JPWO2020111180A1 - Laminate - Google Patents
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- JPWO2020111180A1 JPWO2020111180A1 JP2020557821A JP2020557821A JPWO2020111180A1 JP WO2020111180 A1 JPWO2020111180 A1 JP WO2020111180A1 JP 2020557821 A JP2020557821 A JP 2020557821A JP 2020557821 A JP2020557821 A JP 2020557821A JP WO2020111180 A1 JPWO2020111180 A1 JP WO2020111180A1
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- silicone resin
- inorganic filler
- resin composition
- volume
- laminate
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- 229920002050 silicone resin Polymers 0.000 claims abstract description 58
- 239000011256 inorganic filler Substances 0.000 claims abstract description 53
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 53
- 239000011342 resin composition Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- -1 polyethylene naphthalate Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
Abstract
シリコーン樹脂及び無機フィラーを含有するシリコーン樹脂組成物を硬化してなるシリコーン樹脂組成物層と、シリコーン樹脂組成物層に隣接し、ガラス転移点が２００℃以上である樹脂を含む基材樹脂層と、を有し、シリコーン樹脂組成物層中に上記無機フィラーを６０〜８０体積％含有する、積層体である。 A silicone resin composition layer obtained by curing a silicone resin composition containing a silicone resin and an inorganic filler, and a base resin layer containing a resin adjacent to the silicone resin composition layer and having a glass transition point of 200 ° C. or higher. , And the silicone resin composition layer contains 60 to 80% by volume of the above-mentioned inorganic filler.
Description
本発明は絶縁性の良好な積層体に関し、特に絶縁性と熱伝導性が良好な積層体に関する。 The present invention relates to a laminate having good insulating properties, and particularly to a laminate having good insulating properties and thermal conductivity.
電子部品の小型化、高集積化、及び高出力化に伴い、作動温度がより高温となり、出力電圧もより増加している。発熱する電子部品の冷却のために、電子部品とヒートシンク又は回路基板等の放熱部材との間に放熱シートが設けられるが、電子部品の高性能化によりエネルギー密度が増大し、その作動環境はますます高電界化している。従って、放熱シートには高熱伝導化に加えて、高い電圧が印加されても絶縁破壊が起こらないように、良好な絶縁性が求められている。 With the miniaturization, high integration, and high output of electronic components, the operating temperature has become higher and the output voltage has also increased. A heat-dissipating sheet is provided between the electronic parts and heat-dissipating members such as heat sinks or circuit boards to cool the electronic parts that generate heat. The electric field is getting higher and higher. Therefore, in addition to high thermal conductivity, the heat radiating sheet is required to have good insulating properties so that dielectric breakdown does not occur even when a high voltage is applied.
絶縁性強化の観点から、補強層に絶縁性の高いガラスクロスを用いた金属酸化物固着ガラスクロスが提案されている（例えば、特許文献１参照）。ガラスクロスは複数のガラス繊維が束となって編みこまれている。ガラスクロスは所定の目開きを有することで、熱伝導性充填材の熱伝達の全てを遮断しないため、熱伝導性の低下を小さくすることができる。 From the viewpoint of strengthening the insulating property, a metal oxide-fixed glass cloth using a glass cloth having a high insulating property as the reinforcing layer has been proposed (see, for example, Patent Document 1). The glass cloth is woven with a bundle of multiple glass fibers. Since the glass cloth has a predetermined opening, it does not block all the heat transfer of the heat conductive filler, so that the decrease in heat conductivity can be reduced.
しかし、ガラスクロスの繊維間には空気層が存在するため、電圧をかけると部分放電が生じ絶縁性が完全に担保できていないといった問題がある。また、今後の車載用途、例えば車載用ＰＴＣ（Ｐｏｓｉｔｉｖｅ Ｔｅｍｐｅｒａｔｕｒｅ Ｃｏｅｆｆｉｃｉｅｎｔ）ヒータへの適用等を考慮すると、特に絶縁性が重要になると考えられる。
以上から、本発明は良好な絶縁性を発揮し得る積層体を提供することを目的とする。However, since an air layer exists between the fibers of the glass cloth, there is a problem that partial discharge occurs when a voltage is applied and the insulating property cannot be completely guaranteed. Further, considering future in-vehicle applications such as application to an in-vehicle PTC (Positive Temperature Coefficient) heater, it is considered that insulation is particularly important.
From the above, it is an object of the present invention to provide a laminate capable of exhibiting good insulating properties.
上記課題を解決すべく鋭意検討した結果、本発明者らは、所定の樹脂組成物層と基材樹脂層との積層体により当該課題が解決できることを見出し本発明に想到した。すなわち本発明は下記のとおりである。 As a result of diligent studies to solve the above problems, the present inventors have found that the problems can be solved by a laminate of a predetermined resin composition layer and a base resin layer, and have arrived at the present invention. That is, the present invention is as follows.
［１］ シリコーン樹脂及び無機フィラーを含有するシリコーン樹脂組成物を硬化してなるシリコーン樹脂組成物層と、前記シリコーン樹脂組成物層に隣接し、ガラス転移点が２００℃以上である樹脂を含む基材樹脂層と、を有し、前記シリコーン樹脂組成物層中に前記無機フィラーを６０〜８０体積％含有する、積層体。
［２］ 前記無機フィラーが、平均球形度０．８〜１．０の球状無機フィラーを含有する［１］に記載の積層体。
［３］ 前記基材樹脂層が無機フィラーを含有する［１］又は［２］に記載の積層体。
［４］ 前記シリコーン樹脂組成物中の前記無機フィラーがアルミナである［１］〜［３］のいずれかに記載の積層体。
［５］ 前記アルミナの頻度粒度分布において粒径１５〜８０μｍの領域と、粒径１．０〜１４μｍの領域及び粒径０．１〜０．９μｍの領域の少なくとも１つの領域と、に極大ピークがある［４］に記載の積層体。[1] A group containing a silicone resin composition layer obtained by curing a silicone resin composition containing a silicone resin and an inorganic filler, and a resin adjacent to the silicone resin composition layer and having a glass transition point of 200 ° C. or higher. A laminate having a material resin layer and containing 60 to 80% by volume of the inorganic filler in the silicone resin composition layer.
[2] The laminate according to [1], wherein the inorganic filler contains a spherical inorganic filler having an average sphericity of 0.8 to 1.0.
[3] The laminate according to [1] or [2], wherein the base resin layer contains an inorganic filler.
[4] The laminate according to any one of [1] to [3], wherein the inorganic filler in the silicone resin composition is alumina.
[5] In the frequency particle size distribution of alumina, a maximum peak is formed in a region having a particle size of 15 to 80 μm, a region having a particle size of 1.0 to 14 μm, and at least one region having a particle size of 0.1 to 0.9 μm. The laminate according to [4].
本発明によれば、良好な絶縁性及び熱伝導性を発揮し得る積層体を提供することができる。 According to the present invention, it is possible to provide a laminate capable of exhibiting good insulation and thermal conductivity.
本発明の積層体は、シリコーン樹脂組成物層と、基材樹脂層とが積層されてなる。
（シリコーン樹脂組成物層）
シリコーン樹脂組成物層は、シリコーン樹脂及び無機フィラーを含有するシリコーン樹脂組成物を硬化してなる。シリコーン樹脂を含有することで耐熱性が得られ、無機フィラーを含有することで良好な絶縁性や熱伝導性が得られる。The laminate of the present invention is formed by laminating a silicone resin composition layer and a base resin layer.
(Silicone resin composition layer)
The silicone resin composition layer is formed by curing a silicone resin composition containing a silicone resin and an inorganic filler. Heat resistance can be obtained by containing a silicone resin, and good insulating properties and thermal conductivity can be obtained by containing an inorganic filler.
シリコーン樹脂としては、オルガノポリシロキサンであり、ケイ素原子に直結したアルケニル基を１分子中に少なくとも２個有するものであれば直鎖状でも分岐状でもよい。このオルガノポリシロキサンは、１種類であっても、２種以上の異なる粘度のものの混合物でもよい。上記アルケニル基としては、ビニル基、アリル基、１−ブテニル基、１−へキセニル基などが例示されるが、一般的に合成のし易さ及びコストの面からビニル基であることが好ましい。ケイ素原子に結合する他の有機基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、ドデシル基などのアルキル基、フェニル基などのアリール基、２−フェニルエチル基、２−フェニルプロピル基などのアラルキル基、更にはクロロメチル基、３，３，３，−トリフルオロプロピル基などの置換炭化水素基等が挙げられる。これらのなかでは、メチル基であることが好ましい。ケイ素原子に結合するアルケニル基は、オルガノポリシロキサンの分子鎖の末端、途中の何れに存在してもよい。 The silicone resin is an organopolysiloxane, which may be linear or branched as long as it has at least two alkenyl groups directly linked to silicon atoms in one molecule. The organopolysiloxane may be one kind or a mixture of two or more kinds having different viscosities. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 1-hexenyl group and the like, but in general, a vinyl group is preferable from the viewpoint of ease of synthesis and cost. Other organic groups bonded to the silicon atom include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and dodecyl group, aryl group such as phenyl group, 2-phenylethyl group and 2-phenylpropi. Examples thereof include an aralkyl group such as a ru group, and a substituted hydrocarbon group such as a chloromethyl group and a 3,3,3, -trifluoropropyl group. Of these, a methyl group is preferred. The alkenyl group bonded to the silicon atom may be present at the end or in the middle of the molecular chain of the organopolysiloxane.
シリコーン樹脂が２液型である場合、既述のオルガノポリシロキサンの架橋剤としては、オルガノハイドロジェンポリシロキサンが挙げられる。オルガノハイドロジェンポリシロキサンはとしては、ケイ素原子に結合した水素原子を１分子中に少なくとも２個、好ましくは３個以上有するものが挙げられ、直鎖状、分岐状、及び環状のいずれであってもよい。
シリコーン樹脂組成物中のシリコーン樹脂の含有量は２０〜４０体積％である。下限については２２体積％以上が好ましく、より好ましくは２４体積％以上、さらに好ましくは２６体積％以上である。上限については３８体積％以下が好ましく、より好ましくは３６体積％以下、さらに好ましくは３６体積％以下である。When the silicone resin is a two-component type, examples of the above-mentioned cross-linking agent for organopolysiloxane include organohydrogenpolysiloxane. Examples of the organohydrogenpolysiloxane include those having at least two, preferably three or more hydrogen atoms bonded to silicon atoms in one molecule, and may be linear, branched, or cyclic. May be good.
The content of the silicone resin in the silicone resin composition is 20 to 40% by volume. The lower limit is preferably 22% by volume or more, more preferably 24% by volume or more, and further preferably 26% by volume or more. The upper limit is preferably 38% by volume or less, more preferably 36% by volume or less, still more preferably 36% by volume or less.
無機フィラーは、シリコーン樹脂組成物層中に６０〜８０体積％含有されてなる。無機フィラーの含有率が８０体積％を超えると、組成物の粘度が上昇し成形性が損なわれることやシリコーン樹脂組成物層中にボイドが生じ絶縁性が低下しやすくなる。そこで、無機フィラーの含有量は８０体積％以下とする。好ましくは７８体積％以下、より好ましくは７６体積％以下、さらに好ましくは７４体積％以下である。また、含有率が６０体積％未満であると、組成物の熱伝導性を十分に高めることが困難となる。そこで、無機フィラーの含有量を６０体積％以上とする。６２体積％以上が好ましく、より好ましくは６４体積％以上、さらに好ましくは６６体積％以上である。 The inorganic filler is contained in the silicone resin composition layer in an amount of 60 to 80% by volume. When the content of the inorganic filler exceeds 80% by volume, the viscosity of the composition increases and the moldability is impaired, and voids are generated in the silicone resin composition layer, so that the insulating property tends to decrease. Therefore, the content of the inorganic filler is set to 80% by volume or less. It is preferably 78% by volume or less, more preferably 76% by volume or less, still more preferably 74% by volume or less. Further, if the content is less than 60% by volume, it becomes difficult to sufficiently increase the thermal conductivity of the composition. Therefore, the content of the inorganic filler is set to 60% by volume or more. It is preferably 62% by volume or more, more preferably 64% by volume or more, and further preferably 66% by volume or more.
無機フィラーの熱伝導率は、１０Ｗ／（ｍ・Ｋ）以上であることが好ましく、２０Ｗ／（ｍ・Ｋ）以上であることがより好ましい。１０Ｗ／（ｍ・Ｋ）以上であることで良好な熱伝導性を付与することができる。なお、無機フィラーの熱伝導率は、ＩＳＯ８３０２とＪＩＳ Ａ １４１２−１に基づき、保護熱板法により２５℃における熱伝導率を測定して得られた値を採用する。 The thermal conductivity of the inorganic filler is preferably 10 W / (m · K) or more, and more preferably 20 W / (m · K) or more. When it is 10 W / (m · K) or more, good thermal conductivity can be imparted. As the thermal conductivity of the inorganic filler, a value obtained by measuring the thermal conductivity at 25 ° C. by the protective hot plate method based on ISO8302 and JIS A 1412-1 is adopted.
無機フィラーはその平均球形度が０．８〜１．０の球状無機フィラーを含有することが好ましく、０．８５〜１．０の球状無機フィラーを含有することがより好ましい。無機フィラーが平均球形度０．８〜１．０の球状無機フィラーを含有することで、シリコーン樹脂組成物層を形成する際のスラリーの流動性が良好となって、シリコーン樹脂組成物層と基材樹脂層との間でボイドが発生しづらくなり、ボイドに起因する絶縁性の低下を防ぐことができる。また、混合成型機器の摩耗が大きくなるのを防ぐことができる。本明細書における平均球形度は、フロー式粒子像分析装置を用いて測定することができる。 The inorganic filler preferably contains a spherical inorganic filler having an average sphericity of 0.8 to 1.0, and more preferably contains a spherical inorganic filler having an average sphericity of 0.8 to 1.0. When the inorganic filler contains a spherical inorganic filler having an average spherical degree of 0.8 to 1.0, the fluidity of the slurry when forming the silicone resin composition layer is improved, and the silicone resin composition layer and the base are used. Voids are less likely to be generated between the material and the resin layer, and deterioration of the insulating property due to the voids can be prevented. In addition, it is possible to prevent the wear of the mixing molding equipment from becoming large. The average sphericity in the present specification can be measured using a flow type particle image analyzer.
球状無機フィラーは、無機フィラー中に３０体積％以上含有することが好ましく、５０体積％以上含有することがより好ましい。 The spherical inorganic filler is preferably contained in the inorganic filler in an amount of 30% by volume or more, more preferably 50% by volume or more.
無機フィラーの平均粒子径は特に限定されないが７μｍ以上が好ましい。より好ましくは１０μｍ以上、さらに好ましくは１５μｍ以上である。上限については８０μｍ以下が好ましく、より好ましくは７０μｍ以下、さらに好ましくは６０μｍ以下である。平均粒子径の範囲が好ましい範囲に入るほど、熱伝導率と絶縁性とをさらに良好にすることができる。なお、本明細書における平均粒子径は、レーザー回折式粒度分布測定装置により測定できる。 The average particle size of the inorganic filler is not particularly limited, but is preferably 7 μm or more. It is more preferably 10 μm or more, still more preferably 15 μm or more. The upper limit is preferably 80 μm or less, more preferably 70 μm or less, and further preferably 60 μm or less. As the range of the average particle size falls within a preferable range, the thermal conductivity and the insulating property can be further improved. The average particle size in the present specification can be measured by a laser diffraction type particle size distribution measuring device.
無機フィラーとしては、アルミナ、二酸化チタン等の金属酸化物、窒化アルミニウム、窒化ホウ素、窒化珪素等の窒化物、炭化珪素、水酸化アルミニウム等が挙げられ、単独あるいは数種類を組み合わせて使用することができる。難燃性を考慮すると水酸化アルミニウムが好ましく、熱伝導性を考慮するとアルミナ、窒化ホウ素、窒化アルミニウムが好ましい。 Examples of the inorganic filler include metal oxides such as alumina and titanium dioxide, nitrides such as aluminum nitride, boron nitride and silicon nitride, silicon carbide and aluminum hydroxide, which can be used alone or in combination of several types. .. Aluminum hydroxide is preferable in consideration of flame retardancy, and alumina, boron nitride, and aluminum nitride are preferable in consideration of thermal conductivity.
無機フィラーがアルミナである場合、当該アルミナの粒度分布は、頻度粒度分布において、１５〜８０μｍの領域に極大ピークを有するとともに、粒径１．０〜１４μｍの領域及び粒径０．１〜０．９μｍの領域の少なくとも１つの領域に極大ピークを有することが好ましい（以下、１５〜８０μｍの領域に現れる極大ピークを「ピーク１」、１．０〜１４μｍの領域に現れる極大ピークを「ピーク２」、０．１〜０．９μｍの領域に現れる極大ピークを「ピーク３」ともいう）。これによって、アルミナをより高充填することが可能となり、接触点の増加により熱伝導性を更に高めることができる。また、高充填した際、同じ充填量であれば粒子同士が密に詰まるため、滑りが良くなり流動性を高く維持することができる。 When the inorganic filler is alumina, the particle size distribution of the alumina has a maximum peak in the region of 15 to 80 μm in the frequency particle size distribution, and the particle size is 1.0 to 14 μm and the particle size is 0.1 to 0. It is preferable to have a maximum peak in at least one region of 9 μm (hereinafter, the maximum peak appearing in the region of 15 to 80 μm is “peak 1”, and the maximum peak appearing in the region of 1.0 to 14 μm is “peak 2”. , The maximum peak that appears in the region of 0.1 to 0.9 μm is also referred to as “peak 3”). This makes it possible to fill the alumina at a higher level, and further increase the thermal conductivity by increasing the number of contact points. Further, when the particles are highly filled, the particles are densely packed with the same filling amount, so that the slipperiness is improved and the fluidity can be maintained high.
シリコーン樹脂組成物層を形成するための、上記シリコーン樹脂及び無機フィラーを含有するシリコーン樹脂組成物中には、公知の添加剤等の任意成分を任意の添加量で添加することができる。これにより、添加剤をも含有するシリコーン樹脂組成物層を形成することができる。添加剤としては例えばアルコキシシラン剤、シリコーンオイル、シランカップリング剤、粘度や粘性をコントロールするための各種添加物、その他、改質剤、老化防止剤、熱安定剤、着色剤などが挙げられる。
特に、アルコキシシラン剤、シリコーンオイル、シランカップリング剤を添加することで、ピール強度や絶縁性をより良好にすることができる。
上記の通り、添加剤を任意成分として含む場合や不純物が少量含まれても本発明の効果は害されないが、本発明の効果を得る観点からは、シリコーン樹脂と無機フィラーの含有量の合計が９０体積％以上であることが好ましく、より好ましくは９５％体積％以上、さらに好ましくは９７体積％以上である。An arbitrary component such as a known additive can be added in an arbitrary amount to the silicone resin composition containing the silicone resin and the inorganic filler for forming the silicone resin composition layer. This makes it possible to form a silicone resin composition layer that also contains additives. Examples of the additive include an alkoxysilane agent, a silicone oil, a silane coupling agent, various additives for controlling viscosity and viscosity, a modifier, an antiaging agent, a heat stabilizer, a colorant and the like.
In particular, by adding an alkoxysilane agent, a silicone oil, and a silane coupling agent, the peel strength and the insulating property can be further improved.
As described above, the effect of the present invention is not impaired when an additive is contained as an optional component or a small amount of impurities are contained, but from the viewpoint of obtaining the effect of the present invention, the total content of the silicone resin and the inorganic filler is It is preferably 90% by volume or more, more preferably 95% by volume or more, and further preferably 97% by volume or more.
（基材樹脂層）
基材樹脂層は、ガラス転移点が２００℃以上である樹脂を含む。ガラス転移点が２００℃以上であれば、十分な耐熱性が得られ、積層体の絶縁性や熱伝導性を良好に維持することができる。基材樹脂層は、塗膜から形成される層でも、フィルムから形成される層でもよい。(Base resin layer)
The base resin layer contains a resin having a glass transition point of 200 ° C. or higher. When the glass transition point is 200 ° C. or higher, sufficient heat resistance can be obtained, and the insulating property and thermal conductivity of the laminate can be maintained well. The base resin layer may be a layer formed from a coating film or a layer formed from a film.
基材樹脂層を構成する樹脂としては、ポリイミド、ポリアミドイミド、ポリアミド（特に芳香族ポリアミド）、ポリエーテルサルホン、ポリエーテルイミド、ポリエチレンナフタレート、ポリテトラフルオロエチレン（ＰＴＦＥ）又はテトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）等が挙げられ、なかでもポリイミドが好ましい。また、単独あるいは数種類を組み合わせて使用することができる。
基材樹脂層中の樹脂の含有量は特に限定されないが、下限については、７８体積％以上が好ましく、より好ましくは８０体積％以上、さらに好ましくは８２体積％以上である。上限については９２体積％以下が好ましく、より好ましくは９０体積％以下、さらに好ましくは８８体積％以下である。As the resin constituting the base resin layer, polyimide, polyamideimide, polyamide (particularly aromatic polyamide), polyether sulfone, polyetherimide, polyethylene naphthalate, polytetrafluoroethylene (PTFE) or tetrafluoroethylene per. Fluoroalkyl vinyl ether copolymer (PFA) and the like can be mentioned, and polyimide is preferable. In addition, it can be used alone or in combination of several types.
The content of the resin in the base resin layer is not particularly limited, but the lower limit is preferably 78% by volume or more, more preferably 80% by volume or more, and further preferably 82% by volume or more. The upper limit is preferably 92% by volume or less, more preferably 90% by volume or less, still more preferably 88% by volume or less.
基材樹脂層は無機フィラーを含有することが好ましい。基材樹脂層が無機フィラーを含有することで、絶縁性、熱伝導性、ピール強度等を向上させることができる。特に、ピール強度が上がるのは、無機フィラーにより基材樹脂層とシリコーン樹脂組成物層との界面に凹凸が形成され、アンカー効果が生じるためと推察される。
無機フィラーとしては、シリコーン樹脂組成物層に含有される無機フィラーと同様なものを使用することができる。
基材樹脂層中の無機フィラーの含有量は特に限定されないが、下限については８体積％以上が好ましく、より好ましくは１０体積％以上、さらに好ましくは１２体積％以上である。上限については２２体積％以下が好ましく、より好ましくは２０体積％以下、さらに好ましくは１８体積％以下である。
また、基材樹脂層中には、シリコーン樹脂組成物層と同様に添加剤が少量含まれてもよいし、不純物が少量含まれてもよい。なお、基材樹脂層中において、上記樹脂と無機フィラーの合計含有量は９０体積％以上が好ましく、より好ましくは９５体積％以上、さらに好ましくは９７体積％以上である。The base resin layer preferably contains an inorganic filler. By containing the inorganic filler in the base resin layer, the insulating property, thermal conductivity, peel strength and the like can be improved. In particular, it is presumed that the peel strength is increased because the inorganic filler forms irregularities at the interface between the base resin layer and the silicone resin composition layer, and an anchor effect is generated.
As the inorganic filler, the same one as the inorganic filler contained in the silicone resin composition layer can be used.
The content of the inorganic filler in the base resin layer is not particularly limited, but the lower limit is preferably 8% by volume or more, more preferably 10% by volume or more, still more preferably 12% by volume or more. The upper limit is preferably 22% by volume or less, more preferably 20% by volume or less, still more preferably 18% by volume or less.
Further, the base resin layer may contain a small amount of additives or a small amount of impurities as in the case of the silicone resin composition layer. The total content of the resin and the inorganic filler in the base resin layer is preferably 90% by volume or more, more preferably 95% by volume or more, and further preferably 97% by volume or more.
基材樹脂層となるフィルムとしては、公知のフィルム作製方法に準じて作製できる。また、市場に販売されている製品を入手して用いてもよい。 The film to be the base resin layer can be produced according to a known film production method. In addition, products sold on the market may be obtained and used.
（積層体の製造方法）
本実施形態に係る積層体は、例えば下記のようにして製造することができる。
まず、シリコーン樹脂と無機フィラーとを混合してシリコーン樹脂組成物を作製する。シリコーン樹脂と無機フィラーの混合方法は、特に限定されるのもではなく、少量の場合は手混合も可能であるが、万能混合機、プラネタリーミキサー、ハイブリッドミキサー、ヘンシェルミキサー、ニーダー、ボールミル、ミキシングロール等の一般的な混合機が用いられる。混合に際して、各成形方法に適する混合物とするために、水、トルエン、アルコール等の各種溶剤を添加してもよい。
また、必要に応じて添加される添加剤は、上記の混合時に添加することが好ましい。(Manufacturing method of laminated body)
The laminate according to the present embodiment can be produced, for example, as follows.
First, a silicone resin composition is prepared by mixing a silicone resin and an inorganic filler. The mixing method of the silicone resin and the inorganic filler is not particularly limited, and manual mixing is possible in a small amount, but a universal mixer, a planetary mixer, a hybrid mixer, a Henschel mixer, a kneader, a ball mill, and mixing. A general mixer such as a roll is used. At the time of mixing, various solvents such as water, toluene and alcohol may be added in order to obtain a mixture suitable for each molding method.
Moreover, it is preferable that the additive added as needed is added at the time of the above mixing.
次に、基材樹脂層となる、例えば基材シート上にシリコーン樹脂組成物と塗布する。
基材シートへの塗布方法としては、従来公知の方法、例えば、コーター法、ドクターブレード法、押出成形法、射出成形法、プレス成形法等を用いることができる。Next, the silicone resin composition is applied onto a base resin layer, for example, a base sheet.
As a method of applying to the base sheet, conventionally known methods such as a coater method, a doctor blade method, an extrusion molding method, an injection molding method, a press molding method and the like can be used.
その後、必要に応じて１１０〜１６０℃で熱処理を行って、シリコーン樹脂組成物層と、基材樹脂層とが積層されてなる積層体が得られる。当該積層体において、シリコーン樹脂組成物層と基材樹脂層との間のピール強度は、０．６Ｎ／２５ｍｍ以上であることが好ましい。 Then, if necessary, heat treatment is performed at 110 to 160 ° C. to obtain a laminated body in which the silicone resin composition layer and the base resin layer are laminated. In the laminate, the peel strength between the silicone resin composition layer and the base resin layer is preferably 0.6 N / 25 mm or more.
積層体を構成する基材樹脂層の厚みは、絶縁性、熱伝導性、加工性の観点から以下の範囲が好ましい。下限については０．０１０ｍｍ以上が好ましい。０．０１０ｍｍ以上とすることで、絶縁性をさらに改善できるとともに、加工性も改善できる。より好ましくは０．０１２ｍｍ以上、さらに好ましくは０．０１５ｍｍ以上である。上限については０．１００ｍｍ以下が好ましい。より好ましくは０．０７０ｍｍ以下、さらに好ましくは０．０５０ｍｍ以下である。
積層体を構成するシリコーン樹脂組成物層の厚みは、絶縁性、熱伝導性の観点から以下の範囲にあることが好ましい。下限については０．０８ｍｍ以上が好ましく、より好ましくは０．１０ｍｍ以上、さらに好ましくは０．１２ｍｍ以上である。上限については０．５０ｍｍ以下が好ましく、より好ましくは０．４０ｍｍ以下、さらに好ましくは０．３０ｍｍ以下である。
また、積層体全体の厚みは、特に限定されず、好ましい厚みは用途等により異なるが、下限については０．１０ｍｍ以上が好ましく、より好ましくは０．１２ｍｍ以上、さらに好ましくは０．１４ｍｍ以上である。上限については０．５５ｍｍ以下が好ましく、より好ましくは０．４５ｍｍ以下、さらに好ましくは０．３５ｍｍ以下である。
なお、本発明の積層体は、シリコーン樹脂組成物層と、シリコーン樹脂組成物層に隣接する基材樹脂層と、を有するものであればよく、これらの層以外の層を含む３層以上の積層体としてもよいし、シリコーン樹脂組成物層を複数有する３層以上の積層体としてもよいし、基材樹脂層を複数有する３層以上の積層体としてもよい。
自動車、携帯電子機器、産業用機器、及び家庭用電化製品等に用いられる電子部品に対し、絶縁性を維持するための電子部品用放熱部品またはその一部として好適に用いられる。特に好ましい用途として放熱シートが挙げられる。The thickness of the base resin layer constituting the laminate is preferably in the following range from the viewpoint of insulation, thermal conductivity, and processability. The lower limit is preferably 0.010 mm or more. By setting the thickness to 0.010 mm or more, the insulating property can be further improved and the workability can be improved. It is more preferably 0.012 mm or more, still more preferably 0.015 mm or more. The upper limit is preferably 0.100 mm or less. It is more preferably 0.070 mm or less, still more preferably 0.050 mm or less.
The thickness of the silicone resin composition layer constituting the laminate is preferably in the following range from the viewpoint of insulating property and thermal conductivity. The lower limit is preferably 0.08 mm or more, more preferably 0.10 mm or more, still more preferably 0.12 mm or more. The upper limit is preferably 0.50 mm or less, more preferably 0.40 mm or less, still more preferably 0.30 mm or less.
The thickness of the entire laminate is not particularly limited, and the preferable thickness varies depending on the application and the like, but the lower limit is preferably 0.10 mm or more, more preferably 0.12 mm or more, still more preferably 0.14 mm or more. .. The upper limit is preferably 0.55 mm or less, more preferably 0.45 mm or less, still more preferably 0.35 mm or less.
The laminate of the present invention may have a silicone resin composition layer and a base resin layer adjacent to the silicone resin composition layer, and may have three or more layers including layers other than these layers. It may be a laminate, a laminate having three or more layers having a plurality of silicone resin composition layers, or a laminate having three or more layers having a plurality of base resin layers.
It is suitably used as a heat-dissipating component for electronic components or a part thereof for maintaining insulation with respect to electronic components used in automobiles, portable electronic devices, industrial devices, household electric appliances, and the like. A particularly preferable application is a heat radiating sheet.
以下、実施例により本発明を具体的に説明するが、本発明をこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
（実施例１）
ポリオルガノシロキサンベースポリマー（東レ・ダウコーニング社製商品名「ＣＦ３１１０」）と架橋剤（東レ・ダウコーニング社製商品名「ＲＣ−４」）を重量比で１００：１となるよう混合して、シリコーン樹脂成分を得た。得られたシリコーン樹脂成分と、アルミナとを表１に示す体積％となるように攪拌機で１５時間混合し、アルミナ含有シリコーン樹脂組成物を調製した。使用したアルミナはいずれも熱伝導率が２０Ｗ／（ｍ・Ｋ）以上であった。(Example 1)
A polyorganosiloxane-based polymer (trade name "CF3110" manufactured by Toray Dow Corning) and a cross-linking agent (trade name "RC-4" manufactured by Toray Dow Corning) are mixed so as to have a weight ratio of 100: 1. A silicone resin component was obtained. The obtained silicone resin component and alumina were mixed with a stirrer for 15 hours so as to have a volume% shown in Table 1 to prepare an alumina-containing silicone resin composition. All of the alumina used had a thermal conductivity of 20 W / (m · K) or more.
シリコーン樹脂組成物を表１に示す基材樹脂層としてのポリイミドフィルム（東レ・デュポン社製、商品名Ｋａｐｔｏｎ １００Ｈ、厚さ０．０２５ｍｍ）上にコンマコーター機を用いてに塗工し、７５℃で５分乾燥させて積層体（全厚：０．２３ｍｍ）を作製した。 The silicone resin composition is coated on a polyimide film (manufactured by Toray DuPont, trade name Kapton 100H, thickness 0.025 mm) as a base resin layer shown in Table 1 using a comma coater machine, and at 75 ° C. The laminate was dried for 5 minutes to prepare a laminate (total thickness: 0.23 mm).
なお、使用したアルミナの平均球形度及び平均粒径は下記のようにして求めた。 The average sphericity and average particle size of the alumina used were determined as follows.
（平均球形度）
無機フィラー（アルミナ）の平均球形度は、フロー式粒子像分析装置（シスメックス社製、商品名「ＦＰＩＡ−３０００」）を用い、以下のようにして測定した。粒子像から粒子の投影面積（Ａ）と周囲長（ＰＭ）を測定した。周囲長（ＰＭ）に対応する真円の面積を（Ｂ）とすると、その粒子の球形度はＡ／Ｂとして表示できる。そこで試料粒子の周囲長（ＰＭ）と同一の周囲長を持つ真円を想定するとＰＭ＝２πｒ、Ｂ＝πｒ２であるから、Ｂ＝π×（ＰＭ／２π）２となり、個々の粒子の球形度は、Ａ／Ｂ＝Ａ×４π／（ＰＭ）２として算出できる。これを任意に選ばれた１００個の粒子について測定し、その平均値を２乗したものを平均球形度とした。なお測定溶液はサンプル０．１ｇに蒸留水２０ｍｌとプロピレングリコール１０ｍｌを加え、３分間超音波分散処理を行い調製した。(Average sphericity)
The average sphericity of the inorganic filler (alumina) was measured as follows using a flow-type particle image analyzer (manufactured by Sysmex Corporation, trade name "FPIA-3000"). The projected area (A) and the perimeter (PM) of the particles were measured from the particle image. Assuming that the area of a perfect circle corresponding to the perimeter (PM) is (B), the sphericity of the particle can be displayed as A / B. Therefore, assuming a perfect circle with the same perimeter as the perimeter of the sample particles (PM), PM = 2πr and B = πr 2 , so B = π × (PM / 2π) 2 , and the spherical shape of each particle. The degree can be calculated as A / B = A × 4π / (PM) 2. This was measured for 100 arbitrarily selected particles, and the square of the average value was taken as the average sphericity. The measurement solution was prepared by adding 20 ml of distilled water and 10 ml of propylene glycol to 0.1 g of the sample and performing ultrasonic dispersion treatment for 3 minutes.
（平均粒径）
無機フィラー（アルミナ）の平均粒径および粒度分布は、レーザー回折式粒度分布測定装置（島津製作所製「ＳＡＬＤ−２００」）を用いて測定した。ガラスビーカーに５０ｃｃの純水と無機フィラーを５ｇ添加して、スパチュラを用いて撹拌し、その後超音波洗浄機で１０分間、分散処理を行い、評価サンプル溶液を調製した。評価サンプル溶液を、スポイトを用いて装置のサンプラ部に一滴ずつ添加して、吸光度が測定可能になるまで安定するのを待って測定した。レーザー回折式粒度分布測定装置のセンサで検出した粒子による回折／散乱光の光強度分布のデータから粒度分布を計算した。平均粒子径は測定される粒子径の値に相対粒子量（差分％）を掛けて、相対粒子量の合計（１００％）で割って求めた。また、１５〜８０μｍの領域に現れる極大ピーク（ピーク１）、１．０〜１４μｍの領域に現れる極大ピーク（ピーク２）、０．１〜０．９μｍの領域に現れる極大ピークを（ピーク３）についても求めた。(Average particle size)
The average particle size and particle size distribution of the inorganic filler (alumina) were measured using a laser diffraction type particle size distribution measuring device (“SALD-200” manufactured by Shimadzu Corporation). 5 g of 50 cc of pure water and 5 g of an inorganic filler were added to a glass beaker, stirred with a spatula, and then dispersed with an ultrasonic cleaner for 10 minutes to prepare an evaluation sample solution. The evaluation sample solution was added drop by drop to the sampler part of the apparatus using a dropper, and the measurement was performed after the absorbance was stabilized until it became measurable. The particle size distribution was calculated from the data of the light intensity distribution of the diffracted / scattered light by the particles detected by the sensor of the laser diffraction type particle size distribution measuring device. The average particle size was obtained by multiplying the measured particle size value by the relative particle amount (difference%) and dividing by the total relative particle amount (100%). Further, the maximum peak (peak 1) appearing in the region of 15 to 80 μm, the maximum peak (peak 2) appearing in the region of 1.0 to 14 μm, and the maximum peak appearing in the region of 0.1 to 0.9 μm (peak 3). I also asked for.
（実施例２、及び比較例１、２）
アルミナの割合を表１に示した割合とした以外は実施例１と同様にして、積層体を作製した。
（比較例３）
基材樹脂層としてのポリイミドフィルムを、ユニチカ社製ポリエチレンテレフタレートフィルム「商品名Ｓ２５」（厚さ：０．０２６ｍｍ）とした以外は実施例１と同様にして、積層体を作製した。(Example 2 and Comparative Examples 1 and 2)
A laminate was prepared in the same manner as in Example 1 except that the proportion of alumina was set to the proportion shown in Table 1.
(Comparative Example 3)
A laminate was produced in the same manner as in Example 1 except that the polyimide film as the base resin layer was a polyethylene terephthalate film "trade name S25" (thickness: 0.026 mm) manufactured by Unitika Ltd.
（実施例３〜４）
基材樹脂層としてのポリイミドフィルムを、表２に示すアルミナ含有ポリイミドフィルム（実施例３は東レ・デュポン社製の「商品名１００ＭＴ」（厚み０．０２８ｍｍ）、実施例４は東レ・デュポン社製の「商品名１００ＭＴ」（厚み０．０３１ｍｍ））とした以外は実施例１と同様にして、積層体を作製した。
（実施例５〜６）
基材樹脂層としてのポリイミドフィルムを、表２に示す窒化ホウ素含有ポリイミドフィルム（実施例５は東レ・デュポン社製の「商品名１００ＭＴ＋」（厚み０．０２８ｍｍ）、実施例６は東レ・デュポン社製の「商品名」（厚み０．０３２ｍｍ））とした以外は実施例１と同様にして、積層体を作製した。(Examples 3 to 4)
The polyimide film as the base resin layer is an alumina-containing polyimide film shown in Table 2 (Example 3 is "trade name 100MT" (thickness 0.028 mm) manufactured by Toray DuPont, and Example 4 is manufactured by Toray DuPont. A laminate was produced in the same manner as in Example 1 except that the product name was “100 MT” (thickness 0.031 mm)).
(Examples 5 to 6)
The polyimide film as the base resin layer is a boron nitride-containing polyimide film shown in Table 2 (Example 5 is "trade name 100MT +" (thickness 0.028 mm) manufactured by Toray DuPont, and Example 6 is Toray DuPont. A laminate was produced in the same manner as in Example 1 except that the product had a "trade name" (thickness 0.032 mm)).
（評価）
各例で作製した積層体を下記の評価項目（１）〜（５）によって評価した。結果を表１に示す。(evaluation)
The laminate prepared in each example was evaluated according to the following evaluation items (1) to (5). The results are shown in Table 1.
（１）絶縁破壊電圧
ＪＩＳ Ｃ２１１０に記載の方法に準拠し、各例の積層体の絶縁破壊電圧を、短時間破壊試験（室温：２３℃）にて評価した。(1) Dielectric breakdown voltage According to the method described in JIS C2110, the dielectric breakdown voltage of the laminate of each example was evaluated by a short-time breakdown test (room temperature: 23 ° C.).
（２）熱伝導率
熱伝導率（Ｈ；単位Ｗ／（ｍ・Ｋ））は、積層体の厚み方向に対して評価を行なった。熱拡散率（Ａ；単位ｍ２／ｓｅｃ）と密度（Ｂ；単位ｋｇ／ｍ３）、比熱容量（Ｃ；単位Ｊ／（ｋｇ・Ｋ））から、Ｈ＝Ａ×Ｂ×Ｃとして、算出した。
熱拡散率は、積層体を幅１０ｍｍ×長さ１０ｍｍに加工し、測定用レーザー光の反射防止のため、積層体の両面にカーボンブラックを塗布した後、レーザーフラッシュ法により求めた。測定装置はキセノンフラッシュアナライザ（ＮＥＴＺＳＣＨ社製商品名「ＬＦＡ４４７ＮａｎｏＦｌａｓｈ」）を用いた。
密度はアルキメデス法を用いて求めた。
比熱容量はＪＩＳ Ｋ ７１２３：１９８７に記載の方法に準拠して求めた。(2) Thermal conductivity The thermal conductivity (H; unit W / (m · K)) was evaluated in the thickness direction of the laminated body. Calculated as H = A × B × C from the thermal diffusivity (A; unit m 2 / sec), density (B; unit kg / m 3 ), and specific heat capacity (C; unit J / (kg · K)). bottom.
The thermal diffusivity was determined by processing a laminate to a width of 10 mm and a length of 10 mm, applying carbon black to both sides of the laminate to prevent reflection of laser light for measurement, and then using a laser flash method. A xenon flash analyzer (trade name “LFA447NanoFlash” manufactured by NETZSCH) was used as the measuring device.
The density was determined using the Archimedes method.
The specific heat capacity was determined according to the method described in JIS K 7123: 1987.
（３）ピール強度
島津製作所社製精密万能試験機「ＡＵＴＯＧＲＡＰＨ ＡＧ−２０００Ｄ」を使用して、２３℃の環境下、引張速度２００ｍｍ／ｍｉｎで、ＪＩＳ Ｋ ６８５４−２に従い、１８０度方向の剥離を行って、シリコーン樹脂組成物層と基材樹脂層との間のピール強度を求めた。(3) Peel strength Using the precision universal testing machine "AUTOGRAPH AG-2000D" manufactured by Shimadzu Corporation, peeling in the 180 degree direction in accordance with JIS K 6854-2 at a tensile speed of 200 mm / min in an environment of 23 ° C. The peel strength between the silicone resin composition layer and the base resin layer was determined.
表１、２に記載の通り、条件を揃えた特定の積層体において、シリコーン樹脂組成物中の無機フィラーの含有量が６０〜８０体積％の範囲内にあるか否かで、絶縁性が改善することが確認された。
なお、シリコーン樹脂組成物中の無機フィラーの平均球形度が０．８〜１．０の範囲にない場合であっても、本発明範囲内にあれば、上記平均球形度が０．８〜１．０の範囲外で本発明範囲外のものと比較して、絶縁性等の特性が改善された。また、シリコーン樹脂組成物中の無機フィラーがアルミナ以外であっても、本発明範囲内にあれば、上記無機フィラーがアルミナ以外で本発明範囲外のものと比較して、絶縁性等の特性が改善された。また、シリコーン樹脂組成物中の無機フィラーがアルミナであり、下記条件を満たさない場合であっても、本発明範囲内にあれば、上記無機フィラーがアルミナであり、下記条件を満たさず本発明範囲外のものと比較して、絶縁性等の特性が改善された。
（条件）アルミナの頻度粒度分布において粒径１５〜８０μｍの領域と、粒径１．０〜１４μｍの領域及び粒径０．１〜０．９μｍの領域の少なくとも１つの領域と、に極大ピークがある。As shown in Tables 1 and 2, the insulating property is improved depending on whether or not the content of the inorganic filler in the silicone resin composition is in the range of 60 to 80% by volume in the specific laminate under the same conditions. It was confirmed that
Even if the average sphericity of the inorganic filler in the silicone resin composition is not in the range of 0.8 to 1.0, if it is within the range of the present invention, the average sphericity is 0.8 to 1. Properties such as insulation were improved outside the range of .0 as compared with those outside the range of the present invention. Further, even if the inorganic filler in the silicone resin composition is other than alumina, if it is within the scope of the present invention, the inorganic filler is other than alumina and has characteristics such as insulating properties as compared with those outside the scope of the present invention. Improved. Further, even when the inorganic filler in the silicone resin composition is alumina and does not satisfy the following conditions, if the inorganic filler is within the scope of the present invention, the inorganic filler is alumina and does not satisfy the following conditions and is within the scope of the present invention. Compared with the outside, properties such as insulation were improved.
(Conditions) In the frequency particle size distribution of alumina, a maximum peak is found in a region having a particle size of 15 to 80 μm, a region having a particle size of 1.0 to 14 μm, and at least one region having a particle size of 0.1 to 0.9 μm. be.
本発明の積層体は、自動車、携帯電子機器、産業用機器、及び家庭用電化製品等に用いられる電子部品に対し、絶縁性を維持するためのシート材等として好適に用いられる。
The laminate of the present invention is suitably used as a sheet material or the like for maintaining insulation with respect to electronic parts used in automobiles, portable electronic devices, industrial devices, household electric appliances and the like.
Claims (5)
前記シリコーン樹脂組成物層中に前記無機フィラーを６０〜８０体積％含有する、積層体。A silicone resin composition layer obtained by curing a silicone resin composition containing a silicone resin and an inorganic filler, and a base resin layer containing a resin adjacent to the silicone resin composition layer and having a glass transition point of 200 ° C. or higher. And have
A laminate containing 60 to 80% by volume of the inorganic filler in the silicone resin composition layer.
Claim that there is a maximum peak in a region having a particle size of 15 to 80 μm, a region having a particle size of 1.0 to 14 μm, and at least one region having a particle size of 0.1 to 0.9 μm in the frequency particle size distribution of alumina. Item 4. The laminate according to item 4.
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