JPH0434938B2 - - Google Patents
Info
- Publication number
- JPH0434938B2 JPH0434938B2 JP61159675A JP15967586A JPH0434938B2 JP H0434938 B2 JPH0434938 B2 JP H0434938B2 JP 61159675 A JP61159675 A JP 61159675A JP 15967586 A JP15967586 A JP 15967586A JP H0434938 B2 JPH0434938 B2 JP H0434938B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- adhesive layer
- acrylate
- meth
- resin
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 239000012790 adhesive layer Substances 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 29
- 238000005507 spraying Methods 0.000 claims description 24
- 239000000805 composite resin Substances 0.000 claims description 15
- 239000004925 Acrylic resin Substances 0.000 claims description 14
- 229920000178 Acrylic resin Polymers 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000007751 thermal spraying Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- -1 2-ethylhexyl Chemical group 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 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
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical class CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Coating By Spraying Or Casting (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は金属−樹脂複合体に関するものであ
る。更に詳しくは、樹脂成形品表面に溶射により
形成された金属皮膜を強固に密着させた金属−樹
脂複合体に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a metal-resin composite. More specifically, the present invention relates to a metal-resin composite in which a metal film formed by thermal spraying is tightly adhered to the surface of a resin molded product.
（従来の技術）
樹脂成形品は種々の分野で大量に使用されてい
るが、導電性の要求される電磁シードル用の筐体
あるいは高度な耐摩耗性や金属様の外観を要求さ
れるような用途には十分にその要求を満足するも
のではなく、このような目的に適合させるため、
従来より樹脂成形品に金属溶射法を用いて金属層
を付加せしめることが試みられている。(Prior art) Resin molded products are used in large quantities in various fields, but they are used in cases such as electromagnetic seed casings that require electrical conductivity, and those that require high wear resistance and metal-like appearance. It does not fully satisfy the requirements of the intended use, but in order to adapt it to such a purpose,
Conventionally, attempts have been made to add a metal layer to a resin molded product using a metal spraying method.
最も一般な方法は樹脂成形品の表面をブラスト
処理して疎面化し、その後金属溶射を施して金属
−樹脂複合体を得る方法である。また、特公昭51
−47143号に示されるように、樹脂成形品表面に
半硬化の接着剤層を形成をせしめて後金属溶射を
行い、しかる後に接着剤層を硬化せしめる方法
や、あるいは特開昭57−91261号に示されるよう
に、樹脂成形品表面にゴム弾性を有する被膜を形
成し、しかる後に金属溶射を行つて金属−樹脂複
合体を得ることが提案されている。 The most common method is to roughen the surface of a resin molded article by blasting, and then perform metal spraying to obtain a metal-resin composite. In addition, special public service in Showa 51
As shown in No. 47143, a semi-hardened adhesive layer is formed on the surface of a resin molded product, followed by metal spraying, and then the adhesive layer is hardened, or JP-A No. 57-91261. As shown in , it has been proposed to form a coating having rubber elasticity on the surface of a resin molded product and then perform metal spraying to obtain a metal-resin composite.
さらに、特開昭55−21580号においては、樹脂
成形品表面に接着性塗膜を形成し該塗膜が粘性を
保つ間に薄く金属溶射を行い、その後塗膜を硬化
せしめさらに金属溶射を行う方法や、あるいは該
塗膜が粘性を保つ間に樹枝状金属粒子を散布し、
その後塗膜を硬化せしめさらに金属溶射を行う方
法等が提案されている。 Furthermore, in JP-A No. 55-21580, an adhesive coating film is formed on the surface of a resin molded product, a thin metal spraying is performed while the coating film maintains its viscosity, and then the coating film is cured and further metal spraying is applied. method, or spraying dendritic metal particles while the coating remains viscous,
A method has been proposed in which the coating film is then cured and then metal spraying is performed.
（発明が解決しようとする問題点）
しかしながら、従来一般に行われているよう
な、溶射を施すべく面を予めブラスト処理して疎
面化しておく方法を用いた場合は、樹脂成形品と
溶射により形成された金属層との密着性が悪く、
使用時に金属層が剥離するようなトラブルが発生
しがちであつた。(Problem to be solved by the invention) However, when using the conventional method of blasting the surface in advance to make it rough for thermal spraying, it is difficult to combine the resin molded product and thermal spraying. Poor adhesion with the formed metal layer,
Problems such as peeling of the metal layer tended to occur during use.
また、樹脂成形品表面に形成された半硬化の接
着剤層に金属溶射を行う方法は、溶射した金属の
付着性が悪いため溶射金属の歩留まりが悪く、ま
た接着剤層を適度な半硬化状態に長時間保つこと
が難かしいため作業性が悪く、しかも半硬化の接
着剤層の接着力が不足するために溶射作業を行つ
ている途中に溶射皮膜に蓄積された内部ひずみに
よつて溶射皮膜が剥離してくるようなトラブルが
発生しがちであつた。 In addition, the method of spraying metal onto a semi-cured adhesive layer formed on the surface of a resin molded product has a low yield rate due to poor adhesion of the sprayed metal, and also requires the adhesive layer to be in a moderate semi-cured state. It is difficult to maintain the thermal spray coating for a long time, resulting in poor workability.Moreover, due to the insufficient adhesive strength of the semi-cured adhesive layer, the thermal spray coating may deteriorate due to internal strain accumulated in the spray coating during the spraying process. Problems such as peeling tended to occur.
このような内部ひずみによるトラブルを防ぐた
め前記特開昭55−21580号に示されるように、接
着性塗膜に薄く金属溶射を行つた後に接着性塗膜
を硬化せしめその後必要な厚さに金属溶射するよ
うにすれば、薄い金属溶射層は内部ひずみが小さ
いために溶射時に皮膜が剥離するようなトラブル
を防止することができる。しかしながら、このよ
うな二段階の溶射を行うことは作業性が悪く、ま
た溶射時の金属の付着性が悪いために歩留まりが
悪い点及び接着剤層を適度な半硬化状態に長時間
保つことが難かしいため作業性が悪いという点に
関しては改善されない。また、樹脂成形品表面に
形成された接着性塗膜が粘性を保つ間に樹枝状金
属粒子を散布して後塗膜を硬化せしめさらに金属
溶射を行う方法は、作業性が悪く、また樹枝状金
属粒子と溶射皮膜の密着力が不足して使用時に剥
離するようなトラブルが発生しがちであつた。 In order to prevent such troubles due to internal distortion, as shown in the above-mentioned Japanese Patent Application Laid-Open No. 55-21580, a thin layer of metal is sprayed onto the adhesive coating, the adhesive coating is cured, and then the metal is coated to the required thickness. If thermal spraying is used, problems such as peeling of the coating during thermal spraying can be prevented since the thin metal sprayed layer has small internal strain. However, performing such two-step thermal spraying has poor workability, poor yield due to poor adhesion of metal during thermal spraying, and difficulty in maintaining the adhesive layer in an appropriately semi-cured state for a long period of time. Since it is difficult, the problem of poor workability cannot be improved. In addition, the method of spraying dendritic metal particles while the adhesive coating film formed on the surface of the resin molded product maintains its viscosity to cure the coating film and then performing metal spraying has poor workability and Problems such as peeling during use tended to occur due to insufficient adhesion between the metal particles and the sprayed coating.
一方、樹脂成形品表面にゴム弾性を有する被膜
を形成し、しかる後に金属溶射を行う方法は、作
業性は良いものの、塗布されたゴム弾性を有する
被膜が薄い場合に樹脂成形品と溶射皮膜の接着力
が不足しがちであり、逆にゴム弾性を有する被膜
が厚い場合には、均一な厚さの被膜を形成させる
ことが難しく、シワや段差等の外観不良を生じ易
い。また、ゴム性を有する被膜を形成するために
用いられるクロロプレン系あるいはニトリルゴム
系の接着剤は一般に耐熱性、耐水性、耐候性に劣
るため、得られる成形品を比較的高い温度で使用
したり結露雰囲気あるいは屋外等で使用されるよ
うな場合には、金属皮膜の剥離等の欠陥が発生す
る心配がある。 On the other hand, the method of forming a rubber-elastic coating on the surface of a resin molded product and then applying metal thermal spraying has good workability, but if the applied rubber-elastic coating is thin, there may be problems between the resin molding and the thermal spray coating. Adhesive strength tends to be insufficient, and on the other hand, if the coating having rubber elasticity is thick, it is difficult to form a coating of uniform thickness, and appearance defects such as wrinkles and steps are likely to occur. In addition, chloroprene-based or nitrile rubber-based adhesives used to form rubbery coatings generally have poor heat resistance, water resistance, and weather resistance, so the resulting molded products may not be used at relatively high temperatures. When used in a dew-condensing atmosphere or outdoors, there is a risk that defects such as peeling of the metal film may occur.
（問題点を解決するための手段および作用）
本発明者等はかかる現状に鑑み鋭意研究した結
果、本発明を完成するに至つた。即ち、本発明は
樹脂形成品と、該樹脂形成品表面に密着した、ア
ルミ箔に対する180度剥離強度が500ｇ／25mm以上
で触手可能な粘着剤層と、該粘着剤層上に金属溶
射を施して形成された金属皮膜と、必要に応じて
金属皮膜に塗布された塗装皮膜とより成る金属−
樹脂複合体であつて、該粘着剤層がアルキル基の
炭素数４〜12のアルキル（メタ）アクリレートを
全単量体中60重量％以上含有する重合性単量体か
ら導かれたアクリル系樹脂を主成分としてなる金
属−樹脂複合体を提供するものである。(Means and effects for solving the problems) The present inventors conducted extensive research in view of the current situation, and as a result, completed the present invention. That is, the present invention provides a resin molded product, an adhesive layer that is in close contact with the surface of the resin molded product and has a 180 degree peel strength of 500 g/25 mm or more against aluminum foil and is touchable, and a metal sprayed material on the adhesive layer. A metal film consisting of a metal film formed by
An acrylic resin which is a resin composite and whose adhesive layer is derived from a polymerizable monomer containing an alkyl (meth)acrylate having an alkyl group of 4 to 12 carbon atoms in an amount of 60% by weight or more based on the total monomers. The object of the present invention is to provide a metal-resin composite comprising as a main component.
本発明を構成する粘着剤層は、樹脂成形品と溶
射により形成される金属皮膜とを強固に接合せし
める目的で樹脂成形品上に密着して形成されるも
のであり、アルキル基の炭素数が４〜12のアルキ
ル（メタ）アクリレートを全単量体中の60重量％
以上含有する重合性単量体を重合して得られるア
クリル系樹脂を主成分としてなるものである。 The adhesive layer constituting the present invention is formed in close contact with the resin molded product for the purpose of firmly bonding the resin molded product and the metal coating formed by thermal spraying, and is 60% by weight of 4-12 alkyl (meth)acrylates based on total monomers
The main component is an acrylic resin obtained by polymerizing the polymerizable monomers contained above.
アルキル基の炭素数４〜12アルキル（メタ）ア
クリレートとしては、例えばブチル（メタ）アク
リレート、イソブチル（メタ）アクリレート、
sec−ブチル（メタ）アクリレート、tert−ブチ
ル（メタ）アクリレート、アミル（メタ）アクリ
レート、イソアミル（メタ）アクリレート、ヘキ
シル（メタ）アクリレート、シクロヘキシン（メ
タ）アクリレート、ヘプチル（メタ）アクリレー
ト、オクチル（メタ）アクリレート、２−エチル
ヘキシル（メタ）アクリレート、ノニル（メタ）
アクリレート、イソノニル（メタ）アクリレー
ト、デシル（メタ）アクリレート、ドデシル（メ
タ）アクリレート等を挙げることができる。 Examples of the alkyl (meth)acrylate in which the alkyl group has 4 to 12 carbon atoms include butyl (meth)acrylate, isobutyl (meth)acrylate,
sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, cyclohexine (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate ) acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)
Examples include acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and the like.
また、粘着剤層を構成するアクリル系樹脂を得
るために必要により前記アルキル（メタ）アクリ
レートと共重合し得るその他の重合性単量体とし
ては、例えばアクリル酸、メタクリル酸、マレイ
ン酸、フマル酸、マレイン酸モノアルキルエステ
ル等のカルボキシル基を有する重合性単量体；ヒ
ドロキシエチル（メタ）アクリレート、ヒドロキ
シプロピル（メタ）アクリレート等のヒドロキシ
ル基を有する重合性単量体；アクリルアミド、メ
チロールアクリルアミド、ブトキシメチルアクリ
ルアミド等のアクリルアミド誘導体；グリシジル
メタクリレート、アリルグリシジルエーテル等の
グリシジル基を有する重合性単量体；メチル（メ
タ）アクリレート、エチル（メタ）アクリレー
ト、プロピル（メタ）アクリレート等のアルキル
基の炭素数が１〜３のアルキル（メタ）アクリレ
ート；スチレン、酢酸ビニル、ビニルエーテル
類、フマル酸ジエステル等の１分子中に重合性二
重結合を１個有する重合性単量体や、ジビニルベ
ンゼン、トリメチロールプロパントリ（メタ）ア
クリレート等の１分子中に重合性二重結合を２個
以上有する重合性単量体等を挙げることができ
る。 In addition, other polymerizable monomers that can be copolymerized with the alkyl (meth)acrylate as necessary to obtain the acrylic resin constituting the adhesive layer include, for example, acrylic acid, methacrylic acid, maleic acid, and fumaric acid. Polymerizable monomers having a carboxyl group such as , maleic acid monoalkyl ester; Polymerizable monomers having a hydroxyl group such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate; acrylamide, methylolacrylamide, butoxymethyl Acrylamide derivatives such as acrylamide; polymerizable monomers having a glycidyl group such as glycidyl methacrylate and allyl glycidyl ether; alkyl groups with 1 carbon number such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate ~3 alkyl (meth)acrylate; polymerizable monomers having one polymerizable double bond in one molecule such as styrene, vinyl acetate, vinyl ethers, fumaric acid diester, divinylbenzene, trimethylolpropane tri( Examples include polymerizable monomers having two or more polymerizable double bonds in one molecule, such as meth)acrylate.
本発明で粘着剤層の主成分として用いられるア
クリル系樹脂は、アルキル基の炭素数４〜12アル
キル（メタ）アクリレートを全単量体中60重量％
以上含有する重合性単量体を重合せしめることに
より得ることができるが、該アルキル（メタ）ア
クリレートの量が60重量％未満の少量では、得ら
れる粘着剤層の粘着力が不十分となり、複合体を
苛酷な条件で使用する場合に支障が生じやすくな
る。なお重合方法としては、従来公知の溶液重
合、塊状重合、乳化重合等の方法により実施する
ことができる。 The acrylic resin used as the main component of the adhesive layer in the present invention contains 60% by weight of alkyl (meth)acrylate with an alkyl group having 4 to 12 carbon atoms based on the total monomers.
It can be obtained by polymerizing the polymerizable monomers containing the above, but if the amount of the alkyl (meth)acrylate is less than 60% by weight, the adhesive force of the resulting adhesive layer will be insufficient, resulting in Problems are more likely to occur when the body is used under harsh conditions. As the polymerization method, conventionally known methods such as solution polymerization, bulk polymerization, and emulsion polymerization can be used.
粘着剤層には、このようにして得られたアクリ
ル系樹脂に、その他の添加剤、例えばロジン、ロ
ジン誘導体、テルペン系樹脂、テルペンフエノー
ル系樹脂、フエノール樹脂、キシレン樹脂、クマ
ロン樹脂、クマロンインデン樹脂、脂肪族系石油
樹脂、芳香族系石油樹脂等の樹脂を配合して用い
ることができる。また、架橋剤としてポリイソシ
アネート化合物、メラミン樹脂、エポキシ樹脂、
アルミキレート化合物等を配合して用いることも
可能である。 The adhesive layer contains the acrylic resin obtained in this way and other additives such as rosin, rosin derivatives, terpene resins, terpene phenol resins, phenolic resins, xylene resins, coumaron resins, coumaron indenes. Resins such as resins, aliphatic petroleum resins, and aromatic petroleum resins can be blended and used. In addition, polyisocyanate compounds, melamine resins, epoxy resins,
It is also possible to mix and use an aluminum chelate compound or the like.
さらに、こうして得られらアクリル系樹脂を主
成分としてなる粘着剤層は、JIS−Ｚ−0237の粘
着力試験方法に準拠して測定したアルミ箔に対す
る180度剥離強度（樹脂成形品表面に形成された
粘着剤層に巾25mm、厚さ50ミクロンのアルミ箔テ
ープを貼着した後、引張速度300mm／分、温度23
℃で剥離して測定した。）が500ｇ／25mm以上であ
り、触手可能な程度に凝集力を有するものであ
る。アルミ箔に対する180度剥離強度が500ｇ／25
mm未満の低粘着力の粘着剤層では、溶射時の金属
の付着性が低下するために溶射金属の歩留まりが
悪くなり、また得られる複合体から金属溶射皮膜
が剥離する等のトラブルが発生しやすくなる。ま
た触手が不可能なほどに凝集力が発現していない
粘着剤層では、樹脂成形品と金属溶射皮膜との強
固な接合が達成されず、溶射作業時に溶射皮膜が
剥離する等のトラブルが生じやすくなる。 Furthermore, the adhesive layer obtained in this way, which is mainly composed of acrylic resin, has a 180 degree peel strength against aluminum foil (formed on the surface of a resin molded product) measured in accordance with the adhesion test method of JIS-Z-0237. After pasting an aluminum foil tape with a width of 25 mm and a thickness of 50 microns on the adhesive layer, it was pulled at a tension speed of 300 mm/min and at a temperature of 23
It was peeled off at ℃ and measured. ) is 500 g/25 mm or more, and has a cohesive force to the extent that it can be felt. 180 degree peel strength against aluminum foil is 500g/25
If the adhesive layer has a low adhesive strength of less than mm, the adhesion of the metal during thermal spraying will decrease, resulting in a poor yield of the sprayed metal, and problems such as peeling of the metal sprayed coating from the resulting composite will occur. It becomes easier. In addition, if the adhesive layer does not exhibit such cohesive force that it is impossible to touch it, a strong bond between the resin molded product and the metal sprayed coating cannot be achieved, resulting in problems such as peeling of the sprayed coating during thermal spraying work. It becomes easier.
本発明の実施にあたつては、例えば必要に応じ
て予め適当な粘度に溶剤等で希釈せしめたアクリ
ル系樹脂を主成分としてなる粘着剤溶液を、ハケ
塗りやスプレーあるいはデイツピング等の手法に
より樹脂成形品表面の必要な部分に塗布し、その
後必要に応じて溶剤等を蒸散せしめて樹脂成形品
表面に前記した粘着力を有する触手可能な粘着剤
層を形成する。 In carrying out the present invention, for example, an adhesive solution mainly composed of an acrylic resin that has been diluted with a solvent or the like to an appropriate viscosity as necessary may be applied to the resin by brushing, spraying, dipping, or other methods. The adhesive layer is applied to a required portion of the surface of the resin molded product, and then the solvent or the like is evaporated as required to form a touchable adhesive layer having the adhesive strength described above on the surface of the resin molded product.
しかる後に該粘着剤層上に金属を溶射して金属
皮膜を形成することにより、本発明の金属−樹脂
複合体を得ることができる。また、該金属皮膜上
に耐候性、耐水性の改善や、電気絶縁等の目的で
エポキシ系塗料、アクリル系塗料、アクリルウレ
タン系塗料、ウレタン系塗料等の塗料を塗布する
ことも可能である。 Thereafter, the metal-resin composite of the present invention can be obtained by thermally spraying a metal onto the adhesive layer to form a metal film. Furthermore, it is also possible to apply a paint such as an epoxy paint, an acrylic paint, an acrylic urethane paint, or a urethane paint to the metal film for the purpose of improving weather resistance, water resistance, electrical insulation, or the like.
（発明の効果）
このようにアクリル系樹脂を主成分としてなる
特定の粘着剤層を介して樹脂成形品と金属皮膜と
を強固に結合して得られた本発明の金属−樹脂複
合体は、樹脂成形品と金属皮膜の密着力が高く、
しかも耐候性、耐水性、耐熱性等の耐久性にも優
れているため、苛酷な条件下でも金属皮膜の剥離
等のトラブルなく使用可能なものである。さらに
溶射皮膜を形成するための溶射作業においても、
溶射された金属の付着性が良く、溶射作業時に溶
射皮膜が剥離する等のトラブルは発生しない。(Effects of the Invention) The metal-resin composite of the present invention obtained by firmly bonding a resin molded article and a metal film through a specific adhesive layer mainly composed of an acrylic resin has the following characteristics: High adhesion between resin molded products and metal coating,
Moreover, since it has excellent durability such as weather resistance, water resistance, and heat resistance, it can be used even under severe conditions without problems such as peeling of the metal film. Furthermore, in the thermal spraying work to form a thermal spray coating,
The adhesion of the sprayed metal is good, and problems such as peeling of the sprayed coating do not occur during the spraying process.
また、アクリル系樹脂を主成分としてなる粘着
剤層は、長期に亘つて強い粘着力を保持できるこ
とから溶射時の粘着剤層の性質を厳密に管理する
必要はなく、また十分な粘着力を有する粘着剤層
をハケ塗りやスプレーあるいはデイツピング等の
手法により簡単に得ることができ作業性が良い。 In addition, the adhesive layer, which is mainly composed of acrylic resin, can maintain strong adhesive strength over a long period of time, so there is no need to strictly control the properties of the adhesive layer during thermal spraying, and it has sufficient adhesive strength. The adhesive layer can be easily obtained by brushing, spraying, dipping, etc., and has good workability.
（実施例）
以下、実施例、比較例により本発明をさらに詳
しく説明する。なお、例中の部はすべて重量部を
示すものとする。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that all parts in the examples indicate parts by weight.
実施例 １
還流冷却器、撹拌機、温度計および窒素ガス導
入管を備えた反応器にヒドロキシエチルアクリレ
ート１部、アクリル酸４部、酢酸ビニル10部、２
−エチルヘキシルアクリレート45部、ブチルアク
リレート40部、酢酸エチル120部および過酸化ベ
ンゾイル0.5部を仕込み、窒素ガス気流下にて80
℃で４時間加熱し、さらに酢酸エチル30部、過酸
化ベンゾイル0.5部を加えて、80℃で４時間加熱
した。得られたアクリル系樹脂組成物（不揮発分
39重量％、粘度2000cps）100部に酢酸エチル100
部およびポリイソシアネート化合物（日本ポリウ
レタン工業(株)製、コロネートＬ）１部を混合し、
アクリル系樹脂を主成分としてなる粘着剤溶液
（以下単に粘着剤(1)と称する。）を得た。Example 1 In a reactor equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen gas inlet tube, 1 part of hydroxyethyl acrylate, 4 parts of acrylic acid, 10 parts of vinyl acetate, 2
- 45 parts of ethylhexyl acrylate, 40 parts of butyl acrylate, 120 parts of ethyl acetate and 0.5 parts of benzoyl peroxide were charged and heated to 80 parts under a nitrogen gas stream.
The mixture was heated at 80°C for 4 hours, 30 parts of ethyl acetate and 0.5 parts of benzoyl peroxide were added, and the mixture was heated at 80°C for 4 hours. The obtained acrylic resin composition (non-volatile content
39% by weight, viscosity 2000cps) 100 parts ethyl acetate 100
and 1 part of a polyisocyanate compound (Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.),
An adhesive solution (hereinafter simply referred to as adhesive (1)) containing an acrylic resin as a main component was obtained.
一方別に用意したABS樹脂製で厚さ３mm、縦
横それぞれ300mmの平板の表面に、粘着剤(1)をハ
ケを用いて塗布した後５分間室温で乾燥し、引き
続き70℃で10分間乾燥して、表面に触手可能な粘
着剤層が付着したABS樹脂製の平板を得た。な
お、この粘着剤層のアルミ箔に対する180度剥離
強度は1000ｇ／25mmであつた。次に、該粘着剤層
にアーク溶射機（米国TAFA社製、375EFS）を
用いて亜鉛を約100ミクロンの厚さに溶射して、
ABS樹脂製の平板と、該平板表面に密着した粘
着剤層と、粘着剤層上に亜鉛を溶射して形成され
た亜鉛皮膜とよりなる金属−樹脂複合体を得た。
得られた金属−樹脂複合体は、ABS樹脂製平板
と亜鉛皮膜とが粘着剤層を介して強固に密着して
おり、80℃の乾燥機中に10分間置いた後に−20℃
の恒温機中に10分間置く操作を１サイクルとする
寒熱サイクルテストを20サイクル行つた後も亜鉛
皮膜の剥離等のトラブルは認められなかつた。 On the other hand, the adhesive (1) was applied with a brush to the surface of a separately prepared flat plate made of ABS resin, 3 mm thick and 300 mm in length and width, dried at room temperature for 5 minutes, and then dried at 70℃ for 10 minutes. A flat plate made of ABS resin with a touchable adhesive layer attached to its surface was obtained. The 180 degree peel strength of this adhesive layer against aluminum foil was 1000 g/25 mm. Next, zinc was sprayed onto the adhesive layer to a thickness of about 100 microns using an arc spraying machine (375EFS, manufactured by TAFA, USA).
A metal-resin composite was obtained, which consisted of a flat plate made of ABS resin, an adhesive layer in close contact with the surface of the flat plate, and a zinc film formed by spraying zinc onto the adhesive layer.
The obtained metal-resin composite has a flat plate made of ABS resin and a zinc coating that are firmly attached to each other via an adhesive layer, and after being placed in a dryer at 80°C for 10 minutes, it is heated to -20°C.
No problems such as peeling of the zinc film were observed even after 20 cycles of cold/heat cycle tests, in which one cycle consisted of placing the product in a constant temperature machine for 10 minutes.
比較例 １
実施例１で用いたのと同じABS樹脂製平板の
片面をスチールグリツド＃40でブラストし、その
後ブラスト処理を施した面上に実施例１と同様に
して亜鉛を約100ミクロンの厚さに溶射した。こ
うして得られた金属−樹脂複合体に実施例１と同
様の寒熱サイクルテストを行つたところ、２サイ
クル目に亜鉛皮膜の一部が剥離した。Comparative Example 1 One side of the same ABS resin flat plate used in Example 1 was blasted with steel grid #40, and then zinc was applied to the blasted surface in the same manner as in Example 1 to a thickness of approximately 100 microns. Sprayed to thickness. When the thus obtained metal-resin composite was subjected to the same cold/heat cycle test as in Example 1, part of the zinc coating was peeled off in the second cycle.
比較例 ２
実施例１で用いたのと同じ反応容器にヒドロキ
シエチルアクリレート１部、アクリル酸４部、酢
酸ビニル10部、２−エチルヘキシルアクリレート
50部、メチルメタクリレート35部、酢酸エチル
120部および過酸化ベンゾイル0.5部を仕込み、窒
素ガス気流下にて80℃で４時間加熱し、さらに酢
酸エチル30部、過酸化ベンゾイル0.5部を加えて、
80℃で４時間加熱した。得られたアクリル系樹脂
組成物（不揮発分39重量％、粘着度3500cps）100
部に酢酸エチル100部およびポリイソシアネート
化合物（日本ポリウレタン工業(株)製、コロネート
Ｌ）１部を混合し、アクリル系樹脂を主成分とし
てなる粘着剤溶液（以下単に粘着剤(2)と称する。）
を得た。Comparative Example 2 In the same reaction vessel as used in Example 1, 1 part of hydroxyethyl acrylate, 4 parts of acrylic acid, 10 parts of vinyl acetate, and 2-ethylhexyl acrylate were added.
50 parts, methyl methacrylate 35 parts, ethyl acetate
Charge 120 parts and 0.5 part of benzoyl peroxide, heat at 80°C for 4 hours under a nitrogen gas stream, and then add 30 parts of ethyl acetate and 0.5 part of benzoyl peroxide.
Heated at 80°C for 4 hours. Obtained acrylic resin composition (non-volatile content 39% by weight, tackiness 3500cps) 100
100 parts of ethyl acetate and 1 part of a polyisocyanate compound (Coronate L, manufactured by Nippon Polyurethane Kogyo Co., Ltd.) were mixed into a solution of an adhesive containing an acrylic resin as a main component (hereinafter simply referred to as adhesive (2)). )
I got it.
粘着剤(2)を、実施例１で用いた粘着剤(1)の代わ
りに用いた他は全く実施例１と同様にして、表面
に触手可能な粘着剤層が付着したABS樹脂製の
平板を得た。なお、この粘着剤層のアルミ箔に対
する180度剥離強度は100ｇ／25mmであつた。 A flat plate made of ABS resin with a touchable adhesive layer attached to its surface was prepared in the same manner as in Example 1 except that adhesive (2) was used in place of adhesive (1) used in Example 1. I got it. The 180 degree peel strength of this adhesive layer against aluminum foil was 100 g/25 mm.
次に該粘着剤層に、実施例１と全く同様にし
て、亜鉛を約100ミクロンの厚さに溶射して、金
属−樹脂複合体を得た。得られた金属−樹脂複合
体に実施例１と同様の寒熱サイクルテストを行つ
たところ、１サイクルで亜鉛皮膜の一部が剥離し
た。 Next, zinc was thermally sprayed onto the adhesive layer to a thickness of about 100 microns in exactly the same manner as in Example 1 to obtain a metal-resin composite. When the obtained metal-resin composite was subjected to the same cold/heat cycle test as in Example 1, part of the zinc coating was peeled off after one cycle.
Claims (1)
た、アルミ箔に対する180度剥離強度が500ｇ／25
mm以上で触手可能な粘着剤層と、該粘着剤層上に
金属溶射を施して形成された金属皮膜と、必要に
応じて金属皮膜に塗布された塗装皮膜とよりなる
金属−樹脂複合体であつて、該粘着剤層がアルキ
ル基の炭素数が４〜12のアルキル（メタ）アクリ
レートを全単量体中60重量％以上含有する重合性
単量体から導かれたアクリル系樹脂を主成分とし
てなる金属−樹脂複合体。1 The 180 degree peel strength of the resin molded product and the aluminum foil that adheres to the surface of the resin molded product is 500g/25
A metal-resin composite consisting of an adhesive layer that can be touched with a diameter of mm or more, a metal film formed by metal spraying on the adhesive layer, and a paint film applied to the metal film as necessary. The adhesive layer is mainly composed of an acrylic resin derived from a polymerizable monomer containing an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms in an amount of 60% by weight or more based on the total monomers. A metal-resin composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15967586A JPS6317042A (en) | 1986-07-09 | 1986-07-09 | Metal-resin composite body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15967586A JPS6317042A (en) | 1986-07-09 | 1986-07-09 | Metal-resin composite body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6317042A JPS6317042A (en) | 1988-01-25 |
| JPH0434938B2 true JPH0434938B2 (en) | 1992-06-09 |
Family
ID=15698875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15967586A Granted JPS6317042A (en) | 1986-07-09 | 1986-07-09 | Metal-resin composite body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6317042A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU676726B2 (en) * | 1993-06-04 | 1997-03-20 | Peter Byrne Concepts Pty Ltd | Metal coating process |
| EP0675157A1 (en) * | 1994-03-29 | 1995-10-04 | Ppg Industries, Inc. | Primer for adhering conductive films to acrylic or polycarbonate substrates |
| US5578642A (en) * | 1994-08-17 | 1996-11-26 | Henkel Corporation | Self-emulsifying and/or emollient agents |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58106899A (en) * | 1981-12-18 | 1983-06-25 | 藤森工業株式会社 | Electromagnetic wave shielding sheet for electronic device |
-
1986
- 1986-07-09 JP JP15967586A patent/JPS6317042A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58106899A (en) * | 1981-12-18 | 1983-06-25 | 藤森工業株式会社 | Electromagnetic wave shielding sheet for electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6317042A (en) | 1988-01-25 |
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