JP2009108186A - Resin composition and semiconductor device made by using the resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a die attach paste for a semiconductor, having excellent coating stability and a low elastic modulus, and exhibiting good adhesiveness, and to provide a semiconductor device especially having excellent reliability such as reflow resistance. <P>SOLUTION: The resin composition contains a compound being a polymer or a copolymer of a dienic compound, and having at least one polymerizable carbon-carbon double bond in the molecule, an acrylate compound, a thermal radical polymerization initiator and a filler. The acrylate compound includes a compound having a branched aliphatic hydrocarbon group and a compound having a carboxy group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  The problem of heat generated during the operation of semiconductor products has become more prominent with the increase in capacity, high-speed processing, and fine wiring of semiconductor products. So-called thermal management, which releases heat from semiconductor products, is an increasingly important issue. It has become to. For this reason, a method of attaching a heat dissipating member such as a heat spreader or a heat sink to a semiconductor product is generally adopted, but a material having a higher thermal conductivity has been desired. On the other hand, depending on the form of the semiconductor product, the semiconductor element itself is bonded to a metal heat spreader, the heat spreader is bonded to the die pad part of the lead frame to which the semiconductor element is bonded, or the die pad part is exposed on the package surface to dissipate heat. In some cases, the plate may be attached, and may be adhered to an organic substrate having a heat dissipation mechanism such as a thermal via. In this case as well, a high thermal conductivity is required for the material to which the semiconductor element is bonded. In this way, high thermal conductivity is required for die attach paste or heat dissipation member bonding material, but at the same time, it is necessary to withstand reflow processing when mounting a semiconductor product on a substrate, and even when large area bonding is required In order to suppress the occurrence of warping due to the difference in thermal expansion coefficient between the structural members, it is necessary to have low stress properties.

Here, usually a metal filler such as silver powder or copper powder or a ceramic filler such as aluminum nitride or boron nitride is added to the organic binder at a high content to the high heat conductive adhesive, but the amount can be contained. If there is a limit and high thermal conductivity cannot be obtained, a large amount of solvent is contained, and the thermal conductivity of the cured product is good, but in semiconductor products, after the solvent remains or volatilizes in the cured product, it becomes voids and the thermal conductivity Has not yet been solved. It is also known to use a low-stress agent such as liquid rubber for the purpose of reducing the elastic modulus of the cured product (see, for example, Patent Document 2), but the liquid rubber has a high polarity. It is difficult to obtain good coating workability due to high viscosity when used, and when using products with low polarity, the compatibility with other components is poor and separation occurs during storage, resulting in stable coating. There was nothing that was satisfactory, such as deterioration of sex.
Japanese Patent Laid-Open No. 11-43587 JP 2005-154633 A

  INDUSTRIAL APPLICABILITY The present invention uses a resin composition that is excellent in coating workability, particularly in coating amount stability, has a low elastic modulus, and has a sufficiently low stress, and uses the resin composition as a die attach paste for semiconductors or a material for adhering heat dissipation members Thus, it is to provide a semiconductor device having excellent reliability.

The present invention is achieved by the following [1] to [6].
[1] A resin composition for adhering a semiconductor element or a heat dissipation member to a support,
A diene compound polymer or copolymer having at least one polymerizable carbon-carbon double bond in the molecule (A), an acrylate compound (B), a thermal radical polymerization initiator (C), And filler (D),
50 wt% or more and 99 wt% or less of the acrylate compound (B) is the compound (B1) represented by the general formula (1), and 1 wt% or more of the acrylate compound (B) is 3
0% by weight or less of an acrylic ester compound (B2) having a carboxy group.

Ｒ¹は水素原子、炭素数１〜１２の脂肪族炭化水素基、Ｒ²は炭素数６〜１２の分岐した脂肪族炭化水素基である。

R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ² is a branched aliphatic hydrocarbon group having 6 to 12 carbon atoms.

[2] R ^{2 of the} compound (B1) represented by the general formula (1) is a carbon number of 6 to 1 having a different structure.
2. The resin composition according to item [1], which is a compound having two branched aliphatic hydrocarbon groups.
[3] In the item [1], the compound (A) is a butadiene polymer or copolymer having at least one polymerizable carbon-carbon double bond in the molecule. The resin composition as described.
[4] The item [3], wherein the proportion of 1,4 vinyl bonds contained in the compound (A) is 60% or more based on the total of 1,4 vinyl bonds and 1,2 vinyl bonds. The resin composition described in 1.
[5] A semiconductor device manufactured using the resin composition according to any one of [1] to [4] above as a die attach paste or a heat dissipation member bonding material.

  Since the resin composition of the present invention is excellent in coating amount stability in the dispensing method and has a low elastic modulus and high adhesion, when used as a die attach paste or a heat radiation member adhesion material, the obtained semiconductor device is resistant. As a result, it is possible to obtain a highly reliable semiconductor device.

The present invention relates to a polymer or copolymer of a diene compound having at least one polymerizable carbon-carbon double bond in the molecule (A), an acrylate compound (B), and a thermal radical polymerization initiator. (C) and a filler (D), wherein 50 wt% or more and 99 wt% or less of the acrylate compound (B) is the compound (B1) represented by the general formula (1), and the acrylate ester A resin composition characterized in that 1% by weight or more and 30% by weight or less of the compound (B) is an acrylic ester compound (B2) having a carboxy group, which is excellent in coating amount stability in the dispensing method and The present invention provides a resin composition having a low elastic modulus and high adhesion.
Hereinafter, the present invention will be described in detail.

In the present invention, a compound (A) having at least one polymerizable carbon-carbon double bond in the molecule, which is a polymer or copolymer of a diene compound, is used. This is because by using the compound (A), the elastic modulus of the cured resin composition can be lowered, and as a result, high adhesiveness that hardly causes peeling is obtained. Here, imparting low elastic modulus to the cured resin composition is greatly influenced by the main chain skeleton structure of the compound (A), and a polymer or copolymer of a diene compound is preferable. Among them, particularly preferred diene compounds include butadiene and isoprene, and preferred copolymers are copolymers with at least one selected from acrylic acid esters, acrylonitrile, and styrene. In addition, it is preferable to have at least one polymerizable carbon-carbon double bond in the molecule, but this requires a functional group in order to exhibit good cured product properties by being incorporated into the cured product by reaction, As the functional group, a polymerizable carbon-carbon double bond is preferably used in order to react with an acrylic ester compound (B) described later. Among these, preferred functional groups include acryloyl group, vinyl group, allyl group, maleimide group and the like, and particularly preferred is acryloyl group. Here, the acryloyl group includes those in which the α or β position of the acryloyl group is substituted with an organic group having 1 to 8 carbon atoms such as an alkyl group, an alkenyl group, or a phenyl group. The compound (A) needs to have at least one polymerizable carbon-carbon double bond, but a more preferable number of carbon-carbon double bonds is two or more. As a result, it can be efficiently incorporated into the cured product and can exhibit good cured product properties (mechanical properties).
Particularly preferred are compounds having a polymerizable carbon-carbon double bond at both ends of a polymer or copolymer of a diene compound. This is because the presence of the functional group at both ends can increase the distance between the reaction points and lower the elastic modulus of the cured product.

As described above, in order to impart low elastic modulus to the cured product, the influence of the main chain skeleton structure of the compound (A) is great, and it is preferable to use butadiene or isoprene as the diene compound, but it is particularly preferable. Is butadiene. When attention is paid to the microstructure of the butadiene polymer or copolymer, the proportion of 1,4 vinyl bonds is preferably 60% or more based on the total of 1,4 vinyl bonds and 1,2 vinyl bonds. Particularly preferred is 75% or more. This is because the higher the proportion of 1,4 vinyl bonds, the lower the modulus of elasticity of the cured product obtained with a lower viscosity as the compound (A).
The molecular weight of the compound (A) used in the present invention is preferably in the range of 500 to 10,000. More preferred is 700 to 5000, and particularly preferred is 1000 to 5000. If the molecular weight is lower than this, the intended reduction in the elastic modulus cannot be sufficiently exhibited, and if it is higher than this, the viscosity becomes too high, which causes deterioration in the workability of application of the resin composition. Here, the molecular weight is a number average molecular weight measured using GPC (gel permeation chromatograph).

In the present invention, 50 to 99% by weight of the acrylate compound (B) is the compound (B1) represented by the general formula (1) as the acrylate compound (B), and the acrylate compound (B 1) to 30% by weight of) is used as the acrylate compound (B2) having a carboxy group. An acrylic ester compound is a compound having an acryloyloxy group, and can be obtained, for example, by an esterification reaction of (meth) acrylic acid and an alcohol. Here, the acryloyloxy group includes those in which the α or β position of the acryloyloxy group is substituted with an organic group having 1 to 8 carbon atoms such as an alkyl group, an alkenyl group, or a phenyl group. The acrylic ester compound (B) is suitably used because it has a low viscosity and excellent reactivity, and thus imparts good coating workability to the resin composition and gives good reactivity.
The acrylic ester compound (B) is preferable because of excellent compatibility with the compound (A).

Ｒ¹は水素原子、炭素数１〜１２の脂肪族炭化水素基、Ｒ²は炭素数６〜１２の分岐した脂肪族炭化水素基である。

R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ² is a branched aliphatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the compound (B1) represented by the general formula (1) include isohexyl (meth) acrylate, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, and isoundecyl (meta). ) Acrylate, isododecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, decalyl (meth) acrylate, and the like.

If the compatibility between the compound (A) and the acrylate compound (B) is poor, layer separation proceeds at room temperature where the coating operation is performed, and it becomes difficult to maintain a stable coating amount. Here, the compound (B1) is preferably used because of its good compatibility with the compound (A). When the number of carbons is less than this, the volatility is high, and therefore the amount of volatile components when the resin composition is heat-cured becomes too large, which is not preferable. Although the solubility is good, crystallization may occur at low temperatures because of the high molecular regularity. In general, the resin composition of the present invention is stored at a low temperature such as −15 ° C. or −40 ° C. for the purpose of suppressing the reaction of the resin components and sedimentation of the filler (D) described later. When some components in the resin composition crystallize during low-temperature storage, the uniformity of the resin composition is impaired even after the temperature is returned to room temperature, and stable coating cannot be performed. For this reason, a particularly preferable compound (B1) is a compound in which R ² in the general formula (1) is at least one of an isodecyl group and a 2-ethylhexyl group. The compounding quantity of a compound (B1) is 50 to 99 weight% of an acrylic ester compound (B). This is because within this range, good compatibility is exhibited even at low temperatures, and stable coating properties can be obtained. More preferred is 60 wt% or more and 99 wt% or less. Those having different structures of R ^{2 in} the general formula (1) may be used in combination.

The present invention further includes an acrylate compound (B2) having a carboxy group. This is because having a carboxy group particularly improves the adhesion to a metal. (Meth) acrylic acid also has a carboxy group, but when used as a resin composition, it is usually applied using a device such as a die bonder, and is cured by heating, so that the odor at the time of application and curing, as well as skin irritation It cannot be used because of problems.
The acrylate ester compound (B2) having such a carboxy group is not particularly limited as long as it is an acrylate ester compound having at least one carboxy group in one molecule, but a (meth) acrylate ester compound having a hydroxyl group. A compound obtained by reacting carboxylic acid with dicarboxylic acid is preferable. More preferred are compounds obtained by reacting 2-hydroxyethyl (meth) acrylate and dicarboxylic acid, and preferred dicarboxylic acids are compounds obtained by reacting succinic acid, cyclohexanedicarboxylic acid and derivatives thereof. A reaction product of 2-hydroxyethyl (meth) acrylate and succinic anhydride or cyclohexanedicarboxylic anhydride is particularly preferable from the viewpoint of easy reaction. The acrylate compound (B2) having a carboxy group is preferably in the range of 1% by weight to 30% by weight of the acrylate compound (B). When more than this is contained, there exists a possibility of a resin composition becoming high viscosity and compatibility deterioration with the said compound (A). More preferably, it is contained in the acrylic ester compound (B) in an amount of 1% by weight to 25% by weight, and more preferably 1% by weight to 20% by weight.

  Other usable acrylate compounds (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, and lauryl. (Meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate Relate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, neopentyl glycol (meth) 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, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol mono (meth) acrylate, di (meth) acryloyloxymethyltricyclodecane, N- ( Examples include (meth) acryloyloxyethyl maleimide, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxyethyl phthalimide, and the like.

  In the present invention, a thermal radical polymerization initiator (C) is used. Although it is not particularly limited as long as it is normally used as a thermal radical polymerization initiator, it is desirable that a rapid heating test (decomposition start temperature when a sample is placed on an electric heating plate and heated at 4 ° C./min. In which the decomposition temperature is 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-methylethylperoxyneodecano Eate, t-hexyl pao Cineodecanoate, 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-ethyl Hexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3 , 5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t- Butylperoxy-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) Examples include benzophenone.
These may be used alone or in combination of two or more in order to control curability. Although not particularly limited, it is preferably contained in the resin composition in an amount of 0.001 to 2% by weight.

  Since the resin composition of the present invention is usually used under illumination such as a fluorescent lamp, if a photopolymerization initiator is contained, an increase in viscosity is observed due to reaction during use. I can't do it. “Substantially” means that a small amount of the photopolymerization initiator may be present to such an extent that no increase in viscosity is observed, and it is preferably not contained.

In the present invention, as filler (D), metal powder such as silver powder, gold powder, copper powder, aluminum powder, nickel powder and palladium powder, ceramic powder such as alumina powder, titania powder, aluminum nitride powder and boron nitride powder, Polymer powders such as polyethylene powder, polyacrylic acid ester powder, polytetrafluoroethylene powder, polyamide powder, polyurethane powder, and polysiloxane powder can be used.
When the resin composition is used, it may be discharged using a nozzle. Therefore, in order to prevent nozzle clogging, the average particle size is preferably 30 μm or less, and it is preferable that there are few ionic impurities such as sodium and chlorine. In particular, silver powder is preferably used when electrical conductivity and thermal conductivity are required. If it is the silver powder currently marketed for electronic materials, reduced powder, atomized powder, etc. can be obtained, and as a preferable particle diameter, an average particle diameter is 1 micrometer or more and 30 micrometers or less. Below this, the viscosity of the resin composition becomes too high, and above this can cause nozzle clogging during dispensing as described above, and silver powder other than for electronic materials may have a large amount of ionic impurities. Caution must be taken. The shape is not particularly limited, such as flakes and spheres, but preferably flakes are used and are usually contained in the resin composition in an amount of 70 to 95% by weight. This is because when the proportion of silver powder is less than this, the conductivity deteriorates, and when it is more than this, the viscosity of the resin composition becomes too high.

  In the present invention, a coupling agent can be used. Generally used silane coupling agents and titanium-based coupling agents can be used. In particular, when a silane coupling agent having an S—S bond is used as a filler (D), silver powder is used. Since the bonding with the surface also occurs, not only the adhesion strength to the adherend surface but also the cohesive strength of the cured product is improved, so that it can be suitably used. A combination with other than the silane coupling agent having an S—S bond is also preferred.

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.

  The present invention will be specifically described below with reference to examples. The blending ratio is expressed in parts by weight.

  Compound A1: Polybutadiene having both terminal hydroxyl groups (Idemitsu Kosan Co., Ltd., R-45HT) 140 g, methacrylic acid (reagent) 10.3 g, hydroquinone monomethyl ether (Kawaguchi Chemical Co., Ltd., MQ-F) 0.03 g And 500 g of toluene (reagent) in a separable flask and stirring at room temperature for 10 minutes to make a uniform solution, 1.0 g of paratoluenesulfonic acid monohydrate (reagent) is added, and stirring is further performed for 5 minutes. It was. Thereafter, the mixture was heated using an oil bath and reacted for 4 hours while dehydrating in a Dean-Stark trap under reflux. After cooling to room temperature, the organic solvent layer which has been subjected to liquid separation washing 5 times with ion-exchanged water is filtered to remove solids, and the solvent is removed with an evaporator and a vacuum dryer to obtain a product. Used for testing. (Hereinafter, compound A1, yield: about 92%. A viscous liquid at room temperature. Disappearance of protons in the methylene group to which hydroxyl groups are bonded (4.05 to 4.2 ppm), ester bonds by proton NMR measurement using deuterated chloroform. (4.45 to 4.65 ppm), and 4.9 to 5.05 ppm of 1,2-vinyl bond integral strength and 1.95 to 2.15 ppm of 1,4-vinyl bond integral strength (4 From the ratio of protons, it was confirmed that the ratio of all vinyl bonds of 1,4 vinyl bonds (total of 1,2-vinyl bonds and 1,4 vinyl bonds) was about 80%. (The average molecular weight was about 3100, and it was confirmed that there was no peak based on methacrylic acid.)

Compound A2: Polybutadiene having hydroxyl groups at both ends (Idemitsu Kosan Co., Ltd., R-15HT) 120 g, methacrylic acid (reagent) 17.2 g, hydroquinone monomethyl ether (Kawaguchi Chemical Co., Ltd., MQ-F) 0.06 g A product was obtained in the same manner as Compound A1, except that 1.9 g of paratoluenesulfonic acid monohydrate (reagent) was used and used in the following tests. (Hereinafter referred to as Compound A2
Yield about 94%. A viscous liquid at room temperature. As in compound A1, the ratio of hydroxyl group disappearance, ester bond formation, and 1,4 vinyl bond to the total vinyl bond (total of 1,2-vinyl bond and 1,4 vinyl bond) is about 80 as measured by proton NMR. %. The number average molecular weight in terms of styrene by GPC was about 1500, and it was confirmed that there was no peak based on methacrylic acid. )

[Example 1]
The compound A as the compound (A), the isodecyl methacrylate (produced by Kyoeisha Chemical Co., Ltd., light ester ID) as the compound (B1), R ^{1 in the} general formula (1) is a methyl group, and R ² is an isodecyl group. A compound B11) as a compound (B2)
Methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., light ester HO-MS, esterified compound of 2-hydroxyethyl methacrylate and succinic acid and having a carboxy group, hereinafter referred to as compound B2), a thermal radical polymerization initiator (C ), Dicumyl peroxide (manufactured by NOF Corporation, Park Mill D, decomposition temperature in rapid heating test: 126 ° C., hereinafter initiator), filler (D), average particle size 8 μm, maximum particle size 30 μm Flake silver powder (hereinafter referred to as silver powder), a coupling agent having a glycidyl group (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E, hereinafter referred to as coupling agent 1), a coupling agent having a methacrylic group (Shin-Etsu Chemical Co., Ltd.) ), KBM-503P, hereinafter coupling agent 2) is blended as shown in Table 1, kneaded using three rolls, and defoamed. By doing so, a resin composition was obtained. The blending ratio is parts by weight. The obtained resin composition was evaluated by the following methods. The evaluation results are shown in Table 1.

[Examples 2 to 5, Comparative Examples 1 to 4]
The resin composition was obtained in the same manner as in Example 1 by blending at the ratio shown in Table 1.
In addition, what was used except Example 1 was described below.
The compound A2 as the compound (A), 2-ethylhexyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester EH, hereinafter referred to as compound B12), tetradecyl methacrylate (hereinafter referred to as compound B31) and 1,6-hexane as the compound (B) Diol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 1, 6HX, hereinafter referred to as compound B32), coupling agent having a tetrasulfide bond (manufactured by Nihon Unicar Co., Ltd., A-1289, hereinafter referred to as coupling agent 3), acrylic Modified polybutadiene (manufactured by Shin Nippon Petrochemical Co., Ltd., MM-1000-80, having a carbon-carbon double bond polymerizable by a reaction product of maleated polybutadiene and 2-hydroxyethyl methacrylate as a branched functional group. Number average Molecular weight was about 1000 and measured by proton NMR method All vinyl bond of 1,4-vinyl bond ratio of 32% for (1,2-vinyl bond and 1,4 sum of the vinyl bond), the following compound X).

Evaluation method Viscosity and thixotropy: E-type viscometer (3 ° cone) was used, and the values at 25 ° C., 0.5 rpm and 2.5 rpm were measured immediately after the resin composition was produced. The value at 2.5 rpm was the viscosity, and the viscosity value of 20 ± 10 Pa · S was accepted. The unit of viscosity is Pa · S. A value obtained by dividing the value at 0.5 rpm by the value at 2.5 rpm was defined as thixotropy (an index of workability), and a value of 3.0 or more was determined to be acceptable.
Application test-1: The obtained resin composition was filtered through 100 mesh and filled into two syringes. One of them was used, and 1,000 points were applied using a metal needle 25G single nozzle (inner diameter 0.26 mm, length 15 mm) with a dot tester (manufactured by Musashi Engineering Co., Ltd., SHOTMASTER-300) (coating amount 20 mg / kg). The stability of the coating was confirmed. To check the coating stability, use an optical microscope to visually thread the thread (when the thread breakage part protrudes out of the circle of the dispensed dot when viewed from above), idle driving (liquid resin composition only around the nozzle) ) And the number of overdischarges (when the diameter of the dispensed dot is 20% or more) is measured and the total of these is 5 points (5 locations) or less. Passed.
Application test-2: One unused syringe prepared in application test-1 is stored in a freezer (-38 ° C to -43 ° C) for one week, taken out from the freezer, and temporarily stored in a refrigerator (4 ° C to 10 ° C). After leaving for 2 hours and taking out to room temperature, 1 hour passed was used for the dot test. Applying 1,000 points (coating amount 20 mg / 1 point) using a metal needle 25G single nozzle (inner diameter 0.26 mm, length 15 mm) with a dot tester (Musashi Engineering Co., Ltd., SHOTMASTER-300). The sex was confirmed. To check the coating stability, use an optical microscope to visually thread the thread (when the thread breakage part protrudes out of the circle of the dispensed dot when viewed from above), idle driving (liquid resin composition only around the nozzle) ) And the number of overdischarges (when the diameter of the dispensed dot is 20% or more) is measured and the total of these is 5 points (5 locations) or less. Passed.

Adhesive strength: Using the resin composition shown in Table 1, a 6 × 6 mm silicon chip was mounted on a Ni—Pd / Au plated copper frame and cured in an oven at 150 ° C. for 30 minutes. After curing and after moisture absorption treatment (85 ° C., 85%, 72 hours), the hot die shear strength at 260 ° C. was measured using an automatic adhesive force measuring apparatus. The case where the die shear strength when heated at 260 ° C. was 30 N / chip or more was regarded as acceptable. The unit of adhesive strength is N / chip.
-Elastic modulus: Using the resin composition shown in Table 1, a 4 × 20 × 0.1 mm film-like test piece was prepared (curing conditions: 150 ° C. for 30 minutes), and the dynamic viscoelasticity measuring machine (DMA) was used. The measurement was performed in the pull mode. 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 2000 MPa or less was regarded as acceptable. The unit of elastic modulus is MPa.
-Temperature cycle resistance: Using the resin composition shown in Table 1, a 15 x 15 x 0.5 mm silicon chip was mounted on a Ni-plated copper heat spreader (25 x 25 x 2 mm), and then in a 150 ° C oven. Cured for 30 minutes. The state of peeling after curing and temperature cycle treatment (−65 ° C. ← → 150 ° C., 100 cycles) was measured with an ultrasonic flaw detector (reflection type). A peeling area of 10% or less was accepted.
Reflow resistance: Using the resin composition shown in Table 1, the following lead frame and silicon chip were cured and bonded at 150 ° C. for 30 minutes. Furthermore, sealing was performed using a sealing material (Sumicon EME-7026, 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 peeling area of the die attach part was less than 10% was regarded as acceptable. The unit of the peeled area is%.
Semiconductor device: QFP (14 x 20 x 2.0 mm)
Lead frame: Ni-Pd / Au plated copper frame Chip size: 6 x 6 mm
Curing conditions for resin composition: 150 ° C. in oven for 30 minutes

  Since the resin composition of the present invention is excellent in the coating amount stability in the dispensing method and has a low elastic modulus and high adhesion, when used as a die attach paste or a heat dissipation member adhesion material, the obtained semiconductor device is resistant. As a result, it is possible to obtain a highly reliable semiconductor device.

Claims (5)

A resin composition for adhering a semiconductor element or a heat dissipation member to a support,
A diene compound polymer or copolymer having at least one polymerizable carbon-carbon double bond in the molecule (A), an acrylate compound (B), a thermal radical polymerization initiator (C), And filler (D),
50 wt% or more and 99 wt% or less of the acrylate compound (B) is the compound (B1) represented by the general formula (1), and 1 wt% or more and 30 wt% or less of the acrylate compound (B). Is an acrylic ester compound (B2) having a carboxy group.

R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ² is a branched aliphatic hydrocarbon group having 6 to 12 carbon atoms. The resin according to claim 1, wherein R ² of the compound (B1) represented by the general formula (1) is a compound having a branched aliphatic hydrocarbon group having 6 to 12 carbon atoms having different structures. Composition. 2. The resin composition according to claim 1, wherein the compound (A) is a butadiene polymer or copolymer having at least one polymerizable carbon-carbon double bond in the molecule. 4. The resin composition according to claim 3, wherein the proportion of 1,4 vinyl bonds contained in the compound (A) is 60% or more based on the total of 1,4 vinyl bonds and 1,2 vinyl bonds. object. A semiconductor device manufactured using the resin composition according to any one of claims 1 to 4 as a die attach paste or a heat dissipation member bonding material.