JP5077023B2 - Adhesion method, positive photosensitive adhesive composition used therefor, and electronic component - Google Patents

Description

  The present invention provides an adhesive layer for three-dimensional mounting of a semiconductor device, an adhesive layer (underfill agent) for bonding a semiconductor device to a printed wiring board, or a sealing agent for embedding a semiconductor device in a substrate. The present invention relates to a positive photosensitive adhesive composition to be used, a cured product (insulator) obtained by curing the composition, and an electronic component including the cured product.

  The photosensitive resin composition is used for various uses, and one of them is a permanent film. The term “permanent film” is used as a generic term for a film in which a film formed of a photosensitive resin composition remains on a part constituting a product or between parts after the product is completed.

  Specific examples of the permanent film include a solder resist, a package material, an underfill material (sealing material), and a film used as an adhesive layer of a component package such as a circuit element or an adhesive layer between an integrated circuit element and a circuit board. Etc.

  In Patent Documents 1 and 2, a first substrate on which an electrode is formed and a second substrate on which an electrode is similarly formed at a position corresponding to the electrode are made of a negative photosensitive resin composition. A method for manufacturing an electronic component bonded by a permanent film is described.

  However, the methods described in Patent Documents 1 and 2 have a problem in that the composition is poor in fluidity, resulting in a gap between the adhesive layer and the substrate, and insufficient adhesion of the adhesive layer to the second substrate. It was.

  Therefore, as a technique for improving the fluidity of the composition, in Patent Document 3, a reaction product of an alkali-soluble resin and a crosslinkable polyvinyl ether compound, a compound that generates an acid upon irradiation with radiation, and a chemical amplification type containing an epoxy resin A positive photosensitive thermosetting resin composition was provided.

However, with this resin composition, although the fluidity is improved, there is still a problem that the adhesiveness of the adhesive layer to the substrate is still insufficient and the mounting reliability of the connection portion cannot be sufficiently secured.
JP-A-6-21149 Japanese Patent No. 2660943 JP 2005-181976 A

The present invention has been made in view of the above circumstances, and in a photosensitive thermosetting resin composition used as a permanent film, a resin having excellent fluidity and good adhesion at the time of heat bonding after pattern formation. It aims at providing the technique which can form a layer.

  The inventors have found that when a specific positive photosensitive adhesive composition is used and a specific bonding method is performed, a resin layer having excellent fluidity and good adhesion at the time of heat bonding can be formed after pattern formation. The headline and the present invention were completed.

The bonding method according to the present invention includes:
(A) an alkali-soluble resin having a phenolic hydroxyl group or a carboxyl group;
(B) a compound having a quinonediazide group;
(C) (c1) A compound having an alkyl etherified amino group, (c2) an epoxy resin, and (c3) a positive photosensitive adhesive composition containing at least one crosslinking agent selected from the group consisting of oxetane resins Is applied to the substrate, pre-baked, selectively exposed, then alkali-developed to form a resist pattern, and further heated or exposed, and then the adherend is pressed onto the resist pattern forming surface of the substrate. The substrate and the adherend are bonded together.

  Examples of the alkali-soluble resin (A) containing a phenolic hydroxyl group include a novolak resin, a homopolymer of p-hydroxystyrene, a copolymer of p-hydroxystyrene and other monomers, and a phenolic hydroxyl group (meta It is preferably at least one selected from the group consisting of homopolymers of acrylate esters and copolymers of the (meth) acrylate esters and other monomers.

The positive photosensitive adhesive composition preferably further contains crosslinked polymer particles (D) having an average particle diameter of 10 to 200 nm.
The crosslinked polymer particle (D) preferably contains a copolymer having a structural unit derived from a diene compound and a structural unit derived from a crosslinkable monomer having two or more unsaturated double bonds.

The crosslinking agent (C) is preferably composed of (c1) an alkyl etherified amino group-containing compound and (c2) an epoxy resin.
The positive photosensitive adhesive composition preferably further contains an adhesion assistant (E).

The positive photosensitive adhesive composition according to the present invention is any one of the positive photosensitive adhesive compositions described above.
The electronic component of the present invention is manufactured using a positive photosensitive adhesive composition.

When the positive photosensitive adhesive composition according to the present invention is used, it is possible to form a permanent film composed of a resin layer having excellent fluidity at the time of heat bonding and good adhesion after pattern formation.
In addition, the bonding method of the present invention is capable of bonding with a permanent film made of a resin layer that is excellent in fluidity during heat bonding after pattern formation and has good adhesion.

  Furthermore, since the electronic component of the present invention has a permanent film made of a resin layer that is excellent in fluidity at the time of heat bonding and has good adhesion, the reliability is high.

  Hereinafter, the positive photosensitive adhesive composition according to the present invention, a cured product thereof, and a circuit board will be specifically described.

[Positive photosensitive adhesive composition]
The positive photosensitive adhesive composition according to the present invention contains an alkali-soluble resin (A), a compound having a quinonediazide group (B), and a crosslinking agent (C). 200 nm crosslinked polymer particles (D), adhesion aid (E), metal oxide particles (F) having an average particle size of 10 to 500 nm, solvent (G), surfactant / leveling agent (H) and low phenolicity You may contain molecular compound (a) etc.

(A) an alkali-soluble resin ;
The (A) alkali-soluble resin contained in the positive photosensitive adhesive composition according to the present invention has a phenolic hydroxyl group or a carboxyl group.

[(A) Alkali-soluble resin having phenolic hydroxyl group]
Although it does not specifically limit as alkali-soluble resin (A) which has a phenolic hydroxyl group used for this invention, Alkali-soluble resin (A1) which has phenolic hydroxyl groups other than the following copolymer (A2), and phenolic hydroxyl group are used. The copolymer (A2) of the monomer which has and an acrylic monomer can be mentioned.

<Alkali-soluble resin having phenolic hydroxyl group other than (A1) copolymer (A2)>
Examples of the alkali-soluble resin (A1) having a phenolic hydroxyl group include novolak resins. Such a novolac resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst. Examples of phenols used at this time 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-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol, etc. . Examples of 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.

  Examples of the alkali-soluble resin (A1) having a phenolic hydroxyl group other than the novolak resin include polyhydroxystyrene, a copolymer of hydroxystyrene and another monomer, polyisopropenylphenol, isopropenylphenol and other single monomers. Examples thereof include a copolymer with a monomer, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, and a phenol-dicyclopentadiene condensation resin.

<(A2) Copolymer of Monomer Having Phenolic Hydroxyl Group and Acrylic Monomer>
In the copolymer (A2) of the monomer having a phenolic hydroxyl group and an acrylic monomer, the monomer having a phenolic hydroxyl group may be p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene. , P-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol and the like. The acrylic monomer is (meth) acrylic acid or a derivative thereof. Specific examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, Examples include (meth) acrylic acid alkyl esters such as n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and t-butyl (meth) acrylate. Moreover, the hydrogen atom of the alkyl group in these (meth) acrylic-acid alkylesters may be substituted by the hydroxyl group. Furthermore, in the copolymer (A2), other monomers such as styrene may be copolymerized in addition to the monomer having a phenolic hydroxyl group and the acrylic monomer.

((As) hydroxystyrene-styrene copolymer)
Alkali-soluble resin (A1) having a phenolic hydroxyl group other than the copolymer (A2)
Alternatively, the copolymer (A2) of a monomer having a phenolic hydroxyl group and an acrylic monomer may be a structural unit represented by the following formula (i) (hereinafter also referred to as “structural unit (Ai)”). ) And a structural unit represented by the following formula (ii) (hereinafter also referred to as “structural unit (A-ii)”) (hereinafter also referred to as “hydroxystyrene-styrene copolymer (As)”). .).

  The hydroxystyrene-styrene copolymer (As) is a copolymer of a monomer that can form the structural unit (A-i) and a monomer that can form the structural unit (A-ii).

(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. )

Monomers that can form the structural unit (A-i) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol, and the like. Among these,
p-hydroxystyrene and p-isopropenylphenol are preferably used.

The structural unit (Ai) can also be obtained by polymerizing a monomer whose hydroxyl group is protected with, for example, a t-butyl group or an acetyl group. The obtained polymers and copolymers can be converted into hydroxystyrene-based structural units by a known method, for example, deprotection under an acid catalyst.

Examples of the monomer capable of forming the structural unit (A-ii) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, Examples include 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.
In the hydroxystyrene-styrene copolymer (As), a structural unit other than the structural unit (A-i) and the structural unit (A-ii) (hereinafter also referred to as “structural unit (A-iii)”). A monomer capable of forming the polymer may be further copolymerized.

  Examples of the monomer capable of forming the structural unit (A-iii) include compounds having an alicyclic skeleton, unsaturated carboxylic acids or their anhydrides, esters of the unsaturated carboxylic acids, and unsaturated nitriles. , Unsaturated imides, unsaturated alcohols, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole and the like.

More specifically, for example,
The acrylic monomer,
(Meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride and other unsaturated carboxylic acids 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 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]} compound having an alicyclic skeleton such as decene ;
Examples thereof include unsaturated alcohols such as (meth) allyl alcohol, N-vinylaniline, vinylpyridines, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole and the like.

These monomers can be used singly or in combination of two or more.
The content of the structural unit (Ai) in the hydroxystyrene-styrene copolymer (As) is 10 to 99 mol%, preferably 20 to 97 mol%, more preferably 30 to 95 mol%. And the content of the structural unit (A-ii) is 90 to 1 mol%, preferably 80
It is -3 mol%, More preferably, it is 70-5 mol% (however, the total amount of a structural unit (Ai) and a structural unit (A-ii) shall be 100 mol%).

In the case where the structural unit (A-iii) is contained in the hydroxystyrene-styrene copolymer (As), the content of the structural unit (A-iii) is the structural unit (Ai). Preferably, it is 50 parts by mass or less, and more preferably 25 parts by mass or less with respect to 100 parts by mass in total of the structural unit (A-ii).

  When the hydroxystyrene-styrene copolymer (As) is composed of the above structural units and the content of each structural unit is in the above range, resolution, electrical insulation, thermal shock, adhesion, etc. A cured product excellent in various properties, particularly a cured product excellent in both electrical insulation and thermal shock resistance can be formed.

In the hydroxystyrene-styrene copolymer (As), the arrangement of the structural unit (Ai), the structural unit (A-ii) and the other structural unit (A-iii) is particularly limited. Instead, the hydroxystyrene-styrene copolymer (As) may be either a random copolymer or a block copolymer.

In order to obtain the hydroxystyrene-styrene copolymer (As), a compound capable of forming the structural unit (A-i) or a compound in which the hydroxyl group is protected; and the structural unit (A-ii)
And a monomer capable of forming the structural unit (A-iii) as needed may be polymerized in a solvent in the presence of an initiator. The polymerization method is not particularly limited, but is performed by radical polymerization, anion polymerization, or the like in order to obtain the above-described molecular weight compound.

  Usually, as the monomer capable of forming the structural unit (Ai), a monomer whose hydroxyl group is protected is used. Monomers whose hydroxyl groups are protected are converted into phenol ring-containing structural units after polymerization by deprotection by reaction at a temperature of 50 to 150 ° C. for 1 to 30 hours in an acid catalyst such as hydrochloric acid or sulfuric acid. Is done.

Among these alkali-soluble resins having a phenolic hydroxyl group, a hydroxystyrene-styrene copolymer (As) is preferable.
The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A) having a phenolic hydroxyl group is the resolution, thermal shock resistance, and heat resistance of the resulting insulating film. From the viewpoints of, for example, 50,000 or less, preferably 4,000 to 20,000, and more preferably 7,000 to 15,000.

[(A) Alkali-soluble resin having carboxyl group]
The alkali-soluble resin having a carboxyl group is a resin including a structural unit having a carboxyl group. Examples of the structural unit having a carboxyl group include structural units derived from monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Structural units derived; structural units derived from carboxyl group-containing (meth) acrylic acid derivatives such as 2-malenoyloxyethyl methacrylate, 2-succinoloyloxyethyl methacrylate, 2-hexahydrophthaloylethyl methacrylate Etc.

  The monomers for deriving the structural unit having a carboxyl group can be used singly or in combination of two or more. In these, acrylic acid, methacrylic acid, and 2-hexahydrophthaloyl ethyl methacrylate are preferable.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A) having a carboxyl group is the resolution, thermal shock resistance, heat resistance, etc. of the obtained insulating film. From the above viewpoint, it is, for example, 50,000 or less, preferably 4,000 to 20,000, and more preferably 7,000 to 15,000.

(A) phenolic low molecular weight compounds;
The positive photosensitive adhesive composition according to the present invention may contain a phenolic low molecular compound (hereinafter referred to as “phenol compound (a)”). The phenol compound (a) is a compound other than the (A) alkali-soluble resin having a phenolic hydroxyl group, such as 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, 4,4 '- {1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol and the like. These phenolic compounds (a) are preferably in the range of 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, more preferably 100 parts by weight of the alkali-soluble resin (A) having a phenolic hydroxyl group. It can be used in the range of 3 to 20 parts by mass.

In the composition of the present invention, the total content of the alkali-soluble resin (A) having a phenolic hydroxyl group and the phenol compound (a) is the composition (excluding the solvent (H)) 10.
It is 40-95 mass parts normally with respect to 0 mass part, Preferably it is 50-80 mass parts. When the ratio between the alkali-soluble resin (A) and the phenol compound (a) is in the above range, a film formed using the resulting composition has sufficient developability with an aqueous alkali solution.

(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 , Ester compound with 2-naphthoquinonediazide-5-sulfonic acid. The compound having one or more phenolic hydroxyl groups is not particularly limited, but compounds having the following structures are preferred.

(In General Formula (1), 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 General Formula (2), X _{11 to} X 24 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 (3), 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 (4), 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 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 (formula (5), X ₅₉ ~X ₇₂ may be different even mutually identical, respectively, are similar to those of the X ₁ ~X ₁₀ .X ₅₉ ~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 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds such as [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane or 1,2-naphthoquinonediazide-5-sulfonic acid ester Compound etc. are mentioned.

In the composition of the present invention, the amount of the quinonediazide compound (B) is preferably 5 to 50 parts by mass with respect to a total of 100 parts by mass of the alkali-soluble resin (A) and the phenol compound (a). Preferably it is 10-30 mass parts. If the blending amount is less than 5 parts by mass, 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, if the blending amount exceeds 50 parts by mass, the pattern shape may be deteriorated or foaming may occur during curing.

(C) a crosslinking agent;
The (C) crosslinking agent contained in the positive photosensitive adhesive composition of the present invention comprises (c1) a compound having an alkyl etherified amino group, (c2) an epoxy resin, and (c3) an oxetanyl group-containing compound. It is at least 1 sort chosen from more.
Among these, the combination of (c1) a compound having an alkyl etherified amino group and (c2) an epoxy resin is preferable in terms of adhesiveness.

[(C1) Compound having alkyl etherified amino group]
The compound (c1) having an alkyl etherified amino group functions as a crosslinking agent. The compound (c1) having an alkyl etherified amino group is not particularly limited as long as it is a compound having a group capable of reacting with the alkali-soluble resin (A), but at least two alkyl etherified in the molecule. A compound having an amino group is preferred. In particular,
Nitrogen-containing compounds obtained by alkyl etherifying all or part of active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, and more specifically For example, hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, etc .;
These alkyl etherified amino group-containing compounds (c1) can be used alone or in combination of two or more.

In the composition of this invention, the compounding quantity of the compound (c1) which has these alkyl etherified amino groups is 100 mass parts in total of the said alkali-soluble resin (A) and the said phenolic compound (a). The amount is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass. When the blending amount is in the above range, a cured film having excellent adhesion and chemical resistance can be formed.

[(C2) Epoxy resin]
Examples of the epoxy resin (c2) (hereinafter also referred to as “epoxy resin (c2)”) used in the present invention include bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol A type epoxy, hydrogenated bisphenol F type epoxy, Bisphenol S epoxy, brominated bisphenol A epoxy, biphenyl epoxy, naphthalene epoxy, fluorene epoxy, spirocyclic epoxy, bisphenolalkane epoxy, phenol novolac epoxy, orthocresol novolak epoxy, brominated cresol novolak epoxy Examples include epoxy, trishydroxymethane type epoxy, tetraphenylolethane type epoxy, alicyclic epoxy, alcohol type epoxy, aliphatic-aromatic type epoxy and the like.

In the composition of the present invention, the amount of the epoxy resin (c2) is preferably 1 to 1 with respect to a total of 100 parts by mass of the alkali-soluble resin (A) and the phenol compound (a).
00 parts by mass, more preferably 2 to 80 parts by mass, particularly preferably 5 to 50 parts by mass. When the blending amount is less than 1 part by mass, sufficient adhesiveness cannot be obtained. On the other hand, if the blending amount exceeds 100 parts by mass, development failure may occur.

[(C3) Oxetanyl group-containing compound]
A compound containing an oxetanyl group (hereinafter referred to as “oxetanyl group-containing compound”) has one or more oxetanyl groups in the molecule. Specific examples include compounds represented by the following formulas (A) to (C).

[In each of the formulas (A), (B) and (C), R ⁵ is an alkyl group such as a methyl group, an ethyl group or a propyl group, and R ⁶ is an alkylene such as a methylene group, an ethylene group or a propylene group. R ⁷ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a hexyl group; an aryl group such as a phenyl group or a xylyl group; a dimethylsiloxane residue represented by the following formula (i); a methylene group; An alkylene group such as an ethylene group or a propylene group; a phenylene group; or a group represented by the following formulas (ii) to (vi): i is equal to the valence of R ⁷ , and 1 to 4
Is an integer. ]

In the formula, x and y are integers of 0 to 50, Z is a single bond or —CH ₂ —, —C (CH ₃ ) ₂ —.
, —C (CF ₃ ) ₂ —, or —SO ₂ —.

Examples of the compounds represented by the above formulas (A) to (C) include bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (trade name “XDO” manufactured by Toagosei Co., Ltd.), bis [(3-ethyl -3-Oxetanylmethoxy) methyl-phenyl] methane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] propane, bis [ (3-ethyl-3-oxetanylmethoxy) methyl-phenyl] sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] Hexafluoropropane, tri [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, teto [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and the following formula (D) ~ (H), there can be mentioned the compounds represented by (M) and (N).
In addition to these compounds, compounds having a high molecular weight polyvalent oxetane ring can also be used. Specific examples include oxetane oligomers (trade name “Oligo-OXT” manufactured by Toagosei Co., Ltd.) and compounds represented by the following chemical formulas (I) to (K) and (L).

In the formula, p, q and s are each independently an integer of 0 to 10,000.
Among the above, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene (manufactured by Toagosei Co., Ltd., trade name: OXT-121), 3-ethyl-3-{[ (3-Ethyloxetane-3-yl) methoxy] methyl} oxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-221) and phenol novolac oxetane are preferred.

  When the curability of the composition of the present invention is insufficient, a crosslinking aid can be used in combination. Examples of such crosslinking assistants include oxetanyl group, glycidyl ether group, glycidyl ester group, glycidylamino group, benzyloxymethyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, Examples thereof include compounds having a morpholinomethyl group, an acetoxymethyl group, a benzoyloxymethyl group, an acetyl group, a vinyl group, an isopropenyl group, a (blocked) isocyanate group, and the like.

  These crosslinking aids can be blended to such an extent that the composition of the present invention exhibits sufficient curability and does not impair the object of the present invention. Specifically, it can mix | blend in 1-50 mass parts with respect to 100 mass parts of said crosslinking agents (C).

(D) Crosslinked polymer particles having an average particle size of 10 to 200 nm;
Examples of the (D) crosslinked polymer particles contained in the positive photosensitive adhesive composition of the present invention include a crosslinkable monomer having two or more unsaturated polymerizable groups (hereinafter referred to as “crosslinkable monomer”). And other monomers other than the crosslinkable monomer (hereinafter sometimes referred to as “other monomers”) can be suitably used. The (D) crosslinked polymer particles have an advantage that a cured product having excellent insulating properties and thermal shock properties can be obtained.

  By the way, the conventional photosensitive adhesive composition may contain liquid rubber for the purpose of improving adhesion (see Patent Document 2). However, when this liquid rubber is contained, the resolution tends to decrease. was there. Such a liquid rubber often means a fluid having a fluidity at room temperature. For example, acrylic rubber (ACM), acrylonitrile butadiene rubber (NBR), acrylonitrile acrylate butadiene rubber (NBA), etc. are known. ing. The photosensitive adhesive composition of the present invention is characterized by containing essentially no liquid rubber.

  Here, since the (D) crosslinked polymer particle contained in the photosensitive adhesive composition of the present invention is a particulate crosslinked copolymer, it is in a dispersed state in the composition. On the other hand, the liquid rubber is different from the (D) crosslinked polymer particle in that it is in a state compatible with a solvent or a resin in a solution. Therefore, by containing the (D) crosslinked polymer particles, it is possible to obtain a photosensitive adhesive composition having excellent resolution as compared with the case of containing liquid rubber. Moreover, the cured film obtained by using (D) crosslinked polymer particles is also excellent in thermal shock resistance.

  As described above, the liquid rubber is in a state compatible with other components in the composition. Therefore, in order to ensure compatibility with other components, there are limitations on the molecular weight and the content in the composition. On the other hand, since the (D) crosslinked polymer particles are in a dispersed state in the composition, a sufficient content is obtained to obtain effects such as crack resistance, elongation and insulation of the cured film obtained. Can do. In addition, (D) crosslinked polymer particle has a high glass transition temperature compared with liquid rubber. From the above points, the photosensitive adhesive composition of the present invention is excellent in resolution, crack resistance, elongation, and insulation.

  (D) Examples of the crosslinkable monomer used to obtain the crosslinked polymer particles include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Examples thereof include compounds having two or more polymerizable unsaturated groups such as pentaerythritol tri (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. Among these, divinylbenzene is preferable.

  The crosslinkable monomer (D) is preferably 1 to 20% by mass, more preferably 2 to 10% by mass with respect to 100% by mass of all monomers used for copolymerization when the crosslinked polymer particles are produced. is there.

Other monomers include, for example, diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene, 1,3-pentadiene, (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α- Unsaturated nitrile compounds such as ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile, (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N, N '-Ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide Unsaturated amides such as N, N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as propyl, butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, styrene, α- Aromatic vinyl compounds such as methylstyrene, o-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol, diglycidyl ether of bisphenol A, diglycidyl ether of glycol, (meth) acrylic acid, hydroxyalkyl (meta Acrylate Epoxy (meth) acrylates obtained by reaction with urine and urethane (meth) acrylates obtained by reaction of hydroxyalkyl (meth) acrylate and polyisocyanate, glycidyl (meth) acrylate, (meth) allyl glycidyl ether Epoxy group-containing unsaturated compounds such as (meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β- (meta ) Unsaturated acid compounds such as acryloxyethyl, hexahydrophthalic acid-β- (meth) acryloxyethyl, amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate, diethylamino (meth) acrylate, (meth ) Acrylamide, dimethyl (meth) acrylamide And amide group-containing unsaturated compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like.

  Among these, diene compounds such as 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 can be preferably used.

Among these, it is particularly preferable to use at least one diene compound such as butadiene, at least one hydroxyl group-containing unsaturated compound, and at least one unsaturated acid compound. Specifically, the diene compound is butadiene. Preferably, hydroxybutyl (meth) acrylate is preferred as the hydroxyl group-containing unsaturated compounds, and (meth) acrylic acid is preferred as the unsaturated acid compounds.

  When using a diene compound, it is preferable that content of a diene compound is 20-80 mass% with respect to 100 mass% of all the monomers used for copolymerization, More preferably, it is 30-70 mass%. When the diene compound is copolymerized with a content in the above range, rubber-like soft fine particles are obtained, and therefore, when an adhesive layer is formed, the occurrence of cracks can be particularly prevented. Therefore, an adhesive layer having excellent durability can be obtained. When the diene compound is used, the crosslinked polymer particle (D) contains a copolymer having a structural unit derived from a diene compound and a structural unit derived from a crosslinkable monomer having two or more unsaturated double bonds.

  In the case of using hydroxyl group-containing unsaturated compounds, the content is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, particularly preferably 100% by mass with respect to 100% by mass of all monomers used for copolymerization. Is 10 to 35% by mass. Copolymerization of hydroxyl-containing unsaturated compounds with a content in the above range improves compatibility with alkali-soluble resins having phenolic hydroxyl groups, so that an adhesive layer having excellent mechanical properties and heat resistance can be obtained. it can.

  When using unsaturated acid compounds, the content is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, based on 100% by mass of all monomers used for copolymerization. When unsaturated acid compounds are copolymerized in a content within the above range, since they have acid groups, dispersibility in an alkali developer is improved, and a composition having excellent resolution can be obtained.

  (D) The average particle diameter of the crosslinked polymer particles is 10 to 200 nm, preferably 20 to 100 nm, and more preferably 30 to 80 nm. (D) When the average particle diameter of the crosslinked polymer particles is within the above range, there is an advantage that the dispersibility is excellent and the resolution is not lowered. The method for controlling the particle size of the (D) crosslinked polymer particles is not particularly limited. When the (D) crosslinked polymer particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization depends on the amount of emulsifier used. There is a method for controlling the particle size.

  (D) It is preferable that the compounding quantity of crosslinked polymer particle is 0.5-20 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 1-10 mass parts. When the blending amount is in the range of 0.5 to 20 parts by mass, the obtained cured film has excellent thermal shock resistance and high heat resistance, and can form a pattern with high resolution. It is preferable at the point which is excellent in compatibility dispersibility.

(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.

In the composition of the present invention, the amount of the adhesion assistant (E) is preferably 0.5 with respect to a total of 100 parts by mass of the alkali-soluble resin (A) and the phenol compound (a).
-10 parts by mass, more preferably 0.5-5 parts by mass. When the blending amount is in the above range, the adhesion of the cured product obtained by curing the composition of the present invention to the substrate is improved.

(F) metal oxide particles having an average particle size of 10 to 500 nm;
The metal oxide particles (F) are added to reduce the linear expansion coefficient. Examples of the metal oxide in the metal oxide particles (F) include silicon dioxide, alumina, titanium oxide, and zinc oxide. These metal oxide particles (F) can be used singly or in combination of two or more.

  The average particle diameter of the metal oxide particles (F) is 10 to 500 nm, preferably 15 to 200 nm, and more preferably 20 to 100 nm. When the average particle diameter of the metal oxide particles (F) is within the above range, there is an advantage that the resolution is not lowered.

In the composition of the present invention, the blending amount of the metal oxide particles (F) is preferably 5 to 100 parts by mass in total of the alkali-soluble resin (A) and the phenol compound (a).
100 parts by mass, more preferably 10 to 80 parts by mass. There exists an advantage that adhesiveness is not reduced when a compounding quantity exists in the said range.

(G) solvent;
The solvent (G) is added to improve the handleability of the resin composition and to adjust the viscosity and storage stability. Such a solvent (G) 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;
Lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, 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 (H) is 40-900 mass parts normally with respect to a total of 100 mass parts of components other than the solution in a composition, Preferably it is 60-400 mass parts.

(H) surfactant (leveling agent);
The surfactant (leveling agent) (H) is usually added to improve the coating property of the resin composition. The leveling agent / surfactant (H) is not particularly limited, and examples thereof include polyoxyethylene such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether. Polyoxyethylene alkyl allyl ethers such as ethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxy Nonionic leveling agents / surfactants of polyoxyethylene sorbitan fatty acid esters such as tylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Tochem Products) , Megafuck F171, F172, F173 (Dainippon Ink Chemical Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfynol E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass), Footage 250, 251, 222F, FTX-218 (N Fluorine-based leveling agents and surfactants, organosiloxane polymers KP341, X-70-092, X-70-093 (Shin-Etsu Chemical), SH8400 (Toray Dow Corning), acrylic acid or methacrylic acid 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 (leveling agent) (H) is usually preferably 50 to 1000 ppm, more preferably 70 to 800 ppm in the resin solution. When it is less than 50 ppm, the uniform coating property on the stepped substrate is deteriorated, and when it exceeds 1000 ppm, the adhesion during development or after curing is lowered.

Other additives;
In the positive photosensitive adhesive composition of the present invention, as other additives, a sensitizer, an acid generator and the like can be contained to such an extent that the characteristics of the composition of the present invention are not impaired.

(Method for preparing composition)
The preparation method of the positive photosensitive adhesive 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.

(Use of composition)
The positive photosensitive adhesive composition of the present invention is suitably used in permanent film applications of electronic components such as semiconductor elements and circuit boards, and is formed as a cured resin in the gap between the integrated circuit element and the circuit board. It can be particularly preferably used as an underfill material, a sealing agent used when embedding a semiconductor device in a substrate, an adhesive layer of a package of a component such as a circuit element, or an adhesive layer that bonds an integrated circuit element and a circuit board. .

[Adhesion method]
In the bonding method according to the present invention, the positive photosensitive adhesive composition is applied to a substrate, pre-baked, selectively exposed, then alkali-developed to form a resist pattern, and further heated or exposed. Then, the substrate and the adherend are bonded by pressing the adherend onto the resist pattern forming surface of the substrate.

  In the bonding method of the present invention, the positive photosensitive adhesive composition according to the present invention is first applied to a substrate (a copper foil with resin, a copper clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, or the like).

  As a method of applying the adhesive composition to the substrate, 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.

  Next, the substrate coated with the adhesive composition is pre-baked. By this pre-baking, the organic solvent in the composition is removed and a strong film is formed. The heating temperature in this pre-baking is 50-150 degreeC normally, Preferably it is 80-120 degreeC, and heating time is 0.5 to 60 minutes normally, Preferably it is 1 to 30 minutes.

Next, exposure is selectively performed. 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 suitably selected depending on the light source and a resin film thickness to be used, for example, in the case of ultraviolet radiation from a high pressure mercury lamp, the resin thickness 1 to 50 [mu] m, is approximately 1,000~50,000J / m ² .

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 mass. 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.

Next, the substrate on which the pattern is formed is heated to decompose the remaining compound having a quinonediazide group. The heating temperature at this time is usually 80 to 200 ° C., preferably 100 to 170 ° C., and the heating time is usually 1 to 60 minutes, preferably 5 to 30 minutes. Alternatively, the substrate on which the pattern is formed is exposed to decompose the remaining compound having a quinonediazide group. The exposure amount at this time 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 1 to 50 μm is 1,000 to 50,000 J / m ^2. Degree. In the bonding method of the present invention, since the compound having a quinonediazide group remaining can be decomposed, a decrease in adhesion due to generation of gas due to decomposition of the compound having a quinonediazide group can be suppressed during the press treatment described later. And the adherend can be bonded satisfactorily.

Thereafter, the adherend is pressed onto the surface of the substrate on which the resist pattern is formed. This press processing is performed, for example, by a press machine manufactured by Applied Power Japan (model number; ENERPAC).
ESE-924-00). The processing temperature in this press processing is, for example, 50 to 250 ° C., the pressure is, for example, 0.1 to 10 MPa, and the processing time is, for example, 0.5 seconds to 60 minutes.

In this way, the substrate and the adherend are bonded by the bonding method of the present invention.
Thus, the cured product that is an adhesive layer formed between the substrate and the adherend is excellent in adhesiveness, thermal shock, adhesiveness, electrical insulation, and the like.

In particular, the cured product 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.

The adhesive composition is applied to the evaluation substrate shown in FIG. 3 and heated at 110 ° C. for 5 minutes using a hot plate to produce a resin coating having a thickness of 10 μm on the copper foil. Thereafter, the resin coating film is cured by heating at 200 ° C. for 1 hour using a convection oven to obtain a cured film. 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 atmospheres, and an applied voltage of 5V. The resistance value (Ω) of the test substrate is measured.

  In addition, the cured product 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 1000. Cycles or more, more preferably 1500 cycles or more, and even more preferably 2000 or more. Here, in the present invention, the thermal shock test specifically refers to a test performed as follows.

  The adhesive composition is applied to the evaluation substrate shown in FIGS. 1 and 2 and heated at 110 ° C. for 5 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 product 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.

[Electronic parts]
The electronic component according to the present invention is manufactured using the positive photosensitive adhesive composition. That is, the electronic component according to the present invention is a component manufactured by a manufacturing process including a process of bonding a substrate and an adherend using the positive photosensitive adhesive composition as described above. Here, examples of the electronic component include a semiconductor element, a circuit board, an optical circuit component, a MEMS (microelectromechanical device), and a composite component thereof.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present 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>
The adhesive composition was spin-coated on a 6-inch silicon wafer, and heated at 110 ° C. for 3 minutes using a hot plate to prepare a uniform coating film having a thickness of 20 μm. Then, using an aligner (MAS-150 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 365 nm was 1,000 mJ / cm 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.

<Adhesiveness: Method A>
The adhesive composition was applied to a silicon wafer and heated at 120 ° C. for 5 minutes using a hot plate to produce a uniform adhesive-coated substrate having a thickness of 5 μm. The coated substrate was cut into 1 cm × 6 cm, heated at 150 ° C. for 30 minutes using a convection oven, and the adhesive was semi-cured to obtain a silicon substrate section having a semi-cured film. The silicon substrate piece having the semi-cured film and the 1 cm × 6 cm silicon substrate piece are bonded so as to be orthogonal as shown in FIG. 6 and pressed at an upper temperature of 180 ° C. and a lower temperature of 30 ° C./1 MPa / 3 minutes. Processing (Applied Power Japan press, model number; ENERPAC ESE-924-00) was performed to prepare an evaluation substrate. Using this test piece, a stress was applied at a speed (5 mm / min) as shown in FIG. 7 using an indentation tester (manufactured by Imada Seisakusho; model number: SDWS-0201), and the stress at which the silicon substrate peeled was measured.

<Adhesiveness: Method B>
The adhesive composition was applied to a silicon wafer and heated at 120 ° C. for 5 minutes using a hot plate to produce a uniform adhesive-coated substrate having a thickness of 5 μm. The coated substrate was cut into 1 cm × 6 cm, and exposed to ultraviolet rays from a high-pressure mercury lamp so that the exposure amount at a wavelength of 365 nm was 500 mJ / cm ² using an aligner (MAS150 manufactured by Suss Microtec). The substrate section and a 1 cm × 6 cm silicon substrate section were bonded so as to be orthogonal as shown in FIG. 6 and pressed at an upper temperature of 180 ° C. and a lower temperature of 30 ° C./10 kgf / 3 minutes (Applied Power Japan made) A press machine, model number; ENERPAC ESE-924-00) was performed to produce an evaluation substrate. Using this test piece, a stress was applied at a speed (5 mm / min) as shown in FIG. 7 using an indentation tester (manufactured by Imada Seisakusho; model number: SDWS-0201), and the stress at which the silicon substrate peeled was measured.

<Fluidity>
The adhesive composition was spin-coated on a 6-inch silicon wafer, and heated at 110 ° C. for 3 minutes using a hot plate to prepare a uniform coating film having a thickness of 20 μm. Then, using an aligner (MAS-150 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 365 nm was 1,000 mJ / cm ² . Subsequently, it was immersed and developed at 23 ° C. for 3 minutes using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. The sample after patterning was cut into 1 cm square pieces, placed on a glass plate with the adhesive side down, and pressed at an upper temperature of 180 ° C. and a lower temperature of 30 ° C./10 kgf / 3 minutes (Applied Power Japan press machine) , Model number; ENERPAC ESE-924-00), and after cooling, observe from the glass surface side. If the 20 μm via opening pattern is 10 μm or less due to flow, it is evaluated as “good”. .

<Electrical insulation>
An adhesive composition was applied on a silicon substrate to form an insulating film, and a patterned copper foil 10 as shown in FIG. 5 was formed thereon to produce a base material 13 for electrical insulation evaluation. An adhesive composition is further applied to the base material 13 for electrical insulation evaluation, 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 10. did. A resin film was cured by heating at 200 ° C. for 1 hour using a convection oven to obtain a substrate having a cured film. This substrate was put into a migration evaluation system (manufactured by Tabai Espec Co., Ltd.) and treated for 200 hours under the 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) was measured to confirm the insulating property of the upper cured film.

Synthesis Example 1 Synthesis of Resin (A-1) 100 parts by weight of styrene / vinyl benzoic acid = 80/20 (molar ratio) was dissolved in 150 parts by weight of ethyl lactate, and the reaction temperature was maintained at 70 ° C. in a nitrogen atmosphere. Then, polymerization was carried out for 10 hours using 4 parts by weight of azobisisobutyronitrile. 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.

[Synthesis Example 2] Synthesis of resin (A-2) In a 3 L three-necked separable flask equipped with a stirrer, a condenser and a thermometer, 840 g of mixed cresol (m-cresol / p-cresol = 60/40 (molar ratio)) A 37 mass% aqueous formaldehyde solution (600 g) and oxalic acid (0.36 g) were charged. While stirring, the separable flask was immersed in an oil bath, and the reaction was carried out for 3 hours while maintaining the internal temperature at 100 ° C. Thereafter, the oil bath temperature was raised to 180 ° C., and at the same time, the inside of the separable flask was reduced in pressure to remove water, unreacted cresol, formaldehyde and oxalic acid. Next, the molten novolak resin was recovered by returning to room temperature, and a cresol novolak resin (A-2) having an Mw of 6,500 was obtained.

[Synthesis Example 3] Synthesis of Resin (A-5) 100 parts by weight of pt-butoxystyrene / styrene = 80/20 (molar ratio) was dissolved in 150 parts by weight of propylene glycol monomethyl ether, and the reaction temperature was maintained under a nitrogen atmosphere. Was maintained at 70 ° C. and polymerized for 10 hours using 4 parts by weight of azobisisobutyronitrile. 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 polymer, washing with water was repeated 5 times, the ethyl acetate phase was separated, the solvent was removed, and a p-hydroxystyrene homopolymer (A-5) was obtained.
When the molecular weight of this polymer (A-5) was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 10,000.

[Synthesis Example 4] Synthesis of Resin (A-7) Styrene / acrylic acid / benzyl methacrylate / (meth) acrylic acid (3-ethyl-3-oxetanyl) methyl = 40/20/20/20 (molar ratio) 100 weight A part was dissolved in 150 parts by weight of ethyl lactate, and 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. When the molecular weight of this copolymer (A-7) was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) in terms of polystyrene was 10,000.

[Examples 1 to 8]
In Table 1, an alkali-soluble resin (A), a phenol compound (a), a quinonediazide compound (B), a crosslinking agent (C), a crosslinked polymer particle (D) and an adhesion assistant (E) are used as a solvent (G). Each was dissolved in the amounts shown in Table 1 to prepare a photosensitive adhesive composition. The composition was evaluated according to the above evaluation method. The results are shown in Table 2.

[Comparative Example 1]
In the same manner as in the above Examples, a resin composition comprising the components shown in Tables 1 to 3 and a cured film thereof were prepared and evaluated. The results are shown in Tables 4 and 5.
In addition, the component of Table 1 is as follows.

<Alkali-soluble resin (A)>
A-1: Copolymer comprising styrene / vinyl benzoic acid = 85/15 (molar ratio), weight average molecular weight (Mw) = 10,000
A-2: Cresol novolak resin consisting of m-cresol / p-cresol = 60/40 (molar ratio), Mw = 6,500
A-3: formalin condensation resin of bisphenol A (Dainippon Ink Co., Ltd., trade name: KH-6021), Mw = 3000
A-4: Resin composed of phenol and 1,4-benzenedimethanol (manufactured by Mitsui Chemicals, trade name: XLC-3L), Mw = 2000
A-5: Copolymer comprising p-hydroxystyrene / styrene = 80/20 (molar ratio), Mw = 10,000
A-6: homopolymer of p-hydroxystyrene, Mw = 2,000 (manufactured by Maruzen Petrochemical Co., Ltd., trade name: S-2P)
A-7: Styrene / acrylic acid / benzyl methacrylate / (meth) acrylic acid (3-ethyl-3-oxetanyl) methyl = 40/20/20/20 (molar ratio), Mw = 10,
000

<Phenol compound (a)>
a-1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane

<Quinonediazide compound [B]>
B-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5 Quinonediazidesulfonic acid ester (2.0 molar condensate) obtained by esterification with sulfonic acid
B-2: A quinonediazide sulfonic acid ester (1.B) obtained by esterifying 1,1-bis (4-hydroxyphenyl) -1-phenylethane and 1,2-naphthoquinonediazide-5-sulfonic acid. 5 molar condensate)

<Crosslinking agent (C)>
C-1: 1,4-bis [[(3-ethyloxetane-3-yl) methoxy] methyl] benzene (manufactured by Toagosei Co., Ltd., trade name: OXT-121)
C-2: Sorbitol polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX610U)
C-3: Hexamethoxymethylmelamine (trade name “Nicalak MW-30M”, manufactured by Sanwa Chemical Co., Ltd.)
C-4: Trimethylolpropane polyglycidyl ether (trade name “Epolite 100MF”, manufactured by Kyoeisha Chemical Co., Ltd.)
C-5: Novolac type epoxy resin (trade name “EP-152”, manufactured by Japan Epoxy Resin Co., Ltd.)
C-6: Phenol-dicyclopentadiene type epoxy resin (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.)

<Solvent (G)>
G-1: Ethyl lactate G-2: 2-heptanone G-3: 1-methoxy-2-acetoxypropane

<Crosslinked polymer particles (D)>
D-1: butadiene / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 60/32/6/2 (% by weight), Tg = −40 ° C., average particle diameter = 65 nm
D-2: butadiene / styrene / hydroxybutyl methacrylate / divinylbenzene = 60/24/14/2 (% by weight), Tg = −35 ° C., average particle diameter = 70 nm

<Adhesion aid (E)>
E-1: γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation, trade name; S-
510)
E- 2: 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate (trade name; Y11597 manufactured by GE Toshiba Silicone Co., Ltd.)

<Surfactant (H)>
H-1: Surfactant (trade name “FTX-218” manufactured by Neos Co., Ltd.)
H-2: Surfactant (trade name “SH8400” manufactured by Toray Dow Corning)

<Acid generator (I)>
I-1: 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (trade name: CPI-210S, manufactured by San Apro Co., Ltd.)

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. FIG. 4 is a schematic diagram for explaining an adhesive evaluation method. FIG. 5 is a schematic diagram for explaining an adhesive evaluation method.

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 (6)

(A) an alkali-soluble resin having a phenolic hydroxyl group or a carboxyl group;
(B) a compound having a quinonediazide group;
(C) (c1) a compound having an alkyl etherified amino group, (c2) at least one crosslinking agent selected from the group consisting of an epoxy resin and (c3) oxetane resin After the product is applied to the substrate and pre-baked, it is selectively exposed, then alkali developed to form a resist pattern, and further heated or exposed at 80 to 200 ° C. for 5 to 30 minutes , and then the resist pattern is formed on the substrate A bonding method used for stacking chips, wherein the substrate and the adherend are bonded by pressing the adherend on the surface.   The (A) alkali-soluble resin containing a phenolic hydroxyl group has a novolak resin, a homopolymer of p-hydroxystyrene, a copolymer of p-hydroxystyrene and other monomers, and a phenolic hydroxyl group (meth). The adhesion method according to claim 1, wherein the adhesion method is at least one selected from the group consisting of a homopolymer of an acrylic ester and a copolymer of the (meth) acrylic ester and other monomers.   The adhesion method according to claim 1 or 2, wherein the positive photosensitive adhesive composition further contains crosslinked polymer particles (D) having an average particle diameter of 10 to 200 nm.   The crosslinked polymer particle (D) contains a copolymer having a structural unit derived from a diene compound and a structural unit derived from a crosslinkable monomer having two or more unsaturated double bonds. Item 4. The bonding method according to Item 3.   The adhesion method according to any one of claims 1 to 4, wherein the crosslinking agent (C) comprises (c1) a compound having an alkyl etherified amino group and (c2) an epoxy resin.   The adhesion method according to any one of claims 1 to 5, wherein the positive photosensitive adhesive composition further contains an adhesion assistant (E).