KR20180113210A - Adhesive film and dicing / die bonding film - Google Patents

Abstract

The present invention relates to (a) an α-alumina filler comprising (a) an acrylic resin, (b) an epoxy resin, (c) a curing agent and (d) Wherein the content of the (a) alumina filler is 100 parts by mass based on the total amount of (a) the acrylic resin, (b) the epoxy resin, (c) the curing agent, and (d) And 60 to 95 parts by mass.

Description

Adhesive film and dicing / die bonding film

The present invention relates to an adhesive film and a dicing die-bonding film.

For example, there has been proposed a method of disposing a metal base through an adhesive on a lower portion of a die pad and a lead portion on which semiconductor elements are arranged, thereby enhancing the heat radiating effect of the package for a semiconductor device (for example, refer to Patent Document 1). However, since the thermal expansion rates of the metal base, the semiconductor element, the die pad, and the like are different from each other, there is a problem that the semiconductor element repeats the heat generation, and the metal base peels off and cracks occur.

As an adhesive film, for example, an adhesive film containing a high heat conductive particle or a thermally conductive filler is known (see, for example, Patent Documents 2 and 3).

Patent Document 1: JP-A-5-198701 Patent Document 2: JP-A-2009-235402 Patent Document 3: Japanese Patent Application Laid-Open No. 2014-68020

For example, the adhesive film used in the above applications is required to have excellent adhesiveness and thermal conductivity after heat curing.

However, the above-mentioned conventional adhesive films are not sufficient in terms of both adhesion and heat conductivity after heat curing.

Therefore, it is an object of the present invention to provide an adhesive film excellent in adhesiveness and thermal conductivity after heat curing.

Specific embodiments of the present invention are described below.

(A) an acrylic resin, (b) an epoxy resin, (c) a curing agent, and (d) an? -Alumina filler, wherein the? -Alumina filler (d) Wherein the content of the (a) alumina filler is 100 parts by mass based on the total amount of (a) the acrylic resin, (b) the epoxy resin, (c) the curing agent, and (d) 60 to 95 parts by mass, adhesive film.

[2] The adhesive film according to [1], wherein the average particle diameter (d ₅₀ ) of the α-alumina filler (d) is not more than ½ of the thickness of the adhesive film.

[3] The epoxy resin composition according to the above item (1), wherein the content of the α-alumina filler (d) is 60 to 90 parts by mass relative to the total amount of 100 parts by mass of the (a) acrylic resin, (b) epoxy resin, (c) The mass adhesive composition according to [1] or [2],

[4] The acrylic resin composition according to any one of [1] to [3], wherein the acrylic resin (a) is an acrylic copolymer containing an epoxy group and has a weight average molecular weight of 100000 or more and a glass transition temperature of -50 ° C. to 30 ° C. ≪ / RTI >

[5] The adhesive film according to any one of [1] to [4], wherein the thickness is 50 μm or less.

[6] A dicing die-bonding film comprising a dicing film and a die bonding film laminated on the dicing film, wherein the die bonding film is an adhesive film according to any one of [1] to [5] film.

According to the present invention, it is possible to provide an adhesive film excellent in adhesiveness and thermal conductivity after heat curing, and a dicing die-bonding film using the adhesive film.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[Adhesive film]

The adhesive film of the present embodiment comprises (a) an acrylic resin, (b) an epoxy resin, (c) a curing agent, and (d) an? -Alumina filler, wherein the? -Alumina filler (d) has a purity of 99.90% (A) an epoxy resin, (c) a curing agent, and (d) a-alumina filler, wherein the content of the (a) alumina filler is 100 Is 60 to 95 parts by mass with respect to parts by mass. The adhesive film of this embodiment is excellent in adhesiveness and thermal conductivity after heat curing. In addition, the adhesive film of the present embodiment may be excellent in laminating property and also have a small surface roughness.

Patent Document 2 discloses that an adhesive film is obtained by applying pressure in a thickness direction to a primary film formed using a varnish. On the other hand, according to the adhesive film of the present embodiment, a step of applying a pressure in the thickness direction to the primary film is not necessarily required.

[(a) Acrylic resin]

The acrylic resin (hereinafter sometimes referred to as " component (a) ") according to the present embodiment may be an acrylic polymer having a structural unit derived from one kind of monomer and may be an acrylic polymer having two or more kinds of monomers Or an acrylic copolymer having a structural unit. As the acrylic copolymer, for example, acrylic rubber can be mentioned. As the acrylic rubber, for example, a copolymer of acrylonitrile and at least one kind selected from an acrylate ester and a methacrylate ester can be given. The component (a) may be used alone or in combination of two or more.

The component (a) may have a reactive group (functional group) from the viewpoints of adhesiveness, heat resistance, and moisture absorption after heat curing.

Examples of the reactive group include a carboxy group, an amino group, a hydroxyl group and an epoxy group.

The acrylic resin having a reactive group can be produced, for example, by polymerizing the monomer having the reactive group (glycidyl acrylate, glycidyl methacrylate, etc.) in such a manner that the reactive group remains in the polymerization reaction for obtaining the acrylic polymer, By introducing a reactive group to the acrylic polymer.

From the viewpoint that the gelation in the varnish state is easily reduced and the reactive group has an epoxy contribution from the standpoint that the increase in the degree of curing in the B-stage state and the decrease in the adhesion due to the increase in the degree of curing are unlikely to occur. That is, the component (a) may be an acrylic resin having an epoxy group.

The reason why the effect is exhibited when the reactive group is an epoxy group is presumed as follows.

When the reactive group is, for example, a carboxyl group, the cross-linking reaction tends to proceed, and gelation in the varnish state and increase in the degree of curing in the B-stage state may occur. On the other hand, when the reactive group is an epoxy group, a crosslinking reaction hardly occurs, and gelation in the varnish state and increase in the degree of curing in the B-stage state are unlikely to occur.

Examples of the acrylic resin having an epoxy group include an acrylic resin having a structural unit derived from at least one selected from glycidyl acrylate and glycidyl methacrylate.

The component (a) is preferably a structural unit derived from glycidyl acrylate or glycidyl methacrylate in an amount of, for example, 0.5 (based on the total mass of the component (a)) from the viewpoint of improvement in adhesiveness and heat resistance By mass or more, and 2% by mass or more. The component (a) is preferably a structural unit derived from glycidyl acrylate or glycidyl methacrylate in an amount of, for example, 6 mass% or less based on the total mass of the component (a) from the viewpoint of reducing gelation May be included. From these viewpoints, the component (a) is preferably a copolymer obtained by copolymerizing a structural unit derived from glycidyl acrylate or glycidyl methacrylate with, for example, 0.5 to 6% by mass, based on the total mass of the component (a) , And may contain 2 to 6% by mass.

The component (a) is, for example, at least one member selected from the group consisting of alkyl acrylates having an alkyl group having 1 to 8 carbon atoms, alkyl methacrylates having an alkyl group having 1 to 8 carbon atoms, styrene and acrylonitrile And may contain a structural unit. Examples of the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate and butyl acrylate. Examples of the alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms include methyl methacrylate, ethyl methacrylate and butyl methacrylate. Among them, from the viewpoint of adhesiveness, the component (a) may contain a structural unit derived from ethyl (meth) acrylate and / or a structural unit derived from butyl (meth) acrylate. Herein, in the present specification, "(meth) acrylate" means "acrylate" or the corresponding "methacrylate".

When the component (a) is an acrylic copolymer, the copolymerization ratio of the respective monomers may be adjusted in consideration of the glass transition temperature (hereinafter referred to as " Tg "

The polymerization method for the production of the component (a) is not particularly limited, and examples thereof include pearl polymerization and solution polymerization.

The Tg of the component (a) is preferably -50 占 폚 or higher, and may be -10 占 폚 or higher, for example, from the viewpoint that the tackiness of the adhesive film in the B- The Tg of the component (a) may be, for example, from -50 캜 to 30 캜 or from -10 캜 to 30 캜, from the viewpoint of improving the adhesiveness and heat resistance.

The weight average molecular weight of the component (a) may be 100000 or more from the viewpoint of improvement in adhesiveness and heat resistance.

In the present specification, the weight average molecular weight (Mw) is a polystyrene conversion value measured using a calibration curve by standard polystyrene, as measured by gel permeation chromatography (GPC).

The weight average molecular weight of the component (a) may be, for example, 300000 or more and 500000 or more, from the viewpoint that strength and flexibility are not easily deteriorated and the toughness is unlikely to increase. The weight average molecular weight of the component (a) may be, for example, not more than 3,000,000 or not more than 2,000,000 from the viewpoint of high flow property and excellent circuit packing property of the wiring. From these viewpoints, the weight average molecular weight of the component (a) is preferably 300000 to 3000000, more preferably 500000 to 2000000.

The component (a) is an acrylic resin having a reactive group, preferably has a weight average molecular weight of 100000 or more, is an acrylic copolymer (epoxy group-containing acrylic copolymer) containing an epoxy group, and has a weight average molecular weight of 100000 or more More preferably an epoxy group-containing acrylic copolymer, and has a weight average molecular weight of 100,000 or more, and further preferably has a glass transition temperature of -50 ° C to 30 ° C.

From the viewpoint of improving the adhesiveness and heat resistance, the component (a) contains 0.5 to 6% by mass of a structural unit derived from glycidyl acrylate or glycidyl methacrylate as a reactive group, and has a Tg of -50 Deg.] C to 30 deg. C and a weight average molecular weight of 100000 or more.

Examples of acrylic copolymers containing 0.5 to 6 mass% of structural units derived from glycidyl acrylate or glycidyl methacrylate and having a Tg of -10 ° C to 30 ° C and a weight average molecular weight of 100000 or more include HTR -860P-3 (trade name, manufactured by Nagase ChemteX Corporation).

[(b) Epoxy resin]

The epoxy resin (b) (hereinafter sometimes referred to as " component (b) ") according to this embodiment exhibits an adhesive action by curing, for example.

From the viewpoint of heat resistance, the component (b) is preferably an epoxy resin having two or more functional groups (an epoxy resin of a mosaic or more).

The weight average molecular weight of the component (b) may be, for example, less than 5000, less than 3000, or less than 2000 from the viewpoint of heat resistance.

Examples of the component (b) include a functional epoxy resin such as a bisphenol A type epoxy resin and a bisphenol F type epoxy resin; Novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; Polyfunctional epoxy resins; Amine type epoxy resin; A heterocyclic ring containing epoxy resin; And alicyclic epoxy resins. As the component (b), generally known epoxy resins other than the above may be used.

Examples of the commercially available bisphenol A type epoxy resin include Epikote 807, Epikote 815, Epikote 825, Epikote 827, Epikote 828, Epikote 834, Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1055 , Epicoat 1004, Epicoat 1004AF, Epicoat 1007, Epicoat 1009, Epicoat 1003F and Epicoat 1004F (trade names, manufactured by Mitsubishi Kagaku Kabushiki Kaisha); DER-663U, DER-663U, DER-662U, DER-672U, DER-672U, DER-663U, DER- 668, and DER-669 (all trade names, manufactured by Dow Chemical Company); And YD8125 (trade name, manufactured by Shinnitetsu Sekinigaku Kabushiki Kaisha).

Examples of commercially available bisphenol F type epoxy resins include YDF-2004 and YDF-8170C (trade name, manufactured by Shinnitetsu Sumikin Kagaku Kogyo Co., Ltd.).

Examples of commercially available phenol novolak type epoxy resins include Epikote 152 and Epikote 154 (trade names, manufactured by Mitsubishi Chemical Corporation); EPPN-201 (trade name, manufactured by Nippon Kayaku Co., Ltd.); And DEN-438 (trade name, manufactured by Dow Chemical Company).

As commercially available cresol novolak type epoxy resins, for example, Epikote 180S65 (Mitsubishi Kagaku Kogyo Co., Ltd.); Araldite ECN1273, Araldite ECN1280 and Araldite ECN1299 (all trade names, manufactured by Ciba Specialty Chemicals); YDCN-701, YDCN-702, YDCN-703, and YDCN-704 (trade names, manufactured by Shinnitetsu Sumikin Kagaku Kogyo Co., Ltd.); EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1020, EOCN-1025 and EOCN-1027 (trade names, manufactured by Nippon Kayaku Co., Ltd.); And ESCN-195X, ESCN-200L and ESCN-220 (trade names, manufactured by Sumitomo Chemical Co., Ltd.).

Examples of commercially available polyfunctional epoxy resins include Epon 1031S, Epicote 1032H60 and Epicote 157S70 (trade names, manufactured by Mitsubishi Kagaku Kogyo Co., Ltd.); Araldite 0163 (trade name, manufactured by Ciba Specialty Chemicals); Denacol EX-411, Denacol EX-411, Denacol EX-411, Denacol EX-511, EX-321 (trade name, manufactured by Nagase ChemteX Corporation); And EPPN501H and EPPN502H (manufactured by Nippon Kayaku Co., Ltd., trade name).

Commercially available amine type epoxy resins include, for example, Epikote 604 (Mitsubishi Kagaku Kogyo Co., Ltd.); YH-434 (trade name, manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.); TETRAD-X, and TETRAD-C (trade names, manufactured by Mitsubishi Gas Chemical Company, Ltd.); And ELM-120 (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

As the commercially available heterocyclic ring-containing epoxy resin, for example, Araldite PT810 (trade name, manufactured by Ciba Specialty Chemicals) can be mentioned.

Examples of commercially available alicyclic epoxy resins include ERL4234, ERL4299, ERL4221 and ERL4206 (trade names, manufactured by UCC, Inc.).

The component (b) may be used alone or in combination of two or more.

The component (b) may contain the above-mentioned functional epoxy resin and trifunctional or higher-functional epoxy resin from the viewpoint of heat resistance. When the component (b) contains the above-mentioned functional epoxy resin and a trifunctional or higher-functional epoxy resin, the content of the above-mentioned functional epoxy resin is preferably within a range from the viewpoint of increasing the Tg of the adhesive film after heat- May be, for example, 50 mass% or more and less than 100 mass% or 50 to 90 mass% based on the total mass of the resin. From the same viewpoint, the content of the trifunctional epoxy resin or more may be, for example, from more than 0 to 50 mass% or less and from 10 to 50 mass%, based on the total mass of the epoxy resin and the trifunctional or more epoxy resin.

[(c) Curing agent]

The curing agent (c) (hereinafter sometimes referred to as " component (c) ") according to this embodiment is not particularly limited as long as it can cure the component (b). Examples of the component (c) include polyfunctional phenol compounds, amine compounds, acid anhydrides, organic phosphorus compounds and their halides, polyamides, polysulfides, and boron trifluoride.

Examples of the polyfunctional phenol compound include monocyclic phenolic compounds and polycyclic polyfunctional phenolic compounds. Examples of monocyclic phenols include hydroquinone, resorcinol and catechol, and alkyl group substituents thereof. Examples of the phenolic compound to be subjected to polycyclic action include bisphenol A, bisphenol F, bisphenol S, naphthalene diol and biphenol, and alkyl group substituents thereof. The polyfunctional phenol compound may be, for example, a polycondensation product of at least one phenolic compound selected from the group consisting of the monocyclic active phenolic compound and the polycyclic functional phenolic compound, and an aldehyde compound. The polycondensate is, for example, a phenol resin. Examples of the phenol resin include phenol novolak resin, resol resin, bisphenol A novolak resin and cresol novolak resin.

Phenolite LF2882, phenolite LF2822, phenolite TD-2090, phenolite TD-2149, phenolite VH4150 and phenolite VH4170 (manufactured by DIC Co., Ltd., trade name, manufactured by DIC Corporation) Trade name).

The hydroxyl group equivalent of the phenol resin may be, for example, not less than 250 g / eq, not less than 200 g / eq, or not less than 150 g / eq from the viewpoints of adhesion and heat resistance. The phenolic resin as the component (c) is preferably a novolak type resin or a resole type resin from the viewpoint of improving the corrosion resistance during moisture absorption.

From the standpoint of improving the moisture resistance, the phenol resin preferably has a water absorption rate of not more than 2% by mass after being placed in a constant temperature and humidity bath at 85 캜 and 85% RH for 48 hours. The phenol resin as the component (c) preferably has a heating weight loss rate (temperature raising rate: 5 ° C / min, atmosphere: nitrogen) at 350 ° C measured by a thermogravimetric analyzer (TGA) of less than 5% by weight. When such a phenol resin is used as a curing agent, the volatile content is suppressed at the time of heat treatment or the like, whereby the reliability of various properties such as heat resistance and moisture resistance is enhanced, and the contamination of the device by volatilization during working such as heat processing is reduced I think it is possible.

Specific examples of the phenol resin include a compound represented by the following formula (I).

In formula (I), R ¹ represents a hydrogen atom, a straight chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group, an aralkyl group, an alkenyl group, Represents an integer of 1 to 3, and m represents an integer of 0 to 50. In formula (I), plural R ¹ and n may be the same or different from each other.

Examples of the compound represented by the formula (I) include Mirex XLC-series and X-XL series (manufactured by Mitsui Chemicals, Inc., trade name).

The compound represented by the formula (I) can be obtained, for example, by reacting a phenol compound and a xylylene compound in the presence of a non-catalyst or an acid catalyst (acidic catalyst). On the other hand, the xylylene compound can form a divalent linking group by the above reaction.

Examples of the phenol compound used in the preparation of the compound represented by the formula (I) include phenol compounds such as phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, Propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o- Butylphenol, p-isobutylphenol, octylphenol, nonylphenol, 2,4-xylenol, 2,6-xylenol, 3,5-xylenol, 2,4,6-trimethylphenol, Phenol, p-phenylphenol, p-cyclohexylphenol, o-allylphenol, p-allylphenol, o-benzylphenol, p- O-chlorophenol, o-bromophenol, p-bromophenol, o-iodophenol, p-iodophenol, o-fluorophenol, m-fluorophenol and p - < / RTI > fluorophenol. These phenolic compounds may be used singly or in combination of two or more.

From the viewpoints of adhesiveness, heat resistance, and moisture resistance, the phenol compound used in the production of the compound represented by the formula (I) is preferably phenol, o-cresol, m-cresol or p-cresol.

Examples of the xylylene compound used in the production of the compound represented by the formula (I) include xylylene dihalide and xylylene di glycol, and derivatives thereof.

Specific examples of the xylylene compound include α, α'-dichloro-p-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-o- Xylene, α, α'-dibromo-m-xylene, α, α'-dibromo-o-xylene, Xylylene,?,? '-Diiodo-o-xylene,?,?' - dihydroxy-p-xylene,?,? - dihydroxy- Xylylene, alpha, alpha '-dimethoxy-o-xylene, alpha, alpha' -dimethoxy-p-xylene, Xylylene,?,? '- di-n-propoxy-p-xylene,?,? - diethoxy- x'-n-propoxy-m-xylene,?,? '-di-n-propoxy-o-xylene, Xylylene,?,? '- di-n-butoxy-m-xylene,?,?' -Xylene,?,? '-Di-n-butoxy-o-xylene,? ,? '- diisobutoxy-p-xylene,?,?' -diisobutoxy-m-xylene,?,? '-diisobutoxy- xylene,?,? '- di-tert-butoxy-m-xylene and?,?' - di-tert-butoxy-o-xylene. The xylylene compound may be used singly or in combination of two or more.

From the viewpoint of producing a phenol resin having good adhesiveness, heat resistance and moisture resistance, the xylylene compound is preferably selected from the group consisting of α, α'-dichloro-p-xylene, α, α'-dichloro-m- ? -dihydroxy-o-xylene,?,? '- dihydroxy-o-xylene,?,?' ? -dimethoxy-p-xylene,?,? '-dimethoxy-m-xylene, or?,?' - dimethoxy-o-xylene.

Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid and polyphosphoric acid; Organic carboxylic acids such as dimethylsulfuric acid, diethylsulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and ethanesulfonic acid; Super-strong acids such as trifluoromethanesulfonic acid; Strongly acidic ion exchange resins such as alkane sulfonic acid type ion exchange resins; A super strong acidic ion exchange resin such as a perfluoroalkanesulfonic acid type ion exchange resin (for example, Nafion (trade name, Du Pont), trade name); Natural and synthetic zeolite compounds; And activated clay (e.g., acid clay).

The above reaction is carried out, for example, at a temperature of 50 to 250 캜 until substantially the raw material xylylene compound disappears and the reaction composition becomes constant.

The reaction time can be appropriately adjusted according to the raw material and the reaction temperature. The reaction time may be determined by, for example, GPC (gel permeation chromatography) while tracing the reaction composition. The reaction time may be, for example, about 1 hour to 15 hours.

When the reaction proceeds in the presence of an acid catalyst, water or an alcohol is usually produced.

On the other hand, for example, when a halogenooxylene derivative such as?,? '- dichloro-p-xylene is used as the xylylene compound, the reaction proceeds without generating a hydrogen halide gas while generating hydrogen gas. Do not.

The reaction molar ratio of the phenol compound to the xylylene compound is usually set to a condition in which the phenol compound becomes excessive. In this case, the unreacted phenol compound is recovered after the reaction. The weight average molecular weight of the compound represented by the formula (I) is usually determined by the reaction molar ratio of the phenolic compound and the xylylene compound. The excess of the phenol compound tends to lower the weight average molecular weight of the compound represented by the formula (I).

The phenolic resin may have, for example, an allylphenol skeleton. The phenol resin having an allylphenol skeleton can be obtained by a method in which a phenol resin is produced by, for example, preparing a phenol resin which is not allylated, reacting the phenol resin with an allyl halide, and allylizing the allyl halide via allyl ether Can be obtained.

Examples of the amine compound as the component (c) include aliphatic or aromatic primary amines, secondary amines, tertiary amines, quaternary ammonium salts; Aliphatic cyclic amine compounds; Guanidine compounds; And urea derivatives.

Specific examples of the amine compound include N, N-benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.4.0] But are not limited to, hexamethylenetetramine, hexamethylenetetramine, pyridine, picoline, piperidine, pyrrolidine, dimethylcyclohexylamine, dimethylhexylamine, cyclohexylamine, diisobutylamine, di- N-propylamine, tri-n-octylamine, tri-n-butylamine, triphenylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, triethylene Tetramine, diaminodiphenylmethane, diaminodiphenyl ether, dicyandiamide, tolylbiguanide, guanyl ether and dimethyl ether. The. Examples of the amine compound include dihydrazide compounds such as adipic acid dihydrazide; Guanamine; Melamine acid; An addition compound of an epoxy compound and a dialkylamine compound; An additional compound of amine and thiourea; And an addition compound of amine and isocyanate. These amine compounds may have, for example, an adduct-type structure in view of reducing the activity at room temperature.

Examples of the acid anhydride as the component (c) include phthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride and benzophenonetetracarboxylic acid dianhydride.

The organic phosphorus compound as the component (c) is not particularly limited as long as it is a phosphorus compound having an organic group. Examples of the organic phosphorus compound include hexamethylphosphoric acid triamide, phosphoric acid tri (dichloropropyl), phosphoric acid tri (chloropropyl), triphenyl phosphite, trimethyl phosphate, phenylphosphonic acid, triphenylphosphine, tri- Pin and diphenylphosphine.

The component (c) may be used singly or in combination of two or more.

[(d)? -alumina filler]

(D1) a polylactic a-alumina filler having a purity of at least 99.90% by mass (hereinafter occasionally referred to as (d1)), Component "). On the other hand, in the present specification, a polyhedron means a three-dimensional body having a plurality of planes as constituent parts of the surface. The plurality of existing planes may intersect each other through a curved surface. The polyhedron may have, for example, 4 to 100 planes as constituent parts of the surface.

The component (d) may further contain an? -alumina filler other than the component (d1) (e.g., a spherical? -alumina filler). In this case, the content of the component (d1) in the component (d) may be, for example, not less than 50 mass%, not less than 70 mass%, not less than 80 mass% . The component (d) may be, for example, an embodiment comprising the component (d1), that is, the component (d) may be the component (d1).

The average particle diameter (d ₅₀ ) of the component (d) is preferably 1/2 or less of the thickness of the adhesive film, more preferably 1/3 or less of the thickness of the adhesive film from the viewpoint of further improving the adhesive strength, / 4 or less. The average particle diameter (d ₅₀ ) of the component (d) may be, for example, 1/1000 or more of the thickness of the adhesive film, 1/500 or more, or 1/100 or more.

The average particle diameter (d ₉₀ ) of the component (d) is preferably 1/2 or less of the thickness of the adhesive film, more preferably 1/3 or less of the thickness of the adhesive film from the viewpoint of further improving the adhesive strength, / 4 or less. The average particle diameter d ₉₀ of the component (d) may be, for example, 1/1000 or more of the thickness of the adhesive film, 1/500 or more, or 1/100 or more.

In the present specification, the average particle diameter (d ₅₀ ) refers to a particle diameter at which the integrated value of the particle size distribution corresponds to 50%, and the average particle diameter (d ₉₀ ) .

The component (d) may be a mixture of two or more? -alumina fillers having different average particle diameters (d ₅₀ ), for example. In this case, the average particle diameter (d ₅₀ ) and the average particle diameter (d ₉₀ ) of the mixture are preferably within the above-mentioned range.

(A), the component (b), the component (c) and the component (a) in the adhesive film of the present embodiment from the viewpoint of decreasing the elastic modulus and imparting flow property at the time of molding, based on the total mass of the component (d), for example, 3 mass% or more. The content of the component (a) is preferably such that the total mass of the component (a), the component (b), the component (c) and the component (d) For example, 40 mass% or less, 30 mass% or less, and 20 mass% or less. From these viewpoints, the content of the component (a) is preferably 3 to 40% by mass based on the total mass of the component (a), the component (b), the component (c) , More preferably from 3 to 30 mass%, further preferably from 3 to 20 mass%.

The content of the component (b) in the adhesive film of the present embodiment is, for example, not less than 3% by mass, based on the total mass of the component (a), the component (b), the component (c) . The content of the component (b) may be, for example, 40 mass% or less, 30 mass% or less based on the total mass of the component (a), the component (b), the component (c) , And 20 mass% or less. The content of the component (b) is, based on the total mass of the component (a), the component (b), the component (c) and the component (d), from the viewpoint of adhesiveness after heat curing, heat resistance, , 3 to 40% by mass, 3 to 30% by mass, and 3 to 20% by mass.

The content of the component (c) in the adhesive film of the present embodiment is not particularly limited as long as it can accelerate the curing reaction of the component (b), and the content of the epoxy group and the epoxy group The active group (hydroxyl group, amino group, acid anhydride group, phosphorus atom-containing group, etc.) in the reactionable component (c) may be in the range of 0.01 to 5.0 equivalents or 0.8 to 1.2 equivalents.

For example, when the component (c) is a phenol resin, the content of the component (c) in the adhesive film of the present embodiment is preferably such that the epoxy equivalent of the component (b) , 0.65 / 0.35 to 0.35 / 0.65, 0.60 / 0.30 to 0.30 / 0.60, and 0.55 (epoxy equivalent) / hydroxyl equivalent of phenolic resin (epoxy equivalent / hydroxyl equivalent) / 0.45 to 0.45 / 0.55.

As described above, the content of the component (d) in the adhesive film of the present embodiment is preferably 60 (parts by mass) to 100 parts by mass of the total amount of the component (a), the component To 95 parts by mass. The content of the component (d) is, for example, from 65 parts by mass to 100 parts by mass of the total amount of the component (a), the component (b), the component (c) and the component (d) from the viewpoint of further improving the thermal conductivity of the adhesive film Or more and 70 parts by mass or more. The content of the component (d) is preferably within a range of from 100 parts by mass to 100 parts by mass of the total amount of the component (a), the component (b), the component (c) and the component (d) from the viewpoint of improving the flexibility and adhesiveness of the adhesive film , Or 90 parts by mass or less. From these viewpoints, the content of the component (d) may be, for example, 60 to 90 mass per 100 parts by mass of the total amount of the component (a), the component (b), the component (c) 70 to 90 mass is also good.

[Other components]

The adhesive film of the present embodiment may contain components other than those described above. Examples of such components include a curing accelerator, a filler other than the component (d), a coupling agent, and an ion trapping agent.

(Hardening accelerator)

The curing accelerator is not particularly limited and includes, for example, an imidazole compound. Examples of the imidazole compound include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, Benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline , 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, Methylimidazoline, benzimidazole, 1-cyanoethylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate have. These curing accelerators may be used singly or in combination of two or more. Examples of commercial products of the imidazole compound include 2E4MZ, 2PZ-CN and 2PZ-CNS (both trade names, manufactured by Shikoku Chemical Industry Co., Ltd.).

In addition, from the viewpoint of prolonging the service life of the film, the curing accelerator may be a curing accelerator having latency. Examples of such a curing accelerator include an epoxy compound and an addition compound of an imidazole compound. From the viewpoint that the activity at room temperature is reduced, the curing accelerator may have an adduct-type structure.

The blending amount of the curing accelerator may be 5.0 mass% or less, for example, 3.0 mass% or less based on the total mass of the component (b) and the component (c) from the viewpoint of excellent storage stability, % Or less. The blending amount of the curing accelerator may be, for example, 0.02% by mass or more, more preferably 0.03% by mass or more, from the viewpoint of adhesion after heat curing, heat resistance, . From these viewpoints, the blending amount of the curing accelerator may be, for example, from 0 to 5.0% by mass, from 0.02 to 3.0% by mass, and from 0.03 to 3.0% by mass based on the total mass of the component (b) %.

(filler other than the component (d))

The adhesive film of the present embodiment may contain various fillers other than the component (d) for the purpose of improving handling properties of the film, adjusting the melt viscosity, imparting thixotropic properties, and improving moisture resistance. Examples of the material constituting the filler include alumina other than? -Alumina, aluminum nitride, hexagonal boron nitride, cubic boron nitride, silicon nitride, diamond, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate , Calcium oxide, magnesium oxide, aluminum borate whisker, crystalline silica, amorphous silica and antimony oxide. These may be used singly or in combination of two or more.

From the standpoint of improving the thermal conductivity, the material constituting the filler may be crystalline silica or amorphous silica. From the viewpoints of adjusting the melt viscosity and imparting thixotropic properties, the material constituting the filler is preferably selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, Amorphous silica may be used. From the standpoint of improving moisture resistance, the material constituting the filler may be silica, aluminum hydroxide, or antimony oxide.

When the adhesive film of the present embodiment contains a filler other than the component (d), the content of the filler other than the component (d) is, for example, 50 parts by mass or less based on 100 parts by mass of the total mass of the component Or may be 20 parts by mass or less, and may be 10 parts by mass or less.

(Coupling agent)

The adhesive film of the present embodiment may contain various coupling agents, for example, from the viewpoint of improving interfacial bonding between dissimilar materials. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent and an aluminum coupling agent.

The silane coupling agent is not particularly limited, and examples thereof include vinyl trichlorosilane, vinyltris (? -Methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane (Meth) acryloxypropylmethyldimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldimet Aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane,? - aminopropyltrimethoxysilane, N- aminopropyltrimethoxysilane,? -aminopropyltriethoxysilane, N-phenyl-? -aminopropyltrimethoxysilane,? -mercaptopropyltrimethoxysilane,? -mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane , 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, - (4,5-dihydro) imidazol-1-yl-propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, 3- Triethylsilane, methyldimethoxysilane, 3-chloropropyl-dimethoxysilane, 3-cyanopropyl-triethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyl But are not limited to, triethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, amyltrichlorosilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri (Methacryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, N -? - (N-vinylbenzylaminoethyl) -Aminopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride,? -Chloropropylmethyldichlorosilane,? -Chloropropylmethyldimethoxysilane,? -Chloropropylmethyldiethoxysilane , Trimethylsilylisocyanate, dimethylsilylisocyanate, methylsilyltriisocyanate, vinylsilyltriisocyanate, phenylsilyltriisocyanate, tetraisocyanate silane and ethoxysilane isocyanate. These may be used singly or in combination of two or more.

Examples of the titanium coupling agent include, but are not limited to, isopropyltri octanoyl titanate, isopropyl dimethacryloyl stearoyl titanate, isopropyltridodecyl benzene sulfonyl titanate, isopropyl isostearate Isopropyl tris (dioctylphosphate) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (n-aminoethyl) titanate, isopropyl tris (Ditridecylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate Dicumylphenyl oxyacetate titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranor Butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanacetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester , Titanium triethanolaminate, polyhydroxy titanium stearate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetraisobutyl orthotitanate, stearyl titanate, cresyltitanate (IV), diisopropyl-bis-triethanolaminotitanate, octylene glycol titanate, tetra-n-butyl acrylate, Butoxytitanium polymer, tri-n-butoxytitanium monostearate polymer, and tri-n-butoxytitanium monostearate. These may be used singly or in combination of two or more.

Examples of the aluminum-based coupling agent include, but are not limited to, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethyl acetoacetate) Mono-ethylacetoacetate, aluminum-di-iso-propoxide-mono-ethylacetoacetate, aluminum-di-n-butoxide- Aluminum chelate compounds such as < RTI ID = And aluminum alcoholates such as aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum sec-butylate and aluminum ethylate. These may be used singly or in combination of two or more.

From the viewpoint of adhesion and the like in the case of adhering to a Si wafer, the coupling agent is preferably a silane coupling agent.

When the adhesive film of the present embodiment contains a coupling agent, the content of the coupling agent is preferably 100 parts by mass or less per 100 parts by mass of the total mass of the component (a), the component (b) and the component (c) For example, 10 parts by mass or less, 0.1 to 5 parts by mass may be given, and 0.2 to 3 parts by mass may be given.

(Ion scavenger)

The adhesive film of the present embodiment may contain an ion trap agent, for example, from the standpoint of adsorbing ionic impurities and improving insulation reliability upon moisture absorption. The ion trapping agent includes, for example, an anticorrosive agent used for preventing copper from being ionized and eluted. Examples of the anti-freezing agent include a triazine thiol compound, a bisphenol-based reducing agent, and an inorganic ion adsorbing agent.

As a commercially available product of the antifouling agent containing a triazine thiol compound, for example, Zisunet DB (trade name, manufactured by Sankyo Kasei Kabushiki Kaisha) can be mentioned.

Examples of the bisphenol-based reducing agent include 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), and 4,4'- Butyl phenol). As a commercially available bisphenol-based reducing agent, for example, Yoshinox BB (trade name, a product of Yoshitomi Seiyaku Co., Ltd.) can be mentioned.

Examples of the inorganic ion adsorbent include a zirconium compound, an antimony bismuth compound, and a magnesium aluminum compound. Commercially available inorganic ion adsorbents include, for example, IXE (trade name, manufactured by Toagosei Co., Ltd.).

The content of the ion scavenger is preferably from 1 to 10 mass parts per 100 parts by mass of the total amount of the resin composition (for example, the varnish described below) used for forming the adhesive film from the viewpoint of the effect of the addition and the heat resistance and cost. It is also good.

The thickness of the adhesive film is not particularly limited. The thickness of the adhesive film may be, for example, 5 占 퐉 or more and 8 占 퐉 or more from the viewpoint of improving the stress relaxation effect and filling property. The thickness of the adhesive film may be, for example, 50 탆 or less and 40 탆 or less from the viewpoint of cost reduction. From these viewpoints, the thickness of the adhesive film may be, for example, 5 to 50 占 퐉, 5 to 40 占 퐉, or 8 to 40 占 퐉.

[Method of producing adhesive film]

The adhesive film of the present embodiment can be obtained by, for example, applying a varnish prepared by mixing the aforementioned components (a), (b), (c), (d) , A carrier film), and removing the solvent from the applied varnish.

There is no particular limitation on the solvent used when preparing the varnish. Examples of the solvent include methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol, dimethylacetamide, dimethylformamide, Lt; / RTI > and cyclohexanone. Among them, the solvent is preferably a high boiling solvent such as methyl ethyl ketone, dimethylacetamide, dimethylformamide, methylpyrrolidone, and cyclohexanone from the viewpoint of improving the film property. These solvents may be used singly or in combination of two or more kinds.

The content of the solvent in the varnish is not particularly limited. However, the content of the nonvolatile matter in the varnish is preferably from 1 to 10% by mass, based on the total mass of the varnish, from the viewpoint of reducing the amount of heat required for drying the varnish, For example, it may be 40 mass% or more and 50 mass% or more. The content of the nonvolatile matter in the varnish may be, for example, not more than 90% by mass based on the total mass of the varnish, from the viewpoint that the viscosity of the varnish is not excessively increased and defects of the coating film caused by the varnish are easily reduced , 80 mass% or less. From these viewpoints, the content of nonvolatile matter in the varnish is preferably 40 to 90 mass%, more preferably 50 to 80 mass%, based on the total mass of the varnish, for example.

The mixing of the respective components can be carried out, for example, by a grinder, a triple roll, a bead mill or a combination thereof. In addition, for example, by mixing a filler component and a low molecular weight substance in advance and then mixing a high molecular weight substance, the time required for mixing can be shortened. Further, it is preferable that the varnish is removed by vacuum degassing before the varnish is coated on the base film.

Subsequently, the prepared varnish is applied on a base film, and the solvent is removed, for example, by heating, whereby an adhesive film can be formed on the base film.

The heating conditions are not particularly limited as long as the adhesive film is not completely cured and the solvent can be removed. For example, the heating conditions can be appropriately adjusted depending on the components of the adhesive film and the type of solvent in the varnish. Typical heating conditions are, for example, 80 to 140 占 폚 for 5 to 60 minutes.

The adhesive film may be cured to about B stage by heating. The solvent remaining in the adhesive film is preferably 3 mass% or less, more preferably 1.5 mass% or less, based on the total mass of the adhesive film.

Examples of the base film include a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, a polyimide film, a polyethylene naphthalate film, a polyethersulfone film, Polyether amide imide film, polyamide film, and polyamide imide film.

The base film may be subjected to surface treatment such as primer application, UV treatment, corona discharge treatment, polishing treatment, etching treatment, and release treatment, if necessary.

Examples of commercially available products of the polyimide film include Capton (trade name, manufactured by Toray-DuPont Kabushiki Kaisha) and Apical (trade name, manufactured by Kaneka Corporation).

Commercially available products of the polyethylene terephthalate film include, for example, lumirror (trade name, manufactured by Toray-DuPont Kabushiki Kaisha) and Purex (trade name, manufactured by DAINIPPON INDUSTRIES, LTD.).

[Dicing / Die Bonding Film]

The adhesive film of this embodiment can be applied, for example, to a dicing / die-bonding film. Hereinafter, one embodiment of the dicing / die-bonding film will be described.

The dicing and die-bonding film of the present embodiment includes a dicing film and a die bonding film laminated on the dicing film. The dicing film is not particularly limited and may be suitably determined on the basis of knowledge of those skilled in the art, for example, in consideration of the use and the like. Examples of the dicing film include plastic films such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, and a polyimide film. The dicing film may be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment, and etching treatment, if necessary. The dicing film preferably has adhesiveness. Examples of the dicing film having adhesiveness include those obtained by imparting tackiness to the above-mentioned plastic film, and those obtained by forming a pressure-sensitive adhesive layer on one side of the above-mentioned plastic film. The pressure-sensitive adhesive layer is formed of, for example, a resin composition (pressure-sensitive adhesive layer-forming resin composition) containing a liquid component and a high molecular weight component and having a suitable tack strength. The dicing tape having the pressure-sensitive adhesive layer can be produced, for example, by applying a resin composition for forming a pressure-sensitive adhesive layer onto the above-described plastic film and drying the resin composition, or by applying a resin composition for forming a pressure- And then bonding the pressure-sensitive adhesive layer formed by the above method to the above-mentioned plastic film. The tack strength is set to a desired value, for example, by adjusting the ratio of the liquid component and the Tg of the high molecular weight component. The die bonding film is the above-described adhesive film of the present embodiment. The dicing film and the die bonding film may be in direct contact with each other or may be laminated through another layer such as an adhesive layer.

The method for producing the dicing and die-bonding film of the present embodiment is not particularly limited and can be suitably determined on the basis of knowledge of those skilled in the art. The dicing and die-bonding film of the present embodiment can be produced, for example, by using a dicing film in place of the base film in the method for producing the adhesive film. The dicing and die-bonding film of the present embodiment can also be produced by, for example, preparing the adhesive film of the present embodiment and the dicing film separately, and laminating them and integrating them.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

The following components were prepared.

(a) Acrylic resin component:

- Acrylic rubber containing epoxy group: HTR-860P-3 (trade name, weight average molecular weight 800000, Tg 12 ° C, manufactured by Nagase ChemteX Corporation)

(b) Epoxy resin component:

Bisphenol F type epoxy resin: YDF-8170C (trade name, epoxy equivalent: 156, manufactured by Shin-nettetsu Sumikin Kagaku KK)

Cresol novolak type epoxy resin: YDCN-703 (trade name, manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.)

(c) Curing Agent Component:

Phenol resin: XLC-LL (trade name, manufactured by Mitsui Chemicals, Inc.)

Filler Ingredients:

Polymorph α-alumina: Sumikorandam AA-3 (trade name, purity Al ₂ O ₃ ≥99.90%, average particle size: 2.7 to 3.6 μm, manufactured by Sumitomo Chemical Co., Ltd.)

Spherical a-alumina: alumina beads CB-P05 (trade name, purity Al ₂ O ₃ 99.89%, average particle diameter 4 μm) manufactured by Showa Denko K.K.)

Spherical alumina: DAW-05 (trade name, purity Al ₂ O ₃ > 99.8%, average particle diameter 5 μm) manufactured by Denka Co.,

Spherical alumina: DAW-03 (trade name, purity Al ₂ O ₃ > 99.8%, average particle diameter 4 μm) manufactured by DENKA KOGYO Co.,

Curing accelerator:

Cure Sol 2PZ-CN (trade name, manufactured by Shikoku Kasei Kogyo K.K.)

Coupling agent:

A-189 (trade name,? -Mercaptopropyltrimethoxysilane, manufactured by Nippon Unicar Co., Ltd.)

A-1160 (trade name,? -Ureidopropyltriethoxysilane, manufactured by Nippon Unicar Co., Ltd.)

(Example 1)

, 4.50 parts by mass of an epoxy group-containing acrylic rubber HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation), 4.00 parts by mass of a bisphenol F type epoxy resin YDF-8170C (trade name, manufactured by Shinnitetsu Sumikin Kagaku Kogyo Co., Ltd.) 1.00 parts by mass of a cresol novolak type epoxy resin YDCN-703 (trade name, manufactured by Shinnitetsu Sumikin Kagaku K.K.), 5.50 parts by mass of a phenol resin XLC-LL (trade name, available from Mitsui Kagaku Kogyo Co., Ltd.) , 0.01 part by mass of Sol 2PZ-CN (trade name, manufactured by Shikoku Chemicals Corporation), 0.04 parts by mass of coupling agent A-189 (trade name, manufactured by Nippon Unicar Co., Ltd.), and coupling agent A-1160 (trade name, available from Nippon Unicar Co., 0.08 part by mass), cyclohexanone was added so that the solid content was about 57%, and further, polyhedral alpha -alumina smicollane AA-3 (manufactured by Sumitomo Chemical Co., Ltd., Ltd., trade name) was added to 85.00 parts by mass to obtain a mixture.

To this mixture, zirconia beads of 1 mm? Having an equivalent mass as the total mass of the mixture were added, and the mixture was stirred twice at 600 rpm for 30 minutes using a bead mill. The zirconia beads were removed from the mixture after stirring by filtration to obtain a varnish.

The obtained varnish was applied to a polyethylene terephthalate film A31 (trade name, manufactured by DAIJIN Dupont Film Co., Ltd.) having a thickness of 38 mu m and subjected to a release treatment as a base film. The coated varnish was heated and dried at 120 캜 for 5 minutes to produce an adhesive film having a thickness of 25 탆 on the base film.

(Example 2)

An adhesive film was produced in the same manner as in Example 1 except that the amount of each component was changed to the amount shown in Table 1. On the other hand, the compounding amounts in Table 1 indicate parts by mass.

(Comparative Example 1)

An adhesive film was produced in the same manner as in Example 1 except that polyhedral a-alumina was changed to spherical a-alumina alumina beads CB-P05 (trade name, manufactured by Showa Denko K.K.).

(Comparative Example 2)

An adhesive film was produced in the same manner as in Example 1 except that polyhedral alpha -alumina was changed to spherical alumina DAW-05 (trade name, product of Denka Co., Ltd.).

(Comparative Example 3)

An adhesive film was produced in the same manner as in Example 1, except that polyhedral a-alumina was changed to spherical alumina DAW-03 (trade name, manufactured by Denka Kagaku Co., Ltd.).

(Comparative Example 4 and Comparative Example 5)

An adhesive film was produced in the same manner as in Example 1 except that the amount of each component was changed to the amount shown in Table 1.

[evaluation]

The obtained adhesive films were evaluated for thermal conductivity, surface roughness Ra, adhesive force and lamination property as follows.

(Thermal conductivity)

A plurality of adhesive films peeled from the base film were bonded to each other to produce a laminated film having a thickness of 100 μm or more and less than 600 μm. The obtained laminated film was cured at 110 ° C for 1 hour and at 170 ° C for 3 hours to obtain a cured film (cured product). The obtained cured film was cut into a size of 10 mm in width and 10 mm in length, and this was used as a sample for measurement.

The specific heat Cp (J / (g 占 폚)) and the specific gravity (g / cm3) of the measurement sample were measured by the following method.

Thermal diffusivity? (Mm 2 / s): The thermal diffusivity? At 25 占 폚 was measured using the laser flash method (manufactured by NETZSCH, LFA467HyperFlash (trade name)) with respect to the thickness direction of the adhesive film.

Specific heat Cp (J / (g 占 폚)): Measured at a temperature raising rate of 10 占 폚 / min and a temperature of 20 to 60 占 폚 using a DSC method (Perkin Elmer, DSC8500 Specific heat Cp was measured.

Specific gravity (g / cm 3): Specific gravity was measured using an electronic specific gravity meter SD-200L (trade name, manufactured by Mirage).

The obtained heat diffusion coefficient?, Specific heat Cp and specific gravity were introduced into the following formulas to calculate the thermal conductivity (W / m 占.).

Heat conductivity (W / m 占)) = thermal diffusivity? (Mm2 / s) 占 specific heat Cp (J / (g 占 폚) 占 specific gravity (g /

(Surface roughness Ra)

The adhesive film peeled off from the base film was bonded to a silicon wafer having a thickness of 300 mu m using a hot roll laminator (80 DEG C, 0.3 m / min, 0.3 MPa), and then cured at 110 DEG C for 1 hour and 170 DEG C for 3 hours To obtain a sample. The arithmetic mean roughness (Ra) in the range of 2.5 mm of the obtained sample was calculated using a fine shape measuring instrument Surfcorder ET200 (trade name, manufactured by Kosaka Kenshi Co., Ltd.).

(Adhesive force)

The adhesive film on the base film was bonded to a semiconductor chip (5 mm in length and width) using a hot roll laminator (80 캜, 0.3 m / min, 0.3 MPa). The adhesive film on the semiconductor chip was adhered to a 42-alloy substrate at 120 DEG C for 250 seconds at 5 DEG C for 5 seconds and then cured at 110 DEG C for 1 hour and 170 DEG C for 3 hours to obtain a sample. The shear strength of the obtained sample before and after the moisture absorption test was measured using a universal bond tester (Dage, Series 4000, trade name). The conditions of the moisture absorption test were 85 ° C / 85% RH and 48 hours.

The case where the shear strength is? 2.0 MPa is evaluated as "good" and the case where the shearing strength is 2.0 MPa is evaluated as "poor" to evaluate the adhesive strength.

(Laminated)

The laminate of the base film and the adhesive film was cut into a width of 10 mm. The adhesive film surface of the laminate was bonded to a silicon wafer having a thickness of 300 mu m with a hot-roll laminator (80 DEG C, 0.3 m / min, 0.3 MPa). Thereafter, the bonded adhesive film was peeled at an angle of 90 deg. And at a tensile rate of 50 mm / min in an atmosphere of 25 deg. C using a small tablet tester EZ-S Shimazu Seisakusho Co., Peel strength was measured. The laminate properties were evaluated as "good" when the 90 ° peel strength was 20 N / m or more and "poor" when the 90 ° peel strength was less than 20 N / m.

From the results shown in Table 1, it can be seen that the adhesive films of Examples 1 and 2 have a thermal conductivity of? 2 W / mK after thermosetting and excellent thermal conductivity after thermosetting. It can be seen that the adhesive films of Examples 1 and 2 are excellent in adhesive property (adhesive force) and lamination property, and also have small surface roughness.

Claims (6)

(a) an acrylic resin, (b) an epoxy resin, (c) a curing agent, and (d) an a-
The (a) -alumina filler (d) contains a polyhedral? -Alumina filler having a purity of 99.90% by mass or more,
Wherein the content of the α-alumina filler (d) is 60 to 95 parts by mass relative to 100 parts by mass of the total amount of (a) the acrylic resin, (b) the epoxy resin, (c) the curing agent, and (d) film. The adhesive film according to claim 1, wherein the (d) average particle diameter (d ₅₀ ) of the α-alumina filler is ½ or less of the thickness of the adhesive film. The positive photosensitive composition as claimed in claim 1 or 2, wherein the content of the? -Alumina filler (d) is 100 parts by mass of the total amount of the (a) acrylic resin, (b) epoxy resin, (c) 60 to 90 parts by mass relative to 100 parts by mass of the adhesive film. The acrylic resin composition according to any one of claims 1 to 3, wherein the acrylic resin (a) is an acrylic copolymer containing an epoxy group and has a weight average molecular weight of 100000 or more and a glass transition temperature of -50 ° C to 30 ° C Adhesive film. The adhesive film according to any one of claims 1 to 4, having a thickness of 50 m or less. A dicing film; and a die bonding film laminated on the dicing film,
Wherein the die-bonding film is the adhesive film according to any one of claims 1 to 5.