JPH0699673B2 - Adhesive for copper foil - Google Patents
Adhesive for copper foilInfo
- Publication number
- JPH0699673B2 JPH0699673B2 JP61084356A JP8435686A JPH0699673B2 JP H0699673 B2 JPH0699673 B2 JP H0699673B2 JP 61084356 A JP61084356 A JP 61084356A JP 8435686 A JP8435686 A JP 8435686A JP H0699673 B2 JPH0699673 B2 JP H0699673B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- adhesive
- copper foil
- parts
- sulfur compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000853 adhesive Substances 0.000 title claims description 48
- 230000001070 adhesive effect Effects 0.000 title claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 38
- 239000011889 copper foil Substances 0.000 title claims description 24
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 23
- 150000003464 sulfur compounds Chemical class 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011354 acetal resin Substances 0.000 claims description 7
- 229920006324 polyoxymethylene Polymers 0.000 claims description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 6
- -1 sulfenamide sulfur compound Chemical class 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 11
- 229910000679 solder Inorganic materials 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- LFMQNMXVVXHZCC-UHFFFAOYSA-N 1,3-benzothiazol-2-yl n,n-diethylcarbamodithioate Chemical compound C1=CC=C2SC(SC(=S)N(CC)CC)=NC2=C1 LFMQNMXVVXHZCC-UHFFFAOYSA-N 0.000 description 1
- RCPUUVXIUIWMEE-UHFFFAOYSA-N 2-(2,4-dinitrophenyl)sulfanyl-1,3-benzothiazole Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1SC1=NC2=CC=CC=C2S1 RCPUUVXIUIWMEE-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000003946 cyclohexylamines Chemical class 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GQWNEBHACPGBIG-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-[2-(1,3-benzothiazol-2-ylsulfanylamino)ethoxy]ethanamine Chemical compound C1=CC=C2SC(SNCCOCCNSC=3SC4=CC=CC=C4N=3)=NC2=C1 GQWNEBHACPGBIG-UHFFFAOYSA-N 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
【発明の詳細な説明】 ［発明の目的］ （産業上の利用分野） 本発明は、接着性、半田耐熱性、保存安定性に優れた銅
箔用接着剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to an adhesive for copper foil which is excellent in adhesiveness, solder heat resistance, and storage stability.
（従来の技術） 近年、電子機器工業の発展に伴ない、印刷回路板の需要
は年々増大しているが、電子機器の高密度化、軽薄短小
化により印刷回路板の線間距離が次第に狭くなってきて
いる。また民生機器において、特に安全性の立場から銅
張積層板は、溶融半田浴に浸漬してふくれを生じないこ
と、穴開け加工に支障のないこと、メッキ加工が必要な
場合はメッキ薬品類に侵されないこと等が必要である。
これらの使用、加工条件がますます苛酷になる方向の中
で、銅張積層板の銅箔と基材の接着強さがより強固であ
ることが、基板の信頼性の１つとして強く要求され、そ
れを満たす接着剤の開発が要請されている。(Prior Art) In recent years, the demand for printed circuit boards has been increasing year by year along with the development of the electronic device industry, but the distance between printed circuit board lines has gradually become narrower due to higher density, lighter, thinner and smaller electronic devices. It has become to. In consumer equipment, copper clad laminates should be immersed in a molten solder bath to prevent blistering, do not hinder drilling, and apply plating chemicals when plating is required, especially from the standpoint of safety. It is necessary not to be invaded.
While the use and processing conditions are becoming more and more severe, it is strongly required as one of the reliability of the substrate that the adhesive strength between the copper foil and the base material of the copper clad laminate is stronger. , The development of an adhesive that meets the demand has been demanded.
（発明が解決しようとする問題点） 銅箔と基材の接着力を高める目的で、接着剤の樹脂組成
中にカルボキシル基を有するジエンゴムとエポキシ樹脂
を含ませた組成や、ヒドロキシ基を有する変性樹脂等を
加えた組成で、銅箔と基材という異種材料間の接着をは
かる方法が知られているが、これらはカルボキシル、ヒ
ドロキシル基によって接着剤の両材料へのぬれ性を高め
る効果はあるが、銅の持つ特性を積極的に引き出す効果
は小さい欠点がある。これを改善するためのチオール系
化合物を添加し、該化合物のメルカプト基の働きによっ
て銅表面に積極的に錯体を形成しもしくは銅表面を親油
性に改質する方法がある。しかし、メルカプト基を接着
剤樹脂中にもった場合、樹脂中の他の官能基と容易に相
互作用を起こすため、接着剤の保存安定性がなくなり、
長期保存をした接着剤の接着強度が大幅に低下する欠点
がある。チオール系化合物として２−置換−4.6−ジチ
オール−sym−トリアジン誘導体を添加する方法もある
が、この誘導体は樹脂や溶剤等に対する溶解性が限定さ
れるため、銅箔を予めこの誘導体で処理した後、接着剤
を塗布する必要があるので工程上繁雑且つコスト高とな
り、また広範な樹脂系の接着剤に適用できない欠点があ
った。(Problems to be solved by the invention) For the purpose of enhancing the adhesive force between a copper foil and a substrate, a composition in which a diene rubber having a carboxyl group and an epoxy resin are included in a resin composition of an adhesive, or a modification having a hydroxy group There is a known method of bonding different materials such as a copper foil and a base material with a composition containing a resin, etc., but these have the effect of increasing the wettability of the adhesive to both materials by carboxyl and hydroxyl groups. However, there is a drawback that the effect of actively drawing out the properties of copper is small. There is a method of adding a thiol-based compound to improve this, and positively forming a complex on the copper surface or modifying the copper surface to be lipophilic by the action of the mercapto group of the compound. However, when the mercapto group is present in the adhesive resin, it easily interacts with other functional groups in the resin, so the storage stability of the adhesive is lost,
There is a drawback that the adhesive strength of an adhesive that has been stored for a long period of time is significantly reduced. There is also a method of adding a 2-substituted-4.6-dithiol-sym-triazine derivative as a thiol compound, but since this derivative has limited solubility in a resin, a solvent, etc., after treating a copper foil with this derivative in advance. However, since it is necessary to apply an adhesive, the process is complicated and costly, and there is a drawback that it cannot be applied to a wide range of resin-based adhesives.
本発明は、上記の欠点を解消し、接着性、半田耐熱性、
保存安定性に優れ、容易につくれてコスト高とならず、
かつ広範な樹脂系に応用できる銅箔用接着剤を提供する
ことを目的としている。The present invention eliminates the above drawbacks, adhesiveness, solder heat resistance,
It has excellent storage stability, is easy to make, and does not increase the cost.
Moreover, it aims at providing the adhesive agent for copper foils applicable to a wide range of resin systems.
［発明の構成］ （問題点を解決するための手段と作用） 本発明者らは、上記の目的を達成しようと鋭意検討した
結果、ベンゾチアゾール系若しくはスルフェンアミド系
の硫黄化合物を配合すれば、接着強度、半田耐熱性が改
善され、保存性もよく、また経済的であることを見いだ
し、本発明を完成したものである。即ち、本発明は、 （Ａ）ポリビニルアセタール系樹脂、 （Ｂ）熱硬化性樹脂及び （Ｃ）ベンゾチアゾール系若しくはスルフェンアミド系
の硫黄化合物を必須成分とし、前記（Ｃ）硫黄化合物を
樹脂成分［（Ａ）＋（Ｂ）］100重量部に対して0.1〜10
重量部配合することを特徴とする銅箔用接着剤である。
本発明に用いる（Ａ）ポリビニルアセタール系樹脂とし
ては、ポリビニルアルコールをホルムアルデヒド又はブ
チルアルデヒドでアセタール化したポリビニルホルマー
ル樹脂やポリビニルブチラール樹脂等が挙げられる。こ
の中でも特にポリビニルブチラール樹脂が好ましく用い
られる。[Structure of the Invention] (Means and Actions for Solving Problems) As a result of intensive investigations by the present inventors in order to achieve the above-mentioned object, if a benzothiazole-based or sulfenamide-based sulfur compound is blended, The present invention has been completed by finding that the adhesive strength and the solder heat resistance are improved, the storage stability is good, and it is economical. That is, the present invention uses (A) a polyvinyl acetal resin, (B) a thermosetting resin, and (C) a benzothiazole-based or sulfenamide-based sulfur compound as an essential component, and the (C) sulfur compound as a resin component. [(A) + (B)] 0.1 to 10 per 100 parts by weight
It is an adhesive for copper foil, characterized by being mixed in parts by weight.
Examples of the polyvinyl acetal resin (A) used in the present invention include polyvinyl formal resin and polyvinyl butyral resin obtained by acetalizing polyvinyl alcohol with formaldehyde or butyraldehyde. Among these, polyvinyl butyral resin is particularly preferably used.
ポリビニルブチラール樹脂のブチラール化度、重合度は
特に制限されないが、ブチラール化度60〜65モル％、重
合度1000〜2000のものが最も良好な特性を示す。具体的
な樹脂として、エスレックBX−１（積水化学工業社製、
商品名）、電化ブチラール4000−２（電気化学工業社
製、商品名）ブトバ−Ｂ−72A（シャウイニガン社製、
商品名）等が挙げられる。ポリビニルホルマール樹脂に
ついても同様に市販品が広く用いられ、これらのうちか
ら適宜選択される。これらの樹脂は単独又は２種以上混
合して用いられる。The degree of butyralization and the degree of polymerization of the polyvinyl butyral resin are not particularly limited, but those having a degree of butyralization of 60 to 65 mol% and a degree of polymerization of 1000 to 2000 show the best characteristics. As a specific resin, S-REC BX-1 (manufactured by Sekisui Chemical Co., Ltd.,
Trade name), Denka Butyral 4000-2 (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name) Butova-B-72A (manufactured by Shawinigan Co., Ltd.,
Product name) and the like. Similarly, commercially available polyvinyl formal resin is widely used, and is appropriately selected from these. These resins may be used alone or in combination of two or more.
本発明に用いる（Ｂ）熱硬化性樹脂としては、エポキシ
樹脂、フェノール樹脂、ポリパラビニルフェノール樹
脂、メラミン樹脂、キシレン樹脂、飽和ポリエステル樹
脂、熱硬化型アクリル樹脂等が挙げられ、これらは単独
もしくは２種以上混合して用いる。熱硬化性樹脂は、
（Ａ）のポリビニルアセタール樹脂と合わせて樹脂成分
とするが、本発明の接着力、可とう性、耐熱性を損わな
いように、市販品を適宜選択して配合する。Examples of the (B) thermosetting resin used in the present invention include epoxy resins, phenol resins, polyparavinylphenol resins, melamine resins, xylene resins, saturated polyester resins, thermosetting acrylic resins, etc., which may be used alone or Two or more types are mixed and used. The thermosetting resin is
Although it is used as a resin component together with the polyvinyl acetal resin of (A), a commercially available product is appropriately selected and blended so as not to impair the adhesive strength, flexibility and heat resistance of the present invention.
本発明に用いる（Ｃ）硫黄化合物としては、ベンゾチア
ゾール系若しくはスルフェンアミド系の硫黄化合物が用
いられる。ベンゾチアゾール系化合物としては、ジベン
ゾチアジルジスルフィド、２−メルカプトベンゾチアゾ
ールの亜鉛塩、２−（２′,4′−ジニトロフェニルチ
オ）ベンゾチアゾール、２−メルカプトベンゾチアゾー
ルのシクロヘキシルアミン塩、２−（N,N′−ジエチル
チオカルバモイルチオ）ベンゾチアゾール、２−（４′
−モルホリノジチオ）ベンゾチアゾール等が挙げられ
る。As the (C) sulfur compound used in the present invention, a benzothiazole-based or sulfenamide-based sulfur compound is used. Examples of the benzothiazole compound include dibenzothiazyl disulfide, zinc salt of 2-mercaptobenzothiazole, 2- (2 ', 4'-dinitrophenylthio) benzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- ( N, N'-diethylthiocarbamoylthio) benzothiazole, 2- (4 '
-Morpholinodithio) benzothiazole and the like.
スルフェンアミド系化合物としては、Ｎ−シクロヘキシ
ル−２−ベンゾチアゾリルスルフェンアミド、N,N−ジ
シクロヘキシル−２−ベンゾチアゾリルスルフェンアミ
ド、Ｎ−オキシジエチレン−２−ベンゾチアゾリルスル
フェンアミド等が挙げられる。これらベンゾチアゾール
系若しくはスルフェンアミド系の硫黄化合物は単独もし
くは２種以上混合して用いることができる。硫黄化合物
の配合割合は、ポリビニルアセタール樹脂および熱硬化
性樹脂の合計量である樹脂成分100重量部に対して、0.1
〜10重量部配合することが望ましい。その割合が0.1重
量部未満では銅表面に対する被覆効果が小さく接着強度
が弱く、また10重量部を超えると接着強度がこれ以上向
上せず経済的に不利となり好ましくない。ベンゾチアゾ
ール系およびスルフェンアミド系化合物は、樹脂成分と
容易に均一に溶解することができ、また直接チオール構
造をとらないため、接着剤とした場合でも保存安定性を
有するものである。接着剤中に配合されたこれらの化合
物は、銅箔と基材が積層されるときに加えられる熱によ
って、硫黄原子、硫黄原子間もしは硫黄原子、窒素原子
間でラジカル性の開裂反応もしくはイオン性の開裂反応
を介在して生じた活性種が直接銅箔表面を攻撃して親油
性の被覆層を形成し、接着剤の銅側への接着力が著しく
高まることが接着力向上の機構として考えられる。こう
して銅箔と接着剤の界面に形成された親油性の被覆層
は、水分子の侵入も防止する働きがあるため、この接着
剤を用いることによって接着力、耐熱性、耐湿性が向上
するものである。Examples of the sulfenamide compound include N-cyclohexyl-2-benzothiazolyl sulfenamide, N, N-dicyclohexyl-2-benzothiazolyl sulfenamide, N-oxydiethylene-2-benzothiazolyl sulfenamide and the like. Is mentioned. These benzothiazole-based or sulfenamide-based sulfur compounds may be used alone or in combination of two or more. The mixing ratio of the sulfur compound is 0.1 with respect to 100 parts by weight of the resin component which is the total amount of the polyvinyl acetal resin and the thermosetting resin.
It is desirable to mix it up to 10 parts by weight. If the proportion is less than 0.1 part by weight, the effect of covering the copper surface is small and the adhesive strength is weak, and if it exceeds 10 parts by weight, the adhesive strength is not further improved and it is economically disadvantageous. The benzothiazole-based and sulfenamide-based compounds can be easily and uniformly dissolved with the resin component, and since they do not directly form a thiol structure, they have storage stability even when used as an adhesive. These compounds compounded in the adhesive are formed by radical cleavage reaction or ionic reaction between sulfur atom, sulfur atom or sulfur atom, nitrogen atom by heat applied when the copper foil and the base material are laminated. As a mechanism for improving the adhesive strength, the active species generated through the intermediary cleavage reaction directly attack the copper foil surface to form a lipophilic coating layer, and the adhesive strength of the adhesive to the copper side is significantly increased. Conceivable. The lipophilic coating layer thus formed at the interface between the copper foil and the adhesive also functions to prevent the entry of water molecules, so the adhesive strength, heat resistance, and moisture resistance are improved by using this adhesive. Is.
本発明の銅箔用接着剤は、ポリビニルアセタール樹脂、
熱硬化性樹脂及び硫黄化合物を含むが本発明の効果に悪
影響を及ぼさない限り必要に応じてカオリン、クレー、
タルク、炭酸カルシウム、シリカ、アルミナ、酸化チタ
ン等の充填剤、顔料を添加配合することができる。また
本発明の接着剤には、更にケトン系、エステル系、芳香
族系、アルコール系の溶剤が広く使用され、樹脂成分、
硫黄化合物の溶解性、塗布作業性を考慮して適宜選択さ
れる。The adhesive for copper foil of the present invention is a polyvinyl acetal resin,
Kaolin, clay, if necessary, which contains a thermosetting resin and a sulfur compound but does not adversely affect the effects of the present invention.
Fillers and pigments such as talc, calcium carbonate, silica, alumina and titanium oxide can be added and blended. Further, in the adhesive of the present invention, further, ketone-based, ester-based, aromatic-based, alcohol-based solvents are widely used, resin components,
It is appropriately selected in consideration of the solubility of the sulfur compound and the coating workability.
本発明の接着剤は、上述した各成分を均一に混合して容
易に接着剤とすることができる。The adhesive of the present invention can be easily made into an adhesive by uniformly mixing the above-mentioned components.
（実施例） 次に本発明を実施例によって具体的に説明するが、本発
明はこれらの実施例によって限定されるものではない。
実施例および比較例において「部」とは「重量部」を意
味する。(Examples) Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
In the examples and comparative examples, “part” means “part by weight”.
実施例 １ ポリビニルブチラール樹脂エスレックBX−１（積水化学
工業社製、商品名）63部、ブチル化メラミン樹脂ベッカ
ミンＪ−820−60（大日本インキ化学工業社製、商品
名）９部、エポキシ樹脂エピコート1001（油化シエルエ
ポキシ社製、商品名）11部、フェノール樹脂ペライオー
ヘン5010（日本ライヒホールド社製、商品名）17部をメ
チルエチルケトンおよびエチルアルコールの混合溶剤に
溶解し、更にベンゾチアゾール系の硫黄化合物ジベンゾ
チアジルスルフィド，ノクセラーDM（大内新興化学工業
社製、商品名）を樹脂成分に対して2.0部加えて濃度20
％樹脂溶液を調製し接着剤とした。この接着剤を厚さ30
〜40μｍの電解処理銅箔の処理面に塗布して、風乾後、
120℃で10分間乾燥した。接着剤を片面に塗布した銅箔
と、セルロース紙にフェノール樹脂を含浸してなるプリ
プレグとを重畳して、150℃、130kg/cm21時間の条件で
加熱加圧成形して銅張積層板を製造した。Example 1 Polyvinyl butyral resin S-REC BX-1 (manufactured by Sekisui Chemical Co., Ltd., trade name) 63 parts, butylated melamine resin Beckamine J-820-60 (manufactured by Dainippon Ink and Chemicals Co., trade name) 9 parts, epoxy resin 11 parts of Epikote 1001 (produced by Yuka Shell Epoxy Co., Ltd., trade name) and 17 parts of phenol resin Peraiohen 5010 (produced by Nippon Reichhold Co., Ltd., trade name) are dissolved in a mixed solvent of methyl ethyl ketone and ethyl alcohol, and further benzothiazole-based sulfur Compound dibenzothiazyl sulfide, Nocceller DM (trade name, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) was added to the resin component in an amount of 2.0 parts to give a concentration of 20.
% Resin solution was prepared and used as an adhesive. Thick this adhesive 30
Apply to the treated surface of ~ 40μm electrolytically treated copper foil, air dry,
It was dried at 120 ° C for 10 minutes. Copper foil laminated with copper foil coated with adhesive on one side and prepreg made by impregnating phenolic resin on cellulose paper and heat-pressed under the condition of 150 ° C, 130kg / cm 2 1 hour Was manufactured.
実施例 ２ 実施例１において、ベンゾチアゾール系硫黄化合物ジベ
ンゾチアジルフルフィドノクセラーDMの代わりに、スル
フェンアミドの硫黄化合物Ｎ−シクロヘキシル−２−ベ
ンゾチアゾリルスルフェンアミド，ノクセラーCZ−Ｐ
（大内新興化学工業社製、商品名）を同量の2.0部用い
た以外はすべて実施例１と同一にして接着剤を調製して
銅箔に塗布し、次いで銅張積層板を製造した。Example 2 In Example 1, instead of the benzothiazole-based sulfur compound dibenzothiazylflufidonoxeller DM, the sulfenamide sulfur compound N-cyclohexyl-2-benzothiazolyl sulfenamide, Noxera CZ-P was used.
An adhesive was prepared and applied to a copper foil in the same manner as in Example 1 except that the same amount of 2.0 parts (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) was used, and then a copper clad laminate was manufactured. .
実施例 ３ ポリビニルブチラール樹脂電化ブチラール4000−２（電
気化学工業社製、商品名）36部、ポリビニルホルマール
樹脂ビニレックＥ（チッソ社製、商品名）９部と、ポリ
パラビニルフェノール樹脂マルゼンレジンＭ（丸善石油
社製、商品名）22部、エポキシ樹脂アラルダイトECN−1
280（チバガイギー社製、商品名）22部、キシレン樹脂
ニカノールＨ（三菱ガス化学工業社製、商品名）11部
を、メチルエチルケトン、トルエンおよびイソブタノー
ルの混合溶剤に溶解後、更にスルフェンアミド系化合物
ノクセラーCZ−Ｐ（前出）を樹脂成分に対して2.0部加
えて濃度20％の樹脂溶駅を調製し接着剤とした。この接
着剤を厚さ30〜40μｍの電解処理銅箔の処理面に塗布
し、風乾後120℃で10分間乾燥した。こうして得られた
接着剤を片面に塗布した銅箔と、セルロース紙からなる
紙基材にフェノール樹脂を含浸してなるプリプレグを15
0℃、130kg/cm2、１時間のもとに加熱加圧して銅張積層
板を製造した。Example 3 Polyvinyl butyral resin electrified butyral 4000-2 (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name) 36 parts, polyvinyl formal resin vinylec E (manufactured by Chisso Corp., trade name) 9 parts, and polyparavinylphenol resin marzene resin M ( Maruzen Sekiyu KK, trade name) 22 parts, epoxy resin Araldite ECN-1
280 (Ciba Geigy, trade name) 22 parts, xylene resin Nikanol H (Mitsubishi Gas Chemical Industry Co., trade name) 11 parts were dissolved in a mixed solvent of methyl ethyl ketone, toluene and isobutanol, and then a sulfenamide compound Nox Cellar CZ-P (described above) was added to the resin component in an amount of 2.0 parts to prepare a resin-melting station having a concentration of 20% to prepare an adhesive. This adhesive was applied to the treated surface of an electrolytically treated copper foil having a thickness of 30 to 40 μm, air dried and then dried at 120 ° C. for 10 minutes. A copper foil coated with the adhesive thus obtained on one side and a prepreg obtained by impregnating a phenolic resin on a paper base made of cellulose paper 15
A copper clad laminate was manufactured by heating and pressurizing at 0 ° C., 130 kg / cm 2 for 1 hour.
実施例 ４ 実施例２において、スルフェンアミド系硫黄化合物ノク
セラーCZ−Ｐ（前出）の配合を、0.5部に減少させた以
外すべて実施例２と同一にして接着剤を調製して、銅箔
に塗布し、次いで銅張積層板を製造した。Example 4 An adhesive was prepared in the same manner as in Example 2 except that the content of the sulfenamide-based sulfur compound Nocceller CZ-P (described above) was reduced to 0.5 parts. And then a copper clad laminate was produced.
実施例 ５ 実施例２において、スルフェンアミド系硫黄化合物ノク
セラーCZ−Ｐ（前出）の配合量を5.0部に増した以外は
すべて実施例２と同一にして接着剤を調製して銅箔に塗
布し、次いで銅張積層板を製造した。Example 5 An adhesive was prepared in the same manner as in Example 2 except that the amount of the sulfenamide-based sulfur compound Nocceller CZ-P (described above) was increased to 5.0 parts. It was coated and then a copper clad laminate was manufactured.
実施例 ６ 実施例２において、スルフェンアミド系硫黄化合物ノク
セラーCZ−Ｐ（前出）の配合量を9.0部に増した以外は
すべて実施例２と同一にして接着剤を調製して銅箔に塗
布し、次いで銅張積層板を製造した。Example 6 An adhesive was prepared in the same manner as in Example 2 except that the compounding amount of the sulfenamide-based sulfur compound Nocceller CZ-P (described above) was increased to 9.0 parts. It was coated and then a copper clad laminate was manufactured.
比較例 １ 実施例１において、配合成分のベンゾチアゾール系硫黄
化合物ノクセラーDM（前出）を削除した以外はすべて実
施例１と同一にして接着剤を調製して銅箔に塗布し、次
いで銅張積層板を製造した。Comparative Example 1 An adhesive was prepared in the same manner as in Example 1 except that the compound benzothiazole-based sulfur compound Noxcellar DM (described above) was omitted from Example 1, and the adhesive was applied to a copper foil and then copper-clad. Laminates were manufactured.
比較例 ２ 実施例３において、配合成分のスルフェンアミド系硫黄
化合物ノクセラーCZ−Ｐ（前出）を削除した以外はすべ
て実施例３と同一にして接着剤を調製して銅箔に塗布
し、次いで銅張積層板を製造した。Comparative Example 2 An adhesive was prepared and applied to a copper foil in the same manner as in Example 3, except that the sulfenamide-based sulfur compound Noxceller CZ-P (described above) as a compounding component was omitted in Example 3. Then, a copper clad laminate was manufactured.
実施例１〜６および比較例１〜２で製造された銅張積層
板について、引き剥がし強さ、半田耐熱性、電気特性を
JIS−Ｃ−6481によって試験を行った。With respect to the copper clad laminates manufactured in Examples 1 to 6 and Comparative Examples 1 to 2, the peel strength, the solder heat resistance, and the electrical characteristics were measured.
The test was conducted according to JIS-C-6486.
その結果を第１表に示した。The results are shown in Table 1.
第１表から明らかなように本発明の接着剤は接着性、半
田耐熱性、保存安定性に優れており、本発明の効果が確
認された。 As is clear from Table 1, the adhesive of the present invention was excellent in adhesiveness, solder heat resistance and storage stability, and the effects of the present invention were confirmed.
［発明の効果］ 以上説明したように本発明の銅箔用接着剤は、ベンゾチ
アゾール系若しくはスルフェンアミド系の硫黄化合物を
配合したことによって、接着性、半田耐熱性および保存
安定性に優れたもので、これを使用した銅張積層板はメ
ッキ浴や半田浴に浸漬しても、侵されたり、ふくれが生
じることがなく信頼性の高い電子機器を得ることができ
る。[Advantages of the Invention] As described above, the copper foil adhesive of the present invention is excellent in adhesiveness, solder heat resistance, and storage stability because it contains a benzothiazole-based or sulfenamide-based sulfur compound. The copper-clad laminate using the copper-clad laminate does not get corroded or swells even when immersed in a plating bath or a solder bath, so that a highly reliable electronic device can be obtained.
Claims (3)
の硫黄化合物を必須成分とし、前記（Ｃ）硫黄化合物を
樹脂成分［（Ａ）＋（Ｂ）］100重量部に対して0.1〜10
重量部配合することを特徴とする銅箔用接着剤。1. A polyvinyl acetal resin (A), a thermosetting resin (B), and a benzothiazole or sulfenamide sulfur compound (C) as essential components, and the sulfur compound (C) as a resin component [C]. (A) + (B)] 0.1 to 10 per 100 parts by weight
An adhesive for copper foil, characterized by being mixed in parts by weight.
ルホルマール樹脂又はポリビニルブチラール樹脂である
特許請求の範囲第１項記載の銅箔用接着剤。2. The adhesive for copper foil according to claim 1, wherein the polyvinyl acetal resin is a polyvinyl formal resin or a polyvinyl butyral resin.
ル樹脂、ポリパラビニルフェノール樹脂、メラミン樹
脂、キシレン樹脂、飽和ポリエステル樹脂又は熱硬化型
アクリル樹脂である特許請求の範囲第１項又は第２項記
載の銅箔用接着剤。3. The thermosetting resin is an epoxy resin, a phenol resin, a polyparavinylphenol resin, a melamine resin, a xylene resin, a saturated polyester resin, or a thermosetting acrylic resin. The adhesive for copper foil according to the item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61084356A JPH0699673B2 (en) | 1986-04-14 | 1986-04-14 | Adhesive for copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61084356A JPH0699673B2 (en) | 1986-04-14 | 1986-04-14 | Adhesive for copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62241983A JPS62241983A (en) | 1987-10-22 |
| JPH0699673B2 true JPH0699673B2 (en) | 1994-12-07 |
Family
ID=13828237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61084356A Expired - Lifetime JPH0699673B2 (en) | 1986-04-14 | 1986-04-14 | Adhesive for copper foil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699673B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0691315B2 (en) * | 1988-08-26 | 1994-11-14 | 信越化学工業株式会社 | Bonding sheet |
| JP2650168B2 (en) * | 1991-08-09 | 1997-09-03 | 日立化成工業株式会社 | Adhesive for copper clad laminate |
| JPH0565466A (en) * | 1991-09-05 | 1993-03-19 | Hitachi Chem Co Ltd | Adhesive for copper-clad laminate board |
| JP5866209B2 (en) * | 2011-01-19 | 2016-02-17 | 積水化学工業株式会社 | Adhesive for semiconductor |
| CN102153970A (en) * | 2011-03-18 | 2011-08-17 | 江阴市明康绝缘玻纤有限公司 | Adhesive applied to preparing copper clad laminate copper foils and substrates |
| AU2022202974A1 (en) * | 2022-05-03 | 2023-11-23 | Leader Shining Material Co., Ltd. | Modified polyvinyl butyral material, and preparation and applications thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5135417B2 (en) * | 1973-03-20 | 1976-10-02 | ||
| JPS5496541A (en) * | 1978-01-18 | 1979-07-31 | Teijin Ltd | Photosensitive resin composition |
| JPS5741951A (en) * | 1980-08-26 | 1982-03-09 | Toshiba Chem Prod | Manufacture of copper lined laminated plate |
| NZ201589A (en) * | 1981-11-02 | 1985-08-16 | Grace W R & Co | Heat activatable adhesive or sealant compositions |
| US4463128A (en) * | 1983-05-09 | 1984-07-31 | W. R. Grace & Co. | Reactive plastisol dispersion |
| CA1260647A (en) * | 1983-05-09 | 1989-09-26 | Shiow C. Lin | Reactive plastisol dispersion |
-
1986
- 1986-04-14 JP JP61084356A patent/JPH0699673B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62241983A (en) | 1987-10-22 |
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