JPH0513400B2 - - Google Patents
Info
- Publication number
- JPH0513400B2 JPH0513400B2 JP5439185A JP5439185A JPH0513400B2 JP H0513400 B2 JPH0513400 B2 JP H0513400B2 JP 5439185 A JP5439185 A JP 5439185A JP 5439185 A JP5439185 A JP 5439185A JP H0513400 B2 JPH0513400 B2 JP H0513400B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- adhesive
- printed circuit
- flexible printed
- 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.)
- Expired - Fee Related
Links
- 239000004094 surface-active agent Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- 150000005215 alkyl ethers Chemical class 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 description 36
- 230000001070 adhesive effect Effects 0.000 description 36
- 230000007423 decrease Effects 0.000 description 7
- 238000005476 soldering Methods 0.000 description 7
- -1 ether ester Chemical class 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003475 lamination Methods 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZZAGLMPBQOKGGT-UHFFFAOYSA-N [4-[4-(4-prop-2-enoyloxybutoxy)benzoyl]oxyphenyl] 4-(4-prop-2-enoyloxybutoxy)benzoate Chemical compound C1=CC(OCCCCOC(=O)C=C)=CC=C1C(=O)OC(C=C1)=CC=C1OC(=O)C1=CC=C(OCCCCOC(=O)C=C)C=C1 ZZAGLMPBQOKGGT-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
〔産業上の利用分野〕
本発明はフレキシブル印刷回路用基板の製造に
おいて用いられる優れた接着力、耐熱性および平
滑性を賦与する接着剤およびこの接着剤層を有す
るフレキシブル印刷回路用基板に関するものであ
る。
〔従来技術〕
従来、高度の接着力、耐熱性を賦与するフレキ
シブル印刷回路基板用接着剤として、アクリル系
接着剤（特開昭59−51215号公報）が知られてい
る。しかし、接着剤ワニスをプラスチツクフイル
ムに連続的に塗布し、熱風乾燥機内で乾燥を行な
うと、フイルムの連続方向にすじ状の凹凸が発生
し、金属箔をロールラミネート又はプレスにより
圧着する際、圧着不良を起こすことがある。ま
た、圧着後フイルム面に凹凸が発生し、フレキシ
ブル印刷回路用基板の性能及び外観を損ねるとい
う欠点があつた。
〔発明の目的〕
本発明者らは、フレキシブル印刷回路基板用接
着剤の上記欠点を解消するため、鋭意研究を重ね
た結果、アクリル接着剤に特定の界面活性剤を組
み合わせ添加することにより、接着力、半田耐熱
性を低下させることなく、塗布乾燥後の接着剤面
の外観を改善し、金属箔のプレスおよびロール圧
着性、およびフレキシブル印刷回路用基板の外観
を著しく向上できることを見い出し本発明に到達
した。
〔発明の構成〕
本発明は、
１ 次の(a)〜(e)を含む接着剤
(a) アクリロニトリル 15〜35重量％、炭素数
５以下のアルコールとアクリル酸ないしメタ
クリル酸とのエステル55〜83重量％及びアク
リル酸ないしメタクリル酸２〜10重量％との
共重合によつて得られるアクリル系樹脂
100重量部
(b) エポキシ樹脂 ５〜70重量部
(c) ポリイソシアネート 20〜100重量部
上記(a)〜(c)の混合物100重量部に対し
(d) フツ素化アルキルエステル系界面活性剤
0.03〜0.1重量部
(e) アルキルエーテル系界面活性剤
0.5〜1.3重量部
２ 次の(a)〜(e)を含む接着剤層を有するフレキシ
ブル印刷回路用基板
(a) アクリロニトリル 15〜35重量％、炭素数
５以下のアルコールとアクリル酸ないしメタ
クリル酸とのエステル55〜83重量及びアクリ
ル酸ないしメタクリル酸２〜10重量％との共
重合によつて得られるアクリル系樹脂
100重量部
(b) エポキシ樹脂 ５〜70重量部
(c) ポリイソシアネート 20〜100重量部
上記(a)〜(c)の混合物100重量部に対し、
(d) フツ素化アルキルエステル系界面活性剤
0.03〜0.1重量部
(e) アルキルエーテル系活性剤 0.5〜1.3重量部
に関するものである。
本発明において良好な結果を得るためには、接
着剤成分を上記の配合割合にすることが不可欠で
ある。
各成分について(a)成分中、アクリロニトリルを
15〜35重量％とすることが必要である。15重量％
未満では接着強度、半田耐熱性が低下する。アク
リロニトリル成分が増えるにつれて接着強度、半
田耐熱性が向上するが、35重量％を越えると可撓
性が低下する。充分な接着強度、半田耐熱性、可
撓性を両立させるには、15〜25重量％が望まし
い。炭素数５以下のアルコールとアクリル酸ない
しメタクリル酸とのエステルとしては、アクリル
酸エチル、アクリル酸ｎ−ブチル、アクリル酸２
−エチルヘキシル、メタクリル酸エチル、メタク
リル酸ｎ−ブチル、メタクリル酸２−エチルヘキ
シル等があげられる。アクリル酸ないしメタクリ
ル酸は２〜10重量％とする必要がある。２重量％
未満では、接着強度、半田耐熱性が低下する。10
重量％を越えると可撓性が低下する。(b)成分のエ
ポキシ樹脂としては、ビスフエノール系、レゾー
ル系、ノボラツク系、エーテルエステル系のグリ
シジルエーテル及び環状脂肪族エポキシ化合物な
ど通常のもの、およびそれらの臭素化物を用いる
ことができる。エポキシ樹脂が５重量部未満では
接着剤全体のフローが小さくなり加熱圧着、特に
ロールラミネートで金属箔と均一に接着させるこ
とは難しく、接着強度、半田耐熱性等を不安定な
ものにする。70重量部を越えると可撓性が低下す
る。ポリイソシアネートとしては、２，６−トリ
レンジイソシアネート、２，４−トリレンジイソ
シアネート系、ジフエニルメタン−４，4′−ジイ
ソシアネート系、ポリメチレンポリフエニルポリ
イソシアネート系、ヘキサメチレンジイソシアネ
ート系の各種イソシアネートを使用できる。特に
ヘキサメチレンジイソシアネート（以下MDIと
記す）を原料とするポリイソシアネートは耐候性
に優れており、フレキシブル印刷回路板の回路部
の接着力が熱劣化しにくくなる。エポキシ樹脂に
対するイソシアネートの当量比は0.4〜1.2が適当
で0.4未満では、半田耐熱性、耐溶剤性を低下さ
せ、1.2を越えるとワニスライフを極端に短くし、
好ましくは0.6〜0.9である。
(d)成分のフツ素化アルキルエステル系界面活性
剤としては、FC−430、FC−431（商品名、住友
スリーエム(株)社製）、Ｓ−141、Ｓ−145（商品名・
旭硝子社製）などを使用することができ、数種の
フツ素化アルキルエステル系界面活性剤を併用し
たものでも良い。
また(e)成分のアルキルエーテル系界面活性剤と
してはポリオキシエチレンアルキルエーテル、ポ
リオキシエチレン−アルキルアリルエーテル、ポ
リオキシエチレンポリオキシプロピレンエーテル
等を用いることができ、数種のアルキルエーテル
系界面活性剤を併用したものでも良い。
添加量は、フツ素化アルキルエステル系界面活
性剤を0.03〜0.1重量％にすることが必要である。
0.03重量％未満では接着剤面を平滑にする効果が
ない。また0.1重量％を越えると、接着剤ワニス
の泡立ちが著しく塗布作業性が低下する。アルキ
ルエーテル系界面活性剤は0.5〜1.3重量％とする
ことが必要である。0.5重量％未満ではフツ素化
アルキルエステル系界面活性剤により発生した泡
を消す効果がない。また、1.3重量％を越えると
接着強度半田耐熱性が低下する。
本発明の接着剤には、三酸化アンチモン、水酸
化アルミニウム、ホウ酸バリウム等の難燃性無機
化合物、シリカ、アルミナ、マイカ、酸化チタ
ン、ジルコニア、珪酸カルシウム、水酸化マグネ
シウム、酸化マグネシウム、酸化鉄、炭酸カルシ
ウム、炭化ケイ素等の無機フイラーを接着剤100
重量部に対して45重量部以下の割合で含有させて
もよい。これら無機フイラーが45重量部を越える
と、接着剤フローが小さくなり、ロールラミネー
ト性を低下させ、さらに接着強度が低下する。
これらの無機フイラーは疎水処理を行なつたも
のでもよい。処理剤は例えば、ジメチルジクロロ
シラン、シリコンオイル、ヘキサメチレンジシラ
ザン（HMDS）、C16〜C18アルキルトリエトキシ
シラン、メチルトリエトキシシランが掲げられ
る。これら以外にガラスクロスに含浸させたもの
でもよい。さらに、これら以外の充填剤、安定
剤、界面活性剤溶剤などの通常に使用される種々
の添加剤を目的に応じて配合したものであつても
よい。
本発明の印刷回路用基板としては、使用するプ
ラスチツクフイルムにはポリイミドフイルムのほ
かポリエステルフイルム、ポリエチレンフイル
ム、ポリプロピレンフイルム、ポリ塩化ビニルフ
イルム等があり、金属箔として主に銅箔を用いる
がアルミ箔を用いたものでもよい。これらのプラ
スチツクフイルムと金属箔を本発明の接着剤によ
り加熱圧着して得られるフレキシブル銅張板の他
にフレキシブル印刷回路の絶縁性カバーレイ、フ
レキシブル印刷回路同志の多重積層、さらに硬質
の補強板との接着に上記接着剤を用いた印刷回路
板を含むものである。
〔発明の効果〕
本発明による接着剤を用いることにより、優れ
た接着力耐熱性を保持し、かつ従来の欠点であつ
た接着剤面の凹凸を解消し、ロール又はプレス成
形性、およびフレキシブル印刷回路用基板の外観
を著しく改善できたものである。
〔実施例〕
第１表の配合表に従つて、固形分値20重量％に
なるようにMEKに溶解し接着剤ワニスを調製し
厚さ25μｍのポリイミドフイルム（Du Pont製カ
プトン）に乾燥後厚み30μｍになるように塗布
し、130℃の熱風乾燥機で５分間乾燥させた。接
着剤を塗布した面に厚さ35μｍの銅箔をロールに
より温度160℃速度0.5ｍ／min圧力３Kgｆ／cm2で
ラミネートした。次いで120℃のオーブン中で12
時間キニアを行ない、フレキシブル銅張板を得
た。接着剤を塗布乾燥後の接着剤面の平滑性およ
び得られた銅張板の品質を第２表に示す。
[Industrial Application Field] The present invention relates to an adhesive that imparts excellent adhesive strength, heat resistance, and smoothness to be used in the production of flexible printed circuit boards, and to flexible printed circuit boards having this adhesive layer. be. [Prior Art] Acrylic adhesives (Japanese Unexamined Patent Publication No. 59-51215) have been known as adhesives for flexible printed circuit boards that provide high adhesive strength and heat resistance. However, when adhesive varnish is continuously applied to a plastic film and dried in a hot air dryer, streak-like irregularities occur in the continuous direction of the film, and when the metal foil is crimped by roll lamination or press, it is difficult to bond. May cause defects. Further, there is a drawback that unevenness occurs on the film surface after crimping, impairing the performance and appearance of the flexible printed circuit board. [Object of the Invention] In order to eliminate the above-mentioned drawbacks of adhesives for flexible printed circuit boards, the present inventors have conducted extensive research and found that adhesives can be improved by adding a combination of specific surfactants to acrylic adhesives. We have discovered that it is possible to improve the appearance of the adhesive surface after coating and drying without reducing the strength and soldering heat resistance, and to significantly improve the press and roll crimp properties of metal foils and the appearance of flexible printed circuit boards. Reached. [Structure of the Invention] The present invention provides: 1. An adhesive containing the following (a) to (e): (a) 15 to 35% by weight of acrylonitrile, an ester of acrylic acid or methacrylic acid with an alcohol having 5 or less carbon atoms; Acrylic resin obtained by copolymerization with 83% by weight and 2 to 10% by weight of acrylic acid or methacrylic acid
100 parts by weight (b) Epoxy resin 5 to 70 parts by weight (c) Polyisocyanate 20 to 100 parts by weight For 100 parts by weight of the mixture of (a) to (c) above (d) Fluorinated alkyl ester surfactant
0.03-0.1 parts by weight (e) Alkyl ether surfactant
0.5 to 1.3 parts by weight 2 A flexible printed circuit board having an adhesive layer containing the following (a) to (e) (a) Acrylonitrile 15 to 35% by weight, an alcohol having 5 or less carbon atoms, and acrylic acid or methacrylic acid. Acrylic resin obtained by copolymerization with 55 to 83% by weight of ester of and 2 to 10% by weight of acrylic acid or methacrylic acid
100 parts by weight (b) Epoxy resin 5 to 70 parts by weight (c) Polyisocyanate 20 to 100 parts by weight For 100 parts by weight of the mixture of (a) to (c) above, (d) Fluorinated alkyl ester surfactant agent
0.03 to 0.1 parts by weight (e) Alkyl ether activator 0.5 to 1.3 parts by weight. In order to obtain good results in the present invention, it is essential to mix the adhesive components in the above-mentioned proportions. Regarding each component (a), acrylonitrile is
It is necessary to set it as 15-35 weight%. 15% by weight
If it is less than that, adhesive strength and soldering heat resistance will decrease. As the acrylonitrile content increases, adhesive strength and soldering heat resistance improve, but when it exceeds 35% by weight, flexibility decreases. In order to achieve sufficient adhesive strength, solder heat resistance, and flexibility, the content is preferably 15 to 25% by weight. Examples of esters of alcohols having 5 or less carbon atoms and acrylic acid or methacrylic acid include ethyl acrylate, n-butyl acrylate, and diacrylic acid.
-Ethylhexyl, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. The amount of acrylic acid or methacrylic acid must be 2 to 10% by weight. 2% by weight
If it is less than that, adhesive strength and soldering heat resistance will decrease. Ten
If the weight percentage is exceeded, flexibility decreases. As the epoxy resin of component (b), usual ones such as bisphenol type, resol type, novolak type, ether ester type glycidyl ethers and cycloaliphatic epoxy compounds, and their brominated products can be used. If the epoxy resin is less than 5 parts by weight, the flow of the entire adhesive will be small, making it difficult to uniformly adhere the adhesive to metal foil by heat-press bonding, especially roll lamination, and the adhesive strength, soldering heat resistance, etc. will become unstable. If it exceeds 70 parts by weight, flexibility will decrease. As the polyisocyanate, various isocyanates such as 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, polymethylene polyphenyl polyisocyanate, and hexamethylene diisocyanate can be used. . In particular, polyisocyanate made from hexamethylene diisocyanate (hereinafter referred to as MDI) has excellent weather resistance, and the adhesive strength of the circuit portion of a flexible printed circuit board is resistant to thermal deterioration. The appropriate equivalent ratio of isocyanate to epoxy resin is 0.4 to 1.2. If it is less than 0.4, the soldering heat resistance and solvent resistance will decrease, and if it exceeds 1.2, the varnish life will be extremely shortened.
Preferably it is 0.6 to 0.9. The fluorinated alkyl ester surfactants of component (d) include FC-430, FC-431 (trade name, manufactured by Sumitomo 3M Ltd.), S-141, S-145 (trade name,
(manufactured by Asahi Glass Co., Ltd.), etc., or a combination of several types of fluorinated alkyl ester surfactants may be used. In addition, as the alkyl ether surfactant of component (e), polyoxyethylene alkyl ether, polyoxyethylene-alkyl allyl ether, polyoxyethylene polyoxypropylene ether, etc. can be used, and several types of alkyl ether surfactants can be used. A combination of agents may also be used. The amount of the fluorinated alkyl ester surfactant added must be 0.03 to 0.1% by weight.
If it is less than 0.03% by weight, it will not have the effect of smoothing the adhesive surface. Moreover, if it exceeds 0.1% by weight, the adhesive varnish will foam significantly and the coating workability will deteriorate. The amount of the alkyl ether surfactant needs to be 0.5 to 1.3% by weight. If it is less than 0.5% by weight, it will not be effective in eliminating foam generated by the fluorinated alkyl ester surfactant. Moreover, if it exceeds 1.3% by weight, the adhesive strength and soldering heat resistance will decrease. The adhesive of the present invention includes flame-retardant inorganic compounds such as antimony trioxide, aluminum hydroxide, and barium borate, silica, alumina, mica, titanium oxide, zirconia, calcium silicate, magnesium hydroxide, magnesium oxide, and iron oxide. Adhesive 100% with inorganic fillers such as calcium carbonate, silicon carbide, etc.
It may be contained in a ratio of 45 parts by weight or less to parts by weight. When the amount of these inorganic fillers exceeds 45 parts by weight, adhesive flow becomes small, roll lamination properties are reduced, and adhesive strength is further reduced. These inorganic fillers may be hydrophobically treated. Examples of the treating agent include dimethyldichlorosilane, silicone oil, hexamethylene disilazane (HMDS), C16 to C18 alkyltriethoxysilane, and methyltriethoxysilane. In addition to these, glass cloth impregnated may also be used. Furthermore, various commonly used additives such as fillers, stabilizers, surfactant solvents, etc. other than these may be blended depending on the purpose. In the printed circuit board of the present invention, plastic films used include polyimide films, polyester films, polyethylene films, polypropylene films, polyvinyl chloride films, etc., and copper foils are mainly used as metal foils, but aluminum foils are also used. It may be used. In addition to flexible copper clad boards obtained by heat-pressing these plastic films and metal foils using the adhesive of the present invention, there are also insulating coverlays for flexible printed circuits, multiple laminations of flexible printed circuits, and hard reinforcing plates. This includes a printed circuit board using the above-mentioned adhesive for adhesion. [Effects of the Invention] By using the adhesive according to the present invention, it maintains excellent adhesive strength and heat resistance, eliminates the unevenness of the adhesive surface that was a conventional drawback, and improves roll or press formability and flexible printing. This significantly improves the appearance of circuit boards. [Example] According to the formulation table in Table 1, an adhesive varnish was prepared by dissolving it in MEK to a solid content of 20% by weight, and it was applied to a polyimide film (Kapton manufactured by Du Pont) with a thickness of 25 μm after drying. It was coated to a thickness of 30 μm and dried in a hot air dryer at 130° C. for 5 minutes. A 35 μm thick copper foil was laminated on the surface coated with the adhesive using a roll at a temperature of 160° C. at a speed of 0.5 m/min and a pressure of 3 kgf/cm 2 . Then in the oven at 120℃ for 12
A flexible copper clad board was obtained by time kinearing. Table 2 shows the smoothness of the adhesive surface after the adhesive was applied and dried and the quality of the obtained copper clad board.
【表】【table】
【表】【table】
Claims (1)
ブル印刷回路用基板。 (a) アクリロニトリル15〜35重量％、炭素数５以
下のアルコールとアクリル酸ないしメタクリル
酸とのエステル55〜83重量％及びアクリル酸な
いしメタクリル酸２〜10重量％との共重合によ
つて得られるアクリル系樹脂 100重量部 (b) エポキシ樹脂 ５〜70重量部 (c) ポリイソシアネート20〜100重量部 上記(a)〜(c)の混合物100重量部に対し、 (d) フツ素化アルキルエステル系界面活性剤
0.03〜0.1重量部 (e) アルキルエーテル系界面活性剤
0.5〜1.3重量部。[Scope of Claims] 1. A flexible printed circuit board having an adhesive layer comprising the following (a) to (e). (a) Obtained by copolymerization of 15-35% by weight of acrylonitrile, 55-83% by weight of an ester of an alcohol having 5 or less carbon atoms with acrylic acid or methacrylic acid, and 2-10% by weight of acrylic acid or methacrylic acid. Acrylic resin 100 parts by weight (b) Epoxy resin 5 to 70 parts by weight (c) Polyisocyanate 20 to 100 parts by weight For 100 parts by weight of the mixture of (a) to (c) above, (d) Fluorinated alkyl ester surfactant
0.03-0.1 parts by weight (e) Alkyl ether surfactant
0.5-1.3 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5439185A JPS61213275A (en) | 1985-03-20 | 1985-03-20 | Adhesive and flexible printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5439185A JPS61213275A (en) | 1985-03-20 | 1985-03-20 | Adhesive and flexible printed circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61213275A JPS61213275A (en) | 1986-09-22 |
| JPH0513400B2 true JPH0513400B2 (en) | 1993-02-22 |
Family
ID=12969383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5439185A Granted JPS61213275A (en) | 1985-03-20 | 1985-03-20 | Adhesive and flexible printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61213275A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4425118B2 (en) * | 2003-12-03 | 2010-03-03 | 株式会社有沢製作所 | Flame retardant resin composition, metal-clad laminate for flexible printed wiring board using the composition, coverlay, adhesive sheet, and flexible printed wiring board |
-
1985
- 1985-03-20 JP JP5439185A patent/JPS61213275A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61213275A (en) | 1986-09-22 |
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| LAPS | Cancellation because of no payment of annual fees |