CN109155244A - Adhesive film and cutting chip engage one-piece type film - Google Patents

Adhesive film and cutting chip engage one-piece type film Download PDF

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Publication number
CN109155244A
CN109155244A CN201780024601.8A CN201780024601A CN109155244A CN 109155244 A CN109155244 A CN 109155244A CN 201780024601 A CN201780024601 A CN 201780024601A CN 109155244 A CN109155244 A CN 109155244A
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adhesive film
film
polymer
epoxy resin
resin
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Chinese (zh)
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赖华子
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • 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
    • 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
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Die Bonding (AREA)
  • Dicing (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

This disclosure relates to the adhesive film with Thermocurable.The adhesive film contains: (a) polymer；(b) be at 50 DEG C liquid epoxy resin；(c) at least one of curing agent and curing accelerator；(d) thermal conductivity is the filler of 10W/ (mK) or more, meets condition shown in following inequality (1), and the shear strength after heat cure is 1.5MPa or more.In formula, ma indicates to form the carbonaceous amount of the cyclic structure of (a) polymer, mb indicates to form the carbonaceous amount of the cyclic structure of (b) epoxy resin, mc indicates to form the carbonaceous amount of the cyclic structure of (c) curing agent and curing accelerator, M indicates (a) polymer, (b) epoxy resin and (c) gross mass of curing agent and curing accelerator.(ma+mb+mc)/M≥0.43(1).

Description

Adhesive film and cutting chip engage one-piece type film
Technical field
This disclosure relates to which adhesive film and cutting chip engage one-piece type film.
Background technique
In the past, it proposes various for improving the technology of the heat dissipation effect of semiconductor device.Patent document 1, which discloses, to be passed through Metallic substrates are set in the lower part of the cutting pad and wire portion that are placed with semiconductor element, to improve semiconductor element generation The semiconductor device encapsulation of the heat dissipation effect of heat.Patent document 2 is disclosed by being 12W/ (mK) or more by thermal conductivity Particle cooperates in thermosetting die junction film, so that the thermal conductivity after the heat cure of the chip junction film be made to reach 1W/ (mK) more than.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 5-198701 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2015-103573 bulletin
Summary of the invention
Technical problems to be solved by the inivention
But invention documented by patent document 1 still has room for improvement in the following areas.That is, described in Patent Document 1 Metallic substrates used by inventing are due to having the coefficient of thermal expansion different from semiconductor element and cutting pad, because of semiconductor element Part generates heat repeatedly, has the removing of generation metallic substrates or semiconductor package to load onto the danger cracked.
Although patent document 2 discloses the film that the thermal conductivity after heat cure is 1W/ (mK) or more, expect film into one Walk high thermal conductivity.By further increasing the use level of the filler with high-termal conductivity, adhesive film can be further improved Electrical conductivity.But when the use level of filler is excessively increased, the use level of resin is relatively reduced.Adhesive film as a result, Bonding force (shear strength after solidification) is easy to become inadequate, it becomes difficult to play should have as bonding agent Effect.That is, being only to be difficult to take into account excellent cementability and heat dissipation by adjusting the use level of the filler with high thermal conductivity Property.
The disclosure is made in view of the above subject, its purpose is to provide can with sufficiently high level realize cementability and The adhesive film of both thermal diffusivities and has it as the cutting chip of chip junction film and engage one-piece type film.
For solving the means of technical problem
This disclosure relates to which a kind of adhesive film with Thermocurable, contains: (a) polymer；It (b) is liquid at 50 DEG C Epoxy resin；(c) at least one of curing agent and curing accelerator；(d) thermal conductivity is the filling of 10W/ (mK) or more Object.The adhesive film meets condition shown in following inequality (1), and the shear strength after heat cure is 1.5MPa or more.
(ma+mb+mc)/M≥0.43 (1)
[in formula, ma indicates to form the carbonaceous amount of the cyclic structure of (a) polymer, mb indicates to form the ring of (b) epoxy resin The carbonaceous amount of shape structure, mc indicate to form the carbonaceous amount of the cyclic structure of (c) curing agent and curing accelerator, M expression (a) polymerization Object, (b) epoxy resin and (c) gross mass of curing agent and curing accelerator.]
Composition below can be used in the disclosure.
The arithmetic average roughness Ra of film surface after heat cure is 0.25 μm or less.
(a) polymer contains the polymer for meeting condition shown in following inequality (2).
ma/MA≥0.40 (2)
[in formula, ma indicates to form the carbonaceous amount of the cyclic structure of (a) polymer, MAIndicate the gross mass of (a) polymer.]
(a) polymer contains phenoxy resin.
(d) filler is alpha-alumina particle.
Adhesive film with a thickness of 50 μm or less.
(d) content of filler by (a) polymer, (b) epoxy resin, (c) curing agent and curing accelerator and (d) total amount of filler is set as when 100 mass parts being 60~95 mass parts.
The disclosure provides the one-piece type film of cutting chip engagement for having above-mentioned adhesive film as chip junction film.That is the cutting Chip, which engages one-piece type film, to be had: the chip junction film formed by above-mentioned adhesive film；With the cutting being layered on chip junction film Film.
Invention effect
According to the disclosure, the adhesive film that both cementability and thermal diffusivity can be realized with sufficiently high level can be provided And has the adhesive film as the cutting chip of chip junction film and engage one-piece type film.
Detailed description of the invention
Fig. 1 is to show schematically that the cutting chip of the disclosure engages the sectional view of an embodiment of one-piece type film.
Specific embodiment
Embodiment of the present disclosure is described in detail below.The adhesive film of present embodiment has Thermocurable, It contains by being at least one of epoxy resin, (c) curing agent and curing accelerator of liquid at (a) polymer, 50 DEG C of (b) The resin component of formation and (d) filler being dispersed in the resin component (thermal conductivity is 10W/ (mK) or more).The bonding Film, which is based upon, to be increased the amount of the cyclic structure (especially aromatic rings) in above-mentioned resin component, can make the bonding after solidifying The thermal conductivity of film improves this new opinion and completes.Replace adjustment that there is high fever that is, the adhesive film of present embodiment passes through This existing gimmick of the use level of the filler of conductance or while the existing gimmick also adjust resin component in ring-type This novel gimmick of the amount of structure, realizes the raising of the thermal conductivity of the adhesive film after solidifying.
The adhesive film of present embodiment meets condition shown in following inequality (1) and the shear strength after heat cure is More than 1.5MPa.
(ma+mb+mc)/M≥0.43 (1)
[in formula, ma indicates to form the carbonaceous amount of (a) polymer cyclic structure, mb indicates to form (b) epoxy resin ring-type knot The carbonaceous amount of structure, mc indicate to form the carbonaceous amount of (c) curing agent and curing accelerator cyclic structure, M expression (a) polymer, (b) The gross mass of epoxy resin and (c) curing agent and curing accelerator.]
Constitute the aromatic rings of the ingredient (polymer, epoxy resin and curing agent and/or curing accelerator) of resin component Amount can use ring parameter and evaluated.The value of ring parameter is bigger, then means that the amount of aromatic rings is more.Ring parameter is to pass through Form the value that the carbonaceous amount of the aromatic rings of compound is calculated divided by the gross mass of the compound.When preparing resin component, make It can be increased above-mentioned for polymer, epoxy resin, curing agent or curing accelerator by the substance for selecting the value of ring parameter big The value on the left side of inequality (1).
By using the resin component for meeting condition shown in inequality (1), even excessively increase matching for (d) filler Resultant also can get the sufficiently high adhesive film of thermal conductivity after solidifying.The higher adhesive film of thermal conductivity after being solidified Viewpoint is set out, and resin component preferably satisfies following inequality (1A), more preferably meets following inequality (1B).
(ma+mb+mc)/M≥0.45 (1A)
(ma+mb+mc)/M≥0.47 (1B)
The upper limit value of ((ma+mb+mc)/M) is, for example, 0.70 or so, can be hardened more than the film of the upper limit value, cementability it is easy In becoming insufficient.
The thermal conductivity of adhesive film after heat cure be preferably 1.3W/ (mK) or more, more preferably 1.5W/ (mK) with Above, further preferably more than 1.7W/ (mK).When the thermal conductivity of adhesive film after solidification is 1.3W/ (mK) or more, such as The adhesive film is used as chip junction film can obtain sufficient heat dissipation effect when manufacturing semiconductor device.After solidification The upper limit value of the thermal conductivity of adhesive film is, for example, 6.0W/ (mK), can also be 4.0W/ (mK).
The shear strength of adhesive film after heat cure is 1.5MPa or more, preferably 1.6MPa or more, is more preferably More than 1.7MPa.When the shear strength of adhesive film after solidification is 1.5MPa or more, it can be ensured that sufficiently high bonding force.Solidification The upper limit value of the shear strength of adhesive film afterwards is, for example, 10.0MPa.
The arithmetic average roughness Ra (below simply referred to as " surface roughness Ra ") of adhesive film after heat cure is preferably 0.25 μm or less, more preferably 0.20 μm or less, further preferably 0.16 μm or less.The rough surface of adhesive film after solidification Spending Ra is 0.25 μm or less, it can be ensured that sufficiently high bonding force.The lower limit value of the surface roughness Ra of adhesive film after solidification For example, 0.03 μm.
As long as the thickness of adhesive film is 50 μm or less, such as can be 5~50 μm, preferably 5~40 μm, more preferable It is 8~40 μm.When the thickness of adhesive film is less than 5 μm, have the tendency that stress alleviation effects shortage, have landfill property also reduce incline To, and when more than 50 μm, cost is easy to get higher.
Ingredient contained by adhesive film is illustrated below.
< (a) polymer >
As (a) polymer, from the viewpoint of obtaining film formative, heat resistance and cementability, preferred phenoxy resin, poly- Imide resin, polyamide, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, poly- second Olefine resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin and polyurethane resin.Wherein, it is formed from film From the perspective of property and excellent heat resistance, more preferable phenoxy resin, polyimide resin, polyamide, acrylic resin, cyanogen Acid esters ester resin and polycarbodiimide resin, from the viewpoint of being easy the adjustment such as molecular weight, characteristic imparting, further preferably Phenoxy resin.As (a) polymer, a kind in above-mentioned resin can be used alone, or be mixed with two or more, also The copolymer of two or more monomer can be used.
From the viewpoint of the left side value ((ma+mb+mc)/M) for increasing above-mentioned inequality (1), (a) polymer is preferably comprised The polymer for meeting condition shown in following inequality (2) more preferably meets following inequality (2A), further preferably meets following Inequality (2B).
ma/MA≥0.40 (2)
ma/MA≥0.45 (2A)
ma/MA≥0.50 (2B)
[in formula, ma indicates to form the carbonaceous amount of the cyclic structure of polymer, MAIndicate the gross mass of polymer.]
In other words, (a) polymer is preferably made of one kind or two or more polymer, at least one kind of ring parameter Preferably 0.40 or more, it is more preferably 0.45 or more, further preferably 0.50 or more.
When using phenoxy resin as (a) polymer, weight average molecular weight is preferably 20,000 or more, more preferably 30,000 with On.As commercially available phenoxy resin, can enumerate YP-50, YP-55, YP-70, YPB-40PXM40, YPS-007A30, FX-280S, FX-281S, FX-293 and ZX-1356-2 (the above are Toto Kasei KK's systems, trade name), 1256,4250,4256, 4275, YX7180, YX6954, YX8100, YX7200, YL7178, YL7290, YL7600, YL7734, YL7827 and YL7864 (the above are Japan Epoxy Resin Co. Ltd. systems, trade name) etc. can be used alone a kind therein or and with 2 kinds More than.
The glass transition temperature (Tg) of phenoxy resin is preferably shorter than 85 DEG C, as the commercially available product for meeting the condition, such as YP-50, YP-55, YP-70, ZX-1356-2 can be enumerated (the above are Toto Kasei KK's systems, trade name)；4250,4256, 7275, YX7180 and YL7178 (the above are Japan Epoxy Resin Co. Ltd. systems, trade name).It can be used alone it In a kind, or be used in combination of two or more.
When using acrylic resin as (a) polymer, preferably there is reactive group (functional group) and weight average molecular weight For 100,000 or more persons.As reactive group, such as carboxylic acid group, amino, hydroxyl and epoxy group can be enumerated etc..Wherein, functional group When monomer is the acrylic acid of carboxylic acid type, due to cross-linking reaction is easy to carry out, the gelation under varnish state, under B-stage state Curing degree improves, and has the case where bonding force decline.Therefore, even if more preferably use will not occur these situations or occur, the phase Between the also very long glycidyl acrylate or glycidyl methacrylate with epoxy group.In acrylic resin, more It is preferable to use the acrylic acid series copolymers containing epoxy group that weight average molecular weight is 100,000 or more.(a) polymer can be by obtaining It is polymerize in the polymerization reaction of sub- compound that secures satisfactory grades according to the remaining mode of unreacted monomer and is obtained, or can also be led to It crosses after obtaining high-molecular compound and adds the monomer containing reactive group to obtain.In addition, weight average molecular weight is to utilize It gel permeation chromatography (GPC), the polystyrene scaled value that is obtained using the standard curve obtained by standard polystyren.
As acrylic acid series copolymer, such as being total to as acrylate, methacrylate and acrylonitrile etc. can be enumerated The acrylic rubber of polymers.In addition, it is high for cementability and heat resistance, contain 0.5~6 matter particularly preferable as functional group Measure % glycidyl acrylate or glycidyl methacrylate, glass transition temperature (Tg) be -50 DEG C or more and 50 DEG C or less and then be -10 DEG C or more and 50 DEG C or less and acrylic acid series copolymer that weight average molecular weight is 100,000 or more. As the glycidyl acrylate containing 0.5~6 mass % or glycidyl methacrylate, Tg be -10 DEG C or more and Weight average molecular weight is 100,000 or more acrylic acid series copolymer, such as can enumerate HTR-860P-3 (Imperial Chemical Industries industry strain formula meeting Society's system, trade name).
The amount of the glycidyl acrylate or glycidyl methacrylate that use as monomer is more preferable For the copolymer ratio of 2~6 mass %.In order to obtain higher bonding force, preferably 2 mass % or more, there is hair when more than 6 mass % The possibility of raw gelation.The alkane that methyl acrylate, methyl methacrylate etc. are 1~8 with carbon number can be used in remainder The mixture of alkyl acrylate, alkyl methacrylate and the styrene of base, acrylonitrile etc..Wherein, particularly preferably (methyl) ethyl acrylate and/or (methyl) butyl acrylate.From increase above-mentioned inequality (1) left side value ((ma+mb+mc)/ M from the perspective of), as monomer, it is preferable to use styrene, benzyl acrylate or benzyl methacrylates.Blending ratio It is preferred that considering the Tg of copolymer to be adjusted.When Tg is less than -10 DEG C, there are adhesive layer under B-stage state or adhesive film The tendency that adhesiveness increases, treatability can deteriorate sometimes.Polymerization is not particularly limited, such as can enumerate pearl polymerisation, molten Liquid polymerization etc. obtains copolymer by these methods.
The weight average molecular weight of acrylic acid series copolymer containing epoxy group is preferably 300,000~3,000,000, more preferably 400,000~ 2000000.When weight average molecular weight is less than 300,000, there is the intensity of adhesive film (or adhesive sheet) or flexible reduce or adhesiveness increases Big possibility, and when more than 3,000,000 has the possibility that mobility is small, circuit fillibility of wiring reduces.
The content of (a) polymer in adhesive film is relative to (a) polymer, (b) epoxy resin, (c) curing agent and solidification 100 mass parts of total amount of promotor and (d) filler, preferably 3~40 mass parts, more preferably 3~30 mass parts, into one Step is preferably 3~20 mass parts.(a) when the content of polymer is 3 mass parts or more, elasticity modulus can suitably reduced Mobility when forming is assigned simultaneously, if it exceeds 40 mass parts, then have mobility to reduce, circuit fillibility when attaching loading less Reduced possibility.
< (b) epoxy resin >
As (b) epoxy resin, two functional groups or more can be used, molecular weight is preferably smaller than 5000, more preferably less than Two functional epoxy resins such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, benzene can be used for example in 3000 epoxy resin Phenolic resin varnish type epoxy resins such as phenol phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin etc..Furthermore it is also possible to Using commonly known epoxy resin such as polyfunctional epoxy resin, epoxy resin containing heterocycle.
As commercially available epoxy resin, for example, can enumerate Epikote 152, Epikote 154, Epikote 604, Epikote 630、Epikote 630LSD、Epikote 807、Epikote 815、Epikote 825、Epikote827、 Epikote 828、Epikote 834、Epikote 1001、Epikote 1002、Epikote 1003、Epikote 1055、 Epikote 1004、Epikote 1004AF、Epikote 1007、Epikote 1009、Epikote 1003F、Epikote 1004F、Epikote 180S65、Epon 1031S、Epikote 1032H60、Epikote 157S70、1256、4250、 4256,4275, (the above are Japan by YX6954, YX8100, YL7178, YL7290, YL7175-500, YL7175-1000 Epoxy Resin Co. Ltd. system, trade name), DER-330, DER-301, DER-361, DER-661, DER-662, DER- 663U、DER-664、DER-664U、DER-667、DER-642U、DER-672U、DER-673MF、DER-668、DER-669、 DEN-438 (the above are Dow Chemical corporations, trade name), YDCN-700, YDCN-701, YDCN-702, YDCN-703, (the above are Dongdu by YDCN-704, YD-8125, YDF-8170, YDF-8170C, YD-825, YDF-870, YDF-2004, YH-434 Be melted into Co. Ltd. system, trade name), the cresol novolak type epoxy resins such as ESCN-195X, ESCN-200L, ESCN-220, The amine type such as ELM-120 epoxy resin (the above are Sumitomo Chemical Company Ltd's systems, trade name), EPPN-201, EPPN501H, EPPN502H、RE-3035-L、RE-310S、EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1020、 EOCN-1025, EOCN-1027 (the above are Nippon Kayaku K. K's systems, trade name), Araldit ECN1273, Araldit (the above are Ciba Specialty by ECN1280, Araldit ECN1299, Araldit 0163, Araldit PT810 Chemicals corporation, 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、Denacol (the above are Mitsubishi GAS chemistry by EX-321 (the above are NAGASE to be melted into Co. Ltd. system, trade name), TETRAD-X, TETRAD-C Co. Ltd. system, trade name), ERL4234, ERL4299, ERL4221, ERL4206 (the above are UCC corporations, trade name) etc. (the above are Asahi Denka Co., Ltd.'s systems, commodity by alicyclic epoxy resin, EP-4000, EP-3950L, EP-3980S, EPR-4030 Name) etc., it can be used alone a kind therein, can also be used in combination of two or more.
It the use of at 50 DEG C of a kind or more is liquid person as (b) epoxy resin.The research of people according to the present invention, in order to Manufacture can take into account the adhesive film of cementability and thermal diffusivity, and it is useful for meeting inequality (1) and keeping the flexibility of adhesive film. For example, even if if adhesive film is excessively hard, cementability still becomes insufficient, and thus thermal conductivity is easy when meeting inequality (1) In becoming insufficient.In order to keep the flexibility of adhesive film, the epoxy at 50 DEG C for liquid is used in present embodiment.In addition, As long as being able to maintain the flexibility of adhesive film, can also use epoxy resin non-liquid at 50 DEG C (is the ring of solid at 50 DEG C Oxygen resin).
As at 50 DEG C be liquid epoxy resin, can enumerate Epikote 807, Epikote 815, Epikote 825, Epikote 827、Epikote 828、Epikote 834、Epikote 1001、Epikote 152、Epikote 630、 Epikote 630LSD (the above are Japan Epoxy Resin Co. Ltd. systems, trade name), YD-8125, YDF-8170, YD- 825, YDF-870 (the above are Toto Kasei KK's systems, trade name), (the above are Japanese chemical drugs by RE-3035-L, RE-310S Co. Ltd. system, trade name), EP-4000, EP-3950L, EP-3980S, EPR-4030 (the above are Asahi Denka Co., Ltd.'s system, Trade name) etc., it can be used alone a kind therein, can also be used in combination of two or more, can also be used in combination with solid-state person.From increase From the perspective of the value ((ma+mb+mc)/M) for stating inequality (1) left side, (b) polymer, which particularly preferably contains also, has practical effect The YDF-8170 (Toto Kasei KK's system, trade name) of fruit.
As (b) epoxy resin, when by epoxy resin more than two functional epoxy resins and trifunctional and used time, by them Total amount when being set as 100 mass parts, preferably the amount of two functional epoxy resins is 50 mass parts or more (asphalt mixtures modified by epoxy resin more than trifunctional The amount of rouge is less than 50 mass parts).From the viewpoint of high Tgization, the amount of more preferable two functional epoxy resins is 50~90 mass The amount of epoxy resin more than part, trifunctional is 10~50 mass parts.
The content of (b) epoxy resin in adhesive film is relative to (a) polymer, (b) epoxy resin, (c) curing agent and consolidates Change promotor and (d) 100 mass parts of total amount of filler, preferably 3~40 mass parts, more preferably 3~30 mass parts, into One step is preferably 3~20 mass parts.
< (c) curing agent and curing accelerator >
As long as the adhesive film of present embodiment contains at least 1 conduct (c) ingredients in curing agent and curing accelerator i.e. It can.Hereinafter, enumerating the specific example of curing agent and curing accelerator.
(curing agent)
As (c) curing agent, multifunctional phenols, amine, imidazolium compounds, acid anhydrides, organic phosphorus chemical combination can be used for example Object and their halide, polyamide, polysulfide, boron trifluoride.As the example of multifunctional phenols, conduct can be enumerated Quinhydrones, resorcinol, catechol, the bisphenol-A as polycyclic two functions phenol, Bisphenol F, the bisphenol S, naphthalene two of two function phenol of monocycle Alcohols, biphenyl phenols and their halide, alkyl substituents etc..Furthermore it is also possible to used as these phenols and aldehydes The phenol such as phenol resol resins, resol, bisphenol A novolac resin and the cresol novolac resin of condensation polymer Urea formaldehyde etc..
As commercially available preferred phenolic resin curing agent, such as PHENOLITE LF2882, PHENOLITE can be enumerated LF2822、PHENOLITE TD-2090、PHENOLITE TD-2149、PHENOLITE VH4150、PHENOLITE VH4170 (the above are Dainippon Ink. & Chemicals Inc's systems, trade name), XLC series (Mitsui Chemicals, Inc, trade name) Deng.
As (c) curing agent, it is preferable to use hydroxyl equivalent is the phenolic resin of 150g/eq or more.As this phenolic aldehyde tree Rouge, as long as there is above-mentioned value to be then not particularly limited, but electrocorrosion-resisting when for moisture absorption is excellent, it is preferable to use novolaks The resin of type or solvable phenol aldehyde type.As the specific example of above-mentioned phenolic resin, such as phenolic aldehyde shown in following formula (I)s can be enumerated Resin.
[chemical formula number 1]
[in formula, R1Identical also different, expression hydrogen atom, the linear or branched alkyl group that carbon number is 1~10, ring can be distinguished Shape alkyl, aralkyl, alkenyl, hydroxyl, aryl or halogen atom, n indicate that 1~3 integer, m indicate 0~50 integer.]
It as this phenolic resin, is then not particularly limited as long as meeting formula (I), from the viewpoint of moisture-proof, preferably Water absorption rate after putting into 48 hours in 85 DEG C, the constant temperature and humidity cabinet of 85%RH is 2 mass % or less.In addition, using heat is utilized Heating weight reduction rates (heating rate: 5 DEG C/min, environmental gas: nitrogen) at 350 DEG C of gravimetric analysis meter (TGA) measurement When phenolic resin less than 5 mass %, due to can inhibit volatile ingredient when heating processing etc., thus heat resistance, moisture-proof etc. The reliability of many characteristics improves, and can reduce because of machine pollution caused by heating volatile ingredient when processing etc. operates, Therefore preferably.Phenolic resin shown in formula (I) for example can be by making phenolate in the presence of no catalyst or acid catalyst Object is closed to react and obtain with the penylene dimethyl compound as divalent linker.
As phenolic resin as described above, such as it can enumerate that Mirex XLC- series, (the above are three for Mirex XL series Well Chemical Co., Ltd. system, trade name) etc..Use level when with epoxy composite using above-mentioned phenolic resin is to be respectively ring The equivalent ratio of oxygen equivalent and hydroxyl equivalent, preferably reach 0.70/0.30~0.30/0.70, more preferably up to 0.65/0.35~ 0.35/0.65, further preferably reach 0.60/0.30~0.30/0.60, particularly preferably reach 0.55/0.45~0.45/ 0.55.If match ratio is more than above range, there is a possibility that curability deterioration when bonding agent is made.
Phenolic compounds used in phenolic resin as manufacture formula (I), can example go out phenol, o-cresol, metacresol, right Cresols, o-ethyl phenol, paraethyl phenol, adjacent n-propyl phenol, n-propyl phenol, to n-propyl phenol, o-isopropyl benzene Phenol, 3-Isopropylphenol, australol, adjacent normal-butyl phenol, normal-butyl phenol, to normal-butyl phenol, adjacent isobutyl group Phenol, isobutyl group phenol, to isobutyl group phenol, octyl phenol, nonyl phenol, 2,4- dimethlbenzene, 2,6- dimethlbenzene, 3, 5- dimethlbenzene, 2,4,6- pseudocuminol, resorcinol, catechol, quinhydrones, 4- metoxyphenol, o-phenyl phenol, Phenylphenol, p-phenyl phenol, p-cyclohexylphenol, o-allyl phenol, chavicol, 2- methane, to benzyl Phenol, o-chlorphenol, parachlorophenol, o-bromophenol, p bromophenol, phenol o-iodine, to iodophenol, adjacent fluorophenol, m fluorophenol, P-fluorophenol etc..These phenolic compounds can be used alone, and can also be mixed with two or more.Benzene can particularly preferably be enumerated Phenol, o-cresol, metacresol, paracresol etc..
Penylene dimethyl compound as divalent linker used in phenolic resin as manufacture formula (I), can be with Use penylene dimethyl dihalide, penylene dimethyl diethylene glycol (DEG) and its derivative described below.I.e., it is possible to α is enumerated, α '- Two chloro- paraxylene, α, the chloro- meta-xylene of α '-two, α, α '-dichloro-o-xylene, α, the bromo- paraxylene of α '-two, α, α '- Two bromo- meta-xylenes, α, the bromo- ortho-xylene of α '-two, α, the iodo- paraxylene of α '-two, α, the iodo- meta-xylene of α '-two, α, α '- Two iodo- ortho-xylenes, α, α '-dihydroxy-paraxylene, α, α '-dihydroxy-meta-xylene, α, α '-dihydroxy-ortho-xylene, α, α '-dimethoxy-paraxylene, α, α '-dimethoxy-meta-xylene, α, α '-dimethoxy-ortho-xylene, α, α '-two Ethyoxyl-paraxylene, α, α '-diethoxy-meta-xylene, α, α '-diethoxy-ortho-xylene, α, positive third oxygen of α '-two Base-paraxylene, α, α '-positive propoxy-meta-xylene, α ,-two positive propoxies of α '-ortho-xylene, α, α '-diisopropoxy- Paraxylene, α, α '-diisopropoxy-meta-xylene, α, α '-diisopropoxy-ortho-xylene, α ,-two n-butoxy of α '-right Dimethylbenzene, α ,-two n-butoxies of α '-meta-xylene, α ,-two n-butoxies of α '-ortho-xylene, α ,-two isobutoxy of α '-is to two Toluene, α ,-two isobutoxies of α '-meta-xylene, α ,-two isobutoxies of α '-ortho-xylene, α ,-two tert-butoxy of α '-is to diformazan Benzene, α ,-two tert-butoxies of α '-meta-xylene, α ,-two tert-butoxies of α '-ortho-xylene.It can be used alone a kind therein, or Person is mixed with two or more.These, it is preferred to the chloro- paraxylene of α, α '-two, α, the chloro- meta-xylene of α '-two, α, α '-two Chloro- ortho-xylene, α, α '-dihydroxy-paraxylene, α, α '-dihydroxy-meta-xylene, α, α '-dihydroxy-ortho-xylene, α, α '-dimethoxy-paraxylene, α, α '-dimethoxy-meta-xylene, α, α '-dimethoxy-ortho-xylene.
When reacting above-mentioned phenolic compounds with penylene dimethyl compound, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid etc. are used Mineral acids；The organic carboxyl acids classes such as dimethyl sulfate, diethyl sulfuric acid, p-methyl benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid；Fluoroform The superpower acids such as sulfonic acid；The strong-acid ion exchange resins classes such as alkanesulfonic acid type ion exchange resin；Perfluoroalkanesulfonic acid type from The superpower acidities such as sub-exchange resin Ion exchange resins (trade name: Nafion, Du Pont corporation)；Natural and synthesis boiling Stone class；The acidic catalysts such as atlapulgite (Emathlite) class, make its reaction at 50~250 DEG C, until essentially as original The penylene dimethyl compound of material disappears and reaction composition reaches constant.Although reaction time also depends on raw material and reaction temperature Degree, but about 1 hour~15 hours or so, actually formed on one side using following responses such as GPC (gel permeation chromatographies) It determines on one side.Except that using α, when the halogenations parylene derivative such as chloro- paraxylene of α '-two, due to being in life It is reacted under no catalyst at while corresponding hydrogen halide, therefore is not needed acid catalyst.In other situations Under, reaction carries out in the presence of acid catalyst, generates corresponding water or alcohol.Phenolic compounds is anti-with penylene dimethyl compound Molar ratio is answered usually excessively using phenolic compounds, after the reaction to recycle unreacted phenolic compounds.At this point, according to phenolate The amount for closing object determines average molecular weight, and phenolic compounds is superfluous more, then can get the lower phenolic resin of average molecular weight.This Outside, can for example be prepared by the following as the phenolic resin that phenolic compounds part is allyl phenol: manufacture is without allyl The phenolic resin of change, reacts with it allyl halide, and by allyl ether, allyl occurs by Claisen rearangement Change.
As the example of amine, aliphatic or aromatic primary amine, secondary amine, tertiary amine, quaternary ammonium salt and aliphatic ring can be enumerated Shape amine, guanidine, urea derivative etc..As an example of these compounds, N, N- benzyldimethylamine, 2,4,2- (diformazan can be enumerated Base amino methyl) phenol, 2,4,6- tri- (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, N, N '-dimethyl piperazine Piperazine, 1,4- diazabicyclo [2.2.2] octane, 1,8- diazabicyclo [5.4.0] -7- endecatylene, 1,5- diazabicyclo [4.4.0] -5- nonene, hexa, pyridine, picoline, piperidines, pyrrolidines, dimethylcyclohexylam,ne, dimethyl oneself Base amine, cyclo-hexylamine, diisobutyl amine, di-n-butyl amine, diphenylamine, methylphenylamine, three n-propyl amine, three n-octyls Amine, tri-n-butyl amine, triphenylamine, tetramethyl ammonium chloride, 4 bromide, tetramethyl-ammonium iodide, trien, two Aminodiphenylmethane, diamino-diphenyl ether, dicyandiamide, tolylbigaunide, dicyandiamidines, dimethyl urea etc..
As the example of imidazolium compounds, imidazoles, 2- ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2- methyl miaow can be enumerated Azoles, 2- phenylimidazole, 2- undecyl imidazole, 1 benzyl 2 methyl imidazole, 2- heptadecyl imidazole, 4,5- diphenyl-imidazole, 2-methylimidazole quinoline, 2- benzylimidazoline, 2- undecyl imidazole quinoline, 2- heptadecyl imidazole quinoline, 2 isopropyl imidazole, 2,4- Methylimidazole, 2- phenyl -4-methylimidazole, 2- ethyl imidazol(e) quinoline, 2- phenyl -4-methylimidazole quinoline, benzimidazole, 1- cyano Ethyl imidazol(e) etc..
As the example of acid anhydrides, there are phthalate anhydride, hexahydrophthalic acid anhydride, pyromellitic acid anhydride, benzophenone four Carboxylic acid dianhydride etc..
As organic phosphorus compound, as long as with organic group phosphorus compound, then can be not particularly limited using, Such as can enumerate hexamethylphosphoric triamide, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (chloropropyl) ester, triphenyl phosphite, Trimethyl phosphate, phenyl-phosphonic acid, triphenylphosphine, tri-n-butyl phosphine, diphenylphosphine etc..
It can be used alone a kind of these curing agent, or two or more kinds may be used.The use level of these curing agent is only Want the curing reaction that can make epoxy group to carry out, then can be not particularly limited using, preferably with respect to 1 mole of epoxy group, With the range of 0.0~5.0 equivalent, particularly preferably with the range of 0.0~1.2 equivalent carry out using.In addition, in epoxy resin and admittedly In agent, compound without mutagenicity, for example without using the epoxy resin of bisphenol-A and curing agent due to environment and people The influence of body is small and preferred.
(curing accelerator)
It is not particularly limited as curing accelerator, tertiary amine, imidazoles, quaternary ammonium salt etc. can be used for example.As imidazoles Class, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- cyano ethyl -2- can be enumerated Phenylimidazole trimellitate, 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine isocyanuric acid add At object etc., these substances also can be used a kind or be used in combination of two or more.Imidazoles are for example by Shikoku Chem It is sold with the trade name of 2E4MZ, 2PZ-CN, 2PZ-CNS, 2MA-OK.
During the use of film it is extended in terms of for, preferably with the curing accelerator of potentiality.As its typical example, The dihydrazide compounds such as dicyandiamide, adipic dihydrazide, guanamines acid, melamine amino acid, epoxide and imidazoles can be enumerated Close the additive compound of object, the additive compound of epoxide and dialkyl amine, the additive compound of amine and thiocarbamide, amine with The additive compound etc. of isocyanates.In addition, preferably taking adduct type knot in terms of can reduce at room temperature active The substance of structure.
The use level of curing accelerator on the basis of the total amount of epoxy resin and curing agent, preferably 0~10.0 mass %, More preferably 0.02~5.0 mass %, further preferably 0.03~4.0 mass %.The use level of curing accelerator is more than 4.0 When quality %, there are storage stability reduction, working life to become insufficient tendency.
The total content of (c) curing agent and curing accelerator in adhesive film relative to (a) polymer, (b) epoxy resin, (c) curing agent and curing accelerator and (d) 100 mass parts of total amount of filler, preferably more than 0 mass parts and 5.0 mass Part or less, more preferably 0.02~3.0 mass parts, further preferably 0.03~2.0 mass parts.In addition, " (c) curing agent and The total content of curing accelerator " refers to the content of curing agent when (c) ingredient is only curing agent, is in only curing accelerator Refer to the content of curing accelerator.
< (d) filler >
(d) filler has the thermal conductivity of 10W/ (mK) or more.As (d) filler, aluminium oxide particles, nitrogen can be enumerated Change boron particles, aluminum nitride particle, silicon nitride particles, zinc oxide particles, magnesia particle, aluminum hydroxide particles, magnesium hydroxide grain The electrical insulating properties person such as son and diamond.It can be used alone a kind therein, can also be used in combination of two or more.Wherein, aluminum shot is aoxidized Son, boron nitride particles are high heat conductance, and dispersibility is also excellent, and water-proofing performance is also good, and from starting with, easy aspect is preferred. In aluminium oxide, preferred Alpha-alumina, Al2O3Purity is preferably 99.90% or more, is more preferably 99.92% or more, is further Preferably 99.95% or more.The upper limit of thermal conductivity is not particularly limited, and is more improved the purity of Alpha-alumina filler, can more be mentioned High heat conductance.As the Alpha-alumina of purity is high, AA serial (the Sumitomo Chemical system, commodity of Sumicorundum can be enumerated Name).
(d) average grain diameter (d50) of filler be preferably be bonded film thickness 1/2 or less, more preferably 1/3 or less, into One step is preferably 1/4 or less.(d) when the average grain diameter of filler is more than the 1/2 of bonding film thickness, the concave-convex of film surface increases, Adhesive strength, plyability, reliability etc. have the possibility of reduction.As (d) filler, the average grain diameter that can be used alone (d50) is A kind of filler, can also and the two or more fillers different with average grain diameter (d50).
The content of (d) filler in adhesive film is relative to (a) polymer, (b) epoxy resin, (c) curing agent and solidification 100 mass parts of total amount of promotor and (d) filler, preferably 60~95 mass parts, more preferably 65~95 mass parts, into One step is preferably 70~90 mass parts.If (d) content of filler is lower than 60 mass parts, there is the thermal conductivity of adhesive film to become Insufficient possibility when more than 95 mass parts, there is the flexibility of adhesive film and the possibility of cementability reduction.
The other ingredient > of <
The adhesive composite of present embodiment adhesive film is constituted other than the ingredient of above-mentioned (a)~(d), such as may be used also To contain curing accelerator, filler, coupling agent, ion trap agent, solder flux.
(filler)
For treatability, adjustment melt viscosity, imparting thixotropy, the raising moisture-proof etc. for improving adhesive composite, also It can cooperate in resin combination each in addition to the filler of above-mentioned (d) filler (thermal conductivity is 10W/ (mK) or more) Kind filler.As this filler, can enumerate aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicates, magnesium silicate, Calcium oxide, magnesia, aluminium borate whisker, crystallinity silica, amorphism silica, sb oxide etc..Wherein, in order to mention High-termal conductivity, preferably crystallinity silica, amorphism silica etc..It is excellent in order to adjust melt viscosity or assign thixotropy Select aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicates, magnesium silicate, calcium oxide, magnesia, crystallinity silica, Amorphism silica etc..In order to improve moisture-proof, preferably silica, aluminium hydroxide, sb oxide.These fillers contain Amount is more preferably 0~20 mass parts, is more preferably relative to 100 mass parts of (d) filler, preferably 0~50 mass parts 0~10 mass parts.
(coupling agent)
In order to become the interface cohesion between dissimilar material well, various idols can also be added in adhesive composite Join agent.As coupling agent, silane system, titanium system, aluminium system etc. can be enumerated, wherein it is preferred that silane series coupling agent.The additive amount of coupling agent From its effect, heat resistance and cost aspect, relative to 100 mass parts of total amount of resin component, preferably 0~10 mass Part.
It is not particularly limited as silane series coupling agent, the vinyl trichlorosilane, (β-first of vinyl three can be used for example Oxygroup ethyoxyl) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyl three Methoxy silane, γ-methacryloxypropylmethyl dimethoxysilane, β-(3,4- expoxycyclohexyl) ethyl front three Oxysilane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl dimethoxysilane, γ-glycidoxypropyl diethoxy silane, N- β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N- β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, γ aminopropyltriethoxy silane, N- phenyl-γ-ammonia Base propyl trimethoxy silicane, γ mercaptopropyitrimethoxy silane, γ-Mercaptopropyltriethoxysilane, 3- aminopropyl Methyldiethoxysilane, 3- ureidopropyltriethoxysilane, 3- ureido-propyl trimethoxy silane, 3- aminopropyl front three Oxysilane, 3- aminopropyl-three (2- Mehtoxy-ethoxy-ethyoxyl) silane, N- methyl -3- aminopropyl trimethoxy Silane, triamido propyl-trimethoxysilane, 3- (4,5- dihydro) imidazoles -1- base-propyl trimethoxy silicane, 3- methyl-prop Alkene acryloxypropylethoxysilane-trimethoxy silane, 3- mercaptopropyi-methyl dimethoxysilane, 3- chloropropyl-methyl dimethoxy oxygroup silicon Alkane, 3- chloropropyl-dimethoxysilane, 3- cyanopropyl-triethoxysilane, hexamethyldisilazane, the bis- (trimethyls of N, O- Silicyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyl trichlorosilane, n-propyl trimethoxy Silane, trimethoxysilane, amyl trichlorosilane, octyltri-ethoxysilane, phenyltrimethoxysila,e, phenyl three Ethoxysilane, methyl three (methacroyloxyethoxy) silane, methyl three (glycidoxypropyl) silane, N- β-(N- Vinylbenzylaminoethyl)-gamma-amino propyl trimethoxy silicane, octadecyldimethyl [3- (trimethyoxysilane Base) propyl] ammonium chloride, γ-chloropropyl dichlorosilane, gamma-chloropropylmethyldimethoxysilane, γ-chloropropyl Diethoxy silane, trimethylsilyl isocyanate, dimetylsilyl isocyanates, three isocyanide of methyl silicane base Acid esters, vinyl silyl groups triisocyanate, phenyl silyl groups triisocyanate, tetraisocyanate silane, ethyoxyl silicon Alkane isocyanates etc. can be used alone a kind therein, or be used in combination of two or more.
It is not particularly limited as titanium system coupling agent, three caprylyl titanate esters of isopropyl, isopropyl two can be used for example (methylacryloyl) isostearoyl base titanate esters, isopropyl three (dodecyl benzenesulfonyl) titanate esters, isopropyl are stearic Two acryloyl group titanate esters of acyl group, isopropyl three (dioctyl phosphate) titanate esters, three cumyl phenyl titanate esters of isopropyl, isopropyl Base three (dioctylphyrophosphoric acid ester) titanate esters, isopropyl three (positive amino-ethyl) titanate esters, the bis- (dioctyl phosphitos of tetra isopropyl Ester) titanate esters, bis- (two (tridecyl) phosphite esters) titanate esters of four octyls, four (2,2- diene propoxy methyl -1- butyl) Bis- (two (tridecyl)) phosphite ester titanate esters, dicumylphenyl ethoxyacetic acid ester titanate esters, bis- (dioctylphyrophosphoric acid esters) Ethoxyacetic acid ester titanate esters, tetra isopropyl titanate, tetra-n-butyl titanate esters, butyltitanate dimer, four (2- ethyl hexyls Base) titanate esters, titanium acetylacetone, poly(titanium acetylacetonate), ethohexadiol acid titanium, lactic acid titanium ammonium salt, lactic acid titanium, lactic acid titanium ethyl ester, three Ethanol amine titanium, poly- hydroxy stearic acid titanium, four methyl esters of ortho-titanic acid, tetraethyl orthotitanate, ortho-titanic acid orthocarbonate, four isobutyl of ortho-titanic acid Bis- (2,4- pentanedione) titaniums of ester, metatitanic acid stearyl ester, metatitanic acid toluene ester monomer, metatitanic acid toluene ester polymer, diisopropoxy- (IV), diisopropyl-it is bis--triethanolamine base titanate esters, ethohexadiol titanate esters, four n-butoxy titanium polymers, three n-butoxies Titanium monostearate ester polymer, tri-n-butoxytitanium monostearate etc. can be used alone a kind therein, or and with 2 kinds More than.
It is not particularly limited as aluminium system coupling agent, ethyl acetoacetate aluminium diisopropyl acid esters, three (second can be used for example Ethyl acetoacetic acid ethyl ester) aluminium, Acetacetic acid alkyl ester aluminium diisopropyl acid esters, aluminium monoacylphosphine acetic acid esters bis- (ethyl acetoacetates), three The mono- isopropoxy list oleoyl oxygroup ethyl acetoacetate of aluminium acetylacetonate, aluminium-,-two n-butanol salt of aluminium-mono- ethyl acetoacetate, The aluminium chelate compounds such as aluminium-diiso propoxide-single acetyl ethyl acetate, aluminium isopropylate, single aluminium-sec-butylate diisopropyl acid esters, secondary butyric acid Aluminum alcoholates such as aluminium, aluminium acetate etc. can be used alone a kind therein, or be used in combination of two or more.
(ion trap agent)
It, can also be in adhesive composite for adion impurity so that insulating reliability when moisture absorption becomes well Middle cooperation ion trap agent.The use level of ion trap agent effect, heat resistance and cost aspect caused by add, 100 mass parts of total amount relative to resin component are preferably 1~10 mass parts.As ion trap agent, according to pair to be captured As suitably selecting commercially available product use.It can be used due to preventing copper generation ionization and dissolving out as known to copper evil preventing agent Compound, such as triazine thiol compound, bis-phenol system reducing agent, inorganic ions adsorbent etc..It is with triazine thiol compound Preventing agent is commercially available three Pharmaceutical Co., Ltd of association systems, trade name: ZISNET DB for the copper evil of ingredient.It, can as bis-phenol system reducing agent Enumerate 2,2 '-methylene-it is bis--(4- methyl-6-tert-butylphenol), 4,4 '-thio-bis--(3 methy 6 tert butyl phenols) Deng commercially available to have Yoshitomi Pharmaceutical Industries Co., Ltd's system, trade name: YOSHINOX BB.As inorganic ions adsorbent, zirconium can be enumerated Compound, antimony bismuth based compound, magnalium based compound etc., commercially available to have East Asia synthetic chemical industry Co. Ltd. system, trade name: IXE。
The manufacture > of < varnish
The solvent used when making varnish is not particularly limited, and methyl ethyl ketone, acetone, methyl-isobutyl can be used for example Ketone, cellosolvo, toluene, butyl cellosolve, methanol, ethyl alcohol, 2-methyl cellosolve, dimethyl acetamide, dimethyl methyl Amide, methyl pyrrolidone, cyclohexanone etc..Wherein, film property etc., preferably methyl ethyl ketone, dimethyl acetamide, diformazan are applied in order to improve The high boiling solvents such as base formamide, methyl pyrrolidone, cyclohexanone.These solvents can be used alone a kind or and with 2 kinds with On.
The use level of solvent is not particularly limited, and nonvolatile component when preferred fabrication varnish is 40~90 mass %, more Preferably 50~80 mass %.When nonvolatile component is less than 40 mass %, when the amount for the solvent that varnish volatilizees when making is more, dry Heat need a large amount of, have the tendency that becoming unfavorable in terms of cost；When more than 90 mass %, the viscosity of varnish becomes excessively high, Therefore there is a possibility that defect occurs for film.
When the manufacture of varnish is in view of the dispersibility of (d) filler and other fillers, grater, three can use Roller, ball mill etc. carry out, or carry out after combining them.After filler ingredient and low molecular weight object are mixed in advance Cooperate high molecular weight object again, the time required for mixing can also be shortened.In addition, after varnish is made, preferably by vacuum outgas Bubble in varnish is removed.
The manufacture > of < adhesive film
After the coating on a carrier film of above-mentioned varnish, solvent is removed using heating, it is possible thereby to shape on a carrier film At adhesive film.As long as the condition of heating is in the item that remove resin combination can fully by solvent in cured situation Part is then not particularly limited, different according to the difference of the type of the ingredient of resin combination and solvent, but in general 80~ It is heated 5~60 minutes at 140 DEG C.It is preferred that making resin combination be cured to B-stage degree by heating.The residual solvent of adhesive film Amount is preferably 3 mass % or less, more preferably 1.5 mass % or less.
As carrier film, polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, poly- third can be used Alkene film, polymethylpentene film, polyimide film, poly (ethylene naphthalate) film, poly (ether sulfone) film, polyetheramides film, polyethers acyl The plastic foils such as amine acid imide film, PA membrane, polyamidoimide film.In addition, can also carry out priming paint coating as needed, at UV The surface treatments such as reason, Corona discharge Treatment, milled processed, etching processing, demoulding processing.As the commercially available product of carrier film, such as There are DuPont-Toray Co. Ltd. system, trade name: Kapton (polyimide film), Kanegafuchi Chemical Industry Co., Ltd's system, quotient The name of an article: Apical (polyimide film), DuPont-Toray Co. Ltd. system, trade name: Lumirror (poly terephthalic acid second Diol ester film), Teijin Ltd's system, trade name: Purex (polyethylene terephthalate film) etc..
< cuts chip and engages one-piece type film >
The adhesive film of present embodiment for example can be applied to cutting chip and engage one-piece type film.As shown in Figure 1, this implementation The cutting chip of mode, which engages one-piece type film 30 and has the chip junction film 10 formed by above-mentioned adhesive film and be layered in chip, to be connect Close the cutting film 20 on film 10.
As cutting film 20, for example, can enumerate polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, The plastic foils such as polypropylene screen, polymethylpentene film, polyimide film.Cutting film 20 can also implement priming paint coating, UV as needed The surface treatment such as processing, Corona discharge Treatment, milled processed, etching processing.Cutting film 20 preferably has adherence, such as can lift Film obtained from adherence is assigned to above-mentioned plastic foil out and is arranged obtained from adhering agent layer on the single side of above-mentioned plastic foil Film.Adhering agent layer is for example (viscous by the resin combination containing liquid parts and high molecular weight components and with appropriate adhesion strength Oxidant layer formed use resin combination) formed.The cutting belt for having adhering agent layer can for example manufacture as follows: adhering agent layer is formed It is coated on above-mentioned plastic foil and is dried with resin combination, or adhering agent layer formation is coated with by handle with resin combination On the base material films such as PET film and adhering agent layer that is dry and being formed is pasted on above-mentioned plastic foil.Adhesion strength for example passes through tune The ratios of whole liquid parts, high molecular weight components Tg be set as desired value.Chip junction film is above-mentioned embodiment party The adhesive film of formula.Cutting film and chip junction film for example can be contacted directly, can also be laminated across other layers such as adhesion coating.
Cutting chip engages one-piece type film 30 and for example can replace base material film in the manufacturing method of above-mentioned adhesive film and make It is made with cutting film 20.In addition, the one-piece type film 30 of cutting chip engagement for example can also be by preparing respectively by above-mentioned bonding The chip junction film 10 and cutting film 20 that film is formed, they are laminated and integration manufactures.
Embodiment
The disclosure is illustrated in more detail below according to embodiment, but the present invention is not limited to these.
Ingredient below is used in Examples and Comparative Examples.
(a) polymer
Phenoxy resin: ZX-1356-2 (Toto Kasei KK's system, molecular weight 63000, ring parameter are 0.59)
Acrylic rubber containing epoxy group: (Teikoku Chemical Industries Co., Ltd's system, molecular weight are HTR-860P-3 1000000, Tg is -7 DEG C, 0.0) ring parameter is
(b) epoxy resin
Bisphenol f type epoxy resin: YDF-8170C (Toto Kasei KK's system, epoxide equivalent: 156, the ring of liquid 0.46) oxygen resin, ring parameter are
Cresol novolak type epoxy resin: YDCN-700-10 (Toto Kasei KK's system, ring parameter are 0.40)
Multi-functional epoxy: 1032H60 (Nippon Steel & Sumitomo Metal Corporation's system, ring parameter are 0.49)
YL7175-1000 (Japan Epoxy Resin Co. Ltd. system, ring parameter are 0.34)
(c) curing agent and curing accelerator
Phenolic resin (curing agent): XLC-LL (Mitsui Chemicals, Inc's system, ring parameter are 0.73)
Curing accelerator: Curezol 2PZ-CN (Shikoku Chem's system)
Curing accelerator: Curezol 2MA-OK (Shikoku Chem's system)
(d) filler
Spherical Alpha-alumina: alumina beads CB-P05 (Showa Denko K. K's system, Al2O3Purity be 99.89%, Average grain diameter is 4 μm)
(e) other additives:
A-189 (Japan Unicar Co. Ltd. system, γ mercaptopropyitrimethoxy silane)
A-1160 (Japan Unicar Co. Ltd. system, γ-ureidopropyltriethoxysilane)
2- methylglutaric acid (Wako Pure Chemical Industries, Ltd.'s system)
(embodiment 1)
Firstly, the composition of preparation following component composition.
Bisphenol f type epoxy resin: YDF-8170C (Toto Kasei KK's system) 4.0 mass parts
Cresol novolak type epoxy resin: YDCN-700-10 (Toto Kasei KK's system) 1.0 mass parts
Phenolic resin: XLC-LL (Mitsui Chemicals, Inc's system) 5.5 mass parts
Curezol 2PZ-CN (Shikoku Chem's system) 0.01 mass parts
A-189 (Japan Unicar Co. Ltd. system, γ mercaptopropyitrimethoxy silane) 0.04 mass parts
A-1160 (Japan Unicar Co. Ltd. system, γ-ureidopropyltriethoxysilane) 0.08 mass parts
Cyclohexanone is added in above-mentioned composition in such a way that solid component reaches 80 mass % or so, and then adds ball Shape Alpha-alumina: alumina beads CB-P05 (Showa Denko K. K's system) 85.0 mass parts.In the composition addition with The zirconium oxide bead (1mm φ) of its isodose (quality), using ball mill with 600rpm mixing 30 minutes.Combination upon mixing Phenoxy resin is added in object: ZX-1356-2 (Toto Kasei KK's system) 4.5 mass parts, reuse ball mill with 600rpm is mixed 30 minutes.After mixing, zirconium oxide bead is removed by filtering, obtains varnish.
As carrier film, prepare with a thickness of 38 μm of the progress polyethylene terephthalate film of demoulding processing: A53 (Supreme Being people Dupont Film Co. Ltd. system).It is coated with after varnish on the film, heat drying 5 minutes at 120 DEG C, thus The adhesive film with a thickness of 25 μm has been made on a carrier film.
(embodiment 2~4)
Other than the use level for recording the use level table 1 of each ingredient, reality has been made respectively similarly to Example 1 Apply the adhesive film of example 2~4.
(comparative example 1)
Firstly, the composition of preparation following component composition.
Bisphenol f type epoxy resin: YDF-8170C (Toto Kasei KK's system) 4.0 mass parts
Cresol novolak type epoxy resin: YDCN-700-10 (Toto Kasei KK's system) 1.0 mass parts
Phenolic resin: XLC-LL (Mitsui Chemicals, Inc's system) 5.5 mass parts
Curing accelerator: Curezol 2PZ-CN (Shikoku Chem's system) 0.01 mass parts
Coupling agent: A-189 (Japan Unicar Co. Ltd. system) 0.04 mass parts
Coupling agent: A-1160 (Japan Unicar Co. Ltd. system) 0.08 mass parts
Cyclohexanone is added in above-mentioned composition in such a way that solid component reaches 57 mass % or so, and then adds ball Shape Alpha-alumina: alumina beads CB-P05 (Showa Denko K. K's system) 85.0 mass parts.In the composition addition with The zirconium oxide bead (1mm φ) of its isodose (quality), using ball mill with 600rpm mixing 30 minutes.Combination upon mixing The acrylic rubber containing epoxy group: HTR-860P-3 (Teikoku Chemical Industries Co., Ltd's system) 4.5 mass parts is added in object, then It is secondary to be mixed 30 minutes using ball mill with 600rpm.After mixing, zirconium oxide bead is removed by filtering, obtains varnish.
As carrier film, prepare with a thickness of 38 μm of the progress polyethylene terephthalate film of demoulding processing: A31 (Supreme Being people Dupont Film Co. Ltd. system).It is coated with after varnish on the film, heat drying 5 minutes at 120 DEG C, thus The adhesive film with a thickness of 25 μm has been made on a carrier film.
(comparative example 2~4)
Other than the use level for recording the use level table 2 of each ingredient, ratio has been made respectively in the same manner as comparative example 1 Compared with the adhesive film of example 2~4.
[assessment item]
(thermal conductivity)
By pasting adhesive film, make with a thickness of 100 μm of samples more than and less than 600 μm.By the sample at 110 DEG C Solidify 1 hour and solidifies 3 hours at 170 DEG C.
Thermal diffusivity α (mm2/ s):
By the way that the said sample after solidifying is cut into 10mm square, to obtain the sample of thermal diffusivity measurement.About The thermal diffusivity (thickness direction of adhesive film) of the sample, utilizes laser flash method (NETZSCH system, LFA467HyperFlash) It is measured at 25 DEG C.
Specific heat Cp (J/ (g DEG C)):
About the specific heat of the sample after above-mentioned solidification, using DSC method (Perkin Elmer system, DSC8500), in heating speed Degree is 10 DEG C/min, temperature is measured under conditions of being 10~60 DEG C, acquires the value at 25 DEG C.
Specific gravity (g/cm3):
About the specific gravity of the sample after above-mentioned solidification, specific gravity is found out using electronic hydrometer SD-200L (Mirage system).
According to the value of the thermal diffusivity α, specific heat Cp and specific gravity that obtain by each measurement, thermal conductivity is calculated using following formula (W/(m·K))。
Thermal conductivity (W/ (mK))=thermal diffusivity (mm2/ s) × specific heat (J/ (g DEG C)) × specific gravity (g/cm3)
(surface roughness Ra)
Adhesive film is pasted using heating roller laminating machine (80 DEG C, 0.3m/ minutes, 0.3MPa) and with a thickness of 300 μm of silicon wafer After piece, solidify 1 hour at 110 DEG C, solidify 3 hours at 170 DEG C, obtains sample.Use fine shape measuring machine SURFCORDER ET200 (Kosaka Laboratory Ltd.'s system) acquires the surface roughness of adhesive film in the range of 2.5mm (Ra)。
(bonding force)
Adhesive film is pasted onto semiconductor chip using heating roller laminating machine (80 DEG C, 0.3m/ minutes, 0.3MPa), and (5mm is shown in Side).In turn, which is crimped 5 seconds and is bonded with 120 DEG C, 250g on the substrate of 42 alloys, solidify 1 at 110 DEG C Hour solidifies 3 hours at 170 DEG C.The sample is measured using omnipotent bonding strength-testing machine (Dage corporation, series 4000) Shear strength.
Table 1
Table 2
Industrial availability
According to the disclosure, the adhesive film that both cementability and thermal diffusivity can be realized with sufficiently high level can be provided And has the adhesive film as the cutting chip of chip junction film and engage one-piece type film.
Symbol description
10 chip junction films (adhesive film)
20 cutting films
30 cutting chips engage one-piece type film

Claims (8)

1. a kind of adhesive film with Thermocurable, contains:
(a) polymer；
(b) be at 50 DEG C liquid epoxy resin；
(c) at least one of curing agent and curing accelerator；With
(d) thermal conductivity is the filler of 10W/ (mK) or more,
The adhesive film meets condition shown in following inequality (1),
And the shear strength after heat cure is 1.5MPa or more,
(ma+mb+mc)/M≥0.43(1)
In formula, ma indicates to form the carbonaceous amount of the cyclic structure of (a) polymer, and mb indicates to form the cyclic annular knot of (b) epoxy resin The carbonaceous amount of structure, mc indicate to be formed the carbonaceous amount of the cyclic structure of (c) curing agent and curing accelerator, M indicate (a) polymer, (b) epoxy resin and (c) gross mass of curing agent and curing accelerator.
2. adhesive film according to claim 1, wherein the arithmetic average roughness Ra of the film surface after heat cure is 0.25 μm or less.
3. adhesive film according to claim 1 or 2, wherein (a) polymer, which contains, meets item shown in following inequality (2) The polymer of part,
ma/MA≥0.40(2)
In formula, ma indicates to form the carbonaceous amount of the cyclic structure of polymer, MAIndicate the gross mass of polymer.
4. adhesive film described in any one of claim 1 to 3, wherein (a) polymer contains phenoxy resin.
5. adhesive film according to any one of claims 1 to 4, wherein (d) filler is alpha-alumina particle.
6. adhesive film according to any one of claims 1 to 5, with a thickness of 50 μm or less.
7. adhesive film described according to claim 1~any one of 6, wherein the content of (d) filler by (a) polymer, (b) epoxy resin, (c) curing agent and curing accelerator and be 60~95 matter when (d) total amount of filler is set as 100 mass parts Measure part.
8. a kind of cutting chip engages one-piece type film, have:
The chip junction film formed by adhesive film according to any one of claims 1 to 7；With
The cutting film being layered on the chip junction film.
CN201780024601.8A 2016-06-10 2017-06-09 Adhesive film and cutting chip engage one-piece type film Pending CN109155244A (en)

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