JP6831435B2 - Composite member - Google Patents
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- JP6831435B2 JP6831435B2 JP2019194664A JP2019194664A JP6831435B2 JP 6831435 B2 JP6831435 B2 JP 6831435B2 JP 2019194664 A JP2019194664 A JP 2019194664A JP 2019194664 A JP2019194664 A JP 2019194664A JP 6831435 B2 JP6831435 B2 JP 6831435B2
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- rubber hardness
- carbon powder
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- 239000002131 composite material Substances 0.000 title claims description 32
- 239000000853 adhesive Substances 0.000 claims description 73
- 230000001070 adhesive effect Effects 0.000 claims description 73
- 239000012790 adhesive layer Substances 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 229920002050 silicone resin Polymers 0.000 claims description 31
- 239000000919 ceramic Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 230000004580 weight loss Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 7
- 230000002292 Radical scavenging effect Effects 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000002411 thermogravimetry Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000013005 condensation curing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 229910021485 fumed silica 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 paste-like Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
- Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Description
本開示は複合部材及び接着剤組成物に関する。 The present disclosure relates to composite members and adhesive compositions.
従来、静電チャック等の半導体製造用部品が知られている。静電チャックは、半導体ウェハを固定する機能を有する（特許文献１、２参照）。静電チャックは、セラミック基板と、金属基板と、それらを接着する接着層と、を備える。接着層として、シリコーン樹脂を含むものが知られている。 Conventionally, semiconductor manufacturing parts such as electrostatic chucks are known. The electrostatic chuck has a function of fixing a semiconductor wafer (see Patent Documents 1 and 2). The electrostatic chuck includes a ceramic substrate, a metal substrate, and an adhesive layer for adhering them. As the adhesive layer, one containing a silicone resin is known.
静電チャックが備える接着層は、使用時に高温になることがある。シリコーン樹脂は、長時間高温に曝されると、熱劣化することが知られている。中でも硬化劣化は、酸素起因のラジカルにより次第に酸化され硬くなっていく。シリコーン樹脂が硬化劣化すると、接着層自体も硬化劣化する。 The adhesive layer provided by the electrostatic chuck may become hot during use. Silicone resins are known to thermally deteriorate when exposed to high temperatures for long periods of time. Above all, hardening deterioration is gradually oxidized by radicals caused by oxygen and becomes hard. When the silicone resin is cured and deteriorated, the adhesive layer itself is also cured and deteriorated.
シリコーン樹脂の硬化劣化を抑制するため、ラジカル捕捉能を有する物質を接着層に含有させることが考えられる。しかしながら、この場合、ラジカル捕捉能を有する物質が水分等を放出し、気泡を生成することがある。気泡が生成すると、接着層と、セラミック基板又は金属基板との界面に、接着されていない箇所が生じてしまう。その結果、静電チャックに固定された半導体ウェハの表面温度が不均一になってしまう。 In order to suppress the curing deterioration of the silicone resin, it is conceivable to include a substance having a radical scavenging ability in the adhesive layer. However, in this case, a substance having a radical scavenging ability may release water or the like to generate bubbles. When air bubbles are generated, a non-adhesive portion is formed at the interface between the adhesive layer and the ceramic substrate or the metal substrate. As a result, the surface temperature of the semiconductor wafer fixed to the electrostatic chuck becomes non-uniform.
本開示の一局面は、接着層の硬化劣化を抑制でき、接着層における気泡の発生を抑制できる複合部材及び接着剤組成物を提供することを目的とする。 One aspect of the present disclosure is to provide a composite member and an adhesive composition capable of suppressing curing deterioration of the adhesive layer and suppressing generation of air bubbles in the adhesive layer.
本開示の一態様は、少なくとも一部の表面がセラミックから成る第１の部材と、少なくとも一部の表面が金属から成る第２の部材と、前記第１の部材における前記セラミックから成る表面と、前記第２の部材における前記金属から成る表面とを接着する接着層と、を備える複合部材であって、前記接着層は、シリコーン樹脂と、炭素粉末と、を含み、前記接着層は、２５０℃で１６５時間加熱したときに気泡を発生せず、前記接着層の初期のゴム硬度を（ａ）とし、前記接着層を２５０℃で１０００時間加熱した後の前記接着層のゴム硬度を（ｂ）とした場合、（ｂ）／（ａ）が２．２以下であり、前記ゴム硬度（ａ）が９〜２４であり、前記ゴム硬度（ｂ）が２０〜４３であり、半導体製造用部品の一部又は全部を構成する複合部材である。本開示の一態様である複合部材は、接着層の硬化劣化を抑制でき、接着層における気泡の発生を抑制できる。 One aspect of the present disclosure includes a first member whose surface is at least partially made of rubber, a second member whose surface is at least partially made of metal, and a surface of the first member made of ceramic. A composite member comprising an adhesive layer for adhering a surface made of the metal in the second member, the adhesive layer containing a silicone resin and a carbon powder, and the adhesive layer having a temperature of 250 ° C. The initial rubber hardness of the adhesive layer was set to (a), and the rubber hardness of the adhesive layer after heating the adhesive layer at 250 ° C. for 1000 hours was set to (b) without generating bubbles when heated in 165 hours. , (B) / (a) is 2.2 or less, the rubber hardness (a) is 9 to 24, the rubber hardness (b) is 20 to 43, and the parts for semiconductor manufacturing have. It is a composite member that constitutes a part or all . The composite member according to one aspect of the present disclosure can suppress the hardening deterioration of the adhesive layer and can suppress the generation of air bubbles in the adhesive layer.
本開示の実施形態を説明する。
１．複合部材
本開示の複合部材は、第１の部材、第２の部材、及び接着層を備える。第１の部材の少なくとも一部の表面は、セラミックから成る。第１の部材は、例えば、その全体がセラミックから成るものであってもよいし、一部がセラミックから成り、他の部分は他の材質から成るものであってもよい。第１の部材として、例えば、セラミック基板等が挙げられる。
An embodiment of the present disclosure will be described.
1. 1. Composite Member The composite member of the present disclosure includes a first member, a second member, and an adhesive layer. The surface of at least a part of the first member is made of ceramic. The first member may be, for example, entirely made of ceramic, partly made of ceramic, and other parts made of other materials. Examples of the first member include a ceramic substrate and the like.
セラミックとしては、公知のものを適宜選択して用いることができる。セラミックの材料としては、例えば、酸化アルミニウム（アルミナ）、窒化アルミニウム、酸化イットリウム（イットリア）等が挙げられる。セラミックにはガラス成分も含まれる。 As the ceramic, known ceramics can be appropriately selected and used. Examples of the ceramic material include aluminum oxide (alumina), aluminum nitride, yttrium oxide (yttria), and the like. Ceramic also contains a glass component.
第２の部材の少なくとも一部の表面は、金属から成る。第２の部材は、例えば、その全体が金属から成るものであってもよいし、一部が金属から成り、他の部分は他の材質から成るものであってもよい。第２の部材として、例えば、金属基板等が挙げられる。金属としては、例えば、アルミニウム、鉄、金、銀、銅、ステンレス、チタン等が挙げられる。また、金属は、複数の元素の合金であってもよい。 The surface of at least a portion of the second member is made of metal. The second member may be, for example, entirely made of metal, partly made of metal, and other parts made of other materials. Examples of the second member include a metal substrate and the like. Examples of the metal include aluminum, iron, gold, silver, copper, stainless steel, titanium and the like. Further, the metal may be an alloy of a plurality of elements.
接着層は、第１の部材におけるセラミックから成る表面と、第２の部材における金属から成る表面とを接着する層である。接着層は、シリコーン樹脂と、炭素粉末と、を含む。
シリコーン樹脂としては、例えば、付加硬化型のシリコーン樹脂と、縮合硬化型のシリコーン樹脂とが挙げられる。付加硬化型のシリコーン樹脂を用いる場合、接着層における気泡の生成を一層抑制できる。
The adhesive layer is a layer that adheres the surface made of ceramic in the first member and the surface made of metal in the second member. The adhesive layer contains a silicone resin and carbon powder.
Examples of the silicone resin include an addition-curing type silicone resin and a condensation-curing type silicone resin. When the addition-curable silicone resin is used, the generation of bubbles in the adhesive layer can be further suppressed.
付加硬化型のシリコーン樹脂は、少なくとも、（Ａ）一分子中に少なくとも２個のけい素原子結合アルケニル基を有するオルガノポリシロキサン、（Ｂ）一分子中に少なくとも２個のけい素原子結合水素原子を有するオルガノポリシロキサン、及び（Ｃ）ヒドロシリル化反応用触媒を含む。 The addition-curable silicone resin is (A) an organopolysiloxane having at least two silicate atom-bonded alkenyl groups in one molecule, and (B) at least two silicate atom-bonded hydrogen atoms in one molecule. Includes an organopolysiloxane having (C) a catalyst for a hydrosilylation reaction.
（Ｂ）成分の配合量は、前記（Ａ）成分を架橋させるに十分な量であり、例えば、前記（Ａ）成分中のけい素原子結合アルケニル基１モルに対して、（Ｂ）成分中のけい素原子結合水素原子が０.５〜１０モルの範囲内となる量であることが好ましく、特に、これが
０．８〜１．２モルの範囲内となる量であることが好ましい。
The blending amount of the component (B) is an amount sufficient to crosslink the component (A). For example, in the component (B) with respect to 1 mol of the alkenyl group having a hydrogen atom bond in the component (A). The amount of the silicon atom-bonded hydrogen atom is preferably in the range of 0.5 to 10 mol, and particularly preferably in the range of 0.8 to 1.2 mol.
（Ｃ）成分は、アルケニル基とけい素原子結合水素原子とのヒドロシリル化反応を促進
する成分である。（Ｃ）成分の配合量は、シリコーン樹脂の硬化を促進するに十分な量であり、例えば、（Ｃ）成分が白金系触媒である場合には、シリコーン樹脂における白金金属の濃度が、重量単位で、０.０１〜１０００ｐｐｍの範囲内となる量であることが好ま
しく、０.１〜５００ｐｐｍの範囲内となる量であることが一層好ましい。
The component (C) is a component that promotes the hydrosilylation reaction between the alkenyl group and the hydrogen atom bonded to the chamo atom. The blending amount of the component (C) is an amount sufficient to accelerate the curing of the silicone resin. For example, when the component (C) is a platinum-based catalyst, the concentration of the platinum metal in the silicone resin is a weight unit. The amount is preferably in the range of 0.01 to 1000 ppm, and more preferably in the range of 0.1 to 500 ppm.
炭素粉末としては、例えば、カーボンブラック、カーボンファイバー、カーボンナノチューブ、及びグラフェン等が挙げられる。炭素粉末は、これらから選択される２種以上の混合物であってもよい。炭素粉末は、シリコーン樹脂を劣化させるラジカルを捕捉し、シリコーン樹脂の硬化劣化を抑制する作用を奏する。 Examples of the carbon powder include carbon black, carbon fiber, carbon nanotubes, graphene and the like. The carbon powder may be a mixture of two or more selected from these. The carbon powder has the effect of capturing radicals that deteriorate the silicone resin and suppressing the curing deterioration of the silicone resin.
炭素粉末の添加量は、シリコーン樹脂１００重量部に対し、１重量部以上であることが好ましい。この場合、シリコーン樹脂の硬化劣化を一層抑制できる。炭素粉末の添加量は、シリコーン樹脂１００重量部に対し、４０重量部以下であることが好ましい。この場合、炭素粉末の分散性の点で優れる。 The amount of carbon powder added is preferably 1 part by weight or more with respect to 100 parts by weight of the silicone resin. In this case, the curing deterioration of the silicone resin can be further suppressed. The amount of carbon powder added is preferably 40 parts by weight or less with respect to 100 parts by weight of the silicone resin. In this case, the dispersibility of the carbon powder is excellent.
熱重量測定における炭素粉末の重量減少量（以下では単に重量減少量と呼ぶこともある）は、昇温速度１０℃／ｍｉｎで室温から２５０℃まで昇温させた場合に１重量％未満であることが好ましい。炭素粉末の重量減少量が１重量％未満である場合、接着層において生じる気泡を抑制できる。熱重量測定の方法は以下のとおりである。粉末の試料をアルミパンに入れる。次に、窒素雰囲気下、又は大気雰囲気下にて、昇温速度１０℃／ｍｉｎで室温から６００℃まで昇温する。このとき、サンプル間隔１秒で重量変化を繰り返し測定する。室温における重量から、２５０℃における重量を差し引いた値を、重量減少量とする。 The amount of weight loss of carbon powder in thermogravimetric analysis (hereinafter, also referred to simply as the amount of weight loss) is less than 1% by weight when the temperature is raised from room temperature to 250 ° C. at a heating rate of 10 ° C./min. Is preferable. When the weight loss of the carbon powder is less than 1% by weight, air bubbles generated in the adhesive layer can be suppressed. The method of thermogravimetric measurement is as follows. Place the powder sample in an aluminum pan. Next, the temperature is raised from room temperature to 600 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere or an atmospheric atmosphere. At this time, the weight change is repeatedly measured at a sample interval of 1 second. The value obtained by subtracting the weight at 250 ° C. from the weight at room temperature is defined as the weight loss amount.
なお、炭素粉末の重量減少は、炭素粉末の表面に吸着されていた水分や、カルボキシル基等の官能基が脱離して生じると推測される。
炭素粉末のＢＥＴ比表面積は、９５ｍｍ２／ｇ以下であることが好ましく、９０ｍｍ２／ｇ以下であることが一層好ましい。ＢＥＴ比表面積が９５ｍｍ２／ｇ以下である場合、炭素粉末に含まれる水分の量が少ない。そのため、炭素粉末から水分が揮発して気泡が生じることを抑制できる。ＢＥＴ比表面積が９０ｍｍ２／ｇ以下である場合、炭素粉末から水分が揮発して気泡が生じることを一層抑制できる。
It is presumed that the weight loss of the carbon powder is caused by the desorption of water adsorbed on the surface of the carbon powder and functional groups such as a carboxyl group.
The BET specific surface area of the carbon powder is preferably 95 mm 2 / g or less, and more preferably 90 mm 2 / g or less. When the BET specific surface area is 95 mm 2 / g or less, the amount of water contained in the carbon powder is small. Therefore, it is possible to suppress the volatilization of water from the carbon powder to generate bubbles. When the BET specific surface area is 90 mm 2 / g or less, it is possible to further suppress the volatilization of water from the carbon powder to generate bubbles.
ＢＥＴ比表面積の測定方法は以下のとおりである。粉末の試料を１００℃で６０分間脱気する。次に、ＢＥＴ流動法（１点法）により測定を行う。測定時のガスは、ＨｅとＮ２との混合ガスであって、それらの体積比は、Ｈｅ：Ｎ２＝７：３である。３回の測定値の平均値をＢＥＴ比表面積とする。 The method for measuring the BET specific surface area is as follows. The powder sample is degassed at 100 ° C. for 60 minutes. Next, the measurement is performed by the BET flow method (one-point method). The gas at the time of measurement is a mixed gas of He and N 2, and their volume ratio is He: N 2 = 7: 3. The average value of the three measured values is defined as the BET specific surface area.
接着層は、シリコーン樹脂、炭素粉末に加えて、他の成分を含んでいてもよい。他の成分として、例えば、アルミナ、シリカ（例えば、湿式シリカ、乾式シリカ、ヒュームドシリカ等）、ジルコニア、窒化アルミニウム、窒化けい素、炭化けい素等のセラミック粉末、アルミ、銀、銅等の金属粉末、硫酸バリウム、炭酸カルシウム等が挙げられる。これらの成分は、熱伝導率付与、粘度調整、補強等の作用を奏する。 The adhesive layer may contain other components in addition to the silicone resin and carbon powder. Other components include, for example, alumina, silica (eg, wet silica, dry silica, fumed silica, etc.), zirconia, aluminum nitride, silicon nitride, ceramic powders such as calcium carbonate, metals such as aluminum, silver, and copper. Examples include powder, barium sulfate, calcium carbonate and the like. These components exert actions such as imparting thermal conductivity, adjusting viscosity, and reinforcing.
接着層は、２５０℃で１６５時間加熱したときに気泡が生じないものであることが好ましい。気泡が生じない場合、接着層と、第１の部材又は第２の部材との界面に、接着されていない箇所が一層生じにくい。 The adhesive layer preferably has no bubbles when heated at 250 ° C. for 165 hours. When no air bubbles are generated, it is more unlikely that a non-adhesive portion is generated at the interface between the adhesive layer and the first member or the second member.
接着層の初期のゴム硬度を（ａ）とし、接着層を２５０℃で１０００時間加熱した後のゴム硬度を（ｂ）とした場合、（ｂ）／（ａ）が２．２以下であることが好ましい。（ｂ）／（ａ）が２．２以下である場合、接着層が一層柔らかいので、第１の部材と第２の部
材との熱膨張率の差に起因して生じる、第１の部材と第２の部材との端部付近での接着層の剥がれを一層抑制できる。
When the initial rubber hardness of the adhesive layer is (a) and the rubber hardness after heating the adhesive layer at 250 ° C. for 1000 hours is (b), (b) / (a) is 2.2 or less. Is preferable. When (b) / (a) is 2.2 or less, the adhesive layer is softer, so that the first member and the first member are caused by the difference in the coefficient of thermal expansion between the first member and the second member. It is possible to further suppress the peeling of the adhesive layer near the end portion with the second member.
ゴム硬度の測定方法は以下のとおりである。ＪＩＳ Ａ ＴＹＰＥのゴム硬度計を用い、接着層のゴム硬度を測定する。ゴム硬度は、内径１８ｍｍ、長さ１７ｍｍの硬化体の上下面を測定し、平均値をゴム硬度とする。 The method for measuring the rubber hardness is as follows. The rubber hardness of the adhesive layer is measured using a JIS A TYPE rubber hardness tester. The rubber hardness is measured by measuring the upper and lower surfaces of a cured product having an inner diameter of 18 mm and a length of 17 mm, and the average value is taken as the rubber hardness.
第１の部材と接着層との接着面を第１の接着面とする。第２の部材と接着層との接着面を第２の接着面とする。第１の接着面、及び／又は、第２の接着面は、平面であることが好ましい。そして、第１の接着面が平面である場合、第１の接着面の面積は、直径１００ｍｍの円の面積以上であることが好ましい。また、第２の接着面が平面である場合、第２の接着面の面積は、直径１００ｍｍの円の面積以上であることが好ましい。また、第１の接着面及び第２の接着面がそれぞれ平面である場合、第１の接着面及び第２の接着面の面積は、それぞれ、直径１００ｍｍの円の面積以上であることが好ましい。 The adhesive surface between the first member and the adhesive layer is designated as the first adhesive surface. The adhesive surface between the second member and the adhesive layer is designated as the second adhesive surface. The first adhesive surface and / or the second adhesive surface is preferably flat. When the first adhesive surface is flat, the area of the first adhesive surface is preferably equal to or larger than the area of a circle having a diameter of 100 mm. When the second adhesive surface is flat, the area of the second adhesive surface is preferably equal to or larger than the area of a circle having a diameter of 100 mm. When the first adhesive surface and the second adhesive surface are flat surfaces, the areas of the first adhesive surface and the second adhesive surface are preferably equal to or larger than the area of a circle having a diameter of 100 mm, respectively.
第１の接着面、及び／又は、第２の接着面が上記のものである場合、第１の部材と第２の部材との熱膨張率の差に起因して生じる、第１の部材と第２の部材との端部付近での接着層の剥がれを一層抑制できる。 When the first adhesive surface and / or the second adhesive surface is the above, the first member and / or the first member caused by the difference in the coefficient of thermal expansion between the first member and the second member. It is possible to further suppress the peeling of the adhesive layer near the end portion with the second member.
また、第１の接着面、及び／又は、第２の接着面の面積が、直径１００ｍｍの円の面積以上である場合は、それ未満である場合よりも、第１の部材と第２の部材との間の熱伝導が、面内全体で一層均一になる。 Further, when the area of the first adhesive surface and / or the second adhesive surface is equal to or larger than the area of a circle having a diameter of 100 mm, the first member and the second member are more than those having less than that. The heat conduction between and is more uniform throughout the plane.
複合部材は、例えば、半導体製造用部品の一部又は全部を構成する。半導体製造用部品としては、例えば、シャワーヘッド、静電チャック、ＣＶＤヒーター、真空チャック等が挙げられる。 The composite member constitutes, for example, a part or all of a semiconductor manufacturing component. Examples of semiconductor manufacturing parts include shower heads, electrostatic chucks, CVD heaters, vacuum chucks, and the like.
複合部材は、例えば、以下の方法で製造できる。第１の部材の表面に、後述する接着剤組成物を塗布し、その塗布面に第２の部材を貼り合わせる。また、第２の部材の表面に接着剤組成物を塗布し、その塗布面に第１の部材を貼り合わせてもよい。また、第１の部材の表面と、第２の部材の表面とにそれぞれ接着剤組成物を塗布し、両者の塗布面同士を貼り合わせてもよい。これらの製造方法の場合、塗布した接着剤組成物が硬化して接着層を形成する。 The composite member can be manufactured, for example, by the following method. An adhesive composition described later is applied to the surface of the first member, and the second member is attached to the coated surface. Further, the adhesive composition may be applied to the surface of the second member, and the first member may be attached to the coated surface. Further, the adhesive composition may be applied to the surface of the first member and the surface of the second member, respectively, and the coated surfaces of both may be bonded to each other. In the case of these manufacturing methods, the applied adhesive composition is cured to form an adhesive layer.
また、複合部材は、例えば、以下の方法で製造してもよい。上述した接着層と同様の組成を有する接着シートを作成する。接着シートは流動性を持っていてもよいし、固形であってもよい。第１の部材と第２の部材との間に接着シートを配置する。第１の部材と第２の部材とを、それぞれ、接着シートの側に押し付ける。この製造方法の場合、接着シートが接着層を形成する。 Further, the composite member may be manufactured by, for example, the following method. An adhesive sheet having the same composition as the above-mentioned adhesive layer is prepared. The adhesive sheet may be fluid or solid. An adhesive sheet is placed between the first member and the second member. The first member and the second member are pressed against the adhesive sheet, respectively. In the case of this manufacturing method, the adhesive sheet forms an adhesive layer.
例えば、図１に示すように、複合部材１は、第１の部材３と、第２の部材５と、接着層７と、を備える。例えば、複合部材１が静電チャックである場合、第１の部材３はセラミック基板であり、第２の部材５は、金属基板である。
For example, as shown in FIG. 1, the composite member 1 includes a first member 3, a second member 5, and an
２．接着剤組成物
本開示の接着剤組成物は、上述した接着層と同様の組成を有し、シリコーン樹脂と、炭素粉末と、を含む。シリコーン樹脂、及び炭素粉末の種類、物性、添加量等は、上述した接着層におけるシリコーン樹脂、及び炭素粉末と同様である。接着剤組成物は、シリコーン樹脂、及び炭素粉末以外の成分を含んでいてもよい。
2. 2. Adhesive Composition The adhesive composition of the present disclosure has a composition similar to that of the above-mentioned adhesive layer, and includes a silicone resin and a carbon powder. The type, physical properties, addition amount, etc. of the silicone resin and carbon powder are the same as those of the silicone resin and carbon powder in the adhesive layer described above. The adhesive composition may contain components other than the silicone resin and the carbon powder.
本開示の接着剤組成物は、２５０℃で１６５時間加熱したときに気泡が生じないものであることが好ましい。気泡が生じない場合、接着剤組成物を用いて形成された接着層と、第１の部材又は第２の部材との界面に、接着されていない箇所が一層生じにくい。 The adhesive composition of the present disclosure preferably does not generate bubbles when heated at 250 ° C. for 165 hours. When no bubbles are generated, it is more unlikely that a non-adhesive portion is formed at the interface between the adhesive layer formed by using the adhesive composition and the first member or the second member.
接着剤組成物の初期のゴム硬度を（ａ）とし、接着剤組成物を２５０℃で１０００時間加熱した後のゴム硬度を（ｂ）とした場合、（ｂ）／（ａ）が２．２以下であることが好ましい。（ｂ）／（ａ）が２．２以下である場合、接着剤組成物が一層柔らかいので、接着剤組成部が接着する２つの部材間の熱膨張率の差に起因して生じる、接着剤組成物の剥がれを一層抑制できる。 When the initial rubber hardness of the adhesive composition is (a) and the rubber hardness of the adhesive composition after heating at 250 ° C. for 1000 hours is (b), (b) / (a) is 2.2. The following is preferable. When (b) / (a) is 2.2 or less, the adhesive composition is softer, so that the adhesive is generated due to the difference in the coefficient of thermal expansion between the two members to which the adhesive composition portion adheres. The peeling of the composition can be further suppressed.
接着剤組成物は、例えば、流動性を持っていてもよいし、ペースト状であってもよいし、固形であってもよい。接着剤組成物は、例えば、複合部材の製造に使用することができる。接着剤組成物を複合部材の製造に使用した場合、接着剤組成物は接着層を形成する。＜実施例＞
（１）接着剤組成物の製造
以下の表１に示す特性を有する炭素粉末Ａ１〜Ａ５を用意した。
The adhesive composition may be, for example, fluid, paste-like, or solid. The adhesive composition can be used, for example, in the manufacture of composite members. When the adhesive composition is used in the manufacture of composite members, the adhesive composition forms an adhesive layer. <Example>
(1) Production of Adhesive Composition Carbon powders A1 to A5 having the characteristics shown in Table 1 below were prepared.
Ａ１は、新日カーボン株式会社製のニテロン♯１０Ｋ（商品名）である。Ａ２は、三菱化学株式会社製の♯４０００（商品名）である。Ａ３は、デンカ株式会社製のデンカブラック（商品名）である。Ａ４は、三菱化学株式会社製のＭＡ６００（商品名）である。Ａ５は、旭カーボン株式会社製のＳＢＸ２５（商品名）である。 A1 is Niteron # 10K (trade name) manufactured by Nippon Carbon Co., Ltd. A2 is # 4000 (trade name) manufactured by Mitsubishi Chemical Corporation. A3 is Denka Black (trade name) manufactured by Denka Co., Ltd. A4 is MA600 (trade name) manufactured by Mitsubishi Chemical Corporation. A5 is SBX25 (trade name) manufactured by Asahi Carbon Co., Ltd.
表１における「ＢＥＴ比表面積」及び「重量減少量」の測定方法は、上述した方法である。「重量減少量（Ｎ２）」は、窒素雰囲気での重量減少量であり、「重量減少量（Air
）」は、大気雰囲気での重量減少量である。
The methods for measuring the "BET specific surface area" and the "weight loss amount" in Table 1 are the methods described above. "Weight loss (N 2 )" is the weight loss in a nitrogen atmosphere, and "weight loss (Air)".
) ”Is the amount of weight loss in the atmosphere.
シリコーン樹脂と、炭素粉末Ａ１〜Ａ５のうちのいずれかとを含む原料を混合して、以下の表２、表３に示す接着剤組成物Ｓ１〜Ｓ１６を製造した。ただし、Ｓ１６については、炭素粉末を添加しなかった。 The silicone resin and the raw material containing any of the carbon powders A1 to A5 were mixed to produce the adhesive compositions S1 to S16 shown in Tables 2 and 3 below. However, for S16, carbon powder was not added.
表２、表３における「炭素粉末量」は、シリコーン樹脂の重量を１００重量部とした場合の炭素粉末の添加量（単位は重量部）である。使用したシリコーン樹脂の種類は全て同一であり、付加硬化型のシリコーン樹脂である。接着剤組成物Ｓ１〜Ｓ１６は、ペースト状であり、スクリーン印刷が可能なだけの流動性を有する。表２、表３には、添加した炭素粉末のＢＥＴ比表面積、及び重量減少量を併せて示す。
（２）接着剤組成物の評価
接着剤組成物Ｓ１〜Ｓ１６のそれぞれについて、以下の評価を行った。
The "carbon powder amount" in Tables 2 and 3 is the amount of carbon powder added (unit: parts by weight) when the weight of the silicone resin is 100 parts by weight. The types of silicone resins used are all the same, and they are addition-curable silicone resins. The adhesive compositions S1 to S16 are in the form of a paste and have a fluidity sufficient for screen printing. Tables 2 and 3 also show the BET specific surface area and the amount of weight loss of the added carbon powder.
(2) Evaluation of Adhesive Composition The following evaluations were performed for each of the adhesive compositions S1 to S16.
（２−１）気泡の評価用の試験体の作成
アルミ板の片面に接着剤組成物を塗布し、その塗布面にガラス板を貼り合わせ、試験体を作成した。ガラス板は第１の部材に対応し、アルミ板は第２の部材に対応する。接着剤組成物が硬化して成る層は接着層に対応する。試験体は、ガラス板と、アルミ板と、それらを接着する接着層とを備える。試験体は複合部材に対応する。
(2-1) Preparation of Specimen for Evaluation of Bubbles An adhesive composition was applied to one side of an aluminum plate, and a glass plate was attached to the coated surface to prepare a test piece. The glass plate corresponds to the first member, and the aluminum plate corresponds to the second member. The layer formed by curing the adhesive composition corresponds to the adhesive layer. The test piece includes a glass plate, an aluminum plate, and an adhesive layer for adhering them. The test piece corresponds to a composite member.
ガラス板を構成するガラスはフロートガラスである。アルミ板を構成するアルミニウムはＡ６０６１Ｐ−Ｔ６である。ガラス板は、縦横それぞれ１１０ｍｍの正方形の板であって、厚みは１．１ｍｍである。アルミ板は、縦横それぞれ１３０ｍｍの正方形の板であって、厚みは１．０ｍｍである。接着層の厚みは０．３ｍｍである。接着層とガラス板との接着面は平面であり、その接着面の面積は、直径１００ｍｍの円の面積以上である。また、接着層とアルミ板との接着面は平面であり、その接着面の面積は、直径１００ｍｍの円の面積以上である。 The glass that constitutes the glass plate is float glass. The aluminum constituting the aluminum plate is A6061P-T6. The glass plate is a square plate having a length and width of 110 mm, and has a thickness of 1.1 mm. The aluminum plate is a square plate having a length and width of 130 mm and a thickness of 1.0 mm. The thickness of the adhesive layer is 0.3 mm. The adhesive surface between the adhesive layer and the glass plate is flat, and the area of the adhesive surface is equal to or larger than the area of a circle having a diameter of 100 mm. Further, the adhesive surface between the adhesive layer and the aluminum plate is a flat surface, and the area of the adhesive surface is equal to or larger than the area of a circle having a diameter of 100 mm.
（２−２）気泡の評価
前記（２−１）で作成した試験体を２５０℃で１６５時間加熱した。加熱後、接着層に気泡が生じているか否かを、ガラス板を透して目視で確認した。その結果を前記表２、表３に示す。表２、表３において、「○」は気泡が生じていないことを表し、「×」は気泡が多く生じたことを表す。
(2-2) Evaluation of Bubbles The test piece prepared in (2-1) above was heated at 250 ° C. for 165 hours. After heating, it was visually confirmed through the glass plate whether or not bubbles were generated in the adhesive layer. The results are shown in Tables 2 and 3. In Tables 2 and 3, "◯" indicates that no bubbles were generated, and "x" indicates that many bubbles were generated.
接着剤組成物Ｓ１〜Ｓ９においては、気泡が生じていなかった。それに対し、接着剤組成物Ｓ１０〜Ｓ１５では、気泡が生じていた。その理由は、接着剤組成物Ｓ１〜Ｓ９では、ＢＥＴ比表面積が小さく、重量減少量が小さい炭素粉末を添加しているのに対し、接着剤組成物Ｓ１０〜Ｓ１５では、ＢＥＴ比表面積が大きく、重量減少量が大きい炭素粉末を添加しているためであると推測される。 No bubbles were generated in the adhesive compositions S1 to S9. On the other hand, in the adhesive compositions S10 to S15, bubbles were generated. The reason is that in the adhesive compositions S1 to S9, carbon powder having a small BET specific surface area and a small weight loss is added, whereas in the adhesive compositions S10 to S15, the BET specific surface area is large. It is presumed that this is because carbon powder with a large weight loss is added.
（２−３）ゴム硬度の測定
ＪＩＳ Ａ ＴＹＰＥのゴム硬度計を用い、接着剤組成物のゴム硬度を測定した。ゴム硬度の測定方法は、上述した方法である。ゴム硬度は、硬化劣化の程度を表す指標である。ゴム硬度の測定は、接着剤組成物の製造直後と、２５０℃で１０００時間加熱した後とにそれぞれ行った。測定結果を前記表２、表３に示す。表２、表３において「初期（ａ）」は、接着剤組成物の製造直後におけるゴム硬度を表す。表２、表３において「１０００ｈ後（ｂ）」は、２５０℃で１０００時間加熱した後における接着剤組成物のゴム硬度を表す。表２、表３における「（ｂ）／（ａ）」は、「初期（ａ）」の値に対する、「１０００ｈ後（ｂ）」の値の比率を表す。「（ｂ）／（ａ）」の値が大きいほど、加熱により硬くなったことを示しており、硬化劣化しやすいことを意味する。
(2-3) Measurement of rubber hardness The rubber hardness of the adhesive composition was measured using a JIS A TYPE rubber hardness tester. The method for measuring the rubber hardness is the method described above. Rubber hardness is an index showing the degree of curing deterioration. The rubber hardness was measured immediately after the production of the adhesive composition and after heating at 250 ° C. for 1000 hours, respectively. The measurement results are shown in Tables 2 and 3. In Tables 2 and 3, "initial (a)" represents the rubber hardness immediately after the production of the adhesive composition. In Tables 2 and 3, "after 1000 h (b)" represents the rubber hardness of the adhesive composition after heating at 250 ° C. for 1000 hours. “(B) / (a)” in Tables 2 and 3 represents the ratio of the value of “after 1000 hours (b)” to the value of “initial (a)”. The larger the value of "(b) / (a)" is, the harder it is due to heating, which means that it is more likely to be cured and deteriorated.
接着剤組成物Ｓ１〜Ｓ９においては、「（ｂ）／（ａ）」の値はいずれも小さかった。それに対し、接着剤組成物Ｓ１６では、「（ｂ）／（ａ）」の値は非常に大きかった。その理由は、接着剤組成物Ｓ１〜Ｓ９には、炭素粉末が添加されているのに対し、接着剤組成物Ｓ１６には、炭素粉末が添加されていないためであると推測される。
＜他の実施形態＞
以上、本開示の実施形態について説明したが、本開示は上述の実施形態に限定されることなく、種々変形して実施することができる。
In the adhesive compositions S1 to S9, the values of "(b) / (a)" were all small. On the other hand, in the adhesive composition S16, the value of "(b) / (a)" was very large. It is presumed that the reason is that the carbon powder is added to the adhesive compositions S1 to S9, whereas the carbon powder is not added to the adhesive composition S16.
<Other embodiments>
Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to the above-described embodiments, and can be implemented in various modifications.
（１）前記実施形態における１つの構成要素が有する複数の機能を、複数の構成要素によって実現したり、１つの構成要素が有する１つの機能を、複数の構成要素によって実現したりしてもよい。また、複数の構成要素が有する複数の機能を、１つの構成要素によって実現したり、複数の構成要素によって実現される１つの機能を、１つの構成要素によって実現したりしてもよい。また、前記実施形態の構成の一部を省略してもよい。また、前記実施形態の構成の少なくとも一部を、他の前記実施形態の構成に対して付加又は置換してもよい。なお、特許請求の範囲に記載した文言から特定される技術思想に含まれるあらゆる態様が本開示の実施形態である。 (1) A plurality of functions possessed by one component in the embodiment may be realized by a plurality of components, or one function possessed by one component may be realized by a plurality of components. .. Further, a plurality of functions possessed by the plurality of components may be realized by one component, or one function realized by the plurality of components may be realized by one component. Moreover, you may omit a part of the structure of the said embodiment. In addition, at least a part of the configuration of the embodiment may be added or replaced with the configuration of another embodiment. It should be noted that all aspects included in the technical idea specified from the wording described in the claims are embodiments of the present disclosure.
（２）上述した複合部材及び接着剤組成物の他、複合部材を構成要素とするシステム、接着剤組成物の製造方法、複合部材の製造方法等、種々の形態で本開示を実現することも
できる。
(2) In addition to the above-mentioned composite member and adhesive composition, the present disclosure may be realized in various forms such as a system using the composite member as a component, a method for manufacturing the adhesive composition, and a method for manufacturing the composite member. it can.
１…複合部材、３…第１の部材、５…第２の部材、７…接着層 1 ... Composite member, 3 ... First member, 5 ... Second member, 7 ... Adhesive layer
Claims (6)
少なくとも一部の表面が金属から成る第２の部材と、
前記第１の部材における前記セラミックから成る表面と、前記第２の部材における前記金属から成る表面とを接着する接着層と、
を備える複合部材であって、
前記接着層は、シリコーン樹脂と、ラジカル捕捉能を有する炭素粉末と、を含み、
前記接着層は、前記シリコーン樹脂１００重量部に対し、１重量部以上の前記炭素粉末を含み、
前記接着層は、２５０℃で１６５時間加熱したときに気泡を発生せず、
前記接着層の初期のゴム硬度を（ａ）とし、前記接着層を２５０℃で１０００時間加熱した後の前記接着層のゴム硬度を（ｂ）とした場合、（ｂ）／（ａ）が２．２以下であり、
前記ゴム硬度（ａ）が９〜２４であり、
前記ゴム硬度（ｂ）が２０〜４３であり、
半導体製造用部品の一部又は全部を構成する複合部材。 A first member whose surface is at least partially made of ceramic,
A second member whose surface is at least partially made of metal,
An adhesive layer that adheres the surface made of the ceramic in the first member and the surface made of the metal in the second member.
It is a composite member provided with
The adhesive layer contains a silicone resin and a carbon powder having a radical scavenging ability .
The adhesive layer contains 1 part by weight or more of the carbon powder with respect to 100 parts by weight of the silicone resin.
The adhesive layer did not generate bubbles when heated at 250 ° C. for 165 hours.
When the initial rubber hardness of the adhesive layer is (a) and the rubber hardness of the adhesive layer after heating the adhesive layer at 250 ° C. for 1000 hours is (b), (b) / (a) is 2. .2 or less,
The rubber hardness (a) is 9 to 24, and the rubber hardness (a) is 9 to 24.
The rubber hardness (b) is 20 to 43, and the rubber hardness (b) is 20 to 43.
A composite member that constitutes part or all of a semiconductor manufacturing component.
前記炭素粉末のＢＥＴ比表面積は９５ｍ２／ｇ以下である複合部材。 The composite member according to claim 1.
BET specific surface area of the carbon powder is 95 m 2 / g or less der Ru composite member.
熱重量測定における前記炭素粉末の重量減少率は、窒素雰囲気下、又は大気雰囲気下にて、昇温速度１０℃／ｍｉｎで室温から２５０℃まで昇温させた場合に１重量％未満である複合部材。 The composite member according to claim 1 or 2 .
The weight loss rate of the carbon powder in the thermogravimetric analysis is less than 1% by weight when the temperature is raised from room temperature to 250 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen atmosphere or an air atmosphere. Element.
前記炭素粉末は、カーボンブラック、カーボンファイバー、カーボンナノチューブ、及びグラフェンから成る群から選択される１以上である複合部材。 The composite member according to any one of claims 1 to 3 .
The carbon powder is one or more composite members selected from the group consisting of carbon black, carbon fibers, carbon nanotubes, and graphene.
前記シリコーン樹脂が付加硬化型のシリコーン樹脂である複合部材。 The composite member according to any one of claims 1 to 4 .
A composite member in which the silicone resin is an addition-curable silicone resin.
前記第１の部材と前記接着層との第１の接着面、及び／又は、前記第２の部材と前記接着層との第２接着面は平面であり、
その平面の面積は、直径１００ｍｍの円の面積以上である複合部材。 The composite member according to any one of claims 1 to 5 .
The first adhesive surface between the first member and the adhesive layer and / or the second adhesive surface between the second member and the adhesive layer is a flat surface.
The area of the plane is a composite member having an area of a circle having a diameter of 100 mm or more.
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