TW201908441A - Heat-dissipating film and dicing-mud film - Google Patents

Abstract

The present invention pertains to a heat dissipating die bonding film having a thermal conductivity of 2W/(m*K) or more, wherein the heat dissipating die bonding film contains two or more types of thermally conductive fillers having different Moh's hardnesses, and has an abrasion amount of a blade in a dicing process being 50 [mu]m/m or less, or the heat dissipating die bonding film contains two or more types of thermally conductive fillers having different Moh's hardnesses and a content of 20-85 mass%.

Description

Heat-dissipating crystal bonding film and die-cutting crystal bonding film

The invention relates to a heat-dissipating crystal bonding film and a crystal cutting-crystal bonding film.

After adjusting the thickness of the semiconductor wafer on which the circuit pattern is formed by back-grinding as necessary, the semiconductor element is cut into a wafer-like shape (crystal cutting step). Then, the semiconductor element is fixed to the adherend such as a lead frame using an adhesive (a die bonding step), and then the process moves to the bonding step. For example, there has been proposed a method of disposing a metal base via a bonding agent at a lower portion of a die pad and a lead portion on which a semiconductor element is mounted, thereby improving the heat dissipation effect of a package for a semiconductor device (for example, refer to Patent Document 1) . On the other hand, as an adhesive film having thermal conductivity or heat dissipation, for example, an adhesive film containing highly thermally conductive particles or a heat dissipating die-bonding film containing a thermally conductive filler is known (for example, refer to Patent Document 2 and Patent Document 3). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 5-198701 [Patent Document 2] Japanese Patent Laid-Open No. 2009-235402 [Patent Document 3] Japanese Patent Laid-Open No. 2014-68020

[Problem to be Solved by the Invention] An object of the present invention is to provide a heat-dissipating die-bonding film capable of efficiently manufacturing semiconductor devices and a die-bonding film including the same.

[Means for Solving the Problems] The present invention relates to a heat-dissipating adhesive crystal film, which has a thermal conductivity of 2 W / (m × K) or more, and the heat-dissipating adhesive crystal film contains two or more types with different Mohs hardness Thermally conductive filler, and the abrasion of the blade in the crystal cutting step is 50 μm / m or less.

In addition, the present invention relates to a heat-dissipating viscous crystal film, which contains two or more types of thermally conductive fillers with different Mohs hardness, and the content of the thermally conductive filler is 20% by mass to 85% by mass.

The heat-dissipating viscous crystal film may contain at least two selected from the group consisting of alumina filler, boron nitride filler, aluminum nitride filler and magnesium oxide filler as a thermally conductive filler.

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

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

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

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

The heat-dissipating adhesive film may further contain any high molecular weight component of acrylic resin and phenoxy resin, epoxy resin and hardener.

In the heat-dissipating viscous crystal film, the total mass of the thermally conductive filler may be 20 parts by mass or more relative to 100 parts by mass of the high molecular weight component, epoxy resin, hardener, and thermally conductive filler.

As the thermally conductive filler, the heat-dissipating viscous crystal film may contain alumina filler and boron nitride filler, boron nitride filler and aluminum nitride filler, or boron nitride filler and magnesium oxide filler.

In addition, the present invention relates to a crystal-cut crystal bonding film, which includes a crystal-cut film and a crystal bonding film laminated on the crystal cutting film, and the crystal bonding film is the heat-dissipating crystal bonding film.

[Effects of the Invention] 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 die-cutting die-bonding film including the same.

Hereinafter, embodiments of the present invention will be described in detail with reference to drawings as appropriate. However, the present invention is not limited to the following embodiments. In this specification, "(meth) acrylate" means "acrylate" or "methacrylate" corresponding thereto.

[Heat-dissipating viscous film] The thermal conductivity of the heat-dissipating viscous film according to an embodiment is 2 W / (m × K) or more, and the heat-dissipating viscous film contains two or more types of thermal conductivity with different Mohs hardness Filler, and the wear of the blade in the crystal-cutting step is 50 μm / m or less. According to such a heat-dissipating die-bonding film, a semiconductor device can be manufactured efficiently.

In this specification, the amount of blade wear in the crystal cutting step is calculated according to the following procedure. Laminate the heat-dissipating adhesive film on the dicing tape at room temperature (the substrate thickness is 80 μm and the paste thickness is 10 μm) and integrate, then use a laminator (TEIKOKU TAPING SYSTEM) Co., Ltd., STM-1200FH (trade name)), the surface on the side of the heat-dissipating adhesive film is laminated on an 8-inch wafer with a thickness of 50 μm at 70 ° C. Thereafter, a cutter (made by DISCO Co., Ltd., DFD6361 (trade name)) was used to perform crystal cutting with a blade. The conditions for the crystal cutting of the blade are: using the blade ZH05-SD4000-N1-70 BB (Nanyang Co., Ltd., (trade name)); the wafer thickness is 50 μm; the wafer size is 3 mm × 3 mm; the rotation speed is 50000 rpm ; The dicing tape cutting mark is 10 μm; the shear speed is 30 mm / sec; the shear length is 203 mm; the shear gap starts at 3 mm and ends at 3 mm. Then, according to the following formula, the blade wear (μm / m) is calculated from the radius r1 (μm) of the blade before crystal cutting, the radius r2 (μm) of the blade after crystal cutting and the distance L1 (m) of crystal cutting ). Blade wear (μm / m) = (r1 (μm) -r2 (μm)) / L1 (m)

The heat-dissipating adhesive film of another embodiment may be, for example, the following: it contains two or more types of thermally conductive fillers having different Mohs hardnesses, and the content of the thermally conductive filler is 20% by mass to 85% by mass. According to such a heat-dissipating die-bonding film, a semiconductor device can be manufactured efficiently. This heat-dissipating adhesive film is also excellent in thermal conductivity after thermal hardening and blade abrasion in the crystal cutting step.

In the production of the heat-dissipating die-bonding film of this embodiment, the step of applying pressure in the thickness direction to the primary film formed using the varnish is not necessarily required. In addition, the heat-dissipating die-bonding film of this embodiment is also excellent in adhesion, and even in the case where the manufactured semiconductor element repeatedly generates heat, there is a tendency to easily reduce the thermal expansion coefficient of the metal base, semiconductor element, die-bonding pad, etc. The difference between the metal base caused by the difference and the cracks.

The heat-dissipating die-bonding film of this embodiment may further contain a high-molecular-weight component, an epoxy resin, and a hardener, which will be described later, for example. Hereinafter, each component is demonstrated. In addition, hereinafter, the "high molecular weight component" is also called "a component", the "epoxy resin" is called "b component", the "hardener" is called "c component", and the "thermally conductive filler" is also called It is "d component".

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

From the viewpoint of easily obtaining film formability, heat resistance, and adhesion, the component a may be, for example, phenoxy resin, polyimide, polyamide, polycarbodiimide, cyanate resin, acrylic resin , Polyester, polyethylene, polyether sock, polyether amide imide, polyethylene acetal or urethane resin. These high molecular weight components may be copolymers, for example. The component a may be used alone or in combination of two or more.

From the viewpoint of excellent film formability and heat resistance, the component a is preferably a phenoxy resin, polyimide, polyamide, acrylic resin, cyanate resin, or polycarbodiimide; it is easy From the viewpoint of adjusting the molecular weight and characteristics, the phenoxy resin is preferred as the component a. From these viewpoints, the component a may be any of acrylic resin and 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. The acrylic resin may be used alone or in combination of two or more.

In this specification, the weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography (Gel Permeation Chromatography, GPC) and using a standard curve of standard polystyrene.

Specific examples of acrylic resins include acrylic copolymers. Examples of the acrylic copolymer include acrylic rubber. Examples of the acrylic rubber include a copolymer of at least one selected from acrylate and methacrylate and acrylonitrile.

Examples of the reactive group include carboxylic acid group, amine group, hydroxyl group and epoxy group.

The reactive group may be, for example, from the viewpoint of easily reducing gelation in the varnish state and from the viewpoint of hardly causing an increase in the degree of curing in the B-stage state and a decrease in adhesive force caused by the increase in the degree of curing, for example Epoxy.

When the reactive group is an epoxy group, the present inventors speculate as to the reason for exerting the above-mentioned effects. When the reactive group is, for example, a carboxyl group, it is considered that the cross-linking reaction is easy to proceed, and gelation in the varnish state and increase in the degree of hardening in the B-stage state may occur. On the other hand, when the reactive group is an epoxy group, it is considered that it is difficult to cause a cross-linking reaction, so that it is difficult to cause gelation in the varnish state and increase in the degree of hardening in the B-stage state.

The acrylic resin having a reactive group can be produced, for example, in the following manner: In the polymerization reaction to obtain an acrylic resin, the acrylic monomer having the reactive group (the reactive group ( Groups) acrylic esters, etc.) are polymerized, or reactive groups are introduced into the synthesized acrylic resin.

Examples of the acrylic resin having an epoxy group include acrylic resins 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, or 2 based on the total mass of the acrylic resin from the viewpoint of easily improving adhesion. Mass% or more. In addition, from the viewpoint of easily reducing gelation, 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 these viewpoints, based on the total mass of the acrylic resin, the content of glycidyl (meth) acrylate as a monomer unit may be 0.5% by mass to 6% by mass, or may be 2% by mass to 6% by mass %.

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

In the case where the acrylic resin is an acrylic copolymer, the copolymerization ratio of each monomer can be adjusted in consideration of the glass transition temperature of the copolymer (hereinafter, referred to as “Tg” as appropriate).

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. If the Tg is -50 ° C. or higher, the adhesive layer or adhesive film in the B-stage state tends to be less viscous and excellent in handleability.

The acrylic resin may also have a ring structure. Examples of the acrylic resin having a cyclic structure include acrylic resins having styrene or benzyl (meth) acrylate as a monomer unit. In the case where the acrylic resin has a ring structure, it is considered that the higher the total mass Mcr (Mcr / MTOT) of carbon atoms in the ring structure based on the total mass MTOT of the acrylic resin, the better.

When it is set to a sheet shape or a film shape, the weight average molecular weight of the acrylic resin may be, for example, 200,000 or more, or 300,000 or more, from the viewpoints that it is difficult to reduce the strength and flexibility, and it is difficult to increase the viscosity. It can be above 400,000. From the viewpoint of high fluidity and easy improvement of circuit fillability of wiring, the weight average molecular weight of the acrylic resin may be, for example, 3,000,000 or less, or 2,000,000 or less. From these viewpoints, the weight average molecular weight of the acrylic resin may be, for example, 200,000 to 3,000,000, or 300,000 to 3,000,000, or 400,000 to 2000000.

From the viewpoint of easily obtaining high adhesiveness and heat resistance, the acrylic resin as the component a may be, for example, an acrylic copolymer containing 0.5% to 6% by mass of glycidyl (meth) acrylate. As the monomer unit, Tg is -50 ° C or more and 50 ° C or less (preferably -10 ° C or more and 50 ° C or less), and the weight average molecular weight is 100,000 or more. Examples of such acrylic resins include HTR-860P-3 and HTR-860P-30B (manufactured by Nagase ChemteX Co., Ltd., 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 still more 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, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name); and 1256, 4250, 4256, 4275, YX7180, YX6954, YX8100, YX7200, YL7178, YL7290, YL7600, YL7734, YL7827 and YL7864 (above, Japan Epoxy Resin (Epoxy Resin Japan) Co., Ltd., trade name).

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

[Component b: Epoxy resin] The component b is, for example, hardened and presents a user. From the viewpoint of heat resistance, the component b is preferably an epoxy resin having two or more functional groups (an epoxy resin having two or more functional groups).

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

Examples of the component b include difunctional epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; phenol novolac epoxy resin, cresol novolac epoxy resin and other novolac-type rings Oxygen resins; multifunctional epoxy resins; amine epoxy resins; epoxy resins containing heterocycles; and alicyclic epoxy resins. As the component b, generally known epoxy resins other than the above can also be used.

Examples of commercially available bisphenol A-type epoxy resins include: Epikote 807, Epikote 815, Epikote 825, and Epikote 827 , Epikote 828, Epikote 834, Epikote 1001, Epikote 1002, Epikote 1003, Epikote (Epikote) 1055, Epikote 1004, Epikote 1004AF, Epikote 1007, Epikote 1009, Epikote 1003F and Epikote 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 (above, manufactured by Dow Chemical, trade name); and YD8125 (Nippon Steel Sumikin Chemical Co., Ltd., trade name).

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

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

Examples of commercially available cresol novolac-type epoxy resins include: Epikote 180S65 (manufactured by Mitsubishi Chemical Corporation, trade name); Araldite ECN1273, Araldite ECN1280 and Araldite ECN1299 (above, manufactured by Ciba Specialty Chemicals, trade name); YDCN-700-10, YDCN-701, YDCN-702, YDCN-703 and YDCN-704 ( Above, 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, Nippon Kayaku Co., Ltd., trade name); and ESCN-195X, ESCN-200L and ESCN-220 (above, Sumitomo Chemical Co., Ltd., trade name).

Examples of commercially available multifunctional epoxy resins include Epon 1031S, Epikote 1032H60, and Epikote 157S70 (above, manufactured by Mitsubishi Chemical Corporation, trade name) ; Araldite 0163 (manufactured by Ciba Specialty Chemicals, trade name); Denacol EX-611, Denacol EX-614, Danacau Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-521, Denacol EX- 421, Denacol EX-411 and Denacol EX-321 (above, manufactured by Nagase ChemteX Co., Ltd., trade name); and EPPN501H and EPPN502H (above, Japan Manufactured by Huayao Pharmaceutical Co., Ltd.).

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

Examples of commercially available heterocyclic ring-containing epoxy resins include Araldite PT810 (manufactured by Ciba Specialty Chemicals, trade name).

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

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

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

[Component c: Hardener] The component c can be used without particular limitation if it can harden the component b. Examples of the component c include polyfunctional phenol compounds, amine compounds, acid anhydrides, organic phosphorus compounds and these halides, polyamides, polysulfides, and boron trifluoride.

Examples of polyfunctional phenol compounds include monocyclic bifunctional phenol compounds and polycyclic bifunctional phenol compounds. Examples of monocyclic difunctional phenols include hydroquinone, resorcinol, catechol, and alkyl substituents thereof.

Examples of the polycyclic bifunctional phenol compound include bisphenol A, bisphenol F, bisphenol S, naphthalene diol and biphenol, and alkyl substituents of these. In addition, the polyfunctional phenol compound may be, for example, a polycondensate of at least one phenol compound and an aldehyde compound selected from the group consisting of the monocyclic difunctional phenol compound and the polycyclic difunctional phenol compound. The polycondensate is, for example, a phenol resin. Examples of the phenol resin include phenol novolak resin, resole resin, bisphenol A novolak resin, and cresol novolak resin.

Examples of the commercially available products of the phenol resin (phenol resin hardener) include Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, and Phenolite ) TD-2149, Phenolite VH4150 and Phenolite VH4170 (above, manufactured by DIC Corporation, trade name).

From the viewpoint of adhesiveness and heat resistance, the hydroxyl 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. In addition, from the viewpoint of improving the electrolytic corrosion resistance at the time of moisture absorption, the phenol resin as the component c is preferably a novolak type or a novolak type resin.

From the viewpoint of improving moisture resistance, the phenol resin is preferably one having a water absorption rate of 2% by mass or less after being left in a constant temperature and humidity bath at 85 ° C. and 85% RH for 48 hours. In addition, the phenol resin as the component c is preferably a heating weight reduction rate (heating rate: 5 ° C / min, environment: nitrogen) at 350 ° C measured by a thermogravimetric analyzer (TGA) of less than 5 wt% By. If such a phenol resin is used as a curing agent, volatile components are suppressed during heat processing, thereby improving the reliability of various characteristics such as heat resistance and moisture resistance, and it is considered that volatile components during operations such as heat processing can be reduced The pollution caused by the machine.

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

[Chemical 1]

In formula (I), R ¹ represents 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 Halogen atom, n represents an integer of 1-3, m represents an integer of 0-50. In formula (I), a plurality of R ¹ and n may be the same or different.

Examples of the compound represented by the formula (I) include Miles XLC-series and Miles XL series (above, manufactured by Mitsui Chemicals Co., Ltd., trade name).

The compound represented by the formula (I) can be obtained by reacting a phenol compound and a xylyl compound in the absence of a catalyst or an acid catalyst (acid catalyst), for example. In addition, the xylylene compound can form a divalent linking group by this reaction.

Examples of the phenol compound used in the production of the compound represented by formula (I) include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-n-propylphenol , M-n-propylphenol, p-n-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o Isobutylphenol, m-isobutylphenol, p-isobutylphenol, octylphenol, nonylphenol, 2,4-xylenol, 2,6-xylenol, 3,5-xylenol, 2 , 4,6-trimethylphenol, resorcin, resorcinol, 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 phenol compound may be used alone 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 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 formula (I) include xylylene dihalide, xylylene diethylene 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-p-xylene, α, α'-dibromo-m-xylene, α, α'-dibromo-o-xylene, α, α'-diiodine-p-xylene, α, α'- Diiodine-m-xylene, α, α'-diiodine-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'-x-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'-x-n-butoxy-p-xylene, α , α'-di-n-butoxy-m-xylene, α, α'-di-n-butoxy-o-xylene, α, α'-diisobutoxy-p-dimethyl , Α, α'-diisobutoxy-m-xylene, α, α'-diisobutoxy-o-xylene, α, α'-di-third butoxy-p-xylene, α, α'-Di-third butoxy-m-xylene and α, α'-di-third butoxy-o-xylene. The xylylene compound may be used alone or in combination of two or more.

From the viewpoint of producing a phenol resin with good adhesion, heat resistance, and moisture resistance, the xylylene compound is preferably α, α'-dichloro-p-xylene, α, α'-dichloro- M-xylene, α, α'-dichloro-o-xylene, α, α'-dihydroxy-p-xylene, α, α'-dihydroxy-m-xylene, α, α'-dihydroxy-o-xylene Toluene, α, α'-dimethoxy-p-xylene, α, α'-dimethoxy-m-xylene or α, α'-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 dimethyl sulfuric acid, diethyl sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid; trifluoro Super acid such as methanesulfonic acid; strong acid ion exchange resin such as alkane sulfonic acid type ion exchange resin; super acid acid ion exchange resin such as perfluoroalkane sulfonic acid type ion exchange resin (for example, Nafion, Dupont) Made by the company, trade name)); natural and synthetic zeolite compounds; and activated clay (for example, acid clay).

The reaction proceeds until, for example, at 50 ° C. to 250 ° C., the substantially xylylene compound as a raw material disappears, and the reaction composition becomes fixed.

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

If the reaction is carried out in the presence of an acid catalyst, water or alcohol is usually produced.

On the other hand, for example, in the case of using a halogenated xylene derivative such as α, α'-dichloro-p-xylene as the xylylene compound, it is carried out in the absence of a catalyst while generating hydrogen halide gas Reaction, so an acid catalyst is not necessarily required.

The molar ratio of the reaction between the phenol compound and the xylylene compound is usually set as a condition in which the phenol compound is excessive. In this case, the unreacted phenol compound is recovered after the reaction. The weight average molecular weight of the compound represented by formula (I) is usually determined by the molar ratio of the reaction of the phenol compound and the xylylene compound. There is a tendency that as the phenol compound becomes excessive, the weight average molecular weight of the compound represented by formula (I) decreases.

The phenol resin may be, for example, one having an allylphenol skeleton. A phenol resin having an allylphenol skeleton can be obtained, for example, by producing a non-allylated phenol resin, reacting it with an allyl halide, passing through an allyl ether, and using Claisen rearrangement is allylated.

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.

Specific examples of the amine compound include: N, N-benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol , Tetramethylguanidine, triethanolamine, N, N'-dimethylpiperazine, 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, picoline, 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, triethylidenetetraamine, diaminodiphenylmethane, diamino Diphenyl ether, dicyandiamide, tolyl biguanide, guanidine urea and dimethyl urea. The amine compound may be, for example, dihydrazide compounds such as adipic acid dihydrazine; guanidine acid; melamine acid; addition compounds of epoxy compounds and dialkylamine compounds; addition compounds of amines and thioureas; And amine and isocyanate addition compounds. From the viewpoint of reducing the activity at room temperature, these amine compounds may have an addition-molded structure, for example.

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

The organic phosphorus compound as the component c is not particularly limited if it is a phosphorus compound having an organic group. Examples of the organic phosphorus compound include trisamide hexamethylphosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, triphenylphosphite, trimethyl phosphate, and phenylphosphine Acid, triphenylphosphine, tri-n-butylphosphine and diphenylphosphine.

The component c may be used alone or in combination of two or more.

[component d: thermally conductive filler] The component d is, for example, a person capable of imparting thermal conductivity to the heat-dissipating adhesive film. In the present embodiment, the heat-dissipating die-bonding film contains two or more d components with different Mohs hardness. It is considered that the use of two or more d components with different Mohs' hardnesses makes it difficult to wear the blade. The d component can be appropriately selected from two or more of the d components described below, for example.

Examples of the material constituting the component d include alumina, zinc oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, magnesium hydroxide, aluminum hydroxide, silicon carbide, diamond, magnesium carbonate, aluminum borate, and Antimony oxide and combinations of these. The material constituting the component d may also have electrical insulation properties. Examples of boron nitride include hexagonal boron nitride and cubic boron nitride. Aluminum borate may also be aluminum borate whiskers.

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

In the heat-dissipating die-bonding film of the present embodiment, from the viewpoint of further improving the thermal conductivity after thermal hardening and further reducing the wear of the blade in the crystal-cutting step, it is preferable to contain At least two of the group consisting of boronide filler, aluminum nitride filler and magnesium oxide filler are used as the d component.

From the viewpoint of further improving the thermal conductivity after thermal hardening and further reducing the wear of the blade in the crystal cutting step, the alumina filler preferably contains an alumina filler having a purity of 99.0% by mass or more. The alumina filler may include an alumina filler with a purity of 99.0% by mass or more. Examples of alumina fillers having a purity of 99.0% by mass or more include Sumicorundum AA-3 (made by Sumitomo Chemical Co., Ltd., trade name) and alumina beads CB-P05 (Showa Denko Co., Ltd.) Manufacturing, trade name). The alumina filler preferably contains an α-alumina filler with a purity of 99.0% by mass or more. The purity of the alumina filler may be 100% by mass or less, for example.

From the viewpoint of further improving the thermal conductivity after thermal hardening and further reducing the abrasion of the blade in the crystal cutting step, the boron nitride filler is preferably hexagonal nitridation containing nitrogen with a purity of 95.0% by mass or more Boron filler. Examples of such hexagonal boron nitride fillers include HP-P1 and HP-4W (manufactured by Mizushima Alloy Iron Co., Ltd., trade name) and SHOPN (SHOBN) UHP-S1 (manufactured by Showa Denko Co., Ltd., Product name). Here, the purity of nitrogen is calculated based on the mass of nitrogen in hexagonal boron nitride saturated with nitrogen. 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 3 g / cm ³ to 4 g / cm ^{3, for example} . As such aluminum nitride fillers, for example, Shapal H (Shapal) H grade and Shapal E (Shaman) E grade (manufactured by Toyama Co., Ltd., trade name) and ALN020BF (made by Pakistan Industrial Co., Ltd., trade name) ).

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

In the heat-dissipating die-bonding film of this embodiment, as the component d, the alumina filler and the boron nitride filler may be contained, or the boron nitride filler and the aluminum nitride filler may be contained, or Contains the boron nitride filler and the magnesium oxide filler.

From the viewpoint of further improving adhesion strength, lamination property and reliability, the average particle diameter (d ₅₀ ) of the mixture of d components is preferably 1/2 or less of the thickness of the heat-dissipating die-bonding film, more preferably 1 / 3 or less, and more preferably 1/4 or less. The average particle diameter (d ₅₀ ) of the mixture of component d may be, for example, 1/1000 or more of the thickness of the heat-dissipating adhesive film.

From the viewpoint of further improving adhesive strength, lamination property and reliability, the average particle diameter (d ₉₀ ) of the mixture of d components is preferably 1/2 or less of the thickness of the heat-dissipating die-bonding film, more preferably 1 / 3 or less, and more preferably 1/4 or less. The average particle diameter (d ₉₀ ) of the mixture of component d may be, for example, 1/1000 or more of the thickness of the heat-dissipating adhesive film.

In addition, in this specification, the average particle size is (d ₅₀ ) means that the cumulative value of the particle size distribution is equivalent to 50% of the particle size, and the average particle size is (d ₉₀ ) is that the cumulative value of the particle size distribution is equivalent to 90% Particle size.

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

In the heat-dissipating die-bonding film of the present embodiment, from the viewpoint of easily suppressing the wear of the blade in the crystal-cutting step, it is preferable that at least one of the d components has a Mohs hardness of 10 or less, more preferably 9 Below, and even more preferably 8 or less.

When the Mohs hardness of at least one of the components d is 10 or less, the Mohs hardness is based on the total mass of the heat-dissipating die-bonding film from the viewpoint of easily suppressing the wear of the blade in the crystal cutting step. The content of the d component of 10 or less may be, for example, 10% by mass or more, 15% by mass, or 20% by mass or more.

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

The shape of the d component is not particularly limited. For example, it may be spherical or polyhedral. In addition, in this specification, a polyhedron refers to a three-dimensional structure having a plurality of planes as constituent parts of the surface. There are multiple planes that can be exchanged via curved surfaces. The polyhedron may have, for example, 4 to 100 planes as components of the surface.

In the heat-dissipating die-bonding film of the present embodiment, from the viewpoint of easily reducing the elastic coefficient and the viewpoint of easily giving fluidity during molding, the total mass of the a component, the b component, the c component and the d component is 100 mass Parts, the content of the component a can be, for example, 3 parts by mass or more. From the viewpoint that it is difficult to reduce the flowability and the viewpoint of being excellent in circuit filling property even when there is little attachment load, the content of a component is 100 parts by mass relative to the total of a component, b component, c component and d component. The content may be, for example, 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, or 3 to 30 parts by mass with respect to the total of 100 parts by mass of the a component, the b component, the c component, and the d component. , It may be 3 to 20 parts by mass.

In the heat-dissipating adhesive film of the present embodiment, the content of the component b may be, for example, 3 parts by mass to 55 parts by mass relative to 100 parts by mass of the total of the components a, b, c and d. 5 parts by mass to 45 parts by mass, or 10 parts by mass to 35 parts by mass.

As long as the curing reaction of the component b can proceed, the content of the component c in the heat-dissipating adhesive film of the present embodiment is not particularly limited, and can react with the epoxy group based on 1 equivalent of the epoxy group in the component b The active group (hydroxyl group, amine group, acid anhydride group, phosphorus atom-containing group, etc.) in the component c may be, for example, 0.01 equivalent to 5.0 equivalents, or 0.8 equivalent to 1.2 equivalents.

For example, in the case where the component c is a phenol resin, the content of the component c in the heat-dissipating adhesive film of the present embodiment is the epoxy equivalent of the component b from the viewpoint of improving the hardenability when forming the thermally radiating adhesive film The equivalent ratio to the hydroxy equivalent of the phenol resin (epoxy equivalent / hydroxy equivalent) can be, for example, 0.70 / 0.30 to 0.30 / 0.70, or 0.65 / 0.35 to 0.35 / 0.65, or 0.60 / 0.30 to 0.30 / 0.60, can also be 0.55 / 0.45 ~ 0.45 / 0.55.

In the heat-dissipating die-bonding film of this embodiment, from the viewpoint of further improving the thermal conductivity after thermosetting, the total amount of the d component is 100 parts by mass relative to the total amount of the a component, b component, c component, and d component. The mass may be, for example, 20 parts by mass or more, 22 parts by mass or more, or 25 parts by mass or more. From the viewpoint of film characteristics such as surface roughness, adhesion, and lamination, the total mass of the d component can be, for example, 85 parts by mass with respect to the total of 100 parts by mass of the component a, b component, c component, and d component The following may be 75 parts by mass or less, or 70 parts by mass or less.

The heat-dissipating adhesive film of this embodiment preferably contains any high molecular weight component of acrylic resin and phenoxy resin, epoxy resin and hardener.

[Other components] The heat-dissipating die-bonding film of the present embodiment may contain components other than the above. Examples of such components include curing accelerators, fillers other than component d, coupling agents, and ion trapping agents.

(Curing accelerator) The curing accelerator is not particularly limited, and examples thereof include imidazole compounds. Examples of the imidazole compound include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 1-benzyl- 2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecyl Alkyl imidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-phenyl-4-methylimidazoline , Benzimidazole, 1-cyanoethylimidazole, 1-cyanoethyl-2-phenylimidazole and 1-cyanoethyl-2-phenylimidazolium trimellitate. The hardening accelerator may be used alone or in combination of two or more. Examples of commercially available products of the imidazole compounds include 2E4MZ, 2PZ-CN, and 2PZ-CNS (all manufactured by Shikoku Chemical Industry Co., Ltd., trade names).

In addition, from the viewpoint of prolonging the service life of the film, the curing accelerator may be a latent curing accelerator. Examples of such hardening accelerators include addition compounds of epoxy compounds and imidazole compounds. From the viewpoint of reducing the activity at room temperature, the hardening accelerator may be a structure having addition molding.

From the viewpoint of excellent storage stability and the viewpoint of easily ensuring the pot life, based on the total mass of component b and component c, the blending amount of the hardening accelerator may be, for example, 5.0% by mass or less, or 3.0% by mass the following. From the standpoints of adhesiveness, heat resistance, and moisture resistance after thermal curing, the amount of the curing accelerator may be, for example, 0.02% by mass or more or 0.03% based on the total mass of the component b and component c. %the above. From these viewpoints, based on the total mass of the component b and the component c, the blending amount of the curing accelerator may be, for example, 0% by mass to 5.0% by mass, or 0.02% by mass to 3.0% by mass, or 0.03% by mass to 3.0% by mass.

(Filler other than component d) For the purpose of improving the handleability of the film, adjusting the melt viscosity, imparting thixotropy, and improving the moisture resistance, the heat-dissipating viscous crystal film of the present embodiment may contain components other than the component d Of various fillers. The filler other than the component d may be used alone or in combination of two or more.

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

From the viewpoint of easily adjusting the melt viscosity and the viewpoint of easily imparting thixotropy, the material constituting the filler other than the component d may be calcium carbonate, calcium silicate, magnesium silicate, calcium oxide, crystalline silica, or amorphous Silicon dioxide. From the viewpoint of easily improving the moisture resistance, the material constituting the filler other than the component d may be silicon dioxide.

When the heat-dissipating adhesive film of this embodiment contains fillers other than the component d, the content of the fillers other than the component d may be, for example, 50 parts by mass or less, or 20 with respect to the total mass of the component d. Less than or equal to 10 parts by mass.

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

The silane-based coupling agent is not particularly limited, and examples thereof include vinyl trichlorosilane, vinyl tri (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β -(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyl Diethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl-tri ( 2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-amino Propyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3- (4,5-dihydro) imidazol-1-yl-propyltrimethoxysilane, 3-methacryloxypropyl -Trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, 3-chloropropyl-methyldimethoxysilane, 3-chloropropyl-dimethoxysilane, 3-cyano Propylpropyl-triethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyl Trichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, pentyltrichlorosilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Methyltri (methacryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Trimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethyl Oxysilane, γ-chloropropylmethyl diethoxysilane, trimethylsilyl isocyanate, dimethyl Silicon alkyl isocyanates, alkyl methyl silicone triisocyanate, vinyl alkyl triisocyanate silicon, silicon alkyl phenyl triisocyanates, tetraisocyanates and ethoxy Silane Silane isocyanate. These can be used alone or in combination of two or more.

The titanium-based coupling agent is not particularly limited, and examples thereof include isopropyl trioctyl titanate, isopropyl dimethylpropenyl isostearyl titanate, and isopropyl tri-dodecyl. Benzenesulfonyl titanate, isopropyl isostearyl dipropenyl titanate, isopropyl tris (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate , Isopropyl tri (dioctyl pyrophosphate group) titanate, isopropyl tri (n-aminoethyl) titanate, tetraisopropyl bis (dioctyl phosphite group) titanate , Tetraoctyl bis (di-tridecyl phosphite group) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) Phosphite titanate, dicumylphenyloxyacetate titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetratitanate N-butyl ester, butyl titanate dimer, tetrakis (2-ethylhexyl) titanate, titanium acetyl pyruvate, poly titanium titanium pyruvate, titanium octyl glycolate, titanium ammonium lactate , Titanium lactate, titanium ethyl lactate, titanium triethanolamine, titanium hydroxystearate, tetramethyl orthotitanate, Tetraethyl titanate, tetrapropyl orthotitanate, tetraisobutyl orthotitanate, stearyl titanate, toluene titanate monomer, toluene titanate polymer, diisopropoxy-bis ( 2,4-glutaric acid) titanium (IV), diisopropyl-bis-triethanolamine titanate, octanediol titanate, tetra-n-butoxy titanium polymer, tri-n-butoxy Titanium monostearate polymer and tri-n-butoxy titanium monostearate. These can be used alone or in combination of two or more.

The aluminum-based coupling agent is not particularly limited, and examples thereof include ethyl acetoacetate, aluminum diisopropoxide, aluminum tris (acetate) aluminum, aluminum acetoacetate, aluminum diisopropoxide, and monoethyl acetoacetate. Acetoacetate bis (acetylacetoxyethyl) aluminum, tris (acetylpyruvate) aluminum, monoisopropoxymonooleyloxyethylacetoacetate aluminum, di-n-butaluminum oxide-mono-ethyl Aluminum chelate compounds such as ethyl acetate, di-iso-propylalumina-mono-ethyl acetate, etc .; and aluminum isopropoxide, mono-second butoxy aluminum diisopropoxide, second butanol Aluminum alkoxide such as aluminum and aluminum ethoxide. These can be used alone or in combination of two or more.

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

In the case where the heat-dissipating adhesive film of this embodiment contains a coupling agent, from the viewpoint of its effect, heat resistance, and cost, the coupling agent has an amount of 100 parts by mass relative to the total mass of component a, component b, and component c. The content may be, for example, 10 parts by mass or less, 0.1 to 5 parts by mass, or 0.2 to 3 parts by mass.

(Ion-trapping agent) For example, from the viewpoint of adsorbing ionic impurities and improving insulation reliability during moisture absorption, the heat-dissipating die-bonding film of the present embodiment may contain an ion-trapping agent. Examples of the ion trapping agent include copper inhibitors for preventing copper from being ionized and eluted. Examples of the copper poison inhibitor include triazine thiol compounds, bisphenol-based reducing agents, and inorganic ion adsorbents.

As a commercially available product of a copper poison inhibitor containing a triazine thiol compound as a component, for example, Zisnet DB (manufactured by Sankyo Chemical Co., Ltd., trade name) can be cited.

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-tert-butylphenol). Commercially available bisphenol-based reducing agents include, for example, Yoshinox BB (manufactured by Gifu 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 East Asia Synthetic Co., Ltd., trade name).

From the standpoint of the effects due to the addition and the heat resistance and cost, the ion trapping is relative to 100 parts by mass of the total amount of the resin composition (for example, varnish described later) used in the formation of the heat-dissipating adhesive film. The content of the agent can be, for example, 1 part by mass to 10 parts by mass.

In the heat-dissipating adhesive film of the present embodiment, from the viewpoint of easily reducing the elastic coefficient and giving the fluidity at the time of molding, the content of the a component can be, for example, based on the total mass of the heat-dissipating adhesive film. It is more than 3 parts by mass. From the viewpoint that it is difficult to reduce the fluidity and the circuit fillability is excellent even when the load is small, the content of the a component can be, for example, 40 parts by mass based on the total mass of the heat-dissipating die-bonding film. The following may be 30 parts by mass or less, or 20 parts by mass or less. From these viewpoints, based on the total mass of the heat-dissipating die-bonding film, the content of the component a may be 3 to 40 parts by mass, or 3 to 30 parts by mass, or 3 parts by mass. ~ 20 parts by mass.

In the heat-dissipating die-bonding film of this embodiment, based on the total mass of the heat-dissipating die-bonding film, the content of the component b may be, for example, 3% by mass or more, 5% by mass or more, or 10% by mass the above. The content of the 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 adhesive film. The content of the 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 adhesive film.

In the heat-dissipating die-bonding film of the present embodiment, from the viewpoint of further improving the thermal conductivity after thermosetting, the content of the d component is preferably 20% by mass or more based on the total mass of the heat-dissipating die-bonding film. It is more preferably 25% by mass or more, and still more preferably 30% by mass or more. From the viewpoint of film characteristics such as surface roughness, adhesiveness, and lamination, the content of the d component is preferably 85% by mass or less, more preferably 75% by mass or less based on the total mass of the heat-dissipating die-bonding film. , And more preferably 70% by mass or less. From these viewpoints, the content of the d component is preferably 20% by mass to 85% by mass, more preferably 25% by mass to 75% by mass, and even more preferably 30 based on the total mass of the heat-dissipating adhesive film. Mass% ~ 85% by mass.

There is no particular limitation on the thickness of the heat-dissipating die-bonding film. From the viewpoint of improving the stress relaxation effect and embedding property, 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 cost reduction, 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 μm to 50 μm, 5 μm to 40 μm, or 8 μm to 40 μm.

[Manufacturing method of heat-dissipating die-bonding film] The heat-dissipating die-bonding film of this embodiment can be formed, for example, by mixing the a component, b component, c component, d component, etc. in a solvent to prepare The varnish (resin composition for forming a heat-dissipating adhesive crystal film) is applied on a base film (for example, a carrier film), and the solvent is removed from the applied varnish.

There is no particular restriction on the solvent used when preparing the varnish. Examples of such solvents include methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol, dimethyl ethyl Acetamide, dimethylformamide, methylpyrrolidone and cyclohexanone. Among them, from the viewpoint of improving coating properties, the solvent is preferably a high boiling point such as methyl ethyl ketone, dimethyl acetamide, dimethyl formamide, methyl pyrrolidone, cyclohexanone, etc. Solvent. 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, and from the viewpoint of reducing the amount of heat and cost required for drying the varnish, based on the total mass of the varnish, the content of non-volatile components in the varnish may be, for example, It is 40 mass% or more, and may be 50 mass% or more. From the viewpoint of not excessively increasing the viscosity of the varnish and easily reducing the defects of the coating film caused therefrom, based on the total mass of the varnish, the content of nonvolatile components in the varnish may be, for example, 90% by mass or less, or 80% by mass or less. From these viewpoints, based on the total mass of the varnish, the content of the nonvolatile components in the varnish is preferably, for example, 40% by mass to 90% by mass, and more preferably 50% by mass to 80% by mass.

The mixing of the components can be carried out, for example, by a squeezer, three-roller, bead mill, or a combination of these. In addition, for example, by mixing the filler component and the low-molecular-weight substance in advance, the high-molecular-weight substance can be blended to shorten the time required for mixing. In addition, the varnish is preferably degassed by vacuum to remove bubbles before being applied to the base film.

Then, by applying the prepared varnish on the base film, for example, by heating to remove the solvent, a heat-dissipating adhesive crystal film can be formed on the base film.

The heating conditions are not particularly limited as long as they can remove the solvent without completely curing the heat-dissipating adhesive film, for example, according to the composition of the heat-dissipating adhesive film and the type of solvent in the varnish Appropriate adjustments. General heating conditions are, for example, conditions of 80 ° C to 140 ° C for 5 minutes to 60 minutes.

The heat-dissipating die-bonding film may be hardened to the level of the B stage by heating. Based on the total mass of the heat-emitting adhesive film, the solvent remaining in the heat-emitting adhesive film is preferably 3% by mass or less, and more preferably 1.5% by mass or less.

Examples of the base film include polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polyimide film, and polynaphthalene dicarboxylic acid. Plastic films such as ethylene glycol film, polyether film, polyether amide film, polyether amide imide film, poly amide film, poly amide amide imide film, etc.

The base film may be subjected to surface treatments such as primer coating, ultraviolet (UV) treatment, corona discharge treatment, grinding treatment, etching treatment, and mold release treatment as needed.

Examples of commercially available products of the polyimide film include Kapton (manufactured by Toray Dupont Co., Ltd., trade name) and Apical (Kaneka) ) Manufactured by a company limited by shares, trade name).

Examples of commercially available products of the polyethylene terephthalate film include Lumirror (Toray Dupont Co., Ltd., trade name) and Purex. (Made by Teijin Co., Ltd., trade name).

[Crystal-Crystal Sticky Film] The heat-dissipating crystal-bond film of this embodiment can be applied to a crystal-cut crystal-sticky film, for example. Hereinafter, an embodiment of the slicing-crystal bonding film will be described.

FIG. 1 is a cross-sectional view schematically showing a die-cut crystal film of this embodiment. The die-cut crystal bonding film 1 shown in FIG. 1 includes a die-cutting film 10 and a die-bonding film 20 stacked on the die-cutting film 10. The dicing film 10 is not particularly limited. For example, it can be appropriately determined based on the knowledge of those skilled in the art in consideration of usage and the like. 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. The crystal-cut film 10 may be subjected to surface treatments such as primer coating, UV treatment, corona discharge treatment, polishing treatment, and etching treatment, if necessary. The die-cut film 10 is preferably one having adhesiveness. Examples of the die-cut film having adhesiveness include those obtained by imparting adhesiveness to the plastic film and those provided with an adhesive layer on one side of the plastic film. The adhesive layer is formed of, for example, a resin composition (a resin composition for forming an adhesive layer) that contains a liquid component and a high-molecular-weight component and has moderate adhesion strength. The die-cut adhesive tape including the adhesive layer can be manufactured by, for example, applying the resin composition for forming the adhesive layer on the plastic film and drying it, or allowing the resin composition for forming the adhesive layer to polymerize An adhesive layer is formed by coating and drying a base film such as polyethylene terephthalate (PET) film, and the adhesive layer is attached to the plastic film. The adhesive strength can be set to a desired value by adjusting the ratio of the liquid component and the Tg of the high molecular weight component, for example. The die-bonding film 20 is the heat-dissipating die-bonding film of the present embodiment. In FIG. 1, the die-cutting film 10 and the die-bonding film 20 are in direct contact, but the die-cutting film 10 and the die-bonding film 20 may also be laminated through other layers such as an adhesive layer.

There is no particular limitation on the method of manufacturing the die-cut crystallizing film of this embodiment, and it can be appropriately determined based on the knowledge of those skilled in the art. The die-cut die-bonding film of the present embodiment can be produced, for example, by using the die-cut film instead of the base film in the method of manufacturing the heat-dissipating die-bonding film. In addition, the die-cut crystallizing film of the present embodiment can be manufactured, for example, by separately preparing the heat-dissipating die-bonding film and the crystallizing film of the present embodiment, and integrating these layers. [Example]

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

(Example 1 to Example 7, Comparative Example 1, and Reference Example) [Preparation of varnish (resin composition for heat-dissipating adhesive film formation)] Prepare the following materials as component a, component b, component c, component d, and component d Fillers, coupling agents, hardening accelerators and solvents other than ingredients.

(Component a) · Epoxy group-containing acrylic rubber: HTR-860P-3CSP (manufactured by Nagase ChemteX Co., Ltd., trade name, weight average molecular weight 800,000, Tg 12 ° C) · Epoxy group-containing Acrylic rubber: HTR-860P-30B (manufactured by Nagase ChemteX Co., Ltd., trade name, weight average molecular weight 300,000, Tg 12 ° C) · Bisphenol A / F copolymerized phenoxy resin: ZX-1356-2 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name, weight average molecular weight 63200, Tg 71 ℃) (component b) · Cresol novolac epoxy resin: YDCN-700-10 ( Nippon Steel & Sumitomo Chemical Co., Ltd., trade name, epoxy equivalent: 195 ~ 215) · Bisphenol F type epoxy resin: YDF-8170C (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name, epoxy equivalent : 156) (component c) · Phenol resin: XLC-LL (Mitsui Chemical Co., Ltd., trade name) (component d) · Polyhedron α-alumina filler: Sumicorundum AA-3 (Sumitomo Made by Chemical Co., Ltd., Name, purity Al ₂ O ₃ ≧ 99.90%, average particle diameter of 2.7 μm ~ 3.6 μm, Mohs hardness 9) - α- spherical alumina filler: alumina beads CB-P05 (manufactured by Showa Denko Co., Ltd. , Trade name, purity is Al ₂ O ₃ 99.89%, average particle size is 4 μm, Mohs hardness is 9) · Boron nitride filler: HP-P1 (made by Mizushima Alloy Iron Co., Ltd., trade name, average particle size 1 μm to 3 μm, Mohs hardness is 2) · Boron nitride filler: UHP-S1: Shaobain (SHOBN) UHP-S1 (manufactured by Showa Denko Co., Ltd., trade name, average particle size 0.5 μm, Mohs hardness is 2) · Aluminum nitride filler: Shapal H grade (manufactured by Toyama Co., Ltd., trade name, average particle size 1 μm, Mohs hardness 8) · Magnesium oxide filler: RF- 10C (made by Ube Materials Co., Ltd., trade name, average particle size 10 μm, Mohs hardness 4)

(Fillers other than component d) • Silica filler: SC1030 (Admatechs Co., Ltd., trade name, average particle size 0.5 μm) • Hydrophobic silica filler: R972 (Aero, Japan Made by Aerosil Co., Ltd., trade name, with an average particle size of 60 nm) (hardening accelerator) · Curezol 2PZ-CN (made by Shikoku Chemical Industry Co., Ltd., trade name) (Coupling agent ) · Silane coupling agent: A-189 (made by UNC Co., Ltd., trade name, γ-mercaptopropyltrimethoxysilane) · Silane coupling agent: A-1160 (made by UNC Co., Ltd., trade name, γ-urea Propyltriethoxysilane) (solvent) · Cyclohexanone

The varnishes of each example, comparative example, and reference example were prepared by mixing the prepared components in the amounts shown in Table 1 and Table 2. In Table 1 and Table 2, the numerical values of fillers, coupling agents and hardening accelerators other than component a, component b, component c, component d and component d represent parts by mass.

[Table 1]

[Table 2]

[Preparation of heat-dissipating adhesive crystal film] A polyethylene terephthalate film (manufactured by Teijin Film Solution Co., Ltd., A31, thickness 38 μm) prepared by mold release was prepared as a base film. The prepared varnish was coated on the release treatment surface of the polyethylene terephthalate film, and was heated and dried at 90 ° C for 10 minutes and at 120 ° C for 30 minutes to produce a base The heat dissipation adhesive crystal film of the material film. The thickness of the obtained heat-dissipating adhesive crystal film was 30 μm.

[Evaluation of heat-dissipating adhesive crystal film] The obtained heat-dissipating adhesive crystal film was evaluated for thermal conductivity, blade wear in the crystal-cutting step, surface roughness (Ra), adhesion and lamination according to the following procedure Sex. The evaluation results are shown in Table 3 and Table 4.

(Thermal conductivity) The heat-dissipating die-bonding film peeled from the base film is bonded to a plurality of sheets to produce a laminated film with 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 square and used as a sample for measurement.

The thermal diffusivity α (mm ² / s), specific heat Cp (J / (g · ° C) and specific gravity (g / cm ³ ) of the sample for measurement are measured by the following method. • Thermal diffusivity α (mm ² / s): For the thickness direction of the adhesive film, the laser flash method (manufactured by Netzsch, LFA467 HyperFlash (trade name)) was used to measure the thermal diffusivity α at 25 ° C. Specific heat Cp (J / (g · ℃)): Differential Scanning Calorimeter (DSC) method (manufactured by Perkin Elmer, DSC8500 (trade name)), with a heating rate of 10 ℃ / min and a temperature of 20 ℃ ～ The specific heat Cp at 25 ° C. was measured by measuring at 60 ° C. 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 are introduced into the following formula to calculate the thermal conductivity (W / (m · K)). Thermal conductivity (W / (m · K)) = thermal diffusivity α (mm ² / s) × specific heat Cp (J / (g · ℃)) × specific gravity (g / cm ³ )

(Abrasion of the blade in the crystal cutting step) Laminate the heat-dissipating adhesive film on the crystal cutting tape (base material thickness 80 μm, paste thickness 10 μm) at room temperature, and use a laminator (Made by TEIKOKU TAPING SYSTEM Co., Ltd., STM-1200FH (trade name)), the surface on the side of the heat-dissipating adhesive film is laminated on an 8-inch wafer with a thickness of 50 μm at 70 ° C . Thereafter, a cutter (made by DISCO Co., Ltd., DFD6361 (trade name)) was used to perform crystal cutting with a blade. The conditions for the crystal cutting of the blade are: using the blade ZH05-SD4000-N1-70 BB (Nanyang Co., Ltd., (trade name)); the wafer thickness is 50 μm; the wafer size is 3 mm × 3 mm; the rotation speed is 50000 rpm ; The dicing tape cutting mark is 10 μm; the shear speed is 30 mm / sec; the shear length is 203 mm; the shear gap starts at 3 mm and ends at 3 mm. The amount of blade wear in the crystal cutting step is calculated based on the state of the blade before and after crystal cutting. Specifically, the wear amount (μm / m) of the blade is based on the following formula, and is based on the radius r1 (μm) of the blade before crystal cutting, the radius r2 (μm) of the blade after crystal cutting and the distance L1 ( m) to calculate. Blade wear (μm / m) = (r1 (μm) -r2 (μm)) / L1 (m)

(Surface roughness (Ra)) Using a hot roller laminator (80 ° C, 0.3 m / min, 0.3 MPa), the heat-dissipating adhesive crystal film peeled off from the base film is attached to a silicon crystal with a thickness of 300 μm After rounding, the samples were cured at 110 ° C for 1 hour and 170 ° C for 3 hours. Using a fine shape measuring machine Surf corder ET200 (manufactured by Kosaka Research Institute Co., Ltd., trade name), the arithmetic average roughness (Ra) of the obtained sample in the range of 2.5 mm was calculated.

(Adhesive force) Using a hot roller laminator (80 ° C, 0.3 m / min, 0.3 MPa), the heat-dissipating die-bonding film on the base film was attached to the semiconductor wafer (5 mm square). At 120 ° C and 250 g, the heat-dissipating die-bonding film on the semiconductor wafer was pressure-bonded on the 42 alloy substrate for 5 seconds and then cured at 110 ° C for 1 hour and 170 ° C for 3 hours to obtain a test kind. The shear strength of the obtained sample before and after the moisture absorption test was measured using a universal bond strength tester (manufactured by Dage, 4000 series, trade name). The conditions of the moisture absorption test were set at 85 ° C / 85% RH for 48 hours.

The adhesive strength was evaluated by setting the shear strength ≧ 2.0 MPa to “good” and the shear strength <2.0 MPa to “bad”.

(Laminateability) The laminate of the base film and the heat-dissipating die-bonding film was cut to a width of 10 mm. Using a hot roller laminator (80 ° C, 0.3 m / min, 0.3 MPa), the surface of the heat-dissipating die-bonding film in the laminate was attached to a silicon wafer with a thickness of 300 μm. Then, for the attached heat-dissipating adhesive film, using a small desktop testing machine EZ-S (Shimadzu Manufacturing Co., Ltd.), measured in an environment of 25 ° C at an angle of 90 ° and 50 mm / min 90 ° peel strength at the time of peeling. The case where the 90 ° peel strength is 20 N / m or more is regarded as “good”, and the case where the 90 ° peel strength is less than 20 N / m is regarded as “bad” to evaluate the lamination property.

[table 3]

[Table 4]

From the results in Table 3, it can be seen that the thermal conductivity of the heat-dissipating die-bonding films of Examples 1 to 7 after thermal curing is ≧ 2 W / (m × K), the thermal conductivity after thermal curing is excellent, and the amount of wear is ≦ 50 μm / m and excellent abrasion suppression at the time of blade. In addition, it can be seen that the heat-dissipating die-bonding films of Examples 1 to 7 are also excellent in adhesion (adhesion force) and lamination, and the surface roughness is also small. That is, according to the heat-dissipating die-bonding films of Examples 1 to 7, since the heat dissipation is excellent and the wear of the blade is easily suppressed, it is considered that the semiconductor element can be efficiently manufactured.

1‧‧‧Crystal-stick crystal film

10‧‧‧Crystal film

20‧‧‧Crystal film

FIG. 1 is a cross-sectional view schematically showing a die-bonding film according to an embodiment of the present invention.

Claims (13)

A heat-dissipating viscous crystal film with a thermal conductivity of 2 W / (m × K) or more, and the heat-dissipating viscous crystal film contains two or more kinds of thermally conductive fillers with different Mohs hardness, and the blade in the crystal cutting step The amount of wear is 50 μm / m or less. A heat-dissipating viscous crystal film contains two or more kinds of thermally conductive fillers with different Mohs hardness, and the content of the thermally conductive filler is 20% by mass to 85% by mass. The heat-dissipating viscous crystal film as described in Item 1 or Item 2 of the patent application scope, which contains at least two selected from the group consisting of alumina filler, boron nitride filler, aluminum nitride filler and magnesium oxide filler As the thermally conductive filler. The heat-dissipating adhesive crystal film as described in Item 3 of the patent application range, wherein the alumina filler contains an alumina filler with a purity of 99.0% by mass or more. The heat-dissipating adhesive crystal film as described in item 3 or item 4 of the patent application range, wherein the boron nitride filler contains a hexagonal boron nitride filler with a nitrogen purity of 95.0% by mass or more. The heat-dissipating die-bonding film according to any one of items 3 to 5 of the patent application range, wherein the density of the aluminum nitride filler is 3 g / cm ³ to 4 g / cm ³ . The heat-dissipating adhesive crystal film according to any one of items 3 to 6 of the patent application range, wherein the magnesium oxide filler contains a magnesium oxide filler with a purity of 95.0% by mass or more. The heat-dissipating adhesive film as described in any one of claims 1 to 7 further contains any high molecular weight component of acrylic resin and phenoxy resin, epoxy resin and hardener. The heat-dissipating viscous crystal film as described in item 8 of the patent application range, wherein, relative to 100 parts by mass of the total amount of the high molecular weight component, the epoxy resin, the hardener and the thermally conductive filler, the The total mass of the thermally conductive filler is 20 parts by mass or more. The heat-dissipating viscous crystal film as described in any one of items 1 to 9 of the patent application range contains alumina filler and boron nitride filler as the thermally conductive filler. The heat-dissipating viscous crystal film as described in any one of items 1 to 10 of the patent application range contains a boron nitride filler and an aluminum nitride filler as the thermally conductive filler. The heat-dissipating viscous crystal film according to any one of claims 1 to 11 of the patent application range, which contains boron nitride filler and magnesium oxide filler as the thermally conductive filler. A crystal-cut crystal-bonding film, comprising a crystal-cutting film and a crystal-bonding film laminated on the crystal-cutting film, and the crystal-bonding film is as defined in any one of items 1 to 12 of the patent application The heat-dissipating viscous crystal film.