JP4692219B2 - Positive photosensitive insulating resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a positive photosensitive insulating resin composition used for a surface protective film (overcoat film) or an interlayer insulating film (passivation film) such as a semiconductor element and a cured product (insulator) obtained by curing the same. . More specifically, a cured product having excellent resolution as a permanent film resist and excellent properties such as electrical insulation, thermal shock and adhesion, and positive photosensitive insulation from which such a cured product can be obtained. The present invention relates to a resin composition.

  Conventionally, polyimide resins and polybenzoxazole resins, which are excellent in heat resistance, mechanical properties, and the like, are widely used for interlayer insulating films, surface protective films, and the like used for semiconductor elements of electronic devices. In addition, various studies have been made on photosensitive polyimide and photosensitive polybenzoxazole-based resins imparted with photosensitivity in order to improve productivity and film formation accuracy. For example, a negative type in which a photocrosslinking group is introduced into a polyimide precursor by an ester bond or an ionic bond has been put into practical use. Further, as a positive type, a composition comprising a polyimide precursor and a quinonediazide compound is disclosed in JP-A-5-5996 and JP-A-2000-98601, and a polybenzoxazole precursor is disclosed in JP-A-11-237736. And a composition comprising a quinonediazide compound. However, these systems have problems such as film loss after curing (volume shrinkage), multi-stage baking during curing, atmosphere control, etc., and it is difficult to use them when industrially implemented. Has been.

  In order to improve various properties of the photosensitive resin composition, various compositions have been proposed. For example, a positive photosensitive resin composition using a polyphenylene oxide resin is disclosed in JP 2000-275842 A and It is reported in Japanese Patent Application Laid-Open No. 2001-312064. However, these systems have problems in terms of the balance of performance in terms of resolution, electrical insulation, thermal shock, and adhesion as insulating resins.

  A positive photosensitive resin composition using a (co) polymer formed from hydroxystyrenes as an alkali-soluble resin has also been proposed. As such a composition, JP-A-7-140648 (Patent Document 1) discloses a thermosetting photosensitive material comprising an alkali-soluble resin composed of polyvinylphenol, a specific photosensitive agent, a specific thermosetting agent and a solvent. It is disclosed. JP-A-6-43637 (Patent Document 2) discloses a resin composition containing an alkali-soluble resin, a quinone diad compound and a crosslinking agent, and examples of the alkali-soluble resin include a copolymer containing a p-hydroxystyrene structure. Has been.

  Further, JP 2003-215789 A (Patent Document 3) discloses a positive photosensitive resin composition containing an alkali-soluble resin having a phenolic hydroxyl group, a quinonediazide compound, crosslinked fine particles, a curing agent, and a solvent. JP 2003-215795 A (Patent Document 4) further discloses a positive photosensitive resin composition containing an acid generator, and examples of the alkali-soluble resin include polyhydroxystyrene and a copolymer thereof. In addition, it is possible to use an alkali-soluble resin having a predetermined molecular weight from the viewpoint of resolution, thermal shock, heat resistance, etc. of the insulating film obtained from the composition. It is taught to use a predetermined amount of a curing agent from the viewpoint of electrical insulation.

However, even in these systems, a resin composition capable of forming a cured product having an excellent balance of performance in resolution, electrical insulation, thermal shock, and adhesion has not been obtained. In addition, the polyhydroxystyrene copolymer that can be used in these resin compositions is used to enable development of a cured product with an alkaline aqueous solution. However, in any document, the specific type and composition of the polyhydroxystyrene copolymer are not studied, and the resin composition and its curing can be controlled by controlling the type and composition of the polyhydroxystyrene copolymer. There is no description of the idea of improving various properties other than alkali developability of the product.
Japanese Patent Laid-Open No. 7-140648 JP-A-6-43637 JP 2003-215789 A JP 2003-215595 A

  The present invention solves the problems associated with the prior art as described above, and can obtain a cured product excellent in various properties such as resolution, electrical insulation, thermal shock, adhesion, etc. Another object of the present invention is to provide a positive photosensitive insulating resin composition suitable for applications such as a surface protective film.

  Furthermore, an object of the present invention is to provide a cured product obtained by curing such a positive photosensitive insulating resin composition and excellent in various properties such as resolution, electrical insulation, thermal shock and adhesion. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a positive photosensitive insulating resin composition containing a polyhydroxystyrene copolymer containing a specific structural unit in a specific amount as an alkali-soluble resin. It was found that both the electrical insulation and the thermal shock resistance of the resulting cured product are remarkably improved by using the present invention, and the present invention has been completed.

The positive photosensitive insulating resin composition according to the present invention is:
(A) (A1) 10 to 99 mol% of a structural unit represented by the following general formula (1), and (A2) 90 to 1 mol% of a structural unit represented by the following general formula (2)
Containing a copolymer (the total amount of structural units constituting the copolymer is 100 mol%),

(Ra represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an aryl group.
Rb represents a hydrogen atom or a methyl group.
n is an integer of 0 to 3, and m is an integer of 1 to 3. )

(Rc represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an aryl group.
Rd represents a hydrogen atom or a methyl group.
n is an integer of 0-3. )
(B) a compound having a quinonediazide group,
(C) (C1) From a methylol group and / or an alkoxymethyl group-containing aromatic compound (excluding an aromatic compound containing an amino group), (C2) an aromatic aldehyde compound, and (C3) an aliphatic aldehyde compound At least one compound selected from the group consisting of: (D) a solvent; and (E) an adhesion aid.

  The copolymer (A) is composed of 10 to 99 mol% of the structural unit (A1) represented by the general formula (1) and 90 to 1 mol% of the structural unit (A2) represented by the general formula (2). The sum of (A1) and (A2) is 100 mol%. ] Is preferable.

  The structural unit (A2) is preferably a structural unit represented by the following formula (2 ′).

The positive photosensitive insulating resin composition may further contain (a) a phenol compound.
The amount of the phenol compound (a) is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the copolymer (A).

  The amount of the compound (B) having a quinonediazide group is 10 to 50 parts by weight, and the amount of the compound (C) is 100 parts by weight in total of the copolymer (A) and the phenol compound (a). It is preferable that it is 1-100 weight part.

The positive-type photosensitive insulating resin composition further has (F) an average particle size of 30 to 500 nm, and at least one T _g (glass transition temperature) of the copolymer as a constituent component is 0 ° C. or less. It preferably contains fine particles.

The copolymer that is a constituent component of the crosslinked fine particles (F) is preferably a styrene-butadiene copolymer.
The amount of the crosslinked fine particles (F) is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight as a total of the copolymer (A) and the phenol compound (a).

The cured product according to the present invention is obtained by curing the positive photosensitive insulating resin composition.
The cured product is
(I) The resistance value after the migration test is 10 ¹⁰ Ω or more, and
(Ii) In the thermal shock test in which −65 ° C./30 minutes to 150 ° C./30 minutes is one cycle, the number of cycles until cracks occur in the cured film is preferably 1000 cycles or more.

  When the positive photosensitive insulating resin composition according to the present invention is used, a cured product having excellent resolution, insulating properties, thermal shock properties, adhesiveness, etc., and particularly excellent both insulating properties and thermal shock properties is formed. be able to.

  When the cured product according to the present invention is used, it is excellent in various properties such as resolution, electrical insulation, thermal shock, adhesion, etc., and in particular, an interlayer insulation film for a cured product semiconductor element that is remarkably excellent in both insulation and thermal shock. A surface protective film or the like can be formed.

Hereinafter, the positive photosensitive insulating resin composition and the cured product thereof according to the present invention will be specifically described.
[Positive photosensitive insulating resin composition]
The positive-type photosensitive insulating resin composition according to the present invention comprises 10 to 99 mol% of the structural unit (A1) represented by the general formula (1) and the structural unit (A2) 90 represented by the general formula (2). A copolymer (A) composed of ˜1 mol% (the amount of all structural units constituting the copolymer is 100 mol%), a compound (B) having a quinonediazide group, a methylol group and / or alkoxymethyl Group-containing aromatic compound (excluding an aromatic compound containing an amino group) (C1), aromatic aldehyde compound (C2), at least one compound selected from the group consisting of aliphatic aldehyde compounds (C3) ( C), a solvent (D), and an adhesion assistant (E). In addition, the positive photosensitive insulating resin composition of the present invention may contain other additives such as a phenol compound, a crosslinking aid, crosslinked fine particles, a sensitizer, and a leveling agent, if necessary.

(A) a copolymer;
The copolymer (A) used in the present invention forms a monomer capable of forming a structural unit (A1) represented by the following general formula (1) and a structural unit (A2) represented by the following general formula (2). It is a copolymer with a possible monomer and is an alkali-soluble resin (hereinafter also referred to as “alkali-soluble resin (A)”).

(Ra represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an aryl group.
Rb represents a hydrogen atom or a methyl group.
n is an integer of 0 to 3, and m is an integer of 1 to 3. )

(Rc represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an aryl group.
Rd represents a hydrogen atom or a methyl group.
n is an integer of 0-3. )
Examples of the monomer that can form the structural unit (A1) represented by the general formula (1) include monomers represented by the following formula (1a).

(Ra represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an aryl group.
Rb represents a hydrogen atom or a methyl group.
n is an integer of 0 to 3, and m is an integer of 1 to 3. )
Specific examples include aromatic vinyl compounds having a phenolic hydroxyl group such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol. Of these, p-hydroxystyrene and p-isopropenylphenol are preferably used.

These monomers can be used singly or in combination of two or more.
The structural unit represented by the general formula (1) is obtained by polymerizing a monomer whose hydroxyl group is protected with, for example, a t-butyl group, an acetyl group, and the like. It can be formed by deprotecting and converting to a hydroxystyrene-based structural unit.

  Examples of the monomer that can form the structural unit (A2) represented by the general formula (2) include monomers represented by the following formula (2a).

(Rc represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an aryl group.
Rd represents a hydrogen atom or a methyl group.
n is an integer of 0-3. )
Examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, and p-methoxystyrene. Among these, styrene and p-methoxystyrene are preferable, and styrene is particularly preferable.

These monomers can be used singly or in combination of two or more.
The copolymer (A) is a copolymer of a monomer that can form the structural unit (A1) and a monomer that can form the structural unit (A2), and is essentially the structural unit (A1). And it is preferable to consist only of the structural unit (A2), but other monomers may be copolymerized. In the copolymer (A), the amount of structural units formed from other monomers is preferably 100 parts by weight or less with respect to a total of 100 parts by weight of the structural unit (A1) and the structural unit (A2). More preferably, it is 50 parts by weight or less, and particularly preferably 25 parts by weight or less.

  Examples of such other monomers include compounds having an alicyclic skeleton, unsaturated carboxylic acids or their anhydrides, esters of the unsaturated carboxylic acids, unsaturated nitriles, unsaturated amides, Examples include unsaturated imides and unsaturated alcohols.

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 their acid anhydrides Things;
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 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 . Compounds having an alicyclic skeleton such as 1 ^7,10 ] dodec-3-ene, cyclobutene, cyclopentene, cyclooctene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] 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 can be used singly or in combination of two or more.
The content of the structural unit (A1) represented by the general formula (1) in the copolymer (A) is 10 to 99 mol%, preferably 20 to 97 mol%, more preferably 30 to 95 mol. The content of the structural unit (A2) represented by the general formula (2) is 90 to 1 mol%, preferably 80 to 3 mol%, more preferably 70 to 5 mol% ( (However, the total amount of structural units constituting the copolymer (A) is 100 mol%.) When the content of the structural unit (A1) and the structural unit (A2) is outside this range, the patterning characteristics may be deteriorated, and the physical properties such as thermal shock property of the cured product may be deteriorated.

  In addition, when the copolymer (A) is composed of the above structural units and the content of each structural unit is in the above range, various properties such as resolution, electrical insulation, thermal shock, adhesion and the like can be obtained. An excellent cured product, particularly a cured product excellent in both electrical insulation and thermal shock properties can be formed.

  The molecular weight of the copolymer (A) is not particularly limited, but the polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is, for example, 200,000 or less, preferably 2,000 to 100, About 000. Moreover, 1.0-10.0 are preferable and, as for ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn), 1.0-8.0 are more preferable. When Mw is less than 2,000, physical properties such as heat resistance and elongation of the cured product are lowered, and when it exceeds 200,000, compatibility with other components may be lowered, and patterning characteristics may be lowered. On the other hand, if Mw / Mn exceeds the above upper limit, the heat resistance of the cured product may decrease, compatibility with other components may decrease, and patterning characteristics may decrease. In addition, Mn and Mw are GPC columns manufactured by Tosoh Corporation (G2000HXL: 2, G3000HXL: 1), flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. The dispersion polystyrene was measured with a differential refractometer as a standard substance.

  In the copolymer (A), a structural unit formed from the structural unit (A1) represented by the general formula (1), the structural unit (A2) represented by the general formula (2), and the other monomer. Is not particularly limited, and the copolymer (A) may be either a random copolymer or a block copolymer.

  In order to obtain the copolymer (A), a monomer capable of forming the structural unit (A1) represented by the general formula (1) or a compound in which the hydroxyl group is protected, and a structure represented by the general formula (2) What is necessary is just to superpose | polymerize the monomer which can form unit (A2), and the said other monomer in a solvent in presence of an initiator. The polymerization method is not particularly limited, but is carried out by radical polymerization or anionic polymerization in order to obtain a copolymer having the above molecular weight.

  Usually, as the monomer capable of forming the structural unit represented by the general formula (1), a monomer in which the hydroxyl group is protected is used. After polymerization, the monomer in which the hydroxyl group is protected is converted into a phenolic hydroxyl group-containing structural unit by deprotection by reacting at a temperature of 50 to 150 ° C. for 1 to 30 hours in an acid catalyst such as hydrochloric acid or sulfuric acid after polymerization. Converted.

Moreover, when the alkali solubility of the copolymer (A) is insufficient, a phenol ring-containing compound other than the copolymer (A) (hereinafter also referred to as “phenol compound (a)”) is used in combination. Can do. Examples of the phenol compound (a) include resins having a phenolic hydroxyl group other than the copolymer (A) (hereinafter referred to as “phenol resin”), low-molecular phenol compounds, and the like.

  Examples of the phenol resin include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, a phenol-naphthol / formaldehyde condensed novolak resin, and a hydroxystyrene homopolymer.

  Examples of the low molecular weight phenol compound 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-hydroxypheny ) Such as ethane.

The phenol resin and the low molecular weight phenol compound may be used in combination, but usually either one is used.
When mix | blending these phenolic compounds (a), it can mix | blend to such an extent that sufficient alkali solubility is expressed as a composition. Specifically, the amount is preferably 1 to 200 parts by weight, more preferably 1 to 150 parts by weight, and still more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the copolymer (A). Can be used.

  In the composition of the present invention, the total content of the copolymer (A) and the phenol compound (a) is usually 40 to 100 parts by weight of the composition (excluding the solvent (D)). 95 parts by weight, preferably 50 to 80 parts by weight.

(B) a compound having a quinonediazide group;
The compound having a quinonediazide group used in the present invention (hereinafter also referred to as “quinonediazide compound (B)”) is a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazide-4-sulfonic acid or 1 , 2-naphthoquinonediazide-5-sulfonic acid ester compound. 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. 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 at least 1 in each of the combinations of to X ₄₉ and X ₅₀ to X ₅₄ is a hydroxyl group. Further, R ₆ to R ₈ is 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 at least one in each combination of to X ₆₇ is a hydroxyl group.)
Examples of the quinonediazide compound (B) 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-methylethyl} phenyl] ethane, etc. 1,2-naphthoquinonediazide-4-sulfonic acid ester compound or 1,2-naphthoquinonediazide-5-sulfonic acid ester compound Etc.

  In the composition of the present invention, the amount of the quinonediazide compound (B) is preferably 10 to 50 parts by weight with respect to 100 parts by weight in total of the copolymer (A) and the phenol compound (a). Preferably it is 15-30 weight part. If the blending amount is less than 10 parts by weight, the remaining film ratio in the unexposed part may decrease, or an image faithful to the mask pattern may not be obtained. On the other hand, if the blending amount exceeds 50 parts by weight, the pattern shape may be deteriorated or foaming may occur during curing.

(C) a crosslinking agent;
Methylol group and / or alkoxymethyl group-containing aromatic compound used in the present invention (excluding an aromatic compound containing an amino group) (C1), aromatic aldehyde compound (C2), aliphatic aldehyde compound (C3) ) At least one compound (C) selected from the group consisting of (hereinafter also referred to as “crosslinking agent (C)”) as a crosslinking component that reacts with the copolymer (A) and the phenol compound (a). Works.

  The methylol group and / or alkoxymethyl group-containing aromatic compound (excluding the aromatic compound containing an amino group) (C1) includes a methylol group and / or an alkoxymethyl group in the molecule, and an amino group. If it does not contain a group, it is not particularly limited, and 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-benzenetri Methanol, 2,6-dimethoxymethyl-4-methylphenol, 2,6-dimethoxymethyl-4- (1,1-dimethylethyl) Phenol, 3,3′-methylenebis (2-hydroxy-5-methyl-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-hydroxyphenylpropane), 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. Formaldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, phenylacetaldehyde, α-phenylpropyl Aldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde And so on.

These crosslinking agents (C) can be used singly or in combination of two or more.
In the composition of the present invention, the blending amount of these crosslinking agents (C) is preferably 1 to 100 weights with respect to a total of 100 parts by weight of the copolymer (A) and the phenol compound (a). Parts, more preferably 2 to 70 parts by weight. When the blending amount is less than 1 part by weight, the chemical resistance of the resulting cured film may be lowered, and when it exceeds 100 parts by weight, the resolution may be lowered.

  When the curability of the composition of the present invention is insufficient, a crosslinking aid can be used in combination. Such crosslinking aids include glycidyl ether groups, glycidyl ester groups, glycidylamino groups, benzyloxymethyl groups, dimethylaminomethyl groups, diethylaminomethyl groups, dimethylolaminomethyl groups, diethylolaminomethyl groups, morpholinomethyl groups. And compounds having an acetoxymethyl group, a benzoyloxymethyl group, an acetyl group, a vinyl group, an isopropenyl group, and the like.

  These crosslinking aids can be blended to such an extent that the composition of the present invention exhibits sufficient curability. Specifically, it can mix | blend in the range of 0-100 weight part with respect to 100 weight part of said crosslinking agents (C).

(D) solvent;
The solvent (D) 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 (D) is not particularly limited, and 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 and cyclohexanone;
Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolacun. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

The compounding quantity of a solvent (D) is 40-900 weight part normally with respect to a total of 100 weight part of components other than the solution in a composition, Preferably it is 60-400 weight part.
(E) adhesion aid;
As the adhesion assistant (E), 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. Is 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.

  The compounding amount of the adhesion assistant (E) is usually 0.5 to 10 parts by weight, preferably 0.5 parts per 100 parts by weight in total of the copolymer (A) and the phenol compound (a). -8.0 parts by weight.

(F) crosslinked fine particles;
As the crosslinked fine particles (hereinafter also referred to as “crosslinked fine particles (F)”) that may be used as necessary in the present invention, the glass transition temperature (T _g ) of the polymer constituting the crosslinked fine particles is 100 ° C. or lower. The crosslinkable monomer having two or more unsaturated polymerizable groups (hereinafter referred to as “crosslinkable monomer”) and at least one T _{g of} the crosslinked fine particles (F) is 0 ° C. or less. A copolymer with at least one other monomer (hereinafter referred to as “other monomer (f)”) selected so as to be preferable is preferable. As said other monomer (f), the monomer which has functional groups, such as a carboxyl group, an epoxy group, an amino group, an isocyanate group, a hydroxyl group, for example as functional groups other than a polymeric group is preferable.

In the present invention, the T _g of the crosslinked fine particles (F) means that the dispersion of the crosslinked fine particles is solidified and dried, and then heated in the range of −100 ° C. to 150 ° C. using a DSC of Seiko Instruments SSC / 5200H. There is a value measured at a rate of 10 ° C./min.

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

  The ratio of the crosslinkable monomer constituting the crosslinked fine particles (F) is preferably in the range of 0.1 to 20% by weight, more preferably 0.1% to 100% by weight of the total monomers used for copolymerization. It is in the range of 5 to 10% by weight.

For the other monomer (f),
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 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.

  The ratio of the other monomer (f) constituting the crosslinked fine particles (F) is preferably in the range of 80.0 to 99.9% by weight with respect to 100% by weight of the total monomers used for copolymerization, and more Preferably it is the range of 90.0-99.5 weight%.

  Moreover, it is preferable to use at least one diene compound, specifically butadiene, as the other monomer (f). Such a diene compound is desirably used in an amount of 20 to 80% by weight, preferably 30 to 70% by weight, based on 100% by weight of the total monomers used for copolymerization. The crosslinked fine particles (F) used in the present invention are rubber-like soft fine particles when a diene compound such as butadiene is copolymerized in the above amount with respect to all monomers as the other monomer (f), In particular, it is possible to prevent cracks from occurring in the obtained cured film and to obtain a cured film having excellent durability. Further, it is preferable to use both styrene and butadiene as the other monomer (f) in that a cured film having a low dielectric constant can be obtained.

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

  In the present invention, the average particle diameter of the crosslinked fine particles (F) is a value 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. .

  The amount of the crosslinked fine particles (F) is preferably 0.1 to 50 parts by weight, preferably 100 to 50 parts by weight, preferably 100 parts by weight of the copolymer (A) and the phenol compound (a). 1 to 20 parts by weight. If the blending amount is less than 0.1 part by weight, the thermal shock resistance of the resulting cured film may be reduced, and if it exceeds 50 parts by weight, the heat resistance may be reduced or the compatibility (dispersibility) with other components may be reduced. May decrease.

Other additives;
In the positive photosensitive resin composition of the present invention, as other additives, a sensitizer, a leveling agent, an acid generator, and the like can be contained so as not to impair the properties of the composition of the present invention. .

(Method for preparing composition)
The adjustment method of the positive photosensitive resin resin composition of this invention is not specifically limited, A normal preparation method can be applied. It can also be prepared by stirring a sample bottle with each component in it and completely plugged on the wave rotor.

[Cured product]
The positive photosensitive insulating resin composition according to the present invention includes a copolymer (A), a quinonediazide compound (B), a crosslinking agent (C), a solvent (D), an adhesion assistant (E), and, if necessary, It contains a phenol compound (a), crosslinked fine particles (F), a crosslinking aid, or other additives, and the cured product is excellent in resolution, thermal shock, adhesion, electrical insulation and the like. Therefore, the positive photosensitive insulating resin composition of the present invention can be suitably used particularly as a surface protective film or an interlayer insulating film material of a semiconductor element.

Such a cured product according to the present invention is excellent in electrical insulation, and the resistance value after the migration test is preferably 10 ⁸ Ω or more, more preferably 10 ⁹ Ω or more, and further preferably 10 ¹⁰ Ω or more. . Here, in the present invention, the migration test specifically refers to a test performed as follows.

  A resin composition is apply | coated to the evaluation board | substrate shown in FIG. 3, and it heats for 3 minutes at 110 degreeC using a hotplate, and produces the resin coating film whose thickness on copper foil is 10 micrometers. Thereafter, the resin coating film is cured by heating at 190 ° C. for 1 hour using a convection oven to obtain a cured film. After this substrate 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 5 V The resistance value (Ω) of the test substrate is measured.

  In addition, the cured product according to the present invention has excellent thermal shock properties, and in the thermal shock test in which one cycle is −65 ° C./30 minutes to 150 ° C./30 minutes, the number of cycles until cracks occur in the cured product is Preferably it is 1000 cycles or more, More preferably, it is 1500 cycles or more, More preferably, it is 2000 or more. Here, in the present invention, the thermal shock test specifically refers to a test performed as follows.

The resin composition is applied to the evaluation substrate shown in FIGS. 1 and 2 and heated at 110 ° C. for 3 minutes using a hot plate to produce a resin coating film having a thickness of 10 μm on the copper foil. Thereafter, it is heated at 190 ° C. for 1 hour using a convection oven to obtain a cured product. This substrate is subjected to a resistance test using a thermal shock tester (TSA-40L, manufactured by Tabai Espec Co., Ltd.) with -65 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. The number of cycles until a defect such as a crack occurs in the cured film is confirmed every 100 cycles. Therefore, the greater the number of cycles until a defect such as a crack occurs in the cured product, the more excellent the thermal shock property.

  In order to form the cured product of the present invention, first, a positive photosensitive insulating resin composition according to the present invention is used as a support (a silicon wafer with a resin-coated copper foil, a copper-clad laminate, a metal sputtered film, an alumina substrate, etc. ) And dried to evaporate the solvent and form a coating film. Thereafter, the desired pattern can be obtained by exposing through a desired mask pattern, developing with an alkaline developer, and dissolving and removing the exposed portion. Furthermore, a cured film can be obtained by performing a heat treatment after development in order to develop the insulating film characteristics.

  As a method of 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 can be used. The coating thickness can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of 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 is about 1,000 to 50,000 J / m ² when the resin film thickness is 10 to 50 μm. .

  After the exposure, development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing the exposed portion of the coating film. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, a paddle developing method, and the like. The developing conditions are usually 20 to 40 ° C. for about 1 to 10 minutes. Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of about 1 to 10% by weight. Can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. The coating film is developed with an alkaline developer, washed with water, and dried.

  Furthermore, in order to sufficiently develop the characteristics as an insulating film after development, the coating film can be sufficiently cured by heat treatment. Such curing conditions are not particularly limited, but the coating film can be 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.

  In addition, in order to sufficiently cure the obtained patterned coating film or to prevent deformation of the obtained patterned coating film, the heat treatment can 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. Can also be cured.

Under such curing conditions, a hot plate, an oven, an infrared furnace, or the like can be used as heating equipment.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples. In the following examples and comparative examples, “parts” are used in terms of parts by weight unless otherwise specified.

Moreover, about each characteristic of hardened | cured material, it evaluated in the following way.
Resolution:
The resin composition was spin-coated on a 6-inch silicon wafer and heated at 110 ° C. for 3 minutes using a hot plate to produce a uniform coating film having a thickness of 10 μm. Then, using an aligner (MAS-100 manufactured by Suss Microtec), 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 8,000 J / m ² . Next, immersion development was performed at 23 ° C. for 90 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. The minimum dimension of the obtained pattern was taken as the resolution.
Adhesion:
The resin composition was applied to a silicon wafer sputtered with SiO ₂ and heated at 110 ° C. for 3 minutes using a hot plate to produce a uniform resin film having a thickness of 10 μm. 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 cured film was treated with a pressure cooker test apparatus (EHS-221MD 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.
Thermal shock resistance:
1 and 2, a resin composition is applied to a substrate 3 for thermal shock evaluation having a patterned copper foil 1 on a substrate 2 as shown in FIGS. 1 and 2, and using a hot plate at 110 ° C. for 3 minutes. The base material which heated and produced the resin coating film whose thickness on the copper foil 1 is 10 micrometers was produced. 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.) with -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):
A resin composition is applied to a base material 6 for thermal shock evaluation having a patterned copper foil 4 on a substrate 5 as shown in FIG. 3, and heated at 110 ° C. for 3 minutes using a hot plate. The base material which has the resin coating film whose thickness on the copper foil 4 is 10 micrometers was produced. 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 5V. Thereafter, the resistance value (Ω) of the test substrate was measured to confirm the insulation.

[Synthesis Example 1]
(Synthesis of p-hydroxystyrene / styrene copolymer)
100 parts by weight of pt-butoxystyrene and styrene in a molar ratio of 80:20 were dissolved in 150 parts by weight of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 ° C. in a nitrogen atmosphere. Polymerization was carried out for 10 hours using 4 parts by weight of isobutyronitrile. Thereafter, sulfuric acid was added to the reaction solution, and the reaction temperature was kept at 90 ° C. for reaction for 10 hours, and 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 (hereinafter referred to as “copolymer (A -1) ").

When the molecular weight of this copolymer (A-1) was measured by 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 ( 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 2]
(Synthesis of p-hydroxystyrene homopolymer)
A p-hydroxystyrene homopolymer (hereinafter referred to as “homopolymer (A-)” was prepared in the same manner as in Synthesis Example 1 except that 100 parts by weight of only pt-butoxystyrene was dissolved in 150 parts by weight of propylene glycol monomethyl ether. 2) ").

Mw of this homopolymer (A-2) was 10,000, and Mw / Mn was 3.2.
[Synthesis Example 3]
(Synthesis of p-hydroxystyrene / styrene / hydroxybutyl acrylate copolymer)
Except that p-t-butoxystyrene, styrene, and hydroxybutyl acrylate were dissolved in 150 parts by weight of propylene glycol monomethyl ether in a molar ratio of 80:20:10 in total, 150 parts by weight of propylene glycol monomethyl ether, A p-hydroxystyrene / styrene / hydroxybutyl acrylate copolymer (hereinafter referred to as “copolymer (A-3)”) was obtained.

  Mw of this copolymer (A-3) was 10,000, Mw / Mn was 3.5, and the copolymerization molar ratio of p-hydroxystyrene: styrene: hydroxybutyl acrylate was 80:10:10.

[Synthesis Example 4]
(Synthesis of phenol resin (a-1))
M-cresol and p-cresol are mixed at a molar ratio of 60:40, formalin is added thereto, and condensed by a conventional method using an oxalic acid catalyst, and a cresol novolak resin (hereinafter referred to as Mw) of 6,500. And “phenol resin (a-1)”).

[Synthesis Example 5]
(Synthesis of quinonediazide compounds)
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 2.0 mol was dissolved in dioxane with stirring to prepare a solution. The flask containing the solution is then immersed in a water bath controlled at 30 ° C. When the solution becomes constant at 30 ° C., 2.0 mol of triethylamine is added to the solution so that the solution does not exceed 35 ° C. It dropped slowly using the dropping funnel. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration. The filtrate is poured into a large amount of dilute hydrochloric acid, and the deposited precipitate is collected by filtration and dried for a whole day and night in a vacuum dryer controlled at 40 ° C. (hereinafter referred to as “quinonediazide compound (B-1)”). )

[Synthesis Example 6]
(Synthesis of quinonediazide compounds)
As in Synthesis Example 5, except that 1 mol of 1,1-bis (4-hydroxyphenyl) -1-phenylethane and 1.5 mol of 1,2-naphthoquinonediazide-5-sulfonic acid were used as raw materials, A quinonediazide compound (hereinafter referred to as “quinonediazide compound (B-2)”) was obtained.

[Example 1]
As shown in Table 1, polymer (A-1) 100 parts by weight, quinonediazide compound (B-1) 20 parts by weight, crosslinking agent (C-1) 25 parts by weight, adhesion aid (E-1) 2.5 Part by weight was dissolved in 145 parts by weight of solvent (D-1) to prepare a resin composition. The properties of this composition were measured according to the evaluation method. The obtained results are shown in Table 2.

[Examples 2 to 5]
A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1, and the properties of the composition and its cured film were measured in the same manner as in Example 1. The obtained results are shown in Table 2.

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

Note) The composition described in Table 1 is as follows.
Polymer;
A-1: Copolymer made of p-hydroxystyrene / styrene = 80/20 (molar ratio), polystyrene equivalent weight average molecular weight (Mw) = 10,000
A-2: Homopolymer composed of p-hydroxystyrene, polystyrene equivalent weight average molecular weight (Mw) = 10,000
A-3: Copolymer consisting of p-hydroxystyrene / styrene / hydroxybutyl acrylate = 80/10/10 (molar ratio), polystyrene-reduced weight average molecular weight (Mw) = 10,000
Phenolic compounds;
a-1: Cresol novolak resin (Mw = 6,500) consisting of m-cresol / p-cresol = 60/40 (molar ratio)
Quinonediazide compounds;
B-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid (molar ratio = 1.0: 2.0)
B-2: Condensate of 1,1-bis (4-hydroxyphenyl) -1-phenylethane and 1,2-naphthoquinonediazide-5-sulfonic acid (molar ratio = 1.0: 1.5)
Cross-linking agent;
C-1: o-hydroxybenzaldehyde C-2: 2,6-bis (hydroxymethyl) -p-cresol curing aid;
C-3: Propylene glycol diglycidyl ether (manufactured by Kyoeisha Co., Ltd., trade name: Epolite 70P)
solvent;
D-1: ethyl lactate D-2: 2-heptanone adhesion aid;
E-1: γ-glycidoxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd., trade name: A-187)
Crosslinked fine particles;
F-1: butadiene / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 60/32/6/2 (% by weight), average particle diameter = 65 nm
F-2: butadiene / styrene / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 60/20/12/6/2 (% by weight), average particle diameter = 65 nm

  When the positive photosensitive insulating resin composition according to the present invention is used, a cured product having excellent resolution, insulating properties, thermal shock properties, adhesiveness, etc., and particularly excellent both insulating properties and thermal shock properties is formed. be able to. Therefore, it is possible to provide an interlayer insulating film, a surface protective film, and the like for a semiconductor element that are excellent in these various characteristics.

FIG. 1 is a cross-sectional view of a base material for thermal shock evaluation. FIG. 2 is a schematic diagram of a base material for thermal shock evaluation. FIG. 3 is a schematic diagram of a substrate for evaluation of electrical insulation.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Copper foil 2 ... Board | substrate 3 ... Base material 4 ... Copper foil 5 ... Board | substrate 6 ... Base material

Claims (11)

(A) (A1) 10 to 99 mol% of a structural unit represented by the following general formula (1), and
(A2) 90-1 mol% of structural units represented by the following general formula (2)
Containing a copolymer (the total amount of structural units constituting the copolymer is 100 mol%),

(Ra represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an aryl group.
Rb represents a hydrogen atom or a methyl group.
n is an integer of 0 to 3, and m is an integer of 1 to 3. )

(Rc represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or an aryl group.
Rd represents a hydrogen atom or a methyl group.
n is an integer of 0-3. )
(B) a compound having a quinonediazide group,
(C) (C1) From a methylol group and / or an alkoxymethyl group-containing aromatic compound (excluding an aromatic compound containing an amino group), (C2) an aromatic aldehyde compound, and (C3) an aliphatic aldehyde compound At least one compound selected from the group consisting of :
A positive photosensitive insulating resin composition comprising (D) a solvent, and (E) an adhesion assistant.   The copolymer (A) is 10 to 99 mol% of the structural unit (A1) and 90 to 1 mol% of the structural unit (A2) [the total of (A1) and (A2) is 100 mol%. . ] The positive photosensitive insulating resin composition according to claim 1, wherein The positive photosensitive insulating resin composition according to claim 1, wherein the structural unit (A2) is represented by the following formula (2 ′).

Furthermore, (a) a phenolic compound is contained, The positive photosensitive insulating resin composition as described in any one of Claims 1-3 characterized by the above-mentioned.   The positive photosensitive insulating resin composition according to claim 4, wherein the amount of the phenol compound (a) is 1 to 200 parts by weight with respect to 100 parts by weight of the copolymer (A). The amount of the compound (B) having the quinonediazide group is 10 to 50 parts by weight and the amount of the compound (C) is 100 parts by weight in total with the copolymer (A) and the phenol compound (a). The positive photosensitive insulating resin composition according to claim 4 or 5, wherein the amount is 1 to 100 parts by weight. Further, (F) it contains crosslinked fine particles having an average particle diameter of 30 to 500 nm and at least one T _g (glass transition temperature) of the constituent copolymer being 0 ° C. or less. The positive photosensitive insulating resin composition as described in any one of 1-6.   The positive photosensitive insulating resin composition according to claim 7, wherein the copolymer that is a constituent component of the crosslinked fine particles (F) is a styrene-butadiene copolymer. According claim 7, characterized in that per 100 parts by weight of the copolymer (A) and the phenolic compound (a), the amount of the crosslinked fine particles (F) is 0.1 to 50 parts by weight Or the positive photosensitive insulating resin composition according to 8.   Hardened | cured material formed by hardening | curing the positive photosensitive insulating resin composition in any one of Claims 1-9. (I) The resistance value after the migration test is 10 ¹⁰ Ω or more, and (ii) In the thermal shock test in which one cycle is −65 ° C./30 minutes to 150 ° C./30 minutes, cracks occur in the cured film. The cured product according to claim 10, wherein the number of cycles until is 1000 cycles or more.

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