JP5133673B2 - Adhesive film and method for producing the same - Google Patents
Adhesive film and method for producing the same Download PDFInfo
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- JP5133673B2 JP5133673B2 JP2007321331A JP2007321331A JP5133673B2 JP 5133673 B2 JP5133673 B2 JP 5133673B2 JP 2007321331 A JP2007321331 A JP 2007321331A JP 2007321331 A JP2007321331 A JP 2007321331A JP 5133673 B2 JP5133673 B2 JP 5133673B2
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- 239000002313 adhesive film Substances 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 45
- 239000011256 inorganic filler Substances 0.000 claims description 43
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 43
- 239000000853 adhesive Substances 0.000 claims description 41
- 230000001070 adhesive effect Effects 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 229920001169 thermoplastic Polymers 0.000 claims description 22
- 239000004416 thermosoftening plastic Substances 0.000 claims description 22
- -1 imide compound Chemical class 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims description 13
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920000800 acrylic rubber Polymers 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 35
- 239000003973 paint Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- WYKYKTKDBLFHCY-UHFFFAOYSA-N chloridazon Chemical compound O=C1C(Cl)=C(N)C=NN1C1=CC=CC=C1 WYKYKTKDBLFHCY-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920003987 resole Polymers 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
- 235000012239 silicon dioxide Nutrition 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
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Description
本発明は、電子部品や半導体デバイスの組立工程に用いられる接着フィルムに関する。 The present invention relates to an adhesive film used in an assembly process of an electronic component or a semiconductor device.
電子機器の小型化、半導体機器内部の基板上の部品実装密度の増加が進み、半導体素子も高集積化して単位面積あたりの発熱量が大きくなったため、熱拡散をよくすることが望まれるようになっている。それに伴い、熱対策が重要になっているが、この熱対策として放熱部材を熱伝導率の高い接着剤で貼り付けるという方法が用いられている。通常、接着剤には熱伝導率を高くするために無機充填材を添加したものが用いられ、異種材料との接着に使用することから高い接着性、および熱膨張率の違いにより発生するそりやクラックを生じないことが要求されている。 As electronic devices are miniaturized, the mounting density of components on the board inside semiconductor devices has increased, and semiconductor elements have become highly integrated and the amount of heat generated per unit area has increased, so it is desirable to improve heat diffusion. It has become. Along with this, countermeasures against heat have become important, and as a countermeasure against heat, a method of attaching a heat radiating member with an adhesive having high thermal conductivity is used. Usually, an adhesive is used with an inorganic filler added to increase the thermal conductivity, and since it is used for bonding with dissimilar materials, it has high adhesion and warpage caused by the difference in thermal expansion coefficient. It is required that no cracks occur.
上記要求を満足する方法として、無機充填材を含む樹脂層の両面に、無機充填材を含まない接着剤層を貼り合わせた３層構成の接着フィルムを作製する方法が提案されている（例えば、特許文献１及び特許文献２参照）。この方法では高熱伝導層の両側に低熱伝導層があるため、高熱伝導率を得るためには、両側の接着剤層を薄くする必要があるが、接着剤層を薄くすると充分な接着性が得られないため、この方法では熱伝導率を高くできないという問題を有していた。また、このような接着フィルムは、熱膨張率の違いにより発生するそりやクラックを生じないことが好ましく、そのためには接着剤が低弾性率であり、熱応力を緩和することが望まれる。しかしながら、無機充填材を多量に配合していながら低温低圧で高い接着性を得るためには接着剤成分中に濡れ性のよい低分子化合物成分を多くする必要があるが、前記方法の接着フィルムでは、樹脂成分中の熱硬化成分の割合が大きいため、応力緩和できず、被着材のそりやクラックが問題となっていた。逆に、被着材のそりやクラックを回避するために熱可塑性成分を多く配合した場合には、プレスを用い、高温、高圧で樹脂を熱で溶融させて被着体に接着させることが必要となるため、従来の接着フィルムでは、低温貼り付け性および応力緩和性の双方を満足させることは困難であった。
As a method for satisfying the above requirements, a method for producing an adhesive film having a three-layer structure in which an adhesive layer not containing an inorganic filler is bonded to both surfaces of a resin layer containing an inorganic filler has been proposed (for example, (See
本発明は、かかる状況に鑑みなされたもので、電子部品、他発熱部品の熱伝導性を必要とされる分野において、熱ラミネート、熱プレス等により、低温低圧で熱圧着でき、ポリイミド等のフィルム材料、金属、シリコン、エポキシ、セラミック等の被着材への接着性に優れ、高熱伝導率を有し、かつ被着材の反りやクラックが生じない接着フィルム及びその製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and can be thermocompression bonded at a low temperature and low pressure by heat lamination, heat press, etc. in a field where heat conductivity of electronic parts and other heat generating parts is required, and a film such as polyimide. To provide an adhesive film excellent in adhesiveness to an adherend such as material, metal, silicon, epoxy, ceramic, etc., having high thermal conductivity, and free from warping or cracking of the adherend, and a method for producing the same. Objective.
かかる目的は、接着剤を離型性フィルムに塗布、乾燥して接着剤層を形成した後、離型性フィルムを剥離しないで前記接着剤層どうしを貼り合わせてなる離型性フィルムの間に接着剤層を有する接着フィルムであって、前記接着剤層が、熱硬化成分と熱可塑成分からなる樹脂成分１００体積部に対して無機充填材が８０体積部以上含有し、かつ前記熱可塑成分が樹脂成分中に４０重量％以上含有するものであり、前記接着剤層の中央部の無機充填材が密の状態で含有され、離型性フィルム側の外表面部における無機充填材が疎の状態で含有されていることを特徴とする接着フィルムにて達成される。
また、上記本発明の接着フルムを得るための製造方法は、熱硬化成分と熱可塑成分からなる樹脂成分１００体積部に対して無機充填材が８０体積部以上含有し、かつ前記熱可塑成分が樹脂成分中に４０重量％以上含有する接着剤を離型性フィルムに塗布、乾燥して離型性フィルム側の無機充填材が少なく、接着剤層表面側の無機充填材が多くなるように接着剤層を形成した後、離型性フィルムを剥離しないで前記接着剤層どうしを貼り合わせてなることを特徴とする。
The purpose is to apply an adhesive to a release film, dry it to form an adhesive layer, and then peel off the release film between the release films formed by bonding the adhesive layers together without peeling off the release film. An adhesive film having an adhesive layer, wherein the adhesive layer contains 80 parts by volume or more of an inorganic filler with respect to 100 parts by volume of a resin component comprising a thermosetting component and a thermoplastic component, and the thermoplastic component Is contained in the resin component in an amount of 40% by weight or more, the inorganic filler in the center of the adhesive layer is contained in a dense state, and the inorganic filler in the outer surface portion on the side of the releasable film is sparse. It is achieved by an adhesive film characterized by being contained in a state.
Moreover, the manufacturing method for obtaining the adhesive film of the present invention includes an inorganic filler of 80 parts by volume or more with respect to 100 parts by volume of a resin component comprising a thermosetting component and a thermoplastic component, and the thermoplastic component is Adhesive containing 40% by weight or more in the resin component is applied to the releasable film and dried so that there is little inorganic filler on the releasable film side and more inorganic filler on the adhesive layer surface side. After forming the agent layer, the adhesive layers are bonded together without peeling off the release film .
本発明の発明者らは、無機充填材入り接着剤を離型性フィルムに塗布し、接着フィルムを作製した場合、離型性フィルム側は無機充填材が少なく、接着剤表面側は無機充填材が多くなることを知見した。そこで、本発明においては、接着剤表面同士を貼り合わせることにより、無機充填材の少ない離型性フィルム側を被着材の接着に両面使用できるため、樹脂成分中の熱硬化成分の割合を大きくしなくても高い接着性が得られ、さらに熱可塑性成分の割合をより大きくできることから、応力緩和でき、被着材のそりやクラックを抑制する効果が得られる。
本発明によれば、熱伝導性および低温接着性に優れ、異種材料の被着材を接着した際にも、そりやクラックが発生しない接着フィルム及びその製造方法を提供することができる。
The inventors of the present invention apply an inorganic filler-containing adhesive to a releasable film to produce an adhesive film, and the releasable film side has few inorganic fillers, and the adhesive surface side has an inorganic filler. I found out that there will be more. Therefore, in the present invention, by bonding the adhesive surfaces to each other, the release film side with less inorganic filler can be used on both sides for adhesion of the adherend, so the ratio of the thermosetting component in the resin component is increased. Even if it is not, high adhesiveness can be obtained, and furthermore, since the ratio of the thermoplastic component can be further increased, the stress can be relieved and the effect of suppressing warpage and cracking of the adherend can be obtained.
ADVANTAGE OF THE INVENTION According to this invention, it is excellent in thermal conductivity and low-temperature adhesiveness, and even when it adhere | attaches the adherend of a dissimilar material, the adhesive film which does not generate | occur | produce a warp and a crack, and its manufacturing method can be provided.
以下、本発明の接着フィルムの一例である実施形態について図１に基づいて説明する。
本発明の接着フィルムは、図１に示すように、離型性フィルム１の間に接着剤層２を有し、該接着剤層２における中央部ａと離型性フィルム１近傍の外表面部ｂにおける無機充填材３の含有密度が異なる。中央部ａには無機充填材３が密の状態で含有され、外表面部ｂには無機充填材３が疎の状態で含有されている。したがって、電子部品、他発熱部品の熱伝導性を必要とされる分野において、熱ラミネートや熱プレス等により、金属、シリコン、エポキシ、セラミック等の被着材への接着性に優れ、低温低圧で熱圧着することができる。
また、本発明の接着フィルムは、離型性フィルム１が無い接着剤層２のみのものでもよい。
Hereinafter, an embodiment as an example of the adhesive film of the present invention will be described with reference to FIG.
As shown in FIG. 1, the adhesive film of the present invention has an
Further, the adhesive film of the present invention may be only the
本発明における離型性フィルム１としては、ポリエチレン、ポリプロピレン、塩化ビニル、フッ素系樹脂、シリコーン系樹脂、ポリエチレンナフタレート、ポリエテレンテレフタレート、ポリフェニレンサルファイド等やこれらの樹脂からなるフィルムに離型処理を施したものなどが挙げられるが、特にポリエチレンテレフタレートフィルムに離型処理を施したものが好ましい。
As the
本発明の接着フィルムに用いる無機充填材としては、金、銀、銅、アルミニウム、ニッケルからなる群から選ばれる金属又はその合金、水酸化アルミニウム、水酸化マグネシウム、炭酸マグネシウム、酸化マグネシウム、酸化亜鉛、ほう酸アルミウイスカ、アルミナ、結晶性シリカ、非晶性シリカ、炭化ケイ素、黒鉛、窒化ホウ素、窒化アルミニウム、窒化けい素、ダイヤモンド、グラファイト、あるいはこれらの２種以上の混合物などが挙げられる。特に熱伝導率を良好にするためには、熱伝導率が２０Ｗ／ｍ・Ｋ以上のものが好ましい。無機充填材の形状は、球状、扁平粒状、樹枝状、棒状、針状など、特に制限はないが、球状、扁平粒状が好ましい。また、導電性を付与する場合には導電性を有する無機充填材を含有してもよく、難燃性を付与する場合には難燃性を有する無機充填材を含有してもよい。無機充填材の含有量としては、図１の密度分布を有するために樹脂成分１００体積部に対し、無機充填材が８０体積部以上含有していなければならない。無機充填材が８０体積部未満では、図１の密度分布にはなりにくく、良好な熱伝導性を得ることができない。無機充填材の含有量の上限値としては２００体積部以下が好ましい。
樹脂成分及び無機充填材の体積は、それらの量と比重によって計算して求めることができる。
As an inorganic filler used for the adhesive film of the present invention, a metal selected from the group consisting of gold, silver, copper, aluminum, nickel or an alloy thereof, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, magnesium oxide, zinc oxide, Examples thereof include aluminum borate whisker, alumina, crystalline silica, amorphous silica, silicon carbide, graphite, boron nitride, aluminum nitride, silicon nitride, diamond, graphite, or a mixture of two or more thereof. In particular, in order to improve the thermal conductivity, those having a thermal conductivity of 20 W / m · K or more are preferable. The shape of the inorganic filler is not particularly limited, such as a spherical shape, a flat granular shape, a dendritic shape, a rod shape, or a needle shape, but a spherical shape or a flat granular shape is preferable. Moreover, when providing electroconductivity, you may contain the inorganic filler which has electroconductivity, and when providing flame retardance, you may contain the inorganic filler which has flame retardance. As content of an inorganic filler, in order to have the density distribution of FIG. 1, the inorganic filler must contain 80 volume parts or more with respect to 100 volume parts of resin components. If the inorganic filler is less than 80 parts by volume, the density distribution of FIG. 1 is difficult to be obtained, and good thermal conductivity cannot be obtained. The upper limit of the content of the inorganic filler is preferably 200 parts by volume or less.
The volume of the resin component and the inorganic filler can be calculated and calculated based on their amount and specific gravity.
本発明の接着フィルムの接着剤層は、熱硬化成分と熱可塑成分からなる樹脂成分であり、該熱可塑成分が樹脂成分中に４０重量％以上含有することが必要である。熱可塑性成分が４０重量％未満の場合は、異種材料の被着材を接着した際に応力緩和性が得られないため、被着材にそりやクラックが生じる。熱可塑成分の樹脂成分中における上限値は１００重量％以下が好ましい。
熱可塑性成分の材料としては、公知の熱可塑性樹脂であれば何れも使用できるが、アクリロニトリル−ブタジエン共重合体またはアクリルゴムは接着性が高く特に好ましい。熱可塑性樹脂には、アミノ基、カルボキシル基、エポキシ基、水酸基等の官能基が含有されていても良い。
The adhesive layer of the adhesive film of the present invention is a resin component composed of a thermosetting component and a thermoplastic component, and it is necessary that the thermoplastic component is contained in the resin component by 40% by weight or more. When the thermoplastic component is less than 40% by weight, stress relaxation cannot be obtained when adhering materials of different materials are adhered, so that warpage or cracks occur in the adherend. The upper limit of the thermoplastic component in the resin component is preferably 100% by weight or less.
As the material of the thermoplastic component, any known thermoplastic resin can be used, but acrylonitrile-butadiene copolymer or acrylic rubber is particularly preferable because of its high adhesiveness. The thermoplastic resin may contain a functional group such as an amino group, a carboxyl group, an epoxy group, or a hydroxyl group.
本発明における熱硬化成分の材料としては、公知の熱硬化樹脂は何れも使用できるが、エポキシ樹脂、フェノール樹脂、イミド化合物は、耐熱性および接着性に優れ好適である。これらは単独で用いる他、適宜混合したり、酸無水物、アミン化合物、イミダゾール類等の硬化剤を併用したり、有機過酸化物等の反応促進剤を添加しても良い。エポキシ樹脂は、硬化して接着作用を呈するものであれば何れのものを用いてもよいが、好ましくは分子量が３０００未満のエポキシ樹脂が適し、特にビスフェノールＡ型、ビスフェノールＦ型のような液状樹脂は流動性を向上させることができるため好適である。フェノ−ル樹脂としては、具体的にはアルキルフェノール、ｐ−フェニルフェノール、ビスフェノールＡ型等のノボラックフェノール樹脂およびレゾールフェノール樹脂が挙げられる。イミド化合物としては、ビスマレイミドが好ましく使用される。 As the material of the thermosetting component in the present invention, any known thermosetting resin can be used, but an epoxy resin, a phenol resin, and an imide compound are excellent in heat resistance and adhesiveness and are suitable. These may be used alone, or may be mixed as appropriate, a curing agent such as an acid anhydride, an amine compound, or imidazoles may be used in combination, or a reaction accelerator such as an organic peroxide may be added. Any epoxy resin may be used as long as it cures and exhibits an adhesive action, but is preferably an epoxy resin having a molecular weight of less than 3000, and particularly liquid resins such as bisphenol A type and bisphenol F type. Is preferable because it can improve fluidity. Specific examples of the phenol resin include novolak phenol resins such as alkylphenol, p-phenylphenol, and bisphenol A, and resole phenol resins. As the imide compound, bismaleimide is preferably used.
本発明においては、前記熱硬化成分と熱可塑成分からなる樹脂成分１００体積部に対して無機充填材が８０体積部以上含有し、かつ前記熱可塑成分が樹脂成分中に４０重量％以上含有する接着剤層を離型性フィルムに形成し、前記接着剤層どうしを貼り合わせてなる接着フィルムでもよい。
このような接着フィルムの製造方法は、熱硬化成分と熱可塑成分からなる樹脂成分１００体積部に対して無機充填材が８０体積部以上含有し、かつ前記熱可塑成分が樹脂成分中に４０重量％以上含有する接着剤を離型性フィルムに塗布、乾燥して接着剤層を形成した後、前記接着剤層どうしを貼り合わせて得ることができる。
すなわち、本発明の接着フィルムを作製するには、まず最初に無機充填材および樹脂成分を溶媒中で混合して接着剤塗料を調整し、これを離型性フィルムの片面に塗布し、乾燥する。このように製造することによって、図２に示すような無機充填材の密度分布が異なる積層体を得ることができる。
In the present invention, the inorganic filler is contained in an amount of 80 parts by volume or more with respect to 100 parts by volume of the resin component comprising the thermosetting component and the thermoplastic component, and the thermoplastic component is contained in the resin component by 40% by weight or more. An adhesive film may be formed by forming an adhesive layer on a releasable film and bonding the adhesive layers together.
In such a method for producing an adhesive film, an inorganic filler is contained in an amount of 80 parts by volume or more with respect to 100 parts by volume of a resin component comprising a thermosetting component and a thermoplastic component, and the thermoplastic component is 40% by weight in the resin component. An adhesive containing at least% is applied to a releasable film and dried to form an adhesive layer, and then the adhesive layers can be bonded together.
That is, in order to produce the adhesive film of the present invention, first, an inorganic filler and a resin component are mixed in a solvent to prepare an adhesive paint, and this is applied to one side of a release film and dried. . By manufacturing in this way, it is possible to obtain laminates with different inorganic filler density distributions as shown in FIG.
その後、離型性フィルムに塗布された接着剤同士を貼り合わせる事により作製できる。離型性フィルムに接着剤を塗布する際、塗布厚さは５〜１００μｍ、とりわけ１０〜５０μｍの範囲にあることが好ましい。接着剤塗料を調製する際に用いる溶媒としては、炭化水素類、アルコール類、ケトン類、エーテル類などの有機溶剤、水などが挙げられる。これらは単独もしくは混合して使用する。貼り合わせ方法としては、熱プレス、熱ラミネーターなど何れの方法を用いてもよいが、特に図３に示すような熱ラミネーターが生産性を高くできるために好ましい。図３においては、熱ロール４の間に図２の積層体の接着剤層面を接触させながら貼り合わせて作製する。貼り合わせに用いる接着剤層の厚さは同じでも異なっていても良く、接着剤層の組成は無機充填材を含有していれば同じもの同士を貼り合わせても良いし、異なるもの同士を貼り合わせても良い。好ましくは、貼り合わせ界面の密着性を向上するため、同一の樹脂成分が望ましい。 Then, it can produce by bonding together the adhesive agent apply | coated to the release film. When an adhesive is applied to the releasable film, the coating thickness is preferably in the range of 5 to 100 μm, particularly 10 to 50 μm. Examples of the solvent used for preparing the adhesive paint include hydrocarbons, alcohols, ketones, organic solvents such as ethers, water, and the like. These are used alone or in combination. As a bonding method, any method such as a heat press or a heat laminator may be used. In particular, a heat laminator as shown in FIG. 3 is preferable because productivity can be increased. In FIG. 3, the adhesive layer surface of the laminate of FIG. The thickness of the adhesive layer used for bonding may be the same or different, and the composition of the adhesive layer may be the same as each other as long as it contains an inorganic filler. May be combined. Preferably, the same resin component is desirable in order to improve the adhesion at the bonding interface.
また、離型性フィルムがない本発明の接着フィルムを耐熱性フィルムの少なくとも一面に貼り合わせることにより、無機充填材が含有していながら、高い耐熱性を有する接着フィルムを提供することができる。また、上記耐熱性フィルムの代わりに金属板であっても良い。
耐熱性フィルムとしてはポリイミド、ポリフェニレンサルファイド、ポリエーテルスルホン、ポリエーテルエーテルケトン、液晶ポリマー、ポリエチレンテレフタレート、ポリエチレンナフタレート等の耐熱性プラスチックフィルム、エポキシ樹脂−ガラスクロス等の複合耐熱フィルム等何れも使用できる。
Moreover, by bonding the adhesive film of the present invention having no releasable film to at least one surface of the heat resistant film, an adhesive film having high heat resistance can be provided while the inorganic filler is contained. Moreover, a metal plate may be used instead of the heat resistant film.
As the heat resistant film, any of polyimide, polyphenylene sulfide, polyether sulfone, polyether ether ketone, liquid crystal polymer, heat resistant plastic film such as polyethylene terephthalate, polyethylene naphthalate, and composite heat resistant film such as epoxy resin-glass cloth can be used. .
以下、本発明を実施例によって説明する。
[実施例１]
（接着フィルムの作製）
厚さ３８μｍの離型処理ポリエチレンテレフタレートフィルム（帝人デュポンフィルム社製、商品名：ビューレックス４３ＸＡ）の片面に、下記接着剤塗料を、乾燥後の接着剤層の厚さが約２２μｍとなるように塗布し、１５０℃に設定した熱風循環型オーブン中で２分間乾燥した。その後、熱ラミネーターにより接着剤層どうしを、貼り合わせ温度１００℃、貼り合わせ速度０．２ｍ／分、ロール圧１ｋｇ／ｃｍ２で貼り合わせ、接着剤層の厚さが約４０μｍの本発明の接着フィルムを得た。
（接着剤塗料の組成）
アクリロニトリル−ブタジエン共重合体（重量平均分子量２５０，０００、アクリロニトリル含有率２７％）１００重量部、エポキシ樹脂（ジャパンエポキシレジン社製、商品名：エピコート８２８）７０重量部、ｐ−ｔ−ブチル型フェノール樹脂（昭和高分子社製、商品名：ＣＫＭ２４３２）２８重量部、２−エチル−４−メチルイミダゾール２重量部、アルミナ（昭和電工社製、商品名：ＡＬ-４３-Ｍ）６００重量部、テトラヒドロフラン６００重量部
Hereinafter, the present invention will be described by way of examples.
[Example 1]
(Preparation of adhesive film)
The following adhesive coating is applied to one side of a 38 μm thick release-treated polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: Burex 43XA) so that the thickness of the adhesive layer after drying is about 22 μm. It was applied and dried in a hot air circulating oven set at 150 ° C. for 2 minutes. Thereafter, the adhesive layers are bonded to each other with a thermal laminator at a bonding temperature of 100 ° C., a bonding speed of 0.2 m / min, and a roll pressure of 1 kg / cm 2. A film was obtained.
(Composition of adhesive paint)
100 parts by weight of acrylonitrile-butadiene copolymer (weight average molecular weight 250,000, acrylonitrile content 27%), 70 parts by weight of epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.), pt-butyl type phenol 28 parts by weight of resin (made by Showa Polymer Co., Ltd., trade name: CKM2432), 2 parts by weight of 2-ethyl-4-methylimidazole, 600 parts by weight of alumina (made by Showa Denko KK, trade name: AL-43-M), tetrahydrofuran 600 parts by weight
[実施例２]
接着剤塗料を下記組成に代えた以外は、実施例１と同様にして本発明の接着フィルムを得た。
（接着剤塗料の組成）
アクリロニトリル−ブタジエン共重合体（重量平均分子量２５０，０００、アクリロニトリル含有率２７％）１８０重量部、エポキシ樹脂（ジャパンエポキシレジン社製、商品名：エピコート８２８）１３重量部、ｐ−ｔ−ブチル型フェノール樹脂（昭和高分子社製、商品名：ＣＫＭ２４３２）６重量部、２−エチル−４−メチルイミダゾール１重量部、アルミナ（昭和電工社製、商品名：ＡＬ-４３-Ｍ）４００重量部、窒化ホウ素（水島合金鉄社製、商品名：ＨＰ-１）１００重量部、テトラヒドロフラン６００重量部
[Example 2]
An adhesive film of the present invention was obtained in the same manner as in Example 1 except that the adhesive paint was changed to the following composition.
(Composition of adhesive paint)
180 parts by weight of acrylonitrile-butadiene copolymer (weight average molecular weight 250,000, acrylonitrile content 27%), 13 parts by weight of epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.), pt-butyl type phenol 6 parts by weight of resin (made by Showa Polymer Co., Ltd., trade name: CKM2432), 1 part by weight of 2-ethyl-4-methylimidazole, 400 parts by weight of alumina (made by Showa Denko KK, trade name: AL-43-M), nitriding Boron (manufactured by Mizushima Alloy Iron Company, trade name: HP-1) 100 parts by weight, tetrahydrofuran 600 parts by weight
[実施例３]
接着剤塗料を下記組成に代えた以外は、実施例１と同様にして本発明の接着フィルムを得た。
（接着剤塗料の組成）
アクリルゴム（日本ゼオン社製、商品名：ＡＲ５１）１４０重量部、エポキシ樹脂（日本化薬社製、商品名：ＥＯＣＮ−１０２０−６５）４０重量部、ｐ−ｔ−ブチル型フェノール樹脂（昭和高分子社製、商品名：ＣＫＭ２４３２）１８重量部、２−エチル−４−メチルイミダゾール２重量部、アルミナ（昭和電工社製、商品名：ＡＬ-４３-Ｍ）５００重量部、テトラヒドロフラン６００重量部
[Example 3]
An adhesive film of the present invention was obtained in the same manner as in Example 1 except that the adhesive paint was changed to the following composition.
(Composition of adhesive paint)
140 parts by weight of acrylic rubber (manufactured by Nippon Zeon Co., Ltd., trade name: AR51), 40 parts by weight of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1020-65), pt-butyl type phenol resin (Showa High) 18 parts by weight, trade name: CKM 2432), 2 parts by weight of 2-ethyl-4-methylimidazole, 500 parts by weight of alumina (made by Showa Denko KK, trade name: AL-43-M), 600 parts by weight of tetrahydrofuran
[実施例４]
接着剤塗料を下記組成に代えた以外は、実施例１と同様にして本発明の接着フィルムを得た。
（接着剤塗料の組成）
アクリルゴム（デュポン社製、商品名：ＶＡＭＡＣ Ｇ）１２０重量部、ビスフェノールＡジフェニルエーテル３６重量部、ｐ−ｔ−ブチル型フェノール樹脂（昭和高分子社製、商品名：ＣＫＭ１６３６）４０重量部、４，４‘−ジアミノジフェニルメタン４重量部、アルミナ（昭和電工社製、商品名：ＡＬ-４３-Ｍ）１２００重量部、テトラヒドロフラン８００重量部
[Example 4]
An adhesive film of the present invention was obtained in the same manner as in Example 1 except that the adhesive paint was changed to the following composition.
(Composition of adhesive paint)
120 parts by weight of acrylic rubber (manufactured by DuPont, trade name: VAMAC G), 36 parts by weight of bisphenol A diphenyl ether, 40 parts by weight of pt-butyl type phenol resin (trade name: CKM1636, manufactured by Showa Polymer Co., Ltd.), 4, 4 parts by weight of 4′-diaminodiphenylmethane, 1200 parts by weight of alumina (manufactured by Showa Denko KK, trade name: AL-43-M), 800 parts by weight of tetrahydrofuran
[実施例５]
接着剤塗料を下記組成に代えた以外は、実施例１と同様にして本発明の接着フィルムを得た。
（接着剤塗料の組成）
アクリロニトリル−ブタジエン共重合体（重量平均分子量２５０，０００、アクリロニトリル含有率２７％）８０重量部、エポキシ樹脂（ジャパンエポキシレジン社製、商品名：エピコート８２８）８０重量部、ｐ−ｔ−ブチル型フェノール樹脂（昭和高分子社製、商品名：ＣＫＭ２４３２）３７重量部、２−エチル−４−メチルイミダゾール３重量部、アルミナ（昭和電工社製、商品名：ＡＬ-４３-Ｍ）８００重量部、テトラヒドロフラン７００重量部
[Example 5]
An adhesive film of the present invention was obtained in the same manner as in Example 1 except that the adhesive paint was changed to the following composition.
(Composition of adhesive paint)
80 parts by weight of an acrylonitrile-butadiene copolymer (weight average molecular weight 250,000, acrylonitrile content 27%), 80 parts by weight of an epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.), pt-butyl type phenol 37 parts by weight of resin (made by Showa Polymer Co., Ltd., trade name: CKM2432), 3 parts by weight of 2-ethyl-4-methylimidazole, 800 parts by weight of alumina (made by Showa Denko, trade name: AL-43-M), tetrahydrofuran 700 parts by weight
[実施例６]
厚さ３８μｍの離型処理ポリエチレンテレフタレートフィルム（帝人デュポンフィルム社製、商品名：ビューレックス４３ＸＡ）の片面に、実施例１の接着剤塗料を、乾燥後の接着剤層の厚さが約１２μｍとなるように塗布し、１５０℃に設定した熱風循環型オーブン中で２分間乾燥し、接着剤フィルムＡを得た。さらに、同様に実施例５の接着剤塗料を用いて、乾燥後の接着剤層の厚さが約４２μｍとなるように塗布し、１５０℃に設定した熱風循環型オーブン中で２分間乾燥し、接着剤フィルムＢを得た。その後、熱ラミネーターにより接着剤フィルムＡおよび接着剤フィルムＢの接着剤層どうしを、貼り合わせ温度１００℃、貼り合わせ速度０．２ｍ／分、ロール圧１ｋｇ／ｃｍ２で貼り合わせ、接着剤層の厚さが約５０μｍの本発明の接着フィルムを得た。
[Example 6]
The adhesive coating of Example 1 was applied to one side of a 38 μm thick release-treated polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: Burex 43XA), and the thickness of the adhesive layer after drying was about 12 μm. And dried for 2 minutes in a hot air circulating oven set at 150 ° C. to obtain an adhesive film A. Further, similarly, using the adhesive paint of Example 5, it was applied so that the thickness of the adhesive layer after drying was about 42 μm, and dried in a hot air circulation oven set at 150 ° C. for 2 minutes, An adhesive film B was obtained. Thereafter, the adhesive layers of the adhesive film A and the adhesive film B are bonded with a thermal laminator at a bonding temperature of 100 ° C., a bonding speed of 0.2 m / min, and a roll pressure of 1 kg / cm 2 . An adhesive film of the present invention having a thickness of about 50 μm was obtained.
[比較例１]
（熱硬化性接着フィルムの作製）
厚さ３８μｍの離型処理ポリエチレンテレフタレートフィルム（帝人デュポンフィルム社製、商品名：ビューレックス４３ＸＡ）の片面に、下記接着剤塗料を、乾燥後の接着剤層の厚さが約４０μｍとなるように塗布後、１５０℃に設定した熱風循環型オーブン中で２分間乾燥し、比較用の接着フィルムを得た。
（接着剤塗料の組成）
アクリロニトリル−ブタジエン共重合体（重量平均分子量２５０，０００、アクリロニトリル含有率２７％）６０重量部、エポキシ樹脂（ジャパンエポキシレジン社製、商品名：エピコート８２８）１００重量部、ｐ−ｔ−ブチル型フェノール樹脂（昭和高分子社製、商品名：ＣＫＭ２４３２）３７重量部、２−エチル−４−メチルイミダゾール３重量部、アルミナ（昭和電工社製、商品名：ＡＬ-４３-Ｍ）６００重量部、テトラヒドロフラン６００重量部
[Comparative Example 1]
(Production of thermosetting adhesive film)
The following adhesive paint is applied to one side of a 38 μm thick release-treated polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: Burex 43XA) so that the thickness of the adhesive layer after drying is about 40 μm. After application, the film was dried for 2 minutes in a hot air circulation oven set at 150 ° C. to obtain a comparative adhesive film.
(Composition of adhesive paint)
60 parts by weight of acrylonitrile-butadiene copolymer (weight average molecular weight 250,000, acrylonitrile content 27%), 100 parts by weight of epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.), pt-butyl type phenol 37 parts by weight of resin (made by Showa Polymer Co., Ltd., trade name: CKM2432), 3 parts by weight of 2-ethyl-4-methylimidazole, 600 parts by weight of alumina (made by Showa Denko KK, trade name: AL-43-M), tetrahydrofuran 600 parts by weight
[比較例２]
接着剤塗料を下記組成に代えた以外は、比較例１と同様にして比較用の接着フィルムを得た。
（接着剤塗料の組成）
アクリルゴム（日本ゼオン社製、商品名：ＡＲ５１）３６０重量部、エポキシ樹脂（日本化薬社製、商品名：ＥＯＣＮ−１０２０−６５）１５５重量部、ｐ−ｔ−ブチル型フェノール樹脂（昭和高分子社製、商品名：ＣＫＭ２４３２）８０重量部、２−エチル−４−メチルイミダゾール５重量部、アルミナ（昭和電工社製、商品名：ＡＬ-４３-Ｍ）６００重量部、テトラヒドロフラン３０００重量部
[Comparative Example 2]
A comparative adhesive film was obtained in the same manner as in Comparative Example 1 except that the adhesive paint was changed to the following composition.
(Composition of adhesive paint)
360 parts by weight of an acrylic rubber (manufactured by Nippon Zeon Co., Ltd., trade name: AR51), 155 parts by weight of an epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1020-65), pt-butyl type phenol resin (Showa High) 80 parts by weight, trade name: CKM 2432), 5 parts by weight of 2-ethyl-4-methylimidazole, 600 parts by weight of alumina (trade name: AL-43-M, trade name: AL-43-M), 3000 parts by weight of tetrahydrofuran
[比較例３]
接着剤塗料を比較例１の組成に代えた以外は、実施例１と同様にして比較用の接着フィルムを得た。
[Comparative Example 3]
A comparative adhesive film was obtained in the same manner as in Example 1 except that the adhesive paint was replaced with the composition of Comparative Example 1.
[比較例４]
接着剤塗料を比較例２の組成に代えた以外は、実施例１と同様にして比較用の接着フィルムを得た。
[Comparative Example 4]
A comparative adhesive film was obtained in the same manner as in Example 1 except that the adhesive paint was replaced with the composition of Comparative Example 2.
[比較例５]
接着剤塗料を実施例１の組成に代えた以外は、比較例１と同様にして比較用の接着フィルムを得た。
[Comparative Example 5]
A comparative adhesive film was obtained in the same manner as in Comparative Example 1 except that the adhesive paint was changed to the composition of Example 1.
[比較例６]
接着剤塗料を実施例２の組成に代えた以外は、比較例１と同様にして比較用の接着フィルムを得た。
[Comparative Example 6]
A comparative adhesive film was obtained in the same manner as in Comparative Example 1 except that the adhesive paint was replaced with the composition of Example 2.
[比較例７]
接着剤塗料を実施例４の組成に代えた以外は、比較例１と同様にして比較用の接着フィルムを得た。
[Comparative Example 7]
A comparative adhesive film was obtained in the same manner as in Comparative Example 1 except that the adhesive paint was replaced with the composition of Example 4.
［接着フィルムの評価］
（１）接着性評価
実施例１〜６及び比較例３、４で作製した接着剤層の両面に離型性フィルムを有する接着フィルムの一方の離型性フィルムを剥離した後、熱ラミネータを用いて露出した接着剤層面に１５μｍの厚さのアルミ箔を、貼り合わせ温度１２０℃、貼り合わせ速度０．５ｍ／分、ロール圧１ｋｇｆ／ｃｍ２にて貼り合わせた。そして、他方の離型性フィルムを剥離した後、露出した接着剤層面にポリイミドフィルム（東レ・デュポン社製、商品名：カプトン２００ＥＮ）を貼り合わせ、１８０℃、１時間で熱処理を行った。
また、比較例１、２及び比較例５〜７で作製した接着フィルムの露出した接着剤層面に熱ラミネータを用いて１５μｍの厚さのアルミ箔を、貼り合わせ温度１２０℃、貼り合わせ速度０．５ｍ／分、ロール圧１ｋｇｆ／ｃｍ２にて貼り合わせた。そして、アルミ箔が貼りあわされていないもう一方の面における離型性フィルムを剥離した後、露出した接着剤層面にポリイミドフィルム（東レ・デュポン社製、商品名：カプトン２００ＥＮ）を貼り合わせ、１８０℃、１時間で熱処理を行った。
その後、上記各積層体について、万能引っ張り試験機を用い、引っ張り速度５０ｍｍ／分で１８０度の方向にアルミ箔側から接着剤層を剥離させ、接着力の測定を行った。
[Evaluation of adhesive film]
(1) Adhesive evaluation After peeling off one release film of the adhesive film having a release film on both surfaces of the adhesive layers prepared in Examples 1 to 6 and Comparative Examples 3 and 4, a thermal laminator was used. An aluminum foil having a thickness of 15 μm was bonded to the exposed adhesive layer surface at a bonding temperature of 120 ° C., a bonding speed of 0.5 m / min, and a roll pressure of 1 kgf / cm 2 . Then, after peeling off the other release film, a polyimide film (trade name: Kapton 200EN, manufactured by Toray DuPont Co., Ltd.) was bonded to the exposed adhesive layer surface, and heat treatment was performed at 180 ° C. for 1 hour.
Further, a 15 μm thick aluminum foil was applied to the exposed adhesive layer surface of the adhesive films prepared in Comparative Examples 1 and 2 and Comparative Examples 5 to 7 using a thermal laminator at a bonding temperature of 120 ° C. and a bonding speed of 0. Bonding was performed at a roll pressure of 1 kgf / cm 2 at 5 m / min. Then, after releasing the release film on the other surface where the aluminum foil is not adhered, a polyimide film (product name: Kapton 200EN, manufactured by Toray DuPont Co., Ltd.) is bonded to the exposed adhesive layer surface, 180 Heat treatment was performed at 1 ° C. for 1 hour.
Then, about each said laminated body, the adhesive bond layer was peeled from the aluminum foil side in the direction of 180 degree | times at the tension | pulling speed of 50 mm / min using the universal tensile testing machine, and the adhesive force was measured.
（２）熱伝導率
実施例１〜６および比較例１〜７で作製した接着フィルムを用いて１０ｍｍ×１０ｍｍ×１ｍｍの試験片を得た。この試験片の熱拡散率をレーザーフラッシュ法で測定し、さらに熱拡散率と示差走査熱量測定装置で得られた比熱容量とアルキメデス法で得られた比重の積により熱伝導率を算出した。
(2) Thermal conductivity A test piece of 10 mm × 10 mm × 1 mm was obtained using the adhesive films prepared in Examples 1 to 6 and Comparative Examples 1 to 7. The thermal diffusivity of this test piece was measured by the laser flash method, and the thermal conductivity was calculated from the product of the thermal diffusivity, the specific heat capacity obtained by the differential scanning calorimeter and the specific gravity obtained by the Archimedes method.
（３）反り
実施例１〜６及び比較例３、４で作製した接着剤層の両面に離型性フィルムを有する接着フィルムの一方の離型性フィルムを剥離した後、熱ラミネータを用いて露出した接着剤層面に１５μｍの厚さのアルミ箔を、貼り合わせ温度１２０℃、貼り合わせ速度０．５ｍ／分、ロール圧１ｋｇｆ／ｃｍ２にて貼り合わせた。そして、他方の離型性フィルムを剥離した後、３０ｍｍ×３０ｍｍ、厚さ約０．１２ｍｍのガラス板（ＭＡＴＳＵＮＡＭＩ製、カバーグラス）に貼り合わせて、１８０℃、１時間で熱処理を行った。
また、比較例１、２及び比較例５〜７で作製した接着フィルムの露出した接着剤層面に熱ラミネータを用いて１５μｍの厚さのアルミ箔を、貼り合わせ温度１２０℃、貼り合わせ速度０．５ｍ／分、ロール圧１ｋｇｆ／ｃｍ２にて貼り合わせた。そして、他方の離型性フィルムを剥離した後、３０ｍｍ×３０ｍｍ、厚さ約０．１２ｍｍのガラス板（ＭＡＴＳＵＮＡＭＩ製、カバーグラス）に貼り合わせて、１８０℃、１時間で熱処理を行った。
その後、上記各試料片の端を水平板に固定し、試料片の反り量を測定した。反り量は、試料片が反って該試料片の固定されていない他方の端がもちあがった際の水平板から試料片までの高さをいう。そり量が２ｍｍ超のものを不良とし、反り量が２ｍｍ以下のものは良好、１．５ｍｍ以下のものは極良とした。
(3) Warpage After peeling off one release film of the adhesive film having a release film on both surfaces of the adhesive layers prepared in Examples 1 to 6 and Comparative Examples 3 and 4, it was exposed using a thermal laminator. An aluminum foil having a thickness of 15 μm was bonded to the surface of the adhesive layer at a bonding temperature of 120 ° C., a bonding speed of 0.5 m / min, and a roll pressure of 1 kgf / cm 2 . Then, after the other release film was peeled off, it was bonded to a glass plate (manufactured by MATSUNAMI, cover glass) having a size of 30 mm × 30 mm and a thickness of about 0.12 mm, followed by heat treatment at 180 ° C. for 1 hour.
Further, a 15 μm thick aluminum foil was applied to the exposed adhesive layer surface of the adhesive films prepared in Comparative Examples 1 and 2 and Comparative Examples 5 to 7 using a thermal laminator at a bonding temperature of 120 ° C. and a bonding speed of 0. Bonding was performed at a roll pressure of 1 kgf / cm 2 at 5 m / min. Then, after the other release film was peeled off, it was bonded to a glass plate (manufactured by MATSUNAMI, cover glass) having a size of 30 mm × 30 mm and a thickness of about 0.12 mm, followed by heat treatment at 180 ° C. for 1 hour.
Then, the edge of each said sample piece was fixed to the horizontal plate, and the curvature amount of the sample piece was measured. The amount of warping refers to the height from the horizontal plate to the sample piece when the sample piece is bent and the other end of the sample piece not fixed is raised. A warp amount of more than 2 mm was regarded as defective, a warp amount of 2 mm or less was good, and a warp amount of 1.5 mm or less was considered excellent.
上記評価について、表１及び表２に記した。
なお、実施例１〜６及び比較例１〜７においては、樹脂成分の比重を１．３０ｇ／ｍ３、アルミナの比重を３．９８ｇ／ｍ３、窒化ホウ素の比重を２．２８ｇ／ｍ３とし、樹脂成分および無機充填材の体積を求めた。
The above evaluation is shown in Tables 1 and 2.
In Examples 1-6 and Comparative Example 1-7, the specific gravity of the resin component 1.30 g / m 3, the specific gravity of
上記表１及び表２から明らかなように、実施例１〜６のいずれも樹脂成分１００体積部に対して無機充填材を８０体積部以上含有し、かつ樹脂成分中の熱可塑成分が４０重量％以上含む接着剤である。これらは接着性、熱伝導率に優れ、反りのいずれの特性も良好であった。これに対して、比較例１については樹脂成分中の熱可塑成分が少なく、低分子化合物が多いため接着性が良好であるが、反りが不良であった。比較例２については無機充填材量が少ないため接着性が良好であるが、熱伝導率が悪かった。比較例３は、比較例１と同様に接着性が良好であるが、そりが不良であった。比較例４は、比較例２と同様に接着性が良好であるが、熱伝導率が悪かった。比較例５〜７は、実施例と比較して接着剤層どうしの貼り合わせを行っていないため、接着性が悪かった。 As is clear from Table 1 and Table 2, each of Examples 1 to 6 contains 80 parts by volume or more of an inorganic filler with respect to 100 parts by volume of the resin component, and 40 parts by weight of the thermoplastic component in the resin component. % Adhesive. These were excellent in adhesiveness and thermal conductivity, and all the properties of warping were good. On the other hand, in Comparative Example 1, the thermoplastic component in the resin component was small and the adhesiveness was good because there were many low molecular compounds, but the warpage was poor. In Comparative Example 2, the adhesiveness was good because the amount of the inorganic filler was small, but the thermal conductivity was poor. Comparative Example 3 had good adhesion as in Comparative Example 1, but the warpage was poor. Comparative Example 4 had good adhesion as in Comparative Example 2, but had poor thermal conductivity. In Comparative Examples 5 to 7, the adhesive layers were not bonded to each other as compared with the Examples, and thus the adhesiveness was poor.
１ 離型性フィルム
２ 接着剤層
３ 無機充填材３
1
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| JP5402459B2 (en) * | 2009-09-24 | 2014-01-29 | 日本ゼオン株式会社 | Thermally conductive pressure-sensitive adhesive laminate sheet and electronic component |
| JP5793494B2 (en) * | 2010-07-02 | 2015-10-14 | 昭和電工株式会社 | Ceramic mixture and ceramic-containing thermally conductive resin sheet using the same |
| JP5942641B2 (en) * | 2012-07-02 | 2016-06-29 | 日立化成株式会社 | Resin sheet and manufacturing method thereof, cured resin sheet, and member for heat dissipation |
| JP6182967B2 (en) * | 2013-05-09 | 2017-08-23 | 日立化成株式会社 | High thermal conductive adhesive film for semiconductor devices |
| JP6356456B2 (en) * | 2014-03-27 | 2018-07-11 | デクセリアルズ株式会社 | Manufacturing method of heat conductive sheet |
| JP6390434B2 (en) * | 2015-01-13 | 2018-09-19 | 日立化成株式会社 | Manufacturing method of resin film for embedding electronic component, manufacturing method of electronic component device |
| KR102050826B1 (en) * | 2017-03-28 | 2019-12-02 | 금오공과대학교 산학협력단 | Adhesive dissipation sheet having 3-dimension dissipation structure and manufacturing method for adhesive dissipation sheet having 3-dimension dissipation structure |
| TWI627717B (en) * | 2017-07-21 | 2018-06-21 | 聚鼎科技股份有限公司 | Thermally conductive board |
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