JPH02301568A - Method for coating synthetic resin structure with metal - Google Patents
Method for coating synthetic resin structure with metalInfo
- Publication number
- JPH02301568A JPH02301568A JP11869189A JP11869189A JPH02301568A JP H02301568 A JPH02301568 A JP H02301568A JP 11869189 A JP11869189 A JP 11869189A JP 11869189 A JP11869189 A JP 11869189A JP H02301568 A JPH02301568 A JP H02301568A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- weight
- metal
- plating
- electroless plating
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 19
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 title claims abstract description 11
- 238000000576 coating method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 33
- 238000007772 electroless plating Methods 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- -1 nitrogen-containing compound Chemical class 0.000 claims description 22
- 239000004952 Polyamide Substances 0.000 abstract description 5
- 229920002647 polyamide Polymers 0.000 abstract description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 abstract description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 3
- 239000004471 Glycine Substances 0.000 abstract description 2
- UCSVJZQSZZAKLD-UHFFFAOYSA-N ethyl azide Chemical compound CCN=[N+]=[N-] UCSVJZQSZZAKLD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 17
- 239000010949 copper Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 229920000728 polyester Polymers 0.000 description 12
- 238000011282 treatment Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000004640 Melamine resin Substances 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 5
- 238000003486 chemical etching Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229920000298 Cellophane Polymers 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 238000009991 scouring Methods 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 206010042674 Swelling Diseases 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 235000004279 alanine Nutrition 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 229920001155 polypropylene Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- 238000004381 surface treatment Methods 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
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- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- FYWDUQCSMYWUHV-UHFFFAOYSA-N 3-chloro-5-hydroxypentan-2-one Chemical compound CC(=O)C(Cl)CCO FYWDUQCSMYWUHV-UHFFFAOYSA-N 0.000 description 1
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
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- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
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- 239000004472 Lysine Substances 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
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- JINBYESILADKFW-UHFFFAOYSA-N aminomalonic acid Chemical compound OC(=O)C(N)C(O)=O JINBYESILADKFW-UHFFFAOYSA-N 0.000 description 1
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- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 description 1
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- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
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- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 229960001153 serine Drugs 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
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- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は合成樹脂構造物表面の金属被覆方法に関し、さ
らに詳しくは、合成樹脂構造物表面に無電解メッキ法に
より金属被膜を形成するに際して、無電解メッキに先立
ちメッキすべき表面に塩基性窒素含有化合物を付着せし
めることにより、均一で且つ密着性に優れた金属被膜を
形成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of metal coating the surface of a synthetic resin structure, and more specifically, when forming a metal film on the surface of a synthetic resin structure by electroless plating, a plating process is performed prior to electroless plating. The present invention relates to a method for forming a uniform metal coating with excellent adhesion by attaching a basic nitrogen-containing compound to the surface of the target.
一般にプラスチック類の表面に無電解メッキを施すには
、脱脂、触媒付与、活性化等の前処理を行ったプラスチ
ック類を無電解メッキ浴に浸漬するのが普通であり、そ
の際プラスチック基材表面の濡れを良好にして、触媒の
吸収及び付着能を向上させたり、或いは基材と金属との
密着性の向上を目的として機械的エツチング又は化学的
エツチング等の表面処理を併用することが多く行われて
いる。Generally, in order to perform electroless plating on the surface of plastics, it is common to immerse the plastics that have undergone pretreatment such as degreasing, catalysis, and activation in an electroless plating bath. Surface treatments such as mechanical etching or chemical etching are often used in combination to improve the wetting of the metal and to improve the absorption and adhesion of the catalyst, or to improve the adhesion between the base material and the metal. It is being said.
現在、工業的に無電解メッキの対象とされているプラス
チックとしては、ABS樹脂、ポリプロピレン樹脂、ポ
リアミド樹脂等があげられる。その理由は、これらの素
材が化学エツチングされ易く、また無電解メッキの密着
性も比較的良好であるからである。Currently, plastics that are industrially targeted for electroless plating include ABS resin, polypropylene resin, polyamide resin, and the like. This is because these materials are easily chemically etched and have relatively good adhesion during electroless plating.
一方、メッキし難くいといわれている樹脂には、ポリエ
ステル系樹脂、塩化ビニル系樹脂、塩化ビニリデン系樹
脂等があげられる。On the other hand, examples of resins that are said to be difficult to plate include polyester resins, vinyl chloride resins, and vinylidene chloride resins.
これらの樹脂の化学エツチングに関して、例えば、特公
昭47−19600号公報には、ポリアミド、ポリエス
テル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリオレ
フィン等の樹脂のメッキに先立って、それぞれの樹脂に
適した有機溶剤、例えば、ポリ塩化ビニル系樹脂に対し
ては、酢酸エチル、アセトン、ベンゼン、トリクレン等
を、またポリエステル系樹脂に対してはm−クレゾール
、フェノールの10〜20%の水溶液を、そしてポリプ
ロピレンに対しては5%の苛性ソーダ水溶液に10〜2
0%のデカリンスはテトラリン等の有機溶剤を混入し、
さらに界面活性剤2〜log/Qを加えてエマルジョン
化した浴等において50〜60°Cで膨潤処理を行い、
次いで、50〜60%硫酸水溶液に重クロム酸カリ2〜
5g/12を加えた浴において50〜70°Cで1〜2
分間エツチングを行った後、無電解メッキする方法が開
示されている。しかし、この方法で樹脂の膨潤に使われ
る有機溶剤は蒸発し易く特有の臭気があり且つ可燃性で
あるため、作業環境の汚染及び火災等の危険がある。更
に、膨潤処理後の化学エツチング剤に使われる硫酸と重
クロム酸カリの混合液は強い酸化力を有しており、重合
体物質の欠損、物理的強力の低下等の問題を生ずる懸念
がある。その上、クロム酸が溶存した廃液は公害規制が
厳しく排水処理方法が複雑であり、更に沈澱回収したク
ロムを含んだスラッジの処理等に難問が多いという欠点
がある。Regarding the chemical etching of these resins, for example, Japanese Patent Publication No. 47-19600 describes that prior to plating resins such as polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, and polyolefin, an organic solvent suitable for each resin is used. For example, for polyvinyl chloride resin, ethyl acetate, acetone, benzene, trichlene, etc., for polyester resin, m-cresol, a 10 to 20% aqueous solution of phenol, and for polypropylene, For example, add 10-2 to 5% caustic soda aqueous solution.
0% decalin is mixed with organic solvents such as tetralin,
Furthermore, a swelling treatment is performed at 50 to 60°C in an emulsion bath etc. by adding 2~log/Q of surfactant,
Next, add 2 to 60% potassium dichromate to a 50 to 60% sulfuric acid aqueous solution.
1-2 at 50-70°C in a bath with 5g/12
A method of performing electroless plating after etching for a minute is disclosed. However, the organic solvent used to swell the resin in this method evaporates easily, has a unique odor, and is flammable, which poses a risk of contaminating the working environment and causing fire. Furthermore, the mixed solution of sulfuric acid and potassium dichromate used as a chemical etching agent after swelling treatment has strong oxidizing power, and there is a concern that it may cause problems such as loss of polymer substances and decrease in physical strength. . Moreover, wastewater containing dissolved chromic acid is subject to strict pollution regulations, and the wastewater treatment method is complicated, and furthermore, there are many difficulties in the treatment of chromium-containing sludge collected by precipitation.
他方、無電解メッキ金属皮膜の密着性を改良する方法と
して合成繊維の表面に微細な凹凸を付与することも考え
られるが、プラスチック成型品に対して行われているよ
うなサンドブラスト法などで機械的粗化を施す方法は、
繊維の場合には損傷が著しく実際上は不可能である。On the other hand, one way to improve the adhesion of electroless plated metal films is to add fine irregularities to the surface of synthetic fibers, but mechanical The method of roughening is
In the case of fibers, the damage is so great that it is practically impossible.
また、特開昭60−181362号公報Iこは、ポリエ
ステル繊維に化学メッキを施す改良法として、スルホン
酸基及び/又は金属スルホネート基を有する化合物を含
むポリエステル繊維をアルカリ浴に浸漬及び/又は通過
させることにより、8〜30重量%の減量処理を施し、
繊維表面に金属スルホネート基を露出させた後、触媒付
与、活性化処理することにより均一な無電解メッキ金属
膜を形成させる方法が開示されている。しかしながら、
この方法は、ポリエステル紡糸原料に金属スルホネート
基を存する化合物を共存させて溶融紡糸するために、紡
糸原料段階から特製しなければならず、また、溶融紡糸
時にポリエステル以外の化合物を共存させると、紡糸ノ
ズルの摩耗又は紡糸中の糸切れが起こり易い等の欠点が
ある。In addition, JP-A-60-181362 discloses an improved method for chemically plating polyester fibers, in which polyester fibers containing a compound having sulfonic acid groups and/or metal sulfonate groups are immersed and/or passed through an alkaline bath. By doing so, a weight loss treatment of 8 to 30% by weight is performed,
A method has been disclosed in which a uniform electroless plated metal film is formed by exposing metal sulfonate groups on the fiber surface and then applying a catalyst and activating the group. however,
In this method, in order to carry out melt spinning in which a compound containing a metal sulfonate group coexists in the polyester spinning raw material, it must be specially prepared from the spinning raw material stage. There are disadvantages such as nozzle wear and thread breakage during spinning.
更に、特開昭48−54299号公報には、ポリアミド
繊維の無電解メッキ方法が記載されており、この方法は
、ポリアミド繊維を物理的又は化学的にエツチングする
ことなくN−アルコキシメチルナイロンのアルコール溶
液をナイロン繊維に付着させ、次いで溶剤のアルコール
の沸点以上の温度で急激に乾燥させるものであって、こ
の方法では、乾燥時アルコールが速やかに気化し、微細
な気泡となってN−アルコキシメチルナイロンの表面か
ら離脱し、N−アルコキシメチルナイロンがナイロン繊
維にしっかりと接着される。N−アルコキシメチルナイ
ロンの表面はアルコールの気化散逸により微細な凹凸状
態となるので、重クロム酸と硫酸の混合液による化学エ
ツチングを行うことなく、直接無電解メッキすることに
より金属メッキ層を形成させることが可能となる。しか
し、この方法は、N−アルコキシメチルナイロンの溶媒
としてアルコールを使わなければならず、その上アルコ
ールの沸点以上に急激に加熱気化させる工程を必要とす
るので、火災の危険性があるという欠点を有している。Furthermore, JP-A No. 48-54299 describes a method for electroless plating of polyamide fibers, and this method involves applying alcohol to N-alkoxymethyl nylon without physically or chemically etching the polyamide fibers. The solution is applied to nylon fibers and then rapidly dried at a temperature higher than the boiling point of the solvent alcohol. In this method, the alcohol quickly vaporizes during drying, forming fine bubbles and forming N-alkoxymethyl It detaches from the surface of the nylon and the N-alkoxymethyl nylon is firmly adhered to the nylon fiber. Since the surface of N-alkoxymethyl nylon becomes finely uneven due to vaporization and dissipation of alcohol, a metal plating layer is formed by direct electroless plating without chemical etching with a mixture of dichromic acid and sulfuric acid. becomes possible. However, this method requires the use of alcohol as a solvent for N-alkoxymethyl nylon, and also requires a step of rapidly heating and vaporizing the alcohol above its boiling point, which poses the drawback of a fire hazard. have.
本発明の主たる目的は、合成樹脂製構造物の無電解メッ
キにおける前記の如き欠点を解消すべく、無電解メッキ
すべき合成樹脂製構造物表面を簡単で且つ穏和な条件下
に活性化し、それによって合成樹脂製構造物の物理的強
度の低下や損傷などを生ぜしめることなく均一で且つ堅
固に密着した金属被膜を形成せしめる方法を提供するこ
とである。The main purpose of the present invention is to activate the surface of a synthetic resin structure to be electrolessly plated under simple and mild conditions in order to eliminate the above-mentioned drawbacks in electroless plating of a synthetic resin structure. It is an object of the present invention to provide a method for forming a uniform and firmly adherent metal coating without causing a decrease in physical strength or damage to a synthetic resin structure.
かくして、本発明によれば、合成樹脂構造物表面に無電
解メッキ法により金属被膜を形成する方法において、無
電解メッキに先立ち、該合成樹脂構造物の金属被膜を形
成すべき表面に、塩基性窒素含有化合物を含有する樹脂
バインダーを付着せしめることを特徴とする合成樹脂構
造物表面の金属被覆方法が提供される。Thus, according to the present invention, in the method of forming a metal film on the surface of a synthetic resin structure by electroless plating, prior to electroless plating, a basic base is added to the surface of the synthetic resin structure on which the metal film is to be formed. Provided is a method for metal coating the surface of a synthetic resin structure, which comprises depositing a resin binder containing a nitrogen-containing compound.
本発明が処理の対象としている合成樹脂製構造物として
は、糸条(フィラメント、ファイバー、ヤーンなと)、
綿状物、トウ、織物、編物、不織布などの繊維構造物を
はじめ、棒状、板或はフィルム状筐体、筒状などが包含
される。かかる構造物の材質は特に制限がなく、例えば
、ポリアミド系、ポリオレフィン系、ポリエステル系、
塩化ビニル系、塩化ビニリデン系、ポリアクリル系、ポ
リカーボネート系、ABS等の各種の合成樹脂で構成さ
れていることができる。The synthetic resin structures to be treated by the present invention include threads (filaments, fibers, yarns, etc.);
It includes fiber structures such as cotton-like materials, tows, woven materials, knitted materials, and non-woven materials, as well as rod-like, plate- or film-like casings, and cylindrical shapes. The material of such a structure is not particularly limited, and examples thereof include polyamide, polyolefin, polyester,
It can be made of various synthetic resins such as vinyl chloride, vinylidene chloride, polyacrylic, polycarbonate, and ABS.
このような合成樹脂製構造物(以下、基材という)の表
面に無電解メッキを施すに際して、本発明の方法は、メ
ッキに先立ち、基材のメッキを施すべき表面に、塩基性
窒素含有化合物を含有する樹脂バインダーを付着せしめ
ることにより、基材表面を活性化する点に特徴がある。When performing electroless plating on the surface of such a synthetic resin structure (hereinafter referred to as a base material), the method of the present invention includes applying a basic nitrogen-containing compound to the surface of the base material to be plated prior to plating. It is characterized in that the surface of the base material is activated by attaching a resin binder containing the following.
基材に対してかかる活性化処理を行なう場合、該処理に
先立ち、合成樹脂製基材の無電解メッキにおいて通常行
なわれている前処理、例えば脱脂、精練、表面濡れ性付
与等の処理を適宜行なうことができる。例えば、基材を
適当な界面活性剤を含む水溶液中に加温下に浸漬するこ
とにより脱脂、精練処理することができる。更に、物理
的な表面粗化、或いは化学的エツチング等の処理を施こ
すこともできる。When carrying out such activation treatment on a base material, prior to said treatment, appropriate pretreatments such as degreasing, scouring, surface wettability, etc. that are usually performed in electroless plating of synthetic resin base materials are carried out. can be done. For example, the base material can be degreased and refined by immersing it in an aqueous solution containing a suitable surfactant under heating. Furthermore, treatments such as physical surface roughening or chemical etching can also be applied.
このように適宜前処理した基材の表面には、本発明に従
い、塩基性窒素含有化合物を含有する樹脂バインダーが
付着せしめられる。本発明において用いうる塩基性窒素
化合物としては、アミノ、アンモニウム、アジン、アゾ
、アゾキン、ジアゾ、ジアゾアミノ、ジアゾニウム、ヒ
ドラジ、シドラジノ、ヒドラゾ、ヒドラジン、オキシア
ミノ、イミノ等の塩基性窒素含有基を151)子中に少
なくとも1個有する脂肪族系の化合物が包含され、これ
ら化合物は場合によっては二量体以上の多量体の形態で
存在してもよい。そのような塩基性窒素化合物゛の好適
具体例には例えば次のものが挙げられる。According to the present invention, a resin binder containing a basic nitrogen-containing compound is attached to the surface of the base material which has been appropriately pretreated in this manner. The basic nitrogen compounds that can be used in the present invention include basic nitrogen-containing groups such as amino, ammonium, azine, azo, azoquine, diazo, diazoamino, diazonium, hydrazi, sidragino, hydrazo, hydrazine, oxyamino, and imino. Included are aliphatic compounds having at least one aliphatic compound, and these compounds may exist in the form of a dimer or higher polymer depending on the case. Preferred specific examples of such basic nitrogen compounds include the following.
(1) 脂肪族アミン系化合物:
例えば、メチルアミン、エチルアミン、プロピルアミン
、ブチルアミンなどの第1級脂肪族アミン;ジメチルア
ミン、ジエチルアミン、ジエチルアミンなどの第2級脂
肪族アミンニトリメチルア□ミン、トリエチルアミン、
トリプロピルアミンなどの第3級脂肪族アミン;塩化テ
トラメチルアンモニウム、塩化テトラエチルアンモニウ
ム、水酸化テトラメチルアンモニウム、水酸化テトラエ
チルアンモニウム、ヨウ化テトラメチルアンモニウムな
どの第4級脂肪族アンモニウム化合物。或いは上記アミ
ンの多量体であるポリアミン類。(1) Aliphatic amine compounds: For example, primary aliphatic amines such as methylamine, ethylamine, propylamine, butylamine; secondary aliphatic amines such as dimethylamine, diethylamine, diethylamine, nitrimethylamine, triethylamine ,
Tertiary aliphatic amines such as tripropylamine; quaternary aliphatic ammonium compounds such as tetramethylammonium chloride, tetraethylammonium chloride, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium iodide. Or polyamines which are multimers of the above amines.
(2)アミノM類:
例えば、グリシン、サルコシン、ジメチルグリジン、ベ
タイン、エチレンジアミンテトラ酢酸、ヒダントイン酸
、クレアチン、アラニン、a−アミノ酪酸、バリン、ロ
イシン、σ−アミツカグリル酸、セリン、シクロセリン
、σ−オキシアラニン、システィン、リジン、アルギニ
ン、アルギノフハク酸、アミノマロン酸、アスパラギン
a、a+σ−ジアミノコハク酸、コハク酸イミド、グル
タミン酸等。これらアミノ酸は塩の形、例えばナトリウ
ム塩又はカリウム塩の形で用いることもできる。(2) Amino M: For example, glycine, sarcosine, dimethylglycine, betaine, ethylenediaminetetraacetic acid, hydantoic acid, creatine, alanine, a-aminobutyric acid, valine, leucine, σ-aminobutyric acid, serine, cycloserine, σ- Oxyalanine, cysteine, lysine, arginine, arginofuccinic acid, aminomalonic acid, asparagine a, a+σ-diaminosuccinic acid, succinimide, glutamic acid, etc. These amino acids can also be used in the form of salts, for example sodium or potassium salts.
(3) その他:
エチルアジド、アゾカルボン酸ジエチル、2−アゾキシ
−2,5−ジメチルヘキサン、ジアゾ酢酸エチル、ジシ
アンジアミド、メチルイソジアゾタートナトリウム、ヒ
ドラジン、ヒドラゾ酸、ヒドラゾン、α−オキシアミノ
ニトリル、管ソ尿素など。(3) Others: Ethyl azide, diethyl azocarboxylate, 2-azoxy-2,5-dimethylhexane, ethyl diazoacetate, dicyandiamide, sodium methylisodiazotate, hydrazine, hydrazoic acid, hydrazone, α-oxyaminonitrile, tubusourea Such.
以上に述べた塩基性窒素含有化合物を基材表面に付着さ
せる方法としては、該化合物を適当な樹脂バインダー中
に分散させて、基材表面に適用す“る方法が挙げられる
。ここで用いうる樹脂バインダーには、基材表面に対し
て強力な接着性及び可撓性を有し、且つ塩基性窒素含有
化合物と相溶性があり、溶媒(例えば、水、アルコール
類、エステル類、又はそれらの混合物)に可溶性で、場
合によっては架橋硬化性をもつ樹脂力;適しており、例
えば、ポリオレフィン系、ポリエステル系、ポリアミド
系等の樹脂が挙げられ、これらは必要に応じてメラミン
系樹脂やアクリル樹脂系エマルジョン等と併用すること
ができる。As a method for attaching the basic nitrogen-containing compound described above to the surface of a substrate, there is a method in which the compound is dispersed in a suitable resin binder and applied to the surface of the substrate. The resin binder has strong adhesion and flexibility to the surface of the base material, is compatible with basic nitrogen-containing compounds, and is compatible with solvents (e.g., water, alcohols, esters, or their like). Suitable resins include polyolefin resins, polyester resins, polyamide resins, etc., and these can be combined with melamine resins and acrylic resins as necessary. It can be used in combination with other emulsions.
上記塩基性窒素含有化合物及び樹脂バインダーは、上記
した如き溶媒に溶解ないし分散させた溶液又は分散液と
して基材表面に適用することができる。その際の溶液な
いし分散液中における塩基性窒素含有化合物の濃度は、
該化合物の種類等によっても異なるが、一般には0.O
1〜20g/Q、好ましくは0.05〜l Og/Qの
範囲内とすることができ、また、樹脂バインダーの濃度
は固形分として通常0.1−100 g/Q 、好まし
くは0.1〜50 g/Qの範囲内が適している。The above-mentioned basic nitrogen-containing compound and resin binder can be applied to the surface of the substrate as a solution or dispersion in which they are dissolved or dispersed in the above-described solvent. The concentration of the basic nitrogen-containing compound in the solution or dispersion at that time is
Although it varies depending on the type of compound, etc., it is generally 0. O
It can be within the range of 1 to 20 g/Q, preferably 0.05 to 1 Og/Q, and the concentration of the resin binder is usually 0.1 to 100 g/Q as solid content, preferably 0.1 A range of ~50 g/Q is suitable.
また、かかる溶液ないし分散液の基材表面への適用手段
としては、例えば、浸漬処理、噴霧処理、塗布処理等が
挙げられる。Further, examples of means for applying such a solution or dispersion to the surface of the substrate include dipping treatment, spraying treatment, coating treatment, and the like.
さらに、該溶液ないし分散液には必要に応じて、カチオ
ン系、ノニオン系、両性等の界面活性剤を含有せしめる
ことにより、基材表面の濡れ性を向上させるようにして
もよい。Furthermore, if necessary, the solution or dispersion may contain a cationic, nonionic, amphoteric, or other surfactant to improve the wettability of the substrate surface.
塩基性窒素含有化合物を含む樹脂バインダー液による処
理時の温度は通常、室温で十分であるが、場合によって
は約40°Cまでの温度に加温してもよい。The temperature during treatment with a resin binder solution containing a basic nitrogen-containing compound is usually room temperature, but in some cases it may be heated to a temperature of up to about 40°C.
上記溶液又は分散液が適用された基材は常法により溶媒
を除去することにより、基材表面に塩基性窒素含有化合
物を付着せしめることができる。The basic nitrogen-containing compound can be attached to the surface of the substrate by removing the solvent by a conventional method from the substrate to which the solution or dispersion has been applied.
また、樹脂バインダーに架橋硬化性の樹脂を用いた場合
には、該樹脂が架橋硬化するに要する温度、時間条件下
に熱処理することができる。例えば樹脂バインダーの一
部にメラミン樹脂を用いた場合、通常約80〜約150
°Cの範囲内の温度で1〜5分間分間熱処理するのが望
ましい。Further, when a crosslinking-curing resin is used as the resin binder, heat treatment can be performed under the temperature and time conditions required for crosslinking and curing the resin. For example, when melamine resin is used as part of the resin binder, it usually has a molecular weight of about 80 to about 150.
Preferably, the heat treatment is carried out at a temperature in the range of 1 to 5 minutes.
塩基性窒素含有化合物の付着量は、用いる塩基性窒素含
有化合物の種類等により異なるが、一般には0.05〜
l Og/Q 、好ましくは0.05〜5g/Qの範囲
内とするのが好都合である。The amount of the basic nitrogen-containing compound deposited varies depending on the type of basic nitrogen-containing compound used, but is generally 0.05 to 0.05.
It is convenient to have l Og/Q, preferably in the range from 0.05 to 5 g/Q.
本発明によれば、以上に述べた如く塩基性窒素含有化合
物を付着せしめた基材には、次いで無電解メッキ(化学
メッキ)法により金属被膜が施される。この無電解メッ
キはそれ自体既知の方法、例えば、表面処理技術総覧(
産業技術サービスセンター刊)等の文献に記載の方法に
より行なうことができる。具体的には例えば、無電解銅
メッキはホルムアルデヒドなどの還元剤で溶液中の銅イ
オンを該メッキ処理物の表面に金属として析出させる反
応により行なうことができる。無電解銅メッキ析出の主
反応はメッキ溶液中のCu2+の錯体を(Cu−キレー
ト剤)と表わすと、次式で表される自己触媒反応である
。According to the present invention, the base material to which the basic nitrogen-containing compound is adhered as described above is then coated with a metal coating by electroless plating (chemical plating). This electroless plating can be done using methods known per se, such as the Surface Treatment Technology Directory (
This can be done by the method described in literature such as (published by Industrial Technology Service Center). Specifically, for example, electroless copper plating can be performed by a reaction in which copper ions in a solution are precipitated as metal on the surface of the plated object using a reducing agent such as formaldehyde. The main reaction of electroless copper plating deposition is an autocatalytic reaction expressed by the following formula, when the Cu2+ complex in the plating solution is expressed as (Cu-chelating agent).
[Cu−キレート] +2HCHO+40H−→Cu’
+2HCOO−+H1↑+2H20+キレート剤
また、無電解ニッケルメッキの還元剤としては、次亜リ
ン酸塩が最も一般的である。[Cu-chelate] +2HCHO+40H-→Cu'
+2HCOO-+H1↑+2H20+chelating agent Hypophosphite is the most common reducing agent for electroless nickel plating.
無電解ニッケルメッキの基礎反応式は次のようである(
酸性浴)。The basic reaction formula for electroless nickel plating is as follows (
acid bath).
N i’ +H!PO,−+2H“
次に、実施例を掲げて、本発明の方法を更に具体的に説
明する。Ni'+H! PO, -+2H" Next, the method of the present invention will be explained in more detail with reference to Examples.
実施例1
ポリエステルフィラメント紗(糸径40ミクロン、13
5メツシュ/インチ)をノニオン界面活性剤(ノイゲン
WS−20;第−工業製薬製)5g / Q水溶液中に
て50°Cで30分間脱脂・精練後乾燥した。Example 1 Polyester filament gauze (thread diameter 40 microns, 13
5 meshes/inch) was degreased and scoured for 30 minutes at 50°C in a 5 g/Q aqueous solution of a nonionic surfactant (Noigen WS-20; manufactured by Dai-Kogyo Seiyaku Co., Ltd.), and then dried.
次に、170°Cの雰囲気で1分間皺とりのためヒート
セット後、ポリエステル系樹脂(ファイテックスES−
850;大日本インキ製)50重量部、メラミン樹脂(
ベッカミンPM−N 、大日本インキ製)2重量部、触
媒(キャタリストES−2:大日本インキ製)0.5重
量部、アラニン1重量部及び水947重量部とを混合し
た前処理液に25°C′″C″1分間浸漬し絞液乾燥後
、100℃で3分間熱処理を行った。Next, after heat setting in an atmosphere of 170°C for 1 minute to remove wrinkles, polyester resin (Fitex ES-
850; manufactured by Dainippon Ink) 50 parts by weight, melamine resin (
A pretreatment liquid containing 2 parts by weight of Beckamine PM-N (manufactured by Dainippon Ink), 0.5 parts by weight of a catalyst (Catalyst ES-2 (manufactured by Dainippon Ink), 1 part by weight of alanine, and 947 parts by weight of water). After immersion at 25°C''C'' for 1 minute and drying, heat treatment was performed at 100°C for 3 minutes.
メッキ触媒として塩化パラジウムと塩化錫の混合液(キ
ャタリストA−30;奥野製薬製)159m(1と塩酸
160+RQ及び水690m12の混合液を調製した。A mixed solution of palladium chloride and tin chloride (Catalyst A-30; manufactured by Okuno Pharmaceutical Co., Ltd.) 159 ml (1), hydrochloric acid 160+RQ, and water 690 ml was prepared as a plating catalyst.
前記処理したポリエステル紗を、メッキ触媒溶液に25
°Cで2分間浸漬後、水洗し、次に活性化浴として硫酸
50++++2と水950m(lの混合液に45°Cで
3分間浸漬し、塩化錫を溶解除去後、塩化パラジウムを
繊維に固着させた。The treated polyester gauze was added to the plating catalyst solution for 25 minutes.
After immersing at °C for 2 minutes, washing with water, then immersing in a mixture of 50+++2 sulfuric acid and 950 ml of water as an activation bath at 45°C for 3 minutes, dissolving and removing tin chloride, and fixing palladium chloride to the fibers. I let it happen.
次いで、水洗して過剰の硫酸等を洗い去った後、下記組
成の無電解メッキ浴に28°Cで3分間浸漬したところ
均一な銅メッキ膜を形成された。Next, after washing with water to remove excess sulfuric acid and the like, it was immersed in an electroless plating bath having the composition shown below at 28°C for 3 minutes, and a uniform copper plating film was formed.
銅メツキ浴組成:
硝酸銅 15g/Q炭酸水素ナト
リウム lOl/酒石酸塩
30 l/水酸化ナトリウム 20113
8%ホルマリン液 10(JrnQ/QpH:1
1.5
形成された銅層は25%OWrであり、表面電気抵抗は
0,3Ω/ c m以下であって、良好な金属膜であり
、本発明による方法が極めて効果のあることが確認され
た。Copper plating bath composition: Copper nitrate 15g/Q sodium bicarbonate lOl/tartrate
30 l/sodium hydroxide 20113
8% formalin solution 10 (JrnQ/QpH: 1
1.5 The formed copper layer has a 25% OWr and a surface electrical resistance of 0.3 Ω/cm or less, indicating a good metal film, confirming that the method according to the present invention is extremely effective. Ta.
比較例j
実施例Iと同様にして脱脂、精錬、ヒートセットしたポ
リエステルフィラメント紗を、ポリエステル系樹脂(フ
ァインテックスES−850:大日本インキ製)50重
量部、メラミン樹脂(ベッカミンPM−N、大日本イン
キ製)2重量部、触媒(キャタリストES−2;大日本
インキ製)0゜5重量部、水948重量部を均一に混合
した水溶液に25°Cで1分間浸漬し、絞液乾燥後、1
000Cで3分間熱込理を行った。Comparative Example J A polyester filament gauze that had been degreased, refined, and heat set in the same manner as in Example I was mixed with 50 parts by weight of a polyester resin (Finetex ES-850, manufactured by Dainippon Ink) and a melamine resin (Beccamin PM-N, Dai Nippon Ink). 2 parts by weight of catalyst (Catalyst ES-2; manufactured by Dainippon Ink), 0.5 parts by weight of catalyst (Catalyst ES-2; manufactured by Dainippon Ink), and 948 parts by weight of water were immersed at 25°C for 1 minute, then squeezed and dried. After, 1
Heat treatment was performed at 000C for 3 minutes.
その後、実施例1と同様の条件下で無電解メッキ浴に2
8℃で5分間浸漬したが、部分的に斑状の銅膜を析出し
たのみであった。Then, under the same conditions as in Example 1, 2
Although it was immersed at 8° C. for 5 minutes, only a patchy copper film was deposited on some parts.
形成された銅膜の量は8%OWfに過ぎず、表面電気抵
抗は108Ω/ c m以上の不良導体であつt二 。The amount of copper film formed was only 8% OWf, and the surface electrical resistance was 108 Ω/cm or more, making it a poor conductor.
実施例2
ポリ塩化ビニリデンフィラメントメツシュ(糸径0.1
mm、60メツ7ユ/インチ)をノニオン界面活性剤(
メイセリンX0−7 、凹成化学製)5g/(l水溶液
中にて40°Cで、60分間脱脂、精練、水洗、乾燥し
た。Example 2 Polyvinylidene chloride filament mesh (thread diameter 0.1
mm, 60 mm, 7 units/inch) with a nonionic surfactant (
Degreasing, scouring, washing with water, and drying were carried out for 60 minutes at 40° C. in a 5 g/(l aqueous solution of Meiselin X0-7, manufactured by Okusei Kagaku).
その後、ポリエステル系ウレタン樹脂(ハイトランHW
−333;大日本インキ製)100重量部、ウレタン樹
脂(ハイトランAP−10;大日本インキ製)20重量
部、架橋剤(CR−5L;大日本インキ製)25重量部
、ポリアミン(ハイフィックス:大日本製薬製)1重量
部及び水954重量部の混合水溶液をスプレー法で均一
に塗布し40°Cで乾燥した。After that, polyester urethane resin (Hytran HW
-333; made by Dainippon Ink) 100 parts by weight, urethane resin (Hytran AP-10; made by Dainippon Ink) 20 parts by weight, crosslinking agent (CR-5L; made by Dainippon Ink) 25 parts by weight, polyamine (Hifix: A mixed aqueous solution of 1 part by weight (manufactured by Dainippon Pharmaceutical Co., Ltd.) and 954 parts by weight of water was uniformly applied by a spray method and dried at 40°C.
次いで、50°Cで4分間熱処理を行った後、無電解メ
ッキを行った。無電解メッキの条件は実施例1と同様で
あり、均一なメッキ膜が得られた。Next, heat treatment was performed at 50°C for 4 minutes, and then electroless plating was performed. The conditions for electroless plating were the same as in Example 1, and a uniform plating film was obtained.
メッキ銅膜の量は18%OWfであり、表面電気抵抗は
0.3Ω/ c mであり、良好な導電性金属皮膜であ
って、本発明による方法が効果のあることを確認した。The amount of the plated copper film was 18% OWf, and the surface electrical resistance was 0.3 Ω/cm, indicating a good conductive metal film and confirming that the method according to the present invention is effective.
比較例2
実施例2と同様に7ニオン界面活性剤(メイセリンxo
−7;凹成化学製)5g/+2水溶液中で脱脂、精練、
水洗後、乾燥した。Comparative Example 2 Same as Example 2, 7ionic surfactant (Meiselin xo
-7; Degreasing and scouring in a 5g/+2 aqueous solution
After washing with water, it was dried.
その後、実施例1と同様の無電解メッキ浴に10分間浸
漬したが、斑状の銅膜が形成された。形成された銅膜の
表面電気抵抗は1010Ω/ c m以上であり、不良
導体であった。Thereafter, it was immersed in the same electroless plating bath as in Example 1 for 10 minutes, but a patchy copper film was formed. The surface electrical resistance of the formed copper film was 1010 Ω/cm or more, and it was a poor conductor.
実施例3
ポリ塩化ビニルフイラメントメツンユ(糸径0.12m
m、50メツシュ/インチ)をノニオン界面活性剤(メ
イセリンX0−7 、凹成化学製)5g/Qの水溶液中
にて50°Cで60分間脱脂、精練、水洗後乾燥した。Example 3 Polyvinyl chloride filament yarn (thread diameter 0.12 m)
m, 50 mesh/inch) was degreased in an aqueous solution of 5 g/Q of a nonionic surfactant (Meiselin X0-7, manufactured by Tasei Kagaku) at 50°C for 60 minutes, scoured, washed with water, and then dried.
次に、ポリウレタン樹脂(ハイトランHW311:大日
本インキ製)+00:It量部、架橋剤(CR−5L
、大日本インキ製)3重量部、エチレンジアミンテトラ
酢酸ナトリイウム1重量部及び水896重量部の混合液
に、上記フィラメントメツンユを25°Cで1分間浸漬
し、乾燥し、50°Cで4分間熱処理後、無電解ニッケ
ルメッキを行った。Next, polyurethane resin (Hytran HW311: manufactured by Dainippon Ink) +00:It amount part, crosslinking agent (CR-5L)
, manufactured by Dainippon Ink), 1 part by weight of sodium ethylenediaminetetraacetate, and 896 parts by weight of water, the above filament Metsuyu was immersed at 25°C for 1 minute, dried, and dried at 50°C for 4 minutes. After heat treatment, electroless nickel plating was performed.
メッキ条件は次のとおりである。The plating conditions were as follows.
メッキ触媒として塩化パラジウム塩酸溶液(キャラリス
l−OPC80;奥野製薬製)50mQと塩酸160m
Q及び水790mQの混合液を調製しjこ 。As a plating catalyst, 50 mQ of palladium chloride hydrochloric acid solution (Calaris l-OPC80; manufactured by Okuno Pharmaceutical Co., Ltd.) and 160 m of hydrochloric acid were used.
Prepare a mixture of Q and 790 mQ of water.
先r:処理したポリ塩化ビニルメツシュを上記の溶液に
て25°Cで、2分間浸漬し、水洗した。First r: The treated polyvinyl chloride mesh was immersed in the above solution at 25°C for 2 minutes and washed with water.
次いで、硫酸50mQと水950rAQの混合液に45
°Cで3分間浸漬し、水洗し付着している硫酸等を除去
した。Next, add 45% to a mixture of 50 mQ of sulfuric acid and 950 rAQ of water.
It was immersed at °C for 3 minutes and washed with water to remove adhering sulfuric acid, etc.
その後、下記組成の無電解ニッケルメッキ浴に32°C
で、6分間浸漬した結果、均一なニッケル皮膜を形成す
ることができた。After that, it was placed in an electroless nickel plating bath with the following composition at 32°C.
After dipping for 6 minutes, a uniform nickel film could be formed.
析出したニッケルメッキ量は22%OW「で、表面電気
抵抗は2.2Ω/ c mであって、導電性は良好であ
り、本発明による方法が優れていることを確認した。The amount of nickel plating deposited was 22% OW, the surface electrical resistance was 2.2 Ω/cm, and the conductivity was good, confirming that the method according to the present invention is excellent.
ニッケルメッキ浴組成:
次亜リン酸ニッケル 28g/Qホウ酸
12tt硫酸アンモニウム
3 tt酢酸ナトリウム 5
ttpH:6.0
比較例3
実施例3と同様にして、脱し・精練したポリ塩化ビニル
フィラメント紗をポリウレタン樹脂()1イドランHW
−311;大日本インキ製)100重量部、架橋剤(C
R−5L;大日本インキ製)3重量部及び水897重量
部の混合液に25°Cで1分間浸漬し、乾燥し、50°
Cで4分間熱処理後、実施例3と同様の条件下に無電解
ニッケル浴に15分間浸漬したが、部分的にニッケルメ
ッキ層が析出したのみで、表面電気抵抗は10”Ω/
c m以上で不良導体であった。Nickel plating bath composition: Nickel hypophosphite 28g/Q boric acid
12tt ammonium sulfate
3 tt Sodium acetate 5
ttpH: 6.0 Comparative Example 3 In the same manner as in Example 3, polyvinyl chloride filament gauze which had been removed and refined was treated with polyurethane resin () 1 idran HW.
-311; manufactured by Dainippon Ink) 100 parts by weight, crosslinking agent (C
R-5L (manufactured by Dainippon Ink) and 897 parts by weight of water at 25°C for 1 minute, dried, and 50°
After heat treatment at C for 4 minutes, it was immersed in an electroless nickel bath for 15 minutes under the same conditions as in Example 3, but a nickel plating layer was only partially deposited, and the surface electrical resistance was 10"Ω/
cm or more, it was a poor conductor.
実施例4
ポリエステルフィラメント紗(糸径40ミクロン、13
5メツシュ/インチ)をノニオン界面活性剤(メイセリ
ンX0−7 ;凹成化学製)5g/Q水溶液中にて50
°Cで30分間脱脂、精練、水洗後、乾燥した。Example 4 Polyester filament gauze (thread diameter 40 microns, 13
5 mesh/inch) in a 5 g/Q aqueous solution of a nonionic surfactant (Meiselin
After degreasing at °C for 30 minutes, scouring, washing with water, and drying.
次に、ポリウレタン樹脂()1イドランAP−40;大
日本インキ製)80重量部、メラミン樹脂(ベッカミン
PM−N 、大日本インキ製)5重量部、触媒(キャタ
リストES−2;大日本インキ製)2重量部、コハク酸
イミド3重量部及び水850重量部とアルコール60重
量部の混合物溶液に上記処理したポリエステル紗を25
°Cで、1分間浸漬し、絞液、乾燥した。Next, 80 parts by weight of polyurethane resin (1 Idran AP-40; manufactured by Dainippon Ink), 5 parts by weight of melamine resin (Beccamin PM-N, manufactured by Dainippon Ink), and a catalyst (Catalyst ES-2; manufactured by Dainippon Ink) were added. 25 parts by weight of the above-treated polyester gauze was added to a mixture solution of 2 parts by weight of succinimide, 850 parts by weight of water, and 60 parts by weight of alcohol.
It was soaked for 1 minute at °C, squeezed out, and dried.
次いで、実施例1と同じ条件下に触媒付与、活性化後、
無電解銅メッキ浴に28°Cで2分間浸漬して均一な銅
メッキ膜を形成した。Next, after applying and activating a catalyst under the same conditions as in Example 1,
A uniform copper plating film was formed by immersing it in an electroless copper plating bath at 28°C for 2 minutes.
析出した銅層は28%OWfで、表面電気抵抗は0.2
Ω/ c m以下であって良好な金属皮膜であり、本発
明の方法が極めて効果のあることを確認した。The deposited copper layer has a 28% OWf and a surface electrical resistance of 0.2
It was confirmed that the method of the present invention was extremely effective as it was a good metal film with a resistance value of Ω/cm or less.
比較例4
実施例4で減量処理したポリエステル紗を、ポリウレタ
ン樹脂(ハイトランAP−40;大日本インキ製)80
重量部、メラミン樹脂(ベッカミンPM−N :大日本
インキ製)5重量部、触媒(キャタリストES−2;大
日本インキ製)2重量部、水850重量部及びアルコー
ル60重量部の混合溶液に25°Cで、1分間浸漬し、
絞液、乾燥後、100°Cで5分間熱処理した。Comparative Example 4 The polyester gauze subjected to the weight loss treatment in Example 4 was treated with polyurethane resin (Hytran AP-40; manufactured by Dainippon Ink) 80
parts by weight, 5 parts by weight of melamine resin (Beccamin PM-N, manufactured by Dainippon Ink), 2 parts by weight of catalyst (Catalyst ES-2; manufactured by Dainippon Ink), 850 parts by weight of water, and 60 parts by weight of alcohol. Soak at 25°C for 1 minute,
After squeezing and drying, it was heat-treated at 100°C for 5 minutes.
実施例1と同じ無電解メッキ条件下に無電解銅メッキ浴
に28°Cで5分間浸漬した結果、均一な銅メツキ皮膜
が形成された。As a result of immersion in an electroless copper plating bath at 28° C. for 5 minutes under the same electroless plating conditions as in Example 1, a uniform copper plating film was formed.
メッキ金属皮膜の密着強さを実施例4の製品と比較例4
の製品について比べた結果は、下記表=1のとおりであ
り、本発明の方法の製品の方が密着強さが優れていた。The adhesion strength of the plated metal film was compared to the product of Example 4 and Comparative Example 4.
The results of the comparison of the products are shown in Table 1 below, and the product produced by the method of the present invention had better adhesion strength.
く測定方法〉
学振式摩擦試験: JIS L 0849荷重200g
で50回摩擦した。Measurement method> Gakushin friction test: JIS L 0849 load 200g
I rubbed it 50 times.
セロハンテープ法二市販のセロハンテープを5〜7cm
にカットし、試験面に強く圧
着する。Cellophane tape method 2 Commercially available cellophane tape 5-7cm long
Cut it and firmly press it to the test surface.
10分後、そのセロハンチープラー気 に剥離し、セロハンテープの転写の度 合いを評価した。After 10 minutes, that cellophane cheap plastic Peel off and transfer cellophane tape each time The fit was evaluated.
Claims (1)
形成する方法において、無電解メッキに先立ち、該合成
樹脂構造物の金属被膜を形成すべき表面に、塩基性窒素
含有化合物を含有した樹脂バインダーを付着せしめるこ
とを特徴とする合成樹脂構造物表面の金属被覆方法。In a method of forming a metal film on the surface of a synthetic resin structure by electroless plating, prior to electroless plating, a resin binder containing a basic nitrogen-containing compound is applied to the surface of the synthetic resin structure on which the metal film is to be formed. 1. A method for coating a surface of a synthetic resin structure with metal, the method comprising: adhering metal to the surface of a synthetic resin structure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11869189A JPH02301568A (en) | 1989-05-15 | 1989-05-15 | Method for coating synthetic resin structure with metal |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11869189A JPH02301568A (en) | 1989-05-15 | 1989-05-15 | Method for coating synthetic resin structure with metal |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02301568A true JPH02301568A (en) | 1990-12-13 |
Family
ID=14742785
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11869189A Pending JPH02301568A (en) | 1989-05-15 | 1989-05-15 | Method for coating synthetic resin structure with metal |
Country Status (1)
Country | Link |
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JP (1) | JPH02301568A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016079230A1 (en) * | 2014-11-20 | 2016-05-26 | Solvay Specialty Polymers Italy S.P.A. | Multi-layered elastomer article and method for making the same |
CN105671526A (en) * | 2016-01-22 | 2016-06-15 | 卓达新材料科技集团有限公司 | Polymer material plated with metal film |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5420654A (en) * | 1977-07-15 | 1979-02-16 | Mitsubishi Electric Corp | Series-connection device for thyristor |
JPS5420656A (en) * | 1977-07-15 | 1979-02-16 | Matsushita Electric Ind Co Ltd | Hot cathode |
JPS63111180A (en) * | 1986-10-27 | 1988-05-16 | インタ−ナショナル・ビジネス・マシ−ンズ・コ−ポレ−ション | Substrate conditioning method for electroless plating |
JPH01215983A (en) * | 1987-12-23 | 1989-08-29 | Basf Ag | Polymer state control agent for pretreatment of non-metal surface for chemical plating |
-
1989
- 1989-05-15 JP JP11869189A patent/JPH02301568A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5420654A (en) * | 1977-07-15 | 1979-02-16 | Mitsubishi Electric Corp | Series-connection device for thyristor |
JPS5420656A (en) * | 1977-07-15 | 1979-02-16 | Matsushita Electric Ind Co Ltd | Hot cathode |
JPS63111180A (en) * | 1986-10-27 | 1988-05-16 | インタ−ナショナル・ビジネス・マシ−ンズ・コ−ポレ−ション | Substrate conditioning method for electroless plating |
JPH01215983A (en) * | 1987-12-23 | 1989-08-29 | Basf Ag | Polymer state control agent for pretreatment of non-metal surface for chemical plating |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016079230A1 (en) * | 2014-11-20 | 2016-05-26 | Solvay Specialty Polymers Italy S.P.A. | Multi-layered elastomer article and method for making the same |
CN105671526A (en) * | 2016-01-22 | 2016-06-15 | 卓达新材料科技集团有限公司 | Polymer material plated with metal film |
CN105671526B (en) * | 2016-01-22 | 2018-05-22 | 卓达新材料科技集团有限公司 | A kind of polymer material of metal-coated membrane |
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