KR102451368B1 - Heat dissipation die bonding film and dicing die bonding film - Google Patents

Abstract

The present invention is a heat-dissipating die-bonding film having a thermal conductivity of 2 W/(m·K) or more, containing two or more types of thermally conductive fillers having different Mohs hardness, and the wear amount of the blade in the dicing process is 50 µm/m or less. It is related with the heat dissipation die-bonding film containing a die-bonding film or two or more types of thermally conductive fillers from which Mohs' Hardness differs, and content of a thermally conductive filler is 20-85 mass %.

Description

Heat dissipation die bonding film and dicing die bonding film

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 was formed is diced by a chip-shaped semiconductor element, after adjusting thickness by back surface grinding|polishing as needed (dicing process). Next, after the semiconductor element is fixed to an adherend such as a lead frame with an adhesive (die bonding process), it is transferred to a bonding process. For example, there has been proposed a method of increasing the heat dissipation effect of a package for a semiconductor device by arranging a metal base through an adhesive under a die pad and a lid portion on which a semiconductor element is disposed (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 conductivity particles or a heat dissipation die bonding film containing a thermal conductive filler is known (see, for example, Patent Documents 2 and 3).

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

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 having the same.

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

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

The said heat dissipation die-bonding film may contain at least 2 types selected from the group which consists of an alumina filler, a boron nitride filler, an aluminum nitride filler, and a magnesium oxide filler as a thermally conductive filler.

The said alumina filler may contain the alumina filler whose purity is 99.0 mass % or more.

The said boron nitride filler may contain the hexagonal boron nitride filler whose nitrogen purity is 95.0 mass % or more.

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

The said magnesium oxide filler may contain the magnesium oxide filler whose purity is 95.0 mass % or more.

The said heat dissipation die-bonding film may further contain the high molecular weight component in either one of an acrylic resin and a phenoxy resin, an epoxy resin, and a hardening|curing agent.

The said heat dissipation die-bonding film WHEREIN: The total mass of the thermally conductive filler may be 20 mass parts or more with respect to 100 mass parts of total amounts of the said high molecular weight component, an epoxy resin, a hardening|curing agent, and a thermally conductive filler.

The heat dissipating die bonding film may contain, as a thermally conductive filler, an alumina filler and a boron nitride filler, may contain a boron nitride filler and an aluminum nitride filler, and may contain a boron nitride filler and a magnesium oxide filler.

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

ADVANTAGE OF THE INVENTION According to this invention, the heat dissipation die-bonding film which can manufacture a semiconductor element efficiently, and the dicing die-bonding film provided with the same can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the dicing die-bonding film which concerns on one Embodiment of this invention.

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

[Heat Dissipation Die Bonding Film]

The heat-dissipating die-bonding film according to the 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 thermally conductive fillers having different Mohs hardness, the amount of wear of the blade in the dicing process This is 50 µm/m or less. According to such a heat dissipation die-bonding film, a semiconductor element can be manufactured efficiently.

In the present specification, the wear amount of the blade in the dicing process means that it is calculated according to the following procedure. After the heat dissipation die bonding film was laminated at room temperature on a dicing tape (base material thickness of 80 μm, full thickness 10 μm) and integrated, the side of the heat dissipation die bonding film was applied to an 8-inch wafer with a thickness of 50 μm with a laminator (Teikoku). It laminates at 70 degreeC using the Taping Systems Co., Ltd. make, STM-1200FH (trade name)). Thereafter, blade dicing is performed using a dicer (manufactured by Disco Corporation, DFD6361 (trade name)). The conditions for blade dicing were: blade ZH05-SD4000-N1-70 BB used (Nanyo Co., Ltd., (trade name)), wafer thickness 50 μm, chip size 3 mm×3 mm, rotation speed 50000 rpm, dicing tape cut 10 µm, cut speed 30 mm/sec, cut length 203 mm, cut clearance start 3 mm, end 3 mm. Next, according to the following formula, the blade wear amount (μm/m) 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) .

Blade wear (㎛/m)=(r1(㎛)-r2(㎛))/L1(m)

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

The heat dissipation die-bonding film of this embodiment does not necessarily require the process of applying the pressure of the thickness direction to the primary film formed using the varnish in the manufacture. In addition, the heat dissipation die bonding film of this embodiment is excellent in adhesiveness, and even when the manufactured semiconductor element repeats heat generation, the metal base due to the difference in thermal expansion coefficient of the metal base, semiconductor element, die pad, etc. There exists a tendency for it to be easy to reduce generation|occurrence|production of peeling and a crack.

The heat dissipation die-bonding film of this embodiment may further contain the high molecular weight component mentioned later, an epoxy resin, and a hardening|curing agent, for example. Hereinafter, each component is demonstrated. Hereinafter, "a high molecular weight component" is also referred to as "a component", "epoxy resin" as "b component", "curing agent" as "c component", and "thermal conductive filler" as "d component".

(a component: high molecular weight component)

The heat dissipation die-bonding film of this embodiment may contain the a component. Examples of the component a include a resin having thermoplasticity, and a resin having thermoplasticity at least in an uncured state and forming a crosslinked structure after heating.

Component a is, for example, phenoxy resin, polyimide, polyamide, polycarbodiimide, cyanate ester resin, acrylic resin, polyester, polyethylene, polyether from the viewpoint of easy to obtain film formability, heat resistance, and adhesiveness. Sulfone, polyetherimide, polyvinyl acetal or urethane resin may be used. These high molecular weight components may be, for example, a copolymer. A component may be used individually by 1 type or in combination of 2 or more types.

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

(Acrylic resin)

When component a contains an acrylic resin, it is preferable that the said acrylic resin has a reactive group (functional group) and that a weight average molecular weight is 100000 or more. An acrylic resin may be used individually by 1 type or in combination of 2 or more types.

In this specification, a weight average molecular weight is a polystyrene conversion value using the analytical curve by standard polystyrene by the gel permeation chromatography method (GPC).

Specific examples of the acrylic resin include acrylic copolymers. As this acrylic copolymer, an acrylic rubber is mentioned, for example. Examples of the acrylic rubber include a copolymer of at least one selected from acrylic acid ester and 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.

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

The present inventors speculate as follows why this effect is exhibited when the reactive group is an epoxy group. When the reactive group is, for example, a carboxy group, the crosslinking reaction tends to proceed, and it is considered that gelation in a varnish state and an increase in the degree of curing in a B-stage state may occur. On the other hand, when the reactive group is an epoxy group, it is considered that a crosslinking reaction does not easily occur, and gelation in a varnish state and an increase in curing degree in a B-stage state are unlikely to occur.

The acrylic resin having a reactive group, for example, in a polymerization reaction to obtain an acrylic resin, by polymerizing the acrylic monomer having a reactive group (such as (meth)acrylate having a reactive group) so that the reactive group remains, or reactive with the synthesized acrylic resin It can be prepared by introducing a group.

As an acrylic resin which has an epoxy group, the acrylic resin which contains glycidyl (meth)acrylate as a monomer unit is mentioned, for example. In this case, the content of glycidyl (meth) acrylate as a monomer unit may be, for example, 0.5 mass % or more, or 2 mass % or more, based on the total mass of the acrylic resin, from the viewpoint that adhesiveness is easily improved. also good Moreover, content of glycidyl (meth)acrylate as a monomer unit may be 6 mass % or less, for example based on the total mass of an acrylic resin from a viewpoint of being easy to reduce gelatinization. From these viewpoints, 0.5-6 mass % may be sufficient as content of the glycidyl (meth)acrylate as a monomer unit on the basis of the total mass of an acrylic resin, and 2-6 mass % may be sufficient as it.

In the acrylic resin containing glycidyl (meth) acrylate as a monomer unit, as a monomer unit other than glycidyl (meth) acrylate, for example, an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms, etc. (meth)acrylates other than glycidyl (meth)acrylate, styrene, and acrylonitrile are 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 (hereinafter, referred to as "Tg" in some cases) of the copolymer.

There is no restriction|limiting in particular in the polymerization method of an acrylic resin, For example, pearl polymerization and solution polymerization are mentioned.

Tg of the acrylic resin as a component may be, for example, -50°C or more and 50°C or less, or -10°C or more and 50°C or less. When Tg is -50 degreeC or more, the tackiness of the adhesive bond layer or adhesive film in a B-stage state becomes small easily, and there exists a tendency excellent in handleability.

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

The weight average molecular weight of the acrylic resin may be, for example, 200000 or more, 300000 or more, or 400000 or more, from the viewpoint that strength and flexibility are less likely to decrease and tactility is less likely to increase when in sheet form and film form. . The weight average molecular weight of the said acrylic resin may be large, and from a viewpoint that the circuit fillability of wiring is easy to improve, for example, 3000000 or less may be sufficient, and 2000000 or less may be sufficient as it. From these viewpoints, the weight average molecular weight of the said acrylic resin may be 200000-300000, for example, may be sufficient as 300000-300000, and 400000-20000 may be sufficient as it.

The acrylic resin as component a contains, for example, 0.5 to 6% by mass of glycidyl (meth)acrylate as a monomer unit from the viewpoint of easily obtaining high adhesiveness and heat resistance, and has a Tg of -50°C or more and 50°C or less ( Preferably it is -10 degreeC or more and 50 degrees C or less), and an acrylic copolymer with a weight average molecular weight of 100000 or more may be sufficient. As such an acrylic resin, HTR-860P-3 and HTR-860P-30B (made by Nagase Chemtex Co., Ltd., brand name) are mentioned, for example.

(phenoxy resin)

When component a contains a phenoxy resin, it is preferable that the weight average molecular weight of this phenoxy resin is 20000 or more, It is more preferable that it is 30000 or more, It is still more preferable that it is 50000 or more. A phenoxy resin may be used individually by 1 type or in combination of 2 or more types.

Commercially available phenoxy resins include, for example, YP-50, YP-55, YP-70, YPB-40PXM40, YPS-007A30, FX-280S, FX-281S, FX-293 and ZX-1356-2 (above, Shin-Nitetsu). Sumikin Chemical Co., Ltd., trade name); And 1256, 4250, 4256, 4275, YX7180, YX6954, YX8100, YX7200, YL7178, YL7290, YL7600, YL7734, YL7827 and YL7864 (above, Japan Epoxy Resins Co., Ltd. make, brand name) are mentioned.

It is preferable that the Tg of the phenoxy resin is less than 85°C. As a phenoxy resin whose Tg is less than 85 degreeC, For example, YP-50, YP-55, YP-70, and ZX-1356-2 (above, the Shin-Nittetsu Chemical Co., Ltd. make, brand name); And 4250, 4256, 7275, YX7180, and YL7178 (above, Japan Epoxy Resin Co., Ltd. make, brand name) are mentioned.

[Component b: Epoxy resin]

Component b shows, for example, an adhesive action by curing. The 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.

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

As b component, For example, bifunctional epoxy resins, such as a bisphenol A epoxy resin and a bisphenol F type epoxy resin; novolak-type epoxy resins such as phenol novolak-type epoxy resins and cresol novolak-type epoxy resins; multifunctional epoxy resins; amine-type epoxy resins; Heterocyclic containing epoxy resin; and alicyclic epoxy resins. As b component, a generally known epoxy resin other than the above can also be used.

Commercially available bisphenol A epoxy resins include, for example, 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, Mitsubishi Chemical Co., Ltd. make, brand 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 (manufactured by Nippon Steel Chemicals, trade name).

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

As a commercially available phenol novolak-type epoxy resin, For example, Epicoat 152 and Epicoat 154 (above, Mitsubishi Chemical Co., Ltd. make, brand name); EPPN-201 (manufactured by Nippon Kayaku Co., Ltd., trade name); And DEN-438 (made by Dow Chemical, brand name) is mentioned.

As a commercially available cresol novolak-type epoxy resin, For example, Epicoat 180S65 (made by Mitsubishi Chemical Corporation, brand name); Araldite ECN1273, Araldite ECN1280, and Araldite ECN1299 (above, manufactured by Chiba Specialty Chemicals, trade names); YDCN-700-10, YDCN-701, YDCN-702, YDCN-703 and YDCN-704 (above, manufactured by Shin-Nittetsu Sumikin Chemical, 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 names); And ESCN-195X, ESCN-200L, and ESCN-220 (above, Sumitomo Chemical Co., Ltd. make, brand name) are mentioned.

Commercially available polyfunctional epoxy resins include, for example, EPON 1031S, Epicoat 1032H60, and Epicoat 157S70 (above, manufactured by Mitsubishi Chemical Corporation, trade names); Araldite 0163 (manufactured by Chiba Specialty 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 (above, manufactured by Nagase Chemtex Co., Ltd., trade name); And EPPN501H and EPPN502H (above, the Nippon Kayaku Co., Ltd. make, brand name) are mentioned.

Examples of commercially available amine-type epoxy resins include Epicoat 604 (manufactured by Mitsubishi Chemical Co., Ltd., trade name); YH-434 (manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., trade name); TETRAD-X and TETRAD-C (above, Mitsubishi Gas Chemical Co., Ltd. make, brand name); And ELM-120 (made by Sumitomo Chemical Co., Ltd., brand name) is mentioned.

As a commercially available heterocyclic-containing epoxy resin, Araldite PT810 (made by Chiba Specialty Chemicals, brand name) is mentioned, for example.

As a commercially available alicyclic epoxy resin, ERL4234, ERL4299, ERL4221, and ERL4206 (above, the UCC company make, brand name) are mentioned, for example.

b component may be used individually by 1 type or in combination of 2 or more type.

The component b may contain a bifunctional epoxy resin and a trifunctional or more than trifunctional epoxy resin from a viewpoint that the adhesiveness after thermosetting, heat resistance, and moisture absorption resistance improve easily. When component b contains a bifunctional epoxy resin and a trifunctional or more than trifunctional epoxy resin, the content of the bifunctional epoxy resin is, for example, 3 to 40 based on the total mass of the bifunctional epoxy resin and the trifunctional or more than trifunctional epoxy resin. Mass % may be sufficient, 3-30 mass % may be sufficient, and 3-20 mass % may be sufficient.

[component c: curing agent]

The c component can be used without particular limitation as long as it can harden the b component. Examples of component c include polyfunctional phenol compounds, amine compounds, acid anhydrides, organophosphorus compounds and halides thereof, polyamides, polysulfides, and boron trifluoride.

Examples of the polyfunctional phenol compound include a monocyclic difunctional phenol compound and a polycyclic difunctional phenol compound. Examples of the monocyclic difunctional phenol include hydroquinone, resorcinol and catechol, and alkyl group substituted products thereof.

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

As a commercial item of the said phenol resin (phenolic resin hardening|curing agent), For example, Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH4150 and Phenolite VH4170 (above, the DIC Corporation make, brand name) ) can be mentioned.

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. Moreover, it is preferable that the phenol resin as c component is a novolak-type or resol-type resin from a viewpoint that the corrosion resistance at the time of moisture absorption improves.

From the viewpoint of improving moisture resistance, the phenolic resin preferably has a water absorption of 2% by mass or less after being placed in a thermo-hygrostat at 85°C and 85% RH for 48 hours. Further, it is preferable that the phenol resin as component c has a heating weight reduction rate (temperature increase rate: 5°C/min, atmosphere: nitrogen) of less than 5% by weight at 350°C as measured by a thermogravimetric analyzer (TGA). When such a phenol resin is used as a curing agent, volatile matter is suppressed during heat processing, etc., thereby increasing the reliability of various characteristics such as heat resistance and moisture resistance, and also reducing contamination of equipment due to volatile matter during heat processing, etc. I think there is.

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

In formula (I), R ¹ represents a hydrogen atom, a 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 a halogen atom, and n is 1 The integer of -3 is shown, and m shows the integer of 0-50. In formula (I), two or more R ¹ and n may be the same or different, respectively.

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

The compound represented by the formula (I) can be obtained by, for example, reacting a phenol compound and a xylylene compound in the absence of a catalyst or in the presence of an acid catalyst (acid catalyst). Moreover, the xylylene compound can form a bivalent coupling group by the said reaction.

As a phenolic compound used for manufacture of the compound represented by Formula (I), For example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-n-propylphenol, m-n-propyl Phenol, p-n-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o-isobutylphenol, m-isobutyl Phenol, p-isobutylphenol, octylphenol, nonylphenol, 2,4-xylenol, 2,6-xylenol, 3,5-xylenol, 2,4,6-trimethylphenol, resorcinol, 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 is mentioned. The said phenolic compound may be used individually by 1 type or in combination of 2 or more type.

It is preferable that the phenolic compound used for manufacture of the compound represented by Formula (I) from a viewpoint of adhesiveness, heat resistance, and moisture resistance is phenol, o-cresol, m-cresol, or p-cresol.

As a xylylene compound used for manufacture of the compound of Formula (I), xylylene dihalide and xylylene diglycol, and these derivatives are mentioned, for example.

Specific examples of the xylylene compound include α,α'-dichloro-p-xylene, α,α'-dichloro-m-xylene, α,α'-dichloro-o-xylene, α,α'-dibro parent-p-xylene, α,α′-dibromo-m-xylene, α,α′-dibromo-o-xylene, α,α′-diiodo-p-xylene, α,α′- diiodo-m-xylene, α,α′-diiodo-o-xylene, α,α′-dihydroxy-p-xylene, α,α′-dihydroxy-m-xylene, α,α '-dihydroxy-o-xylene, α,α'-dimethoxy-p-xylene, α,α'-dimethoxy-m-xylene, α,α'-dimethoxy-o-xylene, α,α' -diethoxy-p-xylene, α,α′-diethoxy-m-xylene, α,α′-diethoxy-o-xylene, α,α′-di-n-propoxy-p-xylene, α, α′-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,α'-di-tert -butoxy-o-xylene. The said xylylene compound may be used individually by 1 type or in combination of 2 or more type.

The xylylene compound is α,α′-dichloro-p-xylene, α,α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α,α′-dihydroxy-p-xylene, α,α′-dihydroxy-m-xylene, α,α′-dihydroxy-o-xylene, α, Preference is given to 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; super acids such as trifluoromethanesulfonic acid; strongly acidic ion exchange resins such as alkanesulfonic acid type ion exchange resins; super strong acid ion exchange resins such as perfluoroalkanesulfonic acid type ion exchange resins (for example, Nafion (manufactured by DuPont, trade name)); natural and synthetic zeolitic compounds; and activated clay (eg, acid clay).

The reaction is carried out, for example, at 50 to 250°C until the xylylene compound as a raw material is substantially lost 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 reaction proceeds in the presence of an acid catalyst, water or alcohol is usually produced.

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

The reaction molar ratio of a phenol compound and a xylylene compound makes it the conditions under which a phenol compound becomes excess normally. 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 reaction molar ratio of a phenol compound and a xylene compound. There exists a tendency for the weight average molecular weight of the compound represented by Formula (I) to fall, so that a phenolic compound is excessive.

The phenol resin may have, for example, an allylphenol skeleton. A phenol resin having an allyl phenol skeleton can be obtained, for example, by a method of preparing a phenol resin that has not been allylated, reacting it with an allyl halide, passing through an allyl ether, and allylating by Kleizen rearrangement.

Examples of the amine compound as 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, triethylene tetramine, diaminodiphenylmethane, diaminodiphenylether, dicyandiamide, tolylbiguanide, guanylurea and dimethylurea. The amine compound includes, 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; addition compounds of amines and thioureas; and an addition compound of an amine and an isocyanate. These amine compounds may have, for example, an adduct structure from the viewpoint that the activity at room temperature is reduced.

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

The said organophosphorus compound as c component will not be specifically limited if it is a phosphorus compound which has an organic group. Examples of the organophosphorus compound include triamide hexamethylphosphate, tri(dichloropropyl) phosphate, tri(chloropropyl) phosphate, triphenyl phosphite, trimethyl phosphate, phenylphosphonic acid, triphenylphosphine, and tri-n-butylphosphine. and diphenylphosphine.

c component may be used individually by 1 type or in combination of 2 or more type.

[Component d: Thermally Conductive Filler]

Component d is, for example, one capable of imparting thermal conductivity to a heat-dissipating die bonding film. In this embodiment, the heat dissipation die-bonding film contains two or more types of d components from which Mohs' Hardness differs. By using two or more types of d components from which Mohs' hardness differs, it is thought that a blade becomes difficult to wear. As for d component, two or more types can be suitably selected from d component mentioned later, for example.

Materials constituting the component d include, for example, 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 oxide, and combinations thereof. can be heard The material constituting the component d may have electrical insulation properties. As boron nitride, hexagonal boron nitride and cubic boron nitride are mentioned, for example. The aluminum borate may be an aluminum borate whisker.

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

In the heat dissipating die bonding film of this embodiment, from the viewpoint of further improving the thermal conductivity after thermosetting and from the viewpoint of further reducing the wear of the blade in the dicing process, as component d, alumina filler, boron nitride filler, aluminum nitride It is preferable to contain at least 2 types selected from the group which consists of a filler and a magnesium oxide filler.

The alumina filler preferably contains an alumina filler having a purity of 99.0 mass% or more from the viewpoint of further improving the thermal conductivity after thermal curing and further reducing the wear of the blade in the dicing process. The aspect containing the alumina filler whose purity is 99.0 mass % or more may be sufficient as the said alumina filler. Examples of the alumina filler having a purity of 99.0% by mass or more include Sumikorandam AA-3 (manufactured by Sumitomo Chemical Co., Ltd., trade name) and alumina bead CB-P05 (manufactured by Showa Denko Corporation, trade name). . It is more preferable that the said alumina filler contains the (alpha)-alumina filler whose purity is 99.0 mass % or more. The purity of the alumina filler may be, for example, 100% by mass or less.

The boron nitride filler preferably contains a hexagonal boron nitride filler having a nitrogen purity of 95.0 mass% or more from the viewpoint of further improving the thermal conductivity after thermal curing and further reducing the wear of the blade in the dicing process. do. Examples of the hexagonal boron nitride filler include HP-P1 and HP-4W (manufactured by Mizushima Kokintetsu Co., Ltd., trade name), and Shobien UHP-S1 (manufactured by Showa Denko Co., Ltd., trade name). Here, the purity of nitrogen is calculated based on the mass of nitrogen in the nitrogen-saturated hexagonal boron nitride. In the above hexagonal boron nitride, the purity of nitrogen may be, for example, 100% by mass or less.

It is preferable that the density of the aluminum nitride filler is, for example, 3 to 4 g/cm 3 . Examples of such aluminum nitride fillers include Shaypal H grade and Shapal E grade (manufactured by Tokuyama Corporation, trade name) and ALN020BF (manufactured by Tomoe Kogyo Co., Ltd., trade name).

It is preferable that the said magnesium oxide filler contains the magnesium oxide filler whose purity is 95.0 mass % or more. As such a magnesium oxide filler, RF-10C (made by Ube Materials Co., Ltd., brand name) is mentioned, for example. The purity of the magnesium oxide may be, for example, 100% by mass or less.

In the heat dissipation die bonding film of this embodiment, as d component, the said alumina filler and the said boron nitride filler may be contained, and the said boron nitride filler and the said aluminum nitride filler may be contained, The said boron nitride filler and the said You may contain a magnesium oxide filler.

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

The average particle diameter (d ₉₀ ) of the mixture of the component d is preferably 1/2 or less of the thickness of the heat dissipating die bonding film, more preferably 1/3 or less, from the viewpoint of further improving adhesive strength, laminability and reliability. , 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 die bonding film.

In addition, in the present specification, the average particle size (d ₅₀ ) refers to a particle size corresponding to 50% of the integrated value of the particle size distribution, and the average particle size (d ₉₀ ) refers to a particle size corresponding to 90% of the integrated value of the particle size distribution.

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

In the heat dissipation die bonding film of this embodiment, from the viewpoint of further easily suppressing the wear of the blade in the dicing process, it is preferable that the Mohs' Hardness of at least one of the components d is 10 or less, and more preferably 9 or less, , more preferably 8 or less.

When the Mohs' Hardness of at least one of the components d is 10 or less, the content of the component d having a Mohs hardness of 10 or less is easier to suppress the wear of the blade in the dicing process, the total mass of the heat dissipating die bonding film As a reference, for example, 10 mass % or more may be sufficient, 15 mass % may be sufficient, and 20 mass % or more may be sufficient.

In the heat dissipation die bonding film of this embodiment, from the viewpoint of further improving the thermal conductivity after thermosetting and from the viewpoint of further reducing the wear of the blade in the dicing process, as d component, a thermally conductive filler having Mohs hardness of 1 to 3 It is preferable to contain at least 1 sort(s) and at least 1 sort(s) of the thermally conductive filler of 4-9 Mohs' Hardness. In this case, the content of the thermal conductive filler of Mohs' Hardness 1 to 3 may be, for example, 5 parts by mass or more, or 10 parts by mass or more, with respect to 100 parts by mass of the total mass of the thermal conductive filler of Mohs' Hardness 4 to 9, 30 It may be more than a mass part. Content of the thermally conductive filler of Mohs' Hardness 1-3 may be 300 mass parts or less, for example, may be 300 mass parts or less, 250 mass parts or less may be sufficient with respect to 100 mass parts of total mass of the Mohs' Hardness 4-9 thermal conductive fillers, 200 mass parts or less also good Content of the thermally conductive filler of Mohs' Hardness 1-3 may be 5-300 mass parts, 10-250 mass parts may be sufficient, for example, with respect to 100 mass parts of total mass of the Mohs' Hardness 4-9 thermal conductive fillers, 30- 200 parts by mass may be sufficient.

Although there is no restriction|limiting in particular in the shape of d component, For example, a spherical shape may be sufficient and a polyhedral may be sufficient. In the present specification, a polyhedron refers to a solid having a plurality of planes as constituent parts of the surface. A plurality of planes may intersect each other via a curved surface. The polyhedron may have, for example, 4 to 100 planes as a constituent part of the surface.

In the heat dissipation die-bonding film of this embodiment, the content of the component a is, from the viewpoint of easily reducing the elastic modulus and from the viewpoint of providing flowability during molding, the component a, component b, component c, and component d. With respect to 100 mass parts of total amounts, 3 mass parts or more may be sufficient, for example. The content of component a is, for example, 40 mass parts per 100 parts by mass in total of component a, component b, component c and component d, from the viewpoint that fluidity is hardly reduced even when the sticking load is small and from the viewpoint of excellent circuit fillability. A part or less may be sufficient, 30 mass parts or less may be sufficient, and 20 mass parts or less may be sufficient. 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 with respect to 100 parts by mass in total of component a, component b, component c and component d. also good

In the heat dissipation die-bonding film of this embodiment, content of b component may be 3-55 mass parts with respect to 100 mass parts of total amounts of a component, b component, c component, and d component, for example, 5-45 mass parts. may also be sufficient, and 10-35 mass parts may be sufficient.

The content of component c in the heat dissipation die-bonding film of this embodiment is not particularly limited as long as the curing reaction of component b can proceed, but based on 1 equivalent of the epoxy group in component b, in component c that can react with the epoxy group The active group (hydroxyl group, amino group, acid anhydride group, phosphorus atom-containing group, etc.) may be, for example, in the range of 0.01 to 5.0 equivalents, or in the range of 0.8 to 1.2 equivalents.

For example, when c component is a phenol resin, content of c component in the heat dissipation die-bonding film of this embodiment improves sclerosis|hardenability at the time of setting it as a heat dissipation die-bonding film to the epoxy equivalent of b component and a phenol resin The equivalent ratio (epoxy equivalent/hydroxyl equivalent) of the hydroxyl equivalent of /0.55 is fine.

In the heat dissipation die-bonding film of this embodiment, the total mass of the component d is 100 parts by mass of the total amount of component a, component b, component c and component d from the viewpoint of further improving thermal conductivity after thermal curing, for example, 20 mass parts or more may be sufficient, 22 mass parts or more may be sufficient, and 25 mass parts or more may be sufficient. The total mass of the component d may be, for example, 85 parts by mass or less, relative to 100 parts by mass of the total amount of component a, component b, component c and component d, from the viewpoint of film properties such as surface roughness, adhesiveness, and laminability, 75 mass parts or less may be sufficient, and 70 mass parts or less may be sufficient.

It is preferable that the heat dissipation die-bonding film of this embodiment contains the high molecular weight component in any one of an acrylic resin and a phenoxy resin, an epoxy resin, and a hardening|curing agent.

[Other Ingredients]

The heat dissipation die-bonding film of this embodiment may contain components other than the above. As such a component, a hardening accelerator, fillers other than d component, a coupling agent, and an ion trapping agent are mentioned, for example.

(curing accelerator)

There is no restriction|limiting in particular as a hardening accelerator, For example, an imidazole compound is mentioned. Examples of the imidazole compound include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1 -benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-phenyl-4-methyl imidazoline, benzimidazole, 1-cyanoethylimidazole, 1-cyanoethyl-2-phenylimidazole and 1-cyanoethyl-2-phenylimidazolium trimellitate. The said hardening accelerator may be used individually by 1 type or in combination of 2 or more type. As a commercial item of the said imidazole compound, 2E4MZ, 2PZ-CN, and 2PZ-CNS (all are the Shikoku Chemical Industry Co., Ltd. product, brand names) are mentioned, for example.

Further, the curing accelerator may be a latent curing accelerator from the viewpoint that the service period of the film becomes long. As such a hardening accelerator, the addition compound of an epoxy compound and an imidazole compound is mentioned, for example. From the viewpoint that the activity at room temperature is reduced, the curing accelerator may have an adduct structure.

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

(Fillers other than component d)

The heat dissipation die-bonding film of this embodiment may contain various fillers other than the said component d for the purpose of the improvement of film handling property, adjustment of melt viscosity, provision of thixotropic property, the improvement of moisture resistance, etc. You may use the fillers other than d component individually by 1 type or in combination of 2 or more type.

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

Materials constituting the filler other than component d are calcium carbonate, calcium silicate, magnesium silicate, calcium oxide, crystalline silica or amorphous silica from the viewpoint of easy adjustment of melt viscosity and thixotropic properties. also good The material constituting the filler other than the d component may be silica from the viewpoint that moisture resistance is easily improved.

When the heat dissipation 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 may be, for example, 50 parts by mass or less, with respect to 100 parts by mass of the total mass of the d component, 20 mass parts A part or less may be sufficient, and 10 mass parts or less may be sufficient.

(Coupling agent)

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

The silane coupling agent is not particularly limited, for example, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxy Silane, γ-methacryloxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxy Silane, γ-glycidoxypropylmethyldiethoxysilane, 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-aminopropyltrimethoxysilane, 3-aminopropyl-tris(2-methoxy-ethoxy-ethoxy)silane, N -Methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3-(4,5-dihydro)imidazol-1-yl-propyltrimethoxysilane, 3-methacryloxypropyl -Trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, 3-chloropropyl-methyldimethoxysilane, 3-chloropropyl-dimethoxysilane, 3-cyanopropyl-triethoxysilane, hexamethyldi Silazane, N,O-bis(trimethylsilyl)acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, amyltrichloro Silane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri(methacryloyloxyethoxy)silane, methyltri(glycidyloxy)silane, N-β-(N- Vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane, γ -Chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyltriisocyanate, vinylsilyltriisocyanate, phenylsilyltriisocyanate, tetraisocyanatesilane and ethoxysilane iso and cyanate. These may be used individually by 1 type or in combination of 2 or more type.

There is no restriction|limiting in particular as a titanium type coupling agent, For example, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearo Iyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (n-aminoethyl) titanate, tetra Isopropylbis(dioctylphosphite)titanate, tetraoctylbis(ditridecylphosphite)titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate , Dicumylphenyloxyacetate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra(2-ethylhexyl) titanate, titanium Acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium triethanolaminate, polyhydroxy titanium stearate, tetramethyl ortho titanate, Tetraethyl ortho titanate, tetrapropyl ortho titanate, tetraisobutyl ortho titanate, stearyl titanate, cresyl titanate monomer, cresyl titanate polymer, diisopropoxy-bis (2,4- pentadionate) titanium(IV), diisopropyl-bis-triethanolaminotitanate, octylene glycol titanate, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium monostearate polymer and tri-n -butoxytitanium monostearate is mentioned. 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, ethylacetoacetate aluminum diisopropylate, aluminum tris(ethylacetoacetate), alkylacetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis(ethylacetoacetate), aluminum Tris (acetylacetonate), aluminum monoisopropoxy monooleoxyethyl acetoacetate, aluminum-di-n-butoxide-mono-ethylacetoacetate, aluminum-di-iso-propoxide-mono-ethylacetoacetate, etc. of aluminum chelate compounds; and aluminum alcoholates such as aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butylate, and aluminum ethylate. These may be used individually by 1 type or in combination of 2 or more type.

It is preferable that the said coupling agent is a silane-type coupling agent from a viewpoint, such as adhesiveness in the case of adhering to a Si wafer.

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

(Ion scavenger)

The heat dissipation die-bonding film of this embodiment may adsorb|suck an ionic impurity, for example, and may contain the ion trapping agent from a viewpoint of improving the insulation reliability at the time of moisture absorption. Examples of the ion trapping agent include an anti-freeze agent used to prevent copper from ionizing and eluting. Examples of the antifreeze agent include a triazinethiol compound, a bisphenol-based reducing agent, and an inorganic ion adsorbent.

As a commercial item of the antifreeze agent which has a triazine thiol compound as a component, Disnet DB (made by Sankyo Chemical Co., Ltd., brand name) is mentioned, for example.

Examples of the bisphenol-based reducing agent include 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) and 4,4'-thio-bis(3-methyl-6-tert-butylphenol). can be heard As a commercially available bisphenol-type reducing agent, Yoshinox BB (the Yoshitomi Seiyaku Co., Ltd. make, brand name) is mentioned, for example.

Examples of the inorganic ion adsorbent include zirconium-based compounds, antimony bismuth-based compounds, and magnesium aluminum-based compounds. As a commercially available inorganic ion adsorbent, IXE (made by Toagosei Co., Ltd., brand name) is mentioned, for example.

The content of the ion scavenger is, for example, from 1 to 10 parts by mass relative to 100 parts by mass of the total amount of the resin composition (eg, varnish to be described later) used for formation of the heat dissipating die-bonding film from the viewpoint of the effect of addition, heat resistance, and cost. also good

In the heat-dissipating die-bonding film of this embodiment, the content of component a is based on the total mass of the heat-dissipating die-bonding film from the viewpoint of easily reducing the elastic modulus and from the viewpoint of providing flowability during molding, For example, 3 parts by mass or more may be sufficient. The content of the 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 fluidity is hard to decrease even when the sticking load is small and the circuit fillability is excellent, and may be 30 parts by mass or less. A part or less may be sufficient, and 20 mass parts or less may be sufficient. From these viewpoints, 3-40 mass parts may be sufficient, 3-30 mass parts may be sufficient, and 3-20 mass parts may be sufficient as content of a component on the basis of the total mass of a heat dissipation die-bonding film.

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

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

There is no particular limitation on the thickness of the heat-dissipating die-bonding film. 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 embedding properties. The thickness of the heat-dissipating die-bonding film may be, for example, 50 µm or less, or 40 µm or less, from the viewpoint of reducing cost. From these viewpoints, 5-50 micrometers may be sufficient as the thickness of a heat dissipation die-bonding film, 5-40 micrometers may be sufficient, and 8-40 micrometers may be sufficient, for example.

[Method for producing heat-dissipating die-bonding film]

The heat-dissipating die-bonding film of the present embodiment is, for example, a varnish (resin composition for forming a heat-dissipating die-bonding film) prepared by mixing the above-mentioned component a, component b, component c, component d, etc. in a solvent to a base film (eg, carrier film). It can be formed by applying on the top and removing the solvent from the applied varnish.

There is no restriction|limiting in particular in the solvent used when preparing a varnish. Examples of such solvents include methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol, dimethylacetamide, dimethylformamide, methylpyrroly. don and cyclohexanone. Especially, it is preferable that the said solvent is a high boiling point solvent, such as methyl ethyl ketone, dimethylacetamide, dimethylformamide, methylpyrrolidone, and cyclohexanone from a viewpoint of a coating-film property improving. These solvents may be used individually by 1 type or in combination of 2 or more type.

The content of the solvent in the varnish is not particularly limited, but the content of the non-volatile matter in the varnish is 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 cost. Therefore, for example, 40 mass % or more may be sufficient, and 50 mass % or more may be sufficient. The content of the nonvolatile matter in the varnish may be, 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 become too high and it is easy to reduce the defects of the coating film resulting therefrom. , 80% by mass or less may be sufficient. From these viewpoints, the content of the nonvolatile matter in the varnish is preferably 40 to 90 mass%, more preferably 50 to 80 mass%, based on the total mass of the varnish.

Mixing of each component can be performed, for example, by a lowegger, three rolls, a bead mill, or a combination thereof. Moreover, the time required for mixing can also be shortened by mix|blending a high molecular weight substance after mixing a filler component and a low molecular weight substance beforehand, for example. In addition, before the varnish is applied on the base film, it is preferable to remove air bubbles by vacuum degassing.

Next, a heat dissipation die-bonding film can be formed on a base film by apply|coating the prepared varnish on a base film and removing a solvent by heating, for example.

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, it can be appropriately adjusted depending on the components of the heat-dissipating die-bonding film and the type of solvent in the varnish. General heating conditions are conditions for 5 to 60 minutes at 80-140 degreeC, for example.

The heat dissipation die-bonding film may be cured to a B-stage grade by heating. It is preferable that it is 3 mass % or less, and, as for the solvent remaining in a heat dissipation die-bonding film, based on the total mass of a heat dissipation die-bonding film, it is more preferable that it is 1.5 mass % or less.

Examples of the base film include polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polyimide film, polyethylene naphthalate film, polyethersulfone film, polyetheramide film, poly Plastic films, such as an etheramide-imide film, a polyamide film, and a polyamide-imide film, are mentioned.

The said base film may be surface-treated, such as a primer application|coating, UV treatment, a corona discharge treatment, a grinding|polishing process, an etching process, and a mold release process, as needed.

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

Examples of commercially available polyethylene terephthalate films include Lumira (manufactured by Toray DuPont, trade name) and Purex (manufactured by Teijin Corporation, trade name).

[dicing die bonding film]

The heat dissipation die-bonding film of this embodiment is applicable to a dicing die-bonding film, for example. Hereinafter, one Embodiment of a dicing die-bonding film is demonstrated.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the dicing die-bonding film of this embodiment. The dicing die-bonding film 1 shown in FIG. 1 is equipped with the dicing film 10 and the die-bonding film 20 laminated|stacked on the dicing film 10. As shown in FIG. The dicing film 10 is not particularly limited, and may be appropriately determined based on the knowledge of those skilled in the art in consideration of, for example, use and the like. As the dicing film 10, plastic films, such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, and a polyimide film, are mentioned, for example. If necessary, the dicing film 10 may be subjected to surface treatment such as primer application, UV treatment, corona discharge treatment, polishing treatment, and etching treatment. It is preferable that the dicing film 10 has adhesiveness. Examples of the adhesive dicing film include those in which adhesiveness is imparted to the above-mentioned plastic film and those in which an adhesive layer is formed on one surface of the above-mentioned plastic film. The pressure-sensitive adhesive layer is formed of, for example, a resin composition (resin composition for forming the pressure-sensitive adhesive layer) containing a liquid component and a high molecular weight component and having an appropriate tack strength. The dicing tape with an adhesive layer is an adhesive formed by, for example, applying the resin composition for forming the pressure-sensitive adhesive layer on the above-mentioned plastic film and drying it, or applying and drying the resin composition for forming the pressure-sensitive adhesive layer on a base film such as a PET film and drying it. The layer can be produced by bonding the above-mentioned plastic film. The tack strength is set to a desired value by, for example, adjusting the ratio of the liquid component and the Tg of the high molecular weight component. The die bonding film 20 is the heat dissipation die bonding film of this embodiment mentioned above. 1, the dicing film 10 and the die bonding film 20 are in direct contact, but the dicing film 10 and the die bonding film 20 may be laminated|stacked through other layers, such as an adhesive layer. .

There is no restriction|limiting in particular in the manufacturing method of the dicing die-bonding film of this embodiment, Based on the knowledge of a person skilled in the art, it can determine suitably. The dicing die-bonding film of this embodiment can be manufactured by using a dicing film instead of a base film in the manufacturing method of the said heat dissipation die-bonding film, for example. In addition, the dicing die-bonding film of this embodiment can also be manufactured, for example by separately preparing the heat dissipation die-bonding film and dicing film of this embodiment, and laminating|stacking these and integrating them.

[Example]

Hereinafter, the present invention will be described more specifically 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 heat dissipation die-bonding film formation)]

The following materials were prepared as fillers other than a component, b component, c component, d component, and d component, a coupling agent, a hardening accelerator, and a solvent.

(a component)

· Epoxy group-containing acrylic rubber: HTR-860P-3CSP (manufactured by Nagase Chemtex Co., Ltd., trade name, weight average molecular weight 800000, Tg 12°C)

· Epoxy group-containing acrylic rubber: HTR-860P-30B (manufactured by Nagase Chemtex Co., Ltd., trade name, weight average molecular weight 300000, Tg 12°C)

· Bisphenol A/F copolymerization type phenoxy resin: ZX1356-2 (manufactured by Nippon Steel Chemical Co., Ltd., trade name, weight average molecular weight 63200, Tg 71°C)

(component b)

· Cresol novolak type epoxy resin: YDCN-700-10 (manufactured by Nippon Steel Chemicals, trade name, epoxy equivalent: 195 to 215)

· Bisphenol F-type epoxy resin: YDF-8170C (New Nittetsu Sumikin Chemical Co., Ltd., trade name, epoxy equivalent: 156)

(component c)

· Phenolic resin: XLC-LL (manufactured by Mitsui Chemicals Co., Ltd., trade name)

(component d)

Polyhedral α-alumina filler: Sumikorandam AA-3 (manufactured by Sumitomo Chemical Co., Ltd., trade name, purity Al ₂ O ₃ ≥ 99.90%, average particle diameter 2.7 to 3.6 μm, Mohs hardness 9)

· Spherical α-alumina filler: alumina bead CB-P05 (manufactured by Showa Denko Co., Ltd., trade name, purity Al ₂ O ₃ 99.89%, average particle diameter 4 μm, Mohs hardness 9)

・Boron nitride filler: HP-P1 (manufactured by Mizushima Kokintetsu Co., Ltd., trade name, average particle diameter 1-3 μm, Mohs hardness 2)

Boron nitride filler: UHP-S1: Shobien UHP-S1 (manufactured by Showa Denko Co., Ltd., trade name, average particle diameter 0.5 µm, Mohs hardness 2)

· Aluminum nitride filler: Shaypal H grade (manufactured by Toyama Corporation, trade name, average particle diameter of 1 μm, Mohs hardness 8)

· Magnesium oxide filler: RF-10C (manufactured by Ube Materials Co., Ltd., trade name, average particle diameter 10 µm, Mohs hardness 4)

(Fillers other than component d)

Silica filler: SC1030 (manufactured by Admatex, Inc., trade name, average particle diameter 0.5 µm)

· Hydrophobic silica filler: R972 (manufactured by Nippon Aerosil Co., Ltd., trade name, average particle diameter 60 nm)

(curing accelerator)

· Qazole 2PZ-CN (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name)

(Coupling agent)

· Silane coupling agent: A-189 (manufactured by UNC Corporation, trade name, γ-mercaptopropyltrimethoxysilane)

· Silane coupling agent: A-1160 (manufactured by UNC Corporation, trade name, γ-ureidopropyltriethoxysilane)

(solvent)

· Cyclohexanone

Each prepared component was mix|blended in the quantity shown in Tables 1 and 2, and the varnish of each Example, a comparative example, and a reference example was prepared. In Tables 1 and 2, the numerical values relating to fillers other than the component a, component b, component c, component d and component d, coupling agent, and curing accelerator indicate parts by mass.

[Production of heat dissipation die bonding film]

As the base film, a release-treated polyethylene terephthalate film (manufactured by Teijin Film Solutions, Inc., A31, thickness 38 µm) was prepared. The prepared varnish was applied on the release-treated surface of the polyethylene terephthalate film, and dried by heating at 90° C. for 10 minutes and at 120° C. for 30 minutes to prepare a heat-dissipating die-bonding film having a base film. The film thickness of the obtained heat dissipation die-bonding film was 30 micrometers.

[Evaluation of heat dissipation die bonding film]

The heat dissipation die-bonding film thus obtained was evaluated in accordance with the following procedure for thermal conductivity, blade wear in the dicing process, surface roughness (Ra), adhesive force, and lamination properties. The evaluation results are shown in Tables 3 and 4.

(thermal conductivity)

Several sheets of heat-dissipating die-bonding film peeled from the base film were bonded together to prepare a laminated film having a thickness of 100 µm or more and less than 600 µm. The obtained laminated|multilayer film was hardened at 110 degreeC for 1 hour, and 170 degreeC for 3 hours, and the cured film (hardened|cured material) was obtained. The obtained cured film was cut|disconnected into the rectangle whose one side is 10 mm, and this was made into the sample for a measurement.

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 using a laser flash method (manufactured by NETZSCH, LFA467HyperFlash (trade name)) in the thickness direction of the adhesive film.

Specific heat Cp (J/(g·°C)): using the DSC method (manufactured by Perkin Elmer, DSC8500 (trade name)), measured under the conditions of a temperature increase rate of 10°C/min and a temperature of 20-60°C, to 25°C The specific heat Cp was measured.

· Specific gravity (g/cm 3 ): 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(mm²/s) × specific heat Cp(J/(g·°C)) × specific gravity (g/cm3)

(Amount of wear of blades in the dicing process)

After the heat dissipation die bonding film was laminated at room temperature on a dicing tape (base material thickness of 80 μm, full thickness 10 μm) and integrated, the side of the heat dissipation die bonding film was applied to an 8-inch wafer with a thickness of 50 μm with a laminator (Teikoku). It laminated at 70 degreeC using the Taping System Co., Ltd. product, STM-1200FH (brand name)). Thereafter, blade dicing was performed using a dicer (manufactured by Disco Corporation, DFD6361 (trade name)). The conditions for blade dicing were: blade ZH05-SD4000-N1-70 BB used (Nanyo Co., Ltd., (trade name)), wafer thickness 50 μm, chip size 3 mm×3 mm, rotation speed 50000 rpm, dicing tape cut It was set as 10 micrometers, cut speed 30 mm/sec, cut length 203 mm, cut clearance start 3 mm, and end 3 mm. From the state of the blade before and after dicing, the amount of wear of the blade in the dicing process was calculated. Specifically, the wear amount of the blade (μm/m) is, according to the following formula, the radius r1 (μm) of the blade before dicing, the radius r2 (μm) of the blade after dicing, and the dicing distance L1 (m) was calculated from

Blade wear (㎛/m)=(r1(㎛)-r2(㎛))/L1(m)

(Surface Roughness (Ra))

The heat dissipation die-bonding film peeled from the base film was bonded to a silicon wafer of 300 μm in thickness using a hot roll laminator (80°C, 0.3 m/min, 0.3 MPa), then at 110°C for 1 hour, at 170°C for 3 A sample was obtained by curing with time. The arithmetic mean roughness (Ra) in the 2.5 mm range of the obtained sample was computed using the fine shape measuring instrument Surf corder ET200 (Kosaka Genkyusho Co., Ltd. make, brand name).

(Adhesive force)

The heat dissipation die bonding film on the base film was bonded to a semiconductor chip (square with a side of 5 mm) 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 the substrate of 42 alloy by pressing at 120° C. and 250 g for 5 seconds, and then curing at 110° C. for 1 hour and at 170° C. for 3 hours to obtain a sample. The shear strength before and after the moisture absorption test of the obtained sample was measured using a universal bond tester (manufactured by Dage, series 4000, trade name). The conditions of the moisture absorption test were made into 85 degreeC/85%RH, 48 hours.

Adhesion was evaluated as "good" when shear strength≥2.0 MPa and "poor" when shear strength <2.0 MPa.

(Laminate)

A laminate of the base film and the heat-dissipating die-bonding film was cut to a width of 10 mm. The surface of the heat dissipation die bonding film in 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). Thereafter, the bonded heat dissipation die bonding film was subjected to a tensile rate of 50 mm/min at an angle of 90° in an atmosphere of 25° C. using a small tabletop testing machine EZ-S (manufactured by Shimadzu Corporation) at a tensile rate of 50 mm/min. The 90 degree peeling strength at the time of peeling was measured. The case where 90 degree peeling strength was 20 N/m or more was made into "good|favorableness", and the case where 90 degree peeling strength was less than 20 N/m was considered "poor", and lamination property was evaluated.

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 thermal curing, and excellent thermal conductivity after thermal curing, and a wear amount of ≤ 50 (μm) /m), it can be seen that the wear suppression at the time of the blade is excellent. Moreover, it turns out that the heat dissipation die-bonding film of Examples 1-7 is excellent also in adhesiveness (adhesive force) and lamination property, and also has small surface roughness. That is, according to the heat dissipation die bonding film of Examples 1-7, since it is excellent in heat dissipation and it is easy to suppress abrasion of a blade, it is thought that a semiconductor element can be manufactured efficiently.

1: dicing die-bonding film, 10: dicing film, 20: die-bonding film.

Claims (13)

A heat dissipating die bonding film having a thermal conductivity of 2 W/(m·K) or more,
It contains two or more types of thermally conductive fillers having different Mohs hardness, and the wear amount of the blade in the dicing process is 50 µm/m or less,
The heat dissipating die-bonding film which contains at least 1 type of thermally conductive filler of Mohs' Hardness 1-3, and at least 1 type of thermally conductive filler of 4-9 Mohs' Hardness as said thermally conductive filler. containing two or more types of thermally conductive fillers having different Mohs hardness,
The content of the thermally conductive filler is 20 to 85 mass%,
The heat dissipating die-bonding film which contains at least 1 type of thermally conductive filler of Mohs' Hardness 1-3, and at least 1 type of thermally conductive filler of 4-9 Mohs' Hardness as said thermally conductive filler. The heat dissipation die-bonding film according to claim 1 or 2, wherein the thermally conductive filler contains at least two selected from the group consisting of an alumina filler, a boron nitride filler, an aluminum nitride filler, and a magnesium oxide filler. The heat dissipation die-bonding film according to claim 3, wherein the alumina filler contains an alumina filler having a purity of 99.0 mass% or more. The heat dissipating die-bonding film according to claim 3, wherein the boron nitride filler contains a hexagonal boron nitride filler having a nitrogen purity of 95.0 mass% or more. The heat dissipating die-bonding film according to claim 3, wherein the aluminum nitride filler has a density of 3 to 4 g/cm 3 . The heat dissipation die-bonding film according to claim 3, wherein the magnesium oxide filler contains a magnesium oxide filler having a purity of 95.0 mass% or more. The heat dissipation die-bonding film according to claim 1 or 2, further comprising a high molecular weight component of any one of an acrylic resin and a phenoxy resin, an epoxy resin, and a curing agent. The heat dissipating die-bonding film according to claim 8, wherein the total mass of the thermally conductive filler 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 thermally conductive filler. The heat dissipating die-bonding film according to claim 1 or 2, wherein the thermally conductive filler contains an alumina filler and a boron nitride filler. The heat dissipating die-bonding film according to claim 1 or 2, wherein the thermally conductive filler contains a boron nitride filler and an aluminum nitride filler. The heat dissipating die-bonding film according to claim 1 or 2, wherein the thermally conductive filler contains a boron nitride filler and a magnesium oxide filler. A dicing film and a die bonding film laminated on the dicing film,
The dicing die-bonding film whose said die-bonding film is the heat dissipation die-bonding film of Claim 1 or 2.

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