JPH0325512B2 - - Google Patents
Info
- Publication number
- JPH0325512B2 JPH0325512B2 JP8947085A JP8947085A JPH0325512B2 JP H0325512 B2 JPH0325512 B2 JP H0325512B2 JP 8947085 A JP8947085 A JP 8947085A JP 8947085 A JP8947085 A JP 8947085A JP H0325512 B2 JPH0325512 B2 JP H0325512B2
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene sulfide
- sulfide resin
- molded product
- chloride
- anhydrous
- 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
Links
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 27
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- OFDISMSWWNOGFW-UHFFFAOYSA-N 1-(4-ethoxy-3-fluorophenyl)ethanamine Chemical compound CCOC1=CC=C(C(C)N)C=C1F OFDISMSWWNOGFW-UHFFFAOYSA-N 0.000 claims description 2
- IUFVGONBAUNAOT-UHFFFAOYSA-N 2,4,5-trichloro-6-methylpyrimidine Chemical compound CC1=NC(Cl)=NC(Cl)=C1Cl IUFVGONBAUNAOT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000007747 plating Methods 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000007788 roughening Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920013632 Ryton Polymers 0.000 description 1
- 239000004736 Ryton® Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/26—Roughening, e.g. by etching using organic liquids
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)
Description
〔産業上の利用分野〕
本発明は、改善されたポリフエニレンスルフイ
ド樹脂成形品の表面金属化方法に関する。
〔従来の技術〕
従来、ポリフエニレンスルフイド成形品の表面
を金属化する方法としては、特公昭56−25453号
公報に、該成形品の被金属化面を機械的に粗面化
処理し、次にクロム化合物、硫酸およびリン酸を
主体としてなる強酸化性水溶液でエツチングした
後に化学メツキする方法が提案されている。
〔本発明が解決しようとする問題点〕
しかしながら前記公報記載の方法においては、
被金属化面をサンド・ブラストあるいはサンドペ
ーパーなどにより機械的に粗面化する必要がある
ため、三次元的な凹凸を有する成形品には適用し
がたいという欠点がある。更に、引き続く強酸化
性水溶液の処理により粗表面化効果のないことは
該公報に記載の通りであるが、得られる金属メツ
キ膜と樹脂成形品との接着力も不十分であり有効
な方法とは言えない。
そこで本発明者らは、機械的な粗表面化処理を
行うことなく、化学的エツチングによりポリフエ
ニレンスルフイド樹脂成形品の粗表面化が実現さ
れ、十分な金属メツキ膜との接着力が得られる方
法について鋭意検討を行い、ポリフエニレンスル
フイド樹脂に特定の充填剤を特定量配合せしめて
なる成形品を特定の薬液中で処理し、更に酸また
はアルカリまたは塩で処理を行い次いで通常のメ
ツキ処理を施すことにより特異的にメツキ接着力
のすぐれた表面金属化ポリフエニレンスルフイド
樹脂成形品が得られることを見出だし本発明に到
達した。
〔問題点を解決するための手段〕
すなわち本発明は、ポリフエニレンスルフイド
樹脂100重量部に対して、平均粒子径が0.5〜10μ
の範囲の無機充填剤10〜250重量部を含有せしめ
てなるポリフエニレンスルフイド樹脂成形品を、
無水塩化アルミニウム、五塩化アンチモン、無水
塩化第二鉄、二塩化テルル、四塩化テルル、無水
塩化第二スズ、四塩化チタン、三塩化ビスマス、
塩化亜鉛等からなるフリーデル・クラフツ反応触
媒の群より選ばれた一種または二種以上を有機溶
媒に溶解せしめた液を用いて粗表面化処理した
後、更に酸またはアルカリまたは塩で処理を行つ
たのちメツキ処理することを特徴とするポリフエ
ニレンスルフイド樹脂成形品の表面金属化方法を
提供するものである。
本発明で用いるポリフエニレンスルフイド（以
下PPSと略称する）とは、
構造式
[Industrial Field of Application] The present invention relates to an improved method for surface metallization of polyphenylene sulfide resin molded articles. [Prior Art] Conventionally, as a method for metallizing the surface of a polyphenylene sulfide molded product, Japanese Patent Publication No. 56-25453 discloses a method of mechanically roughening the surface of the molded product to be metallized. Next, a method has been proposed in which etching is performed with a strongly oxidizing aqueous solution mainly consisting of a chromium compound, sulfuric acid, and phosphoric acid, followed by chemical plating. [Problems to be solved by the present invention] However, in the method described in the above publication,
Since it is necessary to mechanically roughen the surface to be metallized by sand blasting or sandpaper, it has the disadvantage that it is difficult to apply to molded products having three-dimensional irregularities. Furthermore, as stated in the publication, the subsequent treatment with a strongly oxidizing aqueous solution does not have the effect of roughening the surface, but the adhesive strength between the resulting metal plating film and the resin molded product is also insufficient, so it cannot be said to be an effective method. do not have. Therefore, the present inventors have developed a method in which the surface of a polyphenylene sulfide resin molded product can be roughened by chemical etching without performing mechanical surface roughening treatment, and sufficient adhesive strength with the metal plating film can be obtained. We conducted extensive research on this, and treated polyphenylene sulfide resin with a specific filler in a specific amount to form a molded product in a specific chemical solution, further treat it with an acid, alkali, or salt, and then perform the usual plating process. The present inventors have discovered that a surface-metalized polyphenylene sulfide resin molded article with excellent plating adhesion can be obtained by applying the above-mentioned method to the present invention. [Means for Solving the Problems] That is, the present invention provides a polyphenylene sulfide resin having an average particle diameter of 0.5 to 10 μm based on 100 parts by weight of polyphenylene sulfide resin.
A polyphenylene sulfide resin molded product containing 10 to 250 parts by weight of an inorganic filler in the range of
Anhydrous aluminum chloride, antimony pentachloride, anhydrous ferric chloride, tellurium dichloride, tellurium tetrachloride, anhydrous stannic chloride, titanium tetrachloride, bismuth trichloride,
After roughening the surface using a solution in which one or more selected from the group of Friedel-Crafts reaction catalysts such as zinc chloride are dissolved in an organic solvent, the surface is further treated with acid, alkali, or salt. The present invention provides a method for metallizing the surface of a polyphenylene sulfide resin molded article, which is characterized by performing a plating treatment. The polyphenylene sulfide (hereinafter abbreviated as PPS) used in the present invention has the following structural formula:
【式】で示される繰返し単
位を70モル％以上、より好ましくは90モル％以上
を含む重合体であり、上記繰返し単位が70モル％
未満では耐熱性が損なわれるため好ましくない。
PPSは一般に、特公昭45−3368号公報で代表さ
れる製造法により得られる比較的分子量の小さい
重合体と特公昭52−12240号公報で代表される製
造法により得られる本質的に線状で比較的高分子
量の重合体等があり、前者の重合体においては、
重合後酸素雰囲気下において加熱することによ
り、あるいは過酸化物等の架橋剤を添加して加熱
することにより高重合度化して用いることも可能
であり、本発明においてはいかなる方法により得
られたPPSを用いることも可能である。成形品自
体の機械特性の面で、また、メツキ接着面での
PPSの凝集剥離に由来するメツキ膜接着力の低下
を回避する意味では、前記特公昭52−12240号公
報で代表される製造法により得られる本質的に線
状の重合体が、より好ましく用いられ得る。
また、PPSはその繰返し単位の30モル％未満を
下記の構造式を有する繰返し単位等で構成するこ
とが可能である。A polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the formula, where the above repeating unit is 70 mol%
If it is less than this, heat resistance will be impaired, which is not preferable. PPS is generally a polymer with a relatively small molecular weight obtained by the production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by the production method typified by Japanese Patent Publication No. 52-12240. There are polymers with relatively high molecular weight, and in the former polymer,
It is also possible to increase the degree of polymerization and use it by heating in an oxygen atmosphere after polymerization, or by adding a crosslinking agent such as peroxide and heating, and in the present invention, PPS obtained by any method can be used. It is also possible to use In terms of the mechanical properties of the molded product itself, and the adhesion surface of the plating,
In order to avoid a decrease in plating film adhesion caused by cohesive peeling of PPS, essentially linear polymers obtained by the production method typified by the above-mentioned Japanese Patent Publication No. 12240/1988 are more preferably used. obtain. Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula, etc.
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
実施例１〜13、比較例１〜４
溶融粘度1200ポアズ（320℃、剪断速度1000秒
-1）の粉末状PPS（米国フイリツプス・ペトロリ
アム社製“ライトン”Ｐ−４）100重量部に対し、
第１表で示した、各種無機充填材を第１表に示し
た割合でドライ・ブレンドし、310℃に設定した
スクリユー押出機により溶融混練したのちストラ
ンド状で引き取り、ストランド・カツターでペレ
タイズした。
次に各ペレツトを310〜320℃に設定したスクリ
ユーインライン型射出成形機に供給し、金型温度
130〜140℃の条件で、一辺が80mmの正方形で、厚
さ約３mmの試験片を成形した。
次いで、無水塩化アルミニウム50ｇをトルエン
500c.c.に溶解させ80℃に加熱してあるエツチング
液に、液を撹拌しつつ各試験片を１分間浸漬し粗
表面化処理を行つた。
これら試験片をエタノール、アセトン、水で洗
浄したのち、更に超音波洗浄を行つたのち、第１
表に記載の酸またはアルカリまたは塩処理を次の
要領で行つた。
(A) 塩酸処理
６規定の塩酸に、60℃で２分間浸漬した。
(B) 硫酸処理
濃硫酸に、120℃で３分間浸漬した。
(C) リン酸処理
濃リン酸に、120℃で３分間浸漬した。
(D) 水酸化ナトリウム処理
10規定の水酸化ナトリウム水溶液に、80℃で
２分間浸漬した。
(E) 硫酸アンモニウム処理
10規定の硫酸アンモニウム水溶液に、80℃で
３分間浸漬した。
次いでこれら試験片に再び水中で超音波洗浄を
施したのち、以下に示す工程を順次行うことによ
りメツキ処理を施した。
(1) キヤタリステイング
Ａ−30キヤタリスト（奥野製薬工業(株)製）溶
液に、25℃で３分間浸漬処理した。
(2) 水洗
(3) アクセレーテイング
10％硫酸溶液に40℃で３分間浸漬処理した。
(4) 水洗
(5) 無電解銅メツキ
硫酸銅（CuSO4・5H2O）100ｇとホルマリ
ンの35％水溶液400c.c.とを水で稀釈して１と
したメツキ液Ａと酒石酸カリウムナトリウム
（４水和物）400ｇと水酸化ナトリウム100ｇを
水で稀釈して１としたメツキ液Ｂ、各200c.c.
を使用直前に混合し水で２に稀釈したメツキ
液に、空気をバブリングしながら、室温で８分
間浸漬処理した。
(6) 水洗
(7) 電気メツキ
無電解メツキを施した試験片を、濃硫酸50
ｇ、硫酸銅（５水和物）200ｇ、光沢剤として
SCB−MU10c.c.、SCB−11c.c.（奥野製薬工業(株)
製）および水1000c.c.からなる酸性銅メツキ浴中
におき、温度約25℃、電流密度3A／ｄm2で15
分間、次いで12A／ｄm2で９分間電気メツキを
行い、厚み約50μの銅メツキ膜を形成した。
得られた表面金属化PPS成形品について、メツ
キ膜を巾10mm、長さ40mmにわたつてＴ剥離する際
に必要な力をメツキ膜の接着力として評価した結
果および外観観察によるメツキ光輝性の評価結果
を第１表に示す。
Examples 1 to 13, Comparative Examples 1 to 4 Melt viscosity 1200 poise (320°C, shear rate 1000 seconds
-1 ) for 100 parts by weight of powdered PPS (“Ryton” P-4 manufactured by Phillips Petroleum Company, USA),
The various inorganic fillers shown in Table 1 were dry-blended in the proportions shown in Table 1, melt-kneaded in a screw extruder set at 310°C, taken out in the form of strands, and pelletized with a strand cutter. Next, each pellet is fed to a screw in-line injection molding machine set at 310 to 320℃, and the mold temperature is
A test piece with a square shape of 80 mm on a side and a thickness of about 3 mm was molded at 130 to 140°C. Next, 50g of anhydrous aluminum chloride was added to toluene.
Each test piece was immersed for 1 minute in an etching solution that had been dissolved in 500 c.c. and heated to 80° C. while stirring the solution to roughen the surface. After cleaning these test pieces with ethanol, acetone, and water, and then ultrasonic cleaning, the first
The acid, alkali, or salt treatments listed in the table were performed in the following manner. (A) Hydrochloric acid treatment It was immersed in 6N hydrochloric acid at 60°C for 2 minutes. (B) Sulfuric acid treatment It was immersed in concentrated sulfuric acid at 120°C for 3 minutes. (C) Phosphoric acid treatment It was immersed in concentrated phosphoric acid at 120°C for 3 minutes. (D) Sodium hydroxide treatment It was immersed in a 10N aqueous sodium hydroxide solution at 80°C for 2 minutes. (E) Ammonium sulfate treatment It was immersed in a 10N ammonium sulfate aqueous solution at 80°C for 3 minutes. These test pieces were then subjected to ultrasonic cleaning in water again, and then plated by sequentially performing the steps shown below. (1) Catalyst staining The sample was immersed in a solution of A-30 Catalyst (manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 3 minutes. (2) Water washing (3) Acceleration Immersed in 10% sulfuric acid solution at 40°C for 3 minutes. (4) Washing with water (5) Electroless copper plating Plating solution A made by diluting 100 g of copper sulfate (CuSO 4.5H 2 O) and 400 c.c. of a 35% aqueous solution of formalin with water and potassium sodium tartrate ( 400 g of tetrahydrate) and 100 g of sodium hydroxide diluted with water to make 1, 200 c.c. each.
It was immersed in a plating solution that had been mixed immediately before use and diluted to 2 with water for 8 minutes at room temperature while bubbling air. (6) Washing with water (7) Electroplating The electroless plated test piece was washed with concentrated sulfuric acid 50%
g, copper sulfate (pentahydrate) 200g, as a brightener
SCB-MU10c.c., SCB-11c.c. (Okuno Pharmaceutical Co., Ltd.)
15 at a temperature of approximately 25°C and a current density of 3A/ dm2.
Then, electroplating was performed for 9 minutes at 12 A/dm 2 to form a copper plating film with a thickness of about 50 μm. For the obtained surface metallized PPS molded product, the force required to peel the plating film over a width of 10 mm and a length of 40 mm was evaluated as the adhesion force of the plating film, and the evaluation of the plating brightness by observing the appearance. The results are shown in Table 1.
【表】【table】
【表】
(2) メツキ光輝性
○(良好)、△(やや良)、×(不良)
実施例 14
実施例３で用いた試験片について、無水塩化ア
ルミニウムのトルエン溶液で粗表面化処理をした
代りに、無水塩化アルミニウム50ｇをキシレン
500c.c.に溶解されたエツチング液を用い、液温を
90℃としたことのほかは、実施例３と全く同様の
操作を行い表面金属化PPS成形品を得た。メツキ
膜の接着力を評価したところ2330ｇ／cmであつ
た。
実施例 15
実施例３で用いた試験片について、無水塩化ア
ルミニウムのトルエン溶液で粗表面化処理をした
代りに、五塩化アンチモン50ｇをトルエン500c.c.
に溶解させたエツチング液を用い、浸漬時間を２
分としたことのほかは、実施例３と全く同様の操
作を行い表面金属化PPS成形品を得た。メツキ膜
の接着力は2280ｇ／cmであつた。
比較例 ５
実施例３で用いた試験片について、無水塩化ア
ルミニウムのトルエン溶液で粗表面化処理したあ
と塩酸処理を施した代りに、重クロム酸カリウム
162ｇ、濃硫酸390c.c.、濃リン酸99c.c.、水999c.c.の
混合液に50℃で３分間浸漬したことのほかは、実
施例３と全く同様の操作を行い表面金属化PPS成
形品を得た。メツキ膜の接着力を評価したところ
210ｇ／cmであつた。
比較例 ６〜16
実施例１〜13で、無水塩化アルミニウムのトル
エン溶液で粗表面化処理を行つたあとの酸または
アルカリまたは塩による処理を行わなかつたこと
のほかは、実施例１〜13と全く同様の操作を行い
表面金属化PPS成形品を得た。得られた成形品に
ついて評価したメツキ膜接着力は第２表記載の通
りであつた。[Table] (2) Plating brightness ○ (good), △ (slightly good), × (poor)
Example 14 Regarding the test piece used in Example 3, instead of roughening the surface with a toluene solution of anhydrous aluminum chloride, 50 g of anhydrous aluminum chloride was treated with xylene.
Using etching solution dissolved in 500c.c., adjust the temperature of the solution.
Except for changing the temperature to 90°C, the same operation as in Example 3 was performed to obtain a PPS molded product with a metallized surface. When the adhesion force of the plating film was evaluated, it was 2330 g/cm. Example 15 For the test piece used in Example 3, instead of roughening the surface with a toluene solution of anhydrous aluminum chloride, 50 g of antimony pentachloride was added to 500 c.c. of toluene.
Using an etching solution dissolved in
A PPS molded product with a metallized surface was obtained by carrying out exactly the same operation as in Example 3, except that the amount was changed. The adhesion force of the plating film was 2280 g/cm. Comparative Example 5 The test piece used in Example 3 was roughened with a toluene solution of anhydrous aluminum chloride and then treated with hydrochloric acid, but instead of being treated with potassium dichromate.
The same procedure as in Example 3 was performed except that 162 g of sulfuric acid, 390 c.c. of concentrated sulfuric acid, 99 c.c. of concentrated phosphoric acid, and 999 c.c. of water were immersed for 3 minutes at 50°C. A PPS molded product was obtained. Evaluation of the adhesive strength of plating film
It was 210g/cm. Comparative Examples 6 to 16 Completely the same as Examples 1 to 13 except that the treatment with acid, alkali, or salt after roughening treatment with a toluene solution of anhydrous aluminum chloride was not performed. A similar operation was performed to obtain a PPS molded product with a metallized surface. The plating film adhesion strength evaluated for the obtained molded product was as shown in Table 2.
本発明のポリフエニレンスルフイド樹脂成形品
の表面金属化方法は、機械的粗面化処理の工程を
経ずに行われるため、三次元的凹凸構造の面を表
面金属化することが可能であり、一方、本発明の
方法により得られた表面金属化ポリフエニレンス
ルフイド樹脂成形品はすぐれたメツキ膜接着力、
表面光輝性およびPPSに由来するすぐれた耐熱、
耐薬品性、機械特性を有し、金属代替用途をはじ
めとする各種部品および、プリント配線基板とし
て有用である。
The method for surface metallizing polyphenylene sulfide resin molded products of the present invention is carried out without a mechanical roughening process, so it is possible to surface metallize surfaces with three-dimensional uneven structures. On the other hand, the surface metallized polyphenylene sulfide resin molded product obtained by the method of the present invention has excellent plating film adhesion,
Excellent heat resistance derived from surface brightness and PPS,
It has chemical resistance and mechanical properties, and is useful as a variety of parts, including metal substitutes, and printed wiring boards.
Claims (1)
対して、平均粒子径が0.5〜10μの範囲の無機充填
剤10〜250重量部を含有せしめてなるポリフエニ
レンスルフイド樹脂成形品を、無水塩化アルミニ
ウム、五塩化アンチモン、無水塩化第二鉄、二塩
化テルル、四塩化テルル、無水塩化第二スズ、四
塩化チタン、三塩化ビスマス、塩化亜鉛等からな
るフリーデル・クラフツ反応触媒の群の中より選
ばれた一種または二種以上を有機溶媒に溶解せし
めた液を用いて粗表面化処理した後、更に酸また
はアルカリまたは塩で処理を行つたのちメツキ処
理することを特徴とするポリフエニレンスルフイ
ド樹脂成形品の表面金属化方法。1. A polyphenylene sulfide resin molded product containing 10 to 250 parts by weight of an inorganic filler with an average particle diameter in the range of 0.5 to 10 μm to 100 parts by weight of polyphenylene sulfide resin is mixed with anhydrous aluminum chloride. , antimony pentachloride, anhydrous ferric chloride, tellurium dichloride, tellurium tetrachloride, anhydrous stannic chloride, titanium tetrachloride, bismuth trichloride, zinc chloride, etc. A polyphenylene sulfide resin characterized in that the surface is roughened using a liquid obtained by dissolving one or more of them in an organic solvent, and then further treated with an acid, an alkali, or a salt, and then plated. Method for surface metallization of molded products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8947085A JPS61250174A (en) | 1985-04-25 | 1985-04-25 | Surface metallizing method for polyphenylene sulfide resin molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8947085A JPS61250174A (en) | 1985-04-25 | 1985-04-25 | Surface metallizing method for polyphenylene sulfide resin molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61250174A JPS61250174A (en) | 1986-11-07 |
| JPH0325512B2 true JPH0325512B2 (en) | 1991-04-08 |
Family
ID=13971601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8947085A Granted JPS61250174A (en) | 1985-04-25 | 1985-04-25 | Surface metallizing method for polyphenylene sulfide resin molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61250174A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015702A (en) * | 1989-10-06 | 1991-05-14 | Phillips Petroleum Company | Treatment of poly(arylene sulfide/sulfone) polymers |
| US5350834A (en) * | 1989-11-06 | 1994-09-27 | Phillips Petroleum Company | Treatment of polyarylene sulfide/sulfone polymers |
| JP2001131444A (en) * | 1999-11-05 | 2001-05-15 | Nippon Sheet Glass Co Ltd | Film-forming stock solution and method of manufacturing glass plate with metal oxide film by using same |
| JP2003335870A (en) * | 2002-05-22 | 2003-11-28 | Idemitsu Petrochem Co Ltd | Optical component |
-
1985
- 1985-04-25 JP JP8947085A patent/JPS61250174A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61250174A (en) | 1986-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4121015A (en) | Cured epoxy polymer having improved adhesive properties | |
| EP0391201B1 (en) | Method for treating polyetherimide substrates and articles obtained therefrom | |
| JPH0397873A (en) | Process for coating plastic product | |
| EP2823084A1 (en) | Method for promoting adhesion between dielectric substrates and metal layers | |
| JPH05502059A (en) | Metal coating on poly(aryletherketone) surface | |
| KR20110110217A (en) | Chrome-free method of conditioning and etching of a thermoplastic substrate for metal plating | |
| BR112017002502B1 (en) | COATING METHOD OF A SUBSTRATE FOR ELECTROGALVANIZING, SUBSTRATE FOR ELECTROGALVANIZING COATED WITH PLASTISOL, METHOD OF METALIZING NON-CONDUCTOR SUBSTRATES AND SUPPORT FOR ELECTROGALVANIZING USED TO SUPPORT NON-CONDUCTOR SUBSTRATES DURING A GALVANIZING PROCESS | |
| US3544432A (en) | Electroplating plastic articles | |
| EP0229495B1 (en) | Polyphenylene sulphide resin composition useful for plating | |
| JPH0325512B2 (en) | ||
| US3655433A (en) | Platable polymers | |
| JPH03197687A (en) | Pretreatment of molded resin product before metal plating | |
| US5178956A (en) | Pretreatment process for electroless plating of polyimides | |
| JPH05339738A (en) | Method for improving adhesion of electroless plated film to resinous article by permanganate treatment | |
| JPS58191722A (en) | Polymer granule with metal layer, manufacture and use | |
| JPH0839728A (en) | Production of metal-clad laminate substrate | |
| JPH0525298A (en) | Surface roughening of resin molding suitable for its metallization | |
| JPH064918B2 (en) | Method for surface metallization of polyphenylene sulfide resin molded product | |
| JPS6263674A (en) | Method for metallizing surface of molded resin article | |
| JPS5966428A (en) | Pretreatment of carbonamide group-containing thermoplastic for manufacturing toughly stuck metal film | |
| JP3560764B2 (en) | Etching solution for polyamide resin | |
| JPH0259870B2 (en) | ||
| JPS62185749A (en) | Electrically conductive coated particle | |
| US4091127A (en) | Cured epoxy polymer having improved adhesive properties | |
| JP3362754B2 (en) | Method for producing plated article and plated article obtained by the method |