JPS59155436A - Plated resin article - Google Patents
Plated resin articleInfo
- Publication number
- JPS59155436A JPS59155436A JP2690083A JP2690083A JPS59155436A JP S59155436 A JPS59155436 A JP S59155436A JP 2690083 A JP2690083 A JP 2690083A JP 2690083 A JP2690083 A JP 2690083A JP S59155436 A JPS59155436 A JP S59155436A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- plating
- graft copolymer
- plated
- thermoplastic graft
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 title claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 23
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 17
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 16
- 239000004417 polycarbonate Substances 0.000 claims abstract description 16
- -1 vinyl cyanide compound Chemical class 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 239000011342 resin composition Substances 0.000 claims abstract description 10
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 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 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 238000003486 chemical etching Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical group C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920006383 Tyril Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Chemically Coating (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は樹脂成形品にメッキ加工した製品に関し、更に
詳しくは芳香族ポリカーボネートと二種の熱可塑性グラ
フト共重合体よりなる樹脂組成物の成形品にメッキ加工
した製品に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a product obtained by plating a resin molded product, and more specifically to the molding of a resin composition comprising an aromatic polycarbonate and two types of thermoplastic graft copolymers. Regarding products that have been plated.
熱可ゆ性樹脂成形品にメッキ加工して金属様外観を賦与
することは良く知られている。 −従来から広く利用
されているメッキ製品にＡＢＳ樹脂メッキ製品があるが
、更に高い耐熱性と機械的性質を有するメッキ製品が望
まれている。It is well known that thermoplastic resin molded articles are plated to give them a metal-like appearance. - ABS resin plated products are conventionally widely used plated products, but plated products with even higher heat resistance and mechanical properties are desired.
芳香族ポリカーボネートは優れた耐熱性と機械的性質を
備えたエンジニアリングプラスチックとして種々の分野
例えば機械的部品に使用されているが、これにメッキ加
工したものは上述の特性を有するものとなり、上記ＡＢ
Ｓ樹脂メッキ製品では使用できなかった分野から強く期
待されている。しかしながら、芳香族ポリカーボネート
のメッキ加工およびメッキ製品には種々未解決の問題が
あって、まだ充分に満足すべきものが得られていない。Aromatic polycarbonate is used in various fields as an engineering plastic with excellent heat resistance and mechanical properties, such as mechanical parts, but when it is plated, it has the above-mentioned characteristics, and the above-mentioned AB
There are strong expectations for this product in areas where it could not be used with S-resin plated products. However, there are various unresolved problems in plating and plating products of aromatic polycarbonate, and a fully satisfactory product has not yet been obtained.
即ち、樹脂成形品のメッキは、一般に（イ）前処理、（
ロ）化学エツチング、（・→触媒イ」与、に）活性化、
（ホ）化学メッキ、（へ）電気メッキの工程からなって
いる。この工程で特に解）前処理と（ロ）化学エツチン
グの工程は、成形品の表面を粗化することによってメッ
キ下地に適した微細な凹凸を形成し、樹脂とメンキした
金属膜との間に良好な密着性を与えるＭｇな工程である
。しかし、これらの工程は樹脂の鋪類によって異なる。That is, plating of resin molded products generally involves (a) pretreatment, (
b) Chemical etching, (・→catalyst i' addition, to) activation,
It consists of (e) chemical plating and (f) electroplating processes. In this process, the pretreatment and (b) chemical etching processes roughen the surface of the molded product to form fine irregularities suitable for the plating base, and create a gap between the resin and the scratched metal film. This is a Mg process that provides good adhesion. However, these steps differ depending on the type of resin.
例えば、ＡＥＳ！脂では、前処理工程は単に成形品表面
に付着した油脂類を除去する程度であり、メッキ下地と
なる成形品の表面粗化は主にりｐム酸−硫酸酸化液で処
理する化学エツチング工程で行なわれ、その後、電気メ
ッキまでの処理を行なえば容易に優れた密着強度を有す
るＡＢＳ樹脂メッキ人品を得ることができる。゛これに
対し、芳香族ポリカーボネートでは、上記のＡ １３ｓ
樹脂の処理力法では十分な表面粗化が行′なゎれないの
で、その後の化学メッキ工程で化学ニッケル或は化学銅
が付着しないが、または付着しても容易に剥離する。こ
れを解決するために、ジメチルホルムアミド等の有機溶
剤で前処理する方法（特公昭４５−１２９９６号）、酸
化アルカリ溶液で前処理する方法（％公昭４４−２９３
９９号）、芳香族ポリカーボネートに特定の化合物を配
合する方法（特公昭５０−３９１０２号）等が提案され
ているが、これらの前処理法は作業環境上あるいはコス
ト的に好ましくな（、また芳香族ポリカーボネートに特
定比合物を配合する方法は化学エツチングの条件がＡＢ
Ｓ、Ｊ脂の場合よりも難かしいなどの欠点を有している
。For example, AES! For oils, the pretreatment process merely removes the fats and oils adhering to the surface of the molded product, and the surface roughening of the molded product, which is the base for plating, is mainly done through a chemical etching process using a phosphoric acid-sulfuric acid oxidizing solution. After that, by performing treatments up to electroplating, it is possible to easily obtain an ABS resin plated product with excellent adhesion strength.゛On the other hand, in aromatic polycarbonate, the above A 13s
Since sufficient surface roughening cannot be achieved by the resin treatment method, chemical nickel or chemical copper does not adhere in the subsequent chemical plating process, or if it does, it is easily peeled off. To solve this problem, a method of pretreatment with an organic solvent such as dimethylformamide (Japanese Patent Publication No. 45-12996), a method of pretreatment with an alkali oxide solution (Japanese Patent Publication No. 44-293)
99) and a method of blending a specific compound into aromatic polycarbonate (Japanese Patent Publication No. 50-39102), but these pretreatment methods are unfavorable from the working environment or cost standpoint (and are The method of blending a specific compound into group polycarbonate is based on chemical etching conditions of AB.
It has drawbacks such as being more difficult than the case of S and J fats.
本発明の目的は、従来のＡＢＳ樹脂メッキと同様の条件
で容易にメッキが出来、かつＡＢＳ樹脂メッキ製品より
も優れた性質例えば耐熱性、機械的性質等を有するメッ
キ製品を提供することにある。An object of the present invention is to provide a plated product that can be easily plated under the same conditions as conventional ABS resin plating and has better properties such as heat resistance and mechanical properties than ABS resin plated products. .
本発明の目的は、熱可塑性樹脂の成形品にメッキ加工し
た製品において、該熱可塑性樹脂がＱ］芳芳香族ポリカ
ーボー−＋ （Ｂ）ジエン系ゴム成分にシアン化ビニル
化合物および芳香族ビニル化合物をグラフトした熱可塑
性グラフト某買合体及び（Ｑジエン系ゴム成分にメタア
クリル酸エステルおよび（または）アクリル酸エステル
及び芳香族ビニル化合物なグラフトシた熱可塑性グラフ
ト共重合体よりなる樹脂組成物であることを特徴とする
樹脂成形品にメッキ加工した製品によって達成される。The object of the present invention is to provide a product in which a thermoplastic resin molded article is plated, in which the thermoplastic resin contains Q] aromatic polycarbo-+ (B) a vinyl cyanide compound and an aromatic vinyl compound in the diene rubber component. It is a resin composition comprising a grafted thermoplastic graft copolymer and a thermoplastic graft copolymer grafted with a methacrylic ester and/or an acrylic ester and an aromatic vinyl compound to a Q diene rubber component. This is achieved by plating a characteristic resin molded product.
本発明において樹脂組成物の囚成分である芳香族ポリカ
ーボネートは、２価フェノールとホスゲンまたは炭酸ジ
エステルとの反応によって製造することができる。２価
フェノールとしては、ビスフェノール類が好ましく、４
９に２．２−ビス（４−ヒドロキシフェニル）プロパン
（以下、ビスフェノールＡという）が好ましい。またビ
スフェノールＡの一部または全部を他の２価フェノール
で置換しても良い。ビスフェノールＡ 以外の２価フェ
ノールとしては、例えばハイドロキノン、４．４’−ジ
ヒドロキシジフェニル、ビス（４−ヒドロキシフェニル
）アルカン、ビス（４−ヒドロキシフェニル）シクロア
ルカン９ビス（４−ヒドロキシフェニル）スルフィド、
ビス（４−ヒドロキシフェニル）スルホン、ビス（４−
ヒトルキシフェル）ニーデルＪ或はこれらのアルキル置
換体、アリール置換体、ハｐグン置換体などがあげられ
る。芳香族ポリカーボネートは、これら２価フェノール
のポモポリマー、２種以上の２価フェノールからのコポ
リマー、または炭酸の一部を他の２塩基酸（例えば、テ
レフタル酸、イソフタル酸）で置換したコポリマーの中
から選ばれるが、２種以上を組合せても良い。In the present invention, the aromatic polycarbonate which is the active component of the resin composition can be produced by reacting dihydric phenol with phosgene or carbonic diester. As the dihydric phenol, bisphenols are preferable, and 4
9 is preferably 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A). Further, part or all of bisphenol A may be replaced with other dihydric phenol. Examples of dihydric phenols other than bisphenol A include hydroquinone, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)alkane, bis(4-hydroxyphenyl)cycloalkane 9bis(4-hydroxyphenyl)sulfide,
Bis(4-hydroxyphenyl)sulfone, bis(4-
Examples include hydroxyfer) Niedel J, or alkyl-substituted products, aryl-substituted products, and Hapgun-substituted products thereof. Aromatic polycarbonates include pomopolymers of these dihydric phenols, copolymers of two or more dihydric phenols, or copolymers in which a portion of carbonic acid is replaced with other dibasic acids (e.g., terephthalic acid, isophthalic acid). However, two or more types may be combined.
また、（Ｂ）成分の熱可塑性グラフト共重合体は、一般
にＡＢＳ樹脂と総称されているものである。該グラフト
共重合体中のジエン系ゴム成分（幹ポリマ−）としては
、例えばポリブタジェン、ズタジエンースチレン共重合
体。The thermoplastic graft copolymer as component (B) is generally referred to as ABS resin. Examples of the diene rubber component (base polymer) in the graft copolymer include polybutadiene and styrene copolymer.
ブタジェン−７りｌＪｐニトリル共重合体等を挙げるこ
とができる。シアン化ビニル化合物としては、例えばア
クリロニトリルッメタ７クリロニトリル、りＩ：Ｉロア
クリロニトリル等を挙げることができる。更に芳香族ビ
ニル化合物としては、例えばスチレン、α−メチルスチ
レン、ビニルトルエン、フルコキシスチレン、ハロゲン
化スチレン、ビニルピリジン等を挙げることができる。Examples include butadiene-7-1Jp nitrile copolymer. Examples of vinyl cyanide compounds include acrylonitrile, 7-acrylonitrile, and I:I acrylonitrile. Furthermore, examples of aromatic vinyl compounds include styrene, α-methylstyrene, vinyltoluene, flukoxystyrene, halogenated styrene, and vinylpyridine.
更にまた（Ｑ成分の熱可塑性グラフト共重合体は、一般
にＭＢＳ樹脂と総称されているものである。該グラフト
共重合体中のジエン系ゴム成分（幹ポリマ−）および芳
香族ビニル化合物、は、前記（Ｂｌ成分の熱可り性グラ
フＦ共重合体の説明で示したものと同じである。メタア
クリル酸エステル及びアクリル酸エステルとしては例え
ばメタアクリル酸メチル、メタアクリル酸エチル、メタ
アクリル酸プロピル、メタアクリル酸ブチル、アクリル
酸メチル、アクリル酸エチル、アクリル酸プロピル。Furthermore, the thermoplastic graft copolymer (component Q) is generally referred to as MBS resin. The diene rubber component (stem polymer) and aromatic vinyl compound in the graft copolymer are: It is the same as that shown in the explanation of the thermoplastic graph F copolymer of the Bl component. Examples of methacrylic esters and acrylic esters include methyl methacrylate, ethyl methacrylate, and propyl methacrylate. , butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate.
アクリル酸ブチル等のメタアクリル酸、アクリル酸の低
級アルキルエステルが好ましい。Preferred are methacrylic acid such as butyl acrylate, and lower alkyl esters of acrylic acid.
（Ｂ）成分および（Ｑ成分のグラフト共重体は、夫々上
記の成分、化合物のほかに、例えば、ポリアクリル酸エ
ステル系ゴム、エチレンープｐピンン系ゴム、無水マレ
イン酸、アクリρニトリル等を含有してもよい。The graft copolymers of component (B) and (component Q) each contain, in addition to the above-mentioned components and compounds, for example, polyacrylic ester rubber, ethylene p-pin rubber, maleic anhydride, acryl ρ nitrile, etc. It's okay.
これらの熱可塑性グラフト共重合体は、塊状重合、溶液
重合、％５句重合、乳化重合、の何れの重合法で製造し
ても良く、またグラフトの方式として一段グラフトでも
、多段グラフトでも差支えない。また、製造の際に８０
生するグラフト成分のみのコポリマーとの混合物であっ
てもよい。These thermoplastic graft copolymers may be produced by any polymerization method such as bulk polymerization, solution polymerization, %5 polymerization, or emulsion polymerization, and the grafting method may be single-stage grafting or multi-stage grafting. . Also, during manufacturing, 80%
It may be a mixture of only the resulting graft component with a copolymer.
本発明に於て使用される樹脂組成物は、前述の３種の成
分を混合することによって製造される。混合割合は、樹
脂メッキ製品に要求される機械的性質、熱的性質、メン
キした金属膜の性能などによって選ばれるが、一般的に
は囚成分、（Ｂｌ成分、（０成分の重量％が夫々３５〜
８０．１０〜５０，１〜２０であることが好ましく、特
に４０〜６５．２０〜５０゜１〜１５であることが好ま
しい。（ん成分の芳香族ポリカーボネートが３５重量係
未満では、機械的、熱的性質が低下し、８０Ｍ景チを超
えるとメッキの付きが悪くなる。また（Ｂ１成分の熱可
塑性グラフト共重合体が１０重量条未満ではメッキの付
きが悪く、５０重量％を超えると熱的性質が低下する。The resin composition used in the present invention is produced by mixing the three components described above. The mixing ratio is selected depending on the mechanical properties, thermal properties, and performance of the peeled metal film required for the resin-plated product, but in general, the weight percent of the captive component, (Bl component, and (0 component) is 35~
It is preferably 80.10 to 50.1 to 20, particularly preferably 40 to 65.20 to 50.1 to 15. (If the aromatic polycarbonate of the B1 component is less than 35% by weight, the mechanical and thermal properties will deteriorate, and if it exceeds 80M, the adhesion of plating will be poor. If it is less than 50% by weight, the plating will not adhere well, and if it exceeds 50% by weight, the thermal properties will deteriorate.
更にまた（Ｑ成分の熱可塑性グラフト共重合体が１重量
％未満ではメッキの付きが遅く、２０重量％を起えると
機械的熱的性質が低下したり、メッキの表面状態が悪く
なる。Furthermore, if the amount of the thermoplastic graft copolymer (component Q) is less than 1% by weight, plating will be slow, and if it is more than 20% by weight, the mechanical and thermal properties will deteriorate and the surface condition of the plating will deteriorate.
樹脂組成物は、これらの３種の成分をタンブラ−２■型
プレンダー、ナウターミキサ−。The resin composition is prepared by mixing these three components in a tumbler, two-type blender, and a Nauta mixer.
バンバリーミキサ−２混練ｐ−ル、押出機等の如き混合
機により混合して製造することができる。更に本発明の
目的を損なわない範囲内でポリエステル、ポリフェニレ
ンエーテル等の池の樹脂、ガラス繊維、カー、ボン繊維
。It can be produced by mixing with a mixer such as a Banbury mixer 2 kneading mill, an extruder, or the like. Further, resins such as polyester and polyphenylene ether, glass fibers, carbon fibers, and carbon fibers may be used within a range that does not impair the object of the present invention.
炭酸カルシウム、シリカ等の補強材、安定剤。Reinforcing agents and stabilizers such as calcium carbonate and silica.
酸化防止剤９着色剤、紫外線防止剤などを添加してもよ
い。Antioxidant 9 Colorants, ultraviolet inhibitors, etc. may be added.
かくして得られる樹°脂組成物は、射出成形、押出成形
、圧、縮成形等の方法によって成形品にされる。そして
この成形品は通常のＡＢＳ樹脂のメッキとはｙ同じ条帥
で、容易にメッキ刀日工することができる。The resin composition thus obtained is made into a molded article by methods such as injection molding, extrusion molding, compression molding, and compression molding. This molded product can be easily plated in the same manner as ordinary ABS resin plating.
本発明のメンキ製品は、（５）成分の芳香族ポリカーボ
ネート＋（Ｂ）成分の熱可塑性グラフト共重合体、（０
成分の熱可塑性グラフト共重合体の夫々単独、或は２成
分のみの混合物よりなる成形品のメッキ製品に比べて機
械的、熱的性質並びにメンキした金属膜の密着性、外観
等をバランスよく備え、広範囲の用途に子分使用できる
ものである。The Menki product of the present invention consists of (5) component aromatic polycarbonate + (B) component thermoplastic graft copolymer, (0
Compared to plated molded products made of thermoplastic graft copolymer components alone or a mixture of only two components, it has a well-balanced mechanical and thermal properties as well as adhesion and appearance of the scratched metal film. , the molecules can be used in a wide range of applications.
以下に実施例を掲げて本発明を詳述する。 The present invention will be described in detail below with reference to Examples.
実施例１゜
ポリカーボネート（帝人化成■製； Ｌ−１２５０）６
０重量部、ＡＢＳ樹脂（宇部サイコン■製；Ｙ５４０Ａ
〜１１００１）３５重量部、ＭＢＳ樹脂（鐘淵化学■製
；カネエースＢ−２８） ５重量部をプレ／グーで混合
した後３０ｖｍｌ押出機を用いシリンダ一温度２６０
’Ｏにて押出ペンット化した。このペンットをｔ ｉ
ｏ ’ａで３時間乾燥した後射出成形によってｔＸｒｘ
Ｌの角板を成形し、メッキテスト片とした。メッキは以
下に示す常法に従って電気銅メッキを施した。Example 1 Polycarbonate (manufactured by Teijin Kasei ■; L-1250) 6
0 parts by weight, ABS resin (manufactured by Ube Cycon ■; Y540A
~11001) 35 parts by weight and 5 parts by weight of MBS resin (manufactured by Kanebuchi Kagaku ■; Kane Ace B-28) were mixed in Pre/Goo, and then heated to a cylinder temperature of 260 using a 30 vml extruder.
It was extruded into pentlets at 'O. This pent i
tXrx by injection molding after drying for 3 hours at o'a
An L square plate was molded and used as a plating test piece. Electrolytic copper plating was performed according to the conventional method shown below.
（１） 脱脂 ５０゛Ｃで５分間
（２） 水洗
（３）エツチング （ｒＯ，４００９／７！６５・Ｃで
１０分間（
硫酸ａｓｏｇ／Ｉ！
（４） 水洗
（５） 中和 ５ ｖｏ６％Ｈ（Ｊ 室
温で１分間（６） 水洗
（８） 水洗
（９）７クセレーター ｃｏｎｃ、、ＦＩＬｓＯ＋１０
０ｇ／Ａ ４ｓ゛Ｏで３分間！５０ 水洗
（１２水洗
（１：４ 活性化 トップザン＊５ｑｂ 室温
で１分間助 水洗
（功電気銅メッキ ２５°Ｏ＋ ａＡ／ ｄｍ’＋
ｉ ２時間性）＊印は奥野製薬工業■の商品名
以上の処理を施して得たＵ樹脂成形品のメッキ品はすぐ
れた密着強度を示し、１．３ ｋｇ、／ ａｒ＊の密着
強度であった。この結果を表−１に示す。(1) Degreasing 5 minutes at 50°C (2) Washing with water (3) Etching (rO, 4009/7! 10 minutes at 65・C (asog/I sulfuric acid!) (4) Washing with water (5) Neutralization 5 vo6%H (J 1 minute at room temperature (6) Wash with water (8) Wash with water (9) 7 xelator conc,, FILsO+10
0g/A 4s゛O for 3 minutes! 50 Water washing (12 water washing (1:4 activation Topzan*5qb 1 minute at room temperature) Water washing (effective electrolytic copper plating 25°O+ aA/ dm'+
i 2 hour resistance) *marked is the product name of Okuno Pharmaceutical Co., Ltd. The plated U resin molded product obtained by the above treatment shows excellent adhesion strength, with an adhesion strength of 1.3 kg/ar*. there were. The results are shown in Table-1.
樹脂の割合を変えて、実施例１と同様の方法によって得
られたメッキ品の密着強度を表−１に示す。Table 1 shows the adhesion strength of plated products obtained by the same method as in Example 1 by changing the proportion of resin.
またＣ ｒ Ｏｓエツチングの条件を変えたものも同時
に示した。In addition, samples with different C r Os etching conditions are also shown.
実施例４〜６ ポリカーポネート：（帝人化成■； Ｌ−１２５０）。Examples 4-6 Polycarbonate: (Teijin Kasei ■; L-1250).
ＡＢＳ樹脂：（ダイセル■；セビアンーＳＤ）ＭＢＳ樹
脂＝（クンハ化学■；ＢＴＡ−Ｉｌｌ）を使用し、実施
例１と同様の方法によって得られたメッキ品の密度強度
を表−２示す。Table 2 shows the density strength of plated products obtained in the same manner as in Example 1 using ABS resin: (Daicel ■; Cevian-SD) MBS resin (Kunha Chemical ■; BTA-Ill).
実施例６によって得られた成形品の性能は引張り強さ５
６０ ｋｇ／ｄ 、曲げ強さ９００ ｋｇ ／ｃｒｌ。The performance of the molded product obtained in Example 6 is that the tensile strength is 5.
60 kg/d, bending strength 900 kg/crl.
曲げ弾性率６０ Ｘ １ ｏ′ｋｇ ／ｃｒｌ 、 １
／８インチフイゾットノツチ付インパクト４５ｋｇ・ス
／歯、熱変形温度１３２°Ｃであった。Flexural modulus: 60 x 1 o'kg/crl, 1
The impact was 45 kg/s/tooth with a /8 inch diameter notch, and the heat deformation temperature was 132°C.
比較例４
実施例１においてＡＢＳ樹脂の代りにＡｓ樹脂（旭ダウ
社；タイリル７６７）を用いて実施したところメッキの
は殆んどつかず、伺着した部分の密着強度は０．２〜０
．３ ｋｇ／ ｔｘと非常に小さかった。Comparative Example 4 When As resin (Asahi Dow Co., Ltd.; Tyril 767) was used instead of ABS resin in Example 1, almost no plating was attached, and the adhesion strength of the adhered portion was 0.2 to 0.
．． It was very small at 3 kg/tx.
＼璽；、 Ｘ（、、”’ｊ、’
手 続 補 正 書
昭和５９年３月７日
特許庁長官 殿
１ 事件の表示
特願昭５８−’２６９００号
２ 発明の名称
樹脂メッキ製品
３ 補正をする者
事件との関係 特許出願人
東京都港区西新槁１＝６−２１
（人相体行虎〕門ビル）
帝人化成株式会社
代表者 山 崎 芳 樹
４ 代 理 人 東京都千代田区内卒町２丁目
１余１号５ 補正の対象
明ＭＢ書の「発明の詳細な説明」の欄
６ 補正の内科
明細書の笥９行目に１．Ｊライのは殆んど」とあるを１
−メッキは殆んど１に訂正する。＼璽;, Relationship with the case of a person who commits a crime Patent applicant 1-6-21 Nishishinkai, Minato-ku, Tokyo (Physiotai Yukitoramon Building) Representative of Teijin Kasei Ltd. Yoshiki Yamazaki 4th Representative Chiyoda-ku, Tokyo Sotomachi 2-chome 1 Yo-1 No. 5 Subject of the amendment ``Detailed explanation of the invention'' column 6 of the Mei MB book 1. In the 9th line of the column of the amended internal medicine specification, it says 1. Most of J Rai's. 1
- Correct most of the plating to 1.
以 上 手 続 補 正 書 昭五］５９年４月 タ日 特許庁長官 殿 ｌ 事件の表示 特―昭５８−２６９０υ号 ２ 発明の名称 樹脂ノツキ製品 ３ 補正をする者 事件との関係 特許出願人 東忌都港区西２ＩＴ搗］−６−２１ （太和釧行ルθ）門ビル） 帝人化成体弐会社 代表者 山 崎 芳 樹 ４、 代 理 人 東京都千代田区内辛町２丁目１番１号 （飯野ビル） 帝人株式・公社内 ６ 補正の対象that's all Manual continuation supplementary book Date of April 1959 Commissioner of the Patent Office l Incident display Special issue - 1984-2690υ 2 Name of the invention resin notsuki products 3 Person making the amendment Relationship to the incident: Patent applicant Higashii Miyako-ku Nishi 2 IT Boku] -6-21 (Taiwa Sengyo Le θ) Gate Building) Teijin Chemicals 2 Company Representative Yoshiki Yamazaki 4. Physician 2-1-1 Uchikaracho, Chiyoda-ku, Tokyo (Iino Building) Teijin Stock/Public Company 6 Target of correction
Claims (1)
いて、該熱可塑性樹脂が（５）芳香族ポリカーボネー）
、 ＣＢ）ジエン系ゴム成分にシアン化ビニル化合物
および芳香族ビニル化合物をグラフトした熱可塑性グラ
フト共重合体及び（Ｑジエン系ゴム成分にメタアクリル
酸エステルおよび（または）アクリル酸エステル及び芳
香族ビニル化合物をグラフトした熱可塑性グラフト共重
合体よりなる樹脂組成物であることを特９とする樹脂成
形品にメッキ加工した製品。 ２ 前記樹脂組成物において（５）成分の芳香族ポリカ
ーボネートが３５〜８０重量％であり、（Ｂ）成分の熱
可塑性グラフト共重合体が１０〜５０重量％であり、
（ＣＩ酸成分熱可塑性グラフト共重合体が１〜２０重量
％であることを特徴とする特許請求の範囲第１項記載の
製品。[Scope of Claims] 1. A product obtained by plating a thermoplastic resin molded article, wherein the thermoplastic resin is (5) aromatic polycarbonate).
, CB) A thermoplastic graft copolymer in which a vinyl cyanide compound and an aromatic vinyl compound are grafted to a diene rubber component, and (Q a methacrylic ester and/or an acrylic ester and an aromatic vinyl compound to the diene rubber component) A product obtained by plating a resin molded article, characterized in that it is a resin composition made of a thermoplastic graft copolymer grafted with 2. In the resin composition, the aromatic polycarbonate component (5) is 35 to 80% by weight. %, the thermoplastic graft copolymer of component (B) is 10 to 50% by weight,
(The product according to claim 1, characterized in that the CI acid component thermoplastic graft copolymer is present in an amount of 1 to 20% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2690083A JPS59155436A (en) | 1983-02-22 | 1983-02-22 | Plated resin article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2690083A JPS59155436A (en) | 1983-02-22 | 1983-02-22 | Plated resin article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59155436A true JPS59155436A (en) | 1984-09-04 |
| JPH0259178B2 JPH0259178B2 (en) | 1990-12-11 |
Family
ID=12206108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2690083A Granted JPS59155436A (en) | 1983-02-22 | 1983-02-22 | Plated resin article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59155436A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62167352A (en) * | 1986-01-21 | 1987-07-23 | Teijin Chem Ltd | Plated resin article |
| US9676938B2 (en) | 2007-06-08 | 2017-06-13 | Lucite International Uk Limited | Polymer composition |
| JP2018507919A (en) * | 2015-11-05 | 2018-03-22 | エルジー・ケム・リミテッド | Polycarbonate-ABS alloy resin composition having excellent plating adhesion and molded product containing the same |
| WO2019087653A1 (en) * | 2017-10-30 | 2019-05-09 | 東レ株式会社 | Thermoplastic resin composition for plated molded article, and molded article and plated molded article both obtained using same |
| WO2021208434A1 (en) * | 2020-04-13 | 2021-10-21 | 金发科技股份有限公司 | Pc/abs alloy material, and preparation method and use therefor |
-
1983
- 1983-02-22 JP JP2690083A patent/JPS59155436A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62167352A (en) * | 1986-01-21 | 1987-07-23 | Teijin Chem Ltd | Plated resin article |
| US9676938B2 (en) | 2007-06-08 | 2017-06-13 | Lucite International Uk Limited | Polymer composition |
| US9944791B2 (en) | 2007-06-08 | 2018-04-17 | Lucite International Uk Ltd. | Polymer composition |
| JP2018507919A (en) * | 2015-11-05 | 2018-03-22 | エルジー・ケム・リミテッド | Polycarbonate-ABS alloy resin composition having excellent plating adhesion and molded product containing the same |
| WO2019087653A1 (en) * | 2017-10-30 | 2019-05-09 | 東レ株式会社 | Thermoplastic resin composition for plated molded article, and molded article and plated molded article both obtained using same |
| WO2021208434A1 (en) * | 2020-04-13 | 2021-10-21 | 金发科技股份有限公司 | Pc/abs alloy material, and preparation method and use therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0259178B2 (en) | 1990-12-11 |
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