CN110945634A - Heat dissipating die bond film and dicing die bond film - Google Patents
Heat dissipating die bond film and dicing die bond film Download PDFInfo
- Publication number
- CN110945634A CN110945634A CN201880048265.5A CN201880048265A CN110945634A CN 110945634 A CN110945634 A CN 110945634A CN 201880048265 A CN201880048265 A CN 201880048265A CN 110945634 A CN110945634 A CN 110945634A
- Authority
- CN
- China
- Prior art keywords
- bonding film
- mass
- heat dissipating
- filler
- die
- Prior art date
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- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 125000003710 aryl alkyl group Chemical group 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
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- 125000005647 linker group Chemical group 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- 239000011707 mineral Substances 0.000 description 1
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- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
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- 230000003449 preventive effect Effects 0.000 description 1
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Die Bonding (AREA)
- Dicing (AREA)
- Adhesive Tapes (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
The invention relates to a heat dissipation chip bonding film, which has a heat conductivity of 2W/(m.K) or more, contains 2 or more kinds of heat conductive fillers with different Mohs hardness, and has a blade wear amount of 50 [ mu ] m/m or less in a dicing step; or it contains 2 or more kinds of thermally conductive fillers having different Mohs' hardnesses, and the content of the thermally conductive filler is 20 to 85 mass%.
Description
Technical Field
The invention relates to a heat dissipating die-bonding film and a dicing die-bonding film.
Background
The semiconductor wafer on which the circuit pattern is formed is diced into chip-shaped semiconductor elements after the thickness thereof is adjusted by back grinding as necessary (dicing step). Next, the semiconductor element is fixed to a fixed body such as a lead frame using an adhesive (die bonding step), and then transferred to a bonding step. For example, a method has been proposed in which a metal base is disposed with an adhesive under a dicing 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 (see, for example, patent document 1). On the other hand, as an adhesive film having thermal conductivity or heat dissipation properties, for example, an adhesive film containing highly thermally conductive particles or a heat dissipation die bonding film containing a thermally conductive filler is known (for example, see patent documents 2 and 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 5-198701
Patent document 2: japanese patent laid-open publication No. 2009-235402
Patent document 3: japanese patent laid-open No. 2014-68020
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a heat dissipation chip bonding film capable of efficiently manufacturing a semiconductor element and a cutting-chip bonding film with the same.
Means for solving the problems
The present invention relates to a heat dissipating die bonding film having a thermal conductivity of 2W/(m.K) or more, which contains 2 or more kinds of heat conductive fillers having different Mohs hardness, and has a blade wear amount of 50 [ mu ] m/m or less in a dicing step.
The invention also relates to a heat dissipation chip bonding film, which contains more than 2 kinds of heat conductive fillers with different Mohs hardness, and the content of the heat conductive fillers is 20-85 mass%.
The heat dissipating die bond film may contain at least 2 kinds of thermally conductive fillers selected from the group consisting of alumina fillers, boron nitride fillers, aluminum nitride fillers, and magnesium oxide fillers.
The alumina filler may contain an alumina filler having a purity of 99.0 mass% or more.
The boron nitride filler may contain a hexagonal boron nitride filler having a nitrogen purity of 95.0 mass% or more.
The density of the aluminum nitride filler can be 3-4 g/cm3。
The magnesium oxide filler may contain a magnesium oxide filler having a purity of 95.0 mass% or more.
The heat dissipating die-bonding film may further include: any one of high molecular weight components of acrylic resin and phenoxy resin; an epoxy resin; and a curing agent.
In the heat dissipating die bonding film, the total mass of the thermally conductive filler may be 20 parts by mass or more with respect to 100 parts by mass of the total amount of the high molecular weight component, the epoxy resin, the curing agent, and the thermally conductive filler.
The heat dissipating die bond film may contain an aluminum nitride filler and a boron nitride filler, a boron nitride filler and an aluminum nitride filler, and a boron nitride filler and a magnesium oxide filler as the thermally conductive filler.
The present invention relates to a dicing die-bonding film including 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.
Effects of the invention
According to the present invention, a heat-dissipating die-bonding film capable of efficiently manufacturing a semiconductor element, and a dicing die-bonding film provided with the same can be provided.
Drawings
Fig. 1 is a cross-sectional view schematically showing a dicing die-bonding film according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings in accordance with the circumstances. However, the present invention is not limited to the following embodiments. In the present specification, "(meth) acrylate" means "acrylate" or "methacrylate" corresponding thereto.
[ Heat dissipating chip bonding film ]
The heat dissipating die bonding film according to one embodiment is a heat dissipating die bonding film having a thermal conductivity of 2W/(m.K) or more, and contains 2 or more kinds of heat conductive fillers having different Mohs hardness, and the blade wear amount in the dicing step is 50 μm/m or less. According to the heat dissipating die bonding film, a semiconductor element can be efficiently manufactured.
In the present specification, the blade wear amount in the cutting step is a value calculated in the following procedure. After the heat dissipating die-bonding film was laminated on a dicing tape (substrate thickness: 80 μm, paste thickness: 10 μm) at room temperature for integration, the surface of the heat dissipating die-bonding film side was laminated on an 8-inch wafer having a thickness of 50 μm at 70 ℃ using a laminator (product name: STM-1200FH, manufactured by Teikoku Taping System Co., Ltd.). Thereafter, the cut piece was cut with a microtome (trade name, DFD6361, manufactured by Disco, Ltd.). The conditions for blade cutting were: the wafer thickness was 50 μm, the chip size was 3 mm. times.3 mm, the rotation speed was 50000rpm, the score of the dicing tape was 10 μm, the dicing speed was 30 mm/sec, the dicing length was 203mm, the dicing gap was 3mm at the beginning and 3mm at the end, using a cutter blade ZH05-SD4000-N1-70BB (Nanyang, trade name, Co., Ltd.). Next, the wear amount (μm/m) of the blade was calculated from the radius r1(μm) of the blade before cutting, the radius r2(μm) of the blade after cutting, and the cutting distance L1(m) according to the following equation.
The consumption of the blade (μm/m) ═ r1(μm) -r2(μm))/L1(m)
The heat dissipating die-bonding film according to another embodiment may contain, for example, 2 or more kinds of thermally conductive fillers having different mohs hardness, and the content of the thermally conductive filler is 20 to 85 mass%. According to the heat dissipating die bonding film, a semiconductor element can be efficiently manufactured. The heat dissipation die bonding film is excellent in thermal conductivity after heat curing and blade wear resistance in the dicing step.
The heat dissipating die-bonding film of the present embodiment does not require a step of applying a pressure in the thickness direction to the primary film formed using the varnish in the production thereof. The heat dissipating die-bonding film of the present embodiment is excellent in adhesion and is likely to reduce the occurrence of peeling and cracking of the metal base due to the difference in thermal expansion coefficient among the metal base, the semiconductor element, the dicing pad, and the like even when the produced semiconductor element repeatedly generates heat.
The heat dissipating die-bonding film of the present embodiment may further contain, for example, a high molecular weight component, an epoxy resin, and a curing agent, which will be described later. The respective components are explained below. Hereinafter, the "high molecular weight component" is referred to as "component a", the "epoxy resin" is referred to as "component b", the "curing agent" is referred to as "component c", and the "thermally conductive filler" is referred to as "component d".
(component a: high molecular weight component)
The heat dissipating die-bonding film of the present embodiment may further contain a component a. The component a includes, for example, a resin having thermoplasticity and at least having thermoplasticity in an uncured state, and forming a crosslinked structure after heating.
The component a may be, for example, a phenoxy resin, polyimide, polyamide, polycarbodiimide, cyanate ester resin, acrylic resin, polyester, polyethylene, polyethersulfone, polyetherimide, polyvinyl acetal, or polyurethane resin, from the viewpoint of easy availability of film formability, heat resistance, and adhesiveness. These high molecular weight components may also be copolymers, for example. The component a may be used alone in 1 kind or in combination of 2 or more kinds.
The component a is preferably a phenoxy resin, polyimide, polyamide, acrylic resin, cyanate ester resin, or polycarbodiimide from the viewpoint of excellent film-forming properties and heat resistance, and is preferably a phenoxy resin from the viewpoint of easy adjustment of molecular weight and properties. From these viewpoints, the component a may be either an acrylic resin or a phenoxy resin.
(acrylic resin)
When the component a contains an acrylic resin, the acrylic resin preferably has a reactive group (functional group) and a weight-average molecular weight of 100000 or more. The acrylic resin may be used alone in 1 kind or in combination of 2 or more kinds.
In the present specification, the weight average molecular weight is a value converted to polystyrene by Gel Permeation Chromatography (GPC) using a calibration curve obtained from standard polystyrene.
Specific examples of the acrylic resin include acrylic copolymers. Examples of the acrylic copolymer include acrylic rubbers. Examples of the acrylic rubber include copolymers of acrylonitrile and at least 1 selected from acrylic acid esters and methacrylic acid esters.
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 of facilitating the reduction of gelation in the varnish state and the viewpoint of preventing the increase in the degree of curing in the B-stage state and the decrease in the adhesive strength due to the increase in the degree of curing.
When the reactive group is an epoxy group, the present inventors presume the reason why such an effect is obtained as follows. When the reactive group is, for example, a carboxyl group, the crosslinking reaction is likely to proceed, and 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, a crosslinking reaction hardly occurs, and gelation in a varnish state and an improvement in the degree of curing in a B-stage state hardly occur.
The acrylic resin having a reactive group can be produced, for example, as follows: in the polymerization reaction for obtaining an acrylic resin, an acrylic monomer having a reactive group (e.g., a (meth) acrylate having a reactive group) is polymerized so that the reactive group remains, or a reactive group is 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 the glycidyl (meth) acrylate as the 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 of easily improving the adhesiveness. The content of glycidyl (meth) acrylate as a monomer unit may be, for example, 6 mass% or less based on the total mass of the acrylic resin, from the viewpoint of facilitating the reduction of gelation. From these viewpoints, the content of the glycidyl (meth) acrylate as the monomer unit may be 0.5 to 6% by mass, and may be 2 to 6% by mass based on the total mass of the acrylic resin.
In the acrylic resin containing glycidyl (meth) acrylate as a monomer unit, examples of the monomer unit other than glycidyl (meth) acrylate include (meth) acrylic acid esters other than glycidyl (meth) acrylate, such as alkyl (meth) acrylate having an alkyl group with 1 to 8 carbon atoms, styrene, and acrylonitrile. Examples of the alkyl (meth) acrylate having an alkyl group with 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 the monomers can be adjusted in consideration of the glass transition temperature (hereinafter, sometimes referred to as "Tg") of the copolymer.
The method of polymerization of the acrylic resin is not particularly limited, and examples thereof include bead polymerization and solution polymerization.
The Tg of the acrylic resin as the component a may be, for example, from-50 ℃ to 50 ℃ or lower, or from-10 ℃ to 50 ℃ or lower. When the Tg is-50 ℃ or higher, the adhesiveness of the adhesive layer or adhesive film in the B-stage state tends to be reduced, and the handling property tends to be excellent.
The acrylic resin may have a cyclic structure. Examples of the acrylic resin having a cyclic structure include acrylic resins having styrene or benzyl (meth) acrylate as a monomer unit. When the acrylic resin has a cyclic structure, it is considered that the higher the total mass Mcr (Mcr/MTOT) of carbon atoms in the cyclic structure based on the total mass MTOT of the acrylic resin, the more preferable.
The weight average molecular weight of the acrylic resin may be, for example, 200000 or more, 300000 or more, and 400000 or more, from the viewpoints that it is difficult to decrease the strength and flexibility and increase the adhesion when the acrylic resin is formed into a sheet or film. The weight average molecular weight of the acrylic resin may be, for example, 3000000 or less, or 2000000 or less, from the viewpoint of high fluidity and easy improvement of circuit filling property of wiring. From these viewpoints, the weight average molecular weight of the acrylic resin may be 200000 to 3000000, may be 300000 to 3000000, or may be 400000 to 2000000, for example.
The acrylic resin as the component a may be, for example, an acrylic copolymer containing 0.5 to 6 mass% of glycidyl (meth) acrylate as a monomer unit, having a Tg of-50 ℃ or higher and 50 ℃ or lower (preferably-10 ℃ or higher and 50 ℃ or lower), and having a weight average molecular weight of 100000 or higher, from the viewpoint of easily obtaining high adhesiveness and heat resistance. Examples of such acrylic resins include HTR-860P-3 and HTR-860P-30B (trade name, manufactured by Nagasechemtex).
(phenoxy resin)
When the component a contains a phenoxy resin, the weight average molecular weight of the phenoxy resin is preferably 20000 or more, more preferably 30000 or more, and still more preferably 50000 or more. The phenoxy resin can be used singly or in combination of 1 or more than 2.
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 (trade name, available from Nippon Tekken chemical Co., Ltd.); and 1256, 4250, 4256, 4275, YX7180, YX6954, YX8100, YX7200, YL7178, YL7290, YL7600, YL7734, YL7827, and YL7864 (trade name, manufactured by Japan Epoxy Resins Co., Ltd.).
The Tg of the phenoxy resin is preferably less than 85 ℃. Examples of the phenoxy resin having a Tg of less than 85 ℃ include YP-50, YP-55, YP-70 and ZX-1356-2 (trade name of "Nippon iron King chemical Co., Ltd."); and 4250, 4256, 7275, YX7180 and YL7178 (trade name, manufactured by Japan Epoxy Resins Co., Ltd.).
[ component b: epoxy resin
The component b is, for example, a component which is cured to exhibit an adhesive effect. The component b is preferably an epoxy resin having 2 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, less than 3000, or less than 2000, from the viewpoint of heat resistance.
Examples of the component b include difunctional epoxy resins such as bisphenol a type epoxy resin and bisphenol F type epoxy resin; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; a multifunctional epoxy resin; amine-type epoxy resins; a heterocycle-containing epoxy resin; and an alicyclic epoxy resin. As the component b, a generally known epoxy resin other than the above may also be used.
Examples of commercially available bisphenol a epoxy resins include Epikote807, Epikote815, Epikote825, Epikote827, Epikote828, Epikote834, Epikote1001, Epikote1002, Epikote1003, Epikote1055, Epikote1004AF, Epikote1007, Epikote1009, Epikote1003F, and Epikote1004F (trade name, product name, mitsubishi corporation); 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 (trade name, manufactured by Dow Chemical Co., Ltd.; mentioned above); and YD8125 (trade name, available from Nissie iron Japan chemical Co., Ltd.).
Examples of commercially available bisphenol F-type epoxy resins include YDF-2004 and YDF-8170C (trade name, available from Nissan King chemical Co., Ltd.).
As a commercially available phenol novolac type epoxy resin; for example, Epikote152 and Epikote154 (trade name, product of Mitsubishi Chemical Co., Ltd.); EPPN-201 (trade name, manufactured by Nippon Kagaku Co., Ltd.); and DEN-438 (trade name, manufactured by Dow Chemical Co., Ltd.).
Examples of commercially available cresol novolak-type epoxy resins include Epikote180S65 (trade name, product of Mitsubishi Chemical corporation); araldite ECN 1273, Araldite ECN1280 and Araldite ECN1299 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.); YDCN-700-10, YDCN-701, YDCN-702, YDCN-703 and YDCN-704 (trade names, manufactured by Nissan iron god chemical Co., Ltd.); EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1020, EOCN-1025, and EOCN-1027 (trade name, manufactured by Nippon chemical Co., Ltd.); and ESCN-195X, ESCN-200L and ESCN-220 (trade name, manufactured by Sumitomo chemical Co., Ltd.).
Examples of commercially available polyfunctional epoxy resins include Epon1031S, Epikote1032H60, and Epikote157S70 (trade name, product of mitsubishi Chemical corporation); araldite 0163 (trade name, manufactured by Ciba specialty Chemicals Co., Ltd.); denacol EX-611, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-421, Denacol EX-411 and Denacol EX-321 (trade name, manufactured by Nagasechemtex Co., Ltd.); and EPPN501H and EPPN502H (trade name, manufactured by nipponica chemical co., ltd.).
Examples of commercially available amine-type epoxy resins include Epikote604 (trade name, product of Mitsubishi Chemical corporation); YH-434 (trade name, available from Nichiku chemical Co., Ltd.); TETRAD-X and TETRAD-C (trade name, manufactured by Mitsubishi gas chemical Co., Ltd.); and ELM-120 (product name, manufactured by Sumitomo chemical Co., Ltd.).
An example of a commercially available heterocyclic ring-containing epoxy resin is Araldite PT810 (product name, Ciba specialty Chemicals).
Examples of commercially available alicyclic epoxy resins include ERL4234, ERL4299, ERL4221 and ERL4206 (trade name, manufactured by UCC Co., Ltd.).
The component b may be used alone in 1 kind or in combination of 2 or more kinds.
The component b may contain a bifunctional epoxy resin and a trifunctional or higher epoxy resin, from the viewpoint of easily improving adhesiveness, heat resistance, and moisture absorption resistance after thermosetting. When the component b contains a bifunctional epoxy resin and a trifunctional or higher epoxy resin, the content of the bifunctional epoxy resin may be, for example, 3 to 40 mass%, further 3 to 30 mass%, further 3 to 20 mass%, based on the total mass of the bifunctional epoxy resin and the trifunctional or higher epoxy resin.
[ component c: curing agent ]
The component c may be used without limitation as long as it can cure the component b. Examples of the component c include polyfunctional phenol compounds, amine compounds, acid anhydrides, organic phosphorus compounds and halides thereof, polyamides, polysulfides, and boron trifluoride.
Examples of the polyfunctional phenol compound include monocyclic bifunctional phenol compounds and polycyclic bifunctional phenol compounds. Examples of the monocyclic bifunctional phenol include hydroquinone, resorcinol, catechol, and alkyl-substituted products thereof.
Examples of the polycyclic bifunctional phenol compound include bisphenol a, bisphenol F, bisphenol S, naphthalene diol, and biphenol, and alkyl-substituted products thereof. The polyfunctional phenol compound may be, for example, a polycondensate of at least 1 phenol compound selected from the monocyclic bifunctional phenol compounds and the polycyclic bifunctional phenol compounds, and an aldehyde compound. The polycondensate is, for example, a phenolic resin. Examples of the phenol resin include phenol novolac resins, resol resins, bisphenol a novolac resins, and cresol novolac resins.
Examples of the commercially available products of the above-mentioned phenol resin (phenol resin curing agent) include Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH4150 and Phenolite VH4170 (trade name, manufactured by DIC corporation).
The hydroxyl group equivalent of the phenol resin may be, for example, 250g/eq or more, 200g/eq or more, or 150g/eq or more, from the viewpoint of adhesiveness and heat resistance. The phenol resin as the component c is preferably a novolac type or resol type resin from the viewpoint of improving the electrical corrosion resistance when absorbing moisture.
The phenol resin preferably has a water absorption of 2 mass% or less after being left in a constant temperature and humidity bath at 85 ℃ and 85% RH for 48 hours, from the viewpoint of improving moisture resistance. The phenolic resin as component c preferably has a heating weight loss rate at 350 ℃ measured by thermogravimetric analysis (TGA) (rate of temperature rise: 5 ℃/min, ambient gas: nitrogen gas) of less than 5% by weight. When such a phenol resin is used as a curing agent, volatile components are suppressed during heating processing, so that reliability of various characteristics such as heat resistance and moisture resistance is improved, and machine contamination due to volatile components during operation such as heating processing can be reduced.
Specific examples of the above phenolic resin include compounds represented by the following formula (I).
[ chemical formula No. 1]
In the formula (I), R1Represents 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, n represents an integer of 1 to 3, and m represents an integer of 0 to 50. In the formula (I), a plurality of R exist1And n may be the same or different.
Examples of the compound represented by the formula (I) include the Milex XLC-series and the Milex XL-series (trade name, manufactured by Mitsui chemical Co., Ltd.).
The compound represented by the formula (I) can be obtained, for example, by reacting a phenol compound with a xylylene compound in the absence of a catalyst or an acid catalyst (acidic catalyst). In addition, xylylene compounds can form a 2-valent linking group by this reaction.
Examples of the phenol compound used for producing the compound represented by the formula (I) include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-n-propylphenol, m-n-propylphenol, 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, resorcinol, catechol, hydroquinone, 4-methoxyphenol, o-phenylphenol, m-phenylphenol, p-cyclohexylphenol, o-allylphenol, p-allylphenol, O-benzylphenol, p-benzylphenol, o-chlorophenol, p-chlorophenol, o-bromophenol, p-bromophenol, o-iodophenol, p-iodophenol, o-fluorophenol, m-fluorophenol and p-fluorophenol. The above phenol compounds may be used singly or in combination of 1 or more.
The phenol compound used for producing the compound represented by the formula (I) is preferably phenol, o-cresol, m-cresol or p-cresol, from the viewpoint of adhesiveness, heat resistance and moisture resistance.
Examples of the xylylene compound used for the production of the compound represented by the formula (I) include xylylene dihalide, xylylene glycol and their derivatives.
Specific examples of the above xylylene compounds include '-dichloro-p-xylene, 0, 1' -dichloro-m-xylene, 2, 3 '-dichloro-o-xylene, 4, 5' -dibromo-p-xylene, 6, 7 '-dibromo-m-xylene, 8, 9' -dibromo-o-xylene, 0 '-diiodo-p-xylene, 1, 2' -diiodo-m-xylene, 3,4 '-diiodo-o-xylene, 5, 6' -dihydroxy-p-xylene, 7, 8 '-dihydroxy-m-xylene, 9' -dihydroxy-o-xylene, 0, 1 '-dimethoxy-p-xylene, 2, 3' -dimethoxy-m-xylene, 4,5 '-dimethoxy-o-xylene, 6, 7' -diethoxy-p-xylene, 8, 9 '-diethoxy-m-xylene, 0' -diethoxy-o-xylene, 1, 2 '-di-n-propoxy-p-xylene, 3, 4' -di-n-propoxy-m-xylene, 5, 6 '-di-n-propoxy-o-xylene, 7, 8' -diisopropoxy-p-n-xylene, 9'-diisopropoxy-m-xylene, 1, 2' -di-n-butoxy-p-xylene, 3,4 '-di-n-butoxy-m-xylene, 5, 6' -di-n-butoxy-o-xylene, 7 '-diisobutoxy-p-xylene, 3' -di-iso-xylene, and combinations of the above.
The above xylylene compound is preferably α ' -dichloro-p-xylene, α 0, α 1 ' -dichloro-m-xylene, α 2, α 3 ' -dichloro-o-xylene, α 4, α 5 ' -dihydroxy-p-xylene, α 6, α 7 ' -dihydroxy-m-xylene, α ' -dihydroxy-o-xylene, α ' -dimethoxy-p-xylene, α ' -dimethoxy-m-xylene or α ' -dimethoxy-o-xylene, from the viewpoint of producing a phenol resin having good adhesiveness, heat resistance and moisture resistance.
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, ethanesulfonic acid, and the like; super strong acids such as trifluoromethanesulfonic acid; strongly acidic ion exchange resins such as alkanesulfonic acid type ion exchange resins; a super strong acid ion exchange resin such as a perfluoroalkanesulfonic acid type ion exchange resin (for example, Nafion (trade name, manufactured by DuPont)); natural and synthetic zeolite compounds; and activated clays (e.g., acid clays).
The above reaction is carried out, for example, until a xylylene compound as a raw material at 50 to 250 ℃ substantially disappears and the reaction composition becomes constant.
The reaction time can be suitably adjusted depending on the raw materials and the reaction temperature. The reaction time can be determined by following the reaction composition by GPC (gel permeation chromatography) or the like, for example. The reaction time may be, for example, about 1 hour to 15 hours.
When the above reaction is carried out in the presence of an acid catalyst, water or alcohol is generally produced.
On the other hand, when a haloxylene derivative such as α' -dichloro-p-xylene is used as the xylylene compound, an acid catalyst is not necessary because the reaction proceeds without a catalyst while generating a hydrogen halide gas.
The reaction molar ratio of the phenol compound to the xylylene compound is usually such a condition that the phenol compound becomes excessive. At this time, the unreacted phenol compound is recovered after the reaction. The weight average molecular weight of the compound represented by the formula (I) is usually determined from the reaction molar ratio of the phenol compound to the xylylene compound. The weight average molecular weight of the compound represented by the formula (I) tends to decrease as the amount of the phenol compound becomes excessive.
The phenol resin may have an allylphenol skeleton, for example. The phenol resin having an allylphenol skeleton can be obtained, for example, by the following method: a phenol-formaldehyde resin is made which is not allylated, an allyl halide is reacted therewith, and allylation is carried out by claisen rearrangement via an allyl ether.
Examples of the amine compound as the component c include aliphatic or aromatic primary amines, secondary amines, tertiary amines, and quaternary ammonium salts; an aliphatic cyclic amine compound; a guanidine compound; and urea derivatives.
Specific examples of the above-mentioned amine compound include N, N-benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, 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, and the like, Tetramethylammonium iodide, triethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, dicyandiamide, tolylbiguanidine, guanylurea and dimethylurea. The amine compound may be, for example, a dihydrazide compound such as adipic acid dihydrazide; cyanuric acid; melamine acid; an addition compound of an epoxy compound and a dialkylamine compound; addition compounds of amines to thiourea; and addition compounds of amines and isocyanates. These amine compounds may have, for example, an adduct type structure from the viewpoint of reducing the activity at room temperature.
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 as long as it is a phosphorus compound having an organic group. Examples of the organic phosphorus compound include hexamethylphosphoric triamide, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, triphenyl phosphite, trimethyl phosphate, phenylphosphonic acid, triphenylphosphine, tri-n-butylphosphine, and diphenylphosphine.
The component c may be used alone in 1 kind or in combination of 2 or more kinds.
[ component d: thermally conductive filler
The component d can impart thermal conductivity to the heat dissipating die bond film, for example. In the present embodiment, the heat dissipating die bonding film contains 2 or more kinds of d components having different mohs hardness. It is considered that the blade is hard to wear by using 2 or more kinds of d-components having different mohs' hardnesses. The component d may be, for example, 2 or more selected as appropriate from the components d described later.
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, antimony oxide, and a combination thereof. The material constituting the component d may have electrical insulation. Examples of the boron nitride include hexagonal boron nitride and cubic boron nitride. The aluminum borate may also be aluminum borate whiskers.
The material constituting the component d may be aluminum hydroxide, magnesium carbonate, calcium oxide or magnesium oxide from the viewpoint of easy adjustment of melt viscosity and easy thixotropy. The material constituting the component d may be aluminum hydroxide or antimony oxide, because moisture resistance is easily improved.
In the heat dissipating die bond film of the present embodiment, it is preferable to contain at least 2 kinds selected from the group consisting of an alumina filler, a boron nitride filler, an aluminum nitride filler, and a magnesium oxide filler as the component d 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 step.
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 from the viewpoint of further reducing the abrasion of the blade in the cutting step, and the alumina filler may be constituted by an alumina filler having a purity of 99.0 mass% or more, and examples of the alumina filler having a purity of 99.0 mass% or more include Sumicorundum AA-3 (product name, manufactured by Sumitomo chemical Co., Ltd.) and alumina beads CB-P05 (product name, manufactured by Showa Denko K.K.), and the alumina filler more preferably contains α -alumina filler having a purity of 99.0 mass% or more, and the purity of the alumina filler may be 100 mass% or less, for example.
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 thermosetting and from the viewpoint of further reducing the wear of the blade in the dicing step. Examples of such hexagonal boron nitride fillers include HP-P1, HP-4W (trade name, available from Shuitai iron Co., Ltd.), and SHOBN UHP-S1 (trade name, available from Showa electric Co., Ltd.). Here, the purity of nitrogen is a value calculated based on the mass of nitrogen in the hexagonal boron nitride saturated with nitrogen. The purity of nitrogen in the hexagonal boron nitride may be, for example, 100 mass% or less.
The density of the aluminum nitride filler is preferably 3 to 4g/cm3. Examples of such aluminum nitride fillers include Shapal H grade, Shapal E grade (trade name, manufactured by Tokuyama corporation), and ALN020BF (trade name, manufactured by Baker industries, Ltd.).
The magnesium oxide filler preferably contains a magnesium oxide filler having a purity of 95.0 mass% or more. Examples of such a magnesium oxide filler include RF-10C (trade name, manufactured by Ube Materials Co., Ltd.). The purity of the magnesium oxide may be, for example, 100 mass% or less.
The heat dissipating die-bonding film of the present embodiment may contain the alumina filler and the boron nitride filler, the boron nitride filler and the aluminum nitride filler, and the boron nitride filler and the magnesium oxide filler as the component d.
Average particle diameter of mixture of component d (d)50) From the viewpoint of further improving the adhesive strength, the lamination property, and the reliability, the thickness of the heat dissipating die bonding film is preferably 1/2 or less, more preferably 1/3 or less, and still more preferably 1/4 or less. Average particle diameter of mixture of component d (d)50) For example, the thickness of the heat dissipation die bonding film may be 1/1000 or more.
Average particle diameter of mixture of component d (d)90) From the viewpoint of further improving the adhesive strength, the lamination property, and the reliability, the thickness of the heat dissipating die bonding film is preferably 1/2 or less, more preferably 1/3 or less, and still more preferably 1/4 or less. Average particle diameter of mixture of component d (d)90) For example, the thickness of the heat dissipation die bonding film may be 1/1000 or more.
In the present specification, the average particle diameter (d) is50) The particle diameter means a particle diameter in which the cumulative value of the particle size distribution corresponds to 50%, and the average particle diameter (d)90) This means that the cumulative value of the particle size distribution corresponds to 90% of the particle size.
The thermal conductivity of the component d may be, for example, 10W/(m · K) or more, 15W/(m · K) or more, or 17W/(m · K) or more, from the viewpoint of further improving the thermal conductivity of the heat dissipating die bonding film.
In the heat dissipating die-bonding film of the present embodiment, the mohs hardness of at least 1 of the d components is preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less, from the viewpoint of more easily suppressing the abrasion of the blade in the dicing step.
When the mohs hardness of at least 1 of the d components is 10 or less, the content of the d component having a mohs hardness of 10 or less may be, for example, 10 mass% or more, 15 mass% or more, and 20 mass% or more based on the total mass of the heat dissipating die bonding film, from the viewpoint of more easily suppressing the wear of the blade in the dicing step.
In the heat dissipating die bonding film of the present embodiment, it is preferable that at least 1 kind of the heat conductive filler having a mohs hardness of 1 to 3 and at least 1 kind of the heat conductive filler having a mohs hardness of 4 to 9 are contained as the component d from the viewpoint of further improving the heat conductivity after heat curing and from the viewpoint of further reducing the wear of the blade in the dicing step. 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, 10 parts by mass or more, or 30 parts by mass or more, based on 100 parts by mass of the total mass of the thermally conductive filler having a mohs hardness of 4 to 9. The content of the thermally conductive filler having a Mohs hardness of 1 to 3 may be, for example, 300 parts by mass or less, 250 parts by mass or less, or 200 parts by mass or less, based on 100 parts by mass of the total mass of the thermally conductive filler having a Mohs hardness of 4 to 9. 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, 10 to 250 parts by mass, or 30 to 200 parts by mass, based on 100 parts by mass of the total mass of the thermally conductive filler having a Mohs hardness of 4 to 9.
The shape of the component d is not particularly limited, and may be, for example, spherical or polyhedral. In the present specification, a polyhedron refers to a solid body having a plurality of planes as a constituent of a surface. The plurality of existing planes may intersect each other via a curved surface. The polyhedron may have 4 to 100 planes as a constituent of a surface, for example.
In the heat dissipating die-bonding film of the present embodiment, the content of the component a may be, for example, 3 parts by mass or more with respect to 100 parts by mass of the total amount of the components a, b, c, and d, from the viewpoint of easily lowering the elastic modulus and easily imparting fluidity during molding. The content of the component a may be, for example, 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less with respect to 100 parts by mass of the total of the components a, b, c, and d, from the viewpoint that the fluidity is not easily lowered even when the paste load is small and the circuit filling property is excellent. From these viewpoints, the content of the component a may be 3 to 40 parts by mass, 3 to 30 parts by mass, or 3 to 20 parts by mass based on 100 parts by mass of the total of the components a, b, c, and d.
In the heat dissipating die-bonding film of the present embodiment, the content of the component b may be, for example, 3 to 55 parts by mass, 5 to 45 parts by mass, or 10 to 35 parts by mass with respect to 100 parts by mass of the total amount of the components a, b, c, and d.
The content of the component c in the heat dissipating die-bonding film of the present embodiment is not particularly limited as long as the curing reaction of the component b can proceed, and the active group (hydroxyl group, amino group, acid anhydride group, phosphorus atom-containing group, etc.) in the component c that can react with the epoxy group may be, for example, in the range of 0.01 to 5.0 equivalents, and may be in the range of 0.8 to 1.2 equivalents, based on1 equivalent of the epoxy group in the component b.
For example, when the component c is a phenol resin, the content of the component c in the heat dissipating die-bonding film of the present embodiment may be, for example, 0.70/0.30 to 0.30/0.70, further 0.65/0.35 to 0.35/0.65, further 0.60/0.30 to 0.30/0.60, further 0.55/0.45 to 0.45/0.55 in terms of the equivalent ratio of the epoxy equivalent of the component b to the hydroxyl equivalent of the phenol resin (epoxy equivalent/hydroxyl equivalent), from the viewpoint of improving the curability when the heat dissipating die-bonding film is produced.
In the heat dissipating die bonding film of the present embodiment, the total mass of the component d may be, for example, 20 parts by mass or more, 22 parts by mass or more, and 25 parts by mass or more, based on 100 parts by mass of the total amount of the components a, b, c, and d, from the viewpoint of further improving the thermal conductivity after heat curing. The total mass of the component d may be, for example, 85 parts by mass or less, 75 parts by mass or less, or 70 parts by mass or less with respect to 100 parts by mass of the total amount of the components a, b, c, and d, from the viewpoint of film properties such as surface roughness, adhesiveness, and lamination properties.
The heat dissipating die-bonding film of the present embodiment preferably contains a high molecular weight component of any one of an acrylic resin and a phenoxy resin, an epoxy resin, and a curing agent.
[ other ingredients ]
The heat dissipating die-bonding film of the present embodiment may contain components other than those described above. Examples of such components include a curing accelerator, a filler other than the component d, a coupling agent, and an ion scavenger.
(curing accelerators)
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-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-methylimidazoline, benzimidazole, 1-cyanoethylimidazole, 1-cyanoethyl-2-phenylimidazole and 1-cyanoethyl-2-phenylimidazolium trimellitate. The curing accelerator can be used singly or in combination of 2 or more. Examples of commercially available products of the imidazole compound include 2E4MZ, 2PZ-CN and 2PZ-CNS (both trade names, product name, manufactured by Shikoku Kagaku K.K.).
In addition, the curing accelerator may be a latent curing accelerator from the viewpoint of extending the life of the film. Examples of such a curing accelerator include an adduct of an epoxy compound and an imidazole compound. The curing accelerator may have an adduct type structure from the viewpoint of reducing the activity at room temperature.
The amount of the curing accelerator to be blended may be, for example, 5.0 mass% or less, or may be 3.0 mass% or less, based on the total mass of the components b and c, from the viewpoint of excellent storage stability and the viewpoint of ensuring a sufficient usable time. The amount of the curing accelerator to be blended may be, for example, 0.02 mass% or more, and may be 0.03 mass% or more, based on the total mass of the components b and c, from the viewpoints of adhesiveness after heat curing, heat resistance and moisture resistance. From these viewpoints, the amount of the accelerator to be added may be, for example, 0 to 5.0 mass%, further 0.02 to 3.0 mass%, and further 0.03 to 3.0 mass%, based on the total mass of the components b and c.
(Filler other than component d)
The heat dissipating die-bonding film of the present embodiment may contain various fillers other than the above-described component d for the purpose of improving handling properties of the film, adjusting melt viscosity, imparting thixotropy, improving moisture resistance, and the like. The fillers other than component d may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the material constituting the filler other than the component d include calcium carbonate, calcium silicate, magnesium silicate, calcium oxide, and silica. Examples of the silica include crystalline silica and amorphous silica.
The material constituting the filler other than the component d may be calcium carbonate, calcium silicate, magnesium silicate, calcium oxide, crystalline silica or amorphous silica, from the viewpoint of easy adjustment of melt viscosity and easy thixotropy. The material constituting the filler other than the component d may be silica in view of easy improvement of moisture resistance.
When the heat dissipating die-bonding film of the present embodiment contains a filler other than the component d, the content of the filler other than the component d may be, for example, 50 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less, based on 100 parts by mass of the total mass of the component d.
(coupling agent)
The heat dissipating die-bonding film of the present embodiment may further contain various coupling agents, for example, from the viewpoint of improving interfacial bonding between different materials. Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents.
Examples of the silane coupling agent include, but are not limited to, vinyltrichlorosilane, vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltris (2-methoxy-ethoxy) silane, N-methylpropyl-3-aminopropyltrimethoxysilane, 3-aminopropyl-trimethoxysilane, 3-tris (2-methacryloxypropyltrimethoxysilane, N-methacryloxypropyltrimethoxysilane, 3-tris (2-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 1-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 1-methacryloxypropyltrimethoxysilane, 3-.
The titanium-based coupling agent is not particularly limited, and examples thereof include isopropyltrioctyl titanate, isopropyldimethacryloylstearyl titanate, isopropyltris (dodecylbenzenesulfonyl) titanate, isopropylisostearyldiacryloyl titanate, isopropyltris (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, isopropyltris (dioctylphosphate) titanate, isopropyltris (n-aminoethyl) titanate, tetraisopropylbis (dioctylphosphate) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetrakis (2, 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, dicumylphenoxyacetate titanate, bis (dioctylphosphate) oxyacetate titanate, titanium oxide, Tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, titanium polyacetylacetonate, titanium octanediol, titanium ammonium lactate, titanium ethyl lactate, titanium triethanolamine, polyhydroxytitanium stearate, tetramethylorthotitanate, tetraethylorthotitanate, tetrapropylorthotitanate, tetraisobutylorthotitanate, stearyl titanate, cresyl titanate monomer, cresyl titanate polymer, diisopropoxy-bis (2, 4-pentanedionate) titanium (IV), diisopropyl-bis-triethanolaminato titanate, octanediol titanate, tetra-n-butoxy titanium polymer, tri-n-butoxy titanium monostearate polymer, and tri-n-butoxy titanium monostearate. These substances may be used alone in 1 kind or in combination of 2 or more kinds.
The aluminum-based coupling agent is not particularly limited, and examples thereof include aluminum chelate compounds such as aluminum ethyl acetoacetate aluminum diisopropylalkoxide, aluminum tri (ethyl acetoacetate), aluminum alkyl acetoacetate aluminum diisopropylalkoxide, aluminum mono acetoacetate di (ethyl acetoacetate), aluminum tri (acetylacetonate), aluminum mono isopropoxy monooleyloxyethyl acetoacetate, aluminum di-n-butoxymonoethylacetoacetate, and aluminum diisopropoxyemonoethylacetoacetate; and aluminum alcoholates such as aluminum isopropoxide, aluminum monosec-butoxide, aluminum sec-butoxide, and aluminum ethoxide. These substances may be used alone in 1 kind or in combination of 2 or more kinds.
The coupling agent is preferably a silane coupling agent from the viewpoint of adhesiveness when bonding to an Si wafer.
When the heat dissipating die-bonding film of the present embodiment contains a coupling agent, the content of the coupling agent 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, based on 100 parts by mass of the total of the components a, b, and c, from the viewpoints of the effect, heat resistance, and cost.
(ion scavenger)
The heat dissipating die-bonding film of the present embodiment may further contain an ion scavenger, for example, from the viewpoint of adsorbing ionic impurities and improving insulation reliability in moisture absorption. Examples of the ion scavenger include a copper poisoning inhibitor used for preventing copper from being eluted to the outside for ionization. Examples of the copper poisoning preventive agent include triazine thiol compounds, bisphenol reducing agents, and inorganic ion adsorbents.
Examples of commercially available copper harm-preventing agents containing triazine thiol compounds as a component include Zisnet DB (trade name, manufactured by Sandy chemical Co., Ltd.).
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). Examples of the commercially available bisphenol reducing agent include Yoshinox BB (product name, manufactured by gefu pharmaceutical corporation).
Examples of the inorganic ion adsorbent include zirconium compounds, antimony-bismuth compounds, and magnesium-aluminum compounds. Examples of commercially available inorganic ion adsorbents include IXE (trade name, manufactured by Toyo chemical Co., Ltd.).
The content of the ion scavenger may be, for example, 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the resin composition (for example, a varnish described later) used for forming the heat dissipating die bonding film, from the viewpoints of the effect of addition, heat resistance, and cost.
The content of the component a in the heat dissipating die bonding film of the present embodiment may be, for example, 3 parts by mass or more based on the total mass of the heat dissipating die bonding film, from the viewpoint of easily lowering the elastic modulus and easily imparting fluidity during molding. The content of the component a may be, for example, 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less based on the total mass of the heat dissipating die bonding film, from the viewpoint that the fluidity is hardly lowered even when the bonding load is small and the viewpoint that the circuit filling property is excellent. From these viewpoints, the content of the component a may be 3 to 40 parts by mass, 3 to 30 parts by mass, or 3 to 20 parts by mass based on the total mass of the heat dissipating die bonding film.
The content of the component b in the heat dissipating die-bonding film of the present embodiment 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 based on the total mass of the heat dissipating die bonding film. The content of the component b may be, for example, 3 to 55 mass%, 5 to 45 mass%, or 10 to 35 mass% based on the total mass of the heat dissipating die bonding film.
In the heat dissipating die-bonding film of the present embodiment, the content of the component d is preferably 20 mass% or more, more preferably 25 mass% or more, and even more preferably 30 mass% or more, based on the total mass of the heat dissipating die-bonding film, from the viewpoint of further improving the thermal conductivity after heat curing. The content of the component d is preferably 85 mass% or less, more preferably 75 mass% or less, and further preferably 70 mass% or less, based on the total mass of the heat dissipating die bonding film, from the viewpoint of film characteristics such as surface roughness, adhesiveness, and lamination properties. From these viewpoints, the content of the component d is preferably 20 to 85 mass%, more preferably 25 to 75 mass%, and still more preferably 30 to 85 mass%, based on the total mass of the heat dissipating die-bonding film.
The thickness of the heat dissipating die bonding film is not particularly limited. The thickness of the heat dissipating die bonding film may be, for example, 5 μm or more, or 8 μm or more, from the viewpoint of improving the stress relaxation effect and the embedding property. The thickness of the heat dissipating die bonding film may be, for example, 50 μm or less, or may be 40 μm or less, from the viewpoint of cost reduction. From these viewpoints, the thickness of the heat dissipating die bonding film may be, for example, 5 to 50 μm, 5 to 40 μm, or 8 to 40 μm.
[ method for producing Heat dissipating die bonding film ]
The heat dissipating die bonding film of the present embodiment can be formed, for example, as follows: the heat-dissipating die-bonding film is formed by mixing the above-described components a, b, c, d, and the like in a solvent to prepare a varnish (a heat-dissipating die-bonding film-forming resin composition), applying the varnish to a base film (for example, a carrier film), and removing the solvent from the applied varnish.
The solvent used in the preparation of the varnish is not particularly limited. Examples of such solvents include methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol, dimethylacetamide, dimethylformamide, methylpyrrolidone, and cyclohexanone. Among them, from the viewpoint of improving the film coatability, the solvent is preferably a high boiling point solvent such as methyl ethyl ketone, dimethylacetamide, dimethylformamide, methylpyrrolidone, and cyclohexanone. These solvents may be used alone in 1 kind or in combination of 2 or more kinds.
The content of the solvent in the varnish is not particularly limited, and the content of the nonvolatile component in the varnish may be, for example, 40 mass% or more, and may be 50 mass% or more, based on the total mass of the varnish, from the viewpoint of reducing the amount of heat required for drying the varnish and being excellent in terms of cost. The content of the nonvolatile component in the varnish may be, for example, 90 mass% or less, or may be 80 mass% or less based on the total mass of the varnish, from the viewpoint that the viscosity of the varnish is not excessively high and the coating film defects caused thereby are easily reduced. From these viewpoints, the content of the nonvolatile component in the varnish is, for example, preferably 40 to 90% by mass, more preferably 50 to 80% by mass, based on the total mass of the varnish.
The mixing of the components can be performed, for example, by using a crusher, a 3-roll mill, a bead mill, or a combination thereof. Further, for example, the time required for mixing can be shortened by mixing the filler component and the low-molecular weight material in advance and then blending the high-molecular weight material. The varnish is preferably degassed by vacuum to remove air bubbles before being applied to the substrate film.
Next, the prepared varnish is applied to a base material film, and the solvent is removed by, for example, heating, whereby a heat-dissipating die bonding film can be formed on the base material film.
The conditions for the heating are not particularly limited as long as the solvent can be removed without completely curing the heat dissipating die bonding film, and may be appropriately adjusted according to the component of the heat dissipating die bonding film and the type of solvent in the varnish, for example. The heating condition is generally 80 to 140 ℃ for 5 to 60 minutes, for example.
The heat dissipating die bond film may be cured to the B-stage level by heating. The solvent remaining in the heat dissipating die-bonding film is preferably 3 mass% or less, more preferably 1.5 mass% or less, based on the total mass of the heat dissipating die-bonding film.
Examples of the substrate film include plastic films such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, a polyimide film, a polyethylene naphthalate film, a polyether sulfone film, a polyether amide imide film, a polyamide film, and a polyamide imide film.
The base material film may be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment, etching treatment, and mold release treatment as necessary.
Examples of commercially available products of the polyimide film include Kapton (trade name, manufactured by DUPONT-TORAY Co., Ltd.) and Apical (trade name, manufactured by Kaneka Co., Ltd.).
Commercially available products of the polyethylene terephthalate film include Lumirror (trade name, manufactured by DUPONT-TORAY Co., Ltd.) and Purex (trade name, manufactured by Imperial corporation).
[ dicing-die bonding film ]
The heat dissipating die bonding film of the present embodiment is applicable to, for example, a dicing die bonding film. One embodiment of the dicing die-bonding film is described below.
Fig. 1 is a cross-sectional view schematically showing a dicing die-bonding film according to the present embodiment. The dicing die-bonding film 1 shown in fig. 1 includes a dicing film 10 and a die-bonding film 20 laminated on the dicing film 10. The dicing film 10 is not particularly limited, and can be appropriately determined according to the knowledge of those skilled in the art, for example, in consideration of the use and the like. Examples of the dicing film 10 include plastic films such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, and a polyimide film. The dicing film 10 may be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, grinding treatment, etching treatment, or the like as necessary. The dicing film 10 preferably has adhesiveness. Examples of the adhesive dicing film include those having adhesiveness to the plastic film and those having an adhesive layer provided on one surface of the plastic film. The pressure-sensitive adhesive layer is formed of, for example, a resin composition (pressure-sensitive adhesive layer-forming resin composition) containing a liquid component and a high-molecular-weight component and having an appropriate adhesive strength. The dicing tape having an adhesive layer can be produced by, for example, applying and drying a resin composition for forming an adhesive layer on the plastic film, or applying and drying a resin composition for forming an adhesive layer on a base film such as a PET film, and attaching the adhesive layer to the plastic film. The adhesive strength is 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 bond film 20 is the heat dissipating die bond film of the present embodiment described above. In fig. 1, the dicing film 10 and the die bonding film 20 are in direct contact with each other, but the dicing film 10 and the die bonding film 20 may be laminated with another layer such as an adhesive layer interposed therebetween.
The method for manufacturing the dicing die-bonding film of the present embodiment is not particularly limited, and can be appropriately determined according to the knowledge of those skilled in the art. The dicing die-bonding film of the present embodiment can be manufactured, for example, by using a dicing film instead of the base material film in the above-described method for manufacturing a heat dissipating die-bonding film. The dicing die-bonding film of the present embodiment may be manufactured by, for example, preparing the heat dissipating die-bonding film of the present embodiment and the dicing film separately, and then laminating and integrating them.
Examples
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 Forming Heat-dissipating die-bonding film) ]
The following materials were prepared as a component a, b component, c component, d component, filler other than component d, coupling agent, curing accelerator, and solvent.
(component a)
Epoxy-containing acrylic rubber: HTR-860P-3CSP (product of Nagasechemtex Co., Ltd., trade name, weight-average molecular weight 800000, Tg of 12 ℃ C.)
Epoxy-containing acrylic rubber: HTR-860P-30B (product name, weight-average molecular weight 300000, Tg of 12 ℃ C., manufactured by Nagasechemtex Co., Ltd.)
Bisphenol a/F copolymer phenoxy resin: ZX1356-2 (trade name, weight-average molecular weight 63200, Tg 71 ℃ C., manufactured by Nippon Tekken chemical Co., Ltd.)
(component b)
Cresol novolac type epoxy resin: YDCN-700-10 (product name, epoxy equivalent: 195 to 215, available from Nissi iron Tokyo chemical Co., Ltd.)
Bisphenol F type epoxy resin: YDF-8170C (product name, epoxy equivalent: 156, available from Nissie iron Tokyo chemical Co., Ltd.)
(component c)
Phenol resin: XLC-LL (trade name of Mitsui chemical Co., Ltd.)
(component d)
Polyhedral α -alumina Filler Sumicurum AA-3 (product name, purity Al, product name, manufactured by Sumitomo chemical Co., Ltd.)2O3Not less than 99.90%, an average particle diameter of 2.7 to 3.6 μm, and a Mohs hardness of 9)
Spherical α -alumina Filler alumina beads CB-P05 (product name, purity Al, Showa Denko K.K.)2O399.89%, an average particle diameter of 4 μm, a Mohs hardness of 9)
Boron nitride filler: HP-P1 (trade name, product name, average particle diameter of 1 to 3 μm, Mohs hardness of 2, available from Shuitai alloy iron Co., Ltd.)
Boron nitride filler: UHP-S1: SHOBN UHP-S1 (product name, average particle diameter 0.5 μm, Mohs hardness 2, available from Showa Denko K.K.)
Aluminum nitride filler: shapal H scale (trade name, product diameter of 1 μm, Mohs hardness of 8, manufactured by Tokuyama K.K.)
Magnesium oxide filler: RF-10C (trade name, product name of Ube Materials Co., Ltd., average particle diameter of 10 μm, Mohs hardness of 4)
(Filler other than component d)
Silica filler: SC1030 (trade name, average particle diameter 0.5 μm, manufactured by Admatech Co., Ltd.)
Hydrophobic silica fillers: r972 (trade name, average particle diameter 60nm, product of Japan Aerosil Co., Ltd.)
(curing accelerators)
Curezol 2PZ-CN (product name of Sizhou Kasei Kogyo)
(coupling agent)
Silane coupling agent: a-189 (trade name, gamma-mercaptopropyltrimethoxysilane, manufactured by UNC Co., Ltd.)
Silane coupling agent: a-1160 (trade name, gamma-ureidopropyltriethoxysilane, product name, manufactured by UNC corporation)
(solvent)
Cyclohexanone
The prepared components were mixed in the amounts shown in tables 1 and 2 to prepare varnishes of examples, comparative examples and reference examples. In tables 1 and 2, the numerical values of the component a, the component b, the component c, the component d, the filler other than the component d, the coupling agent, and the curing accelerator represent parts by mass.
[ Table 1]
[ Table 2]
[ production of Heat dissipating die bonding film ]
As the substrate film, a polyethylene terephthalate film (A31, thickness: 38 μm, manufactured by Teijin film solutions Co., Ltd.) subjected to a mold release treatment was prepared. The prepared varnish was applied to the release-treated surface of the polyethylene terephthalate film, and heat-dried at 90 ℃ for 10 minutes and at 120 ℃ for 30 minutes to prepare a heat-dissipating die-bonding film with a substrate film. The film thickness of the resulting heat dissipating die-bonding film was 30 μm.
[ evaluation of Heat dissipating die bonding film ]
The obtained heat dissipating die bond film was evaluated for thermal conductivity, blade wear in the dicing step, surface roughness (Ra), adhesive force, and lamination property according to the following procedures. The evaluation results are shown in tables 3 and 4.
(thermal conductivity)
A plurality of heat-dissipating die-bonding films peeled off from a base film are bonded to prepare a laminate film having a thickness of 100 μm or more and less than 600 μm. The obtained laminated film was cured at 110 ℃ for 1 hour and at 170 ℃ for 3 hours to obtain a cured film (cured product). The obtained cured film was cut into a 10mm square and used as a sample for measurement.
Thermal diffusivity of α (mm) for the sample for measurement was measured by the following method2S), specific heat Cp (J/(g. DEG C.), and specific gravity (g/cm)3) And (4) carrying out measurement.
Thermal diffusivity α (mm)2Thermal diffusivity α at 25 ℃ was measured in the thickness direction of the adhesive film by a laser flash method (LFA 467HyperFlash (trade name) manufactured by NETZSCH).
Specific heat Cp (J/(g. degree. C.): the specific heat Cp at 25 ℃ is measured by DSC (product name: DSC8500, manufactured by Perkin Elmer) at a temperature rise rate of 10 ℃/min and at a temperature of 20 to 60 ℃.
Specific weight (g/cm)3): the specific gravity was measured using an electron densitometer SD-200L (product name, manufactured by Mirage).
The thermal diffusivity α, specific heat Cp and specific gravity thus obtained were substituted 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. degree. C)) × specific gravity (g/cm)3)
(consumption of blade in cutting step)
After the heat dissipating die-bonding film was laminated on a dicing tape (substrate thickness: 80 μm, paste thickness: 10 μm) at room temperature for integration, the surface of the heat dissipating die-bonding film side was laminated on an 8-inch wafer having a thickness of 50 μm at 70 ℃ using a laminator (product name: STM-1200FH, manufactured by Teikoku Taping System Co., Ltd.). Thereafter, the cut piece was cut with a microtome (trade name, DFD6361, manufactured by Disco, Ltd.). The conditions for blade cutting were: the wafer thickness was 50 μm, the chip size was 3 mm. times.3 mm, the rotation speed was 50000rpm, the score of the dicing tape was 10 μm, the dicing speed was 30 mm/sec, the dicing length was 203mm, the dicing gap was 3mm at the beginning and 3mm at the end, using a cutter blade ZH05-SD4000-N1-70BB (Nanyang, trade name, Co., Ltd.). The wear amount of the blade in the cutting step is calculated from the state of the blade before and after cutting. Specifically, the wear amount (μm/m) of the blade was calculated from the radius r1(μm) of the blade before cutting, the radius r2(μm) of the blade after cutting, and the cutting distance L1(m) according to the following equation.
The consumption of the blade (μm/m) ═ r1(μm) -r2(μm))/L1(m)
(surface roughness (Ra))
The heat dissipating die-bonding film peeled from the substrate film was attached to a silicon wafer having a thickness of 300 μm using a hot roll laminator (80 ℃, 0.3 m/min, 0.3MPa), and then cured at 110 ℃ for 1 hour and 170 ℃ for 3 hours to obtain a sample. The arithmetic mean roughness (Ra) of the obtained sample in the range of 2.5mm was calculated using a Surf corder ET200 (trade name, manufactured by Xiaoshaguo, Ltd.).
(adhesion)
The heat-dissipating die-bonding film on the substrate film was attached to a semiconductor chip (5mm square) using a hot roll laminator (80 ℃, 0.3 m/min, 0.3 MPa). The heat dissipating die bond film on the semiconductor chip was bonded to a 42 alloy substrate at 120 ℃ under 250g pressure for 5 seconds, and then cured at 110 ℃ for 1 hour and 170 ℃ for 3 hours to obtain a sample. The shear strength before and after the moisture absorption test of the obtained sample was measured by using a universal adhesion strength tester (product name, series 4000, manufactured by Dage corporation). The conditions of the moisture absorption test were 85 ℃ C/85% RH for 48 hours.
The adhesion was evaluated as "good" when the shear strength was not less than 2.0MPa and as "poor" when the shear strength was less than 2.0 MPa.
(laminating Property)
The laminate of the base material film and the heat dissipating die bonding film was cut to a width of 10 mm. The heat-dissipating die-bonding film surface of the laminate was bonded to a silicon wafer having a thickness of 300 μm by means of a hot roll laminator (80 ℃, 0.3 m/min, 0.3 MPa). Then, the 90 ° peel strength when the heat dissipating die bonding film after bonding was peeled off at an angle of 90 ° and a pulling speed of 50 mm/min in an atmosphere of 25 ℃ using a small bench tester EZ-S (manufactured by Shimadzu corporation). The laminate type was evaluated as "good" when the 90 ° peel strength was 20N/m or more and as "poor" when the 90 ° peel strength was less than 20N/m.
[ Table 3]
[ Table 4]
From the results in Table 3, it is clear that the heat conductivity after heat curing of the heat dissipating die-bonding films of examples 1 to 7 is not less than 2W/(m.K), the heat conductivity after heat curing is excellent, the abrasion loss is not more than 50(μm/m), and the abrasion resistance of the blade is excellent. It is also clear that the heat dissipating die bond films of examples 1 to 7 are also excellent in adhesiveness (adhesive force) and lamination property and have small surface roughness. That is, according to the heat dissipating die bonding films of examples 1 to 7, since the heat dissipation property is excellent and the abrasion of the blade is easily suppressed, it is considered that the semiconductor element can be efficiently manufactured.
Description of the symbols
1 dicing-die bonding film, 10 dicing film, 20 die bonding film.
Claims (13)
1. A heat dissipating die bonding film having a thermal conductivity of 2W/(m.K) or more, which contains 2 or more kinds of heat conductive fillers having different Mohs hardness, and has a blade wear amount of 50 [ mu ] m/m or less in a dicing step.
2. A heat dissipating die bonding film contains 2 or more kinds of thermally conductive fillers having different Mohs hardness, and the content of the thermally conductive fillers is 20 to 85 mass%.
3. The heat dissipating die-bonding film according to claim 1 or 2, wherein the thermally conductive filler contains at least 2 selected from the group consisting of an alumina filler, a boron nitride filler, an aluminum nitride filler, and a magnesium oxide filler.
4. The heat dissipating die-bonding film according to claim 3, wherein the alumina filler contains an alumina filler having a purity of 99.0 mass% or more.
5. The heat dissipating die bond film according to claim 3 or 4, wherein the boron nitride filler contains a hexagonal boron nitride filler with a nitrogen purity of 95.0 mass% or more.
6. The heat dissipating die-bonding film according to any one of claims 3 to 5, wherein the aluminum nitride filler has a density of 3 to 4g/cm3。
7. The heat dissipating die-bonding film according to any one of claims 3 to 6, wherein the magnesium oxide filler contains a magnesium oxide filler having a purity of 95.0 mass% or more.
8. The heat dissipating die-bonding film according to any one of claims 1 to 7, further comprising:
any one of high molecular weight components of acrylic resin and phenoxy resin;
an epoxy resin;
and a curing agent.
9. 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.
10. The heat dissipating die-bonding film according to any one of claims 1 to 9, wherein the thermally conductive filler contains an alumina filler and a boron nitride filler.
11. The heat dissipating die-bonding film according to any one of claims 1 to 10, wherein the thermally conductive filler contains a boron nitride filler and an aluminum nitride filler.
12. The heat dissipating die-bonding film according to any one of claims 1 to 11, wherein the thermally conductive filler contains a boron nitride filler and a magnesium oxide filler.
13. 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 according to any one of claims 1 to 12.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2017140757A JP6889398B2 (en) | 2017-07-20 | 2017-07-20 | Heat dissipation die bonding film and dicing die bonding film |
| JP2017-140757 | 2017-07-20 | ||
| PCT/JP2018/026571 WO2019017303A1 (en) | 2017-07-20 | 2018-07-13 | Heat dissipating die bonding film, and dicing/die bonding film |
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| CN110945634B CN110945634B (en) | 2023-08-29 |
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| JP7178661B2 (en) * | 2019-02-21 | 2022-11-28 | 東洋紡株式会社 | Thermally conductive insulating rubber composition, thermally conductive insulating rubber molding and method for producing the same |
| WO2022024510A1 (en) | 2020-07-30 | 2022-02-03 | 古河電気工業株式会社 | Composition for adhesive, film-like adhesive, and semiconductor package in which film-like adhesive is used and method for manufacturing same |
| WO2023182226A1 (en) * | 2022-03-25 | 2023-09-28 | 株式会社レゾナック | Adhesive film for semiconductors, integrated dicing/die bonding film and method for producing semiconductor device |
| KR20230158517A (en) * | 2022-03-30 | 2023-11-20 | 후루카와 덴키 고교 가부시키가이샤 | Composition for thermally conductive film adhesive, thermally conductive film adhesive, semiconductor package using thermally conductive film adhesive, and method for manufacturing the same |
| WO2024057803A1 (en) * | 2022-09-16 | 2024-03-21 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
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| KR102451368B1 (en) | 2022-10-05 |
| WO2019017303A1 (en) | 2019-01-24 |
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| TWI765071B (en) | 2022-05-21 |
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