WO2017187823A1 - Procédé de traitement de surface en plastique - Google Patents

Procédé de traitement de surface en plastique Download PDF

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Publication number
WO2017187823A1
WO2017187823A1 PCT/JP2017/010208 JP2017010208W WO2017187823A1 WO 2017187823 A1 WO2017187823 A1 WO 2017187823A1 JP 2017010208 W JP2017010208 W JP 2017010208W WO 2017187823 A1 WO2017187823 A1 WO 2017187823A1
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WO
WIPO (PCT)
Prior art keywords
plastic
sulfuric acid
plastic surface
treatment
treating
Prior art date
Application number
PCT/JP2017/010208
Other languages
English (en)
Japanese (ja)
Inventor
永井　達夫
裕都喜 山本
Original Assignee
栗田工業株式会社
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 栗田工業株式会社 filed Critical 栗田工業株式会社
Priority to US16/091,388 priority Critical patent/US20190136380A1/en
Priority to CN201780022812.8A priority patent/CN108884569B/zh
Priority to KR1020187028806A priority patent/KR102401889B1/ko
Priority to EP17789112.4A priority patent/EP3450590A4/fr
Publication of WO2017187823A1 publication Critical patent/WO2017187823A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/29—Persulfates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/085—Removing impurities
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic

Definitions

  • the present invention relates to a method for treating a plastic (resin molded product) surface, which is performed prior to metallization of the plastic surface.
  • ⁇ Plastic has been substituted for parts where metal is used as a structural material or component material, taking advantage of light weight, low cost, freedom of shape, and ease of mass production. At present, it is widely used not only for decoration but also for automobile exteriors, interior parts, and home appliances. At that time, in order to improve rigidity, wear resistance, weather resistance, heat resistance and the like, the plastic surface is often plated.
  • plastic Since plastic is non-conductive, it is necessary to first form a metal film on the plastic to be a conductor before plating.
  • the methods are roughly classified into dry methods such as CVD and PVD, and wet methods of electroless nickel plating.
  • the dry method is mostly a film formation in a vacuum state and is not suitable for mass production or application to large parts, and the wet method has been adopted so far.
  • Chromic acid is H 2 CrO 4 , and in this etching solution which is a mixed solution with concentrated sulfuric acid, 2CrO 4 2 ⁇ + 2H 3 O + ⁇ Cr 2 O 7 2 ⁇ + 3H 2 O
  • Cr is hexavalent anyway.
  • hexavalent Cr is subject to REACH regulation and RoHS regulation, hexavalent Cr does not remain in the product and is not subject to regulation, but in recent years, interest in environmental issues has increased, and hexavalent Cr has been There is a strong demand for environmentally friendly technologies that are not used.
  • Patent Document 1 As an environmentally conscious technology that replaces chromic acid, Patent Document 1 describes etching with a mixed solution of permanganate and inorganic salt. However, in the method of Patent Document 1, surface treatment of PEEK resin or ABS resin is difficult, and there is a problem in adhesion to metal.
  • An object of the present invention is to provide a Cr-free plastic surface treatment method, and a plating pretreatment method capable of performing plating sufficiently adhered to the plastic surface.
  • the inventors of the present invention treated the plastic surface with a sulfuric acid solution containing persulfuric acid (oxidant) obtained by electrolyzing sulfuric acid, thereby performing subsequent plating.
  • a sulfuric acid solution containing persulfuric acid (oxidant) obtained by electrolyzing sulfuric acid thereby performing subsequent plating.
  • the present invention has been completed, which can obtain sufficiently adhered plating even when the treatment is performed.
  • the present invention is based on such knowledge and is summarized as follows.
  • a method for treating a plastic surface wherein the plastic is treated with a solution obtained by electrolyzing sulfuric acid.
  • the plastic is placed in the treatment tank of a treatment apparatus including a treatment tank for storing a sulfuric acid-containing treatment liquid and a persulfuric acid generation electrolytic cell in which the sulfuric acid-containing treatment liquid in the treatment tank is circulated.
  • the method for treating a plastic surface according to any one of [1] to [4], wherein the surface of the plastic is treated by dipping.
  • the target plastic is not particularly limited, but a highly etchable plastic that cannot be etched unless it is a chromic acid-sulfuric acid solution, such as acrylonitrile-butadiene-styrene (ABS) resin,
  • ABS acrylonitrile-butadiene-styrene
  • examples include polyether ether ketone (PEEK) resin, polyethylene naphthalate (PEN) resin, polyethylene terephthalate (PET) resin, polyphenylene sulfide (PPS) resin, and the like.
  • the plastic surface is first treated by degreasing the plastic and then immersing it in a sulfuric acid solution obtained by electrolyzing sulfuric acid.
  • the sulfuric acid concentration of this sulfuric acid solution is 50 to 92 wt%, particularly 70 to 85 wt%
  • the persulfuric acid concentration is 3 g / L or more, for example 3 to 20 g / L, particularly 3 to 10 g / L
  • the treatment temperature is 80 ° C. or more, for example 80 to 140 ° C, particularly 100 to 130 ° C is preferred.
  • FIG. 1 is a schematic cross-sectional view showing an example of an electrolysis apparatus suitable for carrying out such electrolysis of sulfuric acid.
  • a constant temperature heater 2 is provided on the outer periphery of the treatment tank 1.
  • a plastic plate 5 as a plastic to be processed is arranged with the plate surface in the vertical direction.
  • a stirring means such as an air diffuser for stirring the liquid may be installed in the treatment tank 1.
  • the liquid in the treatment tank 1 is circulated through the pipe 7, the pump 8, the electrolytic cell 9 and the pipe 10.
  • An electrolytic cell 9 is provided with an anode 9a and a cathode 9b made of diamond electrodes, and a bipolar electrode 9c disposed therebetween.
  • a predetermined current is supplied to the anode 9a and the cathode 9b from the power supply unit, and sulfuric acid is electrolyzed to generate persulfuric acid such as peroxodisulfuric acid.
  • the surface treatment of the plastic plate 5 uses the apparatus shown in FIG. 1, contains sulfuric acid in the treatment tank 1, operates the pump 8 and the electrolysis cell 9, and the sulfuric acid and persulfuric acid concentrations in the treatment tank 1 are within the above ranges. After the generated sulfuric acid and persulfuric acid-containing treatment liquid is generated, the plastic plate 5 is immersed in the treatment liquid in the treatment tank 1 for a predetermined time while the pump 8 and the electrolytic cell 9 are operated.
  • the plastic plate 5 taken out from the treatment tank 1 is washed with water and dried and then plated.
  • a plating method there are electroless plating with self-catalyst and electroless plating without self-catalyst, either of which may be used.
  • the metal to be plated may be any of nickel, copper, cobalt, and alloys thereof.
  • ⁇ Persulfuric acid concentration measurement method First, the total oxidant concentration contained in the treatment liquid is measured by iodine titration. And the iodometric titration to free l 2 by adding Kl, determine the amount of l 2 by titrating the l 2 with sodium thiosulfate standard solution, and requests oxidizing agent concentration from the amount of the l 2 . Next, only the hydrogen peroxide concentration was determined by potassium permanganate titration, and the persulfate concentration was determined by subtracting the potassium permanganate titration value from the iodine titration value.
  • ⁇ Adhesion test> Make a notch penetrating up to 6 PEEK resins in both directions vertically at 2 mm intervals on the surface, and check the peeling with adhesive tape with a predetermined transparent pressure sensitivity.
  • the peeled part is compared with the example in the figure, and is evaluated in 6 stages from classification 0 to 5.
  • Class 0 means having the best adhesion that does not peel off at all.
  • Example 1 The surface treatment of the PEEK resin plate was performed using the apparatus shown in FIG.
  • the specifications and conditions of the treatment tank are as follows.
  • a 150 mm ⁇ 100 mm sample was cut out from the electroless nickel-plated plate, and the adhesion was examined by the above method.
  • Example 2 to Comparative Example 5 The test was performed in the same manner as in Example 1 except that the surface treatment conditions were set as shown in Table 2. The results are shown in Table 2. Table 2 also shows the results of Example 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention porte sur un procédé de traitement de surface en plastique, qui est un procédé de traitement de surface en plastique sans chrome capable d'appliquer un placage sur une surface en plastique adhérant suffisamment étroitement à celui-ci. Le procédé est un procédé de traitement de surface en plastique caractérisé en ce que le plastique est traité avec une solution dans laquelle de l'acide sulfurique a été électrolysé. La concentration en acide sulfurique de la solution d'acide sulfurique est de 50 à 92 % en poids. La concentration en acide persulfurique est d'au moins 3 g/L. Il est préférable que la température de traitement soit d'au moins 80 °C, par exemple, de 80 à 140 °C et en particulier de 100 à 130 °C. En immergeant le plastique dans ladite solution d'acide sulfurique pendant 1 à 10 minutes, des groupes fonctionnels hydrophiles sont exposés sur la surface du plastique.
PCT/JP2017/010208 2016-04-28 2017-03-14 Procédé de traitement de surface en plastique WO2017187823A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/091,388 US20190136380A1 (en) 2016-04-28 2017-03-14 Method for treating surface of plastic
CN201780022812.8A CN108884569B (zh) 2016-04-28 2017-03-14 塑料表面的处理方法
KR1020187028806A KR102401889B1 (ko) 2016-04-28 2017-03-14 플라스틱 표면의 처리 방법
EP17789112.4A EP3450590A4 (fr) 2016-04-28 2017-03-14 Procédé de traitement de surface en plastique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016091178A JP6750293B2 (ja) 2016-04-28 2016-04-28 プラスチック表面の処理方法
JP2016-091178 2016-04-28

Publications (1)

Publication Number Publication Date
WO2017187823A1 true WO2017187823A1 (fr) 2017-11-02

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PCT/JP2017/010208 WO2017187823A1 (fr) 2016-04-28 2017-03-14 Procédé de traitement de surface en plastique

Country Status (6)

Country Link
US (1) US20190136380A1 (fr)
EP (1) EP3450590A4 (fr)
JP (1) JP6750293B2 (fr)
KR (1) KR102401889B1 (fr)
CN (1) CN108884569B (fr)
WO (1) WO2017187823A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019045047A1 (fr) * 2017-09-01 2019-03-07 栗田工業株式会社 Procédé de prétraitement de placage pour une surface de résine abs, procédé de traitement de placage pour une surface de résine abs et produit plaqué à base de résine abs

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6477831B1 (ja) * 2017-10-31 2019-03-06 栗田工業株式会社 ポリフェニレンサルファイド樹脂の親水化処理方法
JP6540843B1 (ja) * 2018-03-06 2019-07-10 栗田工業株式会社 ポリプロピレン樹脂の親水化処理方法
JP6551563B1 (ja) * 2018-03-06 2019-07-31 栗田工業株式会社 Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品
JP6566064B1 (ja) * 2018-03-06 2019-08-28 栗田工業株式会社 ポリフェニレンサルファイド樹脂表面の処理方法

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JP2010189748A (ja) * 2009-02-20 2010-09-02 Osaka Prefecture 金属凸部を有するポリマー材料の製造方法
JP2011058010A (ja) * 2009-09-05 2011-03-24 Kurita Water Ind Ltd 硫酸電解方法
JP2015518083A (ja) * 2012-01-23 2015-06-25 マクダーミッド アキューメン インコーポレーテッド 三価マンガンを含む酸性溶液を用いたプラスチックのエッチング

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JP4462146B2 (ja) * 2004-09-17 2010-05-12 栗田工業株式会社 硫酸リサイクル型洗浄システムおよび硫酸リサイクル型過硫酸供給装置
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JP5207529B2 (ja) * 2008-06-30 2013-06-12 クロリンエンジニアズ株式会社 硫酸電解槽及び硫酸電解槽を用いた硫酸リサイクル型洗浄システム
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JP2010189748A (ja) * 2009-02-20 2010-09-02 Osaka Prefecture 金属凸部を有するポリマー材料の製造方法
JP2011058010A (ja) * 2009-09-05 2011-03-24 Kurita Water Ind Ltd 硫酸電解方法
JP2015518083A (ja) * 2012-01-23 2015-06-25 マクダーミッド アキューメン インコーポレーテッド 三価マンガンを含む酸性溶液を用いたプラスチックのエッチング

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019045047A1 (fr) * 2017-09-01 2019-03-07 栗田工業株式会社 Procédé de prétraitement de placage pour une surface de résine abs, procédé de traitement de placage pour une surface de résine abs et produit plaqué à base de résine abs
JP2019044229A (ja) * 2017-09-01 2019-03-22 栗田工業株式会社 Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品

Also Published As

Publication number Publication date
US20190136380A1 (en) 2019-05-09
KR102401889B1 (ko) 2022-05-24
CN108884569B (zh) 2021-02-26
EP3450590A4 (fr) 2019-10-02
CN108884569A (zh) 2018-11-23
KR20190003487A (ko) 2019-01-09
EP3450590A1 (fr) 2019-03-06
JP2017197831A (ja) 2017-11-02
JP6750293B2 (ja) 2020-09-02

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