JPH0649427A - Adhesive composition for flexible printed circuit board - Google Patents
Adhesive composition for flexible printed circuit boardInfo
- Publication number
- JPH0649427A JPH0649427A JP20376292A JP20376292A JPH0649427A JP H0649427 A JPH0649427 A JP H0649427A JP 20376292 A JP20376292 A JP 20376292A JP 20376292 A JP20376292 A JP 20376292A JP H0649427 A JPH0649427 A JP H0649427A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- adhesive composition
- 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.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 59
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 65
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 22
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 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 claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 229920000768 polyamine Polymers 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000004593 Epoxy Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 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 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical class OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides 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
- 230000003078 antioxidant effect Effects 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Manufacturing Of Printed Wiring (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はフレキシブル印刷回路基
板用接着剤組成物に関するものであり、さらに詳しく
は、難燃性フレキシブル印刷回路基板用接着剤組成物に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible printed circuit board adhesive composition, and more particularly to a flame-retardant flexible printed circuit board adhesive composition.
【０００２】[0002]
【従来の技術】近年電子機器はますます小型化、軽量化
が進行しており、フレキシブル印刷回路基板に対しても
導体パターンのファイン化に対応できる接着剤が要求さ
れている。また電子機器の安全性の観点からも難燃性を
有する印刷回路基板用接着剤の開発が要望されている。2. Description of the Related Art In recent years, electronic devices have become smaller and lighter, and there is a demand for an adhesive that can be used for finer conductor patterns even for flexible printed circuit boards. Further, from the viewpoint of safety of electronic devices, development of a flame retardant adhesive for printed circuit boards has been desired.
【０００３】フレキシブル印刷回路基板用接着剤は一般
にエポキシ樹脂および／またはフェノール樹脂などの熱
硬化性樹脂と熱可塑性樹脂を加えて製造される。これま
で数多くの接着剤が提案されているが、中でも接着力が
高く可撓性に優れるという点からカルボキシル基含有ア
クリロニトリルブタジエンゴム系について多く報告され
ている。Adhesives for flexible printed circuit boards are generally manufactured by adding a thermosetting resin such as an epoxy resin and / or a phenol resin and a thermoplastic resin. A large number of adhesives have been proposed so far, but among them, many have been reported on carboxyl group-containing acrylonitrile butadiene rubber-based rubbers because of their high adhesive strength and excellent flexibility.
【０００４】カルボキシル基含有アクリロニトリルブタ
ジエンゴム系接着剤の難燃化については、臭素化エポキ
シ樹脂を使用すること（特公平３−５９９４７号公
報）、臭素化エポキシ樹脂、臭素化ビニルフェノール樹
脂および水酸化アルミニュウムを添加することが述べら
れている（特開昭６２−２０２５８３号公報）。Regarding flame retardation of acrylonitrile butadiene rubber adhesive containing carboxyl group, use of brominated epoxy resin (Japanese Patent Publication No. 3-59947), brominated epoxy resin, brominated vinylphenol resin and hydroxylation. It is described that aluminum is added (Japanese Patent Laid-Open No. 62-202583).
【０００５】しかしながら、これらの従来の接着剤はい
ずれも難燃化の結果としてカルボキシル基含有アクリロ
ニトリルブタジエンゴムの持っている優れた接着性が失
われており、今後要求されている導体パターンのファイ
ン化への対応が難しいのが現状である。接着剤の難燃化
については酸化アンチモンの添加が一般的に行なわれて
いるが、この場合には接着剤の接着性が低下すると共に
透明性が低下し、ファインな導体パターンの位置合わせ
が困難になるという問題がある。However, all of these conventional adhesives lose the excellent adhesiveness possessed by the carboxyl group-containing acrylonitrile butadiene rubber as a result of flame retardancy, and the conductor patterns to be made finer in the future will be required. Currently, it is difficult to deal with. Antimony oxide is generally added to make the adhesive flame-retardant, but in this case, the adhesiveness of the adhesive decreases and the transparency decreases, making it difficult to align fine conductor patterns. There is a problem that becomes.
【０００６】従って難燃性で、かつ高接着性、高透明性
を有する接着剤の出現が望まれている。また、今後要求
される導体パターンのファイン化に対応するためには一
層の絶縁性の向上が必要とされている。Therefore, the advent of a flame retardant, highly adhesive and highly transparent adhesive has been desired. Further, in order to meet the demand for finer conductor patterns in the future, further improvement in insulation is required.
【０００７】[0007]
【発明が解決しようとする課題】したがって、本発明の
目的は、難燃性で、かつ高接着性、高透明性を有し、絶
縁性の向上されたフレキシブル印刷回路基板用接着剤組
成物を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a flame-retardant adhesive composition for a flexible printed circuit board, which has high adhesiveness, high transparency, and improved insulating properties. To provide.
【０００８】[0008]
【課題を解決するための手段】かかる本発明の目的は以
下の構成をとることにより達成される。The object of the present invention is achieved by the following constitution.
【０００９】（１）カルボキシル基含有アクリロニトリ
ルブタジエンゴム、臭素化エポキシ樹脂および非臭素化
エポキシ樹脂から主としてなる樹脂成分、エポキシ樹脂
用硬化剤および水酸化アルミニュウムを含む難燃性フレ
キシブル印刷回路基板用接着剤組成物において、上記樹
脂成分中、カルボキシル基含有アクリロニトリルブタジ
エンゴムと、臭素化エポキシ樹脂と非臭素化エポキシ樹
脂の和は、それぞれ３０〜６０重量％、７０〜４０重量
％の割合で配合されており、エポキシ樹脂用硬化剤中の
活性水素数（［Ｈ］）と臭素化エポキシ樹脂および非臭
素化エポキシ樹脂中のエポキシ基総数（［Ｅ］）の比、
［Ｈ］／［Ｅ］比が０．２０〜０．６５であり、かつ水
酸化アルミニュウムが上記樹脂成分１００重量部に対し
て１０〜５０重量部含有されていることを特徴とする難
燃性フレキシブル印刷回路基板用接着剤組成物。(1) Carboxyl group-containing acrylonitrile-butadiene rubber, resin component mainly composed of brominated epoxy resin and non-brominated epoxy resin, curing agent for epoxy resin and adhesive for flame-retardant flexible printed circuit board containing aluminum hydroxide In the composition, the sum of the carboxyl group-containing acrylonitrile butadiene rubber, the brominated epoxy resin and the non-brominated epoxy resin in the above resin components is blended in the proportions of 30 to 60% by weight and 70 to 40% by weight, respectively. , The ratio of the number of active hydrogen ([H]) in the curing agent for epoxy resin to the total number of epoxy groups ([E]) in brominated epoxy resin and non-brominated epoxy resin,
[H] / [E] ratio is 0.20 to 0.65, and aluminum hydroxide is contained in an amount of 10 to 50 parts by weight based on 100 parts by weight of the resin component. Adhesive composition for flexible printed circuit board.
【００１０】（２）臭素含量が、上記樹脂成分１００重
量部に対して１０〜２０重量部であって、かつ臭素含有
成分として上記臭素化エポキシ樹脂以外の成分を含有し
ないことを特徴とする前記（１）記載の難燃性フレキシ
ブル印刷回路基板用接着剤組成物。(2) The bromine content is 10 to 20 parts by weight with respect to 100 parts by weight of the resin component, and the bromine-containing component contains no components other than the brominated epoxy resin. (1) The flame-retardant flexible printed circuit board adhesive composition.
【００１１】（３）上記水酸化アルミニュウムの平均粒
子径が２．５μｍ以下であることを特徴とする前記
（１）または（２）記載の難燃性フレキシブル印刷回路
基板用接着剤組成物。(3) The flame-retardant flexible printed circuit board adhesive composition as described in (1) or (2) above, wherein the aluminum hydroxide has an average particle size of 2.5 μm or less.
【００１２】次に各構成成分について説明する。Next, each component will be described.
【００１３】本発明における樹脂成分は、カルボキシル
基含有アクリロニトリルブタジエンゴム、臭素化エポキ
シ樹脂および非臭素化エポキシ樹脂から主としてなるも
のである。The resin component in the present invention mainly comprises a carboxyl group-containing acrylonitrile butadiene rubber, a brominated epoxy resin and a non-brominated epoxy resin.
【００１４】本発明において使用されるカルボキシル基
含有アクリロニトリルブタジエンゴムとしては、例えば
アクリロニトリルとブタジエンを約１０／９０〜５０／
５０のｍｏｌ比で共重合させた共重合ゴムの末端基をカ
ルボキシル化したもの、あるいはアクリロニトリル、ブ
タジエンおよびアクリル酸などのカルボキシル基含有重
合性単量体の三元共重合ゴムなどを挙げることができ
る。具体的には、日本合成ゴム（株）製のＰＮＲ−１
Ｈ、日本ゼオン（株）製のＮｉｐｏｌ１０７２などが好
ましく使用できる。The carboxyl group-containing acrylonitrile-butadiene rubber used in the present invention includes, for example, acrylonitrile and butadiene in an amount of about 10/90 to 50 /.
Examples thereof include those obtained by carboxylating a terminal group of a copolymer rubber which is copolymerized at a molar ratio of 50, or a terpolymer rubber of a carboxyl group-containing polymerizable monomer such as acrylonitrile, butadiene and acrylic acid. . Specifically, PNR-1 manufactured by Nippon Synthetic Rubber Co., Ltd.
H, Nipol1072 manufactured by Nippon Zeon Co., Ltd. and the like can be preferably used.
【００１５】カルボキシル基含有量としては、１〜８ｍ
ｏｌ％が好ましい。１ｍｏｌ％未満ではエポキシ樹脂と
の反応点が少なく、最終的に得られる硬化物の耐熱性が
低下しやすい。一方、８ｍｏｌ％を越えると、カルボキ
シル基含有アクリロニトリルブタジエンゴム／臭素化エ
ポキシ樹脂／非臭素化エポキシ樹脂を含む溶液の安定性
が悪くなりやすい。The carboxyl group content is 1 to 8 m
ol% is preferred. If it is less than 1 mol%, the number of reaction points with the epoxy resin is small, and the heat resistance of the finally obtained cured product tends to be lowered. On the other hand, when it exceeds 8 mol%, the stability of a solution containing a carboxyl group-containing acrylonitrile butadiene rubber / brominated epoxy resin / non-brominated epoxy resin tends to be deteriorated.
【００１６】アクリロニトリル量としては、１０〜５０
ｍｏｌ％が好ましい。１０ｍｏｌ％未満では硬化物の耐
薬品性が低下しやすく、５０ｍｏｌ％を越えると通常の
溶剤に溶解しにくくなるので作業性の低下につながる。The amount of acrylonitrile is 10 to 50.
mol% is preferred. If it is less than 10 mol%, the chemical resistance of the cured product tends to be lowered, and if it exceeds 50 mol%, it becomes difficult to dissolve it in an ordinary solvent, resulting in a decrease in workability.
【００１７】また、カルボキシル基含有アクリロニトリ
ルブタジエンゴム中に含まれるアッシュ量（主成分は乳
化重合時および乳化重合体の凝固時に用いる金属塩と考
えられる）が多いと接着剤の電気絶縁性の低下につなが
るので、アッシュ量は３０００ｐｐｍ以下に押さえる方
が好ましい。さらに好ましくは、５００ｐｐｍ以下であ
る。If the amount of ash contained in the carboxyl group-containing acrylonitrile butadiene rubber (the main component is considered to be a metal salt used during emulsion polymerization and during solidification of the emulsion polymer) is large, the electrical insulation of the adhesive is deteriorated. Therefore, it is preferable to keep the ash amount to 3000 ppm or less. More preferably, it is 500 ppm or less.
【００１８】本発明において使用される臭素化エポキシ
樹脂および非臭素化エポキシ樹脂（以下、「エポキシ樹
脂」というときはこの両者をさすものとする）として
は、市販されている公知のエポキシ樹脂を使用すること
ができ、特に限定されないが、分子内に２個以上のエポ
キシ基を持つものが好ましい。また接着性の点からはエ
ポキシ当量の小さいものが好ましい。具体的には２００
０以下のものが好ましく使用される。As the brominated epoxy resin and non-brominated epoxy resin used in the present invention (hereinafter, "epoxy resin" means both of them), known commercially available epoxy resins are used. However, it is not particularly limited, but those having two or more epoxy groups in the molecule are preferable. Further, from the viewpoint of adhesiveness, those having a small epoxy equivalent are preferable. Specifically, 200
Those of 0 or less are preferably used.
【００１９】臭素化エポキシ樹脂としては、油化シェル
（株）製ＥＰ５０５０、ＥＰ５０５１、ダウケミカル
（株）製Ｄ．Ｅ．Ｒ．−５４２、日本化薬（株）製ＢＲ
ＥＮ−Ｓなどが挙げられるが、特に限定されるものでは
ない。Examples of the brominated epoxy resin include EP5050 and EP5051 manufactured by Yuka Shell Co., Ltd., and D.I. E. R. -542, BR manufactured by Nippon Kayaku Co., Ltd.
Examples thereof include EN-S, but are not particularly limited.
【００２０】非臭素化エポキシ樹脂としては、通常使用
される種々のタイプのもの、例えばビスフェノールＡ型
エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂，ビフ
ェノール型エポキシ樹脂あるいはノボラック型エポキシ
樹脂などが挙げられ、特に限定されるものではない。具
体的には、油化シェル（株）製ＥＰ８３４、ＥＰ１００
１、ＥＰ１５２、ダウケミカル（株）製Ｄ．Ｅ．Ｒ．３
３１Ｌなどが好ましく使用される。Examples of the non-brominated epoxy resin include various types which are usually used, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin or novolac type epoxy resin, and are particularly limited. It is not something that will be done. Specifically, Yuka Shell Co., Ltd. product EP834, EP100.
1, EP152, D.W. E. R. Three
31 L and the like are preferably used.
【００２１】本発明においては、エポキシ樹脂として、
臭素化エポキシ樹脂と非臭素化エポキシ樹脂の両方を含
有することが重要である。臭素化エポキシ樹脂と非臭素
化エポキシ樹脂の配合比は、難燃性の付与および接着
性、耐薬品性などを考慮して適宜選択されるが、好まし
くは、８５：１５〜２０：８０重量％、より好ましく
は、７５：２５〜４０：６０重量％である。臭素化エポ
キシ樹脂が多いと、難燃性(UL-94 V-0) の付与はできる
ものの接着剤の耐熱性の低下が大きくなりやすく、非臭
素化エポキシ樹脂が多いと、難燃性が低下しやすくな
る。In the present invention, as the epoxy resin,
It is important to include both brominated and non-brominated epoxy resins. The blending ratio of the brominated epoxy resin and the non-brominated epoxy resin is appropriately selected in consideration of imparting flame retardancy, adhesiveness, chemical resistance, etc., but is preferably 85:15 to 20: 80% by weight. , And more preferably 75:25 to 40: 60% by weight. Flame retardancy (UL-94 V-0) can be imparted with a large amount of brominated epoxy resin, but the heat resistance of the adhesive tends to decrease significantly, and flame retardancy decreases with a large amount of non-brominated epoxy resin. Easier to do.
【００２２】また、難燃性付与のために、接着剤組成物
中の臭素含量が、樹脂成分１００重量部に対して１０〜
３０重量部になるように臭素化エポキシ樹脂を配合する
ことが好ましい。より好ましくは、１０〜２０重量部で
ある。なお、後述のように他の樹脂成分を添加した場
合、臭素含量の基準となる「樹脂成分」とは、該他の樹
脂成分を含む全樹脂成分のことであって、アクリロニト
リルブタジエンゴムとエポキシ樹脂の総量のことではな
い。In order to impart flame retardancy, the bromine content of the adhesive composition is 10 to 100 parts by weight of the resin component.
It is preferable to add the brominated epoxy resin in an amount of 30 parts by weight. More preferably, it is 10 to 20 parts by weight. When other resin components are added as described below, the "resin component" that is the standard for the bromine content is all resin components including the other resin components, such as acrylonitrile butadiene rubber and epoxy resin. Not the total amount of.
【００２３】さらに、接着剤組成物中に、臭素含有成分
として上記臭素化エポキシ樹脂以外の成分を含有してい
ないことが好ましい。Further, it is preferable that the adhesive composition does not contain a component other than the above-mentioned brominated epoxy resin as a bromine-containing component.
【００２４】本発明においては、カルボキシル基含有ア
クリロニトリルブタジエンゴムと、、エポキシ樹脂は、
それぞれ３０〜６０重量％、７０〜４０重量％の割合で
配合されていることが重要である。カルボキシル基含有
アクリロニトリルブタジエンゴムの量が３０重量％未満
では接着力が不安定となり、６０重量％を越えると半田
耐熱性が低下する。より好ましい配合割合としては、カ
ルボキシル基含有アクリロニトリルブタジエンゴムが３
５〜５５重量％の範囲にあることである。In the present invention, the carboxyl group-containing acrylonitrile butadiene rubber and the epoxy resin are
It is important that they are blended in the proportions of 30 to 60% by weight and 70 to 40% by weight, respectively. If the amount of the carboxyl group-containing acrylonitrile butadiene rubber is less than 30% by weight, the adhesive strength will be unstable, and if it exceeds 60% by weight, the solder heat resistance will decrease. A more preferable compounding ratio is 3 for the carboxyl group-containing acrylonitrile-butadiene rubber.
It is in the range of 5 to 55% by weight.
【００２５】また、樹脂成分として、さらに他の樹脂を
少量添加することもできる。添加することのできる他の
樹脂としては、フェノール樹脂、アクリル樹脂、ブチラ
ール樹脂などを挙げることができ、その添加量として
は、基体樹脂１００重量部に対して、０．５〜１０重量
部が好ましい。なお、他の樹脂が添加された場合であっ
ても、上記アクリロニトリルブタジエンゴムとエポキシ
樹脂の配合割合は影響を受けず、それぞれ、３０〜６０
重量％、７０〜４０重量％であることが重要である。Further, a small amount of another resin may be added as a resin component. Examples of other resins that can be added include phenol resins, acrylic resins, butyral resins, and the addition amount thereof is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the base resin. . Even if another resin is added, the compounding ratio of the acrylonitrile butadiene rubber and the epoxy resin is not affected, and the mixing ratio is 30 to 60, respectively.
It is important that it is 70% to 40% by weight.
【００２６】本発明において使用されるエポキシ樹脂用
硬化剤としては、アミン系硬化剤、酸、または酸無水物
などが使用可能であるが、アミン系硬化剤、特に芳香族
ポリアミンが好ましい。エポキシ樹脂用硬化剤は、接着
剤の耐熱性の発現のために必要であり、その添加量は、
エポキシ樹脂用硬化剤中の活性水素数（［Ｈ］）とエポ
キシ樹脂中のエポキシ基総数（［Ｅ］）の比、［Ｈ］／
［Ｅ］比が０．２０〜０．６５になるように調整するこ
とが重要であり、好ましくは、０．３０〜０．６０であ
る。［Ｈ］／［Ｅ］比が０．２０未満では耐薬品性が不
十分となり、０．６５を越えると接着力が低下してく
る。As the epoxy resin curing agent used in the present invention, an amine curing agent, an acid, an acid anhydride or the like can be used, but an amine curing agent, particularly an aromatic polyamine is preferable. The curing agent for epoxy resin is necessary for developing the heat resistance of the adhesive, and the addition amount is
Ratio of the number of active hydrogen ([H]) in the curing agent for epoxy resin and the total number of epoxy groups ([E]) in the epoxy resin, [H] /
It is important to adjust the [E] ratio to be 0.20 to 0.65, and preferably 0.30 to 0.60. If the [H] / [E] ratio is less than 0.20, the chemical resistance becomes insufficient, and if it exceeds 0.65, the adhesive strength decreases.
【００２７】本発明において使用される水酸化アルミニ
ュウムとしては、市販品をアルコール系溶媒などを用い
て湿式粉砕する通常の方法で容易に得られるものを挙げ
ることができる。水酸化アルミニュウムは、難燃性の付
与のみならず、接着剤の流動特性、接着性の向上にも影
響する。また、水酸化アルミニュウムは、透明性を保っ
たまま難燃性の付与を可能にするものであり、このこと
によって本発明の特徴である難燃性でかつ高接着性、高
透明性を有する接着剤調整が可能となる。水酸化アルミ
ニュウムの平均粒子径は透明性の点ではできる限り小さ
い方が好ましいが、０．２μｍより小さい場合は粒子が
再凝集し易く、接着剤各成分の調合、混合が困難となり
やすい。また、透明性、接着力の向上の点からは、粒子
径が２．５μｍ以下であることが好ましい。より好まし
くは、１．５μｍ以下である。Examples of the aluminum hydroxide used in the present invention include those which can be easily obtained by a usual method in which a commercially available product is wet pulverized with an alcohol solvent or the like. Aluminum hydroxide not only imparts flame retardancy, but also affects the flow characteristics and adhesiveness of the adhesive. In addition, aluminum hydroxide is capable of imparting flame retardancy while maintaining transparency, and as a result, it is a feature of the present invention that it is flame-retardant, highly adhesive, and highly transparent. Agent adjustment is possible. The average particle size of aluminum hydroxide is preferably as small as possible in terms of transparency, but if it is smaller than 0.2 μm, the particles are likely to reaggregate, and it becomes difficult to mix and mix the components of the adhesive. From the viewpoint of improving transparency and adhesive strength, the particle diameter is preferably 2.5 μm or less. More preferably, it is 1.5 μm or less.
【００２８】水酸化アルミニュウムの添加量としては、
樹脂成分１００重量部に対して１０〜５０重量部である
ことが重要で、好ましくは、２０〜４０重量部である。
１０重量部未満では難燃性付与効果が小さいうえに接着
剤の流動性および粘着性が大きくなり、銅箔とのラミネ
ート性が困難になりやすい。また５０重量部以上では接
着性が低下するという欠点を有する。ここでも、「樹脂
成分」とは、他の樹脂成分を添加したときは、アクリロ
ニトリルブタジエンゴム、エポキシ樹脂の総量を指すも
のではなく、他の樹脂成分を含む全樹脂成分をさすもの
である。The amount of aluminum hydroxide added is
It is important to be 10 to 50 parts by weight with respect to 100 parts by weight of the resin component, and preferably 20 to 40 parts by weight.
If it is less than 10 parts by weight, the effect of imparting flame retardancy is small, and the fluidity and tackiness of the adhesive are increased, so that the laminating property with the copper foil tends to be difficult. Further, when it is 50 parts by weight or more, there is a drawback that the adhesiveness is lowered. Here again, the "resin component" does not refer to the total amount of acrylonitrile butadiene rubber and epoxy resin when other resin components are added, but refers to all resin components including other resin components.
【００２９】本発明の接着剤組成物には、接着剤の特性
を損なわない範囲で酸化防止剤などの有機、無機成分を
添加することができる。酸化防止剤としては、住友化学
（株）製“Ｓｕｍｉｌｉｚｅｒ”ＭＤＰ−Ｓ、日本チバ
ガイギー（株）製“Ｉｒｇａｎｏｘ”１０１０、“Ｉｒ
ｇａｎｏｘ”１０７６などを挙げることができる。Organic and inorganic components such as antioxidants can be added to the adhesive composition of the present invention within a range that does not impair the properties of the adhesive. As the antioxidant, "Sumilizer" MDP-S manufactured by Sumitomo Chemical Co., Ltd., "Irganox" 1010, "Ir manufactured by Ciba-Geigy Co., Ltd."
ganox "1076 etc. can be mentioned.
【００３０】[0030]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれらの実施例に限定されるものではない。実
施例の説明に入る前に評価方法について述べる。The present invention will be described below with reference to examples.
The invention is not limited to these examples. The evaluation method will be described before the description of the examples.
【００３１】＜評価方法＞ （１）接着力 ＪＩＳ−Ｃ６４８１に準拠して行った。<Evaluation Method> (1) Adhesion Strength It was measured according to JIS-C6481.
【００３２】（２）燃焼性 ＵＬ規格に準拠して行なった。(2) Flammability It was carried out according to the UL standard.
【００３３】（３）電気絶縁性 ＪＩＳ−Ｃ６４８１に準拠して行った。(3) Electrical Insulation Property It was performed in accordance with JIS-C6481.
【００３４】（４）透明性 “カプトン”１００Ｈ（東レ・デュポン（株）製ポリイ
ミドフィルム）の上に乾燥厚みで接着剤を２０μｍ塗
布、乾燥して得られた接着剤付きフィルムの全光線透過
率、ヘイズを測定した。(4) Transparency The total light transmittance of the film with an adhesive obtained by applying 20 μm of the adhesive to a dry thickness on “Kapton” 100H (polyimide film manufactured by Toray-Dupont Co., Ltd.) and drying. , Haze was measured.
【００３５】（５）水酸化アルミニュウム平均粒子径 “カプトン”１００Ｈの上に乾燥厚みで接着剤を２０μ
ｍ塗布、乾燥して得られた接着剤の透過電子顕微鏡写真
（倍率：８０００倍）から平均粒子径を計算した。(5) Aluminum hydroxide average particle diameter 20 μm of the adhesive in dry thickness on “Kapton” 100H
The average particle diameter was calculated from a transmission electron micrograph (magnification: 8000 times) of the adhesive obtained by applying m and drying.
【００３６】実施例１ カルボキシル基含有アクリロニトリルブタジエンゴムＰ
ＮＲ−１Ｈ（日本合成ゴム（株）製、アッシュ量 ２０
０ｐｐｍ）３２．７ｇを１５０ｇのメチルイソブチルケ
トンに溶解した。次に、臭素化エポキシ樹脂“エピコー
ト”５０５０（油化シェル（株）製、臭素含有率４９
％）のトルエン６０重量％溶液を４８．４ｇ，および非
臭素化エポキシ樹脂“エピコート”８３４（油化シェル
（株）製、エポキシ当量２５０）の６０重量％クロルベ
ンゼン溶液を１８．２ｇ加えた。ついで水酸化アルミニ
ュウム分散液Ａ（住友化学（株）製“Ｃ−３００５”、
溶媒：クロルベンゼン／ベンジルアルコール＝８５／１
５（重量％）、濃度：１７重量％、平均粒子径：０．６
μｍ）を１３５ｇ、最後にエポキシ樹脂用硬化剤４，４
´−ジアミノジフェニルスルホン（以下、「４，４´−
ＤＤＳ」と省略する）を３ｇ加え、均一な溶液になるま
で攪拌、混合を続け最終塗料を得た。得られた塗料を用
いて、厚さ２５μｍのポリイミドフィルム（東レ・デュ
ポン（株）製“カプトン”１００Ｈ）に約２０μｍの乾
燥厚さとなるように塗布し，１５０℃で２分間乾燥し
た。Example 1 Carboxyl group-containing acrylonitrile butadiene rubber P
NR-1H (Nippon Synthetic Rubber Co., Ltd., ash amount 20)
0 ppm) 32.7 g was dissolved in 150 g of methyl isobutyl ketone. Next, brominated epoxy resin "Epicoat" 5050 (produced by Yuka Shell Co., Ltd., bromine content 49
%) Of toluene in an amount of 48.4 g, and a non-brominated epoxy resin "Epicoat" 834 (produced by Yuka Shell Co., Ltd., epoxy equivalent: 250) in a weight ratio of 60% by weight of chlorobenzene of 18.2 g. Next, aluminum hydroxide dispersion A (“C-3005” manufactured by Sumitomo Chemical Co., Ltd.)
Solvent: chlorobenzene / benzyl alcohol = 85/1
5 (wt%), concentration: 17 wt%, average particle size: 0.6
μm) 135 g, and finally hardener for epoxy resin 4, 4
′ -Diaminodiphenyl sulfone (hereinafter, “4,4′-
DDS ”is abbreviated), and the mixture is continuously stirred and mixed until a uniform solution is obtained to obtain a final paint. The obtained coating material was applied to a polyimide film having a thickness of 25 μm (“Kapton” 100H manufactured by Toray-Dupont Co., Ltd.) to a dry thickness of about 20 μm, and dried at 150 ° C. for 2 minutes.
【００３７】ついで３５μｍの圧延銅箔のマット面と重
ね合わせて１２０℃、２ｋｇ／ｃｍの圧力でロールラミ
ネートした後１５０℃で５時間キュアしてフレキシブル
銅張積層板を得た。このようにして得られたフレキシブ
ル銅張積層板の特性を表１に示す。Then, it was superposed on a matte surface of a rolled copper foil having a thickness of 35 μm, roll-laminated at a pressure of 2 kg / cm at 120 ° C., and then cured at 150 ° C. for 5 hours to obtain a flexible copper-clad laminate. The characteristics of the flexible copper clad laminate thus obtained are shown in Table 1.
【００３８】このようにして得られたフレキシブル銅張
積層板の最終的な接着剤の固形分組成は次の通りであ
る。なお、エポキシ樹脂用硬化剤（４，４´−ＤＤ
Ｓ）、水酸化アルミニュウムの量は、カルボキシル基含
有アクリロニトリルブタジエンゴムとエポキシ樹脂との
総量を樹脂成分とみなし、樹脂成分１００に対する添加
量（ｐｈｒ）で表示している。The final solid composition of the adhesive of the flexible copper clad laminate thus obtained is as follows. The curing agent for epoxy resin (4,4'-DD
The amounts of S) and aluminum hydroxide are indicated by the addition amount (phr) to the resin component 100, regarding the total amount of the carboxyl group-containing acrylonitrile butadiene rubber and the epoxy resin as the resin component.
【００３９】 ＰＮＲ−１Ｈ ４５．０ 重量％ “エピコート”５０５０ ４０．０ 重量％ “エピコート”８３４ １５．０ 重量％ ４，４´−ＤＤＳ ４．１ ｐｈｒ 水酸化アルミニュウム ３０．０ ｐｈｒ なお、上記接着剤組成における〔Ｈ〕／〔Ｅ〕比および
臭素含量（重量％）はそれぞれ０．４１および１８．８
％である。PNR-1H 45.0 wt% “Epicoat” 5050 40.0 wt% “Epicoat” 834 15.0 wt% 4,4′-DDS 4.1 phr Aluminum hydroxide 30.0 phr The above-mentioned adhesion The [H] / [E] ratio and the bromine content (% by weight) in the agent composition were 0.41 and 18.8, respectively.
%.
【００４０】[0040]
【表１】 実施例２ 実施例１において水酸化アルミニュウム分散液Ｂ（住友
化学（株）製“Ｃ−３０１”、溶媒：クロルベンゼン／
ベンジルアルコール＝８５／１５（重量％）、濃度：１
７重量％、平均粒子径：１．５μｍ）を使用した以外は
実施例１と同様にして得られたフレキシブル銅張積層板
の特性を同じ表１に示す。上記接着剤組成における
〔Ｈ〕／〔Ｅ〕比および臭素含量（重量％）はそれぞれ
０．４１および１８．８％である。[Table 1] Example 2 In Example 1, aluminum hydroxide dispersion liquid B (“C-301” manufactured by Sumitomo Chemical Co., Ltd., solvent: chlorobenzene /
Benzyl alcohol = 85/15 (wt%), concentration: 1
The characteristics of the flexible copper-clad laminate obtained in the same manner as in Example 1 are shown in the same Table 1 except that 7% by weight and an average particle diameter: 1.5 μm) were used. The [H] / [E] ratio and the bromine content (% by weight) in the above adhesive composition are 0.41 and 18.8%, respectively.
【００４１】実施例３ 実施例１において非臭素化エポキシ樹脂を“エピコー
ト”８３４から“エピコート”１００１（油化シェルエ
ポキシ（株）製、エポキシ当量４７５）に変えた以外は
実施例１と同様にして得られたフレキシブル銅張積層板
の特性を表１に示す。Example 3 The same as in Example 1 except that the non-brominated epoxy resin was changed from "Epicoat" 834 to "Epicoat" 1001 (Okaka Shell Epoxy Co., Ltd., epoxy equivalent 475). Table 1 shows the properties of the flexible copper-clad laminate thus obtained.
【００４２】なお、上記接着剤組成における〔Ｈ〕／
〔Ｅ〕比および臭素含量（重量％）はそれぞれ０．５０
および１８．８％である。[H] / in the above adhesive composition
[E] ratio and bromine content (wt%) are 0.50 each
And 18.8%.
【００４３】実施例４ 実施例１において接着剤組成を下記のように変更して得
られたフレキシブル銅張積層板の特性を表１に示す。Example 4 Table 1 shows the characteristics of the flexible copper clad laminate obtained in Example 1 by changing the adhesive composition as follows.
【００４４】 ＰＮＲ−１Ｈ ４４．０ 重量％ “エピコート”５０５０ ２８．０ 重量％ “エピコート”８３４ ２８．０ 重量％ ４，４´−ＤＤＳ ６．０ ｐｈｒ 水酸化アルミニュウム ３０．０ ｐｈｒ なお、上記接着剤組成における〔Ｈ〕／〔Ｅ〕比および
臭素含量（重量％）はそれぞれ０．５２および１２．９
％である。PNR-1H 44.0% by weight “Epicoat” 5050 28.0% by weight “Epicoat” 834 28.0% by weight 4,4′-DDS 6.0 phr Aluminum hydroxide 30.0 phr The above-mentioned adhesion The [H] / [E] ratio and the bromine content (% by weight) in the agent composition were 0.52 and 12.9, respectively.
%.
【００４５】比較例１ 実施例１において接着剤組成を下記のように変更して
（カルボキシル基含有アクリロニトリルブタジエンゴム
の量を減らして）、得られたフレキシブル銅張積層板の
特性を表１に示すが、接着力が著しく低下することが分
かる。Comparative Example 1 The characteristics of the flexible copper clad laminate obtained by changing the adhesive composition in Example 1 as follows (reducing the amount of carboxyl group-containing acrylonitrile butadiene rubber) are shown in Table 1. However, it can be seen that the adhesive strength is significantly reduced.
【００４６】 ＰＮＲ−１Ｈ ２５．０ 重量％ “エピコート”５０５０ ３５．０ 重量％ “エピコート”８３４ ４０．０ 重量％ ４，４´−ＤＤＳ ４．０ ｐｈｒ 水酸化アルミニュウム ３０．０ ｐｈｒ なお、上記接着剤組成における〔Ｈ〕／〔Ｅ〕比および
臭素含量（重量％）はそれぞれ０．２７および１６．５
％である。PNR-1H 25.0% by weight "Epicoat" 5050 35.0% by weight "Epicoat" 834 40.0% by weight 4,4'-DDS 4.0 phr Aluminum hydroxide 30.0 phr The above-mentioned adhesion The [H] / [E] ratio and the bromine content (% by weight) in the agent composition were 0.27 and 16.5, respectively.
%.
【００４７】比較例２ 実施例１において非臭素化エポキシ樹脂を“エピコー
ト”８３４から“エピコート”１０１０（油化シェルエ
ポキシ（株）製、エポキシ当量４０００）に変え、４，
４´−ＤＤＳ量を５ｇに変更した（エポキシ樹脂用硬化
剤の量が減少した）以外は実施例１と同様にして得られ
たフレキシブル銅張積層板の特性を表１に示すが、実施
例１と比較して接着力が著しく低下することが分かる。Comparative Example 2 In Example 1, the non-brominated epoxy resin was changed from "Epicoat" 834 to "Epicoat" 1010 (produced by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 4000).
The characteristics of the flexible copper-clad laminate obtained in the same manner as in Example 1 are shown in Table 1 except that the amount of 4'-DDS was changed to 5 g (the amount of the curing agent for epoxy resin was decreased). It can be seen that the adhesive strength is remarkably reduced as compared with 1.
【００４８】なお、上記接着剤組成における〔Ｈ〕／
〔Ｅ〕比および臭素含量（重量％）はそれぞれ０．７７
および１８．７％である。[H] / in the above adhesive composition
[E] ratio and bromine content (% by weight) are 0.77
And 18.7%.
【００４９】比較例３ 実施例１において水酸化アルミニュウム量を６０ｐｈｒ
使用した以外は実施例１と同様にして得られたフレキシ
ブル銅張積層板の特性を表１に示すが、実施例１と比較
して接着力が低下することが分かる。Comparative Example 3 In Example 1, the amount of aluminum hydroxide was 60 phr.
The characteristics of the flexible copper-clad laminate obtained in the same manner as in Example 1 except that it is used are shown in Table 1, and it can be seen that the adhesive strength is lower than in Example 1.
【００５０】なお、上記接着剤組成における〔Ｈ〕／
〔Ｅ〕比および臭素含量（重量％）はそれぞれ０．５０
および１８．８％である。[H] / in the above adhesive composition
[E] ratio and bromine content (wt%) are 0.50 each
And 18.8%.
【００５１】比較例４ 実施例１において水酸化アルミニュウムの代わりに、酸
化アンチモンを１０ｐｈｒ使用した場合のフレキシブル
銅張積層板の特性を同じ表１に示すが、実施例１と比較
して透明性が著しく低下するとともに接着力も低下する
ことが分かる。なお、上記接着剤組成における〔Ｈ〕／
〔Ｅ〕比および臭素含量（重量％）はそれぞれ０．４１
および１８．８％である。Comparative Example 4 The characteristics of the flexible copper clad laminate in the case of using 10 phr of antimony oxide instead of aluminum hydroxide in Example 1 are shown in the same Table 1, but the transparency is higher than that of Example 1. It can be seen that the adhesive strength is significantly reduced as well as the adhesive strength is significantly reduced. In the above adhesive composition, [H] /
[E] ratio and bromine content (% by weight) are 0.41
And 18.8%.
【００５２】[0052]
【発明の効果】本発明により得られるフレキシブル印刷
回路板用接着剤組成物は、難燃性でかつ、高接着力、高
電気絶縁性を示すとともに、透明性にも優れるという従
来の接着剤にない特徴を持っており、今後ますます進行
する導体のファイン化には最も適していると考えられ
る。EFFECT OF THE INVENTION The adhesive composition for flexible printed circuit boards obtained by the present invention is flame-retardant, shows high adhesive strength and high electric insulation, and is excellent in transparency as well as conventional adhesives. It has no features and is considered to be the most suitable for finer conductors, which is becoming more and more advanced in the future.
Claims (3)
ジエンゴム、臭素化エポキシ樹脂および非臭素化エポキ
シ樹脂から主としてなる樹脂成分、エポキシ樹脂用硬化
剤および水酸化アルミニュウムを含む難燃性フレキシブ
ル印刷回路基板用接着剤組成物において、上記樹脂成分
中、カルボキシル基含有アクリロニトリルブタジエンゴ
ムと、臭素化エポキシ樹脂と非臭素化エポキシ樹脂の和
は、それぞれ３０〜６０重量％、７０〜４０重量％の割
合で配合されており、エポキシ樹脂用硬化剤中の活性水
素数（［Ｈ］）と臭素化エポキシ樹脂および非臭素化エ
ポキシ樹脂中のエポキシ基総数（［Ｅ］）の比、［Ｈ］
／［Ｅ］比が０．２０〜０．６５であり、かつ水酸化ア
ルミニュウムが上記樹脂成分１００重量部に対して１０
〜５０重量部含有されていることを特徴とする難燃性フ
レキシブル印刷回路基板用接着剤組成物。1. A flame-retardant flexible printed circuit board adhesive composition containing a resin component mainly composed of a carboxyl group-containing acrylonitrile-butadiene rubber, a brominated epoxy resin and a non-brominated epoxy resin, a curing agent for an epoxy resin, and aluminum hydroxide. In the above resin component, the sum of the carboxyl group-containing acrylonitrile butadiene rubber, the brominated epoxy resin and the non-brominated epoxy resin is blended in the proportions of 30 to 60% by weight and 70 to 40% by weight, respectively. Ratio of active hydrogen number ([H]) in curing agent for epoxy resin and total number of epoxy groups ([E]) in brominated epoxy resin and non-brominated epoxy resin, [H]
/ [E] ratio is 0.20 to 0.65, and aluminum hydroxide is 10 per 100 parts by weight of the resin component.
The flame-retardant flexible printed circuit board adhesive composition is contained in an amount of ˜50 parts by weight.
対して１０〜２０重量部であって、かつ臭素含有成分と
して上記臭素化エポキシ樹脂以外の成分を含有しないこ
とを特徴とする請求項１記載の難燃性フレキシブル印刷
回路基板用接着剤組成物。2. The bromine content is 10 to 20 parts by weight with respect to 100 parts by weight of the resin component, and the bromine-containing component contains no components other than the brominated epoxy resin. The flame-retardant flexible printed circuit board adhesive composition according to 1.
２．５μｍ以下であることを特徴とする請求項１または
２記載の難燃性フレキシブル印刷回路基板用接着剤組成
物。3. The flame-retardant flexible printed circuit board adhesive composition according to claim 1, wherein the aluminum hydroxide has an average particle diameter of 2.5 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20376292A JPH0649427A (en) | 1992-07-30 | 1992-07-30 | Adhesive composition for flexible printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20376292A JPH0649427A (en) | 1992-07-30 | 1992-07-30 | Adhesive composition for flexible printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0649427A true JPH0649427A (en) | 1994-02-22 |
Family
ID=16479410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20376292A Pending JPH0649427A (en) | 1992-07-30 | 1992-07-30 | Adhesive composition for flexible printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0649427A (en) |
Cited By (4)
| 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 |
| US7506743B2 (en) | 2005-03-28 | 2009-03-24 | Daifuku Co., Ltd. | Changeover system |
| WO2015151960A1 (en) * | 2014-03-31 | 2015-10-08 | 荒川化学工業株式会社 | Adhesive composition for printed wiring board, laminate, and flexible printed wiring board |
| KR20180027373A (en) | 2016-09-05 | 2018-03-14 | 아라까와 가가꾸 고교 가부시끼가이샤 | Copper clad laminate for flexible printed circuit board and flexible printed circuit board |
-
1992
- 1992-07-30 JP JP20376292A patent/JPH0649427A/en active Pending
Cited By (7)
| 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 |
| US7506743B2 (en) | 2005-03-28 | 2009-03-24 | Daifuku Co., Ltd. | Changeover system |
| KR100944402B1 (en) * | 2005-03-28 | 2010-02-25 | 가부시키가이샤 다이후쿠 | Switching facility |
| WO2015151960A1 (en) * | 2014-03-31 | 2015-10-08 | 荒川化学工業株式会社 | Adhesive composition for printed wiring board, laminate, and flexible printed wiring board |
| CN105874028A (en) * | 2014-03-31 | 2016-08-17 | 荒川化学工业株式会社 | Adhesive composition for printed wiring board, laminate, and flexible printed wiring board |
| JPWO2015151960A1 (en) * | 2014-03-31 | 2017-04-13 | 荒川化学工業株式会社 | Adhesive composition for printed wiring board, laminate and flexible printed wiring board |
| KR20180027373A (en) | 2016-09-05 | 2018-03-14 | 아라까와 가가꾸 고교 가부시끼가이샤 | Copper clad laminate for flexible printed circuit board and flexible printed circuit board |
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