JP2581543B2 - Method for producing plated wholly aromatic polyester liquid crystal polymer molded article - Google Patents
Method for producing plated wholly aromatic polyester liquid crystal polymer molded articleInfo
- Publication number
- JP2581543B2 JP2581543B2 JP61156160A JP15616086A JP2581543B2 JP 2581543 B2 JP2581543 B2 JP 2581543B2 JP 61156160 A JP61156160 A JP 61156160A JP 15616086 A JP15616086 A JP 15616086A JP 2581543 B2 JP2581543 B2 JP 2581543B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polymer
- molded article
- aromatic polyester
- wholly aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、メッキした全芳香族系ポリエステル液晶ポ
リマー（以下「液晶ポリマー」という。）成形品の製造
法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing a plated wholly aromatic polyester liquid crystal polymer (hereinafter referred to as “liquid crystal polymer”) molded article.
（従来の技術） 合成樹脂成形品に対するメッキについては、従来から
装飾や導電性あるいは耐熱性などの機能付与の目的から
種々の合成樹脂について試みられており、ABS樹脂やポ
リプロピレン樹脂など数種のものについては実用化され
ている。さらに、これら従来のものより優れた機械的性
質、耐熱性、耐薬品性を有するポリエステル樹脂に対す
るメッキ方法が確立されつつあり、ABS樹脂やポリプロ
ピレン樹脂のメッキ品では利用しなかった耐熱性や機械
的強度を必要とする新規な分野への応用が期待される。
そのため従来から芳香族ポリエステル樹脂、すなわち熱
可塑性結晶性ポリエステル樹脂に対するメッキ処理につ
いては、例えば、予め該ポリエステルに充填剤を含有せ
しめたものをアルカリ水溶液に浸漬する方法（特開昭55
−99929号公報）、該ポリエステルに樹脂族ポリエステ
ルと二酸化チタンを配合したものをアルカリ溶液に浸漬
する方法（特開昭60−63379号公報）などが知られてい
る。(Prior art) With regard to plating on synthetic resin molded products, various types of synthetic resins have been tried for the purpose of imparting functions such as decoration, conductivity, heat resistance, and the like, and several types such as ABS resin and polypropylene resin have been tried. Has been put to practical use. Furthermore, plating methods for polyester resins with better mechanical properties, heat resistance and chemical resistance than these conventional ones are being established, and heat resistance and mechanical properties that were not used for plated ABS resin or polypropylene resin It is expected to be applied to new fields that require strength.
For this reason, conventionally, a plating treatment for an aromatic polyester resin, that is, a thermoplastic crystalline polyester resin, is performed, for example, by immersing a polyester in which a filler is previously contained in an alkaline aqueous solution (Japanese Patent Laid-Open No.
Japanese Patent Application Laid-Open No. 60-63379), and a method of immersing a mixture of the polyester and a resin family polyester and titanium dioxide in an alkaline solution.
（発明が解決しようとする問題点） しかし、いずれの方法も熱安定性において必ずしも満
足のいくものではない。(Problems to be Solved by the Invention) However, none of the methods is necessarily satisfactory in terms of thermal stability.
ところで、合成樹脂成形品は優れた特性を備えたもの
であってもメッキが困難とされているものについては、
導電性，半田付性，色彩，硬度などの面から用途が限定
され、合成樹脂の需要を制約する結果となっている。特
に、液晶ポリマーは、耐熱性はもとより、熱線膨張係数
が広い範囲での温度条件下で金属に近く、金属膜との同
等の伸縮作用をするので、サーマルサイクルテストにお
いてもメッキ層の剥離現象が見られないなど優れた特性
を備え、多くの用途が期待されている。しかし、いまだ
液晶ポリマーについてのメッキ方法が確立しておらず、
用途上での制約を余儀なくしているのが現状である。By the way, even if a synthetic resin molded product has excellent characteristics, it is difficult to plate it.
Applications are limited in terms of conductivity, solderability, color, hardness, and the like, and this has resulted in limiting demand for synthetic resins. In particular, the liquid crystal polymer has not only heat resistance but also a coefficient of linear thermal expansion that is close to metal under temperature conditions in a wide range, and has the same expansion and contraction action as a metal film. It has excellent properties, such as not being seen, and is expected to be used in many applications. However, the plating method for liquid crystal polymer has not been established yet,
At present, it is inevitable to restrict the use.
そこで、本願発明者は、この優れた性質を備える液晶
ポリマーに着目し検討した結果、液晶ポリマー成形品に
アルカリ性水溶液による表面粗化処理をよびメッキ処理
を施すことにより、従来のものより熱安定性が向上する
ことを見出し、本発明を完成させた。Therefore, the inventors of the present application have focused on the liquid crystal polymer having such excellent properties, and as a result, by performing a surface roughening treatment and a plating treatment on the liquid crystal polymer molded product with an alkaline aqueous solution, the thermal stability is higher than that of the conventional one. Have been found, and the present invention has been completed.
すなわち、本発明の目的は、液晶ポリマーのメッキ方
法を確立し、液晶ポリマーの用途の拡大を図るという目
的達成のため、全芳香族系ポリエステル液晶ポリマー成
形品を、アルカリ性水溶液により表面粗化処理した後、
メッキ処理することを特徴とするメッキした全芳香族系
ポリエステル液晶ポリマー成形品の製造法を提供するも
のである。That is, the object of the present invention is to establish a method for plating a liquid crystal polymer, and to achieve the purpose of expanding the applications of the liquid crystal polymer, a wholly aromatic polyester liquid crystal polymer molded article was subjected to surface roughening treatment with an alkaline aqueous solution. rear,
An object of the present invention is to provide a method for producing a plated wholly aromatic polyester liquid crystal polymer molded article characterized by performing a plating treatment.
（問題を解決するための手段） 本発明の特徴は、全芳香族系ポリエステル液晶ポリマ
ー成形品を、アルカリ性水溶液により表面粗化処理した
後、メッキ処理するところにある。(Means for Solving the Problem) A feature of the present invention resides in that a molded article of a wholly aromatic polyester liquid crystal polymer is subjected to a surface roughening treatment with an alkaline aqueous solution and then a plating treatment.
この液晶ポリマーには、無充填のものと、フィラーと
してガラス繊維や炭素繊維等を充填したものである。This liquid crystal polymer is unfilled and filled with glass fiber, carbon fiber, or the like as a filler.
また、本発明の合成樹脂のメッキ前処理としての表面
粗化（エッチング）工程において、エッチング液は苛性
ソーダまたは苛性カリを所定濃度に溶解したアルカリ性
水溶液を所定温度に加熱し、この水溶液中に液晶ポリマ
ー成形品を特定時間浸漬してから、成形品の種類によっ
ては触媒賦与処理を行う。In the surface roughening (etching) step as a pretreatment for plating the synthetic resin of the present invention, an etching solution is heated to a predetermined temperature with an alkaline aqueous solution in which caustic soda or caustic potash is dissolved at a predetermined concentration, and a liquid crystal polymer is formed in the aqueous solution. After soaking the article for a specific time, a catalyst application treatment is performed depending on the type of the molded article.
さらに詳細に説明すると、本発明の表面粗化処理にお
いて、エッチング液に用いるアルカリ性水溶液の苛性ソ
ーダ（NaOH）または苛性カリ（KOH）の量は、特に限定
するものではないが、40〜400g/、望ましくは100〜30
0g/の範囲から選択して水溶液を作る。この範囲で
は、40g/より少ない場合には、エッチング不足となる
ので好ましくなく、400g/より多い場合には、後工程
での水洗性が悪くなる不都合が生ずる。100〜300g/の
範囲が、メッキ金属の密着性付与促進上および作業能率
上効果的である。More specifically, in the surface roughening treatment of the present invention, the amount of caustic soda (NaOH) or caustic potassium (KOH) in the alkaline aqueous solution used for the etching solution is not particularly limited, but is preferably 40 to 400 g /, preferably 100-30
Make an aqueous solution by selecting from the range of 0 g /. In this range, if the amount is less than 40 g /, the etching becomes insufficient, which is not preferable. If the amount is more than 400 g /, there is a disadvantage that the water-washing property in a subsequent step is deteriorated. A range of 100 to 300 g / is effective in promoting adhesion of the plated metal and in work efficiency.
また、アルカリ性水溶液の加熱温度の範囲は、この水
溶液の濃度との関係から適宜選択すればよいが、50〜90
℃の範囲が適当である。加熱温度が50℃より低いとエッ
チング不足になり、90℃より高いと液ならびに設備の管
理が難しくなる不都合が生ずる。Further, the range of the heating temperature of the alkaline aqueous solution may be appropriately selected from the relationship with the concentration of the aqueous solution,
A range of ° C is appropriate. If the heating temperature is lower than 50 ° C., the etching becomes insufficient.
表面粗化処理は、このエッチング液中に液晶ポリマー
の成形品を所定時間浸漬しておくが、この時間もエッチ
ングの程度および液温などとの関係から適宜選択すれば
よい。In the surface roughening treatment, a molded product of a liquid crystal polymer is immersed in the etching solution for a predetermined time, and this time may be appropriately selected depending on the degree of etching, the liquid temperature, and the like.
成形品の表面を活性化するための触媒賦与処理として
は、センシタイジング・アクチベーディング方法と、キ
ャタリスト・アクセラレーター方法などから適宜選択可
能である。The catalyst application treatment for activating the surface of the molded article can be appropriately selected from a sensitizing activating method, a catalyst accelerator method, and the like.
次に、下地メッキとして化学メッキを施し、さらに電
気メッキをするが、これらの両メッキの方法は公知技術
による。Next, chemical plating is applied as a base plating, and then electroplating is performed. Both of these plating methods are based on known techniques.
なお、成形材料中のフイラーとして、導電性フィラー
例えば炭素繊維，炭素微粒子，チタン酸カリウム系導電
繊維、金属系繊維等を用いた成形品は、前記の表面粗化
処理後の化学メッキをせずに、直接電気メッキを行うこ
とが可能である。As a filler in the molding material, a molded product using a conductive filler such as carbon fiber, carbon fine particles, potassium titanate-based conductive fiber, or metal-based fiber is not subjected to the chemical plating after the surface roughening treatment. In addition, it is possible to perform electroplating directly.
（作用） 本発明によると、液晶ポリマー成形品に対し上記エッ
チング液を使用して表面粗化処理を行った場合は、表面
が膨潤し、中のフィラーが表面に露出し、部分的に抜け
落ちたり溶出されたりするために、表面に微細な凹凸が
形成され、表面積の増加と、微細な凹凸面とによるアン
カー効果により、密着性を高める状態を作る。この表面
粗化した成形品に触媒賦与処理を施すと、成形品の表面
は活性化しメッキ金属の吸着反応を促進し易い状態を作
る。(Function) According to the present invention, when the liquid crystal polymer molded article is subjected to a surface roughening treatment using the above-mentioned etching solution, the surface swells, the filler in the surface is exposed to the surface, and a part of the filler is dropped off. Due to elution, fine irregularities are formed on the surface, and a state where the adhesion is enhanced by the increase in surface area and the anchor effect due to the fine irregularities is created. When a catalyst-imparting treatment is applied to the surface-roughened molded product, the surface of the molded product is activated to create a state in which the adsorption reaction of the plated metal is easily promoted.
（発明の効果） 本発明によれば、従来はできなかった液晶ポリマーへ
の表面粗化処理が可能となり、密着性および熱安定性の
向上した液晶ポリマー成形品が得られる。この結果、液
晶ポリマーの成形品の用途拡大を図ることができ、新規
分野への応用が期待できる。(Effects of the Invention) According to the present invention, a surface roughening treatment on a liquid crystal polymer, which has not been possible conventionally, can be performed, and a liquid crystal polymer molded article having improved adhesion and thermal stability can be obtained. As a result, the use of liquid crystal polymer molded articles can be expanded, and application to new fields can be expected.
（実施例） メッキすべき液晶ポリマー成形品として、米国セラニ
ーズ社製ベクトラC130（商品名））を用い、市販の脱脂
液（奥野製薬のエースクリーンＡ−220−／商品名）の5
0g/の水溶液を50℃に加熱し、この中に５分間浸漬し
て水洗いした。(Example) As a liquid crystal polymer molded product to be plated, Vectra C130 (trade name, manufactured by Celanese Corp., USA) was used, and a commercially available degreasing liquid (Ascreen A-220- / trade name, Okuno Pharmaceutical Co., Ltd.) was used.
A 0 g / water solution was heated to 50 ° C., immersed in the solution for 5 minutes, and washed with water.
次に、エッチング処理として200g/の苛性ソーダを
溶解したアルカリ性水溶液を作り、90℃に加熱し、この
中へ前記ポリマー成形品を20分間浸漬してから引き上げ
て、水洗いした。Next, an alkaline aqueous solution in which 200 g / caustic soda was dissolved was prepared as an etching treatment, heated to 90 ° C., the polymer molded article was immersed therein for 20 minutes, pulled up, and washed with water.
次に、触媒賦与処理は、キャタリスト・アクセラレー
ター方法を採用した。すなわち、150ml/の濃塩酸中に
キャタリストＣ（奥野製薬）を30ml/の割合で混合
し、温度を30℃に保持して３分間浸漬し、水洗いした
後、硫酸80ml/からなるアクセラレーター液を50℃に
保持しておき、この中へメッキすべき液晶ポリマー成形
品を４分間浸漬してから水洗いした。Next, the catalyst application treatment employed a catalyst accelerator method. That is, Catalyst C (Okuno Pharmaceutical Co., Ltd.) was mixed at a rate of 30 ml / in 150 ml / concentrated hydrochloric acid, immersed for 3 minutes while maintaining the temperature at 30 ° C., washed with water, and then an accelerator solution comprising 80 ml / sulfuric acid. Was kept at 50 ° C., and a liquid crystal polymer molded product to be plated was immersed in the molded product for 4 minutes, and then washed with water.
その後、TMP化学ニッケル液（奥野製薬）を35℃に保
持し、この中に液晶ポリマー成形品を10分間浸漬して化
学メッキをしてから水洗いをし、最後に公知方法による
電気メッキによりニッケルメッキをした。After that, the TMP chemical nickel solution (Okuno Pharmaceutical Co., Ltd.) is kept at 35 ° C, the liquid crystal polymer molded product is immersed in this for 10 minutes, chemically plated, washed with water, and finally nickel plated by a known method of electroplating. Did.
上記の方法によりメッキ処理した結果、光沢および硬
度ともにABS樹脂へのメッキ処理したものと比較して劣
らず、密着性もピーリング強さで0.8kg/cm以上であり、
下記条件におけるサーマルサイクルテストにおいてもメ
ッキ層の剥離が一切見られず、メッキが完全になされて
いることを示している。As a result of plating by the method described above, both gloss and hardness are not inferior to those plated with ABS resin, and adhesion is 0.8 kg / cm or more in peeling strength,
In the thermal cycle test under the following conditions, no peeling of the plating layer was observed, indicating that plating was completed.
サーマルサイクルテスト条件 記 （ａ） −40℃ 60分 （ｂ） 23℃ 15分 （ｃ） 85℃ 60分 （ｄ） 23℃ 15分 以上の（ａ）〜（ｄ）を１サイクルとして３回行う。Thermal cycle test conditions Notes (a) -40 ° C for 60 minutes (b) 23 ° C for 15 minutes (c) 85 ° C for 60 minutes (d) 23 ° C for 15 minutes Perform at least three times with (a) to (d) as one cycle. .
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭53−6374（ＪＰ，Ａ) 特開 昭54−15977（ＪＰ，Ａ) 特開 昭55−99929（ＪＰ，Ａ) 特開 昭58−65629（ＪＰ，Ａ) 特開 昭58−157827（ＪＰ，Ａ) 特開 昭60−63379（ＪＰ，Ａ) 特開 昭57−56235（ＪＰ，Ａ) 特表 昭55−500214（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-53-6374 (JP, A) JP-A-54-15977 (JP, A) JP-A-55-99929 (JP, A) JP-A-58-58 65629 (JP, A) JP-A-58-1557827 (JP, A) JP-A-60-63379 (JP, A) JP-A-57-56235 (JP, A) Special table 55-500214 (JP, A)
Claims (1)
品を、所定温度および所定濃度のアルカリ性水溶液によ
り表面粗化処理した後、メッキ処理するものであって、 上記アルカリ性水溶液は100〜300g/の苛性ソーダを含
むものであり、上記所定温度は50〜90℃である ことを特徴とするメッキした全芳香族系ポリエステル液
晶ポリマー成形品の製造法。A molded article of a wholly aromatic polyester liquid crystal polymer is subjected to a surface roughening treatment with a predetermined temperature and a predetermined concentration of an aqueous alkaline solution, followed by plating, wherein the alkaline aqueous solution is 100 to 300 g / caustic soda. Wherein the predetermined temperature is from 50 to 90 ° C., wherein the molded product is a wholly aromatic polyester liquid crystal polymer molded article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61156160A JP2581543B2 (en) | 1986-07-04 | 1986-07-04 | Method for producing plated wholly aromatic polyester liquid crystal polymer molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61156160A JP2581543B2 (en) | 1986-07-04 | 1986-07-04 | Method for producing plated wholly aromatic polyester liquid crystal polymer molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6314879A JPS6314879A (en) | 1988-01-22 |
| JP2581543B2 true JP2581543B2 (en) | 1997-02-12 |
Family
ID=15621659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61156160A Expired - Lifetime JP2581543B2 (en) | 1986-07-04 | 1986-07-04 | Method for producing plated wholly aromatic polyester liquid crystal polymer molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2581543B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3884546T3 (en) * | 1987-10-02 | 2000-03-23 | Polyplastics Co | Process for the surface treatment of objects made of liquid crystalline polyester resin. |
| JPH0724328B2 (en) * | 1989-07-03 | 1995-03-15 | ポリプラスチックス株式会社 | Method for manufacturing molded products for fine wire circuits |
| US5085015A (en) * | 1990-06-26 | 1992-02-04 | E. I. Du Pont De Nemours And Company | Process for improving the surface of liquid crystal polymers |
| JPH06298973A (en) * | 1993-04-13 | 1994-10-25 | Nippon Sanmou Senshoku Kk | Electrically conductive polyester-based material and its production |
| IE940943A1 (en) * | 1993-12-09 | 1995-06-14 | Methode Electronics Inc | Printed plastic circuits and contacts and method for making¹same |
| US6923919B2 (en) * | 2000-07-18 | 2005-08-02 | 3M Innovative Properties Company | Liquid crystal polymers for flexible circuits |
| US20120021218A1 (en) * | 2010-07-23 | 2012-01-26 | Syscom Advanced Materials, Inc. | Electrically conductive metal-coated fibers, continuous process for preparation thereof, and use thereof |
| GB2520982B (en) * | 2013-12-05 | 2018-05-30 | Blade & Faith Ltd | Electroplating on Plastic |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS536374A (en) * | 1976-07-06 | 1978-01-20 | Minolta Camera Kk | Method of treating thermoplastic polyester resin for electroless plating |
| JPS5415977A (en) * | 1977-07-05 | 1979-02-06 | Teijin Ltd | Metho of plating polyester resin |
| JPS5599929A (en) * | 1979-01-24 | 1980-07-30 | Teijin Ltd | Preparation of plated molded polyester resin article |
| JPS58157827A (en) * | 1982-03-16 | 1983-09-20 | Toray Ind Inc | Preparation of polyester molded article having metallized surface |
| JPS6063379A (en) * | 1983-09-14 | 1985-04-11 | Toray Ind Inc | Manufacture of surface-metallized molded article of polybutylene terephthalate resin |
| JPS60181324A (en) * | 1984-02-24 | 1985-09-17 | Sumitomo Chem Co Ltd | Method of treatment of yarn |
| US4820553A (en) * | 1984-03-09 | 1989-04-11 | Allied-Signal Inc. | Method for pretreatment of polyesters for metal plating |
-
1986
- 1986-07-04 JP JP61156160A patent/JP2581543B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6314879A (en) | 1988-01-22 |
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