JPS6360558B2 - - Google Patents
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- Publication number
- JPS6360558B2 JPS6360558B2 JP56119362A JP11936281A JPS6360558B2 JP S6360558 B2 JPS6360558 B2 JP S6360558B2 JP 56119362 A JP56119362 A JP 56119362A JP 11936281 A JP11936281 A JP 11936281A JP S6360558 B2 JPS6360558 B2 JP S6360558B2
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- JP
- Japan
- Prior art keywords
- weight
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 polysiloxane Polymers 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 24
- 230000001070 adhesive effect Effects 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002985 plastic film Substances 0.000 claims description 16
- 229920006255 plastic film Polymers 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000003058 platinum compounds Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000013464 silicone adhesive Substances 0.000 claims description 2
- 230000007423 decrease Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- UIEXFJVOIMVETD-UHFFFAOYSA-N P([O-])([O-])[O-].[Pt+3] Chemical class P([O-])([O-])[O-].[Pt+3] UIEXFJVOIMVETD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 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
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PWBYYTXZCUZPRD-UHFFFAOYSA-N iron platinum Chemical compound [Fe][Pt][Pt] PWBYYTXZCUZPRD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical class P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、金属箔と融点が260℃以上のプラス
チツクフイルムとを接着するに於いて、その接着
剤として、
(A) ケイ素原子に結合したビニル基を分子中に平
均２個以上有し、平均重合度が50〜10000のポ
リオルガノシロキサン100重量部、
(B) ケイ素原子に結合した水素原子を分子中に平
均２個を越える数を有するポリオルガノハイド
ロジエンシロキサン、該水素原子が(A)中のケイ
素原子に結合したビニル基１モルに対して、
0.5〜10モルになる量、
(C) シリカ系充填剤20〜150重量部、
(D) 一般式（FeO）X（Fe2O3）Y（ただし、Ｘ／Ｙ
は0.05〜1.0である。）で表わされる酸化鉄又は
（及び）カーボンブラツク0.5〜20重量部、
(E) 白金化合物白金原子として１〜200ppm、
(F) 分子鎖のケイ素原子に結合した水素原子を分
子中に少なくとも１個と、一般式
The present invention provides an adhesive for bonding a metal foil to a plastic film having a melting point of 260°C or higher. 100 parts by weight of a polyorganosiloxane with a degree of polymerization of 50 to 10,000; (B) a polyorganohydrodiene siloxane having an average of more than 2 hydrogen atoms bonded to silicon atoms in the molecule; For 1 mole of vinyl group bonded to silicon atom,
Amount of 0.5 to 10 mol, ( C) 20 to 150 parts by weight of silica filler, ( D ) General formula (FeO )
is between 0.05 and 1.0. ) 0.5 to 20 parts by weight of iron oxide or (and) carbon black, (E) 1 to 200 ppm of platinum atoms in a platinum compound, (F) At least one hydrogen atom in the molecule bonded to a silicon atom in the molecular chain. and the general formula
【式】（ただし、Q1及び
Q2は互いに同一又は相異なる直鎖状又は分枝
状のアルキレン基、Ｒは炭素数１〜４のアルキ
ル基を示す。）で表わされ、分子鎖のケイ素原
子に結合した基を分子中に少なくとも１個有す
るポリシロキサン0.5〜50重量部、
から成る接着剤組成物を基板の構成たる融点が
260℃以上のプラスチツクフイルム又は（及び）
金属箔に塗布して乾燥した後、このプラスチツク
フイルムと金属箔とを重ね加熱圧着し、アフター
キユアーすることを特徴とするフレキシブルプリ
ント配線用基板の製造方法に関するものである。
電子機器の多様化に伴つて、軽量で立体配線の
出来るフレキシブル配線板の普及が著しいが、最
近、安全性の立場から難燃性の要求が強くなつて
きており、特に厳しい難燃性の試験法である
UL94V−Ｏ相当の難燃性が要求されてきている。
然し乍ら、ポリイミドフイルム等の耐熱性プラス
チツクフイルムは耐熱性、難燃性等に勝れている
ものもあるが、接着剤を介して金属箔とプラスチ
ツクフイルムとを加熱圧着により一体化するフレ
キシブルプリント配線用基板に於いては、接着剤
の特性で基板の接着性、耐熱性及び難燃性等の特
性が決まり、接着剤にこれらの特性を兼備させる
ことは極めて困難であつた。これは、融点が260
℃以上のプラスチツクフイルム例えば、ポリイミ
ドフイルムと金属箔との接着剤として耐熱性を発
揮させる為に一般的に用いられているエポキシ樹
脂に難燃性の為に臭素を含有する臭素化エポキシ
樹脂を用いた場合には、耐熱性、接着性が著しく
低下するからである。
本発明者等は種々検討した結果、接着剤として
付加反応架橋型シリコーン樹脂を用いることによ
り、フレキシブルプリント配線用基板として必要
な引き剥がし強さ（接着性）、半田耐熱性、難燃
性等の特性が満たされることを見い出し、本発明
を完成させるに至つた。
以下、本発明を詳細に説明する。
本発明に於ける金属箔としては、銅箔、アルミ
ニウム箔、ニツケル箔、ニクロム箔等の導電性を
有する金属箔が使用出来る。
本発明に於けるプラスチツクフイルムとして
は、ポリイミドフイルム、ポリアミドイミドフイ
ルム、ポリアミドフイルム、ポリスルホンフイル
ム、二軸延伸ポリエステルフイルム等の融点が
260℃以上のプラスチツクフイルムが使用出来る。
接着剤組成物の各成分について説明する。
(A)のポリオルガノシロキサンは、シリコーン接
着剤のベースポリマーであつて実質的に直鎖状の
骨格を為し、(B)によつて網状高分子を形成する為
には、ケイ素原子に結合したビニル基を分子中に
平均２個以上有することが必要である。ケイ素原
子に結合した有機基としては、上記のビニル基の
他に、メチル基、エチル基、プロピル基、ブチル
基、ペンチル基、ヘキシル基、オクチル基、デシ
ル基、ドデシル基の様なアルキシ基、フエニル基
の様なアリール基、ベンジル基、β−フエニルエ
チル基、β−フエニルプロピル基の様なアラルキ
ル基、β−シアノエチル基、３，３，３−トリフ
ルオロプロピル基、クロロフエニル基の様な置換
炭化水素基が例示されるが、ポリジオルガノシロ
キサンの特徴である耐熱性、耐寒性を示し、且つ
合成し易く取扱いも容易な点で、該有機基中の85
％以上がメチル基であることが好ましく、ビニル
基以外の有機基が実質的に総てメチル基であるこ
とが更に好ましい。分子末端は通常トリメチルシ
リル基、ジメチルビニルシリル基、ジメチルフエ
ニルシリル基の様なトリオルガノシリル基か水酸
基で閉塞される。平均重合度はシロキサン単位と
して50〜10000の範囲であることが好ましい。50
未満では架橋によつて十分な機械的強度が得られ
ず引き剥がし強さが弱い。また、ポリジオルガノ
シロキサンの粘度が低くなつて配合した(C)や(D)が
沈降する為に均一な接着剤層が得られない。ま
た、10000を越えると合成し難い上、(C)や(D)を均
一に分散させることが極めて困難になる接着剤層
に十分な機械的強度、特に衝撃や剪断力が働いた
ときに耐える力を与えるには、重合度が3000〜
10000の範囲であることが好ましい。
(B)のポリオルガノハイドロジエンシロキサンは
そのケイ素−水素結合が(E)の触媒作用によつて、
(A)のケイ素原子に結合したビニル基と反応するこ
とにより、(A)を架橋して網状高分子とするもので
あり、斯々る網状化の為には分子中にケイ素原子
に結合した水素原子を平均２個を越える数を有す
ることが必要である。分子骨格は直鎖状、分岐
状、環状の何れでもよい。ケイ素原子に結合した
有機基としては(A)に例示した様なアルキル基、ア
リール基、アラルキル基及び置換炭化水素基が例
示されるが、(A)との間に良好な相溶性をもつ為に
は(A)と同様な有機基の構成であることが好まし
く、(A)の場合と同様な理由から、メチル基である
ことが好ましい。(B)の配合量は、(A)中のケイ素原
子に結合したビニル基１モルに対して(B)のケイ素
原子に結合した水素原子が0.5〜10モルの間であ
る。0.5モル未満では硬化が十分行われず半田耐
熱性が得られず、10モルを越えると硬化後も未反
応のケイ素−水素結合の残存量が多いので耐熱性
が低下する。また、勝れた引き剥がし強さを付与
する為には、上記の水素原子の量が、2.5〜６モ
ルの間であることが好ましい。2.5モル未満又は
６モルを越えると、十分な引き剥がし強さが得ら
れない。
(C)のシリカ系充填剤は、接着剤に機械的強度耐
熱性及び難燃性を与えるもので、煙霧質シリカ、
沈殿シリカ、シリカエアロゲル、焼成シリカの様
な補強性の強いもの、粉砕石英、溶融シリカ、珪
藻土の様な大量に系に配合出来て難燃性を付与す
るものが例示される。接着剤に耐湿性や耐熱水性
を与える為に、上記の補強性充填剤の表面をオル
ガノクロロシラン、ポリジメチルシロキサン、ヘ
キサメチルジシランの様な有機ケイ素化合物で処
理して、表面のシラノール基の一部又は全部を改
質することが好ましい。(C)の配合量は(A)100重量
部に対して20〜150重量部好ましくは40〜100重量
部の範囲である。20重量部以下では引き剥がし強
さや難燃性が十分でなく150重量部を越えると接
着剤層が硬くなり過ぎ十分な引き剥がし強さが得
られない。また、勝れた難燃性を得る為には(C)の
うち粉砕石英又は溶融シリカの量が30〜100重量
部あることが好ましい。30重量部未満では十分な
難燃性が得られず、100重量部を越えると沈降し
易く均一な接着剤層が得られない。
(D)の酸化鉄、カーボンブラツクは、接着剤層に
勝れた難燃性を付与するもので、一般式（FeO））
x（Fe2O3）yで表わされ、ｘとｙの比0.05〜1.0の範
囲である酸化鉄とカーボンブラツクを単独又は併
用して使用出来る。両者を比較すると酸化鉄の方
がより高い難燃性を与える。酸化鉄のｘとｙの比
が上記の範囲以外では、十分な難燃性が得られな
い。(D)の配合量は、(A)100重量部に対して0.5〜20
重量部の範囲である。0.5重量部未満では難燃性
が十分でなく、20重量部を越すと引き剥がし強さ
の低下を来たす。
(E)の白金化合物は、(A)のビニル基と(B)のケイ素
−水素結合を反応させることにより(A)を(B)で架橋
させる為の触媒であり、また、硬化後の接着剤に
難燃性を付与する重要な成分である。(E)として
は、塩化白金酸、塩化白金−オレフイン錯体、塩
化白金−ジアルキルエーテル錯体、塩化白金−ビ
ニル基含有ポリシロキサン錯体、０価及び２価の
白金−ホスフイン錯体並びに白金−ホスフアイト
錯体、アセチルアセトナト白金等が例示される。
(E)の配合量はその種類によつても適正な範囲が相
違するが、(A)に対して、白金原子として１〜
200ppm好ましくは５〜50ppmの範囲である。(E)
が少な過ぎると十分な難燃性が得られず、また、
多すぎると半田耐熱性の低下を来たす。
(F)のポリシロキサンは、勝れた引き剥がし強さ
を付与するもので、シロキサン骨格は、直鎖状、
分岐状、環状の何れでもよいが、合成の容易なこ
とから、通常、直鎖状又は環状のものが用いられ
る。また、水素原子と[Formula] (where Q 1 and Q 2 are the same or different linear or branched alkylene groups, R is an alkyl group having 1 to 4 carbon atoms), and the molecular chain is An adhesive composition consisting of 0.5 to 50 parts by weight of a polysiloxane having at least one group bonded to a silicon atom in the molecule is used when the melting point of the substrate is
Plastic film or (and) over 260℃
The present invention relates to a method for manufacturing a flexible printed wiring board, which comprises coating the plastic film on a metal foil and drying it, then overlapping the plastic film and the metal foil, heat-pressing them, and after-curing the plastic film. With the diversification of electronic devices, flexible wiring boards that are lightweight and capable of three-dimensional wiring are becoming increasingly popular.Recently, demands for flame retardancy have become stronger from a safety standpoint, and particularly stringent flame retardant tests are required. is the law
Flame retardancy equivalent to UL94V-O is now required.
However, although some heat-resistant plastic films such as polyimide films have excellent heat resistance and flame retardancy, they are not suitable for flexible printed wiring, in which metal foil and plastic film are integrated by heat and pressure bonding via an adhesive. Regarding substrates, the properties of the substrate, such as adhesiveness, heat resistance, and flame retardance, are determined by the properties of the adhesive, and it has been extremely difficult to make the adhesive have all of these properties. It has a melting point of 260
℃ or higher plastic film For example, brominated epoxy resin containing bromine is used for flame retardancy in the epoxy resin that is commonly used to exhibit heat resistance as an adhesive between polyimide film and metal foil. This is because heat resistance and adhesion properties will be significantly reduced if such a material is used. As a result of various studies, the present inventors have found that by using an addition reaction cross-linked silicone resin as an adhesive, the peel strength (adhesiveness), soldering heat resistance, flame retardance, etc. required for a flexible printed wiring board can be improved. It was discovered that the characteristics were satisfied, and the present invention was completed. The present invention will be explained in detail below. As the metal foil in the present invention, conductive metal foils such as copper foil, aluminum foil, nickel foil, and nichrome foil can be used. Plastic films used in the present invention include polyimide films, polyamide-imide films, polyamide films, polysulfone films, biaxially oriented polyester films, etc.
Plastic film with a temperature of 260℃ or higher can be used. Each component of the adhesive composition will be explained. The polyorganosiloxane (A) is the base polymer of the silicone adhesive and has a substantially linear skeleton, and in order to form the network polymer in (B), it must be bonded to silicon atoms. It is necessary to have an average of two or more vinyl groups in the molecule. Examples of organic groups bonded to silicon atoms include, in addition to the above-mentioned vinyl group, alkoxy groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl groups; Substituted aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, β-phenylethyl groups, β-phenylpropyl groups, β-cyanoethyl groups, 3,3,3-trifluoropropyl groups, and chlorophenyl groups. Among the organic groups, 85
It is preferable that % or more of the organic groups are methyl groups, and it is more preferable that substantially all organic groups other than vinyl groups are methyl groups. The terminal end of the molecule is usually blocked with a triorganosilyl group such as trimethylsilyl, dimethylvinylsilyl, dimethylphenylsilyl, or a hydroxyl group. The average degree of polymerization is preferably in the range of 50 to 10,000 in terms of siloxane units. 50
If it is less than that, sufficient mechanical strength cannot be obtained due to crosslinking, resulting in weak peel strength. Furthermore, since the viscosity of the polydiorganosiloxane becomes low and the blended components (C) and (D) settle, a uniform adhesive layer cannot be obtained. In addition, if it exceeds 10,000, it will be difficult to synthesize and it will be extremely difficult to uniformly disperse (C) and (D).The adhesive layer must have sufficient mechanical strength, especially when subjected to impact or shearing force. To give power, the degree of polymerization must be 3000~
Preferably, it is in the range of 10,000. The polyorganohydrodiene siloxane (B) has a silicon-hydrogen bond that is formed by the catalytic action of (E).
By reacting with the vinyl group bonded to the silicon atom of (A), (A) is crosslinked to form a network polymer. It is necessary to have more than two hydrogen atoms on average. The molecular skeleton may be linear, branched, or cyclic. Examples of organic groups bonded to silicon atoms include alkyl groups, aryl groups, aralkyl groups, and substituted hydrocarbon groups as exemplified in (A). preferably has the same organic group structure as (A), and for the same reason as (A), is preferably a methyl group. The blending amount of (B) is between 0.5 and 10 moles of silicon-bonded hydrogen atoms in (B) per 1 mole of silicon-bonded vinyl groups in (A). If it is less than 0.5 mol, curing will not be sufficient and soldering heat resistance will not be obtained, and if it exceeds 10 mol, there will be a large amount of unreacted silicon-hydrogen bonds remaining even after curing, resulting in a decrease in heat resistance. Further, in order to provide excellent peel strength, the amount of hydrogen atoms is preferably between 2.5 and 6 moles. If it is less than 2.5 moles or more than 6 moles, sufficient peel strength cannot be obtained. The silica filler (C) gives the adhesive mechanical strength, heat resistance, and flame retardancy.
Examples include those with strong reinforcing properties such as precipitated silica, silica airgel, and calcined silica, and those that can be blended in large quantities into the system and impart flame retardancy, such as crushed quartz, fused silica, and diatomaceous earth. In order to impart moisture resistance and hot water resistance to the adhesive, the surface of the reinforcing filler described above is treated with an organosilicon compound such as organochlorosilane, polydimethylsiloxane, or hexamethyldisilane to remove some of the silanol groups on the surface. Or it is preferable to modify all of them. The blending amount of (C) is in the range of 20 to 150 parts by weight, preferably 40 to 100 parts by weight, per 100 parts by weight of (A). If it is less than 20 parts by weight, the peel strength and flame retardance will not be sufficient, and if it exceeds 150 parts by weight, the adhesive layer will become too hard and sufficient peel strength will not be obtained. Further, in order to obtain excellent flame retardancy, it is preferable that the amount of crushed quartz or fused silica in (C) is 30 to 100 parts by weight. If it is less than 30 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 100 parts by weight, sedimentation tends to occur and a uniform adhesive layer cannot be obtained. (D) Iron oxide and carbon black give the adhesive layer excellent flame retardancy, and have the general formula (FeO))
Iron oxide and carbon black, represented by x (Fe 2 O 3 ) y , in which the ratio of x to y is in the range of 0.05 to 1.0, can be used alone or in combination. When comparing the two, iron oxide provides higher flame retardancy. If the ratio of x and y of iron oxide is outside the above range, sufficient flame retardancy cannot be obtained. The blending amount of (D) is 0.5 to 20 parts by weight per 100 parts by weight of (A).
Parts by weight range. If the amount is less than 0.5 parts by weight, the flame retardance will not be sufficient, and if it exceeds 20 parts by weight, the peel strength will decrease. The platinum compound (E) is a catalyst for crosslinking (A) with (B) by reacting the vinyl group of (A) with the silicon-hydrogen bond of (B), and also serves as a catalyst for crosslinking (A) with (B) after curing. It is an important component that imparts flame retardancy to the agent. Examples of (E) include chloroplatinic acid, platinum chloride-olefin complexes, platinum chloride-dialkyl ether complexes, platinum chloride-vinyl group-containing polysiloxane complexes, zero- and divalent platinum-phosphine complexes, platinum-phosphite complexes, and acetyl chloride. Examples include platinum acetonate.
The appropriate range for the amount of (E) to be blended varies depending on the type, but the amount of platinum in (A) varies from 1 to 1 as platinum atoms.
200 ppm, preferably in the range of 5 to 50 ppm. (E)
If there is too little, sufficient flame retardancy cannot be obtained, and
If it is too large, the soldering heat resistance will decrease. The polysiloxane (F) provides excellent peel strength, and the siloxane skeleton is linear,
Although they may be branched or cyclic, linear or cyclic ones are usually used because they are easy to synthesize. Also, hydrogen atoms
【式】は、通常、シロキサン
骨格の別々のケイ素原子に結合するが、同一のケ
イ素原子に結合しても差支えない。Q1及びQ2は
同一でも相異なつてもよく、メチレン基、エチレ
ン基、プロピレン基、ブチレン基等が例示され、
プロピレン基、ブチレン基は、直鎖状でも分岐状
でもよい。合成の容易なことと耐加水分解性か
ら、Q1はメチレン基又は１，２−プロピレン基、
Q2はケイ素原子とエステル酸素原子を少なくと
も３個の炭素鎖によつて結ぶアルキレン基、特に
１，３−プロピレン基であることが好ましい。Ｒ
としてはメチル基、エチル基、プロピル基、ブチ
ル基が挙げられるが、良好な引き剥がし強さを得
るには、メチル基又はエチル基が好ましい。(F)の
配合量は、(A)100重量部に対して0.5〜50重量部好
ましくは、２〜10重量部の範囲である。0.5重量
部未満では接着性が十分でなく50重量部を越える
と耐熱性と難燃性が低下するからである。
この他、接着剤中には任意の成分として、その
他の難燃剤、耐熱性向上剤、(C)及び(D)を(A)と混和
するときの加工助剤、安定剤等、公知のものを配
合しても差支えない。
本発明の接着剤は、通常(A)、(C)、(D)、(E)及び(G)
から成るベースと(B)及び(F)から成る架橋剤組成物
を別々に調整しておき、使用直前にベースと架橋
剤組成物を混合して調整するが、(A)、(C)及び／又
は(G)の一部を架橋剤組成物に配合してもよく、(E)
を別個に保存してもよい。また、後者の場合、混
合の便宜の為に(A)の一部を(E)と共存させても差支
えない。
本発明に於けるプラスチツクフイルムと金属箔
との貼り合せは常法により行える。例えば、特公
昭55−19438にある様に、プラスチツクフイルム
を送り出し塗布ロールで接着剤をフイルムの片面
に塗布し、次いで乾燥部を通過させて接着剤を乾
かす。一方、金属箔を送り出し、加熱された圧着
ロールで接着剤付きフイルムと連続的に貼合せ
る。次いで、乾燥炉で接着剤をアフターキユアー
し半田耐熱性、引き剥がし強さを向上させる。
以下実施例について説明する。
実施例 １
下記のポリシロキサンＳ−１〜Ｓ−９を用い
て、第１表の様な配合比で接着剤Ａ−１〜Ａ−18
を調整した。即ち、Ａ−１を例にとると、ポリシ
ロキサンＳ−１、煙霧質シリカ、粉砕シリカを混
練機で十分に混練し、更に酸化鉄と白金−ビニル
シロキサン錯体を添加して混練し、ベースコンパ
ウンドを得た。これをトルエンに稀釈し、これに
予め混合しておいたポリシロキサンＳ−４とＳ−
６の混合液を配合して十分に撹拌し、接着剤Ａ−
１を得た。同様にしてＡ−２〜Ａ−18の接着剤を
得た。
次いで、厚さ50μｍのポリイミドフイルム（カ
プトン：デユポン社製）に前記接着剤例えばＡ−
１を乾燥後で厚さが約20μｍになる様に塗布し、
130℃２分間乾燥後、厚さ35μｍ電解銅箔を加熱
ロールで貼合せ、160℃10時間アフターキユアー
し、フレキシブルプリント配線用基板Ｂ−１を得
た。同様にしてＡ−２〜Ａ−18の接着剤を用い
て、Ｂ−２〜Ｂ−18のフレキシブルプリント配線
用基板を得た。このものの性能を表２に示す。
Ｓ−１：0.2モル％のメチルビニルシロキサン単
位と残余のジメチルシロキシ単位から成り、末
端がトリメチルシリル基で閉塞され、平均重合
度が7000のポリジオルガノシロキサン
Ｓ−２：0.2モル％のメチルビニルシロキシ単位、
８モル％のジフエニルシロキシ単位及び残余の
ジメチルシロキシ単位から成り、末端がジメチ
ルビニルシリル基で閉塞され、平均重合度が
5000のポリジオルガノシロキサン
Ｓ−３：ジメチルシロキシ単位から成り、末端が
ジメチルビニルシリル基で閉塞された平均重合
度1500のポリジオルガノシロキサン
Ｓ−４：メチルハイドロジエンシロキシ単位から
成り、末端がトリメチルシリル基で閉塞された
平均重合度30のポリメチルハイドロジエンシロ
キサン
Ｓ−５：60モル％のメチルハイドロジエンシロキ
シ単位と残余のジメチルシロキシ単位から成
り、末端がトリメチルシリル基で閉塞された平
均重合度50のポリメチルハイドロジエンシロキ
サン
で表わされるポリシロキサン
で表わされるポリシロキサン
で表わされるポリシロキサン
Ｓ−９：Ｓ−３と同じ化学構造である平均重合度
45のポリジオルガノシロキサン
ベースポリマーとして、平均重合度50未満のも
のを用いると（Ａ−10）、十分な引き剥がし強さ
が得られない（Ｂ−10）。
ポリオルガノハイドロジエンシロキサンの量と
性能との関係がＡ−11〜A14、Ｂ−11〜14でポリ
オルガノハイドロジエンが少な過ぎても、多過ぎ
ても半田耐熱性及び引き剥がし強さが低い。
シリカ系充填剤の量については、多過ぎると
（Ａ−15）引き剥がし強さが低下し、少な過ぎる
と（Ａ−９）引き剥がし強さ、難燃性が低下す
る。
酸化鉄の量は多過ぎると（Ａ−17）引き剥がし
強さ、表面抵抗が低下し、少な過ぎると（Ａ−
16）難燃性が低下する。また、Ｘ／Ｙ比が０の酸
化鉄では（Ａ−７）難燃性が得られない。
(F)のポリシロキサンの量については、多過ぎて
も、少な過ぎても（Ａ−11、Ａ−14）引き剥がし
強さ、半田耐熱性が低下する。
適正な配合量であるＡ−１〜６では、引き剥が
し強さ、半田耐熱性、難燃性等の良好な特性が得
られた。
実施例 ２
プラスチツクフイルムとしてポリアミドイミド
フイルム（厚さ50μｍ）を、接着剤としてＡ−１
を用いる以外は実施例１と同様の方法により、フ
レキシブルプリント配線用基板（Ｂ−19）を得
た。このものの性能を表２に示す。
実施例 ３
金属箔としてアルミニウム箔（厚さ50μｍ）
を、接着剤としてＡ−１を用いる以外は実施例１
と同様の方法により、フレキシブルプリント配線
用基板（Ｂ−20）を得た。
このものの性能を表２に示す。[Formula] is usually bonded to separate silicon atoms of the siloxane skeleton, but may be bonded to the same silicon atom. Q 1 and Q 2 may be the same or different, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, etc.
The propylene group and butylene group may be linear or branched. For ease of synthesis and hydrolysis resistance, Q 1 is a methylene group or a 1,2-propylene group,
Q 2 is preferably an alkylene group, particularly a 1,3-propylene group, which connects a silicon atom and an ester oxygen atom through at least three carbon chains. R
Examples include methyl group, ethyl group, propyl group, and butyl group, and methyl group or ethyl group is preferable in order to obtain good peel strength. The blending amount of (F) is preferably 0.5 to 50 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of (A). This is because if the amount is less than 0.5 parts by weight, the adhesion will not be sufficient, and if it exceeds 50 parts by weight, the heat resistance and flame retardance will decrease. In addition, the adhesive may include other flame retardants, heat resistance improvers, processing aids and stabilizers used when mixing (C) and (D) with (A), and other known components. There is no problem even if it is mixed. The adhesive of the present invention generally includes (A), (C), (D), (E) and (G).
A base consisting of (B) and a crosslinking agent composition consisting of (F) are prepared separately, and the base and crosslinking agent composition are mixed immediately before use. / or a part of (G) may be blended into the crosslinking agent composition, (E)
may be stored separately. In the latter case, a part of (A) may coexist with (E) for the convenience of mixing. In the present invention, the plastic film and the metal foil can be bonded together by a conventional method. For example, as described in Japanese Patent Publication No. 55-19438, a plastic film is sent out, an adhesive is applied to one side of the film using a coating roll, and then the film is passed through a drying section to dry the adhesive. Meanwhile, the metal foil is sent out and continuously bonded to the adhesive-coated film using a heated pressure roll. Next, the adhesive is after-cured in a drying oven to improve solder heat resistance and peel strength. Examples will be described below. Example 1 Adhesives A-1 to A-18 were prepared using the following polysiloxanes S-1 to S-9 at the compounding ratios shown in Table 1.
adjusted. That is, taking A-1 as an example, polysiloxane S-1, fumed silica, and pulverized silica are thoroughly kneaded in a kneader, and then iron oxide and platinum-vinyl siloxane complex are added and kneaded to form a base compound. I got it. This was diluted in toluene, and polysiloxane S-4 and S-
Blend the mixture of step 6 and stir thoroughly to form adhesive A-
I got 1. Adhesives A-2 to A-18 were obtained in the same manner. Next, the adhesive, for example A-
After drying, apply 1 to a thickness of about 20 μm,
After drying at 130°C for 2 minutes, a 35 μm thick electrolytic copper foil was laminated with a heating roll and after-cured at 160°C for 10 hours to obtain a flexible printed wiring board B-1. Similarly, flexible printed wiring boards B-2 to B-18 were obtained using the adhesives A-2 to A-18. The performance of this product is shown in Table 2. S-1: Polydiorganosiloxane consisting of 0.2 mol% methylvinylsiloxane units and the remaining dimethylsiloxy units, the terminals are blocked with trimethylsilyl groups, and the average degree of polymerization is 7000 S-2: 0.2 mol% methylvinylsiloxy units ,
It consists of 8 mol% diphenylsiloxy units and the remaining dimethylsiloxy units, the terminals are blocked with dimethylvinylsilyl groups, and the average degree of polymerization is
5000 polydiorganosiloxane S-3: consists of dimethylsiloxy units, the terminals are blocked with dimethylvinylsilyl groups Polydiorganosiloxane with an average degree of polymerization of 1500 S-4: consists of methylhydrogensiloxy units, the terminals are blocked with trimethylsilyl groups Blocked polymethylhydrodienesiloxane S-5 with an average degree of polymerization of 30: Polymethyl with an average degree of polymerization of 50, consisting of 60 mol% of methylhydrodienesiloxy units and the remainder dimethylsiloxy units, and whose terminals are blocked with trimethylsilyl groups. hydrogen siloxane polysiloxane represented by polysiloxane represented by Polysiloxane S-9 represented by: Average degree of polymerization which has the same chemical structure as S-3
Polydiorganosiloxane No. 45 When a base polymer having an average degree of polymerization of less than 50 is used (A-10), sufficient peel strength cannot be obtained (B-10). The relationship between the amount of polyorganohydrogen siloxane and performance is A-11 to A14 and B-11 to B-14, and if the amount of polyorganohydrogen is too small or too large, the soldering heat resistance and peel strength will be low. Regarding the amount of silica filler, if it is too large (A-15), the peel strength will decrease, and if it is too small (A-9), the peel strength and flame retardance will decrease. If the amount of iron oxide is too large (A-17), the peel strength and surface resistance will decrease; if it is too small (A-17), the peel strength and surface resistance will decrease.
16) Flame retardancy decreases. Further, with iron oxide having an X/Y ratio of 0, flame retardancy (A-7) cannot be obtained. Regarding the amount of polysiloxane (F), if it is too large or too small (A-11, A-14), the peel strength and soldering heat resistance will decrease. With proper blending amounts of A-1 to A-6, good properties such as peel strength, solder heat resistance, and flame retardancy were obtained. Example 2 Polyamideimide film (thickness 50 μm) was used as the plastic film, and A-1 was used as the adhesive.
A flexible printed wiring board (B-19) was obtained in the same manner as in Example 1 except that the following was used. The performance of this product is shown in Table 2. Example 3 Aluminum foil (thickness 50 μm) as metal foil
Example 1 except that A-1 was used as the adhesive.
A flexible printed wiring board (B-20) was obtained in the same manner as above. The performance of this product is shown in Table 2.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
均２個以上有し、平均重合度が50〜10000のポ
リオルガノシロキサン100重量部、 (B) ケイ素原子に結合した水素原子を分子中に平
均２個を越える数を有するポリオルガノハイド
ロジエンシロキサン、該水素原子が(A)中のケイ
素原子に結合したビニル基１モルに対して、
0.5〜10モルになる量、 (C) シリカ系充填剤20〜150重量部、 (D) 一般式（FeO）X（Fe2O3）Y（ただし、Ｘ／Ｙ
は0.05〜1.0である。）で表わされる酸化鉄又は
（及び）カーボンブラツク0.5〜20重量部、 (E) 白金化合物、白金原子として１〜200PPm、 (F) ケイ素原子に結合した水素原子を分子中に少
なくとも１個と、一般式 【式】（ただしQ1及びQ2 は互いに同一又は相異なる直鎖状又は分枝状の
アルキレン基、Ｒは炭素数１〜４のアルキル基
を示す。）で表わされ、ケイ素原子に結合した
基を分子中に少なくとも１個有するポリシロキ
サン0.5〜50重量部、 からなる接着剤組成物を基板の構成たる融点が
260℃以上のプラスチツクフイルム又は（及び）
金属箔に塗布して乾燥した後、このプラスチツク
フイルムと金属箔とを重ね加熱圧着し、アフター
キユアーすることを特徴とするフレキシブルプリ
ント配線用基板の製造方法。[Scope of Claims] 1 As a silicone adhesive, (A) 100 parts by weight of a polyorganosiloxane having an average of two or more vinyl groups bonded to silicon atoms in the molecule and having an average degree of polymerization of 50 to 10,000, (B ) A polyorganohydrodiene siloxane having an average of more than 2 hydrogen atoms bonded to silicon atoms in the molecule, where the hydrogen atoms are per mole of vinyl groups bonded to silicon atoms in (A),
Amount of 0.5 to 10 mol, ( C) 20 to 150 parts by weight of silica filler, ( D ) General formula (FeO )
is between 0.05 and 1.0. ) 0.5 to 20 parts by weight of iron oxide or (and) carbon black, (E) a platinum compound, 1 to 200 PPm as a platinum atom, (F) at least one hydrogen atom bonded to a silicon atom in the molecule, It is represented by the general formula [Formula] (where Q 1 and Q 2 are the same or different linear or branched alkylene groups, and R is an alkyl group having 1 to 4 carbon atoms), and contains a silicon atom. An adhesive composition consisting of 0.5 to 50 parts by weight of a polysiloxane having at least one group in its molecule bonded to
Plastic film or (and) over 260℃
A method for producing a flexible printed wiring board, which comprises coating the plastic film on metal foil, drying it, and then heat-pressing the plastic film and the metal foil for after-curing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11936281A JPS5821893A (en) | 1981-07-31 | 1981-07-31 | Method of producing flexible printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11936281A JPS5821893A (en) | 1981-07-31 | 1981-07-31 | Method of producing flexible printed circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5821893A JPS5821893A (en) | 1983-02-08 |
| JPS6360558B2 true JPS6360558B2 (en) | 1988-11-24 |
Family
ID=14759612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11936281A Granted JPS5821893A (en) | 1981-07-31 | 1981-07-31 | Method of producing flexible printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5821893A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3010034U (en) * | 1994-10-11 | 1995-04-18 | クリステック株式会社 | Diamond saw blade |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0737709B2 (en) * | 1985-12-25 | 1995-04-26 | カンボウプラス株式会社 | Heat resistant sheet |
| JPH02307294A (en) * | 1989-05-23 | 1990-12-20 | Furukawa Saakitsuto Fuoiru Kk | Copper foil for printed circuit |
| JP2518954B2 (en) * | 1990-05-28 | 1996-07-31 | パイオニア株式会社 | Information recording medium |
| US6004679A (en) * | 1991-03-14 | 1999-12-21 | General Electric Company | Laminates containing addition-curable silicone adhesive compositions |
| TWI437931B (en) * | 2011-12-16 | 2014-05-11 | Prologium Technology Co Ltd | Pcb structure |
| EP3772240A1 (en) * | 2019-08-02 | 2021-02-03 | Prologium Technology Co., Ltd. | Pcb structure with a silicone layer as adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5448853A (en) * | 1977-09-26 | 1979-04-17 | Toshiba Silicone | Organopolysiloxane curable into rubbery state |
| JPS5519438A (en) * | 1978-07-26 | 1980-02-12 | Mitsubishi Electric Corp | Brazing method |
-
1981
- 1981-07-31 JP JP11936281A patent/JPS5821893A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5448853A (en) * | 1977-09-26 | 1979-04-17 | Toshiba Silicone | Organopolysiloxane curable into rubbery state |
| JPS5519438A (en) * | 1978-07-26 | 1980-02-12 | Mitsubishi Electric Corp | Brazing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3010034U (en) * | 1994-10-11 | 1995-04-18 | クリステック株式会社 | Diamond saw blade |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5821893A (en) | 1983-02-08 |
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