JPH0457879A - Adhesive for copper-clad laminate - Google Patents
Adhesive for copper-clad laminateInfo
- Publication number
- JPH0457879A JPH0457879A JP17122890A JP17122890A JPH0457879A JP H0457879 A JPH0457879 A JP H0457879A JP 17122890 A JP17122890 A JP 17122890A JP 17122890 A JP17122890 A JP 17122890A JP H0457879 A JPH0457879 A JP H0457879A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- adhesive
- epoxy
- copper
- molecule
- 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 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000005060 rubber Substances 0.000 claims abstract description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 239000013034 phenoxy resin Substances 0.000 claims description 4
- 229920006287 phenoxy resin Polymers 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract 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 10
- 239000000463 material Substances 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229930182556 Polyacetal Natural products 0.000 description 3
- -1 glycidyl ester Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は銅張積層板用接着剤に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to an adhesive for copper-clad laminates.
従来、基材に熱硬化性樹脂を含浸させたプリプレグと接
着剤を塗布した銅箔を重ね合わせ、これを加熱、必要な
らば加圧する銅張積層板の製造方法において、接着剤と
して、ポリビニルブチラールのようなポリアセタール樹
脂やニトリルゴムのようなゴムにエポキシ樹脂、フェノ
ール樹脂やメラミン樹脂の単独又は混合物を混合したも
のが使用されている。Conventionally, in the manufacturing method of copper-clad laminates, the base material is a prepreg impregnated with a thermosetting resin and a copper foil coated with an adhesive, which are then heated and, if necessary, pressed. Polyacetal resins such as polyacetal resins and rubbers such as nitrile rubber are used, together with epoxy resins, phenol resins, and melamine resins, either singly or in combination.
〔発明が解決しようとする課８］
ポリアセタール樹脂又はゴムにエポキシ樹脂、フェノー
ル樹脂やメラミン樹脂の単独又は混合物を混合したもの
を銅張積層板用の接着剤として用いた場合、接着強度は
良好なものの、エポキシ樹脂、フェノール樹脂、メラミ
ン樹脂が熱硬化性樹脂のため、室温でも反応が進み、保
存安定性が不十分という問題点があった０本発明は接着
強度の低下をきたすことなく、保存安定性の良好な銅張
積層板用の接着剤を提供することを目的とするものであ
る。[Question 8 to be solved by the invention] When polyacetal resin or rubber is used alone or as a mixture of epoxy resin, phenol resin, or melamine resin as an adhesive for copper-clad laminates, the adhesive strength is good. However, since epoxy resin, phenol resin, and melamine resin are thermosetting resins, the reaction proceeds even at room temperature, resulting in insufficient storage stability. The object of the present invention is to provide an adhesive for copper-clad laminates with good stability.
本発明者らは上記問題点を解決するために鋭意研究を行
った結果、接着剤成分として、分子内に２個以上のα、
β−不飽和二重結合を含有する化合竜及び分子内にエポ
キシ基とα、β−不飽和二重結合を含有する化合物を配
合した接着剤により、上記目的が達成されることを見出
し、この知見に基づいて本発明を完成するに至った。The present inventors conducted intensive research to solve the above problems, and found that the adhesive component contains two or more α,
It has been discovered that the above object can be achieved by a compound containing a β-unsaturated double bond and an adhesive containing an epoxy group and a compound containing an α,β-unsaturated double bond in the molecule. The present invention was completed based on the findings.
すなわち、本発明は（ａ）熱可塑性樹脂、ゴム又はこれ
らの混合物、Φ）分子内に２個以上のエポキシ基を含有
するエポキシ樹脂、（ｃ）分子内に２個以上のα、β−
不飽和二重結合を含有する化合物並びに（ロ）分子内に
エポキシ基及びα、β−不飽和二重結合を含有する化合
物からなることを特徴とする銅張積層板用接着剤を提供
するものである。That is, the present invention relates to (a) a thermoplastic resin, a rubber, or a mixture thereof; Φ) an epoxy resin containing two or more epoxy groups in the molecule; (c) an epoxy resin containing two or more α, β-
An adhesive for copper-clad laminates characterized by comprising a compound containing an unsaturated double bond and (b) a compound containing an epoxy group and an α,β-unsaturated double bond in the molecule. It is.
本発明において用いられる（ａ）成分の熱可塑性樹脂と
してはポリビニルブチラール樹脂、フェノキシ樹脂、ポ
リエステル樹脂、スチレンブタジェン樹脂などがある。Thermoplastic resins as component (a) used in the present invention include polyvinyl butyral resins, phenoxy resins, polyester resins, and styrene-butadiene resins.
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６０〜７０モル％
、重合度１，５００〜２，０００のものが好ましい。具
体的にはエスレックＢＸ−１、ＢＸ−２、ＢＸ−５５（
種水化学工業社製、商品名）、電化ブチラール４０００
−２．５０００−Ａ、６０００−Ｃ（電気化学工業社製
、商品名）などが挙げられる。フェノキシ樹脂の分子量
は制限されないが分子量が約７，０００〜２００゜００
０のものが好ましい、具体的にはＹＰ−５０（東部化成
社製、商品名）が挙げられる。ポリエステル樹脂も特に
１ＩＩｌｌＩ！するものではない、具体的にはＰ−３０
Ｂ、Ｐ−４０Ｂ、Ｐ−４０Ｈ（東洋紡社製、商品名）が
挙げられる。スチレンブタジェン樹脂も制限するもので
はなく、具体的にはＭ１９１１、Ｍ１９１３（旭化成工
業社製、商品名）が挙げられる。これらの熱可塑性樹脂
は単独でも２種以上の組み合わせでも使用可能である。The degree of butyralization and degree of polymerization of polyvinyl butyral resin are not particularly limited, but the degree of butyralization is 60 to 70 mol%.
, those having a degree of polymerization of 1,500 to 2,000 are preferred. Specifically, S-LEC BX-1, BX-2, BX-55 (
Manufactured by Tanemizu Kagaku Kogyo Co., Ltd. (trade name), Denka Butyral 4000
-2.5000-A, 6000-C (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name), and the like. The molecular weight of the phenoxy resin is not limited, but the molecular weight is approximately 7,000 to 200°00.
0 is preferable, and a specific example is YP-50 (manufactured by Tobu Kasei Co., Ltd., trade name). Polyester resin is also especially 1IIIllI! Not something to do, specifically P-30
B, P-40B, and P-40H (manufactured by Toyobo Co., Ltd., trade name). The styrene-butadiene resin is not limited either, and specific examples thereof include M1911 and M1913 (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name). These thermoplastic resins can be used alone or in combination of two or more.
接着強度からポリビニルブチラール樹脂、フェノキシ樹
脂が好ましい。更に好ましくはポリビニルブチラール樹
脂である。Polyvinyl butyral resin and phenoxy resin are preferred from the viewpoint of adhesive strength. More preferred is polyvinyl butyral resin.
ゴムとしては、ニトリルゴム、ブタジェンゴム、アクリ
ルゴムなどがある。接着強度からニトリルゴムが好まし
い。Examples of rubber include nitrile rubber, butadiene rubber, and acrylic rubber. Nitrile rubber is preferred from the viewpoint of adhesive strength.
（ｂ）成分の分子内に２個以上のエポキシ基を含有する
エポキシ樹脂としてはフェノールノボラック型エポキシ
樹脂、タレゾールノボラック型エポキシ樹脂、レゾール
型エポキシ樹脂、ビスフェノール型エポキシ樹脂などの
フェノール類のグリシジルエーテルであるエポキシ樹脂
（フェノール型エポキシ樹脂）やグリシジルエステル型
エポキシ樹脂、ハロゲン化エポキシ樹脂、可撓性エポキ
シ樹脂などで分子内に２個以上のエポキシ基を含有して
いればいずれのエポキシ樹脂であっても又はそれらの混
合物であっても使用可能である。ただし、α、β−不飽
和二重結合を含有するものは（ｄ）成分となる。(b) Epoxy resins containing two or more epoxy groups in the molecule of the component include glycidyl ethers of phenols such as phenol novolak epoxy resins, talesol novolac epoxy resins, resol epoxy resins, and bisphenol epoxy resins. Epoxy resins (phenol type epoxy resins), glycidyl ester type epoxy resins, halogenated epoxy resins, flexible epoxy resins, etc. can be used as long as they contain two or more epoxy groups in the molecule. Either or a mixture thereof can be used. However, those containing α,β-unsaturated double bonds are component (d).
（ｃ）成分の分子内に２個以上のα、β−不飽和二重結
合を含有する化合物としては、エポキシアクリレート樹
脂、ウレタンアクリレート樹脂、ポリエステルアクリレ
ート樹脂、ポリエーテルアクリレート樹脂、メラミンア
クリレート樹脂などで分子内に２個以上のα、β型不飽
和二重結合を含有する樹脂がある。ただし、エポキシ基
を含有するものは（ロ）成分となる。Examples of compounds containing two or more α, β-unsaturated double bonds in the molecule of component (c) include epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin, polyether acrylate resin, and melamine acrylate resin. There are resins that contain two or more α,β type unsaturated double bonds in the molecule. However, those containing epoxy groups are component (b).
（イ）成分の分子内にエポキシ基とα、β−不飽和二重
結合を含有する化合物としては、フェノール樹脂をアク
リルエステル化した後、アクリル基の二重結合の一部を
過酢酸でエポキシ化したもの、エポキシ樹脂をアクリル
酸又はメタクリル酸誘導体でエステル化したものなどが
あり、原料樹脂、エポキシ基導入法、α、β−不飽和二
重結合導入法等について特に制限するものではない。(b) For compounds containing an epoxy group and α,β-unsaturated double bonds in the component molecule, after converting the phenol resin into an acrylic ester, some of the double bonds of the acrylic group are epoxied with peracetic acid. There are no particular restrictions on the raw material resin, the method for introducing an epoxy group, the method for introducing an α,β-unsaturated double bond, etc.
（ａ）成分の熱可塑性樹脂、ゴム又はこれらの混合物の
部数（Ａ）〔重量部、以下同じ〕と働）成分の分子内に
２個以上のエポキシ基を含有するエポキシ樹脂の部数（
Ｂ）と（ｃ）成分の分子内に２個以上のα、β−不飽和
二重結合を含有する化合物の部数（ｃ）と（ｄ）成分の
分子内にエポキシ基とα、β−不飽和二重結合を含有す
る化合物の部数（Ｄ）の割合は、次式に示されるような
割合とすることが好ましい。(a) Number of parts of the thermoplastic resin, rubber or mixture thereof (A) [parts by weight, same hereinafter] and parts of the epoxy resin containing two or more epoxy groups in the molecule of the component (A) [parts by weight, same hereinafter]
Number of parts of compounds containing two or more α,β-unsaturated double bonds in the molecule of components B) and (c).Epoxy groups and α,β-unsaturated double bonds in the molecule of components (c) and (d). The ratio of the number (D) of the compound containing a saturated double bond is preferably as shown in the following formula.
また、エポキシ基のモル数（Ｘ）とα、β−不飽和二重
結合のモル数（Ｙ）の割合は、次式に示されるような割
合とすることが好ましい。Further, it is preferable that the ratio between the number of moles of epoxy group (X) and the number of moles of α,β-unsaturated double bond (Y) is as shown in the following formula.
０、１ ＜ ＜ ０．９Ｘ＋Ｙ
更に好ましくは
Ａ／Ａ＋ＢｆＣ十りが０．０５以下であると接着剤の柔
軟性が十分でなく接着強度がでない。一方０゜７以上で
あると柔らかくなりすぎ、これまた接着強度がでない。0, 1 << 0.9 On the other hand, if it is 0°7 or more, it will become too soft and the adhesive strength will also be poor.
Ｘ／Ｘ＋Ｙが０．１以下であると接着強度がでない、０
．９以上であると保存安定性が不十分である。エポキシ
樹脂には必要に応じ、硬化剤、硬化促進剤を配合したも
のを用いる。硬化剤としてアミン系硬化剤、酸無水物系
硬化剤、フェノール樹脂などがあり、特に制限するもの
ではない。また、エポキシ樹脂の硬化促進剤としては、
イミダゾール系促進剤、アミン系促進剤があり、特に制
限するものではない。α、β−不飽和二重結合を含有す
る化合物には必要に応じ、重合開始剤を配合したものを
用いる。重合開始剤としてはアゾ系開始剤、過酸化物系
開始剤があり、特に制限するものではない。If X/X+Y is less than 0.1, the adhesive strength will be poor, 0
．． If it is 9 or more, storage stability is insufficient. The epoxy resin used may contain a curing agent and a curing accelerator, if necessary. Examples of the curing agent include amine curing agents, acid anhydride curing agents, and phenol resins, and are not particularly limited. In addition, as a curing accelerator for epoxy resin,
Examples include imidazole-based accelerators and amine-based accelerators, and are not particularly limited. The compound containing an α,β-unsaturated double bond may be blended with a polymerization initiator, if necessary. Polymerization initiators include azo initiators and peroxide initiators, and are not particularly limited.
本発明の接着剤を使用する銅張積層板は基材として紙基
材、ガラス基材などを用いたものが用いられるが、銅張
積層板に用いられる基材であれば特に制限はない。The copper-clad laminate using the adhesive of the present invention may use a paper base material, a glass base material, or the like as a base material, but there are no particular limitations as long as the base material is used for copper-clad laminates.
また、上記基材に含浸させる熱硬化性樹脂としてはエポ
キシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、
アクリルエステル樹脂など用いられる。また、上記熱硬
化性樹脂の混合物も使用される。さらにこれらに重合可
能なα、β−不飽和二重結合をもつモノマーを配合した
ものであってもよい、熱硬化性樹脂が系中に重合可能な
α、β−不飽和二重結合を含む場合、接着強度が向上し
好ましい。In addition, examples of the thermosetting resin to be impregnated into the base material include epoxy resin, phenol resin, unsaturated polyester resin,
Acrylic ester resin etc. are used. Mixtures of the above thermosetting resins may also be used. Furthermore, a monomer having polymerizable α, β-unsaturated double bonds may be blended with these, such that the thermosetting resin contains polymerizable α, β-unsaturated double bonds in the system. In this case, the adhesive strength is improved, which is preferable.
本発明の接着剤には、水酸化アルミニウム、炭酸カルシ
ウム、シリカなどの充填剤、またシランカップリング剤
、チタンカップリング剤などの処理剤を添加することも
可能である。It is also possible to add fillers such as aluminum hydroxide, calcium carbonate, and silica, and processing agents such as silane coupling agents and titanium coupling agents to the adhesive of the present invention.
本発明の銅張積層板用接着剤は、銅張積層板の連続製造
方式又はバッチ製造方式、いずれの方式への適用も可能
である。The adhesive for copper-clad laminates of the present invention can be applied to either a continuous manufacturing method or a batch manufacturing method of copper-clad laminates.
接着剤の溶剤としてアルコール、ケトン、芳香族、脂肪
族、その他極性のプロチック、アプロチックな溶剤を使
用することができる。また、フェニルグリシジルエテー
ルなどの一官能エボキシ化合物、スチレンやアクリル酸
、メタクリル酸及びそれらの誘導体のエステル化物など
のα、β−不飽和二重結合を分子中に１個含有する、い
わゆる反応性の希釈剤の使用も可能である。As the solvent for the adhesive, alcohol, ketone, aromatic, aliphatic, and other polar protic or aprotic solvents can be used. In addition, monofunctional epoxy compounds such as phenylglycidyl ether, esters of styrene, acrylic acid, methacrylic acid, and their derivatives, which contain one α, β-unsaturated double bond in the molecule, are so-called reactive. The use of diluents is also possible.
以下、本発明を実施例に基づいて詳細に説明するが、本
発明はこれに限定されるものではない。Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.
実施例１〜３、比較例１〜３
第１表に示す接着剤配合で溶剤に均一に溶解させて銅張
積層板用接着剤を得た。この接着剤をロールコータで厚
さ３５μｍの銅箔に塗布し乾燥させて接着剤厚み４０μ
ｍの接着剤付銅箔を得た。Examples 1 to 3, Comparative Examples 1 to 3 Adhesives for copper-clad laminates were obtained by uniformly dissolving them in a solvent using the adhesive formulations shown in Table 1. Apply this adhesive to a 35μm thick copper foil using a roll coater and dry it to make the adhesive 40μm thick.
A copper foil with an adhesive of m was obtained.
水溶性フェノール樹脂で下処理した紙基材に熱硬化性樹
脂を含浸、乾燥してプリプレグを得た。下処理樹脂付着
分１５重量％、全樹脂付着量５０重量％であった。A paper base material pretreated with a water-soluble phenolic resin was impregnated with a thermosetting resin and dried to obtain a prepreg. The pretreatment resin adhesion was 15% by weight, and the total resin adhesion was 50% by weight.
銅箔の接着剤側にプリプレグ８枚を重ねて積層体としス
テンレス鏡板に挟んで１６０℃、１００ｋｇ／ｄで６０
分間加熱加圧成形して銅張積層板を得た。この銅張積層
板の接着強度を第１表に示す。8 sheets of prepreg were stacked on the adhesive side of the copper foil to form a laminate, sandwiched between stainless steel mirror plates, and heated at 160℃ and 100kg/d for 60 minutes.
A copper-clad laminate was obtained by heat-pressing molding for a minute. Table 1 shows the adhesive strength of this copper-clad laminate.
また、接着剤の保存安定性を調べる目的で接着剤を２５
°Ｃで保存したときの結果も第１表に示す。In addition, for the purpose of examining the storage stability of adhesives, 25%
The results when stored at °C are also shown in Table 1.
実施例と比較例の接着強さ、保存安定性を示した第１表
より本発明のものは接着強さの低下をきたすことなく、
保存安定性が良好となっており、本発明の優れているこ
とを確認した。From Table 1 showing the adhesive strength and storage stability of Examples and Comparative Examples, the products of the present invention did not cause a decrease in adhesive strength.
The storage stability was good, confirming the superiority of the present invention.
゛覇９号引σ自工ｋ
〔発明の効果］
本発明により銅箔と基板の接着強度の低下をきたすこと
なく、保存安定性に優れている銅張積層板が得られ、そ
の工業的価値は極めて大である。[Effect of the invention] The present invention makes it possible to obtain a copper-clad laminate with excellent storage stability without reducing the adhesive strength between the copper foil and the substrate, and to increase its industrial value. is extremely large.
Claims (4)
ｂ）分子内に２個以上のエポキシ基を含有するエポキシ
樹脂、（ｃ）分子内に２個以上のα，β−不飽和二重結
合を含有する化合物並びに（ｄ）分子内にエポキシ基及
びα，β−不飽和二重結合を含有する化合物からなるこ
とを特徴とする銅張積層板用接着剤。1. (a) Thermoplastic resin, rubber or mixture thereof, (
b) an epoxy resin containing two or more epoxy groups in the molecule; (c) a compound containing two or more α,β-unsaturated double bonds in the molecule; and (d) an epoxy resin containing two or more epoxy groups in the molecule. An adhesive for copper-clad laminates comprising a compound containing an α,β-unsaturated double bond.
キシ樹脂から選ばれた少なくとも１種の樹脂である請求
項１記載の銅張積層板用接着剤。2. The adhesive for copper-clad laminates according to claim 1, wherein the thermoplastic resin is at least one resin selected from polyvinyl butyral resin and phenoxy resin.
板用接着剤。3. The adhesive for copper-clad laminates according to claim 1, wherein the rubber is nitrile rubber.
性樹脂を基材に含浸硬化させた基板からなる銅張積層板
用の請求項１、２又は３記載の銅張積層板用接着剤。4. The adhesive for copper-clad laminates according to claim 1, 2 or 3, which is used for copper-clad laminates comprising a substrate obtained by impregnating and curing a thermosetting resin containing a compound containing a polymerizable double bond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17122890A JPH0457879A (en) | 1990-06-28 | 1990-06-28 | Adhesive for copper-clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17122890A JPH0457879A (en) | 1990-06-28 | 1990-06-28 | Adhesive for copper-clad laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0457879A true JPH0457879A (en) | 1992-02-25 |
Family
ID=15919422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17122890A Pending JPH0457879A (en) | 1990-06-28 | 1990-06-28 | Adhesive for copper-clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0457879A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5451616A (en) * | 1991-06-29 | 1995-09-19 | Ciba-Geigy Corporation | Photopolymerisable liquid compositions for forming heat curable solid film adhesives |
| DE102004057651A1 (en) * | 2004-11-29 | 2006-06-01 | Tesa Ag | Heat-activable adhesive tape for producing and reprocessing flexible printed circuit board and bonding to polyimide, is based on composition containing acrylonitrile-butadiene copolymer, polyvinyl acetal, epoxide resin and hardener |
| DE102008007749A1 (en) | 2008-02-05 | 2009-08-06 | Tesa Se | Thermally activatable and curable adhesive film, in particular for the bonding of electronic components and flexible printed conductors |
-
1990
- 1990-06-28 JP JP17122890A patent/JPH0457879A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5451616A (en) * | 1991-06-29 | 1995-09-19 | Ciba-Geigy Corporation | Photopolymerisable liquid compositions for forming heat curable solid film adhesives |
| DE102004057651A1 (en) * | 2004-11-29 | 2006-06-01 | Tesa Ag | Heat-activable adhesive tape for producing and reprocessing flexible printed circuit board and bonding to polyimide, is based on composition containing acrylonitrile-butadiene copolymer, polyvinyl acetal, epoxide resin and hardener |
| DE102008007749A1 (en) | 2008-02-05 | 2009-08-06 | Tesa Se | Thermally activatable and curable adhesive film, in particular for the bonding of electronic components and flexible printed conductors |
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