JPH0328285A - Flame-retardant adhesive and flame-retardant coverlay film - Google Patents
Flame-retardant adhesive and flame-retardant coverlay filmInfo
- Publication number
- JPH0328285A JPH0328285A JP16432589A JP16432589A JPH0328285A JP H0328285 A JPH0328285 A JP H0328285A JP 16432589 A JP16432589 A JP 16432589A JP 16432589 A JP16432589 A JP 16432589A JP H0328285 A JPH0328285 A JP H0328285A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- retardant
- film
- epoxy resin
- adhesive
- 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
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 32
- 239000000853 adhesive Substances 0.000 title claims abstract description 31
- 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 title claims abstract description 22
- 239000003063 flame retardant Substances 0.000 title claims abstract description 22
- 239000012787 coverlay film Substances 0.000 title claims abstract description 14
- 239000010408 film Substances 0.000 claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 17
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000002985 plastic film Substances 0.000 claims abstract description 4
- 229920006255 plastic film Polymers 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000679 solder Inorganic materials 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 6
- 229930185605 Bisphenol Natural products 0.000 abstract 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 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 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229910001679 gibbsite Inorganic materials 0.000 abstract 1
- 229920003986 novolac Polymers 0.000 abstract 1
- -1 amine compounds Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000005476 soldering Methods 0.000 description 6
- 241000209219 Hordeum Species 0.000 description 5
- 235000007340 Hordeum vulgare Nutrition 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 238000010030 laminating Methods 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
- 238000004080 punching Methods 0.000 description 2
- 230000035939 shock Effects 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229920000742 Cotton Polymers 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
- 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
- 229920001646 UPILEX Polymers 0.000 description 1
- 239000002253 acid Substances 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
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 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
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 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
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-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
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 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
- 239000000843 powder Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical class 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は，優れた難燃性接着剤および難燃性、半田耐熱
性を有するフレキシブルプリント回路用保護力バーレイ
フィルムに関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an excellent flame-retardant adhesive and a protective barley film for flexible printed circuits having flame retardancy and soldering heat resistance.
（従来の技術）
近年のエレクロトニクス製品の軽薄短小、高機能化に伴
いプリント基板の需要が高まり、中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。それにつれてプリント基板のファインパターン化
、高性能化、耐環境性向上等に対する要求が強くなり、
同時にフレキシブルプリント回路の保護用力バーレイフ
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。また、近年、安全性の
面から，民生機器を中心に難燃化の要求が高くなり、こ
れに伴いフレキシブルプリント基板やフレキシブルプリ
ント回路の保護用カバーレイフィルムにも難燃化が要求
されている。このような背景から、近年、接着性、耐熱
性、吸湿半田耐熱性および難燃性を兼備したフレキシブ
ルプリント回路の保護用力バーレイフィルム・が要求さ
れるようになってきた。(Prior Art) In recent years, demand for printed circuit boards has increased as electronic products have become lighter, thinner, smaller, and more sophisticated, and demand for flexible printed circuit boards in particular has been increasing as the range of use has expanded. As a result, demands for finer patterns, higher performance, and improved environmental resistance of printed circuit boards have become stronger.
At the same time, the use of barley films to protect flexible printed circuits has increased, and improvements in their performance are desired. Environmental resistance is often a problem. In addition, in recent years, there has been an increasing demand for flame retardant properties, especially for consumer equipment, from the standpoint of safety, and with this, flame retardant properties are also required for flexible printed circuit boards and coverlay films used to protect flexible printed circuits. . Against this background, in recent years, there has been a demand for a protective barley film for flexible printed circuits that has adhesive properties, heat resistance, moisture absorption soldering heat resistance, and flame retardancy.
従来力バーレイフィルム用の接着剤としてはＮＢＲ／フ
ェノール樹脂、エポキシ・フェノール／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、難燃性
カバーレイフィルム用の接着剤としては上記樹脂中に、
大量の臭素化合物、無機難燃剤を配合したもの、或は該
樹脂を臭素化した、例えば臭素化エポキシ樹脂等を配合
したもの等が挙げられる。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。Conventional adhesives for Burley film include NBR/phenolic resin, epoxy phenol/NBR%NBR
/epoxy resin, epoxy/polyester resin, epoxy/acrylic resin, acrylic resin, etc. are used, and the adhesive for the flame-retardant coverlay film contains, among the above resins,
Examples include those containing a large amount of bromine compounds and inorganic flame retardants, and those containing brominated resins, such as brominated epoxy resins. However, these adhesives have advantages and disadvantages, and do not necessarily satisfy the above-mentioned properties.
The NBR type has a large thermal deterioration, and this is particularly noticeable when an inorganic flame retardant is added to the NBR type.
エポキシ系は剥離強度が低く、臭素化エポキシ系は耐熱
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、吸湿半田耐熱性および難燃性を
満足するものが少なかった。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 described above, few conventional adhesives satisfy the requirements of adhesiveness, heat resistance, moisture absorption soldering heat resistance, and flame retardancy.
（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、優れた難燃性接着剤
および半田耐熱性、吸湿時の半田耐熱性、難燃性、打ち
抜き性に優れたフレキシブルプリント回路用の保護力バ
ーレイフィルムを提供しようとするものである．
（課題を解決するための手段）
本発明者等は、上記課題を達戊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。(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks and provides an excellent flame-retardant adhesive and a flexible adhesive with excellent solder heat resistance, solder heat resistance when moisture is absorbed, flame retardance, and punchability. The aim is to provide a protective barley film for printed circuits. (Means for Solving the Problems) In order to achieve 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.
即ち、本発明は
１．イ）臭素化エポキシ樹脂 １００重量部、ロ）
カルボキシル基を含有するニトリルゴム４０〜１８０重
量部、
ハ）水酸化アルミニウム ２０〜６０重量部、二
）酸化アンチモン ５〜５０重量部、ホ）硬
化剤 １〜５０重量部からなる難燃
性接着剤と
２．耐熱性プラスチックフィルムの片面に請求項１に記
載の難燃性接着剤を塗布、半硬化状態とし、離型性フィ
ルムまたは離型紙を圧着してなる難燃性カバーレイフィ
ルムを要旨とするものである。That is, the present invention has 1. a) Brominated epoxy resin 100 parts by weight, b)
A flame-retardant adhesive consisting of 40 to 180 parts by weight of nitrile rubber containing a carboxyl group, c) 20 to 60 parts by weight of aluminum hydroxide, 2) 5 to 50 parts by weight of antimony oxide, and e) 1 to 50 parts by weight of a curing agent. and 2. The gist of the film is a flame-retardant coverlay film obtained by applying the flame-retardant adhesive according to claim 1 to one side of a heat-resistant plastic film, bringing it into a semi-cured state, and then press-bonding a release film or release paper. be.
以下、本発明について詳細に説明する．先ず、本発明の
最も特徴とする難燃性接着剤組成物について述べる。The present invention will be explained in detail below. First, the flame-retardant adhesive composition, which is the most characteristic feature of the present invention, will be described.
イ）成分である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どのようなもの
でもよく、例えばビスフェノー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＠製のエビコート５０４
５（ Ｂｒ： １９重量％）、５０４６（ Ｂｒ： ２
１重量％） 、５０４ｇ＜ Ｂｒ： ２５重量％）、５
０４９（ Ｂｒ： ２６重量％） 、５０５０（ Ｂｒ
： ４９重量％）日本化薬■製のＢＲＥＮ−Ｓ（ Ｂｒ
： ３５重量％）等がある。これらのＢｒ含有量の異な
る臭素化エポ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。The brominated epoxy resin that is the component (b) may be of any type as long as it has an epoxy group and a bromine atom in one molecule, such as bisphenol-type brominated epoxy resin, novolac-type brominated epoxy resin, etc. It will be done. Specifically, Ebicoat 504 manufactured by Yuka Shell Epoxy@
5 (Br: 19% by weight), 5046 (Br: 2
1% by weight), 504g<Br: 25% by weight), 5
049 (Br: 26% by weight), 5050 (Br
: 49% by weight) BREN-S (Br
: 35% by weight). These brominated epoxy resins having different Br contents can be used alone or in combination of two or more.
ロ）成分のカルボキシル基を含有するニトリルゴムとし
ては、アクリロニトリルとブタジエンが共重合したアク
リロニトリルーブタジエ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、ハイカー〇ＴＢＮＸ、
ハイカーｌ０７２、日本ゼオン■製のニボール１０７２
Ｊ、ニボール１０７２Ｂ、ニボールＤＮ６ １ ２、ニ
ボールＤＮ６３１，二ボールＤＮＳ０１等がある。Examples of the carboxyl group-containing nitrile rubber of component (b) include acrylonitrile-butadiene copolymer rubber obtained by copolymerizing acrylonitrile and butadiene, and the terminals of which are carboxylated. Specifically, Goodrich's Hiker CTBN, Hiker TBNX,
Hiker l072, Niboru 1072 manufactured by Nippon Zeon ■
J, Niball 1072B, Niball DN6 1 2, Niball DN631, Niball DNS01, etc.
これらのカルボキシル基を含有するニトリルゴムを単独
または２種以上混合して用いることができる。These nitrile rubbers containing carboxyl groups can be used alone or in combination of two or more.
ハ）成分の水酸化アルミニウムは、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２μｍ以
下、好ましくはＩＬＬｍ以下が適当である。このＡＩ
（ＯＨ） １の使用により樹脂の耐吸湿性が向上し、熱
衝撃による接着剤の歪が小さくなる．なおＡＩ （ＯＨ
） ｓ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， Ａｌ（ＯＨ）ｓの使用によりさらに吸湿半
田耐熱性等が向上するのは、樹脂の耐熱性、耐吸湿特性
等が向上し、熱衝撃による接着剤の歪が小さくなるため
と思われる。具体的には、昭和電工■製のＨ−４３Ｍ．
Ｈ−４３ＳＴＥ等が使用される。Regarding aluminum hydroxide, component c), 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 2 micrometers or less, preferably ILLm or less. This AI
The use of (OH) 1 improves the moisture absorption resistance of the resin and reduces the distortion of the adhesive due to thermal shock. Furthermore, AI (OH
) It is convenient to perform hydrophobic treatment to improve the fixation of s to the resin matrix and water resistance. For this purpose, chlorosilanes such as dimethyldichlorosilane, silicone oils, alkyltriethoxysilanes, methyltriethoxysilanes, etc. The use of Al(OH)s further improves the moisture absorption soldering heat resistance, etc., because the heat resistance and moisture absorption properties of the resin are improved, and the adhesion caused by thermal shock is improved. This is thought to be because the distortion of the agent becomes smaller. Specifically, H-43M. manufactured by Showa Denko ■.
H-43STE etc. are used.
二）酸化アンチモンとしては、Ｓｂ．０，，ｓｂ，ｏ４
，ｓｂ．ｏｓ等が挙げられる．この酸化アンチモンの粒
径もＡｌ （ＯＨ）．同様にｌＬＬＩ！１以下が適当で
ある。2) As antimony oxide, Sb. 0,,sb,o4
, sb. Examples include os. The particle size of this antimony oxide is also Al(OH). Similarly lLLI! A value of 1 or less is appropriate.
ホ）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、特に限定するものではなく、
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、ジアミノジフエニルメタンお
よびジアミノジフエニルスルフオン等のアミン系化合物
、無水フタル酸、無水へ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、
２−アルキルー４−メチルイミダゾール、２−アルキル
ー４−エチルイミダゾール、ｌ一（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、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）成分の臭素化エポキシ樹脂１０
０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及び各樹
脂の種類や量によって適宜選択される。e) The curing agent is not particularly limited as long as it is used as a curing agent for ordinary epoxy resins.
For example, amine compounds such as diethyltriamine, triethylenetetramine, metaxylene diamine, diaminodiphenylmethane and diaminodiphenyl sulfone, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, etc. acid anhydride,
2-alkyl-4-methylimidazole, 2-alkyl-4-ethylimidazole, l-(2-cyanoethyl)
Examples include imidazole compounds such as -2-alkylimidazole and 2-phenylimidazole, dicyandiamide, and boron trifluoride amine complex compounds. These can be used alone or in combination of two or more. These curing agents usually contain 10% of the brominated epoxy resin of component (a).
It can be added in a wide range of 1 to 50 parts by weight per 0 parts by weight, and the amount used is appropriately selected depending on the type of curing agent and the type and amount of each resin.
本発明は上記イ） ロ） ハ） 二）およびホ）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を達成
できるのであって、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）成分の臭素化エポキシ樹脂１
００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４０重量部未満では剥離強度が低下し
、 １８０重量部超えると熱劣化が大きくなる。ハ）戊
分の水酸化アルミニウムが２０重量部未満では、半田耐
熱性、打ち抜き性が低下し、６０重量部を超えると剥離
強度が低下する。二）成分の酸化アンチモンが５重量部
未満では、難燃性、抜き打ち性が低下し、５０重量部を
超えると剥離強度、半田耐熱性が低下する。In the present invention, the desired desired effect can be achieved by using an adhesive having a composition consisting of each of the above-mentioned components (a), (b), (c), (2) and (e), but outside the above composition range, the following disadvantages occur. That is, a) component brominated epoxy resin 1
If the carboxyl group-containing nitrile rubber of component (b) is less than 40 parts by weight relative to 00 parts by weight, the peel strength will decrease, and if it exceeds 180 parts by weight, thermal deterioration will increase. c) If the aluminum hydroxide content is less than 20 parts by weight, the soldering heat resistance and punching properties will decrease, and if it exceeds 60 parts by weight, the peel strength will decrease. If the antimony oxide component (2) is less than 5 parts by weight, flame retardancy and punchability will be reduced, and if it exceeds 50 parts by weight, peel strength and soldering heat resistance will be reduced.
次に本発明の難燃性カバーレイフイルムについて述べる
。Next, the flame retardant coverlay film of the present invention will be described.
その構成は耐熱性プラスチックフィルムの片面に前記難
燃性接着剤を塗布し、半硬化状態とした後、離型性フィ
ルムまたは離型紙を圧着した３層構造からなる。この難
燃性カバーレイフイルムを製造するには、前記組成から
なる難燃性接着剤を耐熱性を有するポリイミドフィルム
、ポリフエニレンスルフィドフィルム、ポリバラバン酸
フイルム、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２０〜４０μｍになるように塗布し
、接着剤を半硬化状態とする。この場合必要により １
００℃程度に短時間加熱することができる。Its structure consists of a three-layer structure in which the flame-retardant adhesive is applied to one side of a heat-resistant plastic film, semi-cured, and then a release film or paper is pressure-bonded. In order to produce this flame-retardant coverlay film, a flame-retardant adhesive having the above composition is applied to a heat-resistant polyimide film, a polyphenylene sulfide film, a polybalabanic acid film, a heat-resistant polyester film, a polyether sulfone film, The adhesive is applied to a polyether/ether ketone film or the like to a thickness of 20 to 40 μm in a dry state, and the adhesive is semi-cured. In this case, as necessary 1
It can be heated to about 00°C for a short time.
このようにして得られるカバーレイフィルムは通常ポリ
エチレンフィルム、ＰＰフィルム、丁ＰＸ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、ボリブロビレン等のポリオレフィンフィルムコー
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、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。The coverlay film obtained in this way is usually polyethylene film, PP film, PX 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 It is manufactured by laminating it with a film or the like using a roll laminator or the like, and then winding it up into a roll.
次に本発明の具体的実施態様を実施例を挙げて説明する
が、本発明はこれらに限定されるものではない。なお、
具体例中の部数及び％は全で重量に拠る．
（実施例１）
臭素化エポキシ樹脂（エビコート５０５０．油化シェル
エポキシ株製）１００部にカルボキシル基を含有するニ
トリルゴム（二ボール１０７２Ｊ、日本ゼオン■製）１
００部、水酸化アルミニウム（Ｈ−４３Ｍ ，昭和電工
■製）４０部、二酸化アンチモン５部、硬化剤として４
・４−ジアミノフェニルスルホン２０部を添加し、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。Next, specific embodiments of the present invention will be described with reference to Examples, but the present invention is not limited thereto. In addition,
All parts and percentages in specific examples are based on weight. (Example 1) 100 parts of brominated epoxy resin (Ebicoat 5050, manufactured by Yuka Shell Epoxy Co., Ltd.) and nitrile rubber containing a carboxyl group (Ni-Ball 1072J, manufactured by Nippon Zeon ■) 1
00 parts, 40 parts of aluminum hydroxide (H-43M, manufactured by Showa Denko), 5 parts of antimony dioxide, 4 parts as a hardening agent.
・Add 20 parts of 4-diaminophenyl sulfone,
% MEK solution and uniformly dispersed using a ball mill.
An adhesive solution was obtained.
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（カブトン
１００旧に塗布し、８０℃×２分、 １２０’Ｃ×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℃、ロール圧着の綿圧５ ｋｇ／ｃ
ｍ、速度２ｍ／ｍｉｎで圧着積層し、カバーレイフィル
ムを作成した．次にこのカバーレイフィルムの特性を測
定するためにこのフイルムを電解銅箔３５μｍの光沢面
に積層し、プレス条件１６０℃、５０ｋｇ／ｃｎｆ，
３０分でプレス加工し、積層フィルムを作成した。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−
２に示す。Next, this adhesive solution was coated on a 25 μm polyimide film (Kabuton) so that the coating thickness after drying was 30 μm.
The adhesive was coated on 100°C and heated and dried for 2 minutes at 80°C and 5 minutes at 120°C 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 cotton pressure was 5 kg/c.
A coverlay film was created 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 press conditions were 160°C, 50kg/cnf,
Press processing was carried out in 30 minutes to create a laminated film. The characteristics of the flexible laminated film thus obtained are shown below.
Shown in 2.
（実施例２〜６、比較例１〜５）
表−１に示す接着剤組成物を用い、接着剤溶液を作成し
実施例１と同様にカバーレイフイルムからフレキシブル
積層フイルムを得た。それらの特性を表−２に示す。(Examples 2 to 6, Comparative Examples 1 to 5) An adhesive solution was prepared using the adhesive composition shown in Table 1, and a flexible laminated film was obtained from a coverlay film in the same manner as in Example 1. Their characteristics are shown in Table-2.
以下、実施例に適応したフレキシブル積層フイルムの物
性測定法について述べる。Hereinafter, a method for measuring the physical properties of a flexible laminated film adapted to Examples will be described.
置足恭
ｉ）剥離強度
ＪＩＳ Ｃ６４８１に準処して行う。１０ｍｍのサンプ
ルを９０℃方向に５０ｍｍ／ｍｉｎの速度で銅箔を引き
はがす。i) Peel strength: Performed in accordance with JIS C6481. The copper foil was peeled off from a 10 mm sample in a direction of 90° C. at a speed of 50 mm/min.
ｉｉ）半田耐熱性
半田浴に３０秒間、サンプルをフロートした後、フクレ
等が生じない温度を測定する。ii) Solder heat resistance After floating the sample in a solder bath for 30 seconds, measure the temperature at which no blistering occurs.
吸湿半田は、４０℃×９０％Ｒ｝ｆＸ ｌｈｒの条件下
で吸湿させた後、半田浴に３０秒間サンプルをフロート
し、外観、フクレ等をチェックする。The moisture-absorbing solder is made to absorb moisture under the conditions of 40° C. x 90% R}fX lhr, and then the sample is floated in a solder bath for 30 seconds and checked for appearance, blisters, etc.
ｉｉｉ）難燃性 ＵＬ−９４規格に準処して燃焼試験を行なう。iii) Flame retardant A combustion test is conducted in accordance with the UL-94 standard.
ＵＬ−９４規格は、難燃性をＶ−０， Ｖ−１． Ｖ−
２、ＨＢ（７） ４ ツにランクづけし、ｖ−０が最も
難燃性にすぐれている。The UL-94 standard defines flame retardancy as V-0, V-1. V-
2. HB (7) Ranked on a 4 scale, with v-0 having the best flame retardancy.
ｉｖ）打ち抜き性
２４ｃｍＸ ３０ｃｍサイズのカバーレイフィルムを２
枚積重ね３ｍｍφの穴を５００穴パンチングし、各々の
パンチング穴の外観を検査する。iv) Punchability 24cm x 30cm size coverlay film
500 holes with a diameter of 3 mm were punched in a stack of sheets, and the appearance of each punched hole was inspected.
○ 完全にパンチングされ、外観良好。○ Completely punched and looks good.
Δ 若干パンチング穴の抜けが悪い。Δ Difficulty punching holes through.
× ５％以上のパンチング穴の抜け残がある。× 5% or more of punched holes remain.
（発明の効果）
本発明により、難燃性に優れた接着剤および半田耐熱性
、吸湿時の半田耐熱性、難燃性、および打ち抜き性に優
れたフレキシブルプリント回路用の保護力バーレイフィ
ルムを提供することが可能となり、実用上その利用価値
は高い。(Effects of the Invention) The present invention provides an adhesive with excellent flame retardancy, and a protective barley film for flexible printed circuits that has excellent solder heat resistance, solder heat resistance when moisture is absorbed, flame retardance, and punchability. This makes it possible to do so, and its practical value is high.
Claims (2)
キシル基を含有するニトリルゴム４０〜１８０重量部、 ハ）水酸化アルミニウム２０〜６０重量部、ニ）酸化ア
ンチモン５〜５０重量部、 ホ）硬化剤１〜５０重量部 からなる難燃性接着剤。1. a) 100 parts by weight of brominated epoxy resin, b) 40 to 180 parts by weight of nitrile rubber containing a carboxyl group, c) 20 to 60 parts by weight of aluminum hydroxide, d) 5 to 50 parts by weight of antimony oxide, and e) a curing agent. A flame retardant adhesive consisting of 1 to 50 parts by weight.
載の難燃性接着剤を塗布、半硬化状態とし、離型性フィ
ルムまたは離型紙を圧着してなる難燃性カバーレイフィ
ルム。2. A flame-retardant coverlay film obtained by coating one side of a heat-resistant plastic film with the flame-retardant adhesive according to claim 1, bringing the flame-retardant adhesive into a semi-cured state, and press-bonding a release film or paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1164325A JPH0733501B2 (en) | 1989-06-27 | 1989-06-27 | Flame retardant coverlay film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1164325A JPH0733501B2 (en) | 1989-06-27 | 1989-06-27 | Flame retardant coverlay film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0328285A true JPH0328285A (en) | 1991-02-06 |
| JPH0733501B2 JPH0733501B2 (en) | 1995-04-12 |
Family
ID=15791019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1164325A Expired - Fee Related JPH0733501B2 (en) | 1989-06-27 | 1989-06-27 | Flame retardant coverlay film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0733501B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5807910A (en) * | 1997-06-23 | 1998-09-15 | Industrial Technology Research Institute | Preolymerizing epoxy resin, functionalized rubber with filler to form adhesive |
| US6054509A (en) * | 1997-08-28 | 2000-04-25 | Shin-Etsu Chemical Co., Ltd. | Adhesive of epoxy resin, nitrile rubbers and curing agent |
| JP2008522391A (en) * | 2004-11-29 | 2008-06-26 | テサ・アクチエンゲゼルシヤフト | Adhesive strip based on thermally activated and carboxylated nitrile rubber for bonding electronic components and strip conductors together |
| DE19980666B4 (en) * | 1998-03-20 | 2011-08-18 | Hutchinson | A method of forming an adhesive bond between a fluorinated polymer and an elastomer and tubing obtained by this method for delivering a fluid |
| CN110396385A (en) * | 2019-07-25 | 2019-11-01 | 张家港爱科思汽车配件有限公司 | A kind of flame retardant type automobile structure glue |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176579A (en) * | 1984-09-21 | 1986-04-19 | Mitsui Petrochem Ind Ltd | Heat-resistant adhesive composition |
| JPH01161045A (en) * | 1987-12-16 | 1989-06-23 | Shin Etsu Chem Co Ltd | Flame-retarding cover lay film |
-
1989
- 1989-06-27 JP JP1164325A patent/JPH0733501B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176579A (en) * | 1984-09-21 | 1986-04-19 | Mitsui Petrochem Ind Ltd | Heat-resistant adhesive composition |
| JPH01161045A (en) * | 1987-12-16 | 1989-06-23 | Shin Etsu Chem Co Ltd | Flame-retarding cover lay film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5807910A (en) * | 1997-06-23 | 1998-09-15 | Industrial Technology Research Institute | Preolymerizing epoxy resin, functionalized rubber with filler to form adhesive |
| US6054509A (en) * | 1997-08-28 | 2000-04-25 | Shin-Etsu Chemical Co., Ltd. | Adhesive of epoxy resin, nitrile rubbers and curing agent |
| DE19980666B4 (en) * | 1998-03-20 | 2011-08-18 | Hutchinson | A method of forming an adhesive bond between a fluorinated polymer and an elastomer and tubing obtained by this method for delivering a fluid |
| JP2008522391A (en) * | 2004-11-29 | 2008-06-26 | テサ・アクチエンゲゼルシヤフト | Adhesive strip based on thermally activated and carboxylated nitrile rubber for bonding electronic components and strip conductors together |
| CN110396385A (en) * | 2019-07-25 | 2019-11-01 | 张家港爱科思汽车配件有限公司 | A kind of flame retardant type automobile structure glue |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0733501B2 (en) | 1995-04-12 |
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