JP2011057862A - Resin composition and semiconductor device produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a semiconductor device, excellent in workability, low stress characteristics, moisture resistance, and reflow-peeling resistance, and to provide a semiconductor device with excellent reliability by using the resin composition as a die-attaching paste for semiconductors or an adhesive material for heat dissipation members. <P>SOLUTION: The resin composition includes: (A) a compound prepared by adding maleic anhydride to a polymer containing at least 30 wt.% of a compound represented as a constituent unit by a specific formula (1), CH<SB>2</SB>=CR<SP>1</SP>-CR<SP>2</SP>=CH<SB>2</SB>(R<SP>1</SP>, R<SP>2</SP>are each a hydrogen atom and a 1-6C hydrocarbon group); (B) a compound prepared by reacting polycarbonate diol with a molecular weight of at least 500 to at most 5,000 with (meth)acrylic acid or (meth)acrylate; and (C) a filler. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition and a semiconductor device manufactured using the resin composition.

In recent years, there has been a remarkable progress in higher functionality, smaller size, and lighter weight of mobile phones, portable information terminals, DVC (Digital Video Camera), etc., and there is a strong demand for higher functionality, smaller size, and lighter weight of semiconductor packages. ing. For this reason, single-side sealed type semiconductor packages such as FPBGA (Fine Pitch BGA) and CSP (Chip Scale Package), which are small, thin, and capable of increasing the number of pins, have been widely used.
Furthermore, the form of the semiconductor package becomes more complicated, such as mounting a plurality of semiconductor elements having different functions or a plurality of semiconductor elements having the same function in one package, or stacking a plurality of packages, and there is a problem of warping of the semiconductor package. It is becoming increasingly apparent.
Here, the warpage of the semiconductor package greatly affects the connection reliability when the semiconductor package is mounted on the printed wiring board, but at the same time, a decrease in reliability due to peeling of the die attach material cannot be ignored.

  In order to suppress the peeling of the die attach material, it is necessary to lower the elastic modulus of the die attach material layer and reduce the stress caused by deformation (warping), and to reduce the elastic modulus, the crosslinking density is lowered ( For example, Patent Document 1), a method of blending a thermoplastic component (for example, Patent Document 2), reducing the amount of filler / using a filler having a low elastic modulus (for example, Patent Document 3), and the like are generally known. It has been. However, no matter which method is used, a decrease in adhesion particularly at high temperatures becomes a problem, such as a decrease in Tg (glass transition temperature) and a decrease in cohesive force.

  Accordingly, there is a strong demand for the development of a die attach material that does not cause peeling even when used in applications that require a high level of low stress and high adhesion, such as a single-side sealed semiconductor device.

Japanese Patent Laid-Open No. 06-084974

JP 2005-154687 A

JP 2003-347322 A

  The resin composition of the present invention is excellent in workability, has a low elastic modulus of the cured product and excellent in low stress, has good moisture resistance, and is excellent in reflow peeling resistance. By using it as a paste or a material for adhering heat dissipation members, it is possible to provide a highly reliable semiconductor device.

The present invention is achieved by the following [1] to [4].
[1] A compound (A) obtained by adding maleic anhydride to a polymer containing 30% by weight or more of the compound represented by the general formula (1) as a structural unit, a polycarbonate diol having a molecular weight of 500 or more and 5000 or less and (meth) acrylic acid or The resin composition containing the compound (B) obtained by reacting (meth) acrylic acid ester, and a filler (C).

R ^{1, R 2:} a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms.
[2] The compound (B) is a compound obtained by reacting a polycarbonate diol containing 1,4-cyclohexanedimethanol as a structural unit with (meth) acrylic acid or (meth) acrylic acid ester [1] The resin composition according to Item.
[3] The resin composition according to item [2], wherein the compound (A) is a compound obtained by adding maleic anhydride to the polymer of the general formula (1).
[4] A semiconductor device produced by using the resin composition according to any one of [1] to [3] as a die attach material or a heat dissipation member bonding material.

  The resin composition of the present invention is excellent in workability, has a low elastic modulus of a cured product and is excellent in low stress, and is excellent in moisture resistance and reflow peeling resistance. Therefore, the resin composition is used as a die attach paste for semiconductors or a heat dissipation member. By using it as an adhesive material, it is possible to provide a highly reliable semiconductor device.

It is a schematic sectional drawing which shows an example of the single side sealing type semiconductor package (semiconductor device) which can be produced using the resin composition of this invention as a die attach paste.

The resin composition of the present invention comprises a compound (A) obtained by adding maleic anhydride to a polymer containing 30% by weight or more of the compound represented by the general formula (1) as a structural unit, a polycarbonate diol having a molecular weight of 500 or more and 5000 or less. A resin composition comprising a compound (B) obtained by reacting (meth) acrylic acid or a (meth) acrylic acid ester and a filler (C), the resin composition having excellent workability and a resin The composition cured product has excellent moisture resistance. Furthermore, when the resin composition is used as a die attach paste for semiconductor or a material for adhering heat dissipation members, a highly reliable semiconductor device can be provided because it has good adhesion and excellent reflow peeling resistance.
Hereinafter, the present invention will be described in detail.

  In the present invention, a compound (A) obtained by adding maleic anhydride to a polymer containing 30% by weight or more of the compound represented by the general formula (1) as a structural unit is used. The compound is not particularly limited as long as it is a compound obtained by adding maleic anhydride to a polymer containing 30% by weight or more of the compound represented by the general formula (1) as a structural unit. For example, polybutadiene, polyisoprene, butadiene-acrylonitrile copolymer Polymer containing at least 30% by weight butadiene as a structural unit, butadiene-styrene copolymer containing at least 30% by weight butadiene, acrylonitrile-styrene-butadiene copolymer at 30% butadiene as a structural unit Examples include compounds in which maleic anhydride is added to those containing more than the weight. The molecular weight of these compounds is preferably 700 or more and 50000 or less, and more preferably 700 or more and 5000 or less. This is because it is possible to obtain a resin composition having good workability within the above range.

  Here, the compound (A) needs to add maleic anhydride to a polymer containing 30% by weight or more of the compound represented by the general formula (1) as a structural unit. It is possible to introduce a double bond such as a 1,2 vinyl bond or a 1,4 vinyl bond into the skeleton of the compound (A), thereby comparing the molecular weight with 700 to 5000. In spite of its large size, it can be liquid at room temperature or mixed with the compound (B) described later, and a resin composition exhibiting good fluidity can be obtained even when the filler (C) described later is blended. Because.

Moreover, by introducing a double bond into the skeleton of the compound (A), the elastic modulus of the cured resin composition can be lowered, and good peeling resistance can be exhibited.
Furthermore, it is necessary to add maleic anhydride to the compound (A). This is because a polymer containing 30% by weight or more of the compound represented by the general formula (1) as a structural unit is low in polarity and mixed with other components. In this case, the compatibility is poor and the layers may be separated. The layer separation may cause deterioration of workability and stability of workability. Here, by adding maleic anhydride to a polymer containing 30% by weight or more of the compound represented by the general formula (1) as a structural unit, the resin composition cured product has a low elastic modulus and good peeling resistance. The compatibility with other components can be greatly improved while maintaining.

  Preferred compounds (A) include polybutadiene to which maleic anhydride having a molecular weight of 700 to 5000 is added, polyisoprene to which maleic anhydride is added, and a butadiene-acrylonitrile copolymer to which maleic anhydride is added as a structural unit. Containing 30% or more by weight, butadiene-styrene copolymer with maleic anhydride added as a structural unit, containing butadiene at 30% by weight or more, acrylonitrile-styrene-butadiene copolymer with maleic anhydride added as a structural unit Examples thereof include those containing 30% by weight or more of butadiene.

  Particularly preferred compound (A) is polybutadiene to which maleic anhydride having a molecular weight of 700 or more and 5000 or less is added, and particularly preferred is 1,4 based on the total of 1,2-vinyl bonds and 1,4-vinyl bonds. -Polybutadiene to which maleic anhydride having a vinyl bond ratio of 30% or more is added and having a molecular weight of 700 to 5,000. Here, the ratio of 1,4-vinyl bond to the total of 1,2-vinyl bond and 1,4-vinyl bond is 1.8 to 2.2 ppm (in 1H-NMR (400 MHz) using deuterated chloroform as a solvent). 1,4 vinyl bond) and 4.8 to 5.1 ppm (1,2 vinyl bond) peak area ratios.

  A higher ratio of 1,4-vinyl bonds to the total of 1,2-vinyl bonds and 1,4-vinyl bonds is preferable because the viscosity at room temperature becomes lower. More preferably, the ratio of 1,4-vinyl bond to the total of 1,2-vinyl bond and 1,4-vinyl bond is 50% or more, and particularly preferably 60% or more and 85% or less. This is because the workability of the resin composition is good within this range, and the cured resin composition has a low elastic modulus and excellent peel resistance.

  As the polybutadiene to which maleic anhydride has been added, after reacting polybutadiene having a molecular weight of 700 to 5000 obtained by radical polymerization or ionic polymerization with maleic anhydride at a high temperature of about 200 ° C., unreacted maleic anhydride is reduced under reduced pressure. Those obtained by removing the acid are preferred. More preferably, maleic anhydride is added to polybutadiene having a molecular weight of 700 or more and 3000 or less.

  The compound (A) is preferably contained in an amount of 0.5% by weight or more and 70% by weight or less in the component excluding the filler (C) described later from the resin composition. More preferably, they are 1 weight% or more and 50 weight% or less, Especially preferably, they are 5 weight% or more and 25 weight% or less. If it is the said range, it is because the workability | operativity of a resin composition is favorable and a resin composition hardened | cured material has a low elasticity modulus, and will become the thing excellent in the peeling-proof characteristic.

  In the present invention, it is preferable to use the compound (B) obtained by reacting the compound (A), a polycarbonate diol having a molecular weight of 500 or more and 5000 or less and (meth) acrylic acid or (meth) acrylic acid ester. A preferred compound (B) is a compound obtained by reacting a polycarbonate diol in which an organic group having 3 to 10 carbon atoms is repeated via a carbonate bond with (meth) acrylic acid or (meth) acrylic acid ester, and the carbon What does not contain an aromatic ring as an organic group having a number of 3 to 10 is preferred. This is because when the aromatic ring is contained, the elastic modulus of the cured resin composition may be increased.

  It is preferable that the diol compound shown below is included as a structural unit of the polycarbonate diol. 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1 , 9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1, 2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol and the like. Of these, butanediol, pentanediol, hexanediol, cyclohexanediol, and cyclohexanedimethanol having 4 to 8 carbon atoms are preferred, and these may be used alone or in combination of two or more.

  The polycarbonate diol can be obtained by a transesterification reaction between the diol compound and dialkyl carbonate. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dioctyl carbonate and the like, and dimethyl carbonate is preferable from the viewpoint of reactivity. In the reaction, a catalyst generally used as a transesterification catalyst is used. For example, organic tin compounds such as dibutyl tin oxide and dioctyl tin oxide, tetraalkyl titanates such as tetramethyl titanate, tetraisopropyl titanate, tetraalkyl titanates such as tetrabutyl titanate, alkali metal carbonates or alkaline earth metal carbonates such as potassium carbonate and calcium carbonate, Alkali metal alkyl alkoxides such as potassium methoxide, sodium methoxide, potassium ethoxide, potassium t-butoxide, dimethylaniline, tertiary amines such as 1,4-diazabicyclo (2,2,2) octane, acetylacetone hafnium, etc. An organometallic complex of hafnium. By using an excessive amount of the diol compound relative to the dialkyl carbonate, a polycarbonate diol having a hydroxyl group at the end can be obtained, and when using a plurality of diol compounds, a random copolymer can be obtained by simultaneously charging a plurality of diol compounds. It is also possible to obtain a block copolymer by reacting short-chain polycarbonate diols with each other.

  The reaction between the polycarbonate diol and (meth) acrylic acid or (meth) acrylic acid ester can be carried out by direct esterification reaction when (meth) acrylic acid is used, and methyl (meth) acrylate. When using (meth) acrylate esters such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and octyl (meth) acrylate, it is possible to use a transesterification reaction. is there.

  As described above, the compound (B) is preferably a compound obtained by reacting a polycarbonate diol with (meth) acrylic acid or a (meth) acrylic acid ester. Since the polyether diol used, the ether bond contained in the polyester diol, and the ester bond are superior in moisture resistance, the cured product of the resin composition using the compound (B) has deteriorated characteristics even under high temperature and high humidity conditions. Because there are few.

  The molecular weight of the compound obtained by reacting polycarbonate diol with (meth) acrylic acid or (meth) acrylic acid ester is preferably 500 or more and 5000 or less. This is because, within the above range, both good workability and the above-described moisture resistance can be achieved.

  The compound (B) is preferably contained in an amount of 0.5% by weight or more and 70% by weight or less in the component excluding the filler (C) described later from the resin composition. More preferably, they are 10 weight% or more and 50 weight% or less, Especially preferably, they are 25 weight% or more and 45 weight% or less. It is because the workability | operativity of a resin composition is favorable if it is the said range, and a resin composition hardened | cured material will be the thing excellent in moisture resistance.

  In the present invention, it is also possible to use a thermosetting resin in addition to the compounds (A) and (B). The thermosetting resin is a compound having two or more functional groups capable of reacting by heating. Preferred functional groups include, for example, an acryl group, an allyl group, a vinyl group, a maleate group, a maleimide group, an epoxy group, and an oxetane. Group, cyanate ester group and the like. Of these, preferred functional groups are an acrylic group, an allyl group, a vinyl group, a maleate group, and a maleimide group, and particularly preferred are an acrylic group, an allyl group, and a maleimide group. It is preferable that two or more of these functional groups are contained in one molecule, because when only one functional group is present in one molecule, the crosslink density of the cured product does not increase and the mechanical properties deteriorate. is there. In the present specification, an acryl group including a functional group having a substituent at the α-position and / or β-position of the acryloyl group is used.

The molecular weight of the compound having two or more functional groups is preferably 500 or more and 50000 or less. This is because the elastic modulus of the cured resin composition is too high when it is smaller than the above range, and the viscosity of the resin composition becomes too high when it is larger than the above range.
Examples of compounds having two or more preferred functional groups are shown below, but are not limited thereto.

  Preferred compounds having two or more acrylic groups in one molecule are polyethers, polyesters and poly (meth) acrylates having a molecular weight of 500 or more and 50,000 or less, and compounds having two or more acrylic groups in one molecule. .

  As a polyether, what a C3-C6 organic group repeated via the ether bond is preferable, and what does not contain an aromatic ring is preferable. This is because when an aromatic ring is contained, it becomes a solid or high viscosity as a compound having two or more acrylic groups in one molecule, and the elastic modulus when it is a cured product becomes too high. The molecular weight of the compound having two or more acrylic groups in one molecule is preferably 500 or more and 50000 or less as described above, more preferably 500 or more and 5000 or less, and particularly preferably 500 or more and 2000 or less. It is. It is because workability | operativity is favorable if it is the said range, and the resin composition with a low elasticity modulus of cured | curing material is obtained. Such a polyether compound having two or more acrylic groups in one molecule can be obtained by a reaction between a polyether polyol, (meth) acrylic acid and a derivative thereof.

  As the polyester, those in which an organic group having 3 to 6 carbon atoms is repeated via an ester bond are preferable, and those having no aromatic ring are preferable. This is because when an aromatic ring is contained, it becomes a solid or high viscosity as a compound having two or more acrylic groups in one molecule, and the elastic modulus when it is a cured product becomes too high. The molecular weight of the compound having two or more acrylic groups in one molecule is preferably 500 or more and 50000 or less as described above, more preferably 500 or more and 5000 or less, and particularly preferably 500 or more and 2000 or less. It is. It is because workability | operativity is favorable if it is the said range, and the resin composition with a low elasticity modulus of cured | curing material is obtained. Such a polyester compound having two or more acrylic groups in one molecule can be obtained by reacting a polyester polyol with (meth) acrylic acid and its derivatives.

  Examples of poly (meth) acrylate include a copolymer of (meth) acrylic acid and (meth) acrylate, a copolymer of (meth) acrylate having a hydroxyl group and (meth) acrylate having no polar group, and a glycidyl group. A copolymer of (meth) acrylate having a (meth) acrylate having no polar group is preferred. The molecular weight of the compound having two or more acrylic groups in one molecule is preferably 500 or more and 50,000 or less as described above, but more preferably 500 or more and 25,000 or less. It is because workability | operativity is favorable if it is this range, and the resin composition with the low elasticity modulus of hardened | cured material is obtained. In the case of a copolymer having a carboxy group, such a (meth) acrylate compound having two or more acrylic groups in one molecule reacts with a (meth) acrylate having a hydroxyl group or a (meth) acrylate having a glycidyl group. In the case of a copolymer having a hydroxyl group, it reacts with (meth) acrylic acid and its derivative, and in the case of a copolymer having a glycidyl group, it is obtained by reacting with (meth) acrylic acid and its derivative. It is possible.

  A compound having two or more allyl groups in one molecule is preferably a polyether, polyester, polycarbonate, polyacrylate, polymethacrylate, polybutadiene, butadiene acrylonitrile copolymer having an allyl group having a molecular weight of 500 to 50,000, For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and their derivatives And a reaction product of a diallyl ester compound obtained by reacting dicarboxylic acid or a derivative thereof with allyl alcohol and a diol such as ethylene glycol, propylene glycol or tetramethylene glycol.

  Preferred examples of the compound having two or more maleimide groups in one molecule include N, N ′-(4,4′-diphenylmethane) bismaleimide and bis (3-ethyl-5-methyl-4-maleimidophenyl). And bismaleimide compounds such as methane and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane. More preferred are compounds obtained by reaction of dimer acid diamine and maleic anhydride, and compounds obtained by reaction of maleimidated amino acids such as maleimide acetic acid and maleimide caproic acid with polyols. The maleimidated amino acid is obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid. As the polyol, polyether polyol, polyester polyol, polycarbonate polyol, polyacrylate polyol, and polymethacrylate polyol are preferable. Those not containing are particularly preferred. This is because when an aromatic ring is contained, it becomes a solid or high viscosity as a compound having two or more maleimide groups in one molecule, and the elastic modulus when it is a cured product becomes too high.

  The following compounds can also be used to adjust various properties of the resin composition of the present invention. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di ( (Meth) acrylate having a hydroxyl group such as (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate, and these hydroxyl groups Such as (meth) having an acrylate and a dicarboxylic acid or a carboxy group obtained by reacting the derivative (meth) acrylate. Examples of dicarboxylic acids that can be used here include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and tetrahydrophthalic acid. , Hexahydrophthalic acid and derivatives thereof.

  In addition to the above, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, Tridecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) acrylates, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, Zinc mono (meth) acrylate, zinc di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, neopentyl glycol (meta Acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate, perfluorooctyl ( (Meth) acrylate, perfluorooctylethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, methoxyethyl (Meth) acrylate, Toxiethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, 1,2-di (meth) acrylamide ethylene glycol, di ( (Meth) acryloyloxymethyltricyclodecane, N- (meth) acryloyloxyethylmaleimide, N- (meth) acryloyloxyethylhexahydrophthalimide, N- (meth) acryloyloxyethylphthalimide, n-vinyl-2 -Pyrrolidone, styrene derivative, α-methylstyrene derivative, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, Tylcyclohexyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, isobornyl (meth) acrylate, methylisobornyl (meth) acrylate, ethylisobornyl (meth) acrylate, butylisobornyl (meth) acrylate, hydroxyisoborn Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate Cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylbutyl (meth) acrylate, decalyl (meth) acrylate, methyldecalyl (meth) acrylate, ethyl Decalyl (meth) acrylate, butyl decalyl (meth) acrylate, hydroxydecalyl (meth) acrylate, adamantyl (meth) acrylate, methyl adamantyl (meth) acrylate, ethyl adamantyl (meth) acrylate It is also possible to use butyl adamantyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, and the like. These compounds can be used alone or in combination.

  In addition to the above compounds, it is also preferable to use a compound having an epoxy group. Preferred compounds having an epoxy group include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol, or derivatives thereof, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol, and shijirohexanediethanol. Diols having an alicyclic structure such as these or derivatives thereof, bifunctional ones obtained by epoxidizing aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, decanediol or their derivatives, etc., trihydroxyphenylmethane Skeleton, trifunctional one having aminophenol skeleton, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, na Examples include, but are not limited to, polyfunctional products obtained by epoxidizing tall aralkyl resins and the like, and since the resin composition needs to be liquid at room temperature, it can be liquid alone or as a mixture at room temperature. Those are preferred. It is also possible to use reactive diluents as is usual.

It is also possible to use an epoxy resin curing agent for the purpose of reacting with a compound having an epoxy group. As the curing agent for epoxy resin, known compounds such as phenol compounds, acid anhydrides, amine compounds can be used, and phenol compounds are particularly preferable. This is because the cured product is excellent in moisture resistance reliability. A preferable curing agent is not particularly limited as long as there are two or more phenolic hydroxyl groups in one molecule, but bisphenols such as bisphenol A, bisphenol F, and biphenol, tri (hydroxyphenyl) methane, 1,1,1-tri ( And trifunctional phenolic compounds such as hydroxyphenyl) ethane, phenol novolac, cresol novolac and the like.
A combined use of a phenolic curing agent and imidazoles is also preferred. Particularly preferred imidazoles are adducts of 2-methylimidazole and 2,4-diamino-6-vinyltriazine or 2-phenyl-4-methyl-5-hydroxymethylimidazole. It is also possible to use a reaction catalyst such as phosphorus or amine.

Furthermore, it is also possible to use a thermal radical polymerization initiator as the polymerization initiator. Although it is not particularly limited as long as it is normally used as a thermal radical polymerization initiator, it is desirable that the decomposition start temperature in the rapid heating test (when 1 g of a sample is placed on an electric heating plate and heated at 4 ° C./min) Is preferably 40 to 140 ° C. If the decomposition temperature is less than 40 ° C., the preservability of the resin composition at normal temperature deteriorates, and if it exceeds 140 ° C., the curing time becomes extremely long, which is not preferable. Specific examples of the thermal radical polymerization initiator satisfying this include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) 3, 3, 5 -Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) ) Cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl 4,4-bis (t- Butyl peroxy) valerate, 2,2-bis (t-butylperoxy) Tan, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t -Hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy) diisopropylbenzene, t-butyl Cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide , Octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxide Carbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, α, α′-bis (neo) Decanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexyl peroxy Neodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , T-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5, 5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-butyl Tilperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxy-m-toluoyl Benzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, t-butylperoxyallyl monocarbonate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, etc. These may be used alone or in combination of two or more in order to control curability.

  The filler (C) used in the present invention is not particularly limited, but the average particle size is preferably 30 μm or less, and is preferably a material having few ionic impurities such as sodium and chlorine. This is because if the average particle size is larger than this, nozzle clogging may occur when the resin composition is discharged using a nozzle. A more preferable average particle diameter is 10 μm or less.

  Examples of the filler (C) used in the present invention include silver powder, gold powder, copper powder, aluminum powder, nickel powder, palladium powder and other metal powders, silica powder, alumina powder, titania powder, aluminum nitride powder, and boron nitride. Examples thereof include ceramic powder such as powder, polymer powder such as polyethylene powder, polyacrylate powder, polytetrafluoroethylene powder, polyamide powder, polyurethane powder, polysiloxane powder, and polysilsesquioxane powder.

  When high thermal conductivity is required for the cured resin composition, a thermal conductive filler having a single thermal conductivity of 10 W / mK or more is preferable. Examples of such fillers include metal powders such as silver powder, gold powder, copper powder, aluminum powder, nickel powder, and palladium powder, and ceramic powders such as alumina powder, titania powder, aluminum nitride powder, and boron nitride powder. . Among these, metal powder having a thermal conductivity of 200 W / mK or more as a single substance is more preferable from the viewpoint of thermal conductivity, and particularly preferable is silver powder, gold powder, copper powder, aluminum powder, or beryllium powder. It is at least one filler selected from the group.

Among these fillers, silver powder is most preferable from the viewpoint of good thermal conductivity and stability to oxidation.
Here, the silver powder is a fine powder of pure silver or a silver alloy. Examples of the silver alloy include silver-copper alloy, silver-palladium alloy, silver-tin alloy, silver-zinc alloy, silver-magnesium alloy, silver-nickel alloy containing 50% by weight or more, preferably 70% by weight or more of silver. Can be mentioned.

  If it is the silver powder normally marketed for electronic materials, reduced powder, atomized powder, etc. can be obtained, and an average particle diameter is 0.5 micrometer or more and 30 micrometers or less as a preferable particle size. A more preferable average particle diameter is 1 μm or more and 10 μm or less. This is because the viscosity of the resin composition becomes too high below the lower limit value, and may cause nozzle clogging at the upper limit value or more, and silver powder other than for electronic materials may have a large amount of ionic impurities. is necessary. If necessary, it can be used in combination with metal powder having an average particle size of 1 μm or less.

  The shape of the silver powder is not particularly limited, such as flaky or spherical, but is preferably flaky, and the addition amount is usually preferably 70% by weight or more and 95% by weight or less in the resin composition. When the proportion of silver powder is less than the lower limit, the thermal conductivity of the cured product deteriorates, and when it exceeds the upper limit, the viscosity of the thermal conductive resin composition becomes too high and the coating workability may deteriorate. It is.

In addition, it is also preferable to use a coupling agent in order to enhance the adhesive properties of the resin composition.
Usable coupling agents include silane coupling agents, titanium coupling agents, aluminum coupling agents, and the like, and silane coupling agents are particularly preferably used.

  Usable silane coupling agents include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyl ( Dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyl trimet Xylsilane, 3- (triethoxysilyl) propyl isocyanate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n -Octylsilane, 2-cyanoethyltriethoxysilane, diacetoxydimethylsilane, diethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, hexyltrimethoxysilane, n-dodecyltriethoxysilane, n-octyltri Ethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, pentyltriethoxysilane, triacetoxymethylsilane, triethoxyethylsilane, triethoxymethylsilane, trimethoxy (methyl) silane, trimethoxy ( (Lopyl) silane, trimethoxyphenylsilane, bis (trimethoxysilylpropyl) monosulfide, bis (triethoxysilylpropyl) monosulfide, bis (tributoxysilylpropyl) monosulfide, bis (dimethoxymethylsilylpropyl) monosulfide, bis (Diethoxymethylsilylpropyl) monosulfide, bis (dibutoxymethylsilylpropyl) monosulfide, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (tributoxysilylpropyl) disulfide, bis ( Dimethoxymethylsilylpropyl) disulfide, bis (diethoxymethylsilylpropyl) disulfide, bis (dibutoxymethylsilylpropyl) disulfide, bis (tri Toxisilylpropyl) trisulfide, bis (triethoxysilylpropyl) trisulfide, bis (tributoxysilylpropyl) trisulfide, bis (dimethoxymethylsilylpropyl) trisulfide, bis (diethoxymethylsilylpropyl) trisulfide, bis ( Dibutoxymethylsilylpropyl) trisulfide, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, bis (tributoxysilylpropyl) tetrasulfide, bis (dimethoxymethylsilylpropyl) tetrasulfide, bis (Diethoxymethylsilylpropyl) tetrasulfide, bis (dibutoxymethylsilylpropyl) tetrasulfide, bis (trimethoxysilylpropyl) polysulfide Fido, bis (triethoxysilylpropyl) polysulfide, bis (tributoxysilylpropyl) polysulfide, bis (dimethoxymethylsilylpropyl) polysulfide, bis (diethoxymethylsilylpropyl) polysulfide, bis (dibutoxymethylsilylpropyl) polysulfide These may be used alone, or two or more of them may be used in combination.

  A preferable content of the coupling agent is 0.01% by weight or more and 10% by weight or less in the component obtained by removing the filler (C) from the resin composition. More preferably, it is 0.1 wt% or more and 5 wt% or less. This is because the adhesive properties of the resin composition can be improved within the above range.

  Particularly preferred coupling agents are sulfide silane compounds. The sulfide silane compounds include bis (trimethoxysilylpropyl) monosulfide, bis (triethoxysilylpropyl) monosulfide, bis (tributoxysilylpropyl) monosulfide, bis (dimethoxymethylsilylpropyl) monosulfide, and bis (diethoxymethyl). Silylpropyl) monosulfide, bis (dibutoxymethylsilylpropyl) monosulfide, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (tributoxysilylpropyl) disulfide, bis (dimethoxymethylsilylpropyl) ) Disulfide, bis (diethoxymethylsilylpropyl) disulfide, bis (dibutoxymethylsilylpropyl) disulfide, bis (trimethoxysilyl) (Ropyl) trisulfide, bis (triethoxysilylpropyl) trisulfide, bis (tributoxysilylpropyl) trisulfide, bis (dimethoxymethylsilylpropyl) trisulfide, bis (diethoxymethylsilylpropyl) trisulfide, bis (dibutoxy) Methylsilylpropyl) trisulfide, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, bis (tributoxysilylpropyl) tetrasulfide, bis (dimethoxymethylsilylpropyl) tetrasulfide, bis (di Ethoxymethylsilylpropyl) tetrasulfide, bis (dibutoxymethylsilylpropyl) tetrasulfide, bis (trimethoxysilylpropyl) polysulfide, bis Triethoxysilylpropyl) polysulfide is bis (tributoxysilyl-propyl) polysulfide, bis (dimethoxy methyl silyl propyl) polysulfide, bis (diethoxy methyl silyl propyl) polysulfide, bis (such as dibutoxy methyl silyl propyl) polysulfide.

  Here, the above-mentioned compound names are exemplified as the sulfide silane compound, but in actuality, the value of the number of repetitions n of sulfide bonds is an average value and has a distribution. For example, even if it is bis (triethoxysilylpropyl) tetrasulfide, the average value of the number of repetitions of sulfide bonds n is about 4, and as an example, in the case of Si-69 (trade name, manufactured by Degussa), sulfide bonds The number of repetitions of n is about 3.7, the component of n = 2 is 20.3%, the component of n = 3 is 27.5%, the component of n = 4 is 26.3%, and n = 5 The component is 14.3%, and the component with n = 6 or more is 11.6%.

The first reason why the sulfide silane compound is preferable is to obtain good adhesive properties. It is well known that a compound containing a sulfur atom improves the adhesion with a metal, but in particular, when a sulfide silane compound is used, the effect of improving adhesion is remarkable. 3-Mercaptopropyltrimethoxysilane is generally known as a compound having a sulfur atom and an alkoxysilyl group in the same manner as the sulfide silane compound, but the mercapto group is a glycidyl group or an acrylic group contained in the thermosetting resin. Since it reacts even at room temperature, the preservability of the resin composition deteriorates, which is not preferable. In particular, the reaction with an acrylic group proceeds remarkably even at room temperature, and in some cases, it stops flowing at room temperature in about 10 minutes. The reaction with the glycidyl group is not as rapid as in the reaction with the acryl group, but when the content is large, an increase in viscosity starts to be observed at about 24 hours at room temperature. For this reason, it is necessary to adjust the amount to be contained, but in order to ensure storage stability, an amount sufficient to obtain good adhesiveness cannot be contained.
Here, since there is no active hydrogen group that causes a rapid reaction in the sulfide silane compound, it is possible to improve the adhesion without deteriorating the storage stability at room temperature.

  The second reason why the sulfide silane compound is preferred is that the resin composition not only improves the adhesion between the resin composition and the support by reacting with the metal powder when the metal powder is used as the filler (C) during the curing reaction. It is a point that improves the cohesive strength of itself. As mentioned above, sulfur atoms can be bonded to metals and are often used when good adhesion to metals is required. In the case of bonding of sulfur atoms contained in sulfide silane compounds, metal powder around room temperature is used. The reaction with is, for example, very slow compared to mercapto groups. For this reason, since it exists unreacted in the resin composition at the time of curing, not only the adhesion to the adherend but also the metal powder can be firmly bonded and the cohesive strength of the resin composition itself can be improved. It becomes possible.

  The third reason why the sulfide silane compound is preferable is good storage stability. When the thermosetting resin contains an organic peroxide as a polymerization initiator, decomposition proceeds even during storage, and in particular in the case of a polymerization initiator having a low decomposition temperature, radicals generated by decomposition cause the reaction of the thermosetting resin. This may cause a significant increase in viscosity. Usually, an inhibitor such as hydroquinone is added to suppress an increase in viscosity. However, if a large amount of the inhibitor is contained, if the curability is significantly deteriorated, the properties of the cured product may be adversely affected. Here, since the sulfide bond can trap the generated radical, it acts as an inhibitor and can suppress an increase in viscosity, and an increase in the curing start temperature can be seen, but it is not as bad as a general-purpose inhibitor. In particular, since the deterioration of the cured product properties is not observed, it can be used preferably.

  The fourth reason why the sulfide silane compound is preferable is that it can react with a double bond contained in the skeleton of the compound (A), so that the cured resin composition has a low elastic modulus and excellent peel resistance. It is a point.

Here, as described above, the sulfide silane compound has a distribution in the value of the number of repetitions n of sulfide bonds, but as a result of examination, it has been found that the reactivity varies depending on the value of the number of repetitions n of sulfide bonds. That is, the sulfide silane compound reacted with the metal powder as the filler (C) very slowly even at room temperature, and the reaction was confirmed to selectively react with a component having a large number of repetitions of sulfide bonds n. It was. In particular, it was confirmed that when the value of the number of repetitions n of sulfide bonds 6 selectively reacted and the value of the number n of repetitions of sulfide bonds was 2, the reaction progress was extremely slow.
For the above reason, when the ratio of the component having a large number of repetitions n of sulfide bonds contained in the sulfide silane compound is large, the sulfide silane compound gradually reacts with the metal powder as the filler (C) during storage at room temperature. The amount necessary for improving the adhesive strength with the support may be insufficient, and a decrease in the adhesive strength may be observed. Here, when the ratio of a component having a sulfide bond repetition number n of 4 or more contained in the sulfide silane compound is X%, the smaller value of X is better in consideration of the temporal change in adhesion at room temperature. Particularly preferred is a case where X is 55% or less. The ratio X of the component having the repetition number n of sulfide bonds of 4 or more is the ratio of the component of n = 4 or more to the area of the sulfide silane compound in the chart obtained by measuring the sulfide silane compound with a high performance liquid chromatogram. It is a percentage display.

  On the other hand, it is known that the sulfide silane compound contains a halogenated compound (a halogenated triethoxysilylpropyl when the sulfide silane compound is bis (triethoxysilylpropyl) tetrasulfide) as a starting material. Here, the halogenated compound promotes hydrolysis of the alkoxysilyl group of the sulfide silane compound, and bonds between the alkoxysilyl groups occur. The compound in which the alkoxysilyl groups are bonded to each other reduces the effect of improving the adhesive properties of the resin composition. For this reason, it is necessary to increase the content of the sulfide silane compound, but the halogenated alkyl group contained in the halogenated compound is highly reactive, and the cyanate ester group, epoxy group, acrylic group, maleimide in the thermosetting resin Reacts with functional groups such as groups at room temperature. For this reason, storage at room temperature causes an increase in the viscosity of the resin composition and a decrease in adhesive properties.

Here, when the ratio of the halogenated compound contained in the sulfide silane compound is Y%, it is preferable that Y is small. The value of Y is determined by gas chromatography (for example, apparatus: “GC-14B” manufactured by Shimadzu Corporation), column: TC-5 (diameter 0.25 mm × 30 m), detector: FID, carrier gas: He, temperature. Program: 50 ° C. × 2 minutes → 6.5 ° C./min→260° C. × 15 minutes, internal standard substance: 20% by mass of undecane, measurement sample: 0.5 μl).
A preferable value of Y is 1.0% or less, more preferably 0.8% or less, and particularly preferably 0.5% or less.

As described above, smaller values of both X and Y are preferable, but if the value of X is small, even if the content of the sulfide silane compound is small, sufficient adhesive properties can be obtained even after storage at room temperature for a long time. It was found that even if Y is somewhat large, the content of the halogenated compound contained is within an acceptable range. That is, in order to obtain a resin composition having sufficient storage characteristics and adhesive properties, it is possible to obtain sufficient adhesive properties even after storage at room temperature, even if the value of Y is somewhat large, or if the value of X is small. It was found that it can be suitably used when X and Y satisfy the following relational expression 1.
[Relational expression 1: Y <−2.7 × 10 ⁻³ X + 0.8]
When the values of X and Y of the sulfide silane compound are within the range satisfying the relational expression 1, it is possible to obtain a resin composition having sufficient adhesive properties even after being stored at room temperature for a long time.

  If necessary, additives such as antifoaming agents, surfactants, various polymerization inhibitors and antioxidants can be used in the resin composition of the present invention.

  The resin composition of the present invention can be produced, for example, by premixing the components, kneading using three rolls, and degassing under vacuum.

  As a method of manufacturing a semiconductor device using the resin composition of the present invention, a known method can be used. For example, using a commercially available die bonder, the resin composition is dispensed on a predetermined portion of the lead frame, and then the chip is mounted and heat-cured. Then, a semiconductor device is manufactured by wire bonding and transfer molding using an epoxy resin. Alternatively, the resin composition is dispensed on the back side of a chip such as a flip chip BGA (Ball Grid Array) sealed with an underfill material after flip chip bonding, and a heat dissipation component such as a heat spreader or lid is mounted and cured. Is possible.

EXAMPLES The present invention will be specifically described below using examples, but is not limited thereto. The blending ratio is expressed in parts by weight.
In both Examples and Comparative Examples, the following raw materials were blended in parts by weight shown in Table 1, and then kneaded and defoamed using three rolls to obtain a resin composition.

(Compound (A))
Compound A1: maleated polybutadiene (Rat 131 MA20, manufactured by Sartomer Co., a compound obtained by adding maleic anhydride to a polymer containing 100% of a compound in which R ¹ and R ^{2 in} the general formula (1) are hydrogen atoms as constituent elements, the following compound A1)
Compound A2: Maleated polybutadiene (Rat 130 MA8, manufactured by Sartomer, a compound obtained by adding maleic anhydride to a polymer containing 100% of a compound in which R ¹ and R ^{2 in} the general formula (1) are hydrogen atoms as a constituent element, the following compound A2)

(Compound (B))
Compound B1: Polycarbonate dimethacrylate obtained by reaction of polycarbonate diol obtained by reaction of 1,4-cyclohexanedimethanol / 1,6-hexanediol (= 3/1 (weight ratio)) and dimethyl carbonate and methyl methacrylate Compound (manufactured by Ube Industries, UM-90 (3/1) DM, molecular weight 1000, hereinafter compound B1)
Compound B2: Polycarbonate dimethacrylate obtained by the reaction of 1,4-cyclohexanedimethanol / 1,6-hexanediol (= 1/3 (weight ratio)) and the polycarbonate diol obtained by the reaction of dimethyl carbonate and methyl methacrylate Compound (manufactured by Ube Industries, UM-90 (1/3) DM, molecular weight 1000, hereinafter compound B2)

(Filler)
Filler C1: Flaky silver powder having an average particle size of 6 μm, a tap density of 6.2 g / cm 3 and a specific surface area of 0.23 m 2 / g (hereinafter referred to as filler C1)
Filler C2: Spherical silica powder having an average particle size of 1.5 μm and a specific surface area of 4.0 m2 / g (hereinafter referred to as filler C2)

(Thermosetting resin)
Thermosetting resin 1: Bismaleimide compound obtained by reaction of polytetramethylene glycol and maleimidated acetic acid (DIC Corporation, LUMICURE MIA-200, molecular weight 580, hereinafter thermosetting resin 1)
Thermosetting resin 2: diallyl ester compound obtained by reaction of diallyl ester of cyclohexanedicarboxylic acid and propylene glycol (produced by Showa Denko Co., Ltd., allyl ester resin DA101, molecular weight 1000, but cyclohexanedicarboxylic acid used as a raw material The following thermosetting resin containing about 15% diallyl ester 2)
Thermosetting resin 3: Polypropylene glycol dimethacrylate (Nippon Yushi Co., Ltd., Bremer PDP-700, molecular weight 870, hereinafter thermosetting resin 3)
Thermosetting resin 4: polyester diol dimethacrylate (125 g (0.10 mol) of polyester polyol (Placcel L212AL, manufactured by Daicel Chemical Industries, Ltd., molecular weight 1250) in a glass flask equipped with a distillation apparatus, 50 g of methyl methacrylate ( 0.50 mol), 0.068 g (0.60 mmol) of hydroquinone, 0.34 g (1.00 mmol) of tetrabutoxytitanium and 500 g of toluene were put in a nitrogen stream under normal pressure at a bath temperature of 130 to 140 ° C. for 9 hours. During the reaction, methanol was mixed with the solution by distillation, and after the reaction, 6.0 g of water was added to the reaction solution and accompanied by a bath temperature of 90 ° C. for 2 hours. And toluene is distilled off at 120 ° C. under reduced pressure, and low-boiling components (such as residual toluene of methyl acrylate) are 50-2. Distillation was performed at mmHg and a bath temperature of 120 to 190 ° C. to obtain 138 g of a colorless and transparent polyester diol acrylate compound, which was obtained by NMR from a terminal methacrylate conversion rate (the terminal hydroxyl group of the raw material diol was methacrylated). The average molecular weight measured by GPC was 1400. The following is thermosetting resin 4).

(Sulfide silane compound)
Sulfide silane 1: bis (triethoxysilylpropyl) tetrasulfide (Degussa Co., Ltd., Si69, the number of repetitions of sulfide bond n is about 3.7, the halogenated compound is triethoxysilylpropyl chloride, and X is 52.2. %, Y is 0.590, −2.7 × 10 ⁻³ X + 0.8 = 0.659> Y, hereinafter sulfide silane 1)
Sulfide silane 2: Bis (triethoxysilylpropyl) disulfide (manufactured by Daiso Co., Ltd., Cabras 2A, repetition number n of sulfide bonds is about 2.4, halogenated compound is triethoxysilylpropyl chloride, and X is 9.8. %, Y is 0.703, −2.7 × 10 ⁻³ X + 0.8 = 0.774> Y, hereinafter sulfide silane 2)
Sulfide silane 3: bis (triethoxysilylpropyl) disulfide (manufactured by Daiso Corporation, Cabras 2B, the number of repetitions n of sulfide bonds is about 2.1, the halogenated compound is triethoxysilylpropyl chloride, and X is 1.5. %, Y is 0.157, −2.7 × 10 ⁻³ X + 0.8 = 0.996> Y, hereinafter sulfide silane 3)
Sulfide silane 4: Bis (triethoxysilylpropyl) disulfide (manufactured by Degussa Co., Ltd., Si75, repetition number n of sulfide bonds is about 2.4, halogenated compound is triethoxysilylpropyl chloride, X is 12.4% , Y is 0.332, −2.7 × 10 ⁻³ X + 0.8 = 0.767> Y, hereinafter sulfide silane 4)
Sulfide silane 5: bis (triethoxysilylpropyl) tetrasulfide (manufactured by Nihon Unicar Co., Ltd., A-1289, the number of repetitions n of the sulfide bond is about 3.8, the halogenated compound is triethoxysilylpropyl chloride, and X is 53.1%, Y is 0.703, −2.7 × 10 ⁻³ X + 0.8 = 0.657 <Y, hereinafter sulfide silane 5)
Sulfide silane 6: bis (triethoxysilylpropyl) tetrasulfide (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-846, the number of repetitions of sulfide bond n is about 3.8, the halogenated compound is triethoxysilylpropyl chloride, X Is 55.3%, Y is 0.836, −2.7 × 10 ⁻³ X + 0.8 = 0.651 <Y, hereinafter sulfide silane 6)

(Additive)
Additive 1: 1,4-cyclohexanedimethanol monoacrylate (Nippon Kasei Co., Ltd., CHDMMA, hereinafter additive 1)
Additive 2: 1,6-hexanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 1, 6HX, hereinafter additive 2)
Additive 3: 2-ethylhexyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester EH, hereinafter additive 3)
Additive 4: Hydrogenated bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., YX-8000, epoxy equivalent 205, hereinafter additive 4)
Additive 5: Dicumyl peroxide (manufactured by NOF Corporation, Park Mill D, decomposition start temperature in rapid heating test: 126 ° C., hereinafter additive 5)
Additive 6: Coupling agent having a glycidyl group (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E, hereinafter additive 6)
Additive 7: Coupling agent having a methacryl group (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503P, hereinafter additive 7)

(Other compounds)
Compound D1: Carboxyl group-terminated acrylonitrile butadiene copolymer (manufactured by Ube Industries, Ltd., Hycar CTBN 1300X8, a polymer containing approximately 73% of a compound in which R ¹ and R ^{2 in} the general formula (1) are hydrogen atoms as constituent elements And a compound having a carboxy group at the terminal, hereinafter referred to as compound D1)
Compound D2: Epoxidized polybutadiene (Daicel Chemical Industries, Epolide PB3600, a compound obtained by epoxidizing a polymer containing 100% of a compound in which R ¹ and R ² of the general formula (1) are hydrogen atoms as constituent elements, Compound D2)

(Evaluation test)
The following evaluation tests were performed on the resin compositions of Examples and Comparative Examples obtained above. The evaluation results are shown in Table 1.

(Spreadability test 1)
A silicon chip (10 × 10 × 0.35 mm) was Ni-plated copper heat spreader (25 × 25 × 2 mm) using a syringe filled with 30 g of the resin composition of Examples and Comparative Examples (immediately after filling). Mounted. After applying about 0.01 cc of the resin composition shown in Table 1 on the heat spreader using a dispenser, the mount was applied to the silicon chip using a compact mounter SMT-64RH manufactured by Okuhara Electric Co., Ltd. within 15 minutes. This was carried out by applying a load of 0.5 kgf for 10 seconds at room temperature, and then cured and adhered at 150 ° C. for 60 minutes. The adhesion area of the cured sample was measured using an ultrasonic flaw detector (transmission type). When the adhesion area with respect to the area of the chip is almost 100%, ◎, when it is 90% or more of the chip area, ◯ when it is about 75%, and x when it is 50% or less.

(Spreadability test 2)
Extensiveness test 1 except that a syringe (10 cc) filled with 30 g of the resin composition of the example and the comparative example was used after being stored for 24 hours in a thermostat adjusted to 25 ° C. Similarly, the spreadability of the resin composition was measured. When the adhesion area with respect to the area of the chip is almost 100%, ◎, when it is 90% or more of the chip area, ◯ when it is about 75%, and x when it is 50% or less.

(Moisture resistance test 1)
The sample for which the adhesion area was measured in the spreadability test 1 was treated for 168 hours under the conditions of 125 ° C., 100% RH, 2.3 atm, and the adhesion area after the treatment was measured with an ultrasonic flaw detector (transmission type). When the adhesion area with respect to the area of the chip is almost 100%, ◎, when it is 90% or more of the chip area, ◯ when it is about 75%, and x when it is 50% or less.

(Moisture resistance test 2)
The adhesion area after the treatment was measured in the same manner as the moisture resistance test 1 except that the sample whose adhesion area was measured in the spreadability test 2 was used. When the adhesion area with respect to the area of the chip is almost 100%, ◎, when it is 90% or more of the chip area, ◯ when it is about 75%, and x when it is 50% or less.

(Elastic modulus)
About each resin composition of an Example and a comparative example, a 4x20x0.1mm film-like test piece is produced (hardening conditions 150 degreeC 30 minutes), and it is a tensile mode with a dynamic viscoelasticity measuring machine (DMA). Measurements were made at The measurement conditions are as follows.
Measurement temperature: -100 to 300 ° C
Temperature increase rate: 5 ° C / min Frequency: 10Hz
Load: 100mN
The storage elastic modulus at 25 ° C. was regarded as the elastic modulus, and the case of 5000 MPa or less was regarded as acceptable. The unit of elastic modulus is MPa.

(Reflow resistance 1)
The following lead frames and silicon chips were cured and bonded at 150 ° C. for 60 minutes using the resin compositions of Examples and Comparative Examples (immediately after preparation of the resin composition). Furthermore, sealing was performed using a sealing material (Sumicon EME-G620A, manufactured by Sumitomo Bakelite Co., Ltd.) to manufacture a semiconductor device. This semiconductor device was subjected to moisture absorption treatment at 30 ° C., relative humidity 60%, 168 hours, and then IR reflow treatment (260 ° C., 10 seconds, 3 times reflow). The degree of peeling of the treated semiconductor device was measured by an ultrasonic flaw detector (transmission type). The case where the ratio of the peeled area to the chip area was less than 10% was regarded as acceptable. The unit of the peeled area is%.
Semiconductor device: epLQFP (28 x 28 x 1.4 mm: back side of die pad exposed on back side of package)
Lead frame: Ni-Pd / Au plated copper frame Chip size: 7 x 7 mm
Curing conditions for resin composition: 150 ° C. in oven for 60 minutes

(Reflow resistance 2)
The following substrates and silicon chips were cured and bonded at 150 ° C. for 60 minutes using the resin compositions of Examples and Comparative Examples (immediately after preparation of the resin composition). Furthermore, after sealing using a sealing material (Sumicon EME-G770, manufactured by Sumitomo Bakelite Co., Ltd.), a semiconductor device was fabricated by solidifying using a dicing saw. Using this semiconductor device, moisture absorption treatment was performed at 85 ° C. and relative humidity 60% for 168 hours, and then IR reflow treatment (260 ° C., 10 seconds, 3 times reflow) was performed. The degree of peeling of the treated semiconductor device was measured by an ultrasonic flaw detector (transmission type). The case where the ratio of the peeled area to the chip area was less than 10% was regarded as acceptable. The unit of the peeled area is%.
Semiconductor device: FPBGA (package size after solidification: 14 × 14 × 0.86 mm (excluding solder balls))
Substrate: BT (bismaleimide / triazine) substrate 0.36 mm thick Chip size: 10 × 10 × 0.2 mm
Curing conditions for resin composition: 150 ° C. in oven for 60 minutes

Since the resin composition of the present invention is excellent in workability and has good moisture resistance and reflow peeling resistance of a cured product, it can be used as a die attach paste for semiconductors or a heat radiation member adhesion material.

DESCRIPTION OF SYMBOLS 1 ... Hardened | cured material layer of resin composition 2 ... Die pad 3 ... Semiconductor element 4 ... Lead 5 ... Sealing material 10 ... Semiconductor device

Claims (4)

Compound (A) obtained by adding maleic anhydride to a polymer containing 30% or more by weight of the compound represented by general formula (1) as a structural unit, polycarbonate diol having a molecular weight of 500 to 5000 and (meth) acrylic acid or (meth) The resin composition containing the compound (B) obtained by reacting acrylic ester and a filler (C).

R ^{1, R 2:} a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms.
The resin according to claim 1, wherein the compound (B) is a compound obtained by reacting a polycarbonate diol containing 1,4-cyclohexanedimethanol as a structural unit with (meth) acrylic acid or (meth) acrylic acid ester. Composition. The resin composition according to claim 2, wherein the compound (A) is a compound obtained by adding maleic anhydride to the polymer of the general formula (1). The semiconductor device produced using the resin composition of any one of Claims 1-3 as a die-attach material or a heat dissipation member adhesion material.