JP5364237B2 - Plating resin molding - Google Patents
Plating resin molding Download PDFInfo
- Publication number
- JP5364237B2 JP5364237B2 JP2007017464A JP2007017464A JP5364237B2 JP 5364237 B2 JP5364237 B2 JP 5364237B2 JP 2007017464 A JP2007017464 A JP 2007017464A JP 2007017464 A JP2007017464 A JP 2007017464A JP 5364237 B2 JP5364237 B2 JP 5364237B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- mass
- molded body
- plating
- component
- 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.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 131
- 239000011347 resin Substances 0.000 title claims abstract description 131
- 238000007747 plating Methods 0.000 title claims abstract description 85
- 238000000465 moulding Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011342 resin composition Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 22
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 20
- 239000000057 synthetic resin Substances 0.000 claims abstract description 20
- 238000010521 absorption reaction Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 238000005530 etching Methods 0.000 claims description 11
- 238000000691 measurement method Methods 0.000 claims description 9
- 238000009832 plasma treatment Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- -1 polypropylene Polymers 0.000 description 45
- 230000008569 process Effects 0.000 description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000178 monomer Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000011256 inorganic filler Substances 0.000 description 10
- 229910003475 inorganic filler Inorganic materials 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000005238 degreasing Methods 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920006122 polyamide resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000012765 fibrous filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- RHYBFKMFHLPQPH-UHFFFAOYSA-N N-methylhydantoin Chemical compound CN1CC(=O)NC1=O RHYBFKMFHLPQPH-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920000577 Nylon 6/66 Polymers 0.000 description 2
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
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- 239000000835 fiber Substances 0.000 description 2
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- 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
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- NEXZVOLIDKSFBH-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(COP(O)(O)=O)(OC(=O)C(=C)C)C1=CC=CC=C1 NEXZVOLIDKSFBH-UHFFFAOYSA-N 0.000 description 1
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
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- QLORRTLBSJTMSN-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C QLORRTLBSJTMSN-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
Description
本発明は、めっき強度が高く、外観が美しいめっき樹脂成形体、前記めっき樹脂成形体に使用する樹脂成形体の製造方法、めっき樹脂成形体の製造方法に関する。 The present invention relates to a plated resin molded article having high plating strength and a beautiful appearance, a method for producing a resin molded article used for the plated resin molded article, and a method for producing a plated resin molded article.
自動車を軽量化する目的から、自動車部品としてABS樹脂やポリアミド樹脂等の樹脂成形体が使用されており、この樹脂成形体に高級感や美感を付与するため、銅、ニッケル等のめっきが施されている。 For the purpose of reducing the weight of automobiles, resin molded products such as ABS resin and polyamide resin are used as automotive parts, and copper, nickel, etc. are plated to give this resin molded product a high-class feeling and beauty. ing.
従来、ABS樹脂等の成形体にめっきを施す場合、樹脂成形体とめっき層との密着強度を高めるため、脱脂工程の後に樹脂成形体を粗面化するエッチング工程が必須である。例えば、ABS樹脂成形体やポリプロピレン成形体をめっきする場合、脱脂処理の後に、クロム酸浴(三酸化クロム及び硫酸の混液)を用い、65〜70℃、10〜15分でエッチング処理する必要があり、廃水には有毒な6価のクロム酸イオンが含まれる。このため、6価のクロム酸イオンを3価のイオンに還元した後に中和沈殿させる処理が必須となり、廃水処理時の問題がある。 Conventionally, when plating is performed on a molded body such as an ABS resin, an etching process for roughening the resin molded body after the degreasing process is essential in order to increase the adhesion strength between the resin molded body and the plating layer. For example, when plating an ABS resin molded body or a polypropylene molded body, it is necessary to perform an etching treatment at 65 to 70 ° C. for 10 to 15 minutes using a chromic acid bath (mixed solution of chromium trioxide and sulfuric acid) after the degreasing treatment. Yes, wastewater contains toxic hexavalent chromate ions. For this reason, the process of neutralizing and precipitating the hexavalent chromate ions after reducing them to trivalent ions is essential, and there is a problem during wastewater treatment.
このように現場での作業時の安全性や廃水による環境への影響を考慮すると、クロム酸浴を使用したエッチング処理をしないことが望ましいが、その場合には、ABS樹脂等から得られる成形体へのめっき層の密着強度を高めることができないという問題がある。 In this way, in consideration of safety during work in the field and the environmental impact of wastewater, it is desirable not to perform etching using a chromic acid bath, but in that case, a molded body obtained from ABS resin or the like There is a problem that the adhesion strength of the plating layer to the surface cannot be increased.
特許文献1〜3の発明は、このような従来技術の問題を解決し、クロム酸浴を使用したエッチング処理を不要としたにも拘わらず、高い密着強度を有する金属めっき層を有するめっき樹脂成形体が得られたものである。 The inventions of Patent Documents 1 to 3 solve such a problem of the prior art, and the plating resin molding having a metal plating layer having high adhesion strength in spite of the fact that the etching process using the chromic acid bath is unnecessary. The body is obtained.
特許文献4の発明は、ポリアミド成形品に対するめっき工程において、塩酸エッチングによる表面粗し処理性を向上させ、金属めっきの密着強度を高める目的にて、粒径の大きな無機充填材を多量に配合しており(実施例では、平均粒径2.2μ〜12μのものを40重量%配合している。)、更に無機充填材の配合による衝撃強度の低下を抑制するため、ゴム状物質を配合している。
特許文献1〜3の発明は、めっき前の樹脂成形体の製造法として射出成形法を適用した場合、弾性率が低く固化速度も低いため離型性の点で改善の余地がある。特許文献4の発明は、多量の無機充填材を配合しているため、射出成形時における離型性は良いことが考えられる。しかし、多量の無機充填材を配合しており、前記無機充填材が酸処理時に溶解除去されて凹凸が形成されるため、めっき後の金属めっきの密着強度は大きくなるが、金属めっき後の外観が損なわれるという問題がある。 In the inventions of Patent Documents 1 to 3, when an injection molding method is applied as a method for producing a resin molded body before plating, there is room for improvement in terms of releasability because the elastic modulus is low and the solidification rate is low. Since the invention of Patent Document 4 contains a large amount of an inorganic filler, it is considered that the releasability during injection molding is good. However, since a large amount of inorganic filler is blended and the inorganic filler is dissolved and removed during acid treatment to form irregularities, the adhesion strength of metal plating after plating increases, but the appearance after metal plating There is a problem that is damaged.
本発明は、製造工程においてクロム酸等を用いたエッチングを使用せず、めっき工程前の樹脂成形品の射出成形時における型離れ性が良く、密着強度が高く、美しい外観を有するめっき樹脂成形体を提供することを課題とする。 The present invention does not use etching using chromic acid or the like in the manufacturing process, and has a good mold releasability at the time of injection molding of a resin molded product before the plating process, a high adhesion strength, and a beautiful appearance. It is an issue to provide.
また本発明は、前記めっき樹脂成形体の製造に適した、接触角が調整された樹脂成形体の製造方法を提供することを他の課題とする。 Moreover, this invention makes it another subject to provide the manufacturing method of the resin molding in which the contact angle was adjusted suitable for manufacture of the said plating resin molding.
また本発明は、接触角が調整された樹脂成形体を用いためっき樹脂成形体の製造方法を提供することを他の課題とする。 Moreover, this invention makes it the other subject to provide the manufacturing method of the plating resin molding using the resin molding in which the contact angle was adjusted.
本発明者は、合成樹脂成形体の表面に金属めっき層を有する金属めっき成形体を研究開発する過程において、前記合成樹脂成形体表面の接触角を狭い範囲に限定することにより、めっき作業が容易になり、めっき強度が高められることを見出して、更に前記接触角を狭い範囲に調整する手段を見出して、本発明を完成したものである。 In the process of researching and developing a metal plating molded body having a metal plating layer on the surface of the synthetic resin molded body, the present inventor can easily perform the plating work by limiting the contact angle of the surface of the synthetic resin molded body to a narrow range. Thus, the present invention has been completed by finding that the plating strength can be improved and further finding a means for adjusting the contact angle to a narrow range.
請求項1の発明は、課題の解決手段として、
(A)(A-1)23℃水中下、24hr後の吸水率(ISO62)が0.6%以上である樹脂10〜90質量%と、(A-2)23℃水中下、24hr後の吸水率(ISO62)が0.6%未満である樹脂10〜90質量%を含む合成樹脂混合物、並びに
(B)(A)成分の合成樹脂混合物100質量部に対して、水への溶解度(25℃)が0.01/100g〜10g/100gの水可溶性物質を0.01〜20質量部含有する樹脂組成物からなり、接触角(測定法:液滴法)が55°〜75°である樹脂成形体の表面に金属めっき層を有するめっき樹脂成形体であり、
前記樹脂成形体がクロム及び/又はマンガンを含む酸によりエッチング処理されていないものであるめっき樹脂成形体を提供する。
The invention of claim 1 is a solution to the problem.
(A) (A-1) 10% to 90% by mass of a resin having a water absorption rate (ISO 62) after 24 hr of 0.6% or more in 23 ° C. water, and (A-2) 24 ° C. in 24 ° C. after 24 hr. A synthetic resin mixture containing 10-90% by mass of a resin having a water absorption rate (ISO 62) of less than 0.6%, and (B) solubility in water (25 Resin molding comprising a resin composition containing 0.01 to 20 parts by mass of a water-soluble substance having a temperature of 0.01 / 100 g to 10 g / 100 g, and a contact angle (measurement method: droplet method) of 55 ° to 75 ° It is a plating resin molded body having a metal plating layer on the surface of the body,
Provided is a plated resin molded body in which the resin molded body is not etched with an acid containing chromium and / or manganese.
請求項7の発明は、課題の他の解決手段として、
(A)(A-1)23℃水中下、24hr後の吸水率(ISO62)が0.6%以上である樹脂10〜90質量%と、(A-2)23℃水中下、24hr後の吸水率(ISO62)が0.6%未満である樹脂10〜90質量%を含む合成樹脂混合物からなり、プラズマ処理された、接触角(測定法:液滴法)が55°〜75°である樹脂成形体の表面に金属めっき層を有するめっき樹脂成形体であり、
前記樹脂成形体がクロム及び/又はマンガンを含む酸によりエッチング処理されていないものであるめっき樹脂成形体を提供する。
The invention according to claim 7 is another solution to the problem.
(A) (A-1) 10% to 90% by mass of a resin having a water absorption rate (ISO 62) after 24 hr of 0.6% or more in 23 ° C. water, and (A-2) 24 ° C. in 24 ° C. after 24 hr. The contact angle (measurement method: droplet method) is 55 ° to 75 ° made of a synthetic resin mixture containing 10 to 90% by mass of a resin having a water absorption rate (ISO 62) of less than 0.6% and plasma-treated. It is a plated resin molded body having a metal plating layer on the surface of the resin molded body,
Provided is a plated resin molded body in which the resin molded body is not etched with an acid containing chromium and / or manganese.
請求項8の発明は、他の課題の解決手段として、
(A)(A-1)23℃水中下、24hr後の吸水率(ISO62)が0.6%以上である樹脂10〜90質量%と、(A-2)23℃水中下、24hr後の吸水率(ISO62)が0.6%未満である樹脂10〜90質量%を含む合成樹脂混合物と、
(B)(A)成分の合成樹脂混合物100質量部に対して、水への溶解度(25℃)が0.01/100g〜10g/100gの水可溶性物質0.01〜20質量部を混合して樹脂組成物を得る工程と、
前記樹脂組成物を成形する工程を有する、
接触角(測定法:液滴法)が55°〜75°である樹脂成形体の製造方法を提供する。
The invention of claim 8 is a means for solving other problems.
(A) (A-1) 10% to 90% by mass of a resin having a water absorption rate (ISO 62) after 24 hr of 0.6% or more in 23 ° C. water, and (A-2) 24 ° C. in 24 ° C. after 24 hr. A synthetic resin mixture comprising 10-90% by weight of a resin having a water absorption rate (ISO 62) of less than 0.6%;
(B) To 100 parts by mass of the synthetic resin mixture of component (A), 0.01 to 20 parts by mass of a water-soluble substance having a water solubility (25 ° C.) of 0.01 / 100 g to 10 g / 100 g is mixed. Obtaining a composition;
Having a step of molding the resin composition,
A method for producing a resin molded body having a contact angle (measurement method: droplet method) of 55 ° to 75 ° is provided.
請求項13の発明は、他の課題の解決手段として、請求項7〜11のいずれかに記載の製造方法により得られた樹脂成形体に対して、クロム及び/又はマンガンを含む酸によりエッチング処理することなくめっき処理する、めっき樹脂成形体の製造方法を提供する。 The invention of claim 13 is an etching treatment with an acid containing chromium and / or manganese for the resin molded body obtained by the production method according to any of claims 7 to 11 as a means for solving other problems. Provided is a method for producing a plated resin molded article, in which plating is performed without performing.
本発明のめっき樹脂成形体は、めっき処理前の樹脂成形体の製造法として射出成形法を適用したとき、型離れが良いので生産性を向上させることができる。また、本発明のめっき樹脂成形体は、めっきの密着強度が高いため、めっき直後及びヒートサイクル試験後においても美しい外観を有している。 When the injection molding method is applied as the method for producing the resin molded body before the plating treatment, the plated resin molded body of the present invention can improve productivity because of good mold separation. Moreover, since the plating resin molding of the present invention has high adhesion strength of plating, it has a beautiful appearance immediately after plating and after a heat cycle test.
また本発明の樹脂成形体の製造方法によれば、接触角が狭い範囲に調整された樹脂成形体を得ることができるため、前記樹脂成形体を用いることにより、上記しためっき樹脂成形体を容易に得ることができる。 Further, according to the method for producing a resin molded body of the present invention, a resin molded body having a contact angle adjusted to a narrow range can be obtained. Therefore, by using the resin molded body, the above-described plated resin molded body can be easily obtained. Can get to.
<樹脂組成物>
〔(A)成分〕
(A)成分の合成樹脂混合物としては、(A-1)23℃水中下、24hr後の吸水率(ISO62)が0.6%以上である樹脂と、(A-2)23℃水中下、24hr後の吸水率(ISO62)が0.6%未満である樹脂から選ばれる1種又は2種以上のものが好ましい。
<Resin composition>
[Component (A)]
As the synthetic resin mixture of component (A), (A-1) a resin having a water absorption rate (ISO 62) after 24 hours of 0.6% or more in 23 ° C. water, and (A-2) 23 ° C. water, One or two or more resins selected from resins having a water absorption rate (ISO 62) after 24 hours of less than 0.6% are preferred.
(A-1)成分の樹脂は、吸水率が0.6〜11%のものがより好ましく、0.6〜5%のものが更に好ましく、0.6〜2.5%のものが特に好ましい。(A-2)成分の樹脂は、吸水率が0.4%以下のものがより好ましい。 The resin of component (A-1) preferably has a water absorption of 0.6 to 11%, more preferably 0.6 to 5%, and particularly preferably 0.6 to 2.5%. . The resin as the component (A-2) is more preferably one having a water absorption of 0.4% or less.
本発明では、(A-1)成分の樹脂から選ばれる1種又は2種以上の樹脂と、(A-2)成分の樹脂から選ばれる1種又は2種以上の樹脂を組み合わせて用いることが好ましい。 In the present invention, one or more resins selected from the resin of component (A-1) and one or more resins selected from the resin of component (A-2) are used in combination. preferable.
(A-1)成分の樹脂としては、上記飽和吸水率を満たすポリアミド系樹脂、アクリル酸塩系樹脂、セルロース系樹脂、ビニールアルコール系樹脂、ポリエーテル系樹脂等が好ましく、ポリアミド系樹脂、ポリエーテル系樹脂がより好ましく、ポリアミド系樹脂がもっとも好ましい。 As the resin of component (A-1), a polyamide resin, an acrylate resin, a cellulose resin, a vinyl alcohol resin, a polyether resin, or the like that satisfies the saturated water absorption rate is preferable. Resin is more preferable, and polyamide resin is most preferable.
ポリアミド系樹脂としては、ナイロン66、ポリヘキサメチレンセバカミド(ナイロン6・10)、ポリヘキサメチレンドデカナミド(ナイロン6・12)、ポリドデカメチレンドデカナミド(ナイロン1212)、ポリメタキシリレンアジパミド(ナイロンMXD6)、ポリテトラメチレンアジパミド(ナイロン46)及びこれらの混合物や共重合体;ナイロン6/66、6T成分が50モル%以下であるナイロン66/6T(6T:ポリヘキサメチレンテレフタラミド)、6I成分が50モル%以下であるナイロン66/6I(6I:ポリヘキサメチレンイソフタラミド)、ナイロン6T/6I/66、ナイロン6T/6I/610等の共重合体;ポリヘキサメチレンテレフタルアミド(ナイロン6T)、ポリヘキサメチレンイソフタルアミド(ナイロン6I)、ポリ(2−メチルペンタメチレン)テレフタルアミド(ナイロンM5T)、ポリ(2−メチルペンタメチレン)イソフタルアミド(ナイロンM5I)、ナイロン6T/6I、ナイロン6T/M5T等の共重合体を挙げることができ、そのほかアモルファスナイロンのような共重合ナイロンでもよく、アモルファスナイロンとしてはテレフタル酸とトリメチルヘキサメチレンジアミンの重縮合物等を挙げることができる。 Polyamide resins include nylon 66, polyhexamethylene sebamide (nylon 6 · 10), polyhexamethylene dodecanamide (nylon 6 · 12), polydodecamethylene dodecanamide (nylon 1212), polymetaxylylene azide Pamide (nylon MXD6), polytetramethylene adipamide (nylon 46) and mixtures and copolymers thereof; nylon 6/66, nylon 66 / 6T in which 6T component is 50 mol% or less (6T: polyhexamethylene) Terephthalamide), copolymers such as nylon 66 / 6I (6I: polyhexamethylene isophthalamide), nylon 6T / 6I / 66, nylon 6T / 6I / 610, etc. whose 6I component is 50 mol% or less; polyhexa Methylene terephthalamide (nylon 6T), polyhexamethylene isophthal Copolymers such as imide (nylon 6I), poly (2-methylpentamethylene) terephthalamide (nylon M5T), poly (2-methylpentamethylene) isophthalamide (nylon M5I), nylon 6T / 6I, nylon 6T / M5T In addition, copolymer nylon such as amorphous nylon may be used, and examples of amorphous nylon include polycondensates of terephthalic acid and trimethylhexamethylenediamine.
更に、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物及びこれらの成分からなる共重合体、具体的には、ナイロン6、ポリ−ω−ウンデカナミド(ナイロン11)、ポリ−ω−ドデカナミド(ナイロン12)等の脂肪族ポリアミド樹脂及びこれらの共重合体、ジアミン、ジカルボン酸とからなるポリアミドとの共重合体、具体的にはナイロン6T/6、ナイロン6T/11、ナイロン6T/12、ナイロン6T/6I/12、ナイロン6T/6I/610/12等及びこれらの混合物を挙げることができる。 Further, a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, and a copolymer comprising these components, specifically, nylon 6, poly-ω-undecanamide (nylon 11), poly-ω-dodecanamide. (Nylon 12) and other aliphatic polyamide resins and copolymers thereof, and copolymers with polyamides comprising diamines and dicarboxylic acids, specifically nylon 6T / 6, nylon 6T / 11, nylon 6T / 12, Mention may be made of nylon 6T / 6I / 12, nylon 6T / 6I / 610/12, and mixtures thereof.
ポリアミド系樹脂としては、上記の中でもPA(ナイロン)6、PA(ナイロン)66、PA(ナイロン)6/66が好ましい。 Among the polyamide-based resins, PA (nylon) 6, PA (nylon) 66, and PA (nylon) 6/66 are preferable among the above.
(A-2)成分の樹脂としては、上記飽和吸水率を満たすオレフィン系樹脂、スチレン系樹脂、ポリフェニレンエーテル樹脂、ポリブチレンテレフタレート樹脂やポリエチレンテレフタレート樹脂等のポリエステル樹脂、液晶ポリマー、ポリフエニレンサルファイド樹脂、ポリアセタール樹脂、ポリカーボネート樹脂等の熱可塑性樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、フェノール樹脂等の熱硬化性樹脂等を挙げることができる。 (A-2) Component resins include olefin resins, styrene resins, polyphenylene ether resins, polyester resins such as polybutylene terephthalate resins and polyethylene terephthalate resins, liquid crystal polymers, and polyphenylene sulfide resins that satisfy the saturated water absorption rate. And thermoplastic resins such as polyacetal resins and polycarbonate resins, and thermosetting resins such as epoxy resins, unsaturated polyester resins, and phenol resins.
オレフィン系樹脂は、炭素数2〜8のモノオレフィンを主たる単量体成分とする重合体であり、低密度ポリエチレン、高密度ポリエチレン、線状低密度ポリエチレン、ポリプロピレン、エチレン−プロピレンランダム共重合体、エチレン−プロピレンブロック共重合体、ポリメチルペンテン、ポリブテン−1、これらの変性物等から選ばれる1種又は2種以上を挙げることができ、これらの中でもポリプロピレンが好ましい。 The olefin-based resin is a polymer having a C 2-8 monoolefin as a main monomer component, such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene random copolymer, One type or two or more types selected from ethylene-propylene block copolymers, polymethylpentene, polybutene-1, modified products thereof and the like can be exemplified, and among these, polypropylene is preferable.
スチレン系樹脂は、スチレン及びα置換、核置換スチレン等のスチレン誘導体の重合体を挙げることができる。また、これら単量体を主として、これらとアクリロニトリル、アクリル酸並びにメタクリル酸のようなビニル化合物及び/又はブタジエン、イソプレンのような共役ジエン化合物の単量体から構成される共重合体も含まれる。例えばポリスチレン、耐衝撃性ポリスチレン(HIPS)樹脂、アクリロニトリル−ブタジエン−スチレン共重合体(ABS)樹脂、アクリロニトリル−スチレン共重合体(AS樹脂)、スチレン−メタクリレート共重合体(MS樹脂)、スチレン−ブタジエン共重合体(SBS樹脂)等を挙げることができる。 Examples of the styrenic resin include polymers of styrene and styrene derivatives such as α-substituted and nucleus-substituted styrene. Also included are copolymers composed mainly of these monomers and monomers of vinyl compounds such as acrylonitrile, acrylic acid and methacrylic acid and / or conjugated diene compounds such as butadiene and isoprene. For example, polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-styrene copolymer (AS resin), styrene-methacrylate copolymer (MS resin), styrene-butadiene A copolymer (SBS resin) etc. can be mentioned.
また、ポリスチレン系樹脂として、ポリアミド系樹脂との相溶性や反応性をあげるためのカルボキシル基含有不飽和化合物が共重合されているスチレン系共重合体を含んでもよい。カルボキシル基含有不飽和化合物が共重合されているスチレン系共重合体は、ゴム質重合体の存在下に、カルボキシル基含有不飽和化合物及び必要に応じてこれらと共重合可能な他の単量体を重合してなる共重合体である。 Further, the polystyrene resin may include a styrene copolymer in which a carboxyl group-containing unsaturated compound for increasing compatibility and reactivity with the polyamide resin is copolymerized. The styrene-based copolymer in which the carboxyl group-containing unsaturated compound is copolymerized in the presence of the rubber-like polymer, the carboxyl group-containing unsaturated compound and, if necessary, other monomers copolymerizable therewith Is a copolymer obtained by polymerizing
成分を具体的に例示すると、
1)カルボキシル基含有不飽和化合物を共重合したゴム質重合体の存在下に、芳香族ビニルモノマーを必須成分とする単量体あるいは芳香族ビニルとカルボキシル基含有不飽和化合物とを必須成分とする単量体を重合して得られたグラフト重合体、
2)ゴム質重合体の存在下に、芳香族ビニルとカルボキシル基含有不飽和化合物とを必須成分とする単量体を共重合して得られたグラフト共重合体、
3)カルボキシル基含有不飽和化合物が共重合されていないゴム強化スチレン系樹脂とカルボキシル基含有不飽和化合物と芳香族ビニルとを必須成分とする単量体の共重合体との混合物、
4)上記1)、2)とカルボキシル基含有不飽和化合物と芳香族ビニルとを必須とする共重合体との混合物、
5)上記1)〜4)と芳香族ビニルを必須成分とする共重合体との混合物がある。
Specific examples of ingredients include
1) In the presence of a rubbery polymer copolymerized with a carboxyl group-containing unsaturated compound, a monomer having an aromatic vinyl monomer as an essential component or an aromatic vinyl and a carboxyl group-containing unsaturated compound as an essential component A graft polymer obtained by polymerizing monomers,
2) A graft copolymer obtained by copolymerizing a monomer having an aromatic vinyl and a carboxyl group-containing unsaturated compound as essential components in the presence of a rubbery polymer;
3) A mixture of a rubber-reinforced styrene-based resin in which a carboxyl group-containing unsaturated compound is not copolymerized, a copolymer of monomers having a carboxyl group-containing unsaturated compound and an aromatic vinyl as essential components,
4) A mixture of the above 1), 2), a carboxyl group-containing unsaturated compound and a copolymer essentially comprising an aromatic vinyl,
5) There is a mixture of the above 1) to 4) and a copolymer containing aromatic vinyl as an essential component.
上記1)〜5)において、芳香族ビニルとしてはスチレンが好ましく、また芳香族ビニルと共重合する単量体としてはアクリロニトリルが好ましい。カルボキシル基含有不飽和化合物は、スチレン系樹脂中、好ましくは0.1〜8質量%であり、より好ましくは0.2〜7質量%である。 In the above 1) to 5), styrene is preferable as the aromatic vinyl, and acrylonitrile is preferable as the monomer copolymerized with the aromatic vinyl. The carboxyl group-containing unsaturated compound is preferably 0.1 to 8% by mass, more preferably 0.2 to 7% by mass in the styrene resin.
本発明の(A)成分の合成樹脂混合物において、(A-1)成分及び(A-2)成分を併用する場合は、(A-1)成分の割合は、好ましくは10〜90質量%、より好ましくは20〜80質量%、更に好ましくは25〜75質量%、特に好ましくは30〜70質量%であり、(A-2)成分の割合は、好ましくは90〜10質量%、より好ましくは80〜20質量%、更に好ましくは75〜25質量%、特に好ましくは70〜30質量%である。 In the synthetic resin mixture of the component (A) of the present invention, when the component (A-1) and the component (A-2) are used in combination, the proportion of the component (A-1) is preferably 10 to 90% by mass, More preferably, it is 20-80 mass%, More preferably, it is 25-75 mass%, Most preferably, it is 30-70 mass%, The ratio of (A-2) component becomes like this. Preferably it is 90-10 mass%, More preferably It is 80-20 mass%, More preferably, it is 75-25 mass%, Most preferably, it is 70-30 mass%.
〔(B)成分〕
(B)成分の水可溶性物質は、水への溶解度(25℃)が0.01/100g〜10g/100gのものである。
[(B) component]
The water-soluble substance of component (B) has a solubility in water (25 ° C.) of 0.01 / 100 g to 10 g / 100 g.
(B)成分の水可溶性物質としては、上記溶解度を満たす、デンプン、デキストリン、プルラン、ヒアルロン酸、カルボキシメチルセルロース、メチルセルロース、エチルセルロース又はこれらの塩等の多糖類;プロピレングリコール、エチレングリコール、ジエチレングリコール、ネオペンチルグリコール、ブタンジオール、ペンタンジオール、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、グリセリン等の多価アルコール;ポリビニルアルコール、ポリアクリル酸、ポリマレイン酸、ポリアクリルアミド、ポリビニルピロリドン、ポリエチレンオキシド、アクリル酸−無水マレイン酸コポリマー、無水マレイン酸−ジイソブチレンコポリマー、無水マレイン酸−酢酸ビニルコポリマー、ナフタレンスルホン酸塩ホルマリン縮合物及びこれらの塩等を挙げることができる。 As the water-soluble substance of the component (B), polysaccharides such as starch, dextrin, pullulan, hyaluronic acid, carboxymethylcellulose, methylcellulose, ethylcellulose or salts thereof satisfying the above solubility; propylene glycol, ethylene glycol, diethylene glycol, neopentyl Polyhydric alcohols such as glycol, butanediol, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, glycerin; polyvinyl alcohol, polyacrylic acid, polymaleic acid, polyacrylamide, polyvinyl Pyrrolidone, polyethylene oxide, acrylic acid-maleic anhydride copolymer, maleic anhydride-diisobutylene copolymer Chromatography, maleic anhydride - vinyl acetate copolymer, naphthalene sulfonate formalin condensates and their salts.
(B)成分としては、ペンタエリスリトール(溶解度7.2g/100g)、ジペンタエリスリトールが好ましい。 As the component (B), pentaerythritol (solubility 7.2 g / 100 g) and dipentaerythritol are preferable.
(B)成分の含有割合は、(A)成分の合成樹脂混合物100質量部に対して0.1〜20質量部であり、好ましくは0.1〜10質量部、より好ましくは0.5〜5質量部である。 (B) The content rate of a component is 0.1-20 mass parts with respect to 100 mass parts of the synthetic resin mixture of (A) component, Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-. 5 parts by mass.
〔(C)成分〕
(C)成分の相溶化剤は、必要に応じて含有される成分であり、(A)成分の樹脂として互いに相溶性の低い2種以上の樹脂を選択して用いる場合、使用する樹脂に応じて公知の相溶化剤から選択することが好ましい。
[Component (C)]
The compatibilizer of component (C) is a component that is contained as necessary. When two or more resins having low compatibility are selected and used as the resin of component (A), the compatibilizer depends on the resin used. It is preferable to select from known compatibilizers.
(C)成分の相溶化剤としては、カルボキシル基含有不飽和化合物が共重合されているスチレン系共重合体を挙げることができる。カルボキシル基含有不飽和化合物が共重合されているスチレン系共重合体は、ゴム質重合体の存在下に、カルボキシル基含有不飽和化合物及び必要に応じてこれらと共重合可能な他の単量体を重合してなる共重合体であり、上記した1)〜5)(酸変性ABS樹脂、酸変性ポリプロピレン樹脂等)を用いることができる。 Examples of the compatibilizer for the component (C) include styrene copolymers in which a carboxyl group-containing unsaturated compound is copolymerized. The styrene-based copolymer in which the carboxyl group-containing unsaturated compound is copolymerized in the presence of the rubber-like polymer, the carboxyl group-containing unsaturated compound and, if necessary, other monomers copolymerizable therewith The above-mentioned 1) to 5) (acid-modified ABS resin, acid-modified polypropylene resin, etc.) can be used.
また(C)成分の相溶化剤としては、マレイミド系モノマー単位を有する重合体を挙げることができる。C)成分の相溶化剤としてマレイミド系モノマー単位を有する重合体を用いたときは、樹脂成形体の耐熱性を向上させることができるため好ましい。 Moreover, as a compatibilizing agent of (C) component, the polymer which has a maleimide-type monomer unit can be mentioned. When a polymer having a maleimide monomer unit is used as a compatibilizer for component C), the heat resistance of the resin molded product can be improved, which is preferable.
(C)成分中、マレイミド系モノマー単位となるマレイミド系モノマーは、マレイミド、N−メチルマレイミド、N−エチルマレイミド、N−プロピルマレイミド、N−イソプロピルマレイミド、N−シクロヘキシルマレイミド、N−フェニルマレイミド、N−トルイルマレイミド、N−キシリールマレイミド、N−ナフチルマレイミド、N−t−ブチルマレイミド、N−オルトクロルフェニルマレイミド、N−オルトメトキシフェニルマレイミドから選ばれる1種又は2種以上のものが好ましい。 In the component (C), maleimide monomers that are maleimide monomer units are maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N One or two or more types selected from -toluylmaleimide, N-xylylmaleimide, N-naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, N-orthomethoxyphenylmaleimide are preferable.
(C)成分の含有割合は、(A)成分100質量部に対して0.1〜40質量部であり、好ましくは1〜30質量部、より好ましくは3〜25質量部である。 The content rate of (C) component is 0.1-40 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-30 mass parts, More preferably, it is 3-25 mass parts.
〔(D)成分〕
(D)成分の界面活性剤は、必要に応じて含有される成分である。界面活性剤は、(A-1)成分及び(A-2)成分の製造時において乳化重合を適用した場合に用いる界面活性剤(乳化剤)が樹脂中に残存しているものでもよいし、塊状重合等の乳化剤を使用しない製造法を適用した場合には、別途(A-1)成分及び(A-2)成分中に添加したものでもよい。
[Component (D)]
The surfactant (D) is a component that is contained as necessary. The surfactant may be one in which the surfactant (emulsifier) used in the case of applying emulsion polymerization in the production of the components (A-1) and (A-2) remains in the resin, When a production method that does not use an emulsifier such as polymerization is applied, it may be added separately to the components (A-1) and (A-2).
界面活性剤は、樹脂の乳化重合で使用するもののほか、乳化重合で使用するもの以外のものでもよく、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤が好ましい。 In addition to those used in emulsion polymerization of resins, surfactants other than those used in emulsion polymerization may be used. Anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants may be used. preferable.
界面活性剤としては、脂肪酸塩、ロジン酸塩、アルキル硫酸塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、スルホコハク酸ジエステル塩、α−オレフィン硫酸エステル塩、α−オレフィンスルホン酸塩等のアニオン界面活性剤;モノもしくはジアルキルアミン又はそのポリオキシエチレン付加物、モノ又はジ長鎖アルキル第4級アンモニウム塩等のカチオン界面活性剤;アルキルグルコシド、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、蔗糖脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンプロピレンブロックコポリマー、脂肪酸モノグリセリド、アミンオキシド等のノニオン界面活性剤;カルボベタイン、スルホベタイン、ヒドロキシスルホベタイン等の両性界面活性剤から選ばれる1種又は2種以上のものを挙げることができる。 Surfactants include fatty acid salts, rosinates, alkyl sulfates, alkyl benzene sulfonates, alkyl diphenyl ether sulfonates, polyoxyethylene alkyl ether sulfates, sulfosuccinic acid diester salts, α-olefin sulfate esters, α- Anionic surfactants such as olefin sulfonates; cationic surfactants such as mono- or dialkylamines or their polyoxyethylene adducts, mono- or di-long-chain alkyl quaternary ammonium salts; alkyl glucosides, polyoxyethylene alkyl ethers, Polyoxyethylene alkyl phenyl ether, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene propylene block copolymer Nonionic surfactants such as polymers, fatty acid monoglycerides, and amine oxides; one or two or more types selected from amphoteric surfactants such as carbobetaine, sulfobetaine, and hydroxysulfobetaine.
(D)成分の含有割合は、(A)成分100質量部に対して0.01〜10質量部が好ましく、0.01〜5質量部がより好ましく、0.01〜2質量部が更に好ましい。 (D) As for the content rate of a component, 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) component, 0.01-5 mass parts is more preferable, 0.01-2 mass parts is still more preferable. .
本発明の樹脂組成物において、(B)成分と(D)成分を併用するときは、(B)成分と(D)成分の配合比率である(D)/(B)の値が5/1〜1/100であることが好ましく、より好ましくは2/1〜1/50である。 In the resin composition of the present invention, when the (B) component and the (D) component are used in combination, the value of (D) / (B), which is the blending ratio of the (B) component and the (D) component, is 5/1. It is preferably ˜1 / 100, more preferably 2/1 to 1/50.
〔その他の成分〕
本発明で用いる樹脂組成物は、更に下記のものから選ばれる1種又は2種以上のリン系化合物を含有することができる。
[Other ingredients]
The resin composition used in the present invention can further contain one or more phosphorus compounds selected from the following.
トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス(イソプロピルフェニル)ホスフェート、トリス(o−又はp−フェニルフェニル)ホスフェート、トリナフチルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、ジフェニル(2−エチルヘキシル)ホスフェート、ジ(イソプロピルフェニル)フェニルホスフェート、o−フェニルフェニルジクレジルホスフェート、トリス(2,6−ジメチルフェニル)ホスフェート、テトラフェニル−m−フェニレンジホスフェート、テトラフェニル−p−フェニレンジホスフェート、フェニルレゾルシン・ポリホスフェート、ビスフェノールA−ビス(ジフェニルホスフェート)、ビスフェノールA・ポリフェニルホスフェート、ジピロカテコールハイポジホスフェート等の縮合系リン酸エステル。 Triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o- or p-phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl ( 2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresyl phosphate, tris (2,6-dimethylphenyl) phosphate, tetraphenyl-m-phenylene diphosphate, tetraphenyl-p-phenylene diphosphate , Phenyl resorcinol polyphosphate, bisphenol A-bis (diphenyl phosphate), bisphenol A polyphenyl phosphate Feto, condensation type phosphoric acid ester such as di-pyrocatechol Hi-Posi phosphate.
ジフェニル(2−エチルヘキシル)ホスフェート、ジフェニル−2−アクリロイルオキシエチルホスフェート、ジフェニル−2−メタクリロイルオキシエチルホスフェート、ジフェニルネオペンチルホスフェート、ペンタエリスリトールジフェニルジホスフェート、エチルピロカテコールホスフェート等の正リン酸エステル等の脂肪酸・芳香族リン酸エステル。 Fatty acids such as normal phosphates such as diphenyl (2-ethylhexyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, diphenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, ethyl pyrocatechol phosphate・ Aromatic phosphate esters.
ポリリン酸メラミン、トリポリリン酸、ピロリン酸、オルソリン酸、ヘキサメタリン酸等のアルカリ金属塩、フィチン酸等のリン酸系化合物又はこれらのアルカリ金属塩もしくはアルカノールアミン塩等。 Alkaline metal salts such as melamine polyphosphate, tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid, phosphoric acid compounds such as phytic acid, or alkali metal salts or alkanolamine salts thereof.
更に、上記以外のリン系化合物として、公知の樹脂用の難燃剤及び酸化防止剤として使用されているリン系化合物を用いることができる。 Furthermore, as phosphorus compounds other than the above, phosphorus compounds that are used as known flame retardants and antioxidants for resins can be used.
樹脂組成物中のリン系化合物の含有割合は、(A)成分100質量部に対して0.1〜30質量部が好ましく、0.1〜20質量部がより好ましく、0.1〜10質量部が更に好ましい。 As for the content rate of the phosphorus compound in a resin composition, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) component, 0.1-20 mass parts is more preferable, 0.1-10 mass Part is more preferred.
本発明で用いる樹脂組成物は、更に無機充填材を含有することができる。無機充填材としては、粒状乃至粉状の充填材、繊維状の充填材を用いることができる。無機充填材は、めっき対象となる樹脂成形体を射出成形するときの離型性を向上させるための成分であり、めっき後のめっき密着強度を高めるように作用させるための成分ではない。 The resin composition used in the present invention can further contain an inorganic filler. As the inorganic filler, a granular or powdery filler or a fibrous filler can be used. The inorganic filler is a component for improving releasability when the resin molded body to be plated is injection-molded, and is not a component for acting to increase the plating adhesion strength after plating.
粒状乃至粉状の充填材としては、タルク、カーボンブラック、グラファイト、二酸化チタン、シリカ、マイカ、硫酸カルシウム、炭酸カルシウム(重質炭酸カルシウム、沈降炭酸カルシウム)、炭酸バリウム、炭酸マグネシウム、硫酸マグネシウム、硫酸バリウム、オキシサルフェート、酸化スズ、アルミナ、カオリン、炭化ケイ素、金属粉末、ガラスパウダー、ガラスフレーク、ガラスビーズ等を挙げることができる。 Granular or powdery fillers include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium sulfate, calcium carbonate (heavy calcium carbonate, precipitated calcium carbonate), barium carbonate, magnesium carbonate, magnesium sulfate, sulfuric acid Examples include barium, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, and glass beads.
粒状乃至粉状の充填材は、平均粒径が100μm以下のものが好ましく、50μm以下のものがより好ましく、10μm以下のものが更に好ましく、5μm以下のものが特に好ましい。粒状乃至粉状の充填材の平均粒径を前記範囲内にすることにより、射出成形時における型離れ性が向上できると共に、めっき後の外観を美しくすることができる。平均粒径は、沈降天秤法によって測定し、50%粒度中央値で示したものである。 The granular or powdery filler preferably has an average particle size of 100 μm or less, more preferably 50 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. By making the average particle diameter of the granular or powdery filler within the above range, the mold release property at the time of injection molding can be improved and the appearance after plating can be made beautiful. The average particle size is measured by a sedimentation balance method, and is indicated by the median value of 50% particle size.
繊維状の充填材としては、ウォラストナイト、ガラス繊維、ガラス繊維のミルドファイバー、炭素繊維、炭素繊維のミルドファイバー、チタン酸カリウムウイスカー、ホウ酸アルミニウムウイスカー、酸化亜鉛ウイスカー、アタパルジャイト等を挙げることができる。 Examples of fibrous fillers include wollastonite, glass fiber, glass fiber milled fiber, carbon fiber, carbon fiber milled fiber, potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, and attapulgite. it can.
繊維状充填材としてはウォラストナイトが好ましく、粒状乃至粉状の充填材としてはタルク、炭酸カルシウム(特に平均粒径の小さな沈降炭酸カルシウム)、カオリン等が好ましい。炭酸カルシウムを用いるときは、平均粒径が2μm以下のものが好ましく、1.5μm以下、1.0μm以下、0.5μm以下、0.1μm以下のものがより好ましい。 The fibrous filler is preferably wollastonite, and the granular or powdery filler is preferably talc, calcium carbonate (particularly precipitated calcium carbonate having a small average particle diameter), kaolin, or the like. When calcium carbonate is used, those having an average particle size of 2 μm or less are preferred, and those having a particle size of 1.5 μm or less, 1.0 μm or less, 0.5 μm or less, or 0.1 μm or less are more preferred.
無機充填材の含有割合は、(A)、(B)及び(C)成分の合計量100質量部に対して1〜55質量部であり、好ましくは1〜40質量部、より好ましくは1〜35質量部、特に好ましくは5〜25質量部である。無機充填材の含有量を前記範囲内にすることにより、射出成形時における型離れ性が向上できると共に、めっき後の外観を美しくすることができる。 The content of the inorganic filler is 1 to 55 parts by mass, preferably 1 to 40 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). 35 parts by mass, particularly preferably 5 to 25 parts by mass. By making the content of the inorganic filler within the above range, the mold release property at the time of injection molding can be improved and the appearance after plating can be made beautiful.
本発明の樹脂組成物には、樹脂成形体の用途に応じて、上記の各成分に加えて、更に公知の各種添加剤を配合することができる。 In addition to the above components, various known additives can be further blended in the resin composition of the present invention in accordance with the use of the resin molded body.
本発明の樹脂組成物は、(A)成分の合成樹脂混合物として(A-1)成分の樹脂と(A-2)成分の樹脂を所定割合で混合したものを用い、更に(A)成分に対して所定量の(B)成分を含有させることにより、本発明の樹脂組成物から得られた樹脂成形体表面の接触角を狭い範囲に調整することができる。 The resin composition of the present invention uses a mixture of the resin of component (A-1) and the resin of component (A-2) at a predetermined ratio as the synthetic resin mixture of component (A), and further to component (A) On the other hand, the contact angle of the resin molded body surface obtained from the resin composition of the present invention can be adjusted to a narrow range by containing a predetermined amount of the component (B).
本発明の樹脂組成物から得られた樹脂成形体は、接触角が55°〜75°であり、好ましくは55°〜70°であり、より好ましくは60°〜68°である。接触角を前記範囲に調整することで、めっき樹脂成形体を製造したときのめっき強度が高められる。 The resin molded body obtained from the resin composition of the present invention has a contact angle of 55 ° to 75 °, preferably 55 ° to 70 °, more preferably 60 ° to 68 °. By adjusting the contact angle to the above range, the plating strength when the plated resin molded body is manufactured can be increased.
<樹脂成形体の製造方法>
次に、上記した樹脂組成物を用いた、めっき樹脂成形体の製造に適した樹脂成形体の製造方法を説明する。
<Production method of resin molding>
Next, the manufacturing method of the resin molding suitable for manufacture of the plating resin molding using the above-mentioned resin composition is demonstrated.
上記した樹脂組成物を用い、公知の樹脂成形方法(押出成形法、射出成形法等)を適用して、所望形状の樹脂成形体を製造することにより、接触角(測定法:液滴法)が55°〜75°(好ましくは55°〜70°、より好ましくは60°〜68°)の樹脂成形体を得ることができる。 By using the above resin composition and applying a known resin molding method (extrusion molding method, injection molding method, etc.) to produce a resin molded body having a desired shape, the contact angle (measurement method: droplet method) Of 55 to 75 ° (preferably 55 to 70 °, more preferably 60 to 68 °) can be obtained.
更に樹脂成形体に対してプラズマ処理をすることにより、接触角を再調整することができる。樹脂成形体に対してプラズマ処理することにより、接触角を小さくすることができるため、例えば、接触角75°の樹脂成形体に対してプラズマ処理することにより、接触角を好ましい範囲の70°以下、更にはより好ましい範囲の68°以下に再調整することができる。 Furthermore, the contact angle can be readjusted by performing plasma treatment on the resin molded body. Since the contact angle can be reduced by performing plasma treatment on the resin molded body, for example, the contact angle can be reduced to 70 ° or less in a preferable range by performing plasma treatment on the resin molded body having a contact angle of 75 °. Furthermore, it can be readjusted to a more preferable range of 68 ° or less.
プラズマ処理をすることにより、樹脂成形体表面の濡れ性が変化して、接触角が調整できる。なお、同様の観点から、フレーム処理、プライマー処理、コロナ放電処理、遠紫外線照射処理等の表面改質方法も適用できる。 By performing plasma treatment, the wettability of the surface of the resin molded body changes, and the contact angle can be adjusted. From the same point of view, surface modification methods such as flame treatment, primer treatment, corona discharge treatment, and deep ultraviolet irradiation treatment can also be applied.
樹脂成形体に対してプラズマ処理をするときは、上記した(A)成分と(B)成分を含む樹脂組成物に代えて、(B)成分を使用せずに、(A)成分の合成樹脂混合物のみ又は(A)成分の合成樹脂混合物と必要に応じて(C)成分、(D)成分、その他の成分との混合物を用いて、上記した所定範囲の接触角に調整された樹脂成形体を得ることができる。 When plasma processing is performed on the resin molded body, instead of the resin composition containing the component (A) and the component (B) described above, the synthetic resin of the component (A) is used without using the component (B). Resin molded body adjusted to a contact angle in the above-mentioned predetermined range using a mixture of only the mixture or the synthetic resin mixture of component (A) and, if necessary, a mixture of component (C), component (D) and other components Can be obtained.
<めっき樹脂成形体>
本発明のめっき樹脂成形体は、上記した樹脂組成物を用い、射出成形、押出成形等の公知の成形方法を適用し、必要に応じて更にプラズマ処理(その他、フレーム処理、プライマー処理、コロナ放電処理、遠紫外線照射処理等)することにより、用途に応じた所望形状で所定範囲の接触角を有する樹脂成形体を得た後、下記工程にてめっきする。なお、上記した樹脂組成物を用いないで、(B)成分を含まない上記した合成樹脂混合物を用いた場合には、プラズマ処理をすることにより、用途に応じた所望形状で所定範囲の接触角を有する樹脂成形体を得た後、下記工程にてめっきする。但し、本発明のめっき樹脂成形体は、めっき工程において、めっき対象となる樹脂成形体に対して、クロム及び/又はマンガンを含む酸によりエッチング処理をしないで得られたものである。
<Plating resin molding>
The plated resin molded body of the present invention uses the above-described resin composition, and applies a known molding method such as injection molding or extrusion molding, and further plasma treatment (others, flame treatment, primer treatment, corona discharge as necessary). After obtaining a resin molded body having a contact angle in a predetermined range with a desired shape according to the application by performing treatment, far ultraviolet irradiation treatment, etc., plating is performed in the following steps. In addition, when the above-mentioned synthetic resin mixture which does not use the above-mentioned resin composition and does not contain the component (B) is used, a contact angle within a predetermined range with a desired shape according to the application by performing plasma treatment. After obtaining a resin molded body having, plating is performed in the following steps. However, the plated resin molded body of the present invention is obtained without etching the resin molded body to be plated with an acid containing chromium and / or manganese in the plating step.
めっき方法は、樹脂成形体の表面に金属層又は金属膜を形成できる方法であればよく、めっき浴を用いた湿式めっき、物理蒸着(PVD)、化学蒸着(CVD)等の乾式めっきを適用できる。湿式めっき方法としては、下記に示す特許文献1〜3の発明の実施例に記載の方法(I)(無電解めっき工程を含むめっき方法)、及びダイレクトプレーティング工程を含むめっき方法(II)を適用することができる。いずれのめっき方法においても、めっき対象となる樹脂成形体の表面をクロム及び/又はマンガンを含む酸によりエッチング処理しない。 The plating method may be any method as long as it can form a metal layer or metal film on the surface of the resin molded body, and dry plating such as wet plating using a plating bath, physical vapor deposition (PVD), chemical vapor deposition (CVD), etc. can be applied. . As the wet plating method, the method (I) (plating method including an electroless plating step) described in the examples of the inventions of Patent Documents 1 to 3 shown below and the plating method (II) including a direct plating step are used. Can be applied. In any plating method, the surface of the resin molded body to be plated is not etched with an acid containing chromium and / or manganese.
(I)特許文献1〜3の発明の実施例に記載の方法(無電解めっき工程を含むめっき方法)
(1)脱脂工程
(2)酸による接触処理工程
(3)触媒付与工程
(4)第1活性化工程
(5)第2活性化工程
(6)ニッケルの無電解めっき工程
(7)酸活性化工程
(8)銅の電気めっき工程
(II)ダイレクトプレーティング工程を含むめっき方法
(1)脱脂工程
(2)酸による接触処理工程(エッチング工程)
(3)触媒付与工程
(4)ダイレクトプレーティング工程
(5)銅の電気めっき工程
(II)のめっき方法において、脱脂工程、酸による接触処理工程、触媒付与工程及び銅の電気めっき工程は、特許文献1〜3の発明の実施例に記載の方法と同じである。但し、(II)のめっき方法の「(2)酸による接触処理工程」では、(I)のめっき方法の「(2)酸による接触処理工程」と比べると、濃度の高い酸を用いる。
(I) Method described in Examples of Patent Documents 1 to 3 (plating method including electroless plating step)
(1) Degreasing step (2) Contact treatment step with acid (3) Catalyst application step (4) First activation step (5) Second activation step (6) Electroless plating step of nickel (7) Acid activation Process (8) Electroplating process of copper (II) Plating method including direct plating process (1) Degreasing process (2) Contact treatment process with acid (etching process)
(3) Catalyst application process (4) Direct plating process (5) Copper electroplating process In the plating method of (II), the degreasing process, the contact treatment process with acid, the catalyst application process and the copper electroplating process are patented. This is the same as the method described in the embodiments of the inventions of Documents 1 to 3. However, in the “(2) contact treatment step with acid” of the plating method (II), an acid having a higher concentration is used than in the “(2) contact treatment step with acid” of the plating method (I).
(II)のめっき方法の「(2)酸による接触処理工程」では、酸として、塩酸、リン酸、硫酸のほか、酢酸、クエン酸、ギ酸等の有機酸から選ばれるもの等を用いることができる。 In the “(2) contact treatment step with acid” of the plating method (II), it is possible to use an acid selected from organic acids such as acetic acid, citric acid, formic acid in addition to hydrochloric acid, phosphoric acid, sulfuric acid, etc. it can.
塩酸の場合には、1.5〜3.5規定の塩酸が好ましく、1.8〜3.5規定がより好ましく、2〜3規定が更に好ましい。 In the case of hydrochloric acid, 1.5 to 3.5 N hydrochloric acid is preferable, 1.8 to 3.5 N is more preferable, and 2 to 3 N is more preferable.
この工程の処理は、例えば、樹脂成形体を酸中に浸漬する方法を適用でき、液温度10〜80℃の酸中に0.5〜20分間浸漬する方法を適用できる。1.5〜3.5規定の塩酸を用いる場合は、前記濃度範囲の塩酸水溶液に20〜60℃で、1〜10分間浸漬する方法を適用できる。 The process of this process can apply the method of immersing a resin molding in an acid, for example, and can apply the method of immersing for 0.5 to 20 minutes in the acid of liquid temperature 10-80 degreeC. When 1.5 to 3.5 N hydrochloric acid is used, a method of immersing in an aqueous hydrochloric acid solution in the above concentration range at 20 to 60 ° C. for 1 to 10 minutes can be applied.
(II)のダイレクトプレーティング工程を含むめっき方法は公知であり、特開平5−239660号公報、WO98/45505(特許第3208410号公報)、特開2002−338636号公報(段落番号5)等に開示されている。 The plating method including the direct plating step of (II) is known and disclosed in JP-A-5-239660, WO98 / 45505 (Patent No. 3208410), JP-A-2002-338636 (paragraph No. 5) and the like. It is disclosed.
ダイレクトプレーティング工程では、セレクター液と称される金属化合物、還元性化合物及び金属水酸化物を含むめっき液を用い、従来汎用されている化学めっきにより形成されるめっき層(導電性層)と比べると、ごく薄い導電性層を形成するものである。 In the direct plating process, a plating solution containing a metal compound called a selector solution, a reducing compound, and a metal hydroxide is used and compared with a plating layer (conductive layer) formed by chemical plating that has been widely used conventionally. And forming a very thin conductive layer.
金属化合物としては、銅化合物が好ましく、例えば、硫酸銅、塩化銅、炭酸銅、酸化銅、水酸化銅を挙げることができる。銅化合物の含有量は、銅換算で0.1〜5g/Lが好ましく、より好ましくは0.8〜1.2g/Lである。 As the metal compound, a copper compound is preferable, and examples thereof include copper sulfate, copper chloride, copper carbonate, copper oxide, and copper hydroxide. The content of the copper compound is preferably 0.1 to 5 g / L, more preferably 0.8 to 1.2 g / L in terms of copper.
還元性化合物には、公知の無電解めっき(化学めっき)で汎用されているホルマリン、次亜リン酸のように還元力の強いものは含まれず、これらに比べて還元力の弱いものであり、例えば下記のものを挙げることができる。 Reducing compounds do not include those with strong reducing power such as formalin and hypophosphorous acid, which are widely used in known electroless plating (chemical plating), and those with low reducing power compared to these, For example, the following can be mentioned.
塩化第一錫、水素化ホウ素ナトリウム、ジメチルアミンボラン、トリメチルアミンボラン、蟻酸あるいはその塩類、メタノール、エタノール、プロパノール、エチレングリコール、グリセリン等のアルコール類とその塩類を挙げることができる。 Examples thereof include stannous chloride, sodium borohydride, dimethylamine borane, trimethylamine borane, formic acid or salts thereof, alcohols such as methanol, ethanol, propanol, ethylene glycol, and glycerin and salts thereof.
還元性のある糖類、例えば、ブトウ糖、グルコース、ソルビット、セルロース、ショ糖、マンニット、グルコノラクトンを挙げることができる。糖類の含有量は、3〜50g/Lが好ましく、より好ましくは10〜20g/Lである。 Examples of reducing sugars include butter sugar, glucose, sorbit, cellulose, sucrose, mannitol, and gluconolactone. The saccharide content is preferably 3 to 50 g / L, more preferably 10 to 20 g / L.
金属水酸化物としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等を挙げることができる。金属水酸化物の含有量は、10〜80g/Lが好ましく、より好ましくは30〜50g/Lである。 Examples of the metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. As for content of a metal hydroxide, 10-80 g / L is preferable, More preferably, it is 30-50 g / L.
セレクター液には、必要に応じて、錯化剤を含有することができる。錯化剤としては、ヒダントイン類、有機カルボン酸類等を挙げることができる。ヒダントイン類としては、ヒダントイン、1−メチルヒダントイン、1,3−ジメチルヒダントイン、5,5−ジメチルヒダントイン、アラントイン等を挙げることができ、有機カルボン酸類としては、クエン酸、酒石酸、コハク酸及びこれらの塩類等を挙げることができる。セレクター中の錯化剤の含有量は、2〜50g/Lが好ましく、より好ましくは10〜40g/Lである。 The selector liquid can contain a complexing agent as required. Examples of complexing agents include hydantoins and organic carboxylic acids. Examples of hydantoins include hydantoin, 1-methylhydantoin, 1,3-dimethylhydantoin, 5,5-dimethylhydantoin, and allantoin. Examples of organic carboxylic acids include citric acid, tartaric acid, succinic acid, and these. Examples thereof include salts. The content of the complexing agent in the selector is preferably 2 to 50 g / L, more preferably 10 to 40 g / L.
セレクター液のpHは10.0〜14.0の範囲が好ましく、より好ましくは11.5〜13.5の範囲である。 The pH of the selector liquid is preferably in the range of 10.0 to 14.0, more preferably in the range of 11.5 to 13.5.
セレクター液の具体例としては、特開平5−239660号公報の実験例1の(c)(段落番号31)に記載されているめっき浴、WO98/45505(特許第3208410号公報)の実施例に記載されている本発明浴1〜8を用いることができ、必要に応じて、その他の公知成分も付加することができる。 Specific examples of the selector liquid include the plating bath described in (c) (paragraph number 31) of Experimental Example 1 of JP-A-5-239660, and the example of WO98 / 45505 (Japanese Patent No. 3208410). The described inventive baths 1 to 8 can be used, and other known components can be added if necessary.
ダイレクトプレーティング工程の処理は、セレクター液の液温を好ましくは20〜70℃、より好ましくは35〜50℃に調整した後、樹脂成形体を30秒〜20分程度、好ましくは3〜5分程度浸漬する方法を適用できる。 In the treatment of the direct plating process, the temperature of the selector liquid is preferably adjusted to 20 to 70 ° C., more preferably 35 to 50 ° C., and then the resin molded body is subjected to about 30 seconds to 20 minutes, preferably 3 to 5 minutes. A method of soaking to the extent can be applied.
ダイレクトプレーティング工程の処理により、樹脂成形体の表面に非常に薄い膜厚の導電性層が形成されるため、次工程において、直接電気めっきをすることができる。 Since a conductive layer having a very thin film thickness is formed on the surface of the resin molding by the treatment of the direct plating process, it is possible to perform electroplating directly in the next process.
本発明のめっき樹脂成形体の形状、めっき層の種類、厚み等は、用途に応じて適宜選択することができ、各種用途に適用することができるが、バンパー、エンブレム、ホイールキャップ、内装部品、外装部品等の自動車部品用途、として適している。 The shape of the plated resin molding of the present invention, the type of plating layer, the thickness, etc. can be appropriately selected according to the application, and can be applied to various applications, but bumpers, emblems, wheel caps, interior parts, Suitable for automotive parts such as exterior parts.
(樹脂組成物)
(A)成分
(A-1-1):ポリアミド(ポリアミド6,宇部興産株式会社製,UBEナイロン6 1013B,吸水率1.8%)
(A-2-1):ABS樹脂(スチレン量45質量%、アクリロニトリル15質量%、ゴム量40質量%)(乳化重合法で製造)
(A-2-2):ABS樹脂(スチレン量55質量%、アクリロニトリル20質量%、ゴム量25質量%)
(B)成分
(B-1):ジペンタエリスリトール(広栄化学工業社製)
(C)成分
無水マレイン酸変性ABS(無水マレイン酸4質量%、スチレン量43質量%、アクリロニトリル15質量%、ゴム量38質量%)
(Resin composition)
(A) Component (A-1-1): Polyamide (Polyamide 6, Ube Industries, UBE nylon 6 1013B, water absorption 1.8%)
(A-2-1): ABS resin (styrene content 45% by mass, acrylonitrile 15% by mass, rubber content 40% by mass) (produced by emulsion polymerization method)
(A-2-2): ABS resin (styrene content 55% by mass, acrylonitrile 20% by mass, rubber content 25% by mass)
(B) Component (B-1): Dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.)
Component (C) Maleic anhydride-modified ABS (maleic anhydride 4% by mass, styrene content 43% by mass, acrylonitrile 15% by mass, rubber content 38% by mass)
(測定方法)
接触角:画像処理式固液界面解析システム DropMaster700(協和界面科学(株)製)を使用して、(i)測定方法:液滴法、(ii)解析方法:θ/2法で測定した。溶媒は
、純水を使用した。
(Measuring method)
Contact angle: Using an image processing solid-liquid interface analysis system DropMaster700 (manufactured by Kyowa Interface Science Co., Ltd.), (i) measurement method: droplet method, (ii) analysis method: θ / 2 method. Pure water was used as the solvent.
実施例及び比較例
表1記載の各成分をV型タンブラーで混合後、二軸押出機(日本製鋼製,TEX30,シリンダー温度230℃)にて溶融混練し、ペレットを得た。次に、射出成形機(シリンダー温度240℃、金型温度60℃)により100×50×3mmの樹脂成形体を得た。
Examples and Comparative Examples After mixing each component shown in Table 1 with a V-type tumbler, the mixture was melt-kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 230 ° C) to obtain pellets. Next, a resin molded body of 100 × 50 × 3 mm was obtained by an injection molding machine (cylinder temperature 240 ° C., mold temperature 60 ° C.).
得られた樹脂成形体を試験片として、(I)無電解めっき工程を含むめっき又は(II)ダイレクトプレーティング工程を含むめっきを行い、めっき樹脂成形体を得た。これらのめっき樹脂成形体におけるヒートサイクル試験の結果を表1に示す。 Using the obtained resin molded body as a test piece, (I) plating including an electroless plating process or (II) plating including a direct plating process was performed to obtain a plated resin molded body. The results of the heat cycle test on these plated resin molded products are shown in Table 1.
(I)無電解めっき工程を含むめっき
(1) 脱脂工程
試験片を、エースクリンA−220(奥野製薬工業(株)製)50g/L水溶液(液温40℃)に20分浸漬した。
(I) Plating including electroless plating process (1) Degreasing process The test piece was immersed in an aceclin A-220 (Okuno Pharmaceutical Co., Ltd.) 50 g / L aqueous solution (liquid temperature 40 ° C.) for 20 minutes.
(2) 酸による接触処理工程
1.0規定の塩酸100ml(液温40℃)中に5分間浸漬した。
(2) Step of contact treatment with acid The substrate was immersed in 100 ml of 1.0 N hydrochloric acid (liquid temperature 40 ° C.) for 5 minutes.
(3) 触媒付与工程
35質量%塩酸150ml/Lと、キャタリストC(奥野製薬工業(株)製)40ml/L水溶液との混合水溶液(液温25℃)中に3分間浸漬した。
(3) Catalyst application process It immersed for 3 minutes in the mixed aqueous solution (liquid temperature of 25 degreeC) of 35 mass% hydrochloric acid 150ml / L and catalyst C (Okuno Pharmaceutical Co., Ltd. product) 40ml / L aqueous solution.
(4) 第1活性化工程
試験片を、98質量%硫酸100ml/L水溶液(液温40℃)中に3分間浸漬した。
(4) 1st activation process The test piece was immersed for 3 minutes in 98 mass% sulfuric acid 100ml / L aqueous solution (liquid temperature of 40 degreeC).
(5) 第2活性化工程
試験片を、水酸化ナトリウム15g/L水溶液(液温40℃)中に2分間浸漬した。
(5) 2nd activation process The test piece was immersed for 2 minutes in 15 g / L sodium hydroxide aqueous solution (liquid temperature of 40 degreeC).
(6) ニッケルの無電解めっき工程
試験片を、化学ニッケルHR−TA(奥野製薬工業(株)製)150ml/Lと、化学ニッケルHR−TB(奥野製薬工業(株)製)150ml/Lの混合水溶液(液温40℃)に5分間浸漬した。
(6) Electroless plating step of nickel The test pieces were made of 150 ml / L of chemical nickel HR-TA (Okuno Pharmaceutical Co., Ltd.) and 150 ml / L of chemical nickel HR-TB (Okuno Pharmaceutical Co., Ltd.). It was immersed in a mixed aqueous solution (liquid temperature 40 ° C.) for 5 minutes.
(7) 酸活性化工程
試験片を、トップサン(奥野製薬工業(株)製)100g/L水溶液(液温25℃)に1分間浸漬した。
(7) Acid activation process The test piece was immersed for 1 minute in 100 g / L aqueous solution (liquid temperature 25 degreeC) of top sun (Okuno Pharmaceutical Co., Ltd. product).
(8) 銅の電気めっき工程
試験片を、実施例1と同じめっき浴(液温25℃)に浸漬して、120分間電気めっきを行った。
(8) Copper electroplating process The test piece was immersed in the same plating bath (liquid temperature 25 degreeC) as Example 1, and electroplated for 120 minutes.
(II)ダイレクトプレーティング工程を含むめっき
(1) 脱脂工程
樹脂成形体を、エースクリンA−220(奥野製薬工業(株)製)50g/L水溶液(液温40℃)に5分浸漬した。
(II) Plating including direct plating step (1) Degreasing step The resin molded body was immersed in an aceclin A-220 (Okuno Pharmaceutical Co., Ltd.) 50 g / L aqueous solution (liquid temperature 40 ° C) for 5 minutes.
(2) エッチング工程(酸による接触処理工程)
樹脂成形体を、35質量%塩酸200ml/L(2.3規定)水溶液(液温40℃)中に5分間浸漬した。
(2) Etching process (contact treatment process with acid)
The resin molded body was immersed for 5 minutes in a 35% by mass hydrochloric acid 200 ml / L (2.3 N) aqueous solution (liquid temperature 40 ° C.).
(3) 触媒付与工程
35質量%塩酸150ml/Lと、キャタリストC(奥野製薬工業(株)製)40ml/L水溶液との混合水溶液(液温25℃)中に3分間浸漬した。
(3) Catalyst application process It immersed for 3 minutes in the mixed aqueous solution (liquid temperature of 25 degreeC) of 35 mass% hydrochloric acid 150ml / L and catalyst C (Okuno Pharmaceutical Co., Ltd. product) 40ml / L aqueous solution.
(4) ダイレクトプレーティング工程
樹脂成形体を下記組成のセレクター液(45℃,pH12)に3分間浸漬して、樹脂成形体表面に導電性層を形成させた。
(4) Direct plating process The resin molding was immersed in the selector liquid (45 degreeC, pH12) of the following composition for 3 minutes, and the electroconductive layer was formed in the resin molding surface.
硫酸銅 3g/L
水酸化ナトリウム 30g/L
グルコース 10g/L
ヒダントイン 10g/L
(5) 銅の電気めっき工程
樹脂成形体を下記組成のめっき浴(液温25℃)に浸漬して、120分間電気めっきを行った。
Copper sulfate 3g / L
Sodium hydroxide 30g / L
Glucose 10g / L
Hydantoin 10g / L
(5) Copper electroplating step The resin molded body was immersed in a plating bath (liquid temperature 25 ° C.) having the following composition, and electroplated for 120 minutes.
(めっき浴の組成)
硫酸銅(CuSO4・5H2O)200g/L
硫酸(98%)50g/L
塩素イオン(Cl−)5ml/L、
トップルチナ2000MU(奥野製薬工業(株)製)5ml/L
(Composition of plating bath)
Copper sulfate (CuSO 4 · 5H 2 O) 200g / L
Sulfuric acid (98%) 50g / L
Chloride ion (Cl − ) 5 ml / L,
Top Lucina 2000MU (Okuno Pharmaceutical Co., Ltd.) 5ml / L
銅めっきを行った後、肉眼によるめっき直後の外観の評価を下記の判定基準にて行った。
◎:成形品の表面全面にめっきが均一にきれいに析出したもの
○:成形品の表面全面にめっきが析出したが、表面外観が少し劣るもの
△:成形品の80%以上にめっきが析出したが、析出しない部分があったもの
×:めっきの析出が成形品の表面の80%未満であったもの
After copper plating, the appearance immediately after plating with the naked eye was evaluated according to the following criteria.
A: The plating is uniformly and completely deposited on the entire surface of the molded product. ○: The plating is deposited on the entire surface of the molded product, but the surface appearance is slightly inferior. Δ: The plating is deposited on 80% or more of the molded product , There was a portion that did not precipitate ×: The plating deposition was less than 80% of the surface of the molded product
Claims (5)
(B)(A)成分の合成樹脂混合物100質量部に対して、水への溶解度(25℃)が0.01/100g〜10g/100gの水可溶性物質0.5〜20質量部を混合して樹脂組成物を得る工程と、
前記樹脂組成物を成形することで接触角(測定法:液滴法)が60°〜70°である樹脂成形体を得る工程、
前記樹脂組成物を成形する工程のあと、更にプラズマ処理することで接触角を再調整する工程を有する、
接触角(測定法:液滴法)が60°〜70°である樹脂成形体の製造方法。 (A) (A-1) 30 to 70% by mass of a resin having a water absorption rate (ISO62) after 24 hours of 23% in water at 23 ° C. of 0.6% or more; A synthetic resin mixture comprising 30 to 70% by weight of a resin having a water absorption rate (ISO 62) of less than 0.6%;
(B) 100 parts by mass of the synthetic resin mixture of component (A) is mixed with 0.5 to 20 parts by mass of a water-soluble substance having a water solubility (25 ° C.) of 0.01 / 100 g to 10 g / 100 g. Obtaining a composition;
A step of obtaining a resin molded body having a contact angle (measurement method: droplet method) of 60 ° to 70 ° by molding the resin composition ;
After the step of molding the resin composition, the method further comprises a step of readjusting the contact angle by plasma treatment.
A method for producing a resin molded body having a contact angle (measurement method: droplet method) of 60 ° to 70 °.
(B)(A)成分の合成樹脂混合物100質量部に対して、水への溶解度(25℃)が0.01/100g〜10g/100gの水可溶性物質0.5〜20質量部を混合して樹脂組成物を得る工程と、
前記樹脂組成物を成形することで接触角(測定法:液滴法)が70°を超える樹脂成形体を得る工程と、
前記樹脂組成物を成形する工程のあと、更にプラズマ処理することで接触角を60°〜70°に再調整する工程を有する、
接触角(測定法:液滴法)が60°〜70°である樹脂成形体の製造方法。 (A) (A-1) 30 to 70% by mass of a resin having a water absorption rate (ISO62) after 24 hours of 23% in water at 23 ° C. of 0.6% or more; A synthetic resin mixture comprising 30 to 70% by weight of a resin having a water absorption rate (ISO 62) of less than 0.6%;
( B) 100 parts by mass of the synthetic resin mixture of component (A) is mixed with 0.5 to 20 parts by mass of a water-soluble substance having a water solubility (25 ° C.) of 0.01 / 100 g to 10 g / 100 g. Obtaining a composition;
Obtaining a resin molded body having a contact angle (measurement method: droplet method) exceeding 70 ° by molding the resin composition;
After the step of molding the resin composition, the method further comprises the step of readjusting the contact angle to 60 ° to 70 ° by plasma treatment.
A method for producing a resin molded body having a contact angle (measurement method: droplet method) of 60 ° to 70 °.
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