JPS62170483A - Plating treatment of polyamide resin molding - Google Patents
Plating treatment of polyamide resin moldingInfo
- Publication number
- JPS62170483A JPS62170483A JP984986A JP984986A JPS62170483A JP S62170483 A JPS62170483 A JP S62170483A JP 984986 A JP984986 A JP 984986A JP 984986 A JP984986 A JP 984986A JP S62170483 A JPS62170483 A JP S62170483A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- polyamide resin
- treatment
- post
- molded product
- 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.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 53
- 238000011282 treatment Methods 0.000 title claims abstract description 46
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 28
- 238000000465 moulding Methods 0.000 title abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 75
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000005530 etching Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000009713 electroplating Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 9
- -1 palladium ions Chemical class 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 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 claims 1
- 230000033444 hydroxylation Effects 0.000 claims 1
- 238000005805 hydroxylation reaction Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000004913 activation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000001680 brushing effect Effects 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- 239000000378 calcium silicate Substances 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の技術分野］
本発明は、ポリアミド樹脂成形品のめつき処理方法に関
し、さらに詳しくは、美しい光沢と優れた表面平滑性を
有し、被めっき体表面との密着性が優れためっきをポリ
アミド樹脂成形品に施す方法に関する。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for plating polyamide resin molded articles, and more specifically, it has beautiful gloss and excellent surface smoothness, and has a good bond with the surface of the object to be plated. This invention relates to a method for applying plating with excellent adhesion to polyamide resin molded products.
［発明の技術的背景およびその問題点］従来、めっき処
理されたプラスチック成形品は、金属の代わりに、主に
装飾品として使用されているが、近年、装飾品以外の、
良好な機械的性質、耐熱性および耐候性などの実用特性
が要求される分野においても、金属の代わりに用いられ
ている。後者の、実用特性が要求される分野の具体的製
品には、例えば、自動車のナンバープレートホルダー、
ミラーホルダー、ドアハンドル、高速プリンターの活字
などがある。[Technical background of the invention and its problems] Conventionally, plated plastic molded products have been mainly used as decorative items instead of metal, but in recent years, they have been used for purposes other than decorative items.
They are also used in place of metals in areas where practical properties such as good mechanical properties, heat resistance and weather resistance are required. Specific products in the latter field that require practical characteristics include, for example, automobile license plate holders,
Items include mirror holders, door handles, and high-speed printer type.
めっき処理用のプラスチック成形品としては、ＡＢＳ（
アクリロニトリルーブタジエンースチレン）樹脂成形品
が最も広くかつ多量に使用されているが、ＡＢＳ樹脂成
形品は、その素材の特性から、前述した実用特性が厳し
く要求される用途には、おのずから制限がある０例えば
、自動車の軽量化、材料およびその加工コストの低減に
対する要求が高まり、金属部品の樹脂化が進められてい
るが、優れた金属光沢に加えて、良好な機械的強度、耐
熱性、耐候性が要求される金属部品には、ＡＢＳ樹脂成
形品で代替できないものが相当残されている。ABS (ABS) is a plastic molded product for plating treatment.
Acrylonitrile-butadiene-styrene (acrylonitrile-butadiene-styrene) resin molded products are the most widely used and in large quantities, but due to the characteristics of the material, ABS resin molded products naturally have limitations in applications that require the above-mentioned practical properties. 0 For example, there is an increasing demand for lighter automobiles and lower material and processing costs, and metal parts are being made of resin. There are still quite a few metal parts that require high performance that cannot be replaced with ABS resin molded products.
これらＡＢＳ樹脂成形品では代替できない分野において
、種々の機械的特性、耐熱性、耐候性、寸法安定性など
がＡＢＳ樹脂より優れたポリアミド樹脂製のめっき処理
成形品が注目され、めっき処理技術にも改良が加えられ
、現在、自動車のホイールキャップ、単車のエアーバル
ブキャップなどに実用化されている。In these fields where ABS resin molded products cannot be substituted, plated molded products made of polyamide resin, which are superior to ABS resin in various mechanical properties, heat resistance, weather resistance, dimensional stability, etc., are attracting attention, and plating technology is also increasing. Improvements have been made to this product, and it is now being put into practical use in automobile hubcaps, motorcycle air valve caps, etc.
ポリアミド樹脂のめっき処理は、通常法に示すような一
連の単位処理工程を経て行われている（工業材料、第３
１巻、第３号、第４６頁、１９８２年）。Plating of polyamide resin is carried out through a series of unit processing steps as shown in the normal method (industrial materials, 3rd process).
1, No. 3, p. 46, 1982).
↓（脱 脂）
↓ 水 洗
↓ 水 洗
↓ 水 洗
上記した一連の単位処理工程のうち、エツチング工程お
よびポストエツチング工程は、成形品表面を塩酸などの
酸によって処理することにより、いわゆる四肢を生じせ
しめ、投錨効果によりめっき被膜と成形品表面との密着
性を高めるために行われる。↓ (Degreasing) ↓ Washing with water ↓ Washing with water ↓ Washing with water Among the above-mentioned series of unit processing processes, the etching process and post-etching process produce so-called limbs by treating the surface of the molded product with an acid such as hydrochloric acid. This is done to increase the adhesion between the plating film and the surface of the molded product due to the anchoring effect.
次のキャタリスト（触媒化）工程は、後工程の化学めっ
きを施す際に必要な触媒であるパラジウムおよび錫イオ
ンを成形品表面に吸着させる工程である。The next catalyst step is a step in which palladium and tin ions, which are necessary catalysts for chemical plating in the subsequent step, are adsorbed onto the surface of the molded product.
わ°ｄ〈アクセレータ処理工程は、成形品表面に吸着さ
れた過剰の錫イオンを除去し、パラジウムイオンの還元
を行う工程であるが、ポリアミド樹脂はＡＢＳ樹脂に比
べて錫イオンの吸着量がかなり多くなり、通常、硫酸を
用いるアクセレータ処理工程だけでは、錫イオンの除去
を完全に行うことが困難である。したがって、ポストア
クセレータ処理工程においては、水酸化ナトリウム水溶
液による処理によって、錫イオンの除去が行われる。The accelerator treatment process removes excess tin ions adsorbed on the surface of the molded product and reduces palladium ions, but polyamide resin has a much higher adsorption amount of tin ions than ABS resin. Usually, it is difficult to completely remove tin ions only by an accelerator treatment step using sulfuric acid. Therefore, in the post-accelerator treatment step, tin ions are removed by treatment with an aqueous sodium hydroxide solution.
また、このポストアクセレータ処理工程によって、錫が
除去されると同時に、成形品の表面層の醜が中和される
。Moreover, this post-accelerator treatment step removes tin and at the same time neutralizes the unsightliness of the surface layer of the molded article.
ポストアクセレータ処理工程を経た成形品は。Molded products that have undergone the post-accelerator treatment process.
常法に従って化学めっき処理に付され、銅、ニッケル等
のめっき皮膜が形成され、これを電極として常法により
電気めっきが行われる。It is subjected to chemical plating treatment according to a conventional method to form a plating film of copper, nickel, etc., and electroplating is performed by a conventional method using this as an electrode.
しかしながら、従来のポストアクセレータ処理工程にお
ける処理では、樹脂成形品表面の錫の除去および表面層
の酸の中和が充分ではなく、最終的にポリアミド樹脂成
形品にめっきを施した場合、そのめっき面にいわゆるブ
ツ（小突起）が多発することによる表面平滑性の不足、
ピットおよびスターダストの発生による光沢の低下なら
びに樹脂成形品表面とめっき面との密着性の低下による
めっきの剥離等の問題が生じている。また、これらの問
題は、ポストアクセレータ工程後の水洗処理が不充分で
ある場合にも生じる。これらの問題は、化学めっき工程
後のブラッシング処理により改善されるものの、このブ
ラッシング処理には多大な労力と時間を要し、生産性の
低下を招く原因となっている。However, in the conventional post-accelerator treatment process, the removal of tin from the surface of the resin molded product and the neutralization of the acid in the surface layer are not sufficient, and when the polyamide resin molded product is finally plated, the plating surface Lack of surface smoothness due to frequent occurrence of so-called bumps (small protrusions),
Problems such as a decrease in gloss due to the generation of pits and stardust and peeling of the plating due to a decrease in adhesion between the surface of the resin molded product and the plated surface have occurred. These problems also occur when the water washing treatment after the post-accelerator step is insufficient. Although these problems can be improved by brushing treatment after the chemical plating process, this brushing treatment requires a great deal of labor and time, causing a decrease in productivity.
［発明の目的］
本発明の目的は、上記の問題点を解消し、ポリアミド樹
脂成形品表面に、美しい光沢と優れた表面平滑性を有し
、成形品表面との密着性が優れためっきを施すことがで
きるポリアミド樹脂成形品のめっき処理方法を提供する
ことである。[Object of the Invention] The object of the present invention is to solve the above-mentioned problems and to provide plating on the surface of a polyamide resin molded product that has beautiful gloss, excellent surface smoothness, and has excellent adhesion to the surface of the molded product. An object of the present invention is to provide a method for plating a polyamide resin molded product.
［発明の概要］
木発明者らは上記の目的を達成するこだめに鋭意研究を
行った結果、ポリアミド樹脂成形品にめっきを施すため
の一連の工程の中において、水酸化ナトリウム水溶液に
よるポストアクセレータ処理およびそれに続く水洗の条
件を特定することによって、化学めっき工程を経て最終
的に電算めっきを行った場合に、美しい光沢および優れ
た表面平滑性を有し、成形品との高い密着性を有するめ
っきを施すことができることを見い出し、本発明を完成
するに到った。[Summary of the invention] As a result of intensive research aimed at achieving the above object, the inventors discovered that a post-accelerator using an aqueous sodium hydroxide solution was used in a series of processes for plating polyamide resin molded products. By specifying the treatment and subsequent water washing conditions, when the chemical plating process is followed by computerized plating, it has beautiful gloss, excellent surface smoothness, and high adhesion to molded products. It was discovered that plating can be applied, and the present invention was completed.
すなわち本発明のポリアミド樹脂成形品のめっき方法は
、エツチング工程およびポストエツチング工程を経てポ
リアミド樹脂成形品の表面をエンチングしたのち、パラ
ジウムイオンおよび錫イオンを含む溶液を用いて該表面
の触媒化を行い、次に、酸を用いるアクセレータ処理工
程および水酸化ナトリウム溶液を用いるポストアクセレ
ータ処理工程により触媒の活性化を行い、しかるのち、
化学めっき工程および電気めっき工程によってポリアミ
ド樹脂成形品にめっきを施す方法であって、該ポストア
クセレータ処理工程において、１０〜３０ｇ／ｌの水酸
化ナトリウム水溶液を用いて、２０〜４５℃で２〜８分
間処理したのち５０〜１００℃で３〜１２分間湯洗する
が、あるいは、２０〜ｓｏｇ／ｌの水酸化ナトリウム水
溶液を用いて、５０〜８０℃の温度で、３〜１０分間処
理したのち水洗することを特徴とする。That is, the method for plating polyamide resin molded products of the present invention involves etching the surface of the polyamide resin molding through an etching process and a post-etching process, and then catalyzing the surface using a solution containing palladium ions and tin ions. , then the catalyst is activated by an accelerator treatment step using an acid and a post-accelerator treatment step using a sodium hydroxide solution;
A method of plating a polyamide resin molded article by a chemical plating process and an electroplating process, the post-accelerator treatment process using a 10-30 g/l sodium hydroxide aqueous solution at 20-45°C. After treatment for 3 to 12 minutes at 50 to 100°C, wash with hot water, or alternatively, use a 20 to sog/l aqueous sodium hydroxide solution at 50 to 80°C for 3 to 10 minutes, then wash with water. It is characterized by
本発明のめっき処理方法は、ポリアミド樹脂成形品に適
用されるが、めっき処理されるポリアミド樹脂としては
、例えば、ε−カプロラクタム、アミノカプロン酸、ω
−ラウリンラクタム、１１−アミノウンデカン酸などの
重合体：ヘキサメチレンジアミン、ノナメチレンジアミ
ン、ウンデカメチレンジアミン、ドデカメチレンジアミ
ンなどのジアミンと、アジピン酸、セパチン酸などのジ
カルボン酸とを重縮合して得られる重合体；これらの七
ツマ−の共重合体などを挙げることができる。さらに、
上記のポリアミドと他の熱可塑性樹脂、例えばポリエチ
レン、ポリプロピレン、ＡＢ ５４ａ（脂との配合物も
、本発明におけるポリアミド樹脂に包含される。配合さ
れる熱可塑性樹脂の割合は、上記したポリアミド１００
重量部に対し、通常１００重量部以下、好ましくは５０
重量部以下である。The plating method of the present invention is applied to polyamide resin molded articles. Examples of polyamide resins to be plated include ε-caprolactam, aminocaproic acid, ω
- Polymers such as laurin lactam and 11-aminoundecanoic acid: Polycondensation of diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, and dodecamethylene diamine with dicarboxylic acids such as adipic acid and sepatic acid. Obtained polymers include copolymers of these heptads. moreover,
Blends of the above polyamides with other thermoplastic resins, such as polyethylene, polypropylene, AB 54a (fat), are also included in the polyamide resins of the present invention.The ratio of the thermoplastic resins blended is as follows:
Usually 100 parts by weight or less, preferably 50 parts by weight
Parts by weight or less.
また、本発明のポリアミド樹脂には、めっき性能、特に
密着性を高める目的で適当な無機質充填材を含有せしめ
ることができる。このような無機質充填材としては、例
えば、タルク、カオリン、ケイ酸カルシウム、）父酸カ
ルシウム、アルミナ、シリカ、酸化チタン、フェライト
などの粉末、ガラス短繊維などを挙げることができる。Further, the polyamide resin of the present invention may contain an appropriate inorganic filler for the purpose of improving plating performance, particularly adhesion. Examples of such inorganic fillers include powders of talc, kaolin, calcium silicate, calcium silicate, alumina, silica, titanium oxide, and ferrite, and short glass fibers.
これらの無機質充填材のなかでもケイ酸カルシウム、タ
ルク、カオリン、酸化チタンの粉末が好ましい。粉末状
無機質充填材の粒径は通常０．２〜２０トであり、ガラ
ス短繊維の直径および長さは、通常、それぞれ６〜１３
体および３〜９１ｍ１＋である。Among these inorganic fillers, powders of calcium silicate, talc, kaolin, and titanium oxide are preferred. The particle size of the powdered inorganic filler is usually 0.2 to 20 tons, and the diameter and length of the short glass fibers are usually 6 to 13 tons, respectively.
body and 3 to 91 m1+.
無機質充填材の配合割合は、ポリアミド１００重量部当
り１０〜５０重量部である。無機質充填材の配合割合が
上記下限未満であると、エツチング処理してもポリアミ
ド成形品の表面に形成される四肢が少ないため、ポリア
ミド樹脂成形品と金属被膜の密着力が大きいめっき製品
を与えることができない。無機質充填材の配合割合が上
記上限を超えると、ポリアミド樹脂に無機質充填材を配
合することが困難になり、さらに表面光沢の優れためっ
き製品を与えることができなくなる。The blending ratio of the inorganic filler is 10 to 50 parts by weight per 100 parts by weight of polyamide. If the blending ratio of the inorganic filler is less than the above lower limit, fewer limbs will be formed on the surface of the polyamide molded product even after etching treatment, thereby providing a plated product with high adhesion between the polyamide resin molded product and the metal coating. I can't. If the blending ratio of the inorganic filler exceeds the above upper limit, it becomes difficult to blend the inorganic filler into the polyamide resin, and furthermore, it becomes impossible to provide a plated product with excellent surface gloss.
本発明のポリアミド樹脂成形品には、耐熱剤、酸化防止
剤、滑剤などの添加剤を添加することができる。Additives such as a heat resistant agent, an antioxidant, and a lubricant can be added to the polyamide resin molded article of the present invention.
本発明のポリアミド樹脂は、任意の形状に成形したのち
、その表面にめっきを施すが、この成形には、公知の成
形方法、例えば射出成形、押出成形または圧縮成形方法
を適用することができる。After the polyamide resin of the present invention is molded into an arbitrary shape, the surface thereof is plated, and a known molding method such as injection molding, extrusion molding, or compression molding method can be applied to this molding.
また、成形後の形状は任意であり、使用目的に応じた形
状に成形することができる。Moreover, the shape after molding is arbitrary, and can be molded into a shape depending on the purpose of use.
このようにして得られたポリアミド樹脂成形品（以下、
単に「成形品」という）にめっき処理を行うが、めっき
工程（化学めっき工程および電気めっき工程）に到るま
での前処理工程は、ポストアクセレータ工程以外は、公
知の方法例えば前述した工業材料、第３１巻、第３号、
第４６頁、１９８２年に記載の方法を適用することがで
きる。また、本発明の方法においては、ポストエツチン
グ工程とキャタリスト工程の間にブリテップ工程を設け
ることもできる。このブリテップ工程の処理は、エッチ
クング処理後の不純物の除去およびキャタリスト工程前
の酸の緩和を目的として行うものであり、通常濃度４０
ｍ１／ｆＬの塩酸中、３０℃で４分間処理する。The polyamide resin molded product thus obtained (hereinafter referred to as
(simply referred to as a "molded product"), pretreatment steps before the plating process (chemical plating process and electroplating process), except for the post-accelerator process, are performed using known methods such as the above-mentioned industrial materials, Volume 31, No. 3,
46, 1982 can be applied. Further, in the method of the present invention, a britep step can be provided between the post-etching step and the catalyst step. This Britep process is carried out for the purpose of removing impurities after the etching process and relaxing the acid before the catalyst process, and usually has a concentration of 40%.
Treat in m1/fL hydrochloric acid at 30°C for 4 minutes.
本発明の方法は、その一連の工程中、ポストアクセレー
タ工程に特徴を有するもである。このポストアクセレー
タ工程は、前述したとおり、キャタリスト工程で成形品
表面に吸着された過剰の錫イオンを除去するとともに、
吸着されたパラジウムイオンを還元する。さらに、この
工程により、成形品表面に残留する酸が中和される。こ
れにより、のちに良好な化学めっきを施すことができる
。このポストアクセレータ工程における処理は、所定濃
度の水酸化ナトリウム水溶液中に成形品を所定温度で所
定時間浸漬することにより行う。The method of the present invention is characterized by a post-accelerator step among its series of steps. As mentioned above, this post-accelerator process removes excess tin ions adsorbed on the surface of the molded product during the catalyst process, and
Reduces adsorbed palladium ions. Furthermore, this step neutralizes the acid remaining on the surface of the molded article. This allows good chemical plating to be performed later. The treatment in this post-accelerator step is performed by immersing the molded article in an aqueous sodium hydroxide solution of a predetermined concentration at a predetermined temperature for a predetermined time.
本発明のポストアクセレータ処理工程は、従来から行わ
れている処理条件すなわち、水酸化ナトリウム水溶液の
濃度：１０〜３０ｇ／ｉ、好ましくは、１５〜２５ｇ／
見、温度：２０〜４５℃、好ましくは、２５〜４０℃、
時間＝２〜８分、好ましくは、３〜５分の条件下で処理
したのち。The post-accelerator treatment step of the present invention is carried out under conventional treatment conditions, i.e., concentration of sodium hydroxide aqueous solution: 10 to 30 g/i, preferably 15 to 25 g/i.
temperature: 20-45°C, preferably 25-40°C,
After treatment under conditions of time = 2 to 8 minutes, preferably 3 to 5 minutes.
５０〜１００℃、好ましくは、６０〜８０℃で３〜１２
分間、好ましくは５〜１０分間湯洗するか、あるいは２
０〜６０ｇ／文、好ましくは３０〜５０ｇ／ｌの水酸化
ナトリウム水溶液を用いて５０〜８０℃、好ましくは、
６０〜７０℃で３〜１０分間、好ましくは３〜５分間処
理したのち水洗することによって行われる。50-100°C, preferably 3-12°C at 60-80°C
2 minutes, preferably 5-10 minutes, or 2 minutes.
50-80° C., preferably using an aqueous sodium hydroxide solution of 0-60 g/l, preferably 30-50 g/l,
This is carried out by treating at 60 to 70°C for 3 to 10 minutes, preferably 3 to 5 minutes, and then washing with water.
上記の水酸化ナトリウム水溶液による低温処理後、高温
で湯洗を行う方法において、温度は非常に屯要である。In the method of performing hot water washing at a high temperature after the low-temperature treatment with an aqueous sodium hydroxide solution, the temperature is very important.
湯洗温度が５０℃未満であるとブツが発生し易くなり、
湯洗温度がｉｏｏ’ｃを超えると成形品表面の平滑性が
悪くなる。また、高温で水酸化ナトリウム水溶液を用い
て処理する方法において、その処理温度が５０’Ｃより
低温になるとブツが発生し易くなるために高温での湯洗
が必要になり、また８０’Ｃを超えると成形品表面が侵
されて粗くなりすぎ、のちのめっき処理に支障をきたす
。If the hot water washing temperature is less than 50℃, bumps are likely to occur.
If the hot water washing temperature exceeds ioo'c, the surface smoothness of the molded product will deteriorate. In addition, in the method of treatment using an aqueous sodium hydroxide solution at a high temperature, if the treatment temperature is lower than 50'C, lumps are likely to occur and hot water washing at a high temperature is required; If it is exceeded, the surface of the molded product will be attacked and become too rough, which will interfere with the plating process later.
高温において水酸化ナトリウム水溶液を用いて処理する
場合の水酸化ナトリウムの濃度が２０ｇ／立未満である
と、ブツが多発しやすく、めっき面の表面平滑性が損わ
れ、６０ ｇ／ｌを超えるとめっき面の光沢が低下する
。If the concentration of sodium hydroxide is less than 20g/liter when treating with an aqueous sodium hydroxide solution at high temperature, many bumps will occur and the surface smoothness of the plated surface will be impaired; if it exceeds 60g/l, The gloss of the plated surface decreases.
低温において水酸化ナトリウム水溶液で処理したのちに
行う湯洗時間については、３分未満であると、めっき面
の表面平滑性が損われ、１２分を超えると成形品が吸水
して、その表面がＷ潤し、めっきと成形品表面の密着性
が低下する。また、高温で水酸化ナトリウム水溶液を用
いて処理する場合の処理時間については、３分未満であ
ると、めっき面の表面平滑性が損われ、１０分を超える
と成形品が吸水して、その表面が膨潤し、めっきと成形
品表面の密着性が低下する。Regarding the hot water washing time after treatment with an aqueous sodium hydroxide solution at low temperatures, if it is less than 3 minutes, the surface smoothness of the plated surface will be impaired, and if it is more than 12 minutes, the molded product will absorb water and its surface will deteriorate. W moistens the surface and reduces the adhesion between the plating and the surface of the molded product. Regarding the treatment time when using a sodium hydroxide aqueous solution at high temperature, if the treatment time is less than 3 minutes, the surface smoothness of the plated surface will be impaired, and if the treatment time exceeds 10 minutes, the molded product will absorb water. The surface swells and the adhesion between the plating and the molded product surface decreases.
高温で水酸化ナトリウム水溶液を用いて処理を行ったの
ち、成形品表面を水洗する。上述の湯洗およびこの水洗
は、成形品表面に残留している水酸化ナトリウム水溶液
等を除去するために行うものである。After treatment with an aqueous sodium hydroxide solution at high temperature, the surface of the molded product is washed with water. The above-mentioned hot water washing and water washing are performed to remove the sodium hydroxide aqueous solution and the like remaining on the surface of the molded product.
このように、ポストアクセレータ処理において、湯洗も
しくは水洗を行った成形品に対して化学めっきを施す。In this way, in the post-accelerator process, chemical plating is applied to the molded product that has been washed with hot water or water.
この化学めっきは、成形品表面に導電性被膜を形成する
目的で行うものである。This chemical plating is performed for the purpose of forming a conductive film on the surface of the molded product.
この化学めっきには公知の方法、例えば特開昭５７−１
２３２３１号公報に記載の方法を適用することかでき、
通常銅もしくはニッケルめっきを行う。For this chemical plating, there are known methods such as JP-A-57-1.
The method described in Publication No. 23231 can be applied,
Usually copper or nickel plated.
化学めっきを行ったのち、水洗、乾燥、ストライクめっ
き等の処理を行うが、通常は必須の工程であるめっき面
のブラッシング処理は、本発明においては不要である。After chemical plating, treatments such as water washing, drying, and strike plating are performed, but brushing of the plated surface, which is normally an essential step, is not necessary in the present invention.
これは、湯洗または高温による水酸化ナトリウム水溶液
処理が成形品表面に対して適度な膨潤作用を及ぼし、こ
れがブラッシング処理と同じ効果を示すためである。次
いで電気めっきを行う。この電気めっきは、公知の方法
、例えば、特開昭５７−８２２８号公報に記載の方法を
適用することができる。また、この電気めっき工程では
、例えば銅、ニッケルおよびクロムをこの順序で、それ
ぞれ厚さ３０．１０および０．１５部程度に積層してな
るめっき層を形成させることによって、ブツの発生がよ
り少なく美しいめっき面を形成することができる。This is because hot water washing or high-temperature sodium hydroxide aqueous solution treatment exerts a moderate swelling effect on the surface of the molded product, which has the same effect as brushing treatment. Next, electroplating is performed. This electroplating can be performed by a known method, for example, the method described in Japanese Patent Application Laid-Open No. 57-8228. In addition, in this electroplating process, by forming a plating layer made by laminating copper, nickel, and chromium in this order to a thickness of about 30.10 parts and 0.15 parts, respectively, the occurrence of lumps can be reduced. A beautiful plating surface can be formed.
［発明の実施例］
以下、実施例および比較例を掲げ本発明をさらに詳述す
る。これらの例中、「部」はすべて「重量部」を表す。[Examples of the Invention] Hereinafter, the present invention will be further described in detail with reference to Examples and Comparative Examples. In these examples, all "parts" represent "parts by weight."
Ｌム血ユニ」
成形品材料として、ナイロン６（数平均分子量１３．０
００）１００部、ケイ酸カルシウム２０部および二酸化
チタン５部からなる組成物を使用した。この組成物を射
出成形機（日木製鋼株製、Ｎ１４０ＢＩＩ）によって、
射出圧６００ ｋｇ／ ｃｍ２で射出成形し、各実施例
においてそれぞれ４枚の長さ１２５ｍｍ、幅７５ｍｍ、
厚さ３ｍｍの平板状の成形品を製造した。この成形品に
対して常法により脱脂、エツチング、ポストエツチング
、プリテップ、キャタリストおよびアクセレータの各工
程の処理を行った。その後、水酸化ナトリウム水溶液を
用いて第１表に示す条件でポストアクセレータ処理を行
った。"L Mu Blood Uni" The molded product material is nylon 6 (number average molecular weight 13.0
00), 20 parts of calcium silicate and 5 parts of titanium dioxide was used. This composition was molded using an injection molding machine (manufactured by Nikki Steel Co., Ltd., N140BII).
Injection molding was carried out at an injection pressure of 600 kg/cm2, and in each example, each of the four pieces had a length of 125 mm, a width of 75 mm,
A plate-shaped molded product with a thickness of 3 mm was manufactured. This molded article was subjected to degreasing, etching, post-etching, pre-tipping, catalyst and accelerator processes in a conventional manner. Thereafter, post-accelerator treatment was performed using an aqueous sodium hydroxide solution under the conditions shown in Table 1.
第 １ 表
次いで水洗を行ない、その後常法により、銅およびニッ
ケルめっきを行った。次いで、常法により水洗、乾燥お
よび銅ストライクメッキを行ったのち、電気めっきを行
った。電気めっきは常法により、銅（厚さ３０用）、ニ
ッケル（１０Ｉｊ、）およびクロム（０，１５Ａ１．）
をこの順序で積層し、３層からなるメッキ層を形成した
。Table 1 Next, the sample was washed with water, and then copper and nickel plating was performed by a conventional method. Next, after washing with water, drying, and copper strike plating were performed by a conventional method, electroplating was performed. Electroplating was performed using a conventional method using copper (for thickness 30), nickel (10Ij,) and chromium (0,15A1.)
were laminated in this order to form a three-layer plating layer.
このようにして形成されためつき面は、美しい光沢を有
していた。また、各実施例で得られたそれぞれ４枚の成
形品のめつき面の平滑性および成形品表面とめっき面の
密着強度を下記の方法により測定した。結果を第３表お
よび第４表に示す。The stamped surface thus formed had a beautiful luster. In addition, the smoothness of the plated surface and the adhesion strength between the molded article surface and the plated surface of the four molded articles obtained in each example were measured by the following method. The results are shown in Tables 3 and 4.
平滑性は、図に示す１辺が２００１１１１の正方形中の
ブツの数を投影機によって計測した。密着強度は、電気
銅メンキまで処理した平板状成形品の金属皮膜に、幅１
ｃｍの短冊形の切り込みを入れ、その端片をインストロ
ン引張試験機のチャックに挟み、２０１１１Ｉｌｌ／分
の速度で引張ることによって測定した。The smoothness was determined by measuring the number of dots in a square with sides of 2001111 shown in the figure using a projector. The adhesion strength is determined by applying a width of 1.
Measurements were made by making a rectangular cut of cm in length, holding the end piece in the chuck of an Instron tensile tester, and pulling at a speed of 20111 Ill/min.
実」０江上
実施例１と同様の平板状の成形品を使用し、ポストアク
セレータ工程の処理条件を水酸化ナトリウム水溶液濃度
２０ｇ／文、温度４０’Ｃ，浸漬時間５分間とした以外
は実施例１と同様にしてめっきを行った。ただし、ポス
トアクセレータ処理後の水洗は、温度６０’Ｃの温水で
１０分間行った。Example 1 except that a plate-shaped molded product similar to Example 1 was used, and the post-accelerator process conditions were a sodium hydroxide aqueous solution concentration of 20 g/text, a temperature of 40'C, and a immersion time of 5 minutes. Plating was carried out in the same manner as in 1. However, the water washing after the post-accelerator treatment was performed with warm water at a temperature of 60'C for 10 minutes.
このようにして形成されためつき面は美しい光沢を有し
ていた。また、めっき面の平滑性および密着性について
実施例１と同様の方法で測定した。結果を第３表および
第４表に示す。The stamped surface thus formed had a beautiful luster. Further, the smoothness and adhesion of the plated surface were measured in the same manner as in Example 1. The results are shown in Tables 3 and 4.
よ狡輿」：」
実施例１と同様の上板状の成形品を使用し、水酸化ナト
リウム水溶液を用いたポストアクセレータ工程の処理条
件を第２表に示す条件にした以外は、実施例１と同様の
方法で成形品にめっきを行った。Example 1 except that the same plate-shaped molded product as in Example 1 was used and the treatment conditions for the post-accelerator step using an aqueous sodium hydroxide solution were as shown in Table 2. The molded product was plated in the same manner.
第２表
このようにして形成されためっき面は、光沢が充分では
なく、一部にくもりがあった。また。Table 2 The plated surface thus formed did not have sufficient gloss and was partly cloudy. Also.
めっき面の平滑性および密着性について実施例１と同様
の方法で測定した。結果を第３表および第４表に示す。The smoothness and adhesion of the plated surface were measured in the same manner as in Example 1. The results are shown in Tables 3 and 4.
［発明の効果］
以上の説明により明らかなとおり、本発明のめっき処理
方法によれば、美しい光沢を有し、また従来のめっき処
理法と比較してめっき面にブツの発生が少なく（第３表
参照）表面平滑性が優れためっきを形成することができ
る。さらに、形成されためっき面は、被めっき物である
成形品表面との密着性が良い（第４表参照）ことから、
さらに多くの用途への適用が可能となる。[Effects of the Invention] As is clear from the above explanation, the plating method of the present invention has a beautiful luster, and compared to conventional plating methods, there are fewer spots on the plating surface (third (See table) Can form plating with excellent surface smoothness. Furthermore, since the formed plated surface has good adhesion to the surface of the molded product to be plated (see Table 4),
Application to even more uses becomes possible.
また、本発明方法においては、従来化学めっき処理後に
不可欠であった、成形品表面のブラ、シノグ処理を省略
することができる。したがって、製造工程の簡略化、製
造蒔間の短縮化を図ることができる。Furthermore, in the method of the present invention, it is possible to omit the brushing and sinog treatment of the surface of the molded product, which was conventionally indispensable after chemical plating treatment. Therefore, the manufacturing process can be simplified and the manufacturing time can be shortened.
４ 図面のｌｉｉ ｒｌｉな説明
図はめっき後の成形品表面のブッの計測方法を説明する
図である。4 The lii rli explanatory diagrams in the drawings are diagrams illustrating a method for measuring the bulges on the surface of a molded product after plating.
Claims (1)
アミド樹脂成形品の表面をエッチングしたのち、パラジ
ウムイオンおよび錫イオンを含む溶液を用いて該表面の
触媒化を行い、次に、酸を用いるアクセレータ処理工程
および水酸化ナトリウム水溶液を用いるポストアクセレ
ータ処理工程により触媒の活性化を行い、しかるのち、
化学めっき工程および電気めっき工程によってポリアミ
ド樹脂成形品にめっきを施す方法であって、該ポストア
クセレータ処理工程において、１０〜３０ｇ／ｌの水酸
化ナトリウム水溶液を用いて、２０〜４５０℃で２〜８
分間処理したのち５０〜１００℃で３〜１２分間湯洗す
るか、あるいは、２０〜６０ｇ／ｌの水酸化ナトリウム
水溶液を用いて、５０〜８０℃の温度で、３〜１０分間
処理したのち水洗することを特徴とするポリアミド樹脂
成形品のめっき処理方法。After etching the surface of the polyamide resin molded product through an etching process and a post-etching process, the surface is catalyzed using a solution containing palladium ions and tin ions, and then an accelerator treatment process using acid and hydroxylation are performed. The catalyst is activated by a post-accelerator treatment step using an aqueous sodium solution, and then
A method of plating a polyamide resin molded article by a chemical plating process and an electroplating process, the post-accelerator treatment process using a 10 to 30 g/l aqueous sodium hydroxide solution at 20 to 450°C.
After treatment for 3 to 12 minutes at 50 to 100°C, or using a 20 to 60 g/l aqueous sodium hydroxide solution at 50 to 80°C for 3 to 10 minutes, then washing with water. A method for plating polyamide resin molded products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP984986A JPH0627350B2 (en) | 1986-01-22 | 1986-01-22 | Method for plating of polyamide resin molded products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP984986A JPH0627350B2 (en) | 1986-01-22 | 1986-01-22 | Method for plating of polyamide resin molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62170483A true JPS62170483A (en) | 1987-07-27 |
| JPH0627350B2 JPH0627350B2 (en) | 1994-04-13 |
Family
ID=11731580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP984986A Expired - Lifetime JPH0627350B2 (en) | 1986-01-22 | 1986-01-22 | Method for plating of polyamide resin molded products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0627350B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5279899A (en) * | 1992-03-17 | 1994-01-18 | Monsanto Company | Sulfonated polyamides |
| WO2001038604A1 (en) * | 1999-11-22 | 2001-05-31 | Learonal Japan Inc. | Accelerator solution for direct plating and method for direct plating |
| JP2002141226A (en) * | 2000-11-01 | 2002-05-17 | Murata Mfg Co Ltd | Electronic component and its manufacturing method |
| JP2006152337A (en) * | 2004-11-26 | 2006-06-15 | Okuno Chem Ind Co Ltd | Composition for etching resin molding |
-
1986
- 1986-01-22 JP JP984986A patent/JPH0627350B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5279899A (en) * | 1992-03-17 | 1994-01-18 | Monsanto Company | Sulfonated polyamides |
| WO2001038604A1 (en) * | 1999-11-22 | 2001-05-31 | Learonal Japan Inc. | Accelerator solution for direct plating and method for direct plating |
| JP2001214278A (en) * | 1999-11-22 | 2001-08-07 | Learonal Japan Inc | Accelerator bath solution for direct plating and direct plating method |
| JP4646376B2 (en) * | 1999-11-22 | 2011-03-09 | 日本リーロナール有限会社 | Accelerator bath solution for direct plating and direct plating method |
| JP2002141226A (en) * | 2000-11-01 | 2002-05-17 | Murata Mfg Co Ltd | Electronic component and its manufacturing method |
| JP2006152337A (en) * | 2004-11-26 | 2006-06-15 | Okuno Chem Ind Co Ltd | Composition for etching resin molding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0627350B2 (en) | 1994-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4349421A (en) | Preparation of metal plated polyamide thermoplastic articles having mirror-like metal finish | |
| JP5969053B2 (en) | Aluminum alloy resin composite and preparation method thereof | |
| JP5869153B2 (en) | Method for preparing aluminum alloy resin composite and aluminum alloy resin composite obtained thereby | |
| KR102587634B1 (en) | Method for overmolding plastic onto metal surfaces and plastic-metal hybrid parts | |
| JPH0151545B2 (en) | ||
| JP7480450B2 (en) | Method for overmolding plastic onto metal surfaces and plastic-metal hybrid parts | |
| JP6002683B2 (en) | Molded part for slide fastener and slide fastener having the same | |
| US20110135949A1 (en) | Metal-Coated Plastic Articles and Methods Therefor | |
| US4452858A (en) | Production of plated shaped product of polyamide | |
| JPS62170483A (en) | Plating treatment of polyamide resin molding | |
| WO2012047454A1 (en) | Process for surface preparation of polyamide articles for metal-coating | |
| US3686017A (en) | Surface treatment of nylon shaped articles with aqueous reducing agents | |
| US4444836A (en) | Metal plated polyamide articles | |
| US20040228971A1 (en) | Modified polyacetals for decorative applications | |
| EP1636297B1 (en) | Modified polyacetals for plating | |
| JPH0220708B2 (en) | ||
| JP6810576B2 (en) | Manufacturing method of plated molded product | |
| JPS60155680A (en) | Pretreatment of molded article of polyamide resin before plating | |
| JPS63149384A (en) | Method for plating polyamide resin | |
| EP3389976B1 (en) | Process for plastic overmolding on a metal surface and plastic-metal hybrid part | |
| JPS6238374B2 (en) | ||
| JPH0364333A (en) | Method for surface treatment of molding based on polyamide | |
| JPS587655B2 (en) | Etching method for polyamide molded products | |
| JPS584733B2 (en) | Method of plating polyacetal resin | |
| JPS63118342A (en) | Molded article of adherent polyphenylene sulfide resin |