JP5236134B2 - Adhesive composition, adhesive member, semiconductor mounting support member, semiconductor device, etc. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new adhesive composition having heat resistance, water vapor absorption resistance and reflow crack resistance. SOLUTION: This adhesive composition comprises (a) an epoxy resin, 100 wt.% of a mixture of a phenol resin represented by formula (1) (R1 is hydrogen, a 1-10C straight-chain or branched-chain alkyl, cyclic alkyl, aralkyl, alkenyl, OH, an aryl group or a halogen; l is an integer of 1-3; m is an integer of 0-50) (the equivalent ratio of epoxy equivalent of epoxy resin/hydroxy group of phenol resin is 0.70/0.30-0.30/0.70) and (b) 0-400 wt.% of an acrylic copolymer containing 0.5-6 wt.% of a reactive group-containing monomer and having >=100,000 weight- average molecular weight.

Description

  The present invention relates to an adhesive composition fraction, an adhesive film thereof, a semiconductor mounting wiring board provided with the adhesive film, a semiconductor device, and a manufacturing method thereof.

  In recent years, with the development of electronic devices, the mounting density of electronic components has increased, and a semiconductor package or semiconductor having a size substantially equivalent to a semiconductor chip size, such as a chip scale package or a chip size package (hereinafter abbreviated as CSP). New types of mounting methods, such as bare chip mounting, are beginning to be adopted.

  Reliability is one of the most important characteristics as a mounting board on which various electronic components such as semiconductor elements are mounted. Among them, the connection reliability against thermal fatigue is a very important item because it is directly related to the reliability of the equipment using the mounting substrate. As a cause of lowering the connection reliability, there is a thermal stress generated by using various materials having different thermal expansion coefficients. This is because the thermal expansion coefficient of the semiconductor element is as small as about 4 ppm / ° C, whereas the thermal expansion coefficient of the wiring board on which the electronic component is mounted is as large as 15 ppm / ° C or more, so that thermal distortion occurs due to thermal shock. The thermal strain is generated by the thermal strain.

  In a conventional substrate on which a semiconductor package having a lead frame such as QFP or SOP is mounted, the thermal stress is absorbed in the lead frame portion to maintain reliability. However, in bare chip mounting, a solder ball is used to connect a semiconductor chip electrode and a wiring board pad of the wiring board, or a small protrusion called a bump is formed and connected with a conductive paste, and thermal stress is reduced. The connection reliability was reduced by concentrating on this connection part. In order to disperse the thermal stress, it has been found that it is effective to inject a resin called underfill between the semiconductor element and the wiring board. However, this has increased the number of mounting steps and increased the cost. In addition, there is a method of connecting the electrode of the semiconductor element and the wiring pad of the wiring board using conventional wire bonding, but in order to protect the wire, the sealing material resin must be covered, and the mounting process is increased. .

  Since CSP can be packaged together with other electronic components, Table 1 on page 5 in the article “Surface of Fine-Pitch BGA (CSP) that has been put into practical use” published by Nikkan Kogyo Shimbun, Ltd. Various structures as shown in Fig. 1 have been proposed. Among them, a system using a tape or a carrier substrate for a wiring substrate called an interposer has been put into practical use. This includes the methods developed by Tessera and TI in the above table. Since these are connected to a wiring board called an interposer, the IEICE Technical Report CPM 96-121, ICD 96-160 (1996-12) “Development of Tape BGA Size CSP” and Sharp Technical Report No. 66 (1996-12) “Chip As shown in “Development of Size Package (Chip Size Package)”, it shows excellent connection reliability.

  It is preferable to use an adhesive member between these CSP semiconductor elements and a wiring board called an interposer so as to reduce the thermal stress caused by the respective thermal expansion differences. In addition, moisture resistance and high temperature durability are also required. Furthermore, a film-type adhesive member is required for ease of manufacturing process management.

  Film type adhesives are used in flexible printed wiring boards and the like, and a system mainly composed of acrylonitrile butadiene rubber is used.

  As a printed wiring board material having improved moisture resistance, there is an adhesive containing an acrylic resin, an epoxy resin, a polyisocyanate and an inorganic filler as disclosed in JP-A-60-243180. There are an acrylic resin, an epoxy resin, and an adhesive in which both terminals having a urethane bond in a molecule include a primary amine compound and an inorganic filler as disclosed in JP-A-138680.

  Many film-type adhesives are mainly composed of acrylonitrile butadiene rubber. However, there are drawbacks such as a large decrease in adhesive strength after long-time treatment at high temperatures and poor corrosion resistance. In particular, the deterioration was significant when the moisture resistance test was performed under severe conditions such as PCT (pressure cooker test) processing used in the reliability evaluation of semiconductor-related components.

  In the ones disclosed in JP-A-60-243180 and JP-A-61-138680, when the moisture resistance test was performed under severe conditions such as PCT treatment, the deterioration was large.

  When mounting a semiconductor element on a wiring board using an adhesive as a material related to these printed wiring boards, the difference in the thermal expansion coefficient between the semiconductor element and the wiring board called an interposer is large. could not. Moreover, when the moisture resistance test under severe conditions such as a temperature cycle test and PCT treatment was performed, the deterioration was so great that it could not be used.

Problems to be solved by the invention

  When a semiconductor element having a large difference in thermal expansion coefficient is mounted on a semiconductor mounting support member, an adhesive composition that can form an adhesive member having heat resistance and moisture resistance is particularly necessary. An object of the present invention is to provide an adhesive composition that can achieve such an object and is excellent in heat resistance, moisture resistance, and reflow crack resistance.

Means to solve the problem

  Accordingly, the present invention provides (a) an epoxy resin and a formula (1):

(Where
R ₁ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom,
1 represents an integer of 1 to 3, and m represents an integer of 0 to 50). 100% by weight of a phenol resin mixture represented by: and (b) 0.5 to 6% by weight of a reactive group 10 to 400% by weight of an acrylic copolymer containing a monomer and having a weight average molecular weight of 100,000 or more
It is related with the adhesive composition characterized by the peeling strength in 240 degreeC of the laminated cured material of this adhesive composition and a polyimide film being 50 N / m or more.

  The present invention is also an adhesive composition comprising 100 parts by weight of the component (a), 10 to 400% by weight of the component (b), and 1 to 50% by weight of an inorganic filler as the component (c). It is related with the adhesive composition characterized by the peeling strength in 240 degreeC of the laminated cured material of a composition and a polyimide film being 50 N / m or more.

  The adhesive composition of the present invention has an excellent moisture absorption resistance by using the low hygroscopic phenol resin represented by the formula (1), and forms an appropriate crosslinked structure using an acrylic copolymer containing a reactive group-containing monomer. Excellent reflow crack resistance and heat resistance by forming a clear sea-island structure after curing by using an acrylic copolymer that is incompatible with epoxy resin. It is an adhesive composition. Furthermore, the addition of an inorganic filler increases the high-temperature elastic modulus, increases the high-temperature peel strength, works to prevent reflow cracks, and provides an adhesive composition that is excellent in resistance to flow cracks.

  The present invention also relates to an adhesive member obtained by forming the adhesive composition of the present invention into a film shape, and a semiconductor mounting support member provided on a semiconductor element mounting surface of the support member.

  The present invention relates to a semiconductor device in which a semiconductor element and a support member are bonded through the bonding member of the present invention.

  The epoxy resin in the component (a) of the present invention is not particularly limited as long as it cures and exhibits an adhesive action. Bifunctional epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type A novolak type epoxy resin such as an epoxy resin or a cresol novolac type epoxy resin can be used, and other commonly known ones such as a polyfunctional epoxy resin and a heterocyclic ring-containing epoxy resin can be applied. . From the viewpoint of heat resistance, it is preferable that the softening point measured by a ring and ball system is 50 ° C. or higher. Examples of such epoxy resins include Epicoat 1001, 1002, 1003, 1055, 1004, 1004AF, 1007, 1009, 1003F, and 1004F manufactured by Yuka Shell Epoxy Co., Ltd. E. R. Bisphenol A type epoxy resins such as 661, 662, 663U, 664, 664U, 667, 642U, 672U, 673MF, 668, 669, etc., bisphenol F type epoxy resin such as YDF-2004 manufactured by Tohto Kasei Co., Ltd., Nippon Kayaku ( Phenol novolac type epoxy resin such as EPPN-201 manufactured by Eisai Co., Ltd., Epicoat 180S65 manufactured by Yuka Shell Epoxy Co., Ltd., Araldite ECN1273, 1280, 1299, YDCN-701, 702 manufactured by Toto Kasei 703, 704, Nippon Kayaku Co., Ltd. EOCN-1020, 102S, 103S, 104S, Sumitomo Chemical Co., Ltd. ESCN-195X, 200L, 220, etc. Cresol novolac epoxy resin, Yuka Shell Epoxy Co., Ltd. E on 1031S, Epikote 1032H60,157S70, manufactured by Nippon Kayaku Co., Ltd. EPPN 501H, polyfunctional epoxy resins such as 502H, manufactured by Ciba Specialty Chemicals Araldite PT810 such heterocycle-containing epoxy resins and the like.

  Formula (1) used in the present invention:

(Where
R ₁ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom,
1 represents an integer of 1 to 3, and m represents an integer of 0 to 50), as long as it matches the formula (I), there is no particular limitation, but from the viewpoint of moisture resistance It is preferable that the water absorption after introduction into a constant temperature and humidity chamber at 85 ° C. and 85% RH for 48 hours is 2% by weight or less. In addition, the heating weight reduction rate at 350 ° C. (temperature increase rate: 5 ° C./min, atmosphere: nitrogen) measured with a thermogravimetric analyzer (TGA) is less than 5% by weight. Suppressing volatile matter, etc., increase the reliability of various properties such as heat resistance and moisture resistance, and reduce contamination of equipment due to volatile matter during work such as heat processing ,preferable.

  The phenol resin of the present invention represented by the formula (1) can be obtained, for example, by reacting a phenol compound and a xylylene compound which is a divalent linking group in the presence of no catalyst or an acid catalyst. Typical examples of such a phenol resin include Millex XLC-series and XL series manufactured by Mitsui Chemicals.

  Examples of the phenol compound used in the production of the phenol resin of the formula (1) include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, on-propylphenol, m- n-propylphenol, pn-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, octylphenol, nonylphenol, 2,4-xylenol, 2,6-xylenol, 3,5-xylenol, 2,4,6-trimethylphenol, resorcin, catechol, hydro Non, 4-methoxyphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, p-cyclohexylphenol, o-allylphenol, p-allylphenol, o-benzylphenol, p-benzylphenol, o-chloro Examples include phenol, p-chlorophenol, o-bromophenol, p-bromophenol, o-iodophenol, p-iodophenol, o-fluorophenol, m-fluorophenol, p-fluorophenol and the like. These phenol compounds may be used alone or in combination of two or more. Particularly preferred are phenol, o-cresol, m-cresol, p-cresol and the like.

  As the xylylene compound which is a divalent linking group used for the production of the phenol resin of the formula (1), the following xylylene dihalide, xylylene glycol and derivatives thereof can be used. That is, α, α′-dichloro-p-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α, α′-dibromo-p-xylene, α, α ′ -Dibromo-m-xylene, α, α'-dibromo-o-xylene, α, α'-diiodo-p-xylene, α, α'-diiodo-m-xylene, α, α'-diiodo-o-xylene , Α, α′-dihydroxy-p-xylene, α, α′-dihydroxy-m-xylene, α, α′-dihydroxy-o-xylene, α, α′-dimethoxy-p-xylene, α, α′- Dimethoxy-m-xylene, α, α′-dimethoxy-o-xylene, α, α′-diethoxy-p-xylene, α, α′-diethoxy-m-xylene, α, α′-diethoxy-o-xylene, α, α′-di-n-propoxy-p-xylene, α, α′-n-propyl Poxy-m-xylene, α, α′-di-n-propoxy-o-xylene, α, α′-di-isopropoxy-p-xylene, α, α′-diisopropoxy-m-xylene, α, α'-diisopropoxy-o-xylene, α, α'-di-n-butoxy-p-xylene, α, α'-di-n-butoxy-m-xylene, α, α'-di-n- Butoxy-o-xylene, α, α′-diisobutoxy-p-xylene, α, α′-diisobutoxy-m-xylene, α, α′-diisobutoxy-o-xylene, α, α′-di-tert-butoxy- Examples thereof include p-xylene, α, α′-di-tert-butoxy-m-xylene, and α, α′-di-tert-butoxy-o-xylene. One of these may be used alone or in combination of two or more. Among these, α, α′-dichloro-p-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α, α′-dihydroxy-p-xylene, α, α'-dihydroxy-m-xylene, α, α'-dihydroxy-o-xylene, α, α'-dimethoxy-p-xylene, α, α'-dimethoxy-m-xylene, α, α'-dimethoxy-o -Xylene.

  When the above phenol compound and xylylene compound are reacted, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid and polyphosphoric acid; organic carboxylic acids such as dimethyl sulfuric acid, diethyl sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and ethanesulfonic acid Super strong acids such as trifluoromethane sulfonic acid; strongly acidic ion exchange resins such as alkane sulfonic acid type ion exchange resins; super strong acid ion exchange resins such as perfluoroalkane sulfonic acid type ion exchange resins; (Product name: Nafion, Nafion, manufactured by Du Pont); natural and synthetic zeolites; xylylene compounds that are substantially raw materials disappear at 50 to 250 ° C. using acidic catalysts such as activated clay (acid clay). The reaction is continued until the reaction composition becomes constant. Although the reaction time depends on the raw materials and the reaction temperature, it is generally about 1 to 15 hours. In practice, it may be determined while tracking the reaction composition by GPC (gel permeation chromatography) or the like. In exceptional cases, when a halogenoxylene derivative such as α, α′-dichloro-p-xylene is used, an acid catalyst is necessary because the reaction proceeds without a catalyst while generating a corresponding hydrogen halide gas. And not. In other cases, the reaction proceeds in the presence of an acid catalyst to produce the corresponding water or alcohol. In addition, the reaction molar ratio of a phenol compound and a xylylene compound usually uses a phenol compound excessively, and collect | recovers an unreacted phenol compound after reaction. At this time, the average molecular weight is determined by the amount of the phenol compound, and the phenol compound having a lower average molecular weight can be obtained as the phenol compound is more excessive. In addition, the phenol resin whose phenol compound part is allylphenol is obtained by, for example, producing a non-allylated phenol resin, reacting it with allyl halide, allyl ether, and then allylating by Claisen transition. Can do.

The blending amount of the epoxy resin in the component (a) of the present invention and the phenol resin of the formula (1) component is 0.70 in terms of the ratio of the number of epoxy groups and the number of hydroxyl groups, respectively, from the viewpoint of curability when used as an adhesive. /0.30 to 0.30 / 0.70, more preferably 0.65 / 0.35 to 0.35 / 0.65, and 0.60 / 0.40 to 0.00. 40 / 0.60 is more preferable, and 0.55 / 0.45 to 0.45 / 0.55 is particularly preferable.

  The component (b) of the present invention is an acrylic copolymer having a weight average molecular weight of 100,000 or more and containing 0.5 to 6% by weight of a reactive group-containing monomer. The reactive group of the present invention is a carboxylic acid group, amino group, hydroxyl group or epoxy group. The component (b) of the present invention is obtained by polymerization so that unreacted monomers remain in the polymerization reaction for obtaining the acrylic copolymer, or after the acrylic copolymer is obtained, the reactive group-containing monomer is added. Can also be obtained. The component (b) of the present invention is preferably such that the monomer having a reactive group is glycidyl acrylate or glycidyl methacrylate, and the acrylic copolymer having a weight average molecular weight of 100,000 or more is an epoxy group-containing acrylic copolymer. is there. The epoxy group-containing acrylic copolymer of the present invention is preferably one that is not “compatible” with the epoxy resin in the component (a) of the present invention.

  In the present invention, the compatibility of the resin was defined from the visible light (600 nm) transmittance of a film (50 μm) prepared from a varnish (component ratio = 1: 1) containing the epoxy resin and the acrylic copolymer. The transmittance of 50% or more was defined as “compatible”, and the transmittance of less than 50% was defined as “incompatible (not compatible)”. The epoxy group-containing acrylic copolymer of the present invention more preferably has a transmittance of less than 30%.

  The epoxy group-containing acrylic copolymer having a weight average molecular weight of 0.5 to 6% by weight containing glycidyl acrylate or glycidyl methacrylate is not particularly limited, and is HTR-860P-3 manufactured by Teikoku Chemical Industry Co., Ltd. Etc. can be used. The amount of glycidyl (meth) acrylate used as the functional group monomer is 2 to 6% by weight of the copolymer. If it is 2% by weight or less, the adhesive strength may be reduced, and if it is 6% by weight or more, gelation may occur. The balance can be ethyl (meth) acrylate, butyl (meth) acrylate or a mixture of both. The mixing ratio is usually determined in consideration of the glass transition temperature (hereinafter abbreviated as Tg) of the copolymer, and Tg is preferably −10 ° C. or higher. If Tg is less than −10 ° C., the tackiness of the adhesive layer in the B-stage state is increased, and the handleability may be deteriorated. Tg is preferably 100 ° C. or less, particularly preferably 50 ° C. or less, and further preferably 30 ° C. or less because strength, flexibility and tackiness in sheet form and film form may be lowered. The polymerization method for obtaining the copolymer of the present invention is not particularly limited, and pearl polymerization, solution polymerization and the like can be used.

  The weight average molecular weight of the epoxy group-containing acrylic copolymer is preferably 300,000 to 3,000,000, and more preferably 500,000 to 2,000,000. If the weight average molecular weight is less than 300,000, there is a possibility that the strength and flexibility in sheet form and film form will decrease and tackiness will increase. May be reduced. The compounding amount of the epoxy group-containing acrylic copolymer is 10 to 400% by weight. If the blending amount is less than 10% by weight, there is a tendency that the elastic modulus is reduced and the flowability suppressing effect at the time of molding tends to be small. In addition, the weight average molecular weight in this invention is measured by GPC method, and is calculated using the calibration curve by standard polystyrene.

  There is no restriction | limiting in particular as an inorganic filler of (c) component of this invention, For example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, Aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica, and the like can be used, and these can be used alone or in combination of two or more. In order to improve thermal conductivity, it is preferable that aluminum oxide, aluminum nitride, boron nitride, crystalline silica, amorphous silica or the like is contained. For the purpose of adjusting melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline silica, It is preferable that amorphous silica or the like is contained. The amount of the inorganic filler used is preferably 1 to 20 parts by volume with respect to 100 parts by volume of the adhesive composition. If it is less than 1 part by volume, the effect of addition is not sufficient, and if it exceeds 20 parts by volume, problems such as an increase in the storage elastic modulus of the adhesive layer, a decrease in adhesiveness, and a decrease in electrical properties due to residual voids may occur. is there. In the present invention, the volume part is calculated from the specific gravity of each material and the weight composition ratio of the adhesive. Further, the average particle size of the inorganic filler is preferably 0.005 μm to 0.1 μm, and when it is smaller than 0.005 μm or larger than 0.1 μm, the adhesiveness tends to decrease in any case.

  In addition to the components (a), (b) and (c), a curing accelerator can be further added to the adhesive composition of the present invention. There is no restriction | limiting in particular in a hardening accelerator, Various imidazoles can be used. Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like. Two or more kinds can be used in combination.

  The addition amount of the curing accelerator is preferably from 0.1 to 5% by weight, more preferably from 0.2 to 3% by weight, based on 100% by weight of the total amount of the epoxy resin and the phenol resin as the component (a). When the addition amount is 0.1% by weight or less, the curability tends to be inferior, and when it is 5% by weight or more, the storage stability tends to decrease.

  The storage elastic modulus of the cured adhesive obtained by curing the adhesive composition of the present invention is preferably 10 to 2000 MPa at 25 ° C., and more preferably a low elastic modulus of 3 to 50 MPa at 260 ° C. The storage elastic modulus was measured using a dynamic viscoelasticity measuring device (DVE-V4 manufactured by Rheology), applying a tensile load to the cured adhesive product at a frequency of 10 Hz and a heating rate of 5 to 10 ° C./min. The measurement was performed in a temperature dependence measurement mode in which measurement was performed from 50 ° C to 300 ° C. If the storage elastic modulus exceeds 2000 MPa at 25 ° C. and 50 MPa at 260 ° C., the effect of relieving the thermal stress generated by the difference in thermal expansion coefficient between the semiconductor element and the support member will be reduced, and peeling or cracking may occur. There is. Further, when the storage elastic modulus is less than 10 MPa at 25 ° C., the handling property of the adhesive and the thickness accuracy of the adhesive layer may be deteriorated, and when it is less than 3 MPa at 260 ° C., reflow cracks are likely to occur. is there.

  In addition, various coupling agents commonly used in the art can be added to the adhesive composition of the present invention in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and silane-based coupling agents are most preferable.

  There is no restriction | limiting in particular as a silane coupling agent, For example, vinyl silanes, such as vinyl trichlorosilane and vinyl tris ((beta) -methoxyethoxy) silane, methacryloylsilanes, such as (gamma) -methacryloxy propyl trimethoxysilane, (beta)-(3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and other epoxy group-containing silanes, N-β (aminoethyl) γ-aminopropyl Trimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- Aminopropyl Limethoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3-4,5-dihydroimidazole Aminosilanes such as 1-yl-propyltrimethoxysilane and amyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptosilanes such as 3-mercaptopropyl-methyldimethoxysilane, and 3-ureido Urea bond-containing silanes such as propyltriethoxysilane and 3-ureidopropyltrimethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate Isocyanates, isocyanate group-containing silanes such as phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate, 3-chloropropyl-methyldimethoxysilane, 3-chloropropyl-dimethoxysilane, 3-cyanopropyl-triethoxysilane, hexamethyl Disilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyl Triethoxysilane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilane Ryl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, etc. can be used, and one or more of these are used in combination. You can also

  The aluminum coupling agent is not particularly limited. For example, ethyl acetoacetate aluminum diisopropylate, aluminum toys (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethyl acetoacetate), Aluminum tris (acetylacetonate), aluminum = monoisopropoxymonooroxyethyl acetoacetate, aluminum-di-n-butoxide-mono-ethylacetoacetate, aluminum-di-iso-propoxide-mono-ethylacetoacetate, etc. Aluminum chelate compound, aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butylene , Can be used, such as aluminum alcoholates of aluminum ethylate and the like, may be used in combination one or more of them.

  The addition amount of the coupling agent is preferably 0.1 to 10% by weight with respect to the total 100% by weight of the resin, from the effect, heat resistance and cost.

  Furthermore, an ion scavenger can be added to the adhesive composition of the present invention in order to improve the insulation reliability during moisture absorption. As the ion scavenger, there is no particular limitation, and a compound known as a copper damage preventive agent to prevent copper from ionizing and dissolving, for example, a triazine thiol compound, a bisphenol-based reducing agent, etc. can be used. Inorganic ion adsorbents such as zirconium-based and antimony bismuth-based magnesium aluminum compounds can also be used.

  The addition amount of the ion scavenger is preferably 1 to 10% by weight from the viewpoint of the effect of addition, heat resistance, cost, and the like.

  The adhesive member of the present invention can be obtained by dissolving or dispersing the adhesive composition of the present invention in a solvent to form a varnish, applying the varnish on the support film, and then removing the solvent by heat treatment or the like.

  As the support film, a plastic film such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, or a polyimide film can be used. It can also be processed and used. The support film can be peeled off at the time of use and only the adhesive layer can be used, or it can be used together with the support film and removed later.

  The varnishing solvent is not particularly limited, but considering the volatility during film production, methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, xylene, butyl cellosolve, methanol, ethanol, It is preferable to use a solvent having a relatively low boiling point such as 2-methoxyethanol. For the purpose of improving the coating properties, a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone can be added.

  In the production of the varnish from the adhesive composition of the present invention, in consideration of the dispersibility of the inorganic filler, it is preferable to use a raking machine, a three-roll, a ball mill, a bead mill, etc., which are used in combination. You can also In addition, after mixing the inorganic filler and the low molecular weight material in advance, the mixing time can be shortened by blending the high molecular weight material. Further, after the varnish is formed, bubbles in the varnish can be removed by vacuum degassing or the like.

  As a method for applying the varnish to the support film, a known method can be used, and examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. .

  Although the thickness of an adhesive bond layer is not restrict | limited, 25-250 micrometers is preferable respectively. If it is thinner than 25 μm, the stress relaxation effect tends to be poor, and if it is thicker than 250 μm, it is not economical.

  Further, two or more adhesive layers in the adhesive member of the present invention can be bonded together in order to obtain a desired thickness. In this case, the bonding conditions are necessary so that the adhesive layers are peeled off.

  The adhesive layer in the adhesive member of the present invention can be used by adhering to both surfaces of the core material. The thickness of the core material is preferably in the range of 5 to 200 μm, but is not limited.

  Although there is no restriction | limiting in particular as a film used for a core material, Preferably, it is a heat resistant thermoplastic film, More preferably, it is a heat resistant thermoplastic film whose softening point temperature is 260 degreeC or more. When a heat-resistant thermoplastic film having a softening point temperature of less than 260 ° C. is used for the core material, the adhesive film may be peeled off at a high temperature such as solder reflow. Furthermore, heat-resistant thermoplastic film using liquid crystal polymer, polyamideimide, polyimide, polyetherimide, polyethersulfone, wholly aromatic polyester, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoro Propylene copolymers, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers and the like are preferably used. Moreover, a porous film can also be used for a heat resistant thermoplastic film for the elastic modulus reduction of an adhesive bond layer.

  The adhesive layer formed on both surfaces of the core material can be made into a varnish by dissolving or dispersing the adhesive composition in a solvent. The adhesive film can be formed on the heat resistant thermoplastic film by applying this varnish on the heat resistant thermoplastic film as the core material and heating to remove the solvent. As a coating method, the above-described methods can be used. By performing this process on both sides of the heat-resistant thermoplastic film, an adhesive member in which an adhesive layer is formed on both sides of the core material can be produced. In this case, it is preferable to protect the surface with a cover film so that the adhesive layers on both sides do not block each other. However, when blocking does not occur, it is preferable not to use a cover film for economic reasons, and no limitation is imposed.

  Further, an adhesive composition is dissolved or dispersed in a solvent to form a varnish, which is applied to the above support film and heated to remove the solvent, thereby forming an adhesive layer on the support film. An adhesive member in which an adhesive layer is formed on both surfaces of the core material can also be produced by bonding the adhesive layer to both surfaces of the core material. In this case, the support film can be used as a cover film.

  The semiconductor mounting support member of the present invention can be used without being limited to substrate materials such as a lead frame having a die pad, a ceramic substrate, and an organic substrate. As the ceramic substrate, an alumina substrate, an aluminum nitride substrate, or the like can be used. As an organic substrate, an FR-4 substrate in which an epoxy resin is impregnated in a glass cloth, a BT substrate in which a bismaleimide-triazine resin is impregnated, a polyimide film substrate using a polyimide film as a base material, or the like is used. Can do.

  The shape of the wiring may be any of single-sided wiring, double-sided wiring, and multilayer wiring, and may be provided with through-holes and non-through-holes that are electrically connected as necessary. Further, when the wiring appears on the outer surface of the semiconductor device, it is preferable to provide a protective resin layer.

  As a method of attaching the adhesive member to the support member, a method of cutting the adhesive member into a predetermined shape and thermocompression bonding the cut adhesive member to a desired position of the support member is generally limited. Not what you want.

  The structure of the semiconductor device of the present invention is a structure in which the electrode of the semiconductor element and the support member are connected by wire bonding, and the electrode of the semiconductor element and the support member are connected by inner lead bonding of tape automated bonding (TAB). However, the present invention is not limited to these structures and is effective in any case.

  As the semiconductor element, a general semiconductor element such as an IC, LSI, VLSI can be used.

  The thermal stress generated between the semiconductor element and the support member is significant when the area difference between the semiconductor element and the support member is small, but the semiconductor device of the present invention relieves the thermal stress by using a low elastic modulus adhesive member. To ensure reliability. These effects appear very effectively when the area of the semiconductor element is 70% or more of the area of the support member. In such a semiconductor device having a small area difference between the semiconductor element and the support member, the external connection terminals are often provided in an area.

  In addition, as a characteristic of the adhesive member of the present invention, the volatile matter from the adhesive layer is reduced in the heated step such as the step of thermocompression bonding the adhesive member to a desired position of the support member or the step of connecting by wire bonding. Can be suppressed.

  The wiring board used for the wiring board for a semiconductor mounting board of the present invention can be used without being limited to a substrate material such as a ceramic substrate or an organic substrate. As the ceramic substrate, an alumina substrate, an aluminum nitride substrate, or the like can be used. As an organic substrate, an FR-4 substrate in which an epoxy resin is impregnated in a glass cloth, a BT substrate in which a bismaleimide-triazine resin is impregnated, a polyimide film substrate using a polyimide film as a base material, or the like is used. Can do.

  The shape of the wiring may be any of single-sided wiring, double-sided wiring, and multilayer wiring, and may be provided with through-holes and non-through-holes that are electrically connected as necessary.

  Further, when the wiring appears on the outer surface of the semiconductor device, it is preferable to provide a protective resin layer.

  As a method of attaching the adhesive member to the wiring board, a method of cutting the adhesive member into a predetermined shape and thermocompression bonding the cut adhesive member to a desired position on the wiring board is generally limited. Not what you want.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

Example 1
YDCN-703 (trade name, manufactured by Toto Kasei Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent (unit: g / eq) 210) 55% by weight as an epoxy resin, and Mirex XLC-LL (manufactured by Mitsui Chemicals, Inc.) as a phenol resin Product name, phenol resin, hydroxyl group equivalent (unit: g / eq) 175, water absorption: 1.8%, heating weight reduction rate at 350 ° C .: 4%, 45% by weight, NUC A-1160 (Nihon Unicar ( Co., Ltd., trade name, γ-ureidopropyltriethoxysilane) 0.7% by weight, and as a filler Aerosil R972 (Nippon Aerosil Co., Ltd., trade name, silica, average particle size 0.016 μm) 10% by weight Further, cyclohexanone was added and mixed with stirring, and further kneaded for 90 minutes using a bead mill. 200% by weight of acrylic rubber HTR-860P-3 (trade name manufactured by Teikoku Chemical Industry Co., Ltd., weight average molecular weight 1 million) containing 2 to 6% by weight of glycidyl acrylate or glycidyl methacrylate, and Curazole 2PZ- as a curing accelerator CN (trade name, 1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd.) 0.5% by weight was vacuum degassed. An adhesive film provided with a carrier film by applying a varnish on a polyethylene terephthalate film having a thickness of 75 μm and drying by heating at 140 ° C. for 5 minutes to form a B-stage coating film having a thickness of 75 μm. Was made.

Example 2
Instead of using 55% by weight of YDCN-703 in Example 1 and using 51% by weight of Epon 1031S (trade name, polyfunctional epoxy resin, epoxy equivalent (unit: g / eq) 200, manufactured by Yuka Shell Epoxy Co., Ltd.) The same operation was performed to produce an adhesive film.

Example 3
Instead of 45% by weight of Millex XLC-LL of Example 1, Milex XLC-4L (trade name, phenol resin, hydroxyl equivalent (unit: g / eq) 169 manufactured by Mitsui Chemicals, Inc.), water absorption 1.6%, 350 The adhesive film was prepared in exactly the same manner except that 43% by weight was used.

Reference example 4
An adhesive film was prepared in the same manner as in Example 1 except that the filler Aerosil R972 was not added and the bead mill kneading was not performed.

Comparative Example 1
In place of 45% by weight of Millex XLC-LL of Example 1, Praiofen LF2882 (trade name, manufactured by Dainippon Ink and Chemicals, bisphenol A novolak resin, hydroxyl equivalent (unit: g / eq) 118, water absorption: 4.4 %, Heating weight reduction rate at 350 ° C. 18%) Except for using 37% by weight, the same operation was performed to prepare an adhesive film.

Comparative Example 2
Except that 60% by weight of Aerosil R972 of Example 1 was used, the same operation was performed to produce an adhesive film.

Comparative Example 3
The same as Example 1 except that Bis A type bifunctional epoxy resin (manufactured by Toto Kasei Kogyo Co., Ltd., YD8125) was used as the epoxy resin. A mixture varnish of epoxy resin and rubber was cast on a protective film and dried at 90 ° C. for 30 minutes to prepare a film (50 μm thickness). The visible light (600 nm) transmittance was 60%, which was compatible.

Comparative Example 4
Example 1 is the same as Example 1 except that a silica filler (ES-03 manufactured by Tokai Mineral Co., Ltd.) having an average particle diameter of 4 μm is used as the filler. The tensile modulus at 240 ° C. was 0.7 MPa.

Comparative Example 5
Example 1 is the same as Example 1 except that an acrylic copolymer (WS-023DR manufactured by Teikoku Chemical Industry Co., Ltd.) containing a monomer whose reactive group is OH is used. The tensile elastic modulus at 240 ° C. was 0.5 MPa.

[Peel strength measurement method]
A 50 μm polyimide film was bonded to both sides of the adhesive film with a hot roll laminator (80 ° C., 0.3 m / min, 0.3 MPa) and cured at 170 ° C. for 1 hour. The laminated cured product was cut into a width of 10 mm and used as an evaluation sample. Using a UTM-4-100 type Tensilon made by TOYO BALWIN, the value when peeled at a pulling speed of 50 mm / min at an angle of 180 ° C. was obtained. The value is a simple average of 3 samples.

[Measurement method of elastic modulus]
An adhesive film having an initial length (L) was prepared, and a constant load (W) was applied to the adhesive film, which was then placed in a constant temperature bath at 240 ° C. The elongation (ΔL) and the cross-sectional area (S) of the adhesive film after charging were determined, and the tensile elastic modulus (E ′) was calculated from the following formula.
E ′ = L · W / (ΔL · S)

[Reflow resistance test]
A wiring board using a semiconductor chip and a polyimide film having a thickness of 25 μm as a base material was attached to the adhesive film and cured to prepare a semiconductor device sample. According to JEDEC standard J-STD-020A, the semiconductor device sample was passed three times through an IR reflow furnace set at a maximum temperature of 245 ° C. or 265 ° C. on the sample surface. Cracks in the sample were observed visually and with an ultrasonic microscope. Table 1 shows the case where no cracks occurred, and the case where cracks occurred as x.

[Solder heat resistance test]
A polyimide film having a thickness of 50 μm was bonded to both surfaces of the obtained adhesive film using a hot roll laminator at a temperature of 80 ° C., a pressure of 0.3 MPa, and a speed of 0.3 m / min, and then cured at 170 ° C. for 1 hour. . Several 30 mm × 30 mm test pieces of this sample were prepared and examined for heat resistance. The evaluation method of heat resistance is that a sample left in an environment of 85 ° C./85% relative humidity for 48 hours in a hygroscopic solder heat test is floated in a solder bath at 240 ° C. to 280 ° C. and abnormalities such as blistering up to 120 seconds occur. I investigated. Table 1 shows the case where an abnormality was observed in all the samples as x, the case where a sample where an abnormality occurred and a sample where no abnormality was observed was indicated as Δ, and the case where no abnormality was observed in all samples was indicated as ◯.

[PCT resistance test]
The PCT resistance evaluation was performed by observing the peeling of the adhesive agent after 168 hours in an atmosphere (pressure cooker test: PCT treatment) at a temperature of 121 ° C., a humidity of 100%, and 2 atmospheres. Indicated.

From the said Table 1, the adhesive film of Examples 1-3 produced using the phenol resin of Formula (1) of this invention has the outstanding peel strength compared with the film of Comparative Examples 1-5 , It is apparent that semiconductor devices using these adhesive films have good moisture-absorbing solder heat resistance and PCT resistance.

Effect of the invention

  The adhesive composition of the present invention is an adhesive composition having moisture absorption resistance, reflow crack resistance, and heat resistance characteristics due to the above-described configuration, and further has a high temperature elastic modulus and high temperature peel strength due to the addition of an inorganic filler. As a result, it was possible to obtain an adhesive composition having an effect of preventing reflow cracks and having excellent resistance to flow cracks. Further, by using the adhesive composition of the present invention, an adhesive member having excellent heat resistance and PCT resistance can be produced, and a semiconductor device using these has high heat resistance and PCT resistance.

Claims (8)

(A) a mixture of an epoxy resin and a phenol resin,
(B) an acrylic copolymer, and (c) an adhesive composition containing an inorganic filler,
The epoxy resin blended in the component (a) is an epoxy resin having a softening point of 50 ° C. or higher,
The phenolic resin has the formula (1):
[Chemical 1]

(Wherein R ₁ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom; 3 represents an integer of 3 and m represents an integer of 0 to 50),
The ratio of the number of epoxy groups of the epoxy resin to the number of hydroxyl groups of the phenol resin is 0.70 / 0.30 to 0.30 / 0.70,
Wherein component (b), wherein in component (b), comprises a reactive group-containing monomer is 0.5 to 6% by weight of glycidyl acrylate or glycidyl methacrylate, Ru der weight average molecular weight of 100,000 or more, epoxy groups Containing acrylic copolymer ,
The average particle size of the component (c) is 0.005 μm to 0.1 μm,
The component (b) is 10 to 400% by weight relative to 100% by weight of the component (a),
The adhesive composition, wherein the component (c) is 1 to 20 parts by volume with respect to 100 parts by volume of the adhesive composition.
The adhesive composition according to claim 1, wherein the water absorption of the phenol resin in the component (a) is 2% by weight or less.
The adhesive composition according to claim 1, wherein the phenol resin in the component (a) has a heating weight reduction rate at 350 ° C. of less than 5% by weight.
Ratio of the number of hydroxyl groups the component (a) in the epoxy equivalent number and the phenol resin of the epoxy resin, 0. 65 /0.3 5 to 0.3 5/0. The adhesive composition according to any one of claims 1 to 3 , which is 65 .
The adhesive composition according to any one of claims 1 to 4, wherein the epoxy group-containing acrylic copolymer is incompatible with the epoxy resin in the component (a).
The adhesive member obtained by forming the adhesive composition of any one of Claims 1-5 in a film form.
A semiconductor mounting support member comprising the adhesive member according to claim 6 on a semiconductor element mounting surface of the support member.
A semiconductor device, wherein the semiconductor element and the support member are bonded via the bonding member according to claim 6 .