JPH04328183A - Cover lay film - Google Patents
Cover lay filmInfo
- Publication number
- JPH04328183A JPH04328183A JP12672791A JP12672791A JPH04328183A JP H04328183 A JPH04328183 A JP H04328183A JP 12672791 A JP12672791 A JP 12672791A JP 12672791 A JP12672791 A JP 12672791A JP H04328183 A JPH04328183 A JP H04328183A
- Authority
- JP
- Japan
- Prior art keywords
- film
- weight
- adhesive
- pts
- parts
- 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.)
- Granted
Links
- 239000012787 coverlay film Substances 0.000 title claims abstract description 20
- 239000000853 adhesive Substances 0.000 claims abstract description 29
- 230000001070 adhesive effect Effects 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- 239000010408 film Substances 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 5
- 239000011135 tin Substances 0.000 claims abstract description 5
- 239000002985 plastic film Substances 0.000 claims abstract description 3
- 229920006255 plastic film Polymers 0.000 claims abstract description 3
- 150000002222 fluorine compounds Chemical class 0.000 claims description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 abstract description 25
- 238000005476 soldering Methods 0.000 abstract description 11
- -1 imidazole compound Chemical class 0.000 abstract description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- QQKYFCAJVVQWPC-UHFFFAOYSA-N Cl.[B] Chemical compound Cl.[B] QQKYFCAJVVQWPC-UHFFFAOYSA-N 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000009193 crawling Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920001646 UPILEX Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound 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
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000007706 flame test Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は優れた耐半田性、特に耐
半田付け性、耐半田リフロ−性を有するフレキシブルプ
リント回路保護用カバ−レイフィルムに関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coverlay film for protecting flexible printed circuits having excellent solder resistance, particularly solder resistance and solder reflow resistance.
【０００２】0002
【従来の技術】近年エレクトロニクス製品の軽薄短小、
高性能化に伴いプリント基板の需要が増え、なかでもフ
レキシブルプリント基板は、その使用範囲が広がり需要
が伸びてきている。それにつれてフレキシブルプリント
回路の保護用カバ−レイフィルムの使用が多くなり、そ
の性能向上が望まれているが、具体的にはフレキシブル
プリント回路基板との接着性、半田耐熱性、電気絶縁性
、屈曲性、および耐環境性等がしばしば問題になってい
る。特に最近は、フレキシブルプリント回路基板にカバ
−レイフィルムを貼り合せた後、部品実装時の半田付け
、あるいは半田リフロ−工程において、半田がカバ−レ
イフィルムの下部にもぐり込む現象が問題になってきて
いる。[Prior art] In recent years, electronic products have become lighter, thinner, and smaller.
Demand for printed circuit boards is increasing as performance improves, and demand for flexible printed circuit boards in particular is increasing as their range of use expands. As a result, the use of coverlay films to protect flexible printed circuits has increased, and improvements in their performance are desired. The properties, environmental resistance, etc. are often a problem. Particularly recently, after bonding a coverlay film to a flexible printed circuit board, the phenomenon of solder creeping into the bottom of the coverlay film during soldering during component mounting or during the solder reflow process has become a problem. There is.
【０００３】このような背景から、近年、接着性、耐熱
性とともに耐半田付け性、耐半田リフロ−性を兼備した
フレキシブルプリント回路の保護用カバ−レイフィルム
が要求されるようになってきた。従来カバ−レイフィル
ム用の接着剤としては ＮＢＲ／フェノ−ル樹脂、エポ
キシ・フェノ−ル／ＮＢＲ 、ＮＢＲ／エポキシ樹脂、
エポキシ／ポリエステル樹脂、エポキシ／アクリル樹脂
、アクリル樹脂等が用いられる。しかしこれらの接着剤
は、一長一短があり、必ずしも前記諸特性を満足してい
ない。 ＮＢＲ系は熱劣化が大きく、特にこれに無機難
燃剤を配合したものはそれが著しい。エポキシ系は剥離
強度が低く、臭素化エボキシ系は耐熱性が低下する。ま
た、エポキシ／ポリエステル系、アクリル系等について
も同様である。
以上のように従来の接着剤は接着性、耐熱性、を満足す
るものが少なかった。さらに、これら接着剤を用いたカ
バ−レイフィルムは、フレキシブル回路基板との貼り合
せ加工時に １７０〜 １８０℃で３０分〜１時間程度
の高温長時間を必要としていた。Against this background, in recent years there has been a demand for a coverlay film for protecting flexible printed circuits that has not only adhesion and heat resistance but also solderability and solder reflow resistance. Conventional adhesives for coverlay films include NBR/phenol resin, epoxy phenol/NBR, NBR/epoxy resin,
Epoxy/polyester resin, epoxy/acrylic resin, acrylic resin, etc. are used. However, these adhesives have advantages and disadvantages, and do not necessarily satisfy the above-mentioned characteristics. The NBR type has a large thermal deterioration, and this is particularly noticeable when an inorganic flame retardant is added to the NBR type. Epoxy systems have low peel strength, and brominated epoxy systems have low heat resistance. The same applies to epoxy/polyester, acrylic, and the like. As mentioned above, few conventional adhesives satisfy the requirements of adhesiveness and heat resistance. Furthermore, coverlay films using these adhesives require high temperature and long hours of about 30 minutes to 1 hour at 170 to 180 DEG C. when bonded to flexible circuit boards.
【０００４】0004
【発明が解決しようとする課題】本発明は、前記諸欠点
を解消して、半田耐熱性、耐半田付け性、耐半田リフロ
−性、さらに低温短時間加工性に優れたフレキシブルプ
リント回路の保護用カバ−レイフィルムを提供しようと
するものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks and provides protection for flexible printed circuits that have excellent soldering heat resistance, soldering resistance, solder reflow resistance, and low-temperature short-time processability. The purpose of the present invention is to provide a coverlay film for
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記課題
を解決するために接着剤組成に重点を置き、鋭意研究を
行ってきた結果、本発明に到達した。すなわち、本発明
は耐熱性プラスチックフィルムの片面に下記組成の接着
剤を塗布、半硬化状態とし、これに離型性フィルムまた
は離型紙を圧着してなるカバ−レイフィルムを要旨とす
るものである。イ）エポキシ樹脂 １００重量部。
ロ）カルボキシル基含有ニトリルゴム １０〜４０重
量部。ハ）硬化剤 １〜５０重量部。ニ）イミダゾ−
ル化合物、第三アミン類のテトラフェニルほう素酸塩及
び亜鉛、スズ、ニッケルのほうふっ化物の一種以上から
選ばれる硬化促進剤 ０．１〜５重量部。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have focused on adhesive compositions and have conducted extensive research, and as a result, have arrived at the present invention. That is, the gist of the present invention is a coverlay film made by applying an adhesive having the composition below to one side of a heat-resistant plastic film, bringing it to a semi-cured state, and pressing a release film or release paper onto the adhesive. . b) Epoxy resin 100 parts by weight. b) Carboxyl group-containing nitrile rubber 10 to 40 parts by weight. c) Curing agent 1 to 50 parts by weight. d) Imidazo-
0.1 to 5 parts by weight of a curing accelerator selected from one or more of fluorine compounds, tetraphenyl borates of tertiary amines, and fluorides of zinc, tin, and nickel.
【０００６】以下、本発明について詳細に説明するが、
先ず接着剤組成物について述べる。イ）エポキシ樹脂と
しては、１分子中に２個以上のエポキシ基をもつもので
あればよく、例えばビスフェノ−ル型エポキシ樹脂、ノ
ボラック樹脂等のグリシジルエ−テル型、環状脂肪族エ
ポキシ樹脂、芳香族型エポキシ樹脂、ハロゲン化エポキ
シ樹脂等を単独または２種以上混合して用いることがで
きる。また上記例示されたエポキシ樹脂の中で、ハロゲ
ン化エポキシ樹脂、好ましくは臭素化エポキシ樹脂を用
いることにより難燃性に優れた接着剤を得ることができ
る。この臭素化エポキシ樹脂は、１分子中にエポキシ基
と臭素原子を有するものであればよく、例えばビスフェ
ノ−ル型臭素化エポキシ樹脂、ノボラック型臭素化エポ
キシ樹脂等が挙げられる。具体的には、油化シェルエポ
キシ （株） 製のエビコ−ト５０４５（Ｂｒ含有量：
１９重量％）、５０４６（Ｂｒ：２１重量％）、５０４
８（Ｂｒ：２５重量％），５０４９（Ｂｒ：２６重量％
）、５０５０（Ｂｒ：４９重量％）、日本化薬 （株）
製のＢＲＥＮ−Ｓ（Ｂｒ：３５重量％）等がある。こ
れらのＢｒ含有量の異なる臭素化エボキシ樹脂を単独ま
たは２種以上混合して用いることができる。なおＢｒ含
有量は２１〜１５重量％の臭素エボキシ樹脂が好ましい
。[0006] The present invention will be explained in detail below.
First, the adhesive composition will be described. b) The epoxy resin may be one having two or more epoxy groups in one molecule, such as bisphenol type epoxy resin, glycidyl ether type such as novolac resin, cycloaliphatic epoxy resin, aromatic epoxy resin, etc. Type epoxy resins, halogenated epoxy resins, etc. can be used alone or in combination of two or more. Further, among the above-mentioned epoxy resins, an adhesive having excellent flame retardancy can be obtained by using a halogenated epoxy resin, preferably a brominated epoxy resin. This brominated epoxy resin may have an epoxy group and a bromine atom in one molecule, and examples thereof include bisphenol type brominated epoxy resin, novolac type brominated epoxy resin, and the like. Specifically, Ebicoat 5045 (Br content:
19% by weight), 5046 (Br: 21% by weight), 504
8 (Br: 25% by weight), 5049 (Br: 26% by weight
), 5050 (Br: 49% by weight), Nippon Kayaku Co., Ltd.
There are BREN-S (Br: 35% by weight) manufactured by Co., Ltd. These brominated epoxy resins having different Br contents can be used alone or in combination of two or more. Note that the bromine epoxy resin preferably has a Br content of 21 to 15% by weight.
【０００７】ロ）成分のカルボキシル基含有ニトリルゴ
ムとしては、アクリルニトリルとブタジェンが共重合し
たアクリロニトリル−ブタジェン共重合ゴムの末端をカ
ルボキシル化したもの等が挙げられる。具体的には、グ
ッドリッチ社製のハイカーＣＴＢＮ、ハイカーＣＴＢＮ
Ｘ 、ハイカー１０７２、日本ゼオン （株） 製のニ
ポール１０７２Ｊ 、ニポール１０７２、ニポールＤＮ
６１２ 、ニポールＤＮ６３１ 、ニポールＤＮ６０１
等がある。これらのカルボキシル基含有ニトリルゴム
は単独または２種以上混合して用いることができる。カ
ルボキシル基の含有率は２〜８重量％が好ましい。[0007] As the carboxyl group-containing nitrile rubber of component (b), there may be mentioned an acrylonitrile-butadiene copolymer rubber obtained by copolymerizing acrylonitrile and butadiene, and the terminals of which are carboxylated. Specifically, Goodrich's Hiker CTBN, Hiker CTBN
X, Hiker 1072, Nipole 1072J, Nipole 1072, Nipole DN manufactured by Nippon Zeon Co., Ltd.
612, Nipaul DN631, Nipaul DN601
etc. These carboxyl group-containing nitrile rubbers can be used alone or in combination of two or more. The content of carboxyl groups is preferably 2 to 8% by weight.
【０００８】ハ）硬化剤としては通常のエポキシ樹脂の
硬化剤として用いられるものであれば特に限定する必要
はなく、例えば、ジエチルトリアミン、トリエチレンテ
トラミン、メタキシレンジアミン、ジアミノジフェニル
メタンおよびジアミノジフェニルスルフォン等のアミン
系化合物、無水フタル酸、無水ヘキサヒドロフタル酸、
無水テトラヒドロフタル酸、無水トリメリット酸等の酸
無水物、ジシアンジアミド、三ふっ化ほう素アミン錯化
合物等が挙げられる。これらは単独または２種以上混合
して用いることができる。これらの硬化剤は、通常、イ
）成分のエポキシ樹脂 １００重量部当たり１〜５０重
量部の広い範囲の量で添加することができるが、その使
用量は硬化剤の種類および各樹脂の種類や量によって適
宜選択される。c) The curing agent is not particularly limited as long as it is used as a curing agent for ordinary epoxy resins, and examples thereof include diethyltriamine, triethylenetetramine, metaxylene diamine, diaminodiphenylmethane, and diaminodiphenylsulfone. amine compounds, phthalic anhydride, hexahydrophthalic anhydride,
Examples include acid anhydrides such as tetrahydrophthalic anhydride and trimellitic anhydride, dicyandiamide, and boron trifluoride amine complex compounds. These can be used alone or in combination of two or more. These curing agents can be added in a wide range of amounts, usually from 1 to 50 parts by weight per 100 parts by weight of the epoxy resin component (a), but the amount used depends on the type of curing agent and the type of each resin. It is selected appropriately depending on the amount.
【０００９】ニ）成分の硬化促進剤としては２−アルキ
ル−４−メイチルイミダゾール、２−アルキル−４−エ
チルイミダゾール、１−（２−シアノエチル）−２−ア
ルキルイミダゾール、２−フェニルイミダゾール等のイ
ミダゾール系化合物、トリエチルアンモニウムテトラフ
ェニルボレート等の第三級アミン類のテトラフェニルほ
う素酸塩およびほうふっ化亜鉛、ほうふっ化スズ、ほう
ふっ化ニッケルが挙げられ、これは単独または２種以上
混合して用いられる。これらの添加量は ０．１〜５重
量部、好ましくは ０．２〜３重量部が適当である。ま
た、上記イミダゾール系化合物、第三アミン類のテトラ
フェニルほう素酸塩および亜鉛、スズ、ニッケルのほう
ふっ化物の中では、第三アミン類のテトラフェニルほう
素酸塩と亜鉛、スズ、ニッケルのほうふっ化物が好しく
、さらに好ましくは亜鉛、スズ、ニッケルのほうふっ化
物が好しい。[0009] Component curing accelerators include 2-alkyl-4-methylimidazole, 2-alkyl-4-ethylimidazole, 1-(2-cyanoethyl)-2-alkylimidazole, 2-phenylimidazole, etc. Examples include imidazole compounds, tetraphenyl borates of tertiary amines such as triethylammonium tetraphenylborate, zinc borofluoride, tin borofluoride, and nickel borofluoride, which may be used alone or in combination of two or more. It is used as The appropriate amount of these additives to be added is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight. In addition, among the imidazole compounds, tetraphenyl borates of tertiary amines, and fluorides of zinc, tin, and nickel, there are Fluorides of fluorides are preferred, and fluorides of zinc, tin, and nickel are more preferred.
【００１０】また、上記接着剤には、必要により微粒子
状無機質粉末を添加できる。微粒子状無機質粉末として
は、水酸化アルミニウム、水酸化マグネシウム等の金属
水酸物、酸化亜鉛、酸化マグネシウム、三酸化アンチモ
ン等の酸化物、炭酸カルシウム、炭酸マグネシウム等の
炭酸塩、ケイ酸アルミニウム、ケイ酸マグネシウム、ケ
イ酸カルシウム等のケイ酸塩、ケイ酸および窒化ほう素
が挙げられる。これらは単独または２種以上混合して使
用することができる。最近フレキシブルプリント回路が
ファイン化し、数１０μｍのパターンも実用化されてい
るので、無機粉末の粒子は粒径が１０μｍ以下、好まし
くは５μｍ以下が適当である。なおこれら微粒子状無機
質粉末の樹脂マトリックスへの定着性や耐水性を向上さ
せるため疎水化処理を行うと好都合であり、このために
は、ジメチルジクロロシラン等のクロロシラン、シリコ
ーンオイル、アルキルトリエトキシシラン、メチルトリ
エトキシシラン等のシランカップリング剤等の処理剤が
用いられる。[0010] Furthermore, fine particulate inorganic powder can be added to the above adhesive if necessary. Fine particulate inorganic powders include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, oxides such as zinc oxide, magnesium oxide, and antimony trioxide, carbonates such as calcium carbonate and magnesium carbonate, aluminum silicate, and silicate. Examples include silicates such as magnesium acid, calcium silicate, silicic acid, and boron nitride. These can be used alone or in combination of two or more. Recently, flexible printed circuits have become finer and patterns of several tens of micrometers have been put into practical use, so the particle size of the inorganic powder particles is suitably 10 micrometers or less, preferably 5 micrometers or less. In order to improve the adhesion to the resin matrix and water resistance of these fine particulate inorganic powders, it is convenient to perform hydrophobization treatment, and for this purpose, chlorosilanes such as dimethyldichlorosilane, silicone oils, alkyltriethoxysilanes, A processing agent such as a silane coupling agent such as methyltriethoxysilane is used.
【００１１】本発明は上記イ）、ロ）、ハ）およびニ）
の各成分からなる組成の接着剤によって所期の目的効果
が達成されるのであって、上記組成範囲外では次のよう
な不都合が生じる。すなわちイ）成分のエポキシ樹脂
１００重量部に対してロ）成分のカルボキシル基を含有
するニトリルゴムが１０重量部未満では剥離強度が低下
し、４０重量部を超えると耐半田付け性、耐半田リフロ
ー性が低下する。ハ）成分の硬化剤が１重量部未満では
、硬化不十分となり半田耐熱性が低下し、５０重量部を
超えると接着剤のライフが短かくなるのに加えて、半田
耐熱性、剥離強度が低下する。ニ）成分の硬化促進剤は
、 ０．１重量部未満では、半田耐熱性が低下し、接着
剤の流れが大きくなり過ぎるとともに、高温長時間の加
工が必要となり、５重量部を超えると接着剤のライフが
短くなるとともに接着剤の流れの剥離強度が低下する。[0011] The present invention provides the above a), b), c) and d).
The desired desired effect can be achieved by an adhesive having a composition consisting of each of the above components, and if the composition is outside the above range, the following disadvantages will occur. In other words, the epoxy resin of component (a)
If the carboxyl group-containing nitrile rubber of component (b) is less than 10 parts by weight relative to 100 parts by weight, the peel strength will decrease, and if it exceeds 40 parts by weight, the solderability and solder reflow resistance will decrease. If the amount of curing agent in the component (c) is less than 1 part by weight, curing will be insufficient and the soldering heat resistance will decrease, and if it exceeds 50 parts by weight, the life of the adhesive will be shortened and the soldering heat resistance and peel strength will decrease. descend. If the curing accelerator component (d) is less than 0.1 parts by weight, the soldering heat resistance will decrease, the flow of the adhesive will become too large, and long-term processing at high temperatures will be required; if it exceeds 5 parts by weight, the adhesive will deteriorate. As the life of the adhesive becomes shorter, the peel strength of the adhesive flow decreases.
【００１２】次に本発明のカバ−レイフィルムの製造方
法について述べる。前記組成からなる接着剤を、耐熱性
を有するポリイミドフィルム。ポリフェニレンスルフィ
ドフィルム、ポリパラバン酸フィルム、耐熱性ポリエス
テルフィルム、ポリエーテルスルホンフィルム、ポリエ
ーテル・エーテルケトンフィルム等に乾燥状態で１０〜
６０μｍになるように塗布し、接着剤を半硬化状態とす
る。
この場合必要に応じて １００℃程度に短時間加熱する
ことができる。このようにして得られる半硬化状態のフ
ィルムは通常ポリエチレンフィルム、ＰＰフィルム。
ＴＰＸフィルム、シリコーン系離型剤付きポリエステル
フィルム、ポリエチレン、ポリプロピレン等のポリオレ
フィンのフィルムコート紙、塩化ビニリデンフィルムコ
ート紙等の離型紙あるいは、離型性フィルム等と重ね合
わせロールラミネーター等により積層し、ロール状に巻
き取って製造される。Next, the method for manufacturing the coverlay film of the present invention will be described. A heat-resistant polyimide film using an adhesive having the above composition. Polyphenylene sulfide film, polyparabanic acid film, heat-resistant polyester film, polyether sulfone film, polyether/ether ketone film, etc.
The adhesive is applied to a thickness of 60 μm and left in a semi-cured state. In this case, it can be heated to about 100° C. for a short time if necessary. The semi-cured film obtained in this way is usually a polyethylene film or a PP film.
TPX film, polyester film with silicone release agent, polyolefin film coated paper such as polyethylene or polypropylene, release paper such as vinylidene chloride film coated paper, or release film, etc. are laminated using a roll laminator, etc., and then rolled. It is manufactured by winding it up into shapes.
【００１３】[0013]
【実施例】次に本発明の実施態様を実施例を挙げて具体
的に説明するが、本発明はこれらに限定されるものでは
ない。なお、具体例中の部数および％は全て固形分の重
量による。
（実施例１〜６、比較例１〜６）
表１に示す接着剤組成物を用い３０％ＭＥＫ 溶液とし
ボールミルにより均一に分散させ、接着剤溶液を得た。
次いで、この接着剤溶液を乾燥後の塗布厚さ３０μｍに
なるように２５μｍのポリイミドフィルム（カプトン１
００Ｈ）に塗布し、８０℃×２分、 １２０℃×５分加
熱乾燥し、溶剤を除去し、接着剤をＢステージにした。
次にシリコーン離型剤付き離型紙とロールラミネーター
により、温度５０℃、ロール圧着の線圧５ｋｇ／ｃｍ
、速度２ｍ／ｍｉｎ で圧着積層し、カバ−レイフィル
ムを作製した。次にこのカバ−レイフィルムの特性を測
定するためにこのフィルムを電解銅箔３５μｍの光沢面
に積層し、プレス条件 １６０℃、５０ｋｇ／ｃｍ２、
１０分でプレス加工し、積層フィルムを作製した。
このようにして得たフレキシブル積層フィルムの特性を
表１に示す。[Examples] Next, embodiments of the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Note that all parts and percentages in the specific examples are based on the weight of solid content. (Examples 1 to 6, Comparative Examples 1 to 6) Using the adhesive composition shown in Table 1, the adhesive composition was made into a 30% MEK solution and uniformly dispersed using a ball mill to obtain an adhesive solution. Next, this adhesive solution was coated on a 25 μm polyimide film (Kapton 1) so that the coating thickness after drying was 30 μm.
00H) and heated and dried at 80°C for 2 minutes and at 120°C for 5 minutes to remove the solvent and bring the adhesive to the B stage. Next, using release paper with a silicone release agent and a roll laminator, the temperature was 50°C and the linear pressure of roll crimping was 5kg/cm.
A coverlay film was produced by pressure-bonding and laminating at a speed of 2 m/min. Next, in order to measure the characteristics of this coverlay film, this film was laminated on the glossy surface of 35 μm electrolytic copper foil, and the press conditions were: 160°C, 50 kg/cm2,
Pressing was carried out in 10 minutes to produce a laminated film. Table 1 shows the properties of the flexible laminated film thus obtained.
【００１４】表１に示したフレキシブル積層フィルムの
物性測定法は以下のとおりである。
１）剥離強度：ＪＩＳ Ｃ６４８１ に準拠して行う。
幅１０ｍｍのサンプルを９０°方向に５０ｍｍ／ｍｉｎ
の速度で銅箔を引き剥す。
２）半田耐熱性：半田浴に３０秒間、サンプルを浮かべ
、フクレ等が生じない温度を測定する。吸湿半田は、サ
ンプルを４０℃×９０％ＲＨ×１ｈｒの条件下で吸湿さ
せた後、半田浴に３０秒間サンプルを浮かべ、外観、フ
クレ等をチェックする。
３）難燃性：ＵＬ−９４ 規格に準拠して燃焼試験を行
なう。
ＵＬ−９４規格は、難燃性をＶー０、 Ｖ−１、 Ｖ−
２、ＨＢの４つにランクづけし、 Ｖ−０が最も難燃性
にすぐれている。
４）接着剤滲み出し：カバ−レイフィルムに３ｍｍφの
穴をあけ、これを銅箔光沢面とプレス加工により貼り合
せた後、穴への接着剤の滲み出しを測定する。
５）耐半田もぐり性：３ｍｍφの穴をあけたカバ−レイ
フィルムと５重量％塩酸で１分間のソフトエッチングを
行った銅箔光沢面とをプレス加工により貼り合せた後、
穴の銅箔露出部に半田フラックスまたは半田ペーストを
塗布して、２６０℃×１０秒の半田付けまたは半田リフ
ローを行う。
ここに半田付け：半田フラックスを塗布したサンプルを
半田浴に浸積する。半田リフロー：半田ペーストを塗布
したサンプルを半田浴に浮かべ、ペーストをリフローさ
せる処理をいう。その後、半田のカバ−レイフィルム下
部へのもぐり込みを調べる。判定：○・・・もぐり込み
無し。 ×・・・もぐり込み有り。The physical properties of the flexible laminated film shown in Table 1 were measured as follows. 1) Peel strength: Performed in accordance with JIS C6481. Sample width 10mm at 50mm/min in 90° direction
Peel off the copper foil at a speed of 2) Soldering heat resistance: Float the sample in a solder bath for 30 seconds and measure the temperature at which no blistering occurs. For moisture-absorbing solder, the sample is made to absorb moisture under the conditions of 40° C. x 90% RH x 1 hr, and then the sample is floated in a solder bath for 30 seconds to check the appearance, blisters, etc. 3) Flame retardancy: Conduct a flame test in accordance with UL-94 standard. The UL-94 standard classifies flame retardancy as V-0, V-1, and V-.
Ranked into four categories: 2, HB, and V-0 has the best flame retardancy. 4) Adhesive oozing: After making a hole of 3 mm in diameter in the coverlay film and bonding it to the glossy surface of the copper foil by press working, the oozing of the adhesive into the hole was measured. 5) Resistance to solder penetration: After bonding the coverlay film with a hole of 3 mm diameter and the glossy surface of the copper foil that was soft-etched for 1 minute with 5% by weight hydrochloric acid by press working,
Solder flux or solder paste is applied to the copper foil exposed portion of the hole, and soldering or solder reflow is performed at 260° C. for 10 seconds. Soldering here: Dip the sample coated with solder flux into a solder bath. Solder reflow: A process in which a sample coated with solder paste is floated in a solder bath and the paste is reflowed. Then, check to see if the solder has penetrated into the bottom of the coverlay film. Judgment: ○...No crawling. ×...There is crawling.
【００１５】[0015]
【表１】[Table 1]
【００１６】[0016]
【表２】[Table 2]
【００１７】[0017]
【発明の効果】本発明により低温短時間での加工性、接
着性、耐半田性、特に耐半田付け性、耐半田リフロー性
に優れたフレキシブルプリント回路用の保護カバ−レイ
フィルムを提供することが可能となり、実用上その利用
価値は極めて高い。[Effects of the Invention] According to the present invention, there is provided a protective coverlay film for a flexible printed circuit which is excellent in processability, adhesiveness, and solder resistance at low temperatures and in a short time, particularly in soldering resistance and solder reflow resistance. is possible, and its practical value is extremely high.
Claims (1)
組成の接着剤を塗布、半硬化状態とし、これに離型性フ
ィルムまたは離型紙を圧着してなるカバ−レイフィルム
。イ）エボキシ樹脂 １００重量部。ロ）カルボキ
シル基含有ニトリルゴム １０〜４０重量部。ハ）硬
化剤 １〜５０重量部。ニ）イミダゾ−ル化合物、第
三アミン類のテトラフェニルほう素酸塩及び亜鉛、スズ
、ニッケルのほうふっ化物から選ばれる１種以上の硬化
促進剤 ０．１ 〜５重量部。1. A coverlay film obtained by coating one side of a heat-resistant plastic film with an adhesive having the composition shown below to a semi-cured state, and pressing a release film or paper onto the adhesive. b) Epoxy resin 100 parts by weight. b) Carboxyl group-containing nitrile rubber 10 to 40 parts by weight. c) Curing agent 1 to 50 parts by weight. d) 0.1 to 5 parts by weight of one or more curing accelerators selected from imidazole compounds, tetraphenyl borates of tertiary amines, and fluorides of zinc, tin, and nickel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12672791A JP2898120B2 (en) | 1991-04-30 | 1991-04-30 | Coverlay film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12672791A JP2898120B2 (en) | 1991-04-30 | 1991-04-30 | Coverlay film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04328183A true JPH04328183A (en) | 1992-11-17 |
| JP2898120B2 JP2898120B2 (en) | 1999-05-31 |
Family
ID=14942379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12672791A Expired - Fee Related JP2898120B2 (en) | 1991-04-30 | 1991-04-30 | Coverlay film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2898120B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001288445A (en) * | 2000-04-07 | 2001-10-16 | Nagase Chemtex Corp | Electrically connectable semiconductor adhesive |
-
1991
- 1991-04-30 JP JP12672791A patent/JP2898120B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001288445A (en) * | 2000-04-07 | 2001-10-16 | Nagase Chemtex Corp | Electrically connectable semiconductor adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2898120B2 (en) | 1999-05-31 |
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