-soluble resin (B1) (when phenol compound (B ′) is used, alkali-soluble resin (B1) and phenol compound (B ′). The total amount is preferably 0.01 to 20 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight.

[Surfactant (H)]
Surfactant (H) is usually added in order to improve the applicability of the resin composition.

Such a surfactant (H) is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether and the like. Kind;
Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether;
Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate;
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether;
Polyoxyethylene polyoxypropylene block copolymers;
Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate;
Nonionic interfaces of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Active agent;
EFTOP EF301, EF303, EF352 (Tochem Products), MegaFuck F171, F172, F173 (Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass), Footage 250, 251, 222F, FTX-218 (Neos), etc. Fluorinated surfactants of
Organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (Shin-Etsu Chemical), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, Silicon-based surfactants such as DC-57 and DC-190 (Toray Dow Corning Silicone);
Acrylic acid or methacrylic acid copolymer polyflow no. 75, no. 77, no. 90, no. 95 (Kyoeisha Oil Chemical Co., Ltd.).

  These can be used alone or in combination of two or more.

  The compounding amount of the surfactant (H) is usually preferably 50 to 1000 ppm, more preferably 70 to 800 ppm, and still more preferably 100 to 500 ppm in the resin composition. When it is less than 50 ppm, the uniform coating property on a substrate having a step may be deteriorated, and when it exceeds 1000 ppm, the adhesion during development or after curing may be lowered.

[Other additives]
In the resin composition according to the present invention, as other additives, a sensitizer, a leveling agent, an acid generator (an acid generator other than the acid generator (D2)), and the like are added to the characteristics of the resin composition. You may make it contain to the extent which is not impaired.

<Method for preparing radiation-sensitive insulating resin composition>
The preparation method of the resin composition concerning this invention is not specifically limited, A normal preparation method is applicable. For example, each component is put in a sample bottle, completely stoppered, and then stirred on a wave rotor. When using a resin composition, it is preferable to use what was filtered suitably.

<Hardened product>
The cured product according to the present invention is obtained using the radiation-sensitive insulating resin composition. According to the present invention, a cured product having an excellent balance of adhesion, electrical insulation, resolution, and thermal shock resistance can be obtained for various metals such as silicon, gold, copper, titanium, solder, and aluminum.

  In order to form the cured product of the present invention, first, the resin composition according to the present invention is applied to a support (a copper foil with a resin, a copper-clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.), Dry and volatilize the solvent to form a coating film.

  Thereafter, in the case of a positive resin composition, exposure is made through a desired mask pattern, development is performed with an alkaline developer, and the exposed portion is dissolved and removed to obtain a desired positive pattern. On the other hand, in the case of a negative-type resin composition, exposure is performed through a desired mask pattern, and heat treatment (this heat treatment is also referred to as “PEB” in this specification) is performed. Promote the reaction. Next, development is performed with an alkaline developer, and an unexposed portion is dissolved and removed to obtain a desired negative pattern.

  In order to fully express the insulating film characteristics of the pattern obtained as described above, the coating film may be sufficiently cured by further heat treatment after development.

  As a method for applying the resin composition to the support, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin coating method is used. Further, the thickness of the coating film may be appropriately controlled by adjusting the solid content concentration and viscosity of the coating means and the composition solution.

Examples of the radiation used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-line stepper, and an i-line stepper, an electron beam, and a laser beam. The exposure amount is appropriately selected depending on the light source used, the resin film thickness, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the resin film thickness of 10 to 50 μm is about 1,000 to 50,000 J / m ² . is there.

  As described above, when a negative resin composition is used, PEB treatment is performed after exposure and prior to development. Although this condition changes with the compounding quantity of the said resin composition, a film thickness, etc., it is 70-150 degreeC normally, Preferably it is 80-120 degreeC, and is about 1 to 60 minutes.

  Examples of the developing method after exposure include shower developing method, spray developing method, immersion developing method, paddle developing method and the like. The development conditions are usually about 20 to 40 ° C. and about 1 to 10 minutes. Examples of the alkaline developer include an alkaline solution having a concentration of about 1 to 10% by weight obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide and choline in water. An aqueous solution may be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline aqueous solution. The coating film is developed with an alkaline developer, washed with water, and dried.

  Furthermore, in the heat treatment performed after development, the curing conditions are not particularly limited, but the coating film is cured by heating at a temperature of 50 to 200 ° C. for about 30 minutes to 10 hours depending on the use of the cured product. Just do it.

  In order to sufficiently cure the obtained patterned coating film or to prevent deformation of the obtained patterned coating film, the heat treatment may be performed in two or more steps. For example, in the first stage, heating is performed at a temperature of 50 to 120 ° C. for about 5 minutes to 2 hours, and in the second stage, heating is performed at a temperature of 80 to 200 ° C. for about 10 minutes to 10 hours. The film may be cured.

  Under such curing conditions, a hot plate, oven, infrared furnace or the like can be used as heating equipment.

  The semiconductor element according to the present invention has a cured film formed as described above. This cured film can be suitably used as a surface protective film or an interlayer insulating film in a semiconductor element.

  As said semiconductor element, the semiconductor element (board | substrate with a circuit) shown in FIG. 1 and 2 is mentioned, for example. In the circuit-equipped substrate shown in FIG. 1, first, metal pads 2 are formed in a pattern on a substrate 1, and then an insulating film (cured film) 3 is formed in a pattern using the resin composition. Next, the metal wiring 4 is formed in a pattern, and further an insulating film (cured film) 6 is formed. 2 further has a metal wiring 4 formed in a pattern on the circuit board shown in FIG. 1, and then an insulating film (cured film) 6 is formed using the resin composition. Is obtained.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following examples and comparative examples, “parts” are used in terms of parts by weight unless otherwise specified.

  Moreover, about the characteristic of hardened | cured material, it evaluated by the following method.

<Resolution>
A 6-inch silicon wafer was spin-coated with the radiation-sensitive insulating resin composition, and heated at 100 ° C. for 5 minutes using a hot plate to prepare a uniform coating film having a thickness of 20 μm. Thereafter, using an aligner (MA-150 manufactured by Suss Mitotec), UV light from a high-pressure mercury lamp was exposed through a pattern mask so that the exposure amount at a wavelength of 350 nm was 3,000 J / m ² . Subsequently, it was immersed and developed at 23 ° C. for 3 minutes using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. The minimum dimension of the obtained pattern was taken as the resolution.

<Thermal shock resistance>
As shown in FIGS. 3 and 4, a base material 13 for thermal shock evaluation having a copper foil 11 having gold on the surface in a pattern on a substrate 12 was used. The resin composition was applied onto the substrate 13 and heated at 110 ° C. for 3 minutes using a hot plate. Thereby, the resin coating film whose thickness is 10 micrometers was produced on the copper foil 11 which has gold | metal | money on the surface. Then, it heated at 190 degreeC for 1 hour using the convection oven, the resin coating film was hardened, and the cured film was obtained. This substrate was subjected to a resistance test using a thermal shock tester (TSA-40L manufactured by Tabai Espec Co., Ltd.) at -65 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. The number of cycles until a defect such as a crack occurred in the cured film was confirmed every 100 cycles.

<Electrical insulation (migration test)>
As shown in FIG. 5, the base material 13 for thermal shock evaluation which has the pattern-shaped copper foil 10 on the board | substrate 12 was used. The resin composition was applied onto the substrate 13 and heated at 110 ° C. for 3 minutes using a hot plate. Thereby, a resin coating film having a thickness of 10 μm was produced on the copper foil 10. Then, it heated at 190 degreeC for 1 hour using the convection oven, the resin coating film was hardened, and the cured film was obtained. This base material was put into a migration evaluation system (AEI, EHS-221MD manufactured by Tabai Espec Co., Ltd.) and treated for 200 hours under conditions of a temperature of 121 ° C., a humidity of 85%, a pressure of 1.2 atm, and an applied voltage of 10V. Thereafter, the resistance value (Ω) of the test substrate was measured to confirm the insulation.

<Adhesion>
The resin composition was applied to a silicon wafer sputtered with copper, gold and aluminum, and heated on a hot plate at 120 ° C. for 5 minutes to produce a uniform resin film having a thickness of 10 μm. Then, using an inert gas oven (under nitrogen), it heated at 250 degreeC for 1 hour, the resin coating film was hardened, and the cured film was obtained. This cured film was treated with a pressure cooker test apparatus (manufactured by Tabai Espec Co., Ltd.) under the conditions of a temperature of 121 ° C., a humidity of 100%, and a pressure of 2.1 atmospheres for 168 hours. The adhesion before and after the test was evaluated by performing a cross-cut test (cross cut tape method) according to JIS K 5400.

  Moreover, the applicability | paintability of the resin composition was evaluated as follows.

<Applicability>
The resin composition was applied by spin coating to a 4-inch silicon wafer on which the metal wiring pattern shown in FIG. 5 was formed, and heated at 110 ° C. for 3 minutes using a hot plate. The obtained resin coating film was visually evaluated according to the following criteria.
AA: No application unevenness (the upper surface of the metal wiring, the side surface of the metal wiring, and the upper surface of the silicon wafer are also uniformly applied).
BB: Slight striation is observed starting from the metal wiring.
CC: There is uneven thickness on the entire surface of the substrate.

[Synthesis Example 1]
Synthesis of polybenzoxazole precursor (B2-1) 2,8.6 g of 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane was dissolved in 400 mL of N-methyl-2-pyrrolidone and 10.0 g of triethylamine. . A solution of 28.4 g of isophthalic acid chloride in 400 mL of γ-butyrolactone was added dropwise at 10 ° C. or lower. After completion of the dropwise addition, the mixture was reacted at room temperature for 3 hours and at 60 ° C. for 3 hours, and then placed in 10 L of distilled water to collect a precipitate.

[Synthesis Example 2]
Synthesis of cresol novolak resin (B2-2) comprising m-cresol / p-cresol = 60/40 (molar ratio) m-cresol and p-cresol were mixed at a molar ratio of 60:40, and formalin was mixed therewith. Was added and condensed by a conventional method using an oxalic acid catalyst to obtain a cresol novolak resin (B2-2) having an Mw of 6,500.

[Synthesis Example 3]
Synthesis of p-hydroxystyrene / styrene copolymer (B2-3) A mixture of pt-butoxystyrene and styrene (pt-butoxystyrene: styrene = 80: 20 (molar ratio)) in total 100 parts by weight of propylene The polymer was dissolved in 150 parts by weight of glycol monomethyl ether, the reaction temperature was maintained at 70 ° C. in a nitrogen atmosphere, and polymerization was carried out for 10 hours using 4 parts by weight of azobisisobutyronitrile. Thereafter, sulfuric acid was added to the reaction solution, the reaction temperature was kept at 90 ° C., and the reaction was carried out for 10 hours. The pt-butoxystyrene was deprotected and converted to hydroxystyrene. Ethyl acetate was added to the obtained copolymer, washing with water was repeated 5 times, the ethyl acetate phase was separated, the solvent was removed, and a p-hydroxystyrene / styrene copolymer (B2-3) was obtained.

When the molecular weight of the copolymer (B2-1) measured by gel permeation chromatography (GPC) was measured, the polystyrene equivalent weight average molecular weight (Mw) was 10,000, the weight average molecular weight (Mw) and the number average molecular weight. The ratio (Mw / Mn) to (Mn) was 3.5. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and styrene was 80:20.

[Synthesis Example 4]
2.0 of 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfonic acid Mole condensate (D1-1)
1 mol of 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride 1.5 mol was dissolved in dioxane with stirring. Next, the flask containing the solution was immersed in a water bath controlled at 30 ° C. When the internal temperature became constant at 30 ° C., 1.5 mol of triethylamine was added to the solution, and the internal temperature did not exceed 35 ° C. The solution was slowly dropped using a dropping funnel. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of dilute hydrochloric acid to cause precipitation. Next, the precipitate was collected by filtration and dried overnight in a vacuum drier controlled at 40 ° C. to obtain a quinonediazide compound (D1-1).

[Example 1]
As shown in Table 1-1, 5 parts by weight of a disulfide compound (A-1), 100 parts by weight of a polybenzoxazole precursor (B2-1), 30 parts by weight of a quinonediazide compound (D1-1) and an adhesion assistant (G- 1) 3 parts by weight was dissolved in 200 parts by weight of solvent (F-1) to prepare a resin composition. The properties of the cured film obtained from this composition and the applicability of this composition were measured by the above evaluation methods. The obtained results are shown in Tables 2 and 3.

[Examples 2 to 4]
A composition comprising the components shown in Table 1-1 was prepared in the same manner as in Example 1, and the properties of the cured film obtained from this composition and the coating properties of this composition were measured in the same manner as in Example 1. The obtained results are shown in Tables 2 and 3.

[Comparative Examples 1-3]
A composition comprising the components shown in Table 1-1 was prepared in the same manner as in Example 1, and the properties of the cured film obtained from this composition and the coating properties of this composition were measured in the same manner as in Example 1. The obtained results are shown in Tables 2 and 3.

[Example 5]
As shown in Table 1-2, 5 parts by weight of disulfide compound (A-1), 100 parts by weight of cresol novolac resin (B2-2), 15 parts by weight of hexamethoxymethylmelamine (C-1), propylene glycol diglycidyl ether ( C-3) 5 parts by weight, 3 parts by weight of a photoacid generator (D2-1), 3 parts by weight of an adhesion assistant (G-1), and 200% by weight of solvent 251 (H-1) as solvent (F-1) The resin composition was prepared by dissolving in part. The properties of the cured film obtained from this composition and the applicability of this composition were measured by the above evaluation methods. The obtained results are shown in Tables 2 and 3.

[Example 6]
A composition comprising the components shown in Table 1-2 was prepared in the same manner as in Example 5, and the properties of the cured film obtained from this composition and the coating properties of this composition were measured in the same manner as in Example 5. The obtained results are shown in Tables 2 and 3.

  Each component described in Tables 1-1 and 1-2 is as follows.

<Disulfide compound (A)>
A-1: Dithiobisphenol (Toyo Kasei)
A-2: 2-hydroxyethyl disulfide (Aldrich)
<Alkali-soluble resin (B1)>
[Phenolic resin (B2)]
B2-1: Polybenzoxazole precursor
B2-2: Cresol novolak resin (Mw = 6,500) consisting of m-cresol / p-cresol = 60/40 (molar ratio)
B2-3: Copolymer comprising p-hydroxystyrene / styrene = 80/20 (molar ratio), polystyrene-reduced weight average molecular weight (Mw) = 10,000
<Crosslinking agent (C)>
C-1: Hexamethoxymethylmelamine (Mitsui Cytec Co., Ltd., trade name: Cymel 300)
C-2: Bisphenol A epoxy resin (Japan Epoxy Resin Co., Ltd., trade name: EP-828)
C-3: Propylene glycol diglycidyl ether (manufactured by Kyoeisha Co., Ltd., trade name: Epolite 70P)
<Radiation sensitive compound (D)>
[Quinonediazide compound (D1)]
D1-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfone 2.0 molar condensate with acid [photoacid generator (D2)]
D2-1: 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate <crosslinked fine particles (E)>
E-1: butadiene / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 60/32/6/2 (% by weight), Tg = −40 ° C., average particle diameter = 65 nm
E-2: Butadiene / styrene / hydroxybutyl methacrylate / divinylbenzene = 60/24/14/2 (wt%), Tg = −35 ° C., average particle size = 70 nm
<Adhesion aid (G)>
G-1: γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation, trade name: S-510)
G-2: 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate (GE Toshiba Silicone Co., Ltd .; Y11597)
<Solvent (F)>
F-1: N-methylpyrrolidone
F-2: Ethyl lactate <Surfactant (H)>
H-1: Footogen 251 (trade name, manufactured by Neos Co., Ltd.)
H-2: Polyflow No. 90 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)

  According to the radiation-sensitive insulating resin composition according to the present invention, a cured product having an excellent balance between electrical insulation, resolution, adhesion, and thermal shock resistance can be obtained. For this reason, the said hardened | cured material is used suitably as interlayer insulation films (passivation film | membrane) and surface protective films (overcoat film | membrane), such as a semiconductor element.

Claims (11)

Hydroxyl, vinyl group, having a reactive group selected from the group consisting of a mercapto group and an aldehyde group, and, seen containing a compound having a disulfide structure (A), resin (B) and radiation-sensitive compound (D),
A radiation-sensitive insulating resin composition , wherein the radiation-sensitive compound (D) is a quinonediazide compound (D1) .   Resin (B) is alkali-soluble resin (B1), The radiation sensitive insulating resin composition of Claim 1 characterized by the above-mentioned.   The radiation-sensitive insulating resin composition according to claim 2, wherein the alkali-soluble resin (B1) is an alkali-soluble resin (B2) having a phenolic hydroxyl group. An alkali-soluble resin (B2) having a phenolic hydroxyl group is a novolak resin, polyhydroxystyrene, a copolymer of hydroxystyrene, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, a phenol-dicyclopentadiene condensation resin. The radiation-sensitive insulating resin composition according to claim 3, wherein the composition is at least one resin selected from the group consisting of a polybenzoxazole precursor. 5. The alkali-soluble resin (B2) having a phenolic hydroxyl group is at least one resin selected from a novolak resin, polyhydroxystyrene, a copolymer of hydroxystyrene, and a polybenzoxazole precursor. The radiation-sensitive insulating resin composition described. The radiation-sensitive insulating resin composition according to any one of claims 2 to 5, further comprising a compound (C) having a functional group capable of reacting with the alkali-soluble resin (B1).   The radiation-sensitive insulating resin composition according to claim 1, further comprising crosslinked fine particles (E) having an average particle diameter of 30 to 500 nm. The radiation-sensitive insulating resin composition according to claim 1, wherein the compound (A) having a disulfide structure is represented by the following general formula (A1).

(In the above formula, A ′ represents a monovalent organic group which may have a substituent, and A represents a divalent organic group which may have a substituent. When there are a plurality of A, (It may be the same or different. N represents an integer of 1 to 10.)   Furthermore, 50-1000 ppm of surfactant (H) is contained, The radiation sensitive insulating resin composition in any one of Claims 1-8 characterized by the above-mentioned. Cured product obtained by using a radiation-sensitive insulating resin composition according to any one of claims 1-9. Semiconductor device characterized by having a cured film formed using the radiation-sensitive insulating resin composition according to any one of claims 1-9.

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