JP2006249415A5 - - Google Patents

Description

That is, the present invention is an acrylic ester and / or methacrylic ester having a side chain having 1 to 8 carbon atoms, which is an epoxy group, hydroxyl group, carboxyl group, amino group, hydroxyalkyl group, vinyl group, silanol group, isocyanate. A thermoplastic resin having at least one functional group selected from a group, a trifunctional epoxy resin, and a tetrafunctional epoxy resin , a reaction rate in DSC after heating is 70 to 100%, and 200 ° C. after heating It is an adhesive composition for a semiconductor device having at least one softening point in the above temperature range, and is an adhesive sheet for a semiconductor device, a substrate for semiconductor connection, and a semiconductor device using the same.

The adhesive composition of the present invention includes a thermoplastic resin and a thermosetting resin . Thermoplastic resins have functions such as adhesion, flexibility, relaxation of thermal stress, and improvement of insulation due to low water absorption, and thermosetting resins have heat resistance, insulation at high temperatures, chemical resistance, adhesion There is an effect of realizing a balance of physical properties such as the strength of the agent layer.

Examples of thermoplastic resins include acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene rubber-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEBS), and acrylic having 1 to 8 carbon side chains. Examples include acid and / or methacrylic acid ester resin (acrylic rubber), polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, polyurethane and the like. Moreover, these thermoplastic resins may have a functional group capable of reacting with a thermosetting resin described later. Specific examples include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a hydroxyalkyl group, an isocyanate group, a vinyl group, and a silanol group. These functional groups are preferable because the bond with the thermosetting resin becomes stronger and the heat resistance is improved. The adhesive composition for semiconductor devices of the present invention contains a copolymer having acrylic acid and / or methacrylic acid ester having a side chain having 1 to 8 carbon atoms as an essential copolymerization component . As a result , the heated adhesive composition can have a softening point in the temperature range of −65 to 50 ° C., and the adhesiveness with a material such as a wiring board layer, flexibility, and relaxation of thermal stress can be achieved. Ru excellent effect. Further, these copolymers have an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a hydroxyalkyl group, isocyanate group, vinyl group, at least one functional group selected from a silanol group. Further, in this case, it is more preferable to use a copolymer having a carboxyl group and / or a hydroxyl group as a functional group in combination with a copolymer having another functional group because the adhesiveness is improved. The functional group content is preferably 0.07 eq / kg or more and 0.7 eq / kg or less, more preferably 0.07 eq / kg or more and 0.45 eq / kg or less, and further preferably 0.07 eq / kg or more and 0.0. 14 eq / kg or less. Further, from the viewpoint of flexibility after heating for a long time, the weight average molecular weight (Mw) is preferably 300,000 or more, more preferably 500,000 or more, more preferably 1,000,000 or more, and still more preferably 1,200,000 or more. The glass transition temperature (Tg) is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, more preferably −20 ° C., and still more preferably −40 ° C. or lower. By setting it within this range, a composition having excellent flexibility after heating for a long time can be obtained. When two or more kinds of thermoplastic resins are used, it is sufficient that at least one of them satisfies this range. The weight average molecular weight was measured by GPC (gel permeation chromatography) method and calculated in terms of polystyrene. Tg was calculated by the DSC method. In addition, polyamide resin is also preferably used because of its good deterioration at high temperatures and good electrical characteristics. Various known polyamide resins can be used. In particular, it is preferable that the adhesive layer has flexibility and a dicarboxylic acid (so-called dimer acid) having a low water absorption carbon number of 36 as an essential component. Polyamide resin containing dimer acid is obtained by polycondensation of dimer acid and diamine according to a conventional method, and at this time, dicarboxylic acid other than dimer acid, azelaic acid, sebacic acid or the like is contained as a copolymer component. Also good. As the diamine, known ones such as ethylene diamine, hexamethylene diamine, and piperazine can be used, and two or more kinds may be mixed from the viewpoint of hygroscopicity and solubility.

The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, but bisphenol F, bisphenol A, bisphenol S, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, dicyclopentadienedixylenol, etc. Alicyclic epoxies such as diglycidyl ether, epoxidized phenol novolak, epoxidized cresol novolak, epoxidized trisphenylol methane, epoxidized tetraphenylol ethane, epoxidized metaxylene diamine, and cyclohexane epoxide. Among them, those having three or more epoxy groups in one molecule are preferably used in order to increase the crosslinking density of the adhesive composition and increase the softening point after heating. As these polyfunctional epoxy resins, orthocresol novolak type: specifically, E180H65 manufactured by JER (Japan Epoxy Resin Co., Ltd.), ESCN195 manufactured by Sumitomo Chemical Co., Ltd., EOCN1020 manufactured by Nippon Kayaku Co., Ltd., EOCN102S, 103S, 104S, etc., DPP novolac type: specifically J157 E157S65, etc., trishydroxyphenylmethane type: specifically Nippon Kayaku Co., Ltd. EPPN501H, JER E1032, etc., tetraphenylolethane type: specifically E1031S made by JER, dicyclopentadiene phenol type: Specifically, HP7200 made by DIC (Dainippon Ink Chemical Co., Ltd.), other polyfunctional epoxy resins having a naphthalene structure, ESN made by Nippon Steel Chemical Co., Ltd. , YL6241 made by JER with special skeleton, etc. Epoxy resins have been sales. Two or more of these epoxy resins may be used in combination. The adhesive composition for a semiconductor device of the present invention contains a trifunctional epoxy resin and a tetrafunctional epoxy resin . Thus, more easy to control the softening point, Ru can be suppressed softening point variation after prolonged high temperature exposure. Furthermore, it is effective to use a halogenated epoxy resin, particularly a brominated epoxy resin, for imparting flame retardancy. At this time, it is effective to use a mixed system with a non-brominated epoxy resin because the brominated epoxy resin alone can impart flame retardancy, but the heat resistance of the adhesive decreases greatly. Examples of brominated epoxy resins include copolymerized epoxy resins of tetrabromobisphenol A and bisphenol A, or brominated phenol novolac type epoxy resins such as “BREN” -S (manufactured by Nippon Kayaku Co., Ltd.). . These brominated epoxy resins may be used in combination of two or more in consideration of bromine content and epoxy equivalent. However, brominated epoxies and the like contain bromine, which is a barogen, and may have an adverse effect on the environment. Recently, epoxy resins that do not contain barogen, specifically phosphorous epoxy Many resins and nitrogen-containing epoxy resins are also used. These epoxy resins may be used for imparting flame retardancy.

Example 1-2 and Comparative Example 1-12
(Preparation of adhesive sheet for semiconductor devices)
Each inorganic filler listed in Tables 2-3 was mixed with toluene, and then ball milled to prepare a dispersion. To this dispersion, each thermoplastic resin, thermosetting resin, curing agent, curing accelerator, other additives, and an equal weight of methyl ethyl ketone to the dispersion were added so as to have the composition ratios shown in Tables 2 and 3, respectively. The mixture was stirred and mixed to prepare an adhesive solution. This adhesive solution was applied with a bar coater to a dry thickness required for a 38 μm-thick polyethylene terephthalate film with a silicone release agent (“Film Binner” GT manufactured by Fujimori Kogyo Co., Ltd.) It dried for minutes and bonded the protective film and produced the adhesive sheet for semiconductor devices of this invention. Each composition and characteristic are shown in Tables 2-3.

Claims (7)

Acrylic acid ester and / or methacrylic acid ester having a side chain having 1 to 8 carbon atoms, selected from an epoxy group, a hydroxyl group, a carboxyl group, an amino group, a hydroxyalkyl group, a vinyl group, a silanol group, and an isocyanate group It contains a thermoplastic resin having at least one kind of functional group, a trifunctional epoxy resin and a tetrafunctional epoxy resin , a reaction rate in DSC after heating is 70 to 100%, and after heating, in a temperature range of 200 ° C. or higher An adhesive composition for a semiconductor device having at least one softening point. The reaction rate in DSC after heating is 70 to 100%, and has at least one softening point in the temperature range of −65 ° C. or more and 50 ° C. or less and 200 ° C. or more and 300 ° C. or less after heating. The adhesive composition for a semiconductor device according to claim 1. The softening point A after heating at 150 ° C. for 2 hours and the softening point B after heating at 150 ° C. for 2 hours and further at 200 ° C. for 168 hours are B / A ≦ 1.5. Item 2. An adhesive composition for a semiconductor device according to Item 1. The adhesive composition for a semiconductor device according to claim 1 , wherein the thermoplastic resin has a glass transition temperature of 20 ° C or lower. An adhesive sheet for a semiconductor device comprising an adhesive layer comprising the adhesive composition for a semiconductor device according to any one of claims 1 to 4 and at least one peelable protective film layer. The board | substrate for semiconductor connection using the adhesive composition for semiconductor devices in any one of Claims 1-4 . A semiconductor device using the semiconductor connection substrate according to claim 6 .