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EP0604131B1 - Procédé de revêtement de résine moulée - Google Patents

Procédé de revêtement de résine moulée Download PDF

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Publication number
EP0604131B1
EP0604131B1 EP93310217A EP93310217A EP0604131B1 EP 0604131 B1 EP0604131 B1 EP 0604131B1 EP 93310217 A EP93310217 A EP 93310217A EP 93310217 A EP93310217 A EP 93310217A EP 0604131 B1 EP0604131 B1 EP 0604131B1
Authority
EP
European Patent Office
Prior art keywords
resin
electroless plating
acid
plating film
coating
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
Application number
EP93310217A
Other languages
German (de)
English (en)
Other versions
EP0604131A2 (fr
EP0604131A3 (en
Inventor
Koji Myojo
Hiromichi Uohashi
Kiyotaka Funada
Yoshinori Amaya
Eiji Aoki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Innovative Plastics Japan KK
Original Assignee
GE Plastics Japan Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by GE Plastics Japan Ltd filed Critical GE Plastics Japan Ltd
Publication of EP0604131A2 publication Critical patent/EP0604131A2/fr
Publication of EP0604131A3 publication Critical patent/EP0604131A3/en
Application granted granted Critical
Publication of EP0604131B1 publication Critical patent/EP0604131B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions

Definitions

  • This invention is concerned with a coating method for a molded resin which is effective for the production of a molded resin having both good coating contact properties and the high conductivity required for electrostatic coating.
  • an undercoat which was called a conductive primer was usually used to achieve good contact properties with the top coat and good adhesion by means of electrostatic coating.
  • the conductive primer had to contain either a conductive filler or a conductive additive such as a surfactant at the time of coating in order to achieve conductivity.
  • conductive fillers include the following: nonmetallic fillers such as carbon powder or graphite metallic fillers such as silver, copper, nickel, tin, zinc, titanium, palladium, aluminum; composite fillers made by plating fine particles of the following, e.g., glass, mica, plastic, carbon, with either copper or silver.
  • the paint for the above-mentioned conductive primer was expensive. As the film had to be very thick in order to achieve a satisfactory conductivity for the electrostatic coating, the cost for the complete process was very high. As automatic coating by an electrostatic coating apparatus was difficult to implement, the process had to be done by hand, which caused an increase in cost.
  • a molded product that was conductive could be made by molding a mixture of conductive filler and resin.
  • a very large amount of filler was required; this resulted in a poor appearance of the coating.
  • the conductive filler was expensive, the cost was high.
  • JP-A-4225869 discloses a method for coating a molded resin comprising the steps of forming an electroless plating film of copper, nickel, tin or cobalt on the surface of a molded resin and applying an electrostatic coating material directly onto the electroless plating film. There is no mention of the surface resistance of the electrolessly plated film.
  • This invention provides a coating method for a molded resin with none of the above-mentioned problems which conventional techniques had and that is effective for achieving the following, e.g., satisfactory adhesion of the coating material, contact properties; inexpensive production; good coating appearance.
  • the present invention provides a method for coating a molded resin comprising the steps of forming at least one electroless plating film on the surface of a molded resin wherein said film has a surface resistance of at least 3 but not more than 4 x 10 7 ⁇ cm; and applying at least one electrostatic coating material directly onto said electroless plating film.
  • the present invention further provides a method for coating a molded resin, without first applying a conductive primer, comprising the steps of etching the surface of said resin; sensitizing and activating said surface; forming at least one electroless plating film on said surface wherein the surface resistance of said film is at least 3 but not more than 4 x 10 7 ⁇ cm; and applying at least one electrostatic coating material directly onto said electroless plating film.
  • the coating method of this invention is suitable for any type of molded resin.
  • the method is especially suitable for a molded resin containing a polyamide resin.
  • a resin composition chiefly containing a polyamide resin and a polypropylene resin is also preferred.
  • Any conventional polyphenylene ether can be used. Examples include the following: poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, and copolymers of styrene and the above mentioned polyphenylene ethers.
  • a conventional polyamide can be used for this case; examples include the following: polycapramide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 6 10), polyundecanamide (nylon 11), polydecanamide (nylon 12), amorphous nylon, their copolymers.
  • polypropylene resins include the following: isotactic propylene monomers that show crystallinity, ethylene/propylene random copolymer consisting of either a copolymer made of an ethylene/ethylene/propylene random copolymer containing minimal amounts of the ethylene unit, or a homopolymer made of a propylene monomer and comparatively large amounts of the ethylene unit. Besides a crystalline resin, an amorphous polypropylene may be suitable. The type of polypropylene is not specifically restricted.
  • the molded resin is etched after being washed in the coating method of this invention.
  • the following mineral acids e.g., hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, chromic acid
  • Examples of organic acids include the following: organic carboxylic acids such as formic acid, acetic acid, or citric acid.
  • hydrochloric acid containing 10-400 mL/L (36% HCL) is preferable.
  • the resin surface is dissolved with the mineral acid, which results in formation of projections and indentations on the resin that may be brought into contact with the electroless plating film (coated) at the molded resin surface.
  • concentrations are desirable, e.g., 0.01-50 g/L for the cationic surfactant; 0.01-50 g/L for the cationic surfactant + 0.01-50 g/L for the nonionic surfactant.
  • a suitable surface roughness for good contact with an electroless plating film can be achieved by soaking in an etching solution at 10-60°C for 1-30 min.
  • the etching solution is allowed to contain an inorganic salt to promote the effects of the surfactants.
  • concentration is preferably in a range of 1-1000 gL.
  • the surface roughness suitable for providing an electroless plating film (coating) with good adhesion is carried out by dipping in this etching solution at 10-60°C for 1-30 min.
  • the material is sensitized and activated after etching.
  • the following methods which are usually used for plating plastics e.g., a catalyst-accelerator method, a sensitizer-activator method, soaking in a palladium solution-reduction solution which is used for either a polyamide resin or a through-hole substrate, can be used.
  • Satisfactory conductivity can be achieved by sensitization and activation, however, electroless plating is done to improve the conductivity.
  • the following e.g., Ni-P, Ni-Co-P, Ni-Zn-P, Ni-Sn-P, Ni-Pd-P, Ni-Cu-P, Ni-B, Cu, can be used for electroless plating.
  • Either an alkali, neutral or an acid solution can be used.
  • the following total metal concentration in the electroless nickel plating solution is desirable, e.g., 0.1-10 g/L, especially 0.5-5 g/L.
  • An alkali solution is preferable.
  • the material is desirably soaked in the electroless nickel plating solution at 20-90°C, preferably at 30-50°C, for 10 sec to 20 min, preferably for 10 sec to 10 min.
  • the molded product in the above-mentioned process has a surface with high conductivity.
  • a metal having a low electrical resistance can be adhered to the electroless plated film.
  • the following metals e.g., Ni, Cu, Pd, Pt, Au, Ag, can be used. Either electroless plating deposition or substitution deposition may be used.
  • a molded resin having a surface with the improved conductivity can be made by the above-mentioned process.
  • the molded resin treated by electroless plating in the above-mentioned process can be either naturally dried at normal temperature or dried by heating after electroless plating at 50-150°C for 3 min to 20 h.
  • electrostatic coating with either a middle coating material or a top coating material can be done without applying any conductive primer for coating. Any top coating material can be used in this case.
  • a suitable coating material such as a melamine crosslinking polyester polyol resin coat, or an acrylic urethane coat, can be applied.
  • test sample made by molding GTX6006 base material, brand: made by Nippon G.E. Plastic K.K., a resin composition containing both polyphenylene ether resin and polyamide resin was used for both Application Examples 1 and 2.
  • test sample was etched with the following etching solution at 30°C for 10 min.
  • the sample was then soaked at normal temperature for 1 min in 35% hydrochloric acid (50 mL/L), then washed with water, then sensitized by soaking at 30°C for 3 min in the following sensitizing solution.
  • an electroless nickel plated film was made by soaking in an electroless nickel plating solution at 40°C for the specific time shown in Table I (10, 20, 30 sec).
  • the treated sample was dried at 120°C for 10 min with hot air.
  • the surface resistance of the test sample was measured by JIS K6911, "The Conventional Test Method for Thermosetting Plastic". After electroless plating, the test sample was repeatedly baked at 160°C in a hot-air oven to measure the surface resistance in each baking process. The results are shown in Table I.
  • Haiepiko [transliteration] #100 (brand: made by Nippon Yushi K.K., middle coating material) was applied as a coating material using electrostatic coating, then left for 10 min, then baked for 30 min at 140°C in a hot-air oven, then removed from the oven, and left at normal temperature for 30 min.
  • Neoamirak [transliteration] brand: made by Kansai Paint K.K., top coating material was applied for coating by the electrostatic coating, then left for 10 min, then baked at 140°C for 30 min, then removed from the oven, then left at normal temperature for 24 h; the following evaluation was then done.
  • Crosshatch test 100 crosshatches, 1 mm [x 1 mm]) based on JIS K5400, was used for tape exfoliation. The numbers of residual coated film out of 100 crosshatches were counted.
  • the appearance of the coated film surface was evaluated by visual observation.
  • the cross section of the coated film was observed with an electron microscope to measure the film thickness.
  • test results are shown in Table I. Time (seconds) required for soaking in the electroless nickel plating solution Surface resistance ( ⁇ .cm) First time Baked once Baked twice Primary contact property Secondary contact property Coating appearance Coated film thickness ( ⁇ m) 10 4x10 7 4x10 7 4x10 7 100 100 Satisfactory 51 20 7x10 5 6x10 5 6x10 5 100 100 Satisfactory 65 30 130 147 153 100 100 Satisfactory 70
  • Electroless plating solution CP-CU 305 (brand: Kizai K.K.)
  • the product test sample was dried at 120°C for 10 min. After washing with water, the sample was activated with the following activating solution, which was done in Application Example 1.
  • the sample was dried for 10 min at 120°C.
  • the surface resistance of the test sample was measured by JIS K6911, "Conventional Test Method for Thermoset Plastics".
  • the test sample was repeatedly baked in a hot-air oven at 160°C after electroless plating, then the surface resistance was measured each time the sample was baked. The results are shown in Table III.
  • Haiepiko #100 (brand: made by Nippon Yushi K.K., middle coating material) was applied as a coating by the electrostatic coating method, then left for 10 min, then baked for 30 min at 140°C in a hot-air oven, then taken out, then left at normal temperature for 30 min.
  • Neoamirakku brand: made by Kansai Paint K.K., top coating, material
  • a crosshatch (100 crosshatch, 1 mm square) based on JIS K5400, was done for tape exfoliation, and the residual coated film out of 100 crosshatch was counted.
  • the coated surface appearance was evaluated by visual observation.
  • a ground is required for the specific electric potential between the material to be coated and the coating material in the case of electrostatic coating.
  • a conductive coating material was sprayed on the back surface of the product to form a conductive ground region.
  • electroless plated films can be formed on both the front and back surfaces of the product by electroless plating, the ground can be connected to any desired location on the back surface, which means no special treatment is required.
  • the coating material could not be applied to the entire surface of the resin using the conductive primer coating method; this resulted in uneven coating.
  • an even film can be formed and even coating can be achieved using this invention's electroless plating method.

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  • 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)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (10)

  1. Procédé de revêtement d'un objet moulé en résine, comprenant les étapes suivantes :
    former par dépôt sans courant, sur la surface d'un objet moulé en résine, au moins un film dont la résistance surfacique vaut au moins 3.107 et au plus 4.107 Ω.cm, et
    appliquer au moins un matériau de revêtement électrostatique directement par-dessus le film formé par dépôt sans courant.
  2. Procédé de revêtement d'un objet moulé en résine sans application préalable d'un primaire conducteur, lequel procédé comprend les étapes suivantes :
    attaquer chimiquement la surface de l'objet en résine,
    sensibiliser et activer cette surface,
    former par dépôt sans courant, sur ladite surface, au moins un film dont la résistance surfacique vaut au moins 3.107 et au plus 4.107 Ω.cm, et
    appliquer au moins un matériau de revêtement électrostatique directement par-dessus le film formé par dépôt sans courant.
  3. Procédé conforme à la revendication 1 ou 2, dans lequel la résine moulée comporte une résine de polyamide, combinée avec une résine de poly(phénylène éther) ou avec une résine de polypropylène.
  4. Procédé conforme à la revendication 2, dans lequel on réalise l'étape d'attaque chimique en lavant l'objet en résine avec une solution d'attaque qui contient un acide choisi parmi l'acide chlorhydrique, l'acide sulfurique, l'acide phosphorique, l'acide nitrique, l'acide chromique, l'acide formique, l'acide acétique et l'acide citrique.
  5. Procédé conforme à la revendication 4, dans lequel la solution d'attaque chimique contient en outre un sel inorganique et/ou un tensioactif cationique, non-ionique, anionique ou amphotère.
  6. Procédé conforme à la revendication 4 ou 5, dans lequel on effectue l'étape d'attaque chimique à une température de 10 à 60 °C et on la fait durer de 1 à 30 minutes.
  7. Procédé conforme à la revendication 1, dans lequel le film formé par dépôt sans courant est en un matériau choisi parmi Ni-P, Ni-Co-P, Ni-Zn-P, Ni-Sn-P, Ni-Pd-P, Ni-Cu-P, Ni-B et Cu.
  8. Procédé conforme à la revendication 7, qui comporte le fait d'appliquer par dépôt sans courant, avant ledit revêtement électrostatique, un deuxième film en un métal à faible résistance électrique.
  9. Procédé conforme à la revendication 8, dans lequel ledit métal est choisi parmi le nickel, le cuivre, le palladium, le platine, l'or et l'argent.
  10. Objet moulé en résine, doté d'un revêtement électrostatique, comprenant :
    une surface de résine chimiquement attaquée,
    au moins un film formé par dépôt sans courant et adhérent à cette surface, et dont la résistance surfacique vaut au moins 3.107 et au plus 4.107 Ω.cm, et
    au moins un revêtement électrostatique, appliqué directement par-dessus le film formé par dépôt sans courant.
EP93310217A 1992-12-24 1993-12-17 Procédé de revêtement de résine moulée Expired - Lifetime EP0604131B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP35743092 1992-12-24
JP357430/92 1992-12-24
JP35743092A JPH06192842A (ja) 1992-12-24 1992-12-24 樹脂成形品の塗装方法

Publications (3)

Publication Number Publication Date
EP0604131A2 EP0604131A2 (fr) 1994-06-29
EP0604131A3 EP0604131A3 (en) 1995-12-13
EP0604131B1 true EP0604131B1 (fr) 2000-05-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP93310217A Expired - Lifetime EP0604131B1 (fr) 1992-12-24 1993-12-17 Procédé de revêtement de résine moulée

Country Status (4)

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EP (1) EP0604131B1 (fr)
JP (1) JPH06192842A (fr)
DE (1) DE69328715T2 (fr)
ES (1) ES2146220T3 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000015695A1 (fr) * 1998-09-14 2000-03-23 H.B. Fuller Licensing & Financing, Inc. Composition de primaire et procede d'utilisation correspondant
DE10053681B4 (de) * 2000-10-28 2004-08-26 W.L. Gore & Associates Gmbh Gehäuse mit mindestens einem EMI abschirmender Kunststoffkörper bzw. Be- und Entlüftungselement und Verfahren zur Herstellung eines solchen Kunststoffkörpers
JP4593036B2 (ja) * 2001-09-11 2010-12-08 ダイセルポリマー株式会社 メッキ樹脂成形体
JP2006152337A (ja) * 2004-11-26 2006-06-15 Okuno Chem Ind Co Ltd 樹脂成形体に対するエッチング処理用組成物
JP4801362B2 (ja) * 2005-03-25 2011-10-26 ダイセル化学工業株式会社 めっき樹脂成形体の製造方法
JP4617445B2 (ja) * 2005-04-22 2011-01-26 奥野製薬工業株式会社 樹脂成形体へのめっき方法
KR100856687B1 (ko) * 2007-11-29 2008-09-04 동진P&I산업(주) 유전체로 사용한 소재에 전도체 물질을 형성하는 무전해도금방법
KR101258145B1 (ko) * 2013-01-23 2013-04-26 이도연 합성수지의 도금방법
KR101608220B1 (ko) * 2014-01-20 2016-04-01 주식회사 부광피엘 합성수지제품 도금 방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04225869A (ja) * 1990-12-26 1992-08-14 Art Kogyo Kk 無電解メッキプラスチック成形品の静電塗装方法
EP0604132A2 (fr) * 1992-12-24 1994-06-29 Ge Plastics Japan Limited Procédé de revêtement d'un produit moulé à base de résine

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4349421A (en) * 1979-09-17 1982-09-14 Allied Corporation Preparation of metal plated polyamide thermoplastic articles having mirror-like metal finish
US4552626A (en) * 1984-11-19 1985-11-12 Michael Landney, Jr. Metal plating of polyamide thermoplastics
JPH0723537B2 (ja) * 1986-12-12 1995-03-15 三菱瓦斯化学株式会社 ポリアミド樹脂のメツキ方法
JPH0238578A (ja) * 1988-07-27 1990-02-07 Kizai Kk ポリフェニレンエーテル／ポリアミドアロイ樹脂成形品の表面処理方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04225869A (ja) * 1990-12-26 1992-08-14 Art Kogyo Kk 無電解メッキプラスチック成形品の静電塗装方法
EP0604132A2 (fr) * 1992-12-24 1994-06-29 Ge Plastics Japan Limited Procédé de revêtement d'un produit moulé à base de résine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 16, no. 57 (C - 1011) 15 December 1992 (1992-12-15) *

Also Published As

Publication number Publication date
EP0604131A2 (fr) 1994-06-29
EP0604131A3 (en) 1995-12-13
DE69328715T2 (de) 2000-11-30
JPH06192842A (ja) 1994-07-12
DE69328715D1 (de) 2000-06-29
ES2146220T3 (es) 2000-08-01

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