JP5356763B2 - Resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition exhibiting low curing shrinkage and low stress property, good adhesion at high temperature and excellent in coatability; and to provide a semiconductor device excellent in reliability such as resistance to solder cracking by using the resin composition as an adhesive for a die attachment material or a heat dissipation member of a semiconductor. <P>SOLUTION: This resin composition contains, as essential components, (A) a compound having (meth)acryloyl group in a molecule, (B) a compound having glycidyl group, and (C) a compound having allyl ester group. A semiconductor is made by using the resin composition. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

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

In recent years, the speed of semiconductor devices has been remarkably increased, and transmission delay due to a decrease in signal propagation speed due to wiring resistance and parasitic capacitance between wirings has become a problem. Such a problem tends to become more prominent because the wiring resistance increases and the parasitic capacitance increases as the wiring width and the wiring interval become finer due to higher integration of semiconductor devices. Therefore, in order to prevent signal delay due to increase in wiring resistance and parasitic capacitance, copper wiring is introduced instead of the conventional aluminum wiring, and the relative dielectric constant of the silicon dioxide film of the interlayer insulating film of the semiconductor element is 3 An insulating film having a low dielectric constant smaller than .9 has been applied. In particular, the relative dielectric constant of the interlayer insulating film is strongly demanded to be about 2.0 or less as the design standard is reduced from 65 nm to 45 nm. There is a need for a porous insulating film having a reduced dielectric constant by increasing the porosity.
Such a porous insulating film has a problem that its mechanical strength is generally weak due to its structure. That is, compared with a semiconductor element using a conventional insulating film, it is more sensitive to external stress, and the insulating film may be destroyed even by stress that has not been a problem until now.
In order to reduce the stress generated there, semiconductor constituent materials such as a sealing material and a die attach material are required to have low stress, and the semiconductor production process has been reviewed.

The semiconductor element is bonded to a support such as a lead frame, a glass epoxy substrate (glass fiber reinforced epoxy resin substrate), a BT substrate (a BT resin substrate made of cyanate monomer and oligomer thereof and bismaleimide), and an organic substrate such as a polyimide film. In the die attach process, warping occurs due to the difference in coefficient of thermal expansion between the semiconductor element and the support after die attaching. However, excessive warpage causes damage to the interlayer insulating film, and thus warpage is unlikely to occur. There is a need for touch materials.
Here, in order to reduce warpage, it is necessary to lower the cure shrinkage and elastic modulus of the die attach material.
(1) A method of adding a liquid low-stress agent (for example, see Patent Document 1),
(2) A method of adding a solid low stress agent (for example, see Patent Document 2),
(3) A method of reducing the crosslinking density (for example, see Patent Document 3),
(4) A method of introducing a flexible structure into the resin skeleton (see, for example, Patent Document 4),
(5) A method of adding a polymer having a low glass transition temperature (Tg) (for example, see Patent Document 5) has been studied. For example, in the method of (1), the liquid low-stress agent itself has a high viscosity. Therefore, when a blending amount capable of obtaining a sufficiently low elastic modulus is added, it tends to be difficult to handle due to high viscosity. In the method (2), since the ratio of solid content in the liquid resin composition increases, the viscosity is high. In the method (3), mechanical properties such as strength at high temperatures tend to deteriorate. In the method (4), the viscosity of the resin into which the flexible skeleton is introduced is high. In the method (5), a liquid resin composition cannot be obtained unless a solvent is used, and the solvent must be volatilized during the curing of the liquid resin composition. Missing items such as contamination of parts It is also left.
On the other hand, while lead elimination from semiconductor products including semiconductor devices is being promoted as part of environmental measures, lead-free solder is also used as the solder used when mounting semiconductor packages, etc. It is necessary to increase the reflow temperature. The reflow treatment at high temperature increases the stress inside the semiconductor package, so that peeling and cracking are likely to occur in the semiconductor product during reflow, and the die attach material is also difficult to peel off. Material is desired. Thus, a liquid resin composition having a low cure shrinkage and a low elastic modulus, showing a good adhesive force even at a high temperature and excellent in workability at the time of application is desired as a die attach material, but none is sufficiently satisfactory. .
Japanese Patent Laid-Open No. 05-120914 JP 2003-347322 A Japanese Patent Laid-Open No. 06-084974 Japanese Patent Laid-Open No. 08-176409 JP 2005-154687 A

  INDUSTRIAL APPLICABILITY The present invention uses a resin composition that exhibits low curing shrinkage and low stress, exhibits good adhesive strength at high temperatures, and is excellent in coating workability, and the present invention as a die attach paste for semiconductors or an adhesive for heat dissipation members In this case, a semiconductor device having excellent reliability such as solder crack resistance is provided.

Such an object is achieved by the present invention described in the following (1) to (7).
(1) A resin composition comprising as essential components (A) a compound having a (meth) acryloyl group in the molecule, (B) a compound having a glycidyl group, and (C) a compound having an allyl ester group object.
(2) The resin composition according to (1), wherein the compound (C) having an allyl ester group is an allyl ester compound that does not contain an aromatic ring and is liquid at room temperature.
(3) The resin composition according to (1) or (2), wherein the compound (C) has a functional group represented by the general formula (1).

In the formula, R ¹ is hydrogen or a methyl group.

(4) The compound (C) having the allyl ester group according to any one of (1) to (3), wherein the main chain skeleton has a structure represented by the general formula (2). Resin composition.

In the formula, R ² is a hydrocarbon group having 3 to 11 carbon atoms, or an organic group represented by the general formula (3).
R ³ is a hydrocarbon group having 3 to 11 carbon atoms,
X ¹ is either —O—, —OCO— or —OCOO—,
X ² is equal to X ¹ when X ¹ is —O— or —OCOO—, and is —OCO—.
-COO-,
n is 0 or more and 50 or less.

In the formula, R ⁴ is a hydrocarbon group having 3 to 11 carbon atoms,
X ³ is either —O—, —OCO— or —OCOO—,
m is 1 or more and 50 or less.

(5) The resin composition according to any one of (1) to (4), wherein the compound (C) having the allyl ester group has a molecular weight of 500 or more and 5000 or less as measured by GPC.
(6) The resin composition according to any one of (1) to (5), further including a filler. (7) A semiconductor device manufactured using the resin composition according to any one of (1) to (6) as a die attach paste or an adhesive for a heat dissipation member.

  Since the resin composition of the present invention exhibits low curing shrinkage and low stress, exhibits good adhesive strength at high temperatures, and is excellent in coating workability, the present invention is used as a die attach paste for semiconductors or an adhesive for heat dissipation members. As a result, it is possible to provide a highly reliable semiconductor device such as unprecedented solder crack resistance.

The present invention comprises a resin comprising (A) a compound having a (meth) acryloyl group in the molecule, (B) a compound having a glycidyl group, and (C) a compound having an allyl ester group as essential components. Use of the present invention as a die attach material because it is a composition that exhibits low cure shrinkage and low stress, exhibits low stress, exhibits good adhesion at high temperatures, and is excellent in coating workability. Therefore, it is possible to provide a highly reliable semiconductor device that has never been obtained.
Hereinafter, the present invention will be described in detail.

In the present invention, (A) a compound having a (meth) acryloyl group in the molecule is used. The compound (A) having a (meth) acryloyl group in the molecule can be obtained, for example, by an esterification reaction of (meth) acrylic acid and an alcohol. 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. Since the compound (A) has low viscosity and excellent reactivity, it is suitably used because it imparts good coating workability to the resin composition and gives good reactivity.
Usable compounds (A) include 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, cetyl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Other alkyl (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclohexyl ( Data) acrylate, tert-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth)
Acrylate, phenoxyethyl (meth) acrylate, isobornyl (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 (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, methoxypolyalkylene glycol mono ( (Meth) acrylate, octoxy polyalkylene glycol mono (meth) acrylate, lauroxy polyalkylene glycol mono (meth) acrylate, stearoxy polyalkylene glycol mono (meth) acrylate, Liloxy polyalkylene glycol mono (meth) acrylate, nonylphenoxy polyalkylene glycol mono (meth) acrylate, di (meth) acryloyloxymethyltricyclodecane, N- (meth) acryloyloxyethylmaleimide, N- (meth) Examples include acryloyloxyethyl hexahydrophthalimide and N- (meth) acryloyloxyethyl phthalimide.

Among these, compounds having two (meth) acryloyl groups in one molecule are preferably used. This is because a compound having two (meth) acryloyl groups in one molecule has low viscosity and excellent compatibility with a compound having two functional groups of the same kind in one molecule, such as an organic peroxide. This is because the reaction catalyst (reaction initiator) is used to react quickly. The number of functional groups contained in one molecule is limited to 2, but this is because when the number of functional groups is 1, the cohesive force of the cured product decreases and good adhesiveness cannot be maintained. This is because the elastic modulus of the cured product becomes too high and may cause peeling of an organic substrate or a lead frame as a support.
For example, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, zinc di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polybutanediol 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, Ritetramethylene glycol di (meth) acrylate, cyclohexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, cyclohexanediethanoldi (meth) acrylate, cyclohexanedialkyl alcohol di (meth) acrylate, dimethanoltricyclodecandi (Meth) acrylate, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, 1,2-di (meth) acrylamide ethylene glycol, and the like, among them, preferred compound (A) Is ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethanoltri And cyclodecanedi (meth) acrylate.

  As a compound (B) which has a glycidyl group used for this invention, it is preferable that two or more glycidyl groups are contained in 1 molecule. This is because even if the glycidyl group is reacted with only one compound, sufficient cured product characteristics cannot be exhibited. Compounds containing two or more glycidyl groups per molecule include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol, or derivatives thereof, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, and cyclohexanedimethanol. Diols having an alicyclic structure such as shidilohexanediethanol or derivatives thereof, bifunctional ones obtained by epoxidizing aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, or derivatives thereof , Trihydroxyphenylmethane skeleton, trifunctional one having aminophenol skeleton, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, bif Ruararukiru resins and a naphthol aralkyl resin as polyfunctional epoxidized include, without limitation thereto. Moreover, as a resin composition, the thing liquid at room temperature as single or a mixture thereof is preferable. It is also possible to use reactive diluents as is usual.

Moreover, in this invention, although a well-known thing can be used as a hardening | curing agent of the compound (B) which has a glycidyl group, since it is a semiconductor use, a phenol type compound is preferable. This is because the cured product is excellent in moisture resistance reliability. A preferable curing agent is not particularly limited as long as it has 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, or cresol novolac.
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. These imidazoles are used in an amount of 0.5 to 20% by weight based on the compound (B) having a glycidyl group. If it is less than this, the curability is poor, and if it is more than this, the properties of the cured product such as a decrease in adhesive strength are deteriorated. It is also possible to use a reaction catalyst such as phosphorus or amine.

In the present invention, the compound (C) having a (meth) allyl ester group is used. The compound (C) is preferably an allyl ester compound that does not contain an aromatic ring and is liquid at room temperature. In the case of diallyl phthalate, which is generally known as a compound having a (meth) allyl ester group, since it contains an aromatic ring, it is rigid as a main chain structure, and the interaction between molecules is also strong and cured. It has a high elastic modulus and is brittle (breaks with a small amount of deformation), but it does not contain an aromatic ring and lowers the elastic modulus of the cured product by using a liquid allyl ester compound at room temperature. This is because it becomes possible.
Examples of the allyl ester compound that does not contain an aromatic ring and is liquid at room temperature include compounds containing a functional group represented by the general formula (1). At least one functional group represented by the general formula (1) is required in one molecule, but two or three functional groups are preferably included from the viewpoint of curability. As the number of functional groups in one molecule increases, the molecular weight increases accordingly, so that the viscosity generally tends to increase. For this reason, when considering the balance between curability and workability, the most preferable number of functional groups is two in one molecule. R ^{1 in the} general formula (1) is hydrogen or a methyl group, and is preferably a methyl group from the viewpoint of curability.

Furthermore, in order to realize low stress properties, the compound (C) preferably has a structure represented by the general formula (2). R ^{2 in the} general formula (2) is a hydrocarbon group having 3 to 11 carbon atoms or an organic group represented by the general formula (3), and R ³ is a hydrocarbon group having 3 to 11 carbon atoms. . R ² and R ³ are more hydrophilic when the carbon number is less than the above range, so that the moisture resistance of the cured product is deteriorated. On the other hand, when the carbon number is more than the above range, the hydrophobicity becomes too high and the adhesion is too high. This is because sex may deteriorate. A more preferable carbon number is 3 or more and 6 or less. R ²
Is an organic group represented by the general formula (3), R ⁴ is preferably a hydrocarbon group having 3 to 11 carbon atoms, which is hydrophilic when the carbon number is less than the above range. This is because the moisture resistance of the cured product is deteriorated due to the increase in the viscosity, and when the carbon number is more than the above range, the hydrophobicity is excessively increased and the adhesion may be deteriorated. A more preferable carbon number is 3 or more and 6 or less. X ³ is selected from —O—, —OCO—, and —OCOO—. By including these bonds, the molecular chain becomes flexible and it is possible to reduce the elastic modulus as a cured product, and the raw material tends to be liquid at room temperature, so that it can be suitably used. Although m is 1 or more and 50 or less, when it is more than this, since the molecular weight becomes too large, the viscosity of the resin composition becomes too high. X ^{1 in the} general formula (2) is —O—, —OCO—, or —OCOO.
Selected from −. By including these structures, the molecular chain becomes flexible, and it is possible to reduce the elastic modulus as a cured product, and the raw material tends to be liquid at room temperature, so that it can be suitably used. In the case where X ¹ is a structure selected from —O— or —OCOO—, X ² is X ^1.
And when X ¹ is —OCO—, X ² is —COO—. A preferable structure represented by the general formula (2) is an esterified diol and a dicarboxylic acid or a derivative thereof. Particularly when a branched aliphatic diol is used as the diol, the obtained compound (C) is preferable because it has a low viscosity.

The preferred compound (C) has a molecular weight of 500 or more and 5000 or less, and a more preferred molecular weight range is 800 or more and 2000 or less. If the value is smaller than the lower limit, the number of functional groups in the resin composition tends to increase, and the elastic modulus of the cured product tends to increase. If the value is larger than the upper limit, the viscosity of the resin composition becomes too high to be practical. Because.
Such a compound (C) can be obtained by reacting cyclohexanedicarboxylic acid or a derivative thereof with a diol and allyl alcohol. The molecular weight can be controlled by the charging ratio. It is preferable to use at least one selected from polyether diol, polyester diol, and polycarbonate diol as the diol because a cured product having a lower elastic modulus can be obtained. The compound having a (meth) allyl ester group and having an aliphatic ring (C) can obtain a cured product having a low elastic modulus and is liquid at room temperature, so that it can be blended with a filler described later. It is possible to obtain a resin composition having a low viscosity and excellent workability.

In the present invention, a filler may be further included. As filler, metal powder such as silver, gold, nickel and iron is used to give conductivity, ceramic particles like silica and alumina, thermosetting resin or thermoplastic to give insulation. Resin resin particles can be used. The shape of particles generally used as a filler has various shapes such as a scale, a sphere, a resin, and a powder, but the shape is not particularly limited in the present invention.
Although content of the said filler is not specifically limited, 60 to 90 weight% of the whole said resin composition is desirable, and 70 to 85 weight% is especially desirable. If the content is less than the lower limit, the viscosity and thixotropy may be too low and workability may be reduced, and if the content exceeds the upper limit, the viscosity may be too high and workability may be reduced. is there.
The average particle diameter of the filler is not particularly limited, but is preferably 1 to 10 μm, and particularly preferably 2 to 7 μm. If the average particle size is less than the lower limit, the viscosity may be high, and thus it may be difficult to adjust the viscosity. The average particle diameter can be measured using, for example, a particle size distribution measuring apparatus using a laser diffraction or scattering method.

Further, a thermal radical polymerization initiator is preferably used 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 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. When the decomposition temperature is less than 40 ° C., the storage stability of the conductive paste at normal temperature is deteriorated, and when 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 compounding quantity of a polymerization initiator is 0.1 to 10 weight% with respect to a thermosetting resin. More preferably, it is 0.5 to 10% by weight.
Here, 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 a reaction during use. It is not preferable to contain an agent. Here, “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.

If necessary, additives such as a coupling agent, an antifoaming agent, and a surfactant 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 semiconductor element is mounted and heat-cured. Then, a semiconductor device is manufactured by wire bonding and transfer molding using an epoxy resin. Alternatively, a resin composition is dispensed on the back surface of a semiconductor element such as a flip chip BGA (Ball Grid Array) sealed with an underfill material after flip chip bonding, and heat radiation components such as a heat spreader and a lid are mounted and cured.

<< Preparation of Compound (C) >>
Compound C1: 58 g of allyl alcohol (reagent), 344 g of 1,4-cyclohexanedicarboxylic acid (reagent), 177 g of 3-methyl-1,5-pentanediol (manufactured by Kuraray Co., Ltd., MPD) and a toluene / MIBK mixed solvent (7 : 3) 1 L was put into a separable flask, stirred at room temperature for 30 minutes, paratoluenesulfonic acid was added, and the reaction was performed under reflux for 8 hours. Water generated during the reaction was removed by a Dean Stark trap. After cooling to near room temperature, ion exchange water was added, stirred for 30 minutes, and then allowed to stand to obtain a solvent layer. Further, after performing separation washing with ion exchange water at 70 ° C. three times and with ion exchange water at room temperature twice, the solvent was removed with an evaporator and a vacuum dryer to obtain a product. (Hereinafter, compound C1, yield of about 87%, liquid at room temperature, styrene equivalent molecular weight by GPC is about 1200. Proton NMR measurement using deuterated chloroform and protons of hydroxyl group of allyl alcohol and 3-methyl-1,5-pentane) Disappearance of peak near 2.0 ppm based on proton of hydroxyl group of diol, disappearance of peak near 11.9 ppm based on proton of carboxyl group of 1,4-cyclohexanedicarboxylic acid, esterification of proton of methylene group of allyl alcohol A shift (near 4.6 ppm) and a shift due to esterification of protons of the 1- and 5-position methylene groups of 3-methyl-1,5-pentanediol (near 4.1 ppm) were confirmed. From the intensity ratio of the peak around 2.3 ppm and around 4.6 ppm Narubutsu is a structure represented by the formula (4) containing the general formula (1) in structural functionality and the general formula of which is shown the structure of (2), R ¹ is hydrogen in the general formula (1), the general formula ( 2) R ² had 6 carbon atoms, R ³ had 6 carbon atoms, X ¹ was —OCO—, X ² was —COO—, and the average number of repetitions n was about 1.8.

Compound C2: Allyl alcohol (reagent) 128 g, 1,4-cyclohexanedicarboxylic acid (reagent) 378 g, polypropylene glycol diol (manufactured by Nippon Oil & Fats Co., Ltd., Uniol D-400) and toluene / MIBK mixed solvent (7: 3) 1 L was put into a separable flask, stirred at room temperature for 30 minutes, paratoluenesulfonic acid was added, and the reaction was performed under reflux for 8 hours. Water generated during the reaction was removed by a Dean Stark trap. After cooling to near room temperature, ion exchange water was added, stirred for 30 minutes, and then allowed to stand to obtain a solvent layer. Further, after performing separation washing with ion exchange water at 70 ° C. three times and with ion exchange water at room temperature twice, the solvent was removed with an evaporator and a vacuum dryer to obtain a product. (Hereinafter, compound C2, yield: about 82%, liquid at room temperature. Styrene-equivalent molecular weight by GPC is about 1000. Based on protons of hydroxyl group of allyl alcohol and protons of hydroxyl group of polypropylene glycol diol as measured by proton NMR using deuterated chloroform. Disappearance of peak near 2.0 ppm, disappearance of peak near 11.9 ppm based on proton of carboxyl group of 1,4-cyclohexanedicarboxylic acid, shift due to esterification of proton of methylene group of allyl alcohol (near 4.6 ppm) And a shift (around 4.2 ppm) due to the esterification of the proton of the methylene group of polypropylene glycol diol was confirmed, and the product of the general formula was obtained from the intensity ratio of the peak around 2.3 ppm, around 4.2 ppm, and around 4.6 ppm. Shown in (1) A structure represented by the formula (5) containing the functional groups and the general formula of the structure the structure of (2), R ¹ is hydrogen of general formula (1), R ² is of the general formula (2) (3 ), R ⁴ has 3 carbon atoms, X ³ is —O—, R ³ has 6 carbon atoms, X ¹ is —OCO—, X ² is —COO—, and the average number of repetitions m Was about 6 and n was about 0.1.)

[Example 1]
1,6-hexanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 1, 6HX, hereinafter referred to as compound A) as the compound (A) having a (meth) acryloyl group, and bisphenol as the compound (B) having a glycidyl group Diglycidyl bisphenol A (epoxy equivalent 180, liquid at room temperature, hereinafter referred to as compound B) obtained by reaction of A with epichlorohydrin is compound C1 as the compound (C) having an allyl ester group, and bisphenol F (large) as the curing agent. DIC-BPF manufactured by Nippon Ink Industry Co., Ltd., hydroxyl equivalent 100, hereinafter referred to as Compound D), dicyandiamide (hereinafter referred to as Compound E1), 2-phenyl-4-methyl-5-hydroxymethylimidazole (Cureazole 2P4MHZ: Shikoku Chemical Industries ( Co., Ltd., melting point 248-258 ° C. Compound E2), coupling agent having a tetrasulfide bond as a coupling agent (manufactured by Nihon Unicar Co., Ltd., A-1289, hereinafter referred to as compound F1), coupling agent having a glycidyl group (manufactured by Shin-Etsu Chemical Co., Ltd., KBM) -403E, hereinafter referred to as Compound F2), 1,1-di (tert-butylperoxy) cyclohexane (manufactured by NOF Corporation, Perhexa CS, hereinafter referred to as Compound G) as the radical polymerization initiator, and average particle size as the filler A resin composition is obtained by blending flaky silver powder (hereinafter referred to as silver powder) having a diameter of 8 μm and a maximum particle diameter of 30 μm as shown in Table 1, kneading and defoaming using three rolls, and using the following evaluation method. Table 1 shows the results of the evaluation. In addition, a mixture ratio is a weight part.

(Evaluation method)
Application workability: E type viscometer (3 ° cone) was used, and values at 25 ° C., 0.5 rpm, and 2.5 rpm were measured immediately after the liquid resin composition was prepared. A value of 2.5 rpm viscosity of 20 ± 10 Pa · S was considered acceptable. 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 coating workability), and a value of 3.0 or more was determined as acceptable.
Adhesive strength: A 6 × 6 mm silicon chip was mounted on a silver-plated copper frame using the resin composition shown in Table 1, and cured in a 150 ° C. oven for 30 minutes. After curing and after moisture absorption (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 45 N / chip or more was regarded as acceptable. The unit of adhesive strength is N / chip.
Curing shrinkage: The resin composition shown in Table 1 was weighed 1.0 ml, and the specific gravity was 1.
Next, the resin composition shown in Table 1 was cured in an oven at 175 ° C. for 30 minutes, and a weight of about 1.0 cm ³ was measured to obtain a specific gravity of 2.
The shrinkage was calculated from specific gravity 1 and specific gravity 2, and 6.5% or less was accepted.
Curing shrinkage (%) = [(specific gravity 2) − (specific gravity 1)] / (specific gravity 2) × 100

-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
When the storage elastic modulus at 30 ° C. is the elastic modulus 1 and the storage elastic modulus at 260 ° C. is the elastic modulus 2, the elastic modulus 1 is 6000 MPa or less and the elastic modulus 2 is 200 MPa or less. The unit of elastic modulus is MPa.

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 semiconductor device after the IR reflow treatment was measured with 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%.
Package: QFP (14 x 20 x 2.0 mm)
Lead frame: Silver plated copper frame Chip size: 6x6mm
Curing conditions for resin composition: 150 ° C. in oven, 30 minutes / temperature cycle resistance: copper heat spreader (25 × 15 × 15 × 0.5 mm silicon chip Ni-plated using the resin composition shown in Table 1) × 25 × 2 mm) and cured on a hot plate at 175 ° C. for 120 minutes. After curing and temperature cycle treatment (−65 ° C. ← → 150 ° C., 100 cycles), peeling of the cured portion of the resin composition and voids were measured with an ultrasonic flaw detector (reflection type). An exfoliation and void area of 10% or less was accepted.

[Examples 2 to 5 and Comparative Examples 1 to 3]
The resin composition was obtained in the same manner as in Example 1 by blending at the ratio shown in Table 1.
The obtained resin composition was evaluated by the following methods. The evaluation results are shown in Table 1.
In Example 2, the compound C2 prepared above was used as the compound (C) having an allyl ester group. About Examples 3-5, allyl ester resin (the Showa Denko Co., Ltd. make, allyl ester resin DA101, the functional group shown by General formula (1) as a compound (C) which has an allyl ester group, and it is liquid at room temperature In the following, compound C3) was used.

  The resin composition of the present invention is excellent in low curing shrinkage, has a low elastic modulus and exhibits good adhesiveness, and is excellent in coating workability. Therefore, it is preferably used as a die attach paste material for semiconductors or a material for adhering heat dissipation members. Can do.

Claims (6)

(A) a compound having a (meth) acryloyl group in the molecule, (B) a compound having a glycidyl group, and (C) a compound having an allyl ester group, (D) a filler as an essential component,
(B) The component is a bisphenol compound or a derivative thereof, trihydroxyphenylmethane skeleton, trifunctional one having an aminophenol skeleton, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin One or more selected from the group consisting of :
(B) The compounding quantity of a component is 5.56-12.96 weight% of the whole resin composition,
(C) The compounding quantity of a component is 3.70-14.81 weight% of the whole resin composition,
(D) The compounding quantity of a component is 60 to 90 weight% of the whole resin composition, The resin composition characterized by the above-mentioned.   The resin composition according to claim 1, wherein the compound (C) having an allyl ester group is an allyl ester compound that does not contain an aromatic ring and is liquid at room temperature. The resin composition according to claim 1 or 2, wherein the compound (C) has a functional group represented by the general formula (1).

In the formula, R ¹ is hydrogen or a methyl group.
The resin composition according to any one of claims 1 to 3, wherein the compound (C) having an allyl ester group is a compound having a structure represented by the general formula (2) in a main chain skeleton.
In the formula, R ² is a hydrocarbon group having 3 to 11 carbon atoms, or an organic group represented by the general formula (3).
R ³ is a hydrocarbon group having 3 to 11 carbon atoms,
X ¹ is either —O—, —OCO— or —OCOO—,
X ² is equal to X ¹ when X ¹ is —O— or —OCOO—, and —COO— when it is —OCO—;
n is 0 or more and 50 or less.

In the formula, R ⁴ is a hydrocarbon group having 3 to 11 carbon atoms,
X ³ is either —O—, —OCO— or —OCOO—,
m is 1 or more and 50 or less.   The resin composition according to any one of claims 1 to 4, wherein the compound (C) having an allyl ester group has a molecular weight of 500 or more and 5000 or less as measured by GPC. A semiconductor device produced using the resin composition according to claim 1 as a die attach paste or an adhesive for a heat dissipation member.