JP2015012069A - Resin composition for die attachment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for die attachment which has good workability and allows an adequate bonding strength to be achieved after hardening, and which can provide a solution to the problem of warp of a substrate or the like owing to the hardening accompanied by shrinkage.SOLUTION: A resin composition for die attachment comprises (A) a thermosetting resin, (B) a setting agent, (C) thermoplastic resin particles, and (D) an inorganic filler. The thermoplastic resin cited in the item (C) has a glass transition point of -60 to 30°C, and a melting point of 90 to 160°C, and accounts for 0.5 to 9 pts.mass to a total of 100 pts.mass of the constituents of the items (A) to (D). A semiconductor device comprises the resin composition for die attachment. A method for manufacturing a semiconductor device is arranged by use of the resin composition for die attachment. In the resin composition for die attachment, the thermoplastic resin particles of the item (C) are composed of polyester resin particles, polyolefin resin particles and polyacetal resin particles which have an average particle diameter of 8-50 μm. The thermosetting resin of the item (A) includes an epoxy resin, and further includes a (meth) acrylic resin, and the setting agent of the item (B) includes a phenol resin setting agent.

Description

  The present invention relates to a resin composition for die attach, and relates to a semiconductor device using the resin composition for die attach and a method for manufacturing the semiconductor device.

  In the manufacture of a semiconductor device, a resin composition for die attach is used in order to bond and connect a substrate and a semiconductor element or semiconductor elements. The die attach resin composition contains a thermosetting resin, and can be bonded and connected by placing the resin composition between the substrate and the semiconductor element or between the semiconductor elements and then heat-curing the resin composition.

  However, the conventional resin composition for die attach has a problem that the substrate or the like is warped by the stress of curing shrinkage due to heating. In order to solve this problem, techniques for blending a highly flexible resin into a resin composition have been proposed (Patent Documents 1 to 3).

JP 2004-285307 A JP 2011-26602 A Japanese National Patent Publication No. 9-501197

  However, in the proposed technique, since a highly flexible resin is used in a large amount, a desired adhesive strength cannot be obtained, and the viscosity of the composition becomes high, and workability can be deteriorated.

  The present invention relates to a resin composition for die attachment, which has good workability, has sufficient adhesive strength after curing, and can solve the problem of warping of a substrate or the like due to curing shrinkage, and the die attachment. An object of the present invention is to provide a semiconductor device using the resin composition for use, and a method for manufacturing the semiconductor device.

  The present invention can relieve stress due to curing shrinkage without deteriorating workability by blending specific thermoplastic resin particles in a specific amount with a resin composition for die attach containing a thermosetting resin. This is based on the knowledge that sufficient adhesive strength can be obtained even after curing. Since the resin composition for die attach of the present invention is blended with a thermoplastic resin in the form of particles, a sudden increase in viscosity due to the blending of the thermoplastic resin is suppressed, and stress is caused by the elasticity of the particles during heat curing. It is considered that sufficient adhesion strength can be obtained because the particles are relaxed and maintain their form after being cured and are dispersed in the cured product.

The present invention 1 comprises (A) a thermosetting resin,
(B) a curing agent,
(C) thermoplastic resin particles, and (D) an inorganic filler,
The thermoplastic resin of (C) has a glass transition point (Tg) of 30 ° C. or lower and a melting point (Tm) of 160 ° C. or lower,
And (C) is 0.5-9 mass parts to a total of 100 mass parts of (A)-(D).
The present invention relates to a resin composition for die attach.
The present invention 2 relates to the resin composition for die attach of the present invention 1, wherein the glass transition point of (C) is −60 to 30 ° C.
The present invention 3 relates to the resin composition for die attach of the present invention 1 or 2, wherein the melting point of (C) is 90 to 160 ° C.
This invention 4 is related with the resin composition for die attachment in any one of this invention 1-3 whose glass transition point of (C) is 0-30 degreeC, and melting | fusing point is 95-130 degreeC.
The present invention 5 relates to the resin composition for die attach according to any one of the present invention 1 to 4, wherein (C) is one or more selected from the group consisting of polyester resin particles, polyolefin resin particles, and polyacetal resin particles. .
This invention 6 is related with the resin composition for die attach in any one of this invention 1-5 whose (C) is an average particle diameter of 8-50 micrometers.
This invention 7 is related with the resin composition for die attach in any one of this invention 1-6 in which (A) contains an epoxy resin.
The present invention 8 relates to the resin composition for die attach of the present invention 7, wherein (A) further contains a (meth) acrylic resin.
The present invention 9 relates to the resin composition for die attach according to the present invention 7 or 8, wherein (B) comprises a phenolic resin curing agent.
This invention 10 relates to the resin composition for die attachment in any one of this invention 1-9 whose (D) is 20-50 mass parts with respect to a total of 100 mass parts of (A)-(D). .
This invention 11 relates to the resin composition for die attach of any one of this invention 1-10 whose (D) is a silica.
This invention 12 relates to the semiconductor device which connected the board | substrate and the semiconductor element, or semiconductor elements using the resin composition for die attachment in any one of this invention 1-11.
This invention 13 arrange | positions the resin composition for die attach of any one of this invention 1-11 between a board | substrate and a semiconductor element, or semiconductor elements, and then from the same temperature as melting | fusing point of (C), (C) The present invention relates to a method for manufacturing a semiconductor device in which a resin composition for die attachment is heated to a temperature between 30 ° C. and a melting point, and a substrate and a semiconductor element or semiconductor elements are connected to each other.

  ADVANTAGE OF THE INVENTION According to this invention, it has favorable workability | operativity, sufficient adhesive strength is obtained after hardening, and the resin composition for die attach which can solve the problem of the curvature of the board | substrate etc. by hardening shrinkage, and this A semiconductor device using the resin composition for die attach and a method for manufacturing the semiconductor device are provided.

2 is a cross-sectional photograph of the cured product of Example 1. It is a result of the DMA measurement regarding Example 1 and Comparative Example 1.

  The composition of the present invention includes (A) a thermosetting resin. Examples of the thermosetting resin include an epoxy resin, a (meth) acrylic resin, and a cyanate resin, but are not particularly limited. From the viewpoint of adhesive strength, epoxy resin and (meth) acrylic resin are preferable, and using these in combination is sufficient in a wide temperature range during the use of the composition and / or in the semiconductor device manufacturing process after use. This is preferable from the viewpoint of securing strength.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin, polyfunctional tetrakis (hydroxyphenyl) ethane type or tris ( Hydroxyphenyl) methane type epoxy resin, biphenyl type epoxy resin, triphenolmethane type epoxy resin, polybutadiene type epoxy resin (epoxidized polybutadiene), naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, aminophenol type epoxy resin, silicone epoxy Examples thereof include resins. Polyglycidyl ester such as diglycidyl ether of bisphenol A ethylene oxide adduct, diglycidyl ether of bisphenol A propylene oxide adduct, reaction product of p-xylylene glycol and 1-chloro-2,3-epoxypropane, etc. are also used. be able to.

  Among them, a polybutadiene type epoxy resin is preferable from the viewpoint of ensuring the flexibility of the cured product, and the viscosity at 25 ° C. is 3 Pa · s or less from the viewpoint of ensuring the viscosity of the composition and the strength and flexibility of the cured product. Diglycidyl ether of bisphenol A propylene oxide adduct (BPA-PO type epoxy resin is preferred.

  A (meth) acrylic resin can be used as the thermosetting resin. The (meth) acrylic resin can be a compound having a (meth) acryloyl group in the molecule, and a (meth) acryloyl group reacts to form a three-dimensional network structure and can be cured. (Meth) acrylic resins 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, others Alkyl (meth) acrylate, cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (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, neopentyl glycol di (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 (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 (meta ) Acrylate, methoxy polyalkylene glycol mono (meth) acrylate, octoxy polyalkylene glycol mono (meth) acrylate, lauroxy polyalkylene glycol mono (meth) acrylate, stearoxy poly Lucylene glycol mono (meth) acrylate, allyloxypolyalkylene glycol mono (meth) acrylate, nonylphenoxy polyalkylene glycol mono (meth) acrylate, di (meth) acryloyloxymethyltricyclodecane, N- (meth) acryloyloxyethyl Maleimide, N- (meth) acryloyloxyethyl hexahydrophthalimide, and N- (meth) acryloyloxyethyl phthalimide may be mentioned. (Meth) acrylamides such as N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, 1,2-di (meth) acrylamide ethylene glycol can also be used. Vinyl compounds such as n-vinyl-2-pyrrolidone, styrene derivatives and α-methylstyrene derivatives can also be used.

  Furthermore, as the (meth) acrylic resin, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,2-cyclohexanediol mono (meth) acrylate, 1,3-cyclohexanediol mono (meth) acrylate, 1,4-cyclohexanediol mono (meth) acrylate 1,2-cyclohexanedimethanol mono (meth) acrylate, 1,3-cyclohexanedimethanol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1,2-cyclohex Diethanol mono (meth) acrylate, 1,3-cyclohexanediethanol mono (meth) acrylate, 1,4-cyclohexanediethanol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane mono Hydroxyl groups such as (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate, etc. (Meth) acrylates having a carboxy group obtained by reacting (meth) acrylates having these and (meth) acrylates having these hydroxyl groups with dicarboxylic acids or their derivatives. It is also possible to use rates. Examples of the dicarboxylic acid usable 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, poly (meth) acrylate can be used as the (meth) acrylic resin. The poly (meth) acrylate is preferably a copolymer of (meth) acrylic acid and (meth) acrylate, or a copolymer of (meth) acrylate having a hydroxyl group and (meth) acrylate having no polar group. .

  A maleimide resin can be used as the thermosetting resin. The maleimide resin is a compound containing one or more maleimide groups in one molecule, and can be cured by forming a three-dimensional network structure by reacting the maleimide group by heating. For example, N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimidophenoxy) phenyl ] A bismaleimide resin such as propane may be mentioned. More preferred maleimide resins 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, poly (meth) acrylate polyol is preferable, and an aromatic ring is formed. What does not contain is especially preferable. Since the maleimide group can react with an allyl group, the combined use with an allyl ester resin is also preferable. The allyl ester resin is preferably an aliphatic one, and particularly preferred is a compound obtained by transesterification of a cyclohexane diallyl ester and an aliphatic polyol.

  (A) preferably has a high glass transition point (Tg) of the cured product from the viewpoint of adhesive strength, and can be, for example, 30 ° C to 70 ° C.

  (A) may be used alone or in combination of two or more.

  The composition of the present invention contains (B) a curing agent. (B) can be appropriately selected depending on the type of (A). For example, when an epoxy resin is used as (A), a phenol resin-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent is used. Curing agents, hydrazide compounds, dicyandiamide and the like can be used.

  As the phenol resin-based curing agent, a known phenol resin can be used as a curing agent for an epoxy resin. For example, a resol type or novolac type phenol resin can be used, and an alkyl resole type, an alkyl novolak type, an aralkyl novolak type. Phenol resin, xylene resin, allylphenol resin, and the like. As a number average molecular weight, it is preferable that it is 220-1000, and 220-500 are more preferable. In the case of an alkylresole type or alkyl novolac type phenolic resin, the alkyl group can be one having 1 to 18 carbon atoms, such as ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl. The thing of 2-10 is preferable.

  As the acid anhydride curing agent, known acid anhydrides can be used as epoxy resin curing agents, such as phthalic anhydride, maleic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid dicarboxylic acid. Anhydrides, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and the like can be mentioned.

Amine-based curing agents include aliphatic amines and aromatic amines as well as imidazoles.
Examples of aliphatic amines include aliphatic polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, m-xylenediamine, and 2-methylpentamethylenediamine, isophoronediamine, and 1,3-bisamino. Cycloaliphatic polyamines such as methylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine And piperazine type polyamines such as Aromatic amines include diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), and polytetramethylene oxide-di-p-aminobenzoate. Can be mentioned. Tertiary amines such as tris (dimethylaminomethyl) phenol, benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undensen-7, and the like can also be used.

  Further, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2 -Imidazole compounds such as phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole can also be used.

  Modified imidazole-based curing agents can also be used, and examples include epoxy-imidazole adduct compounds and acrylate-imidazole adduct compounds. Examples of commercially available epoxy-imidazole adduct compounds include Amicure PN-23, Amicure PN-40 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Novacure HX-3721 (manufactured by Asahi Kasei E-Materials Co., Ltd.), Fuji Cure FX-1000 ( Fuji Chemical Industry Co., Ltd.). Examples of commercially available acrylate-imidazole adduct compounds include EH2021 (manufactured by ADEKA).

  For example, when a (meth) acrylic resin is used as (A), a thermal radical polymerization initiator can be used as (B).

  Specific examples of the thermal radical polymerization initiator 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-butylperoxy) ) Valerate, 2,2-bis (t-butylperoxy) butane, 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-butylcumyl 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, cinnamate peroxide, m-torr Ile peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di -Sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, α, α'-bis (neodecanoylper) Oxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexyl Peroxyneode Noate, 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-butyl peroxyisopropyl monocarbonate, t-butyl para Oxy-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. Is mentioned. These may be used alone or in combination of two or more.

  (B) can be appropriately selected depending on the type of (A). For example, when an epoxy resin is used as (A), the curing agent of (B) includes the number of epoxy groups of the epoxy resin, The number of functional groups in the curing agent can be an amount that is 1: 0.2 to 1: 0.6, and preferably an amount that is 1: 0.3 to 1: 0.5. The functional group in the curing agent is a phenolic hydroxyl group in the case of a phenol resin curing agent, an acid anhydride group in the case of an acid anhydride curing agent, an amino group in the case of an amine curing agent, or these Is a derivative. Moreover, when using (meth) acrylic resin as (A), a thermal radical polymerization initiator can use 0.05-1 mass part with respect to 100 mass parts of (meth) acrylic resin, Preferably 0.1 to 0.5 parts by mass.

  The composition of the present invention includes (C) thermoplastic resin particles. In (C), the thermoplastic resin has a glass transition point (Tg) of 30 ° C. or lower and a melting point (Tm) of 160 ° C. or lower. By using such a thermoplastic resin in the form of particles, an increase in viscosity due to blending is prevented, and the elastic modulus of (C) is remarkably lowered during heat curing, and the stress of curing shrinkage is relieved to warp the substrate and the like. In addition, after curing, the particle shape is maintained and is in a dispersed state, which is considered to provide sufficient adhesive strength.

  The glass transition point (Tg) of (C) is 30 ° C. or lower, and those of −60 to 30 ° C. can be used. The glass transition point (Tg) is preferably -30 to 30 ° C, more preferably 0 to 30 ° C.

  The melting point (Tm) of (C) is 160 ° C. or lower, and 90 to 160 ° C. can be used. The melting point (Tm) is preferably 95 to 140 ° C, more preferably 105 to 130 ° C.

  Here, the glass transition point (Tg) and the melting point (Tm) are values measured by differential scanning calorimetry (DSC) based on JIS K 7121, and the melting point (Tm) showed the top of the maximum endothermic peak. Let it be temperature.

  Examples of such thermoplastic resin particles include polyester resin particles represented by CAS numbers 25214-81-7 and 30580-17-7, polyolefin resin particles such as polyethylene and polypropylene, and polyacetal resin particles such as polyoxymethylene. It is done.

  The shape of the thermoplastic resin particles is not particularly limited, and examples thereof include a spherical shape, an indefinite shape, and a pulverized powder shape. The average particle diameter can be 8 to 50 μm, and is preferably 10 to 35 μm from the viewpoint of ensuring workability and preventing warpage of the substrate and the like. Here, the average particle diameter refers to a volume-based median diameter measured by a laser diffraction method.

  (C) may be used alone or in combination of two or more.

  The composition of the present invention includes (D) an inorganic filler. (D) may be an insulating filler or a conductive filler, and is preferably an insulating filler from the viewpoint of cost.

  The insulating filler is not particularly limited, and silica, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium oxide, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, silicic acid Examples include calcium, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, boron nitride and the like. Silica, alumina and aluminum nitride are preferred.

  When applied to a silicon chip, silica is particularly preferable because the hardness can be made lower than that of a silicon chip. As the silica, either crystalline silica or amorphous silica can be used, but amorphous silica is preferred. Moreover, although fused silica, fumed silica, pulverized silica or the like can be used, fused silica is preferred. Silica that has been surface-treated can also be used. Moreover, it is preferable that it is spherical from the point which can make a contact area small.

  The conductive filler is not particularly limited, and metal particles such as silver (Ag), gold (Au), copper (Cu), nickel (Ni), palladium (Pd), tin (Sn) and alloys thereof, gold, Examples thereof include inorganic fillers coated with silver and palladium, and silver or an alloy containing silver is preferable.

  The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, a flake shape, a needle shape, and an indefinite shape. From the viewpoint of workability, a spherical shape is preferable. The average particle size can be 0.05 to 10 μm, preferably 0.1 to 10 μm. Here, the average particle diameter refers to a volume-based median diameter measured by a laser diffraction method.

  (D) may be used alone or in combination of two or more.

  The composition of this invention contains 0.5-9 mass parts of (C) with respect to a total of 100 mass parts of (A)-(D). When the content of (C) is less than 0.5 parts by mass, stress relaxation due to curing shrinkage is insufficient, and the effect of suppressing warpage of the substrate and the like becomes insufficient. When the content of (C) is more than 9 parts by mass, the viscosity increases rapidly, workability deteriorates, and adhesive strength decreases. The content of (C) is preferably 1.5 to 8.5 parts by mass.

  The composition of this invention can contain (D) at 20-50 mass parts with respect to a total of 100 mass parts of (A)-(D). By blending (D) within this range, the elastic modulus at high temperature of the cured product is improved, and reliability is not impaired even when exposed to a high temperature process in the manufacture of a semiconductor device. The blending amount of (D) is preferably 25 to 45 parts by mass.

  The composition of the present invention comprises a coupling agent (for example, silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, sulfide silane, titanate coupling agent, aluminum coupling agent, etc.), Additives such as a colorant (e.g., carbon black), an antifoaming agent, a surfactant, a polymerization inhibitor, and an antioxidant can be contained as long as the effects of the present invention are not impaired. However, it is preferable that the composition of the present invention does not use a solvent in order to prevent generation of voids in the cured product.

  The method for producing the composition of the present invention is not particularly limited, and for example, it can be produced by premixing each component, kneading using a three roll, and then degassing under vacuum.

  From the viewpoint of workability, the composition of the present invention preferably has a viscosity of 1 to 50 Pa · s, more preferably 3 to 30 Pa · s. Here, the viscosity is a value measured at 25 ° C. and 5 rpm using a Brookfield HB viscometer. In addition, using a Brookfield HB viscometer at 25 ° C., TI (viscosity at 0.5 rpm / 5 viscosity), which is the ratio of the viscosity measured at 0.5 rpm to the viscosity measured at 5 rpm, From the point of workability at the time of dispensing application, it is preferably 2 to 8, more preferably 4 to 6.

  The composition of the present invention can be applied to a predetermined part of a substrate or a semiconductor element, and then the semiconductor element is mounted and heat-cured, whereby the substrate, the semiconductor element, and the semiconductor can be bonded and connected. The temperature of heat curing is usually 100 to 160 ° C., but can be changed as appropriate. In the composition of the present invention, since (C) is in the form of particles, an increase in the viscosity due to the compounding is suppressed in the composition, and at the time of heat curing, the elastic modulus of (C) decreases and the stress of curing shrinkage It is considered that the warpage of the substrate or the like is suppressed by relaxing and the shape of the particles is maintained after being cured and is in a dispersed state, so that sufficient adhesive strength is brought about.

  From the viewpoint of low warpage, the curing temperature is preferably lower, and can be set to, for example, 100 ° C to 130 ° C. Moreover, it is preferable that the temperature of heat-curing exists in the range of the temperature which is 30 degreeC higher than the melting point of (C) from the same temperature as the melting point of (C). By using such (C), the elastic modulus of (C) in the composition is significantly reduced by exposing it to a temperature equal to or higher than the melting point of (C) during heat curing, and the effects of the present invention are exhibited. Can be made. Heat curing is usually performed by raising the temperature to a predetermined temperature and holding at that temperature. In this case, this holding temperature is referred to as the temperature of heat curing.

  After bonding and connecting the substrate, the semiconductor, and the semiconductor, wire bonding is performed, and then the semiconductor device is manufactured by sealing.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this. Unless otherwise specified, the amount is shown in parts by mass.

The measurement of the characteristic in an Example is as follows.
(1) Average particle diameter of thermoplastic resin particles A volume-based median diameter measured by a laser diffraction method.
(2) Average particle diameter of inorganic filler The volume-based median diameter measured by a laser diffraction method.
(3) Glass transition point (Tg) and melting point (Tm)
This is a value obtained by differential scanning calorimetry (DSC) based on JIS K7121. The melting point is the temperature showing the maximum endothermic peak.
(4) Viscosity and TI value These are values measured at 25 rpm and 5 rpm using Brookfield HB type (Cone Plate CP51). The same measurement was performed at 0.5 rpm, and (viscosity at 0.5 rpm / 5 viscosity at 5 rpm) was calculated as the TI value.
(5) Warpage amount A composition of Examples and Comparative Examples was applied onto a P-BGA substrate, a 10 mm x 10 mm silicon chip was mounted, and the temperature was raised from room temperature to 130 ° C in 60 minutes. It was held for 30 minutes to cure. After curing, the warpage of the chip was measured with a surface roughness meter.
(6) Die shear strength On the P-BGA substrate, the compositions of Examples and Comparative Examples were applied, a 2 mm × 2 mm silicon chip was mounted thereon, and cured under the same temperature conditions as the warpage test. . After curing, the die shear strength was measured using a die shear tester manufactured by Dage.
(7) Cross-sectional photograph About Example 1, the cross-sectional photograph of the hardened | cured material hardened on the conditions of said (5) was image | photographed. The results are shown in FIG.
(8) DMA measurement The compositions of Example 1 and Comparative Example 1 were cured while sandwiched between glasses with a gap of 130 μm to obtain a coating film, which was processed into a size of 40 mm × 5 mm and used for DMA measurement. A test piece was obtained. Using a viscoelasticity measuring device (DMS6100, manufactured by Seiko Instruments Inc.), DMA measurement was performed under the conditions of measurement mode tension, temperature rising rate of 3 ° C./min, and measurement frequency of 10 Hz. The results are shown in FIG.

  The compositions of Examples and Comparative Examples were prepared by dispersing each component with a three-roll in the amount shown in Table 1 and then performing vacuum stirring for 30 to 60 minutes. The results of measuring the above (1) to (6) for the compositions of Examples and Comparative Examples are also shown in Table 1.

Each component used in Examples and Comparative Examples is as follows.
(A-1) Epoxy resin 1
Diglycidyl ether of bisphenol A propylene oxide adduct (BPA-PO 4000S, manufactured by ADEKA Corporation)
(A-2) Epoxy resin 2
Epoxidized polybutadiene (PB-3600, manufactured by Daicel Corporation)
(A-3) Epoxy resin 3
Reaction product of p-xylylene glycol and 1-chloro-2,3-epoxypropane (TX-0929A, Nippon Steel & Sumikin Chemical Co., Ltd.)
(A-4) (Meth) acrylic resin Neopentyl glycol dimethacrylate (B-1) Phenol-based curing agent Novolak type phenolic resin (MEH-8000H, manufactured by Meiwa Kasei Co., Ltd.)
(B-2) Modified imidazole-based curing agent Novacure HX-3721 (manufactured by Asahi Kasei E-Materials Corporation)
(B-3) Thermal radical polymerization initiator 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (C-1) polyester powder Polyester powder with CAS No. 25214-81-7 (Fix386, (Schaetti Switzerland), glass transition point 8 ° C., melting point 124 ° C., average particle size 20 μm
(C-2) Polyester powder Polyester powder with CAS number 25214-81-7 (Fix386, manufactured by Schaetti Switzerland), glass transition point 8 ° C., melting point 124 ° C., average particle size 42 μm
(C-3) Polyester powder Polyester powder with CAS number 30580-17-7 (Fix 3110, manufactured by Schaetti Switzerland), glass transition point 28 ° C., melting point 123 ° C., average particle size 21 μm
(C-4) Polyester solution (C-1) A solution obtained by thermally dissolving (150 ° C.) at a concentration of 8% by mass in the epoxy resin (A-1) (C-5) Polypropylene powder PPW-5 (Co., Ltd.) Made by Seishin Corporation) Glass transition point -19 ° C, melting point 153 ° C, average particle size 5μm
(C-6) Silicone powder KMP600 (manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 5 μm
(D-1) Silica filler SE1050 (manufactured by Admatechs), average particle size 0.3 μm
(E) Coupling agent 3-Glycidoxypropyltrimethoxysilane

  Each composition of the examples had low viscosity and excellent workability, sufficient adhesive strength was obtained after curing, and the amount of warpage was small. In particular, when the compositions of Examples 1 to 6 in which the melting point of the thermoplastic resin particles is 123 to 124 ° C. (within a range lower than the curing temperature (130 ° C.) by 10 ° C.), the effect of suppressing the warpage is excellent. It was. On the other hand, when the composition of Comparative Example 1 in which the thermoplastic resin particles were not blended was used, a large warp was observed.

  From FIG. 1, it was confirmed that in the cured product of Example 1, the thermoplastic resin particles maintained a particulate form. Moreover, from FIG. 2, it was confirmed that the result of DMA measurement for Example 1 was almost the same as the result of DMA measurement for Comparative Example 1 in which no thermoplastic resin particles were blended. From these results, when the composition of Example 1 is used, the stress is relieved by the elasticity of the thermoplastic resin particles at the time of heat curing, and the particle shape is maintained after the curing, so the amount of warpage is reduced. It is considered that sufficient adhesion can be secured without causing a change in the elastic modulus while decreasing.

  In addition, when the thermoplastic resin particles were blended as a solution, as shown in Comparative Example 2, the viscosity increased and a problem occurred in workability. Moreover, when the silicone powder which is a thermosetting resin particle was used, as shown by the comparative example 3, big curvature was seen. Further, even when a large amount of thermoplastic resin particles are blended, as shown in Comparative Example 4, the effect of suppressing the warping amount does not reach Example 3 within the range defined by the present invention. The adhesive strength was inferior to that of Example 3.

  ADVANTAGE OF THE INVENTION According to this invention, it has favorable workability | operativity, sufficient adhesive strength is obtained after hardening, and the resin composition for die attach which can solve the problem of the curvature of the board | substrate etc. by hardening shrinkage, and this A semiconductor device using the resin composition for die attach and a method for manufacturing the semiconductor device are provided.

Claims (13)

(A) thermosetting resin,
(B) a curing agent,
(C) thermoplastic resin particles, and (D) an inorganic filler,
(C) the thermoplastic resin has a glass transition point of 30 ° C. or lower and a melting point of 160 ° C. or lower;
And (C) is 0.5-9 mass parts to a total of 100 mass parts of (A)-(D).
Resin composition for die attach.   The resin composition for die attach according to claim 1, wherein the glass transition point of (C) is -60 to 30 ° C.   The resin composition for die attach according to claim 1 or 2, wherein the melting point of (C) is 90 to 160 ° C.   The resin composition for die attach according to any one of claims 1 to 3, wherein the glass transition point of (C) is 0 to 30 ° C and the melting point is 95 to 130 ° C.   The resin composition for die attach according to any one of claims 1 to 4, wherein (C) is at least one selected from the group consisting of polyester resin particles, polyolefin resin particles, and polyacetal resin particles.   The resin composition for die attach according to any one of claims 1 to 5, wherein (C) has an average particle diameter of 8 to 50 µm.   The resin composition for die attach according to any one of claims 1 to 6, wherein (A) comprises an epoxy resin.   The resin composition for die attach according to claim 7, wherein (A) further contains a (meth) acrylic resin.   The resin composition for die attach according to claim 7 or 8, wherein (B) contains a phenolic resin curing agent.   The resin composition for die attachment according to any one of claims 1 to 9, wherein (D) is 20 to 50 parts by mass with respect to 100 parts by mass in total of (A) to (D).   The resin composition for die attach according to any one of claims 1 to 10, wherein (D) is silica.   The semiconductor device which connected the board | substrate and the semiconductor element, or semiconductor elements using the resin composition for die attach of any one of Claims 1-11.   The resin composition for die attach according to any one of claims 1 to 11 is disposed between a substrate and a semiconductor element, or between semiconductor elements, and then from the same temperature as the melting point of (C) to the melting point of (C). The manufacturing method of the semiconductor device which heats to the temperature between the temperature which exceeds 30 degreeC, hardens the resin composition for die-attach, and connects a board | substrate and a semiconductor element or semiconductor elements.