JP6889398B2 - Heat dissipation die bonding film and dicing die bonding film - Google Patents

Description

The present invention relates to a heat-dissipating die bonding film and a dicing die bonding film.

The semiconductor wafer on which the circuit pattern is formed is diced to a chip-shaped semiconductor element after adjusting the thickness by polishing the back surface as necessary (dicing step). Next, the semiconductor element is fixed to an adherend such as a lead frame with an adhesive (die bonding step), and then transferred to a bonding step. For example, a method has been proposed in which a metal base is arranged under an adhesive on a die pad on which a semiconductor element is placed and a lead portion to enhance the heat dissipation effect of a package for a semiconductor device (see, for example, Patent Document 1). ). On the other hand, as an adhesive film having thermal conductivity or heat dissipation, for example, an adhesive film containing high thermal conductive particles or a heat dissipation die bonding film containing a thermal conductive filler is known (for example, Patent Document 2 and See 3).

Japanese Unexamined Patent Publication No. 5-198701 JP-A-2009-235402 Japanese Unexamined Patent Publication No. 2014-68020

An object of the present invention is to provide a heat-dissipating die bonding film capable of efficiently manufacturing a semiconductor element and a dicing die bonding film provided with the heat-dissipating die bonding film.

The present invention is a heat-dissipating die bonding film having a thermal conductivity of 2 W / (m · K) or more, which contains two or more types of heat conductive fillers having different moth hardness, and the amount of wear of the blade in the dicing process. The present invention relates to a heat-dissipating dicing film having a temperature of 50 μm / m or less.

The present invention also relates to a heat-dissipating die-bonding film containing two or more types of thermally conductive fillers having different Mohs hardnesses and having a content of the thermally conductive fillers of 20 to 85% by mass.

The heat-dissipating die-bonding film may contain at least two types of thermally conductive fillers selected from the group consisting of alumina fillers, boron nitride fillers, aluminum nitride fillers and magnesium oxide fillers.

The alumina filler may contain an alumina filler having a purity of 99.0% by mass or more.

The boron nitride filler may contain a hexagonal boron nitride filler having a nitrogen purity of 95.0% by mass or more.

The density of the aluminum nitride filler may be ^{3 to 4 g / cm 3.}

The magnesium oxide filler may contain a magnesium oxide filler having a purity of 95.0% by mass or more.

The heat-dissipating die bonding film may further contain a high molecular weight component of either an acrylic resin or a phenoxy resin, an epoxy resin, and a curing agent.

In the heat-dissipating die bonding film, the total mass of the heat conductive filler may be 20 parts by mass or more with respect to 100 parts by mass of the total amount of the high molecular weight component, the epoxy resin, the curing agent and the heat conductive filler. Good.

The heat-dissipating die bonding film may contain an alumina filler and a boron nitride filler as the heat conductive filler, or may contain a boron nitride filler and an aluminum nitride filler, and nitrided. It may contain a boron filler and a magnesium oxide filler.

The present invention also relates to a dicing die bonding film comprising a dicing film and a dicing film laminated on the dicing film, wherein the dicing film is the heat-dissipating die bonding film.

According to the present invention, it is possible to provide a heat-dissipating die bonding film capable of efficiently manufacturing a semiconductor element and a dicing die bonding film including the heat-dissipating die bonding film.

It is sectional drawing which shows typically the dicing die bonding film which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings in some cases. However, the present invention is not limited to the following embodiments. As used herein, the term "(meth) acrylate" means "acrylate" or its corresponding "methacrylate".

[Heat-dissipating die bonding film]
The heat-dissipating die bonding film according to one embodiment is a heat-dissipating die bonding film having a thermal conductivity of 2 W / (m · K) or more, and contains two or more types of heat conductive fillers having different moth hardness. The amount of wear of the blade in the dicing step is 50 μm / m or less. According to such a heat-dissipating die bonding film, a semiconductor element can be efficiently manufactured.

In the present specification, the amount of wear of the blade in the dicing process is calculated according to the following procedure. After laminating the heat-dissipating die-bonding film on a dicing tape (base material thickness 80 μm, glue thickness 10 μm) at room temperature and integrating it, the surface on the heat-dissipating die-bonding film side is attached to an 8-inch wafer with a thickness of 50 μm with a laminator (TEIKOKU). , STM-1200FH (trade name)) is used for laminating at 70 ° C. Then, blade dicing is performed using a dicer (manufactured by DISCO, DFD6361 (trade name)). The conditions for blade dicing are: blade ZH05-SD4000-N1-70 BB (manufactured by Nanyo, (trade name)), wafer thickness 50 μm, chip size 3 mm × 3 mm, rotation speed 50,000 rpm, dicing tape notch 10 μm, cutting speed 30 mm / sec. , Cut length 203 mm, cut clearance start 3 mm, end 3 mm. Next, the amount of wear (μm / m) of the blade is calculated from the radius r1 (μm) of the blade before dicing, the radius r2 (μm) of the blade after dicing, and the dicing distance L1 (m) according to the following formula. To do.
Blade wear amount (μm / m) = (r1 (μm) -r2 (μm)) / L1 (m)

The heat-dissipating die-bonding film according to another embodiment contains, for example, two or more types of thermally conductive fillers having different Mohs hardnesses, and the content of the thermally conductive fillers is 20 to 85% by mass. You may. According to such a heat-dissipating die bonding film, a semiconductor element can be efficiently manufactured. Such a heat-dissipating die bonding film is also excellent in thermal conductivity after thermosetting and blade wear resistance in a dicing process.

The heat-dissipating die-bonding film of the present embodiment does not necessarily require a step of applying pressure in the thickness direction to a primary film formed by using a varnish in its production. Further, the heat-dissipating die bonding film of the present embodiment has excellent adhesiveness, and even when the manufactured semiconductor element repeatedly generates heat, the coefficient of thermal expansion of the metal base, the semiconductor element, the die pad, etc. It tends to be easy to reduce the peeling of the metal base and the occurrence of cracks due to the difference.

The heat-dissipating die bonding film of the present embodiment may further contain, for example, a high molecular weight component described later, an epoxy resin, and a curing agent. Hereinafter, each component will be described. Hereinafter, the "high molecular weight component" is also referred to as "a component", the "epoxy resin" is also referred to as "b component", the "curing agent" is also referred to as "c component", and the "thermally conductive filler" is also referred to as "d component".

(Component a: High molecular weight component)
The heat-dissipating die bonding film of the present embodiment may contain a component. Examples of the component a include a resin having thermoplasticity and a resin having at least thermoplasticity in an uncured state and forming a crosslinked structure after heating.

From the viewpoint of easily obtaining film formability, heat resistance, and adhesiveness, component a contains, for example, phenoxy resin, polyimide, polyamide, polycarbodiimide, cyanate ester resin, acrylic resin, polyester, polyethylene, polyether sulfone, and polyetherimide. , Polypolyacetal or urethane resin. These high molecular weight components may be, for example, copolymers. As the a component, one type may be used alone or two or more types may be used in combination.

As the component a, phenoxy resin, polyimide, polyamide, acrylic resin, cyanate ester resin or polycarbodiimide are preferable from the viewpoint of excellent film formability and heat resistance, and phenoxy resin is preferable from the viewpoint of easy adjustment of molecular weight and properties. preferable. From these viewpoints, the component a may be either an acrylic resin or a phenoxy resin.

(acrylic resin)
When the component a contains an acrylic resin, the acrylic resin preferably has a reactive group (functional group) and has a weight average molecular weight of 100,000 or more. As the acrylic resin, one type may be used alone or two or more types may be used in combination.

In the present specification, the weight average molecular weight is a polystyrene-equivalent value using a calibration curve of standard polystyrene by gel permeation chromatography (GPC).

Specific examples of the acrylic resin include an acrylic copolymer. Examples of the acrylic copolymer include acrylic rubber. Examples of the acrylic rubber include a copolymer of at least one selected from an acrylic acid ester and a methacrylic acid ester and acrylonitrile.

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

From the viewpoint that gelation in the varnish state is easily reduced, and from the viewpoint that the increase in the degree of curing and the decrease in the adhesive force due to the increase in the degree of curing in the B stage state are unlikely to occur, the reactive group is, for example, an epoxy group. It may be.

The present inventors speculate the reason why such an effect is exhibited when the reactive group is an epoxy group as follows. When the reactive group is, for example, a carboxy group, it is considered that the bridging reaction is likely to proceed, and gelation in the varnish state and an 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, it is considered that the bridging reaction is unlikely to occur, and gelation in the varnish state and an increase in the degree of curing in the B stage state are unlikely to occur.

For example, in a polymerization reaction for obtaining an acrylic resin, an acrylic resin having a reactive group polymerizes an acrylic monomer having a reactive group (such as a (meth) acrylate having a reactive group) so that a reactive group remains. It can be produced by introducing a reactive group into the synthetic acrylic resin.

Examples of the acrylic resin having an epoxy group include an acrylic resin containing glycidyl (meth) acrylate as a monomer unit. In this case, the content of glycidyl (meth) acrylate as a monomer unit may be, for example, 0.5% by mass or more based on the total mass of the acrylic resin from the viewpoint of easily improving the adhesiveness. It may be mass% or more. Further, the content of glycidyl (meth) acrylate as a monomer unit may be, for example, 6% by mass or less based on the total mass of the acrylic resin from the viewpoint of easily reducing gelation. From these viewpoints, the content of glycidyl (meth) acrylate as a monomer unit may be 0.5 to 6% by mass or 2 to 6% by mass based on the total mass of the acrylic resin. Good.

In an acrylic resin containing glycidyl (meth) acrylate as a monomer unit, examples of the monomer unit other than glycidyl (meth) acrylate include glycidyl (meth) acrylate such as alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms. Other (meth) acrylates, styrene and acrylonitrile can be mentioned. Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms include ethyl (meth) acrylate and butyl (meth) acrylate.

When the acrylic resin is an acrylic copolymer, the copolymerization ratio of each monomer may be adjusted in consideration of the glass transition temperature of the copolymer (hereinafter, sometimes referred to as "Tg").

The polymerization method of the acrylic resin is not particularly limited, and examples thereof include pearl polymerization and solution polymerization.

The Tg of the acrylic resin as the component a may be, for example, −50 ° C. or higher and 50 ° C. or lower, or −10 ° C. or higher and 50 ° C. or lower. When the Tg is −50 ° C. or higher, the tackiness of the adhesive layer or the adhesive film in the B stage state tends to be small, and the handleability tends to be excellent.

The acrylic resin may have an annular structure. Examples of the acrylic resin having a cyclic structure include an acrylic resin having styrene or benzyl (meth) acrylate as a monomer unit. When the acrylic resin has a cyclic structure, it is considered that the higher the total mass Mcr (Mcr / MTOT) of the carbon atoms in the cyclic structure based on the total mass MTOT of the acrylic resin, the more preferable.

The weight average molecular weight of the acrylic resin may be, for example, 200,000 or more from the viewpoint that the strength and flexibility are less likely to decrease and the tackiness is less likely to increase when the acrylic resin is formed into a sheet or a film. It may be 300,000 or more, or 400,000 or more. The weight average molecular weight of the acrylic resin may be, for example, 3000000 or less, or 20000 or less, from the viewpoint of high flowability and easy improvement in circuit filling property of wiring. From these viewpoints, the weight average molecular weight of the acrylic resin may be, for example, 200,000 to 3,000, 300,000 to 3,000, or 400,000 to 20,000.

From the viewpoint that high adhesiveness and heat resistance can be easily obtained, the acrylic resin as the component a contains, for example, 0.5 to 6% by mass of glycidyl (meth) acrylate as a monomer unit, and has a Tg of −50 ° C. or higher and 50 ° C. or lower. (Preferably, it may be an acrylic copolymer having a weight average molecular weight of -10 ° C. or higher and 50 ° C. or lower) and a weight average molecular weight of 100,000 or higher. Examples of such an acrylic resin include HTR-860P-3 and HTR-860P-30B (manufactured by Nagase ChemteX Corporation, trade name).

(Phenoxy resin)
When the component a contains a phenoxy resin, the weight average molecular weight of the phenoxy resin is preferably 20,000 or more, more preferably 30,000 or more, and further preferably 50,000 or more. The phenoxy resin may be used alone or in combination of two or more.

Examples of commercially available phenoxy resins include YP-50, YP-55, YP-70, YPB-40PXM40, YPS-007A30, FX-280S, FX-281S, FX-293 and ZX-1356-2 (above, Nippon Steel). 1256, 4250, 4256, 4275, YX7180, YX6954, YX8100, YX7200, YL7178, YL7290, YL7600, YL7734, YL7827 and YL7864 ).

The Tg of the phenoxy resin is preferably less than 85 ° C. Examples of the phenoxy resin having a Tg of less than 85 ° C. include YP-50, YP-55, YP-70, and ZX-1356-2 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name); and 4250, 4256. , 7275, YX7180, and YL7178 (all manufactured by Japan Epoxy Resin Co., Ltd., trade name).

[B component: epoxy resin]
The b component is, for example, one that cures and exhibits an adhesive action. From the viewpoint of heat resistance, component b is preferably an epoxy resin having two or more functional groups (epoxy resin having two or more functional groups).

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

Examples of component b include bifunctional epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin; polyfunctional epoxy resin; amine type. Epoxy resins; heterocyclic-containing epoxy resins; and alicyclic epoxy resins can be mentioned. As the component b, a generally known epoxy resin other than the above can also be used.

Examples of commercially available bisphenol A type epoxy resins include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1055, Epicoat 1004, Epicoat 1004AF, Epicoat 1007. , Epicoat 1009, Epicoat 1003F and Epicoat 1004F (above, manufactured by Mitsubishi Chemical Corporation, trade name); DER-330, DER-301, DER-361, DER-661, DER-662, DER-663U, DER-664, DER-664U, DER-667, DER-642U, DER-672U, DER-673MF, DER-668, and DER-669 (all manufactured by Dow Chemical Co., Ltd., trade name); and YD8125 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., Product name).

Examples of commercially available bisphenol F type epoxy resins include YDF-2004 and YDF-8170C (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name).

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

Examples of commercially available cresol novolac type epoxy resins include Epicoat 180S65 (manufactured by Mitsubishi Chemical Corporation, trade name); Araldite ECN1273, Araldite ECN1280 and Araldite ECN1299 (manufactured by Chivas Specialty Chemicals, trade name); YDCN-700. -10, YDCN-701, YDCN-702, YDCN-703 and YDCN-704 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name); EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN- 1020, EOCN-1025 and EOCN-1027 (above, manufactured by Nippon Kayaku Co., Ltd., trade name); and ESCN-195X, ESCN-200L and ESCN-220 (above, manufactured by Sumitomo Chemical Co., Ltd., trade name). ..

Examples of commercially available polyfunctional epoxy resins include Epon 1031S, Epicoat 1032H60 and Epicoat 157S70 (above, Mitsubishi Chemical Corporation, trade name); Araldite 0163 (Ciba Speciality Chemicals, trade name); Denacol EX-611. , Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-421, Denacol EX-411 and Denacol EX-321 (all manufactured by Nagase ChemteX Corporation, Product name); and EPPN501H and EPPN502H (all manufactured by Nippon Kayaku Corporation, product name).

Examples of commercially available amine-type epoxy resins include Epicoat 604 (manufactured by Mitsubishi Chemical Corporation, trade name); YH-434 (manufactured by Nippon Steel & Sumitomo Chemical Corporation, trade name); TETRAD-X and TETRAD-C (above, above, Mitsubishi Gas Chemical Corporation, product name); and ELM-120 (Sumitomo Chemical Corporation, product name).

Examples of the commercially available heterocyclic epoxy resin include Araldite PT810 (manufactured by Ciba Speciality Chemicals, trade name).

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

As the component b, one type may be used alone or two or more types may be used in combination.

The component b may contain a bifunctional epoxy resin and a trifunctional or higher functional epoxy resin from the viewpoint of easily improving the adhesiveness, heat resistance, and moisture absorption resistance after heat curing. When component b contains a bifunctional epoxy resin and a trifunctional or higher functional epoxy resin, the content of the bifunctional epoxy resin is, for example, based on the total mass of the bifunctional epoxy resin and the trifunctional or higher functional epoxy resin. It may be 3 to 40% by mass, 3 to 30% by mass, or 3 to 20% by mass.

[C component: hardener]
The c component can be used without particular limitation as long as the b component can be cured. Examples of the c component include polyfunctional phenol compounds, amine compounds, acid anhydrides, organic phosphorus compounds and halides thereof, polyamides, polysulfides, and boron trifluoride.

Examples of the polyfunctional phenol compound include a monocyclic bifunctional phenol compound and a polycyclic bifunctional phenol compound. Examples of the monocyclic bifunctional phenol include hydroquinone, resorcinol and catechol, and alkyl group substituents thereof.

Examples of the polycyclic bifunctional phenol compound include bisphenol A, bisphenol F, bisphenol S, naphthalenediol and biphenol, and alkyl group substituents thereof. Further, the polyfunctional phenol compound may be, for example, a polycondensate of at least one phenol compound selected from the group consisting of the monocyclic bifunctional phenol compound and the polycyclic bifunctional phenol compound and an aldehyde compound. Good. The polycondensate is, for example, a phenol resin. Examples of the phenol resin include phenol novolac resin, resol resin, bisphenol A novolak resin and cresol novolak resin.

Examples of commercially available products of the phenol resin (phenol resin curing agent) include Phenolite LF2882, Phenolite LF2282, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH4150 and Phenolite VH4170 (all, DIC Co., Ltd.). Made, trade name).

From the viewpoint of adhesiveness and heat resistance, the hydroxyl group equivalent of the phenol resin may be, for example, 250 g / eq or more, 200 g / eq or more, or 150 g / eq or more. Further, the phenol resin as the c component is preferably a novolak type or resol type resin from the viewpoint of improving the electrolytic corrosion resistance at the time of moisture absorption.

From the viewpoint of improving the moisture resistance, the phenol resin preferably has a water absorption rate of 2% by mass or less after being placed in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 48 hours. Further, the phenol resin as the c component has a heating weight reduction rate (heating rate: 5 ° C./min, atmosphere: nitrogen) at 350 ° C. measured by a thermogravimetric analyzer (TGA) of less than 5% by weight. It is preferable to have. When such a phenol resin is used as a curing agent, volatile components are suppressed during heat processing, so that the reliability of various properties such as heat resistance and moisture resistance is increased, and during work such as heat processing. It is considered that the contamination of equipment due to the volatile matter of the plastic can be reduced.

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

In formula (I), R ¹ is a hydrogen atom, a linear 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, a hydroxyl group, an aryl group, or It represents a halogen atom, n represents an integer of 1 to 3, and m represents an integer of 0 to 50. In the formula (I), a plurality of R ¹ and n existing may be the same or different, respectively.

Examples of the compound represented by the formula (I) include the Millex XLC-series and the XL series (all 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 (acid catalyst). The xylylene compound can form a divalent linking group by the reaction.

Examples of the phenol compound used for producing the compound represented by the formula (I) include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol and on-propyl. Phenol, mn-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, hydroquinone , 4-methoxyphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, p-cyclohexylphenol, o-allylphenol, p-allylphenol, o-benzylphenol, p-benzylphenol, o-chlorophenol , P-chlorophenol, o-bromophenol, p-bromophenol, o-iodophenol, p-iodophenol, o-fluorophenol, m-fluorophenol and p-fluorophenol. The above-mentioned phenol compound may be used individually by 1 type or in combination of 2 or more type.

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

Examples of the xylylene compound used for producing the compound represented by the formula (I) include xylylene halides and xylylene diglycols, and derivatives thereof.

Specific examples of the above xylene compound include 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' -Diode-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'-di-n-propoxy-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-p-xylene, α, α'-di-tert-butoxy-m-xylene and α , Includes α'-di-tert-butoxy-o-xylene. The xylylene compound may be used alone or in combination of two or more.

The above xylene compound is α, α'-dichloro-p-xylene, α, α'-dichloro-m-xylene, α, α'from the viewpoint of being able to produce a phenol resin having good adhesiveness, heat resistance and moisture resistance. -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, or α, α'-dimethoxy-o-xylene is preferred.

Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and polyphosphoric acid; organic carboxylic acids such as dimethylsulfate, diethylsulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid; trifluoromethane. Super-strong acids such as sulfonic acid; Strongly acidic ion exchange resin such as alkane sulfonic acid type ion exchange resin; Super strong acidic ion exchange resin such as perfluoroalkane sulfonic acid type ion exchange resin (for example, Nafion, Du Pont) Manufacture, trade name)); natural and synthetic zeolite compounds; and active white clay (eg, acidic white clay).

The above reaction is carried out, for example, at 50 to 250 ° C. until the xylylene compound which is a raw material is substantially eliminated 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 while tracking the reaction composition by, for example, GPC (gel permeation chromatography) or the like. The reaction time may be, for example, about 1 hour to 15 hours.

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

On the other hand, for example, when a halogenoxylen derivative such as α, α'-dichloro-p-xylene is used as the xylylene compound, an acid catalyst is not always required because the reaction proceeds without a catalyst while generating hydrogen halide gas. Do not.

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

The phenol resin may have, for example, an allyl phenol skeleton.
The phenol resin having an allylphenol skeleton can be obtained, for example, by producing a phenol resin that has not been allylated, reacting it with allyl halide, and then allylating it by the Claisen rearrangement via allyl ether.

Examples of the amine compound as the component c include aliphatic or aromatic primary amines, secondary amines, tertiary amines, and quaternary ammonium salts; aliphatic cyclic amine compounds; guanidine compounds; and urea. Derivatives can be mentioned.

Specific examples of the above amine compounds include N, N-benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, N, N. '-Dimethylpiperazin, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.4.0] -5 -Nonene, hexamethylenetetramine, pyridine, picolin, piperidine, pyrrolidine, dimethylcyclohexylamine, dimethylhexylamine, cyclohexylamine, diisobutylamine, di-n-butylamine, diphenylamine, N-methylaniline, tri-n-propylamine, tri -N-octylamine, tri-n-butylamine, triphenylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, triethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, dicyandiamide, trirubiguanide, guanylurea and Contains dimethyl urea. The amine compound is, for example, a dihydrazide compound such as adipic acid dihydrazide; guanamic acid; melamic acid; an addition compound of an epoxy compound and a dialkylamine compound; an addition compound of amine and thiourea; and an addition compound of amine and isocyanate. There may be. From the viewpoint of reducing the activity at room temperature, these amine compounds may have, for example, an adduct-type structure.

Examples of the acid anhydride as the c component include phthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride.

The organic phosphorus compound as the c component is not particularly limited as long as it is a phosphorus compound having an organic group. Examples of the organic phosphorus compound include hexamethylphosphate triamide, triphosphate (dichloropropyl), triphosphate (chloropropyl), triphenyl phosphate, trimethyl phosphate, phenylphosphonic acid, and triphenylphosphine. , Tri-n-butylphosphine and diphenylphosphine.

As the c component, one type may be used alone, or two or more types may be used in combination.

[D component: thermally conductive filler]
The d component can impart thermal conductivity to the heat-dissipating die bonding film, for example. In the present embodiment, the heat-dissipating die bonding film contains two or more types of d components having different Mohs hardness. It is considered that the blade is less likely to be worn by using two or more kinds of d components having different Mohs hardness. As the d component, for example, two or more types can be appropriately selected from the d components described later.

Examples of the material constituting the component d include aluminum oxide, zinc oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, magnesium hydroxide, aluminum hydroxide, silicon carbide, diamond, magnesium carbonate, aluminum borate and antimony. Oxides and combinations thereof can be mentioned. The material constituting the d component may have electrical insulating properties. Examples of boron nitride include hexagonal boron nitride and cubic boron nitride. The aluminum borate may be an aluminum borate whiskers.

The material constituting the component d may be aluminum hydroxide, magnesium hydroxide, magnesium carbonate, calcium oxide or magnesium oxide from the viewpoint of easily adjusting the melt viscosity and easily imparting thixotropic properties. The material constituting the d component may be aluminum hydroxide or antimony oxide from the viewpoint of easily improving the moisture resistance.

In the heat-dissipating die bonding film of the present embodiment, from the viewpoint of further improving the thermal conductivity after heat curing and further reducing the wear of the blade in the dicing step, as the d component, an alumina filler, a boron nitride filler, etc. It is preferable to contain at least two kinds selected from the group consisting of aluminum nitride filler and magnesium oxide filler.

The alumina filler may contain an alumina filler having a purity of 99.0% by mass or more from the viewpoint of further improving the thermal conductivity after thermosetting and further reducing the wear of the blade in the dicing step. preferable. The alumina filler may be made of an alumina filler having a purity of 99.0% by mass or more. Examples of the alumina filler having a purity of 99.0% by mass or more include Sumiko Random AA-3 (manufactured by Sumitomo Chemical Co., Ltd., trade name) and alumina beads CB-P05 (manufactured by Showa Denko Co., Ltd., trade name). .. It is more preferable that the alumina filler contains α-alumina filler having a purity of 99.0% by mass or more. The purity of the alumina filler may be, for example, 100% by mass or less.

The above-mentioned boron nitride filler is a hexagonal boron nitride filler having a nitrogen purity of 95.0% by mass or more from the viewpoint of further improving the thermal conductivity after thermosetting and further reducing the wear of the blade in the dicing process. It is preferable to contain it. Examples of such hexagonal boron nitride fillers include HP-P1 and HP-4W (manufactured by Mizushima Ferroalloy Co., Ltd., trade name) and ShoBN UHP-S1 (manufactured by Showa Denko KK, trade name). Be done. Here, the purity of nitrogen is calculated based on the mass of nitrogen in hexagonal boron nitride in which nitrogen is saturated. In the hexagonal boron nitride, the purity of nitrogen may be, for example, 100% by mass or less.

The density of the aluminum nitride filler is preferably ^{, for example, 3 to 4 g / cm 3.} Examples of such an aluminum nitride filler include Shapel H grade and Shapel E grade (manufactured by Tokuyama Corporation, trade name) and ALN020BF (manufactured by Tomoe Engineering Co., Ltd., trade name).

The magnesium oxide filler preferably contains a magnesium oxide filler having a purity of 95.0% by mass or more. Examples of such magnesium oxide filler include RF-10C (manufactured by Ube Material Industries Ltd., trade name). The purity of the magnesium oxide may be, for example, 100% by mass or less.

The heat-dissipating die bonding film of the present embodiment may contain the alumina filler and the boron nitride filler as the d component, or may contain the boron nitride filler and the aluminum nitride filler. , The above-mentioned boron nitride filler and the above-mentioned magnesium oxide filler may be contained.

_{The average particle size (d 50} ) of the mixture of the d components is preferably 1/2 or less, preferably 1/3 of the thickness of the heat-dissipating die bonding film, from the viewpoint of further improving the adhesive strength, laminateability and reliability. It is more preferably less than or equal to, and even more preferably 1/4 or less. _{The average particle size (d 50} ) of the mixture of the d components may be, for example, 1/1000 or more of the thickness of the heat-dissipating die bonding film.

_{The average particle size (d 90} ) of the mixture of the d components is preferably 1/2 or less, preferably 1/3 of the thickness of the heat-dissipating die bonding film, from the viewpoint of further improving the adhesive strength, laminateability and reliability. It is more preferably 1/4 or less, and further preferably 1/4 or less. _{The average particle size (d 90} ) of the mixture of the d components may be, for example, 1/1000 or more of the thickness of the heat-dissipating die bonding film.

In the present specification, the average particle size (d ₅₀ ) means the particle size corresponding to the integrated value of the particle size distribution of 50%, and the average particle size (d ₉₀ ) means the integrated value of the particle size distribution of 90%. Corresponding particle size.

The thermal conductivity of the d component may be, for example, 10 W / (m · K) or more, or 15 W / (m · K) or more, from the viewpoint of further improving the heat conductivity of the heat-dissipating die bonding film. It may be 17 W / (m · K) or more.

In the heat-dissipating die bonding film of the present embodiment, the Mohs hardness of at least one of the d components is preferably 10 or less, preferably 9 or less, from the viewpoint of further suppressing the wear of the blade in the dicing step. It is more preferably present, and further preferably 8 or less.

When the Mohs hardness of at least one of the d components is 10 or less, the content of the d component having a Mohs hardness of 10 or less is a heat-dissipating die bonding film from the viewpoint of further suppressing the wear of the blade in the dicing process. For example, it may be 10% by mass or more, 15% by mass, or 20% by mass or more based on the total mass of.

In the heat-dissipating die bonding film of the present embodiment, heat having a moth hardness of 1 to 3 is used as the d component from the viewpoint of further improving the thermal conductivity after heat curing and further reducing the wear of the blade in the dicing step. It is preferable to contain at least one conductive film and at least one thermally conductive film having a moth hardness of 4 to 9. In this case, the content of the thermally conductive filler having a Mohs hardness of 1 to 3 may be, for example, 5 to 300 parts by mass with respect to 100 parts by mass of the total mass of the thermally conductive filler having a Mohs hardness of 4 to 9. , 10 to 250 parts by mass, or 30 to 200 parts by mass.

The shape of the d component is not particularly limited, but may be spherical or polyhedral, for example. In addition, in this specification, a polyhedron means a solid which has a plurality of planes as a constituent part of a surface. A plurality of existing planes may intersect each other via a curved surface. The polyhedron may have, for example, 4 to 100 planes as a surface component.

In the heat-dissipating die bonding film of the present embodiment, the content of the a component is the sum of the a component, the b component, the c component and the d component from the viewpoint of easily reducing the elastic modulus and easily imparting flowability during molding. For example, it may be 3 parts by mass or more with respect to 100 parts by mass. The content of the a component is, for example, with respect to a total of 100 parts by mass of the a component, the b component, the c component and the d component from the viewpoint that the fluidity does not easily decrease even when the sticking load is small and the circuit filling property is excellent. , 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less. From these viewpoints, the content of the a component may be 3 to 40 parts by mass with respect to a total of 100 parts by mass of the a component, the b component, the c component and the d component, and is 3 to 30 parts by mass. It may be 3 to 20 parts by mass.

In the heat-dissipating die bonding film of the present embodiment, the content of the b component may be, for example, 3 to 55 parts by mass with respect to 100 parts by mass of the total amount of the a component, the b component, the c component and the d component. It may be 5 to 45 parts by mass, or 10 to 35 parts by mass.

The content of the c component in the heat-dissipating die bonding film of the present embodiment is not particularly limited as long as the curing reaction of the b component can proceed, but the epoxy group and the epoxy group are based on 1 equivalent of the epoxy group in the b component. The active group (hydroxyl group, amino group, acid anhydride group, group containing a phosphorus atom, etc.) in the reactive c component may be, for example, in the range of 0.01 to 5.0 equivalents, and 0. It may be in the range of 8 to 1.2 equivalents.

For example, when the c component is a phenol resin, the content of the c component in the heat-dissipating die bonding film of the present embodiment is the epoxy equivalent of the b component from the viewpoint of improving the curability when the heat-dissipating die bonding film is used. The equivalent ratio of the hydroxyl group equivalents of the phenol resin (epoxy equivalent / hydroxyl group equivalent) may be, for example, 0.70 / 0.30 to 0.30 / 0.70, 0.65 / 0.35-. It may be 0.35 / 0.65, 0.60 / 0.30 to 0.30 / 0.60, 0.55 / 0.45-0.45 / 0.55. There may be.

In the heat-dissipating die bonding film of the present embodiment, the total mass of the d component is 100 parts by mass in total of the a component, the b component, the c component and the d component from the viewpoint of further improving the thermal conductivity after heat curing. On the other hand, for example, it may be 20 parts by mass or more, 22 parts by mass or more, or 25 parts by mass or more. The total mass of the d component is, for example, 85 parts by mass with respect to 100 parts by mass of the total amount of the a component, the b component, the c component and the d component from the viewpoint of film characteristics such as surface roughness, adhesiveness and laminateability. It may be less than or equal to, 75 parts by mass or less, and 70 parts by mass or less.

The heat-dissipating die bonding film of the present embodiment preferably contains a high molecular weight component of either an acrylic resin or a phenoxy resin, an epoxy resin, and a curing agent.

[Other ingredients]
The heat-dissipating die bonding film of the present embodiment may contain components other than the above. Examples of such a component include a curing accelerator, a filler other than the d component, a coupling agent, and an ion scavenger.

(Curing accelerator)
The curing accelerator is not particularly limited, and examples thereof include an imidazole compound. Examples of the imidazole compound include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-. Heptadecyl imidazole, 4,5-diphenyl imidazole, 2-methyl imidazoline, 2-phenyl imidazoline, 2-undecyl imidazoline, 2-heptadecyl imidazoline, 2-isopropyl imidazole, 2,4-dimethyl imidazole, 2-phenyl-4 -Methylimidazole, 2-ethylimidazolin, 2-phenyl-4-methylimidazoline, benzimidazole, 1-cyanoethylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate. Be done. The curing accelerator may be used alone or in combination of two or more. Examples of commercially available products of the imidazole compound include 2E4MZ, 2PZ-CN and 2PZ-CNS (all manufactured by Shikoku Chemicals Corporation, trade name).

Further, from the viewpoint of extending the period of use of the film, the curing accelerator may be a potential curing accelerator. Examples of such a curing accelerator include an addition compound of an epoxy compound and an imidazole compound. From the viewpoint of reducing the activity at room temperature, the curing accelerator may have an adduct-type structure.

The blending amount of the curing accelerator is, for example, 5.0% by mass or less based on the total mass of the b component and the c component from the viewpoint of excellent storage stability and easy to secure a sufficient pot life. It may be 3.0% by mass or less. The blending amount of the curing accelerator may be, for example, 0.02% by mass or more based on the total mass of the b component and the c component from the viewpoint of adhesiveness, heat resistance, and moisture resistance after heat curing. It may be 0.03% by mass or more. From these viewpoints, the blending amount of the curing accelerator may be, for example, 0 to 5.0% by mass, or 0.02 to 3.0% by mass, based on the total mass of the b component and the c component. It may be 0.03 to 3.0% by mass.

(Fila other than d component)
The heat-dissipating die-bonding film of the present embodiment may contain various fillers other than the above d component for the purpose of improving the handleability of the film, adjusting the melt viscosity, imparting thixotropic properties, improving the moisture resistance, and the like. Good. As the filler other than the d component, one type may be used alone, or two or more types may be used in combination.

Examples of the material constituting the filler other than the d component include calcium carbonate, calcium silicate, magnesium silicate, calcium oxide and silica. Examples of the silica include crystalline silica and amorphous silica.

The materials constituting the filler other than the d component are calcium carbonate, calcium silicate, magnesium silicate, calcium oxide, crystalline silica, or amorphous from the viewpoint of easily adjusting the melt viscosity and easily imparting thixotropic properties. It may be sex silica. The material constituting the filler other than the d component may be silica from the viewpoint of easily improving the moisture resistance.

When the heat-dissipating die bonding film of the present embodiment contains a filler other than the d component, the content of the filler other than the d component is, for example, 50 parts by mass or less with respect to 100 parts by mass of the total mass of the d component. It may be 20 parts by mass or less, or 10 parts by mass or less.

(Coupling agent)
The heat-dissipating die-bonding film of the present embodiment may contain various coupling agents from the viewpoint of improving the interfacial bond between different materials, for example. Examples of the coupling agent include a silane-based coupling agent, a titanium-based coupling agent, and an aluminum-based coupling agent.

The silane coupling agent is not particularly limited, and is, for example, vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, vinyl triethoxysilane, vinyl trimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacry. Loxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxy Silane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ- Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3- (4,5-dihydro) ) Imidazole-1-yl-propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, 3-chloropropyl-methyldimethoxysilane, 3-chloropropyl-dimethoxysilane, 3- Cyanopropyl-triethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, amyltri Chlorosilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri (methacryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltri Methoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosila , Γ-Chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, trimethylsilylisocyanate, dimethylsilylisocyanate, methylsilyltriisocyanate, vinylsilyltriisocyanate, phenylsilyltriisocyanate, tetraisocyanatesilane and ethoxysilaneisocyanate. Be done. These may be used individually by 1 type or in combination of 2 or more type.

The titanium-based coupling agent is not particularly limited, and examples thereof include isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacrylic titanate, and isopropyltri (dioctyl phosphate) titanate. Isopropyltricylphenyl titanate, isopropyltris (dioctylpyrophosphate) titanium, isopropyltris (n-aminoethyl) titanium, tetraisopropylbis (dioctylphosphate) titanium, tetraoctylbis (ditridecylphosphite) titanium, tetra (2,2) 2-Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanium, dicumylphenyloxyacetate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (dioctylpyrophosphate) 2-Ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium chili ethanolaminate, polyhydroxytitanium stearate, tetramethyl Orthotitanate, Tetraethyl orthotitanate, Tetarapropyl orthotitanate, Tetraisobutyl orthotitanate, Stearyl titanate, Cresyl titanate monomer, Cresyl titanate polymer, Diisopropoxy-bis (2,4-pentadionate) Titanium (IV), Diisopropyl Examples thereof include -bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium monostearate polymer, and tri-n-butoxytitanium monostearate. These may be used individually by 1 type or in combination of 2 or more type.

The aluminum-based coupling agent is not particularly limited, and for example, ethyl acetoacetate aluminum diisopropirate, aluminum toys (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropirate, aluminum monoacetyl acetate bis (ethyl acetoacetate), Aluminum such as aluminum tris (acetylacetonate), aluminum monoisopropoxymonooleoxyethylacetate, aluminum-di-n-butoxide-mono-ethylacetate, aluminum-di-iso-propoxide-mono-ethylacetate Chelate compounds; and aluminum alcoholates such as aluminum isopropyrate, mono-sec-butoxyaluminum diisopropirate, aluminum-sec-butyrate, and aluminum ethylate. These may be used individually by 1 type or in combination of 2 or more type.

From the viewpoint of adhesiveness when adhering to a Si wafer, the coupling agent is preferably a silane-based coupling agent.

When the heat-dissipating die bonding film of the present embodiment contains a coupling agent, the content of the coupling agent is 100 mass in total of the a component, the b component and the c component from the viewpoint of its effect, heat resistance and cost. For example, it may be 10 parts by mass or less, 0.1 to 5 parts by mass, or 0.2 to 3 parts by mass.

(Ion scavenger)
The heat-dissipating die-bonding film of the present embodiment may contain, for example, an ion scavenger from the viewpoint of adsorbing ionic impurities and improving insulation reliability during moisture absorption. Examples of the ion scavenger include a copper damage inhibitor used to prevent copper from being ionized and leached out. Examples of the copper damage inhibitor include triazine thiol compounds, bisphenol-based reducing agents, and inorganic ion adsorbents.

Examples of commercially available products of copper damage inhibitors containing a triazine thiol compound as a component include disnet DB (manufactured by Sankyo Kasei Co., Ltd., trade name).

Examples of the bisphenol-based reducing agent include 2,2'-methylene-bis- (4-methyl-6-third-butylphenol) and 4,4'-thio-bis- (3-methyl-6-third). -Butylphenol). Examples of commercially available bisphenol-based reducing agents include Yoshinox BB (manufactured by Yoshitomi Pharmaceutical Co., Ltd., trade name).

Examples of the inorganic ion adsorbent include zirconium-based compounds, antimony bismuth-based compounds, and magnesium-aluminum-based compounds. Examples of commercially available inorganic ion adsorbents include IXE (manufactured by Toagosei Co., Ltd., trade name).

The content of the ion scavenger is based on 100 parts by mass of the total amount of the resin composition (for example, the varnish described later) used for forming the heat-dissipating die bonding film from the viewpoint of the effect of the addition, heat resistance and cost. For example, it may be 1 to 10 parts by mass.

In the heat-dissipating die-bonding film of the present embodiment, the content of component a is, for example, based on the total mass of the heat-dissipating die-bonding film from the viewpoint of easily reducing the elastic modulus and imparting flowability during molding. It may be 3 parts by mass or more. The content of component a is, for example, 40 parts by mass or less based on the total mass of the heat-dissipating die bonding film from the viewpoint that the fluidity does not easily decrease even when the sticking load is small and the circuit filling property is excellent. It may be 30 parts by mass or less, or 20 parts by mass or less. From these viewpoints, the content of component a may be 3 to 40 parts by mass, 3 to 30 parts by mass, or 3 to 20 parts by mass, based on the total mass of the heat-dissipating die bonding film. It may be a department.

In the heat-dissipating die bonding film of the present embodiment, the content of component b may be, for example, 3% by mass or more, or 5% by mass or more, based on the total mass of the heat-dissipating die bonding film. It may be 10% by mass or more. The content of component b may be, for example, 55% by mass or less, 45% by mass or less, or 35% by mass or less, based on the total mass of the heat-dissipating die bonding film. .. The content of component b may be, for example, 3 to 55% by mass, 5 to 45% by mass, or 10 to 35% by mass, based on the total mass of the heat-dissipating die bonding film. You may.

In the heat-dissipating die-bonding film of the present embodiment, the content of the d component is 20% by mass or more based on the total mass of the heat-dissipating die-bonding film from the viewpoint of further improving the thermal conductivity after heat curing. It is preferably 25% by mass or more, more preferably 30% by mass or more. The content of the d component is preferably 85% by mass or less, preferably 75% by mass or less, based on the total mass of the heat-dissipating die bonding film, from the viewpoint of film characteristics such as surface roughness, adhesiveness, and laminateability. It is more preferable that it is 70% by mass or less. From these viewpoints, the content of the d component is preferably 20 to 85% by mass, more preferably 25 to 75% by mass, and 30 to 85% based on the total mass of the heat-dissipating die bonding film. It is more preferably mass%.

The thickness of the heat-dissipating die bonding film is not particularly limited. The thickness of the heat-dissipating die bonding film may be, for example, 5 μm or more, or 8 μm or more, from the viewpoint of improving the stress relaxation effect and the embedding property. From the viewpoint of reducing the cost, the thickness of the heat-dissipating die bonding film may be, for example, 50 μm or less, or 40 μm or less. From these viewpoints, the thickness of the heat-dissipating die bonding film may be, for example, 5 to 50 μm, 5 to 40 μm, or 8 to 40 μm.

[Manufacturing method of heat-dissipating die bonding film]
The heat-dissipating die-bonding film of the present embodiment is based on, for example, a varnish (resin composition for forming a heat-dissipating die-bonding film) prepared by mixing the above-mentioned a component, b component, c component, d component and the like with a solvent. It can be formed by applying it on a material film (for example, 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 such a solvent include methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cell solve, methanol, ethanol, 2-methoxyethanol, dimethylacetamide, dimethylformamide, methylpyrrolidone and cyclohexanone. .. Above all, from the viewpoint of improving the coating film property, the solvent is preferably a high boiling point solvent such as methyl ethyl ketone, dimethylacetamide, dimethylformamide, methylpyrrolidone and cyclohexanone. These solvents may be used alone or in combination of two or more.

The content of the solvent in the varnish is not particularly limited, but the content of the non-volatile content in the varnish is, for example, based on the total mass of the varnish from the viewpoint of reducing the amount of heat required for drying the varnish and being excellent in terms of cost. , 40% by mass or more, or 50% by mass or more. The content of the non-volatile content in the varnish is, for example, 90% by mass or less based on the total mass of the varnish from the viewpoint that the viscosity of the varnish does not increase too much and the defects of the coating film caused by the viscosity are easily reduced. It may be 80% by mass or less. From these viewpoints, the non-volatile content in the varnish is preferably, for example, 40 to 90% by mass, more preferably 50 to 80% by mass, based on the total mass of the varnish.

Mixing of each component can be carried out by, for example, a raker, a three-roll, a bead mill, or a combination thereof. Further, for example, the time required for mixing can be shortened by mixing the filler component and the low molecular weight substance in advance and then blending the high molecular weight substance. Further, it is preferable to remove air bubbles by vacuum degassing of the varnish before applying it on the base film.

Next, the prepared varnish is applied onto the base film, and the solvent is removed by heating, for example, so that a heat-dissipating die bonding film can be formed on the base film.

The heating conditions are not particularly limited as long as the solvent can be removed without completely curing the heat-dissipating die-bonding film. For example, the components of the heat-dissipating die-bonding film and the solvent in the varnish It can be adjusted appropriately according to the type. General heating conditions are, for example, 80 to 140 ° C. for 5 to 60 minutes.

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

Examples of the base film include polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polyimide film, polyethylene naphthalate film, polyether sulfone film, polyetheramide film, and polyether. Examples thereof include plastic films such as amidoimide films, polyamide films and polyamideimide films.

If necessary, the base film may be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment, etching treatment, and mold release treatment.

Examples of commercially available products of the polyimide film include Kapton (manufactured by Toray DuPont Co., Ltd., trade name) and Apical (manufactured by Kaneka Corporation, trade name).

Examples of commercially available polyethylene terephthalate films include Lumirer (manufactured by Toray DuPont Co., Ltd., trade name) and Purex (manufactured by Teijin Limited, trade name).

[Dicing die bonding film]
The heat-dissipating die bonding film of the present embodiment can be applied to, for example, a dicing die bonding film. Hereinafter, an embodiment of the dicing die bonding film will be described.

FIG. 1 is a cross-sectional view schematically showing the dicing die bonding film of the present embodiment. The dicing die bonding film 1 shown in FIG. 1 includes a dicing film 10 and a die bonding film 20 laminated on the dicing film 10. The dicing film 10 is not particularly limited, and can be appropriately determined based on the knowledge of those skilled in the art, for example, in consideration of the intended use. Examples of the dicing film 10 include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. If necessary, the dicing film 10 may be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment, and etching treatment. The dicing film 10 is preferably one having adhesiveness. Examples of the adhesive dicing film include those obtained by imparting adhesiveness to the above-mentioned plastic film and those provided with an adhesive layer on one side of the above-mentioned plastic film. The pressure-sensitive adhesive layer is formed from, for example, a resin composition (resin composition for forming a pressure-sensitive adhesive layer) containing a liquid component and a high molecular weight component and having an appropriate tack strength. The dicing tape provided with the pressure-sensitive adhesive layer is, for example, a resin composition for forming a pressure-sensitive adhesive layer applied on the above-mentioned plastic film and dried, or a resin composition for forming a pressure-sensitive adhesive layer is applied to a base film such as a PET film. It can be produced by laminating the pressure-sensitive adhesive layer formed by applying and drying to the above-mentioned plastic film. The tack strength is set to a desired value by adjusting, for example, the ratio of the liquid component and the Tg of the high molecular weight component. The die bonding film 20 is the heat-dissipating die bonding film of the present embodiment described above. In FIG. 1, the dicing film 10 and the die bonding film 20 are in direct contact with each other, but the dicing film 10 and the die bonding film 20 may be laminated via another layer such as an adhesive layer.

The method for producing the dicing die bonding film of the present embodiment is not particularly limited and can be appropriately determined based on the knowledge of those skilled in the art. The dicing die bonding film of the present embodiment can be produced, for example, by using a dicing film instead of the base film in the above-mentioned method for producing a heat-dissipating die bonding film. Further, the dicing die bonding film of the present embodiment can be manufactured, for example, by separately preparing the heat-dissipating die bonding film of the present embodiment and the dicing film, and laminating and integrating them.

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

(Examples 1 to 7, Comparative Example 1 and Reference Example)
[Preparation of varnish (resin composition for forming heat-dissipating die bonding film)]
The following materials were prepared as fillers other than a component, b component, c component, d component, and d component, a coupling agent, a curing accelerator, and a solvent.

(Component a)
-Epoxy group-containing acrylic rubber: HTR-860P-3CSP (manufactured by Nagase ChemteX Corporation, trade name, weight average molecular weight 800,000, Tg 12 ° C)
-Epoxy group-containing acrylic rubber: HTR-860P-30B (manufactured by Nagase ChemteX Corporation, trade name, weight average molecular weight 300,000, Tg 12 ° C)
-Bisphenol A / F copolymer phenoxy resin: ZX1356-2 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name, weight average molecular weight 63200, Tg 71 ° C)
(B component)
-Cresol novolac type epoxy resin: YDCN-700-10 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., product name, epoxy equivalent: 195-215)
-Bisphenol F type epoxy resin: YDF-8170C (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name, epoxy equivalent: 156)
(C component)
-Phenol resin: XLC-LL (manufactured by Mitsui Chemicals, Inc., product name)
(D component)
-Polyhedron α-alumina filler: Sumiko Random AA-3 (manufactured by Sumitomo Chemical Co., Ltd., trade name, purity Al ₂ O ₃ ≥ 99.90%, average particle size 2.7 to 3.6 μm, Mohs hardness 9)
-Spherical α-alumina filler: Alumina beads CB-P05 (manufactured by Showa Denko KK, trade name, purity Al ₂ O ₃ 99.89%, average particle size 4 μm, Mohs hardness 9)
-Boron nitride filler: HP-P1 (manufactured by Mizushima Ferroalloy Co., Ltd., trade name, average particle size 1-3 μm, Mohs hardness 2)
Boron Nitride Filler: UHP-S1: Showa N UHP-S1 (manufactured by Showa Denko KK, trade name, average particle size 0.5 μm, Mohs hardness 2)
-Aluminum nitride filler: Shapeal H grade (manufactured by Tokuyama Corporation, trade name, average particle size 1 μm, Mohs hardness 8)
-Magnesium oxide filler: RF-10C (manufactured by Ube Material Industries Ltd., trade name, average particle size 10 μm, Mohs hardness 4)

(Fila other than d component)
-Silica filler: SC1030 (Admatic Co., Ltd., trade name, average particle size 0.5 μm)
-Hydrophobic silica filler: R972 (Nihon Aerosil Co., Ltd., trade name, average particle size 60 nm)
(Curing accelerator)
・ Curesol 2PZ-CN (manufactured by Shikoku Chemicals Corporation, product name)
(Coupling agent)
-Silane coupling agent: A-189 (manufactured by Nippon Unicar Co., Ltd., trade name, γ-mercaptopropyltrimethoxysilane)
-Silane coupling agent: A-1160 (manufactured by Nippon Unicar Co., Ltd., trade name, γ-ureidopropyltriethoxysilane)
(solvent)
・ Cyclohexanone

The prepared varnishes of Examples, Comparative Examples and Reference Examples were prepared by blending the prepared components in the amounts shown in Tables 1 and 2. In Tables 1 and 2, the numerical values relating to the filler, the coupling agent and the curing accelerator other than the a component, the b component, the c component, the d component and the d component indicate parts by mass.

[Making a heat-dissipating die bonding film]
As a base film, a release-treated polyethylene terephthalate film (manufactured by Teijin DuPont Film Co., Ltd., A31, thickness 38 μm) was prepared. The prepared varnish was applied onto the release-treated surface of the polyethylene terephthalate film and dried by heating at 90 ° C. for 10 minutes and 120 ° C. for 30 minutes to prepare a heat-dissipating die-bonding film with a base film. The film thickness of the obtained heat-dissipating die bonding film was 30 μm.

[Evaluation of heat-dissipating die bonding film]
The obtained heat-dissipating die-bonding film was evaluated for thermal conductivity, blade wear amount in dicing step, surface roughness (Ra), adhesive strength and laminateability according to the following procedure. The evaluation results are shown in Tables 3 and 4.

(Thermal conductivity)
A plurality of heat-dissipating die-bonding films peeled from the base film were laminated to prepare 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 170 ° C. for 3 hours to obtain a cured film (cured product). The obtained cured film was cut into 10 mm squares and used as a measurement sample.

The thermal diffusivity α (mm ² / s), the specific heat Cp (J / (g · ° C.), and the specific gravity (g / cm ³ )) of the measurement sample were measured by the following methods.
-Thermal diffusivity α (mm ² / s): The thermal diffusivity α at 25 ° C. was measured in the thickness direction of the adhesive film by using a laser flash method (manufactured by NETZSCH, LFA467 HyperFlash (trade name)).
-Specific heat Cp (J / (g · ° C)): By measuring using the DSC method (manufactured by PerkinElmer, DSC8500 (trade name)) at a heating rate of 10 ° C./min and a temperature of 20 to 60 ° C. , The specific heat Cp at 25 ° C. was measured.
-Specific gravity (g / cm ³ ): The specific gravity was measured using an electronic hydrometer SD-200L (manufactured by Mirage, trade name).

The obtained thermal diffusivity α, specific heat Cp, and specific gravity were introduced into the following formula to calculate the thermal conductivity (W / m · K).
Thermal conductivity (W / m · K) = thermal diffusivity α (mm ² / s) x specific heat Cp (J / (g · ° C)) x specific gravity (g / cm ³ )

(Amount of blade wear in the dicing process)
After laminating the heat-dissipating die-bonding film on a dicing tape (base material thickness 80 μm, glue thickness 10 μm) at room temperature and integrating it, the surface on the heat-dissipating die-bonding film side is attached to an 8-inch wafer with a thickness of 50 μm with a laminator (TEIKOKU). , STM-1200FH (trade name)) was used for laminating at 70 ° C. Then, blade dicing was carried out using a dicer (manufactured by DISCO, DFD6361 (trade name)). The conditions for blade dicing are: blade ZH05-SD4000-N1-70 BB (manufactured by Nanyo, (trade name)), wafer thickness 50 μm, chip size 3 mm × 3 mm, rotation speed 50,000 rpm, dicing tape notch 10 μm, cutting speed 30 mm / sec. The cut length was 203 mm, the cut clearance was set to 3 mm at the beginning and 3 mm at the end. The amount of wear of the blade in the dicing process was calculated from the state of the blade before and after dicing. Specifically, the amount of wear of the blade (μm / m) is determined by the radius r1 (μm) of the blade before dicing, the radius r2 (μm) of the blade after dicing, and the dicing distance L1 (m) according to the following formula. It was calculated from.
Blade wear amount (μm / m) = (r1 (μm) -r2 (μm)) / L1 (m)

(Surface roughness (Ra))
The heat-dissipating die bonding film peeled off from the base film is bonded to a silicon wafer having a thickness of 300 μm using a hot roll laminator (80 ° C, 0.3 m / min, 0.3 MPa), and then at 110 ° C. A sample was obtained by curing at 170 ° C. for 3 hours. The arithmetic mean roughness (Ra) of the obtained sample in the range of 2.5 mm was calculated using a fine shape measuring machine Surf corder ET200 (manufactured by Kosaka Laboratory, trade name).

(Adhesive strength)
The heat-dissipating die bonding film on the base film was attached to a semiconductor chip (5 mm square) using a hot roll laminator (80 ° C., 0.3 m / min, 0.3 MPa). The heat-dissipating die-bonding film on the semiconductor chip was adhered to a 42alloy substrate by pressure bonding at 120 ° C. and 250 g for 5 seconds, and then cured at 110 ° C. for 1 hour and 170 ° 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 (manufactured by Dage, series 4000, trade name). The conditions of the moisture absorption test were 85 ° C./85% RH and 48 hours.

The adhesive strength was evaluated as "good" when the shear strength ≥ 2.0 MPa and as "poor" when the shear strength <2.0 MPa.

(Laminated)
A laminate of the base film and the heat-dissipating die bonding film was cut into a width of 10 mm. The heat-dissipating die-bonding film surface of the laminate was bonded to a silicon wafer having a thickness of 300 μm with a hot roll laminator (80 ° C., 0.3 m / min, 0.3 MPa). After that, when the bonded heat-dissipating die bonding film was peeled off at a tensile speed of 50 mm / min at an angle of 90 ° in an atmosphere of 25 ° C. using a small desktop tester EZ-S Shimadzu Corporation. The 90 ° peel strength was measured. The laminate property was 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 in Table 3, the heat-dissipating die-bonding films of Examples 1 to 7 have a thermal conductivity of ≧ 2 W / (m · K) after thermosetting, are excellent in thermal conductivity after thermosetting, and wear. The amount is ≦ 50 (μm / m), and it can be seen that the blade is excellent in suppressing wear. Further, it can be seen that the heat-dissipating die bonding films of Examples 1 to 7 are excellent in adhesiveness (adhesive force) and laminating property, and have a small surface roughness. That is, according to the heat-dissipating die bonding films of Examples 1 to 7, it is considered that the semiconductor element can be efficiently manufactured because the heat-dissipating die bonding film is excellent and the wear of the blade is easily suppressed.

1 ... Dicing die bonding film, 10 ... Dicing film, 20 ... Die bonding film.

Claims (13)

A heat-dissipating die-bonding film with a thermal conductivity of 2 W / (m · K) or more.
Contains two or more types of thermally conductive fillers with different Mohs hardness,
The thermally conductive filler contains at least one thermally conductive filler having a Mohs hardness of 1 to 3 and at least one thermally conductive filler having a Mohs hardness of 4 to 9.
A heat-dissipating die bonding film in which the amount of wear of the blade in the dicing process is 50 μm / m or less. It has a layer containing two or more types of thermally conductive fillers with different Mohs hardnesses.
The thermally conductive filler contains at least one thermally conductive filler having a Mohs hardness of 1 to 3 and at least one thermally conductive filler having a Mohs hardness of 4 to 9.
The content of the thermally conductive filler is, Ri 20 to 85% by mass,
Thick Ru 5~50μm der, heat dissipation die bonding film. The heat-dissipating die-bonding film according to claim 1 or 2, which contains at least two types of the thermally conductive filler selected from the group consisting of an alumina filler, a boron nitride filler, an aluminum nitride filler and a magnesium oxide filler. The heat-dissipating die bonding film according to claim 3, wherein the alumina filler contains an alumina filler having a purity of 99.0% by mass or more. The heat-dissipating die-bonding film according to claim 3 or 4, wherein the boron nitride filler contains a hexagonal boron nitride filler having a nitrogen purity of 95.0% by mass or more. The heat-dissipating die-bonding film according to any one of claims 3 to 5, wherein the density of the aluminum nitride filler ^{is 3 to 4 g / cm 3.} The heat-dissipating die-bonding film according to any one of claims 3 to 6, wherein the magnesium oxide filler contains a magnesium oxide filler having a purity of 95.0% by mass or more. The heat-dissipating die-bonding film according to any one of claims 1 to 7, further containing a high molecular weight component of either an acrylic resin or a phenoxy resin, an epoxy resin, and a curing agent. The eighth aspect of the present invention, wherein the total mass of the heat conductive film is 20 parts by mass or more with respect to 100 parts by mass of the total amount of the high molecular weight component, the epoxy resin, the curing agent and the heat conductive film. Heat dissipation die bonding film. The heat-dissipating die-bonding film according to any one of claims 1 to 9, which contains an alumina filler and a boron nitride filler as the thermally conductive filler. The heat-dissipating die-bonding film according to any one of claims 1 to 10, which contains a boron nitride filler and an aluminum nitride filler as the heat conductive filler. The heat-dissipating die-bonding film according to any one of claims 1 to 11, which contains a boron nitride filler and a magnesium oxide filler as the thermally conductive filler. A dicing film and a die bonding film laminated on the dicing film are provided.
A dicing die bonding film, wherein the die bonding film is the heat-dissipating die bonding film according to any one of claims 1 to 12.

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