WO2010022641A1 - Plastic composition and method of selective metallization on the surface thereof - Google Patents

Plastic composition and method of selective metallization on the surface thereof Download PDF

Info

Publication number
WO2010022641A1
WO2010022641A1 PCT/CN2009/073466 CN2009073466W WO2010022641A1 WO 2010022641 A1 WO2010022641 A1 WO 2010022641A1 CN 2009073466 W CN2009073466 W CN 2009073466W WO 2010022641 A1 WO2010022641 A1 WO 2010022641A1
Authority
WO
WIPO (PCT)
Prior art keywords
plastic composition
photocatalyst
metal
polymer
molybdate
Prior art date
Application number
PCT/CN2009/073466
Other languages
French (fr)
Chinese (zh)
Inventor
林信平
宫清
刘倩倩
陈炎
Original Assignee
比亚迪股份有限公司
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 比亚迪股份有限公司 filed Critical 比亚迪股份有限公司
Publication of WO2010022641A1 publication Critical patent/WO2010022641A1/en

Links

Classifications

    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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

Definitions

  • the present invention relates to a plastic composition and a surface selective metallization process thereof. Background technique
  • the circuit manufacturing of the traditional electronics industry and the information industry mainly relies on chemical and photochemical methods. These methods must be completed in a plurality of processes such as photographic film, exposure, development and etching in the initial wiring process. With the rapid development of the electronics industry, higher requirements have been placed on the time, price, and small-scale production capacity of product design and development.
  • the traditional technology shows the disadvantages of too many processes and long cycles.
  • LPKF invented a laser direct structuring (LDS) technology, which uses a plastic with a non-conductive organometallic composite as a raw material to directly project a laser beam onto the surface of an injection molded part.
  • the part can be electrolessly deposited with metal.
  • plastic parts do not need special roughening, sensitization and activation treatment, and can be electrolessly plated directly after laser irradiation, and the process flow is short, the operation is simple, the production flexibility is large, the line width and the line spacing precision are high.
  • LDS technology must use plastics with LDS properties, which contain certain non-conductive organometallic composites.
  • CN1772949A discloses a laser-induced selective electroless plating method, which is coated on a substrate with polyvinylpyrrolidone/silver colloid, selectively irradiated with an ultraviolet laser, and silver ions in colloidal silver in the irradiated region are reduced.
  • the metal silver particles are embedded in the matrix, the colloidal silver in the unirradiated region is washed away, and then electroless plating is performed to obtain a micron-scale patterned electroless plating on the substrate.
  • selective electroless plating using this method involves silver contamination problems.
  • the non-laser radiation area on the surface of the substrate may also be partially plated; in addition, by coating the polyvinylpyrrolidone/silver colloid, then the laser particles are embedded in the matrix by laser irradiation.
  • the present invention addresses the deficiencies of the prior art and proposes a plastic composition and its surface selective metallization process.
  • the present invention provides a plastic composition comprising a high molecular polymer and a photocatalyst, wherein the mass ratio of the high molecular polymer to the photocatalyst is from 1 to 100:1.
  • the invention also provides a surface selective metallization process for a plastic composition, the plastic composition comprising a high molecular polymer and a photocatalyst, wherein the mass ratio of the high molecular polymer to the photocatalyst is from 1 to 100:1;
  • the method comprises the following steps: (a) treating the surface of the plastic composition by etching, placing the etched plastic composition in an aqueous solution containing a metal ion salt and a hole sacrificial agent, under the condition of illumination of the light source, engraving The photoreduction reaction of the metal ion is caused by the photocatalytic reduction reaction of the metal ion on the surface of the exposed portion of the plastic composition; and (b) electroless plating is performed on the plastic composition in which the metal particles are selectively deposited to obtain a plated member.
  • the etching method may be a laser etching method.
  • the plastic composition containing the high molecular polymer and the photocatalyst has a high instantaneous temperature in the region irradiated by the laser under laser irradiation, higher than the glass transition temperature of the plastic composition, and the high molecular polymer in the plastic composition.
  • the photocatalyst in the plastic composition is relatively floated out of the high molecular polymer, so that part of the photocatalyst in the plastic composition is exposed; then the laser etched plastic composition is placed In an aqueous solution containing a metal ion salt or a hole sacrificial agent, the photocatalyst exposed on the surface of the plastic composition can reduce the metal ions in the solution to obtain nano-sized metal particles under irradiation with a light source capable of exciting the photocatalyst; Metal electroless plating is performed.
  • the photocatalyst is distributed inside the plastic composition, and a part of the photocatalyst is exposed under the laser irradiation condition, and the nano metal particles are deposited on the surface and electrolessly plated, and the plating layer has high bonding force;
  • nano metal particles are deposited only on the exposed photocatalyst surface, and then electroless plating is performed using the nano metal particles as an active center, and the precision is very high.
  • the present invention provides a plastic composition comprising a high molecular polymer and a photocatalyst, wherein the mass ratio of the high molecular polymer to the photocatalyst is from 1 to 100:1.
  • the high molecular weight polymer is a polymer which is well known to those skilled in the art for use in the plastics field.
  • the high molecular polymer comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate, butylene terephthalate.
  • the photocatalyst is a class of substances which can catalyze under the excitation of photons.
  • Common photocatalysts include titanium oxide (Ti02), zinc oxide (ZnO), tin oxide (Sn02), zirconium dioxide (ZrO2), cadmium sulfide (CdS) and other oxide sulfide semiconductors.
  • the photocatalyst is selected from the group consisting of Ti0 2 , Cu 2 0, Fe 2 0 3 , ZnO, ZnS, Nb 2 0 5 , Mo0 3 , CdS, ln 2 0 3 , Sn0 2 , Ta 2 0 5 , W0.
  • the invention also provides a surface selective metallization process for the plastic composition, comprising the steps of:
  • the laser etching is: placing the plastic composition substrate under laser irradiation, because the instantaneous temperature of the laser irradiation region is high, higher than the glass transition temperature of the plastic composition, the plastic combination
  • the high molecular polymer in the material instantaneously softens and sinks, and the photocatalyst in the plastic composition relatively floats out of the high molecular polymer, so that part of the photocatalyst in the plastic composition is exposed.
  • a photocatalyst is selectively distributed on the surface of the substrate of the plastic composition.
  • the marking current is 0 ⁇ 24A
  • the frequency is l ⁇ 60KHz
  • the intermediate delay is 0 ⁇ 30ms
  • the filling interval is ⁇ 0.01mm
  • the etching time is l ⁇ 60s.
  • the laser light used in the laser etching is 200 to 1064 nm, and according to an embodiment of the present invention, the laser wavelength is 1064 nm, but is not limited thereto.
  • the laser-etched plastic composition is placed in an aqueous solution containing a metal ion salt and a hole sacrificial agent, and the metal ion undergoes a photocatalytic reduction reaction under light conditions to deposit metal particles on the exposed photocatalyst surface.
  • the metal used for the metal ion salt comprises one or more of Cu, Au, M, Co, Fe, Zn, Pd, Pt, Ru, Rh, Re, Os, Ir.
  • the hole sacrificial agent also known as an organic electron donor, is a type of substance used to trap photogenerated holes to promote carrier separation, thereby improving photocatalytic efficiency.
  • the hole sacrificing agent is one or more selected from the group consisting of decyl alcohol, sulfite, and organic dye.
  • the organic dye is various dyes well known in the art, such as N3, N719, N621, N712, N749, Z235, N773, N790, N820, N823, N845, N886, N945, K8, K9, K19, K23, K27, K29, K51, K60, K66, K69, K73, K77, Z316, Z907, Z910.
  • the mass ratio of the metal ion salt to the hole sacrificial agent is from 0.1 to 100:1.
  • the photocatalyst leaves electrons in the molecular orbital away from the valence band under illumination of a certain wavelength of light
  • the (Valence band) transitions to a conduction band to generate an electron-hole pair which is subjected to a photocatalytic reduction reaction of electrons, the hole sacrificial agent providing electrons and eliminating holes.
  • the main emission wavelength of the light source used in the photocatalytic reduction reaction of the metal ion is
  • metal particles are deposited on the surface of the photocatalyst. With the metal particles as an active center, conventional electroless plating is performed to obtain desired plating parts.
  • the electroless plating technique is well known to those skilled in the art and may be a metal plating layer which is less reducible than metal particles. In the examples provided by the present invention, electroless copper plating is preferred, but is not limited thereto.
  • the metal particles are of a nanometer order and have an average particle diameter of 10 to 100 nm.
  • pretreatment is required before the plastic composition is subjected to laser etching.
  • the pretreatment the techniques of which are known to those skilled in the art.
  • the present invention has no particular requirements for the method of pretreatment.
  • the pretreatment comprises sequentially degreasing and roughening the surface of the substrate of the plastic composition.
  • the purpose of degreasing in the pretreatment is to remove grease and its oxides from the surface of the substrate of the plastic composition.
  • Methods of degreasing are various methods known to those skilled in the art.
  • the substrate of the plastic composition is soaked to contain NaOH lmol. 1 , Na 2 C0 3 lmol. L, sodium dodecyl sulfate 0.1 mol. L solution in 5 ⁇ 10min, the solution temperature is 50 ⁇ 60 ° C. After taking out, it is washed with water, soaked in 1 mol. L" 1 phosphoric acid solution for 5 to 10 min, and then taken out and washed with water.
  • the purpose of the roughening in the pretreatment is to produce sponge-like micropores and hydrophilic properties on the surface of the plastic composition, and to meet the requirements of the strength of the metal plating adhesion.
  • the method of roughening is various methods known to those skilled in the art.
  • the substrate of the plastic composition is immersed in a solution containing chromic anhydride, sulfuric acid, CrCl 3 *6H 2 0 for 10-15 minutes, the temperature of the solution is 60-70 ° C, and it is taken out and washed with water.
  • the plastic composition substrate may also be immersed in a solution containing NaOH and KMn0 4 for 10-15 minutes, and the solution temperature is 60-70 °C. Then, it is immersed in dilute hydrochloric acid at 40 ⁇ 50 °C for 5 ⁇ 8min. After taking out, wash with water.
  • the number of times of washing is not particularly limited as long as the treatment liquid on the surface of the plastic composition substrate is sufficiently removed and washed, according to an embodiment of the present invention,
  • the number of times of washing after the degreasing is 1 to 3 times; the number of washings performed after the roughening is 4 to 6 times.
  • the water used in the water washing step is various waters of the prior art, such as municipal tap water, deionized water, distilled water, purified water or a mixture thereof. According to an embodiment of the present invention, deionized water is used in the present invention.
  • the substrate of the plastic composition impregnated with the aqueous solution containing the metal ion salt and the hole sacrificial agent before the electroless plating.
  • the cleaning is well known to those skilled in the art, and the present invention has no special requirements and will not be described herein.
  • the surface of the non-laser radiation region has no photocatalyst, metal particles are not deposited, and a metal plating layer is not generated, so that the electroless plating precision is high.
  • the plastic composition provided by the present invention and its surface selective metallization process are described in detail below by way of specific examples. The following examples are merely illustrative of the invention and are not intended to limit the scope of the invention.
  • This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
  • plastic composition Preparation of plastic composition: Weigh lkgABS plastic granules (Dongguan Tongxin Engineering Plastics Co., Ltd., C2950) and lkg titanium dioxide powder, mix evenly, use extruder (Nanjing New Times Machine Electric Co., Ltd., XSD-35 The extrusion was carried out, and then injection molding was carried out using an injection molding machine (Haitian Plastic Machinery Co., Ltd., HTF60W1) to obtain a 4.5 cm x 14.5 cm ABS plastic composition substrate, which was designated as ABS-I.
  • the ABS-I obtained in the step (1) is placed in a NaOH containing 1 mol of L. ⁇ Na 2 C0 3 lmol. L" ⁇ O.lmol. I 1 sodium lauryl sulfate. In the solution, it was immersed for 10 min at 50 ° C, taken out and washed with deionized water, then immersed in a solution containing 1 mol of silicic acid for 1 min, taken out and rinsed with deionized water. The washed ABS-I was placed in a solution containing H 2 SO 4 200 ml. ⁇ Cr0 3 4 mol. ⁇ CrCl 3 -6H 2 0 0.02 mol. I/ 1 , the solution temperature was 70 ° C, and the soaking time was 10 min. After removal, rinse with deionized water.
  • Electroless copper plating ABS-I subjected to photocatalytic reduction reaction is washed in 100 mL of deionized water; after being taken out, it is placed in the electroless plating solution prepared in the step (3) for electroless copper plating, 50 ° C The water bath was kept at a constant temperature and taken out after 15 minutes to obtain a plated Al.
  • This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
  • the surface of the plastic composition substrate ABS-I was subjected to selective metal electroless plating in the same manner as in Example 1, except that: 2 kg of ABS plastic granules were weighed in step (1) (Dongguan Tongxin Engineering Plastic Co., Ltd., C2950) And 20 g of titanium dioxide powder.
  • the prepared ABS plastic composition substrate was designated as ABS-II.
  • the plated member was obtained in the above manner and was designated as A2.
  • This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
  • the surface of the plastic composition substrate ABS-I was subjected to selective metal electroless plating in the same manner as in Example 1, except that: Infrared lamp was used in step (5) (Shenzhen Anhongda Technology Co., Ltd., PHILIPS infrared The lamp IN R95E, wavelength 850 nm) was replaced with the UV lamp used in Example 1, and the irradiation time was 10 min.
  • the plated member was obtained in the above manner and was designated as A3.
  • This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
  • the surface of the plastic composition substrate ABS-II was subjected to selective metal electroless plating in the same manner as in Example 2, except that: Infrared lamp was used in step (5) (Shenzhen Anhongda Technology Co., Ltd., PHILIPS infrared The lamp IN 95E, wavelength 850 nm) was replaced with the UV lamp used in Example 2, and the irradiation time was 10 min.
  • the plated member obtained according to the above method was designated as A4.
  • This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
  • the surface of the plastic composition substrate ABS-1 was subjected to selective metal electroless plating in the same manner as in Example 1, except that: in the step (3), 2 g of palladium chloride was weighed to replace the nitric acid in Example 1. Copper is formulated as an aqueous metal ion-hole sacrificial solution.
  • the plated member was obtained in the above manner and was designated as A5.
  • This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
  • the surface of the plastic composition substrate ABS-II was subjected to selective metal electroless plating in the same manner as in Example 2 except that: in the step (3), 2 g of palladium chloride was weighed to replace the nitric acid in Example 2. Copper is formulated as an aqueous metal ion-hole sacrificial solution.
  • the plated member was obtained in the above manner and was designated as A6.
  • This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
  • the surface of the plastic composition substrate ABS-1 was subjected to selective metal electroless plating in the same manner as in Example 1, except that in the step (3), 20 mg of the organic dye N3 was weighed and replaced with 20 mL of the Example 1.
  • the sterol was added to deionized water to prepare a 200 mL aqueous metal ion-hole sacrificial solution.
  • the plated member was obtained in the above manner and was designated as A7.
  • This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
  • the surface of the plastic composition substrate ABS-II was subjected to selective metal electroless plating in the same manner as in Example 2 except that: in the step (3), 20 mg of the organic dye N3 was weighed and replaced with 20 mL of the Example 2.
  • the sterol was added to deionized water to prepare a 200 mL aqueous metal ion-hole sacrificial solution.
  • the plated member was obtained in the above manner and was designated as A8.
  • the surface of the plastic substrate commonly used in the prior art was subjected to selective metal electroless plating in the same manner as in Example 1, except that: In the step (1), 2 kg of ABS plastic particles were directly weighed (Dongguan Tongxin Engineering Plastics) Co., Ltd., C2950), in place of the lkgABS plastic pellets of Example 1 and 1 kg of titanium dioxide powder, was compression molded into a 4.5 cm x 14.5 cm ABS engineering plastic substrate, designated ABS-III. The ABS-III was subjected to pretreatment, laser etching, photocatalytic reduction reaction and electroless copper plating in the same manner as in Example 1, and the obtained plated member was designated as D1.
  • ABS engineering plastic substrate ABS-III prepared in Comparative Example 1 was used, and then ABS-III was pretreated in the same manner as in Example 1.
  • the polyvinylpyrrolidone/silver colloid-coated ABS-rhenium was subjected to ultraviolet laser selective irradiation and electroless copper plating in the same manner as in Example 1.
  • the resulting plated member was designated as D2. Performance Testing:
  • Sample coating adhesion test referred to as the cross-cut method:
  • A1 A8 and D1 ⁇ D2 were tested for binding force: Samples A1 A8 and D1 ⁇ D2 were applied to the sample plate, and after drying, a cross-cut tester with a multi-blade cutter with 6 cutting faces was used (BYK, Germany) The company, 511 system ⁇ ' parallel pull 3 ⁇ 4cm, cutter gap is lmm, there are six cut marks, should be cut through the paint film; then the same method is used to perpendicular to the former, six cut; thus forming many small squares. The soft brush is brushed 5 times from the diagonal direction or taped to the grid and quickly pulled open. The cut surface of the test coating is inspected with a 4x magnifying glass, and the adhesion level of the coating is determined by comparison. The 0-level adhesion is the best, generally More than 2 grades in anti-corrosion coating
  • Level 2 The thickness of the coating at the edge or intersection of the cut is significantly greater than 5%, but is affected by no more than 15%; the level 3 coating is partially or completely peeled off along the edge, between 15% and 35%.
  • Comparative Example 1 By comparing the experimental results, it was found that in Comparative Example 1, since there was no photocatalyst, there was no deposition of nano metal, and no plating was formed at the time of electroless plating; the plated part obtained in Comparative Example 2 was coated except for the laser etched region. In addition, the areas not laser etched are also coated, which does not meet the requirements of the board pattern. Because before and after laser etching, even at room temperature, silver salts are easy to see light, decompose by heat,
  • the unetched areas of the laser are contaminated with silver, which ultimately results in poor precision of the plated parts.
  • the plating members ⁇ 1 to ⁇ 8 because there is no photocatalyst on the surface of the laser unetched region, there is no deposition of nano metal particles, so the electroless copper plating after plating The surface pattern is clear and precise.

Abstract

A plastic composition and the method of selective metallization on the surface thereof. The plastic composition comprises polymer and photocatalyst, and the mass ratio of polymer and photocatalyst is 1-100: 1. The method of selective metallization on the surface of plastic composition comprises the following steps: subjecting the surface of the plastic composition to etching, and placing the etched plastic composition into an aqueous solution containing metal ion salt and cavity victim agent for photocatalytic reduction to obtain a plastic composition with nano-size metal particles on the surface, finally carrying out metal chemical plating.

Description

塑料组合物及其表面选择性金属化方法 技术领域  Plastic composition and surface selective metallization method thereof
本发明涉及一种塑料组合物及其表面选择性金属化工艺。 背景技术  The present invention relates to a plastic composition and a surface selective metallization process thereof. Background technique
传统的电子行业、信息产业的电路制备主要依赖化学和光化学的方法， 这 些方法在初期的布线过程中， 必须经过照相底片、 曝光、 显影和蚀刻等多道工 序才能完成。 随着电子工业的迅速发展， 对产品设计开发的时间， 价格， 小规 模生产能力都提出了更高的要求。 而传统的技术显示出工序过多、 周期过长的 缺点。  The circuit manufacturing of the traditional electronics industry and the information industry mainly relies on chemical and photochemical methods. These methods must be completed in a plurality of processes such as photographic film, exposure, development and etching in the initial wiring process. With the rapid development of the electronics industry, higher requirements have been placed on the time, price, and small-scale production capacity of product design and development. The traditional technology shows the disadvantages of too many processes and long cycles.
因此， 电子工业中的激光直写技术应运而生。 LPKF公司发明了一种激光 直接成型 （ Laser Direct Structuring-LDS )技术， 釆用添加有某种非导电性有机 金属复合物的塑料为原料， 直接把激光光束投射在注塑件表面上，被照射过的 部分可进行化学镀沉积金属。 该技术中塑料件无需经过专门的粗化、 敏化、 活 化处理， 直接经激光照射后即可进行化学镀， 且工艺流程短， 操作简单， 生产 柔性大， 线宽、 线距精度高。 但是釆用 LDS技术必须要用具有 LDS性能的塑 料， 该塑料内含某种非导电性有机金属复合物， 而进行激光照射塑料件时， 只 有表面需要化学镀的部位经激光照射发生了活化，其他未经激光照射的部位不 发生活化，因此未活化塑料中的有机金属复合物没有得到利用，造成很大浪费。  Therefore, laser direct writing technology in the electronics industry came into being. LPKF invented a laser direct structuring (LDS) technology, which uses a plastic with a non-conductive organometallic composite as a raw material to directly project a laser beam onto the surface of an injection molded part. The part can be electrolessly deposited with metal. In this technology, plastic parts do not need special roughening, sensitization and activation treatment, and can be electrolessly plated directly after laser irradiation, and the process flow is short, the operation is simple, the production flexibility is large, the line width and the line spacing precision are high. However, LDS technology must use plastics with LDS properties, which contain certain non-conductive organometallic composites. When laser-irradiated plastic parts, only the parts whose surface needs electroless plating are activated by laser irradiation. Other parts that are not irradiated with laser light are not activated, so the organometallic complex in the unactivated plastic is not utilized, resulting in great waste.
CN1772949A中公开了一种激光诱导选择性化学镀方法，该方法釆用聚乙 烯吡咯烷酮 /银胶体涂布在基体上， 用紫外激光进行选择性辐射， 在辐射区域 的胶体银中的银离子被还原成金属银粒子并嵌入基体中，未经辐射区域的胶体 银被清洗掉， 然后实施化学镀即可得到基体上微米级图形化的化学镀层。但采 用该方法进行选择性化学镀，涉及到银污染问题。由于该专利中使用的硝酸银、 曱酸银、 乙酸银、 丙酸银、 丁酸银在日光照射和受热情况下容易分解， 因此在 实际操作过程中， 容易造成非激光辐射区域的银污染， 即使清洗， 也难以完全 清除， 在化学镀铜后， 基体表面非激光辐射区域也会有部分镀层； 另外， 通过 涂布聚乙烯吡咯烷酮 /银胶体的方式， 然后采用激光辐射使银粒子嵌入基体中，  CN1772949A discloses a laser-induced selective electroless plating method, which is coated on a substrate with polyvinylpyrrolidone/silver colloid, selectively irradiated with an ultraviolet laser, and silver ions in colloidal silver in the irradiated region are reduced. The metal silver particles are embedded in the matrix, the colloidal silver in the unirradiated region is washed away, and then electroless plating is performed to obtain a micron-scale patterned electroless plating on the substrate. However, selective electroless plating using this method involves silver contamination problems. Since the silver nitrate, silver citrate, silver acetate, silver propionate, and silver butyrate used in the patent are easily decomposed under sunlight and heat, it is easy to cause silver contamination in the non-laser radiation area during actual operation. Even if it is cleaned, it is difficult to completely remove it. After electroless copper plating, the non-laser radiation area on the surface of the substrate may also be partially plated; in addition, by coating the polyvinylpyrrolidone/silver colloid, then the laser particles are embedded in the matrix by laser irradiation. ,
1 PIDM090739P 最后化学镀时镀层结合力较差。 发明内容 1 PIDM090739P At the end of the electroless plating, the plating adhesion is poor. Summary of the invention
本发明针对现有技术的不足，提出了一种塑料组合物及其表面选择性金属 化工艺。  The present invention addresses the deficiencies of the prior art and proposes a plastic composition and its surface selective metallization process.
本发明提供了一种塑料组合物， 包含高分子聚合物、 光催化剂， 其中高分 子聚合物、 光催化剂的质量比为 1~100： 1。  The present invention provides a plastic composition comprising a high molecular polymer and a photocatalyst, wherein the mass ratio of the high molecular polymer to the photocatalyst is from 1 to 100:1.
本发明还提供了一种塑料组合物的表面选择性金属化工艺方法，所述塑料 组合物包含高分子聚合物和光催化剂 ,其中高分子聚合物和光催化剂的质量比 为 1~100： 1 , 所述方法包括以下步骤： （a) 用刻蚀法处理塑料组合物表面， 将 刻蚀后的塑料组合物置于含有金属离子盐和空穴牺牲剂的水溶液中，在光源照 射的条件下， 在刻蚀造成的棵露部分发生金属离子光催化还原反应，使塑料组 合物表面发生选择性沉积金属粒子； 以及 (b) 对发生选择性沉积金属粒子的塑 料组合物进行化学镀， 得到镀件。  The invention also provides a surface selective metallization process for a plastic composition, the plastic composition comprising a high molecular polymer and a photocatalyst, wherein the mass ratio of the high molecular polymer to the photocatalyst is from 1 to 100:1; The method comprises the following steps: (a) treating the surface of the plastic composition by etching, placing the etched plastic composition in an aqueous solution containing a metal ion salt and a hole sacrificial agent, under the condition of illumination of the light source, engraving The photoreduction reaction of the metal ion is caused by the photocatalytic reduction reaction of the metal ion on the surface of the exposed portion of the plastic composition; and (b) electroless plating is performed on the plastic composition in which the metal particles are selectively deposited to obtain a plated member.
根据本发明的一个实施例， 所述刻蚀法可以为激光刻蚀法。  According to an embodiment of the invention, the etching method may be a laser etching method.
本发明的构思为：含有高分子聚合物和光催化剂的塑料组合物在激光照射 条件下， 激光辐射的区域瞬间温度很高， 高于塑料组合物玻璃化温度， 塑料组 合物中的高分子聚合物瞬间软化下沉，而塑料组合物中的光催化剂则相对的从 高分子聚合物中浮出来， 使得塑料组合物中的部分光催化剂棵露出来； 然后将 激光刻蚀后的塑料组合物放入含有金属离子盐、 空穴牺牲剂的水溶液中， 在能 够激发光催化剂的光源照射条件下，棵露于塑料组合物表面的光催化剂可将溶 液中的金属离子还原， 得到纳米级金属颗粒； 最后进行金属化学镀。  The idea of the invention is that the plastic composition containing the high molecular polymer and the photocatalyst has a high instantaneous temperature in the region irradiated by the laser under laser irradiation, higher than the glass transition temperature of the plastic composition, and the high molecular polymer in the plastic composition. Instantly softening and sinking, and the photocatalyst in the plastic composition is relatively floated out of the high molecular polymer, so that part of the photocatalyst in the plastic composition is exposed; then the laser etched plastic composition is placed In an aqueous solution containing a metal ion salt or a hole sacrificial agent, the photocatalyst exposed on the surface of the plastic composition can reduce the metal ions in the solution to obtain nano-sized metal particles under irradiation with a light source capable of exciting the photocatalyst; Metal electroless plating is performed.
釆用本发明所提供的塑料组合物及其表面选择性金属化工艺，与现有技术 相比有以下优点：  The plastic composition provided by the present invention and its surface selective metallization process have the following advantages over the prior art:
(1)光催化剂分布在塑料组合物内部， 激光照射条件下棵露出部分光催化 剂， 在此表面上沉积纳米金属粒子并进行化学镀， 镀层结合力高；  (1) The photocatalyst is distributed inside the plastic composition, and a part of the photocatalyst is exposed under the laser irradiation condition, and the nano metal particles are deposited on the surface and electrolessly plated, and the plating layer has high bonding force;
(2)选择性金属化工艺时， 只在棵露出来的光催化剂表面沉积纳米金属粒 子， 然后以纳米金属粒子为活性中心进行化学镀， 精度非常高。  (2) In the selective metallization process, nano metal particles are deposited only on the exposed photocatalyst surface, and then electroless plating is performed using the nano metal particles as an active center, and the precision is very high.
PIDM090739P 具体实施方式 PIDM090739P detailed description
本发明提供了一种塑料组合物， 包含高分子聚合物和光催化剂， 其中高分 子聚合物和光催化剂的质量比为 1~100： 1。  The present invention provides a plastic composition comprising a high molecular polymer and a photocatalyst, wherein the mass ratio of the high molecular polymer to the photocatalyst is from 1 to 100:1.
根据本发明所提供的塑料组合物，其中所述高分子聚合物为本领域技术人 员所公知的各种用于塑料领域的高分子聚合物。 本发明中， 所述高分子聚合物 包含聚乙烯、 聚丙烯、 聚苯乙烯、 聚氯乙烯、 聚曱基丙烯酸甲酯、 聚对苯二甲 酸乙二醇酯、 聚对苯曱酸丁二醇酯、 聚酰胺、 聚碳酸酯、 丙烯腈-丁二烯 -苯乙 烯共聚物、 聚酰亚胺、 聚酰胺-酰亚胺、 聚苯并咪唑、 聚氨酯、 聚吡咯、 聚噻 吩、 聚苯胺、 聚对亚曱基苯、 苯乙烯-丙烯腈共聚体、 酚醛树脂、 脲醛树脂、 聚甲醛、 聚醚醚酮、 聚醚酮、 聚醚砜、 聚苯^ 醚、 氯化聚乙烯、 苯乙烯 -丁二 烯-苯乙烯嵌段聚合物、 苯乙烯-乙烯-丁二烯-苯乙烯嵌段聚合物、 聚四氟乙烯、 环氧树脂、 聚曱醛、 聚苯醚、 聚砜、 醋酸纤维素、 醋酸丁酸纤维素、 赛璐珞、 玻璃纸、 脲曱醛、 三聚氰胺曱醛、 三聚氰胺脲曱醛、 聚醚砜、 聚苯砜、 聚氨基 双马来酰胺、 聚三嗪中的一种或几种。 根据本发明的一个实施例， 釆用 ABS, 但不局限于此。  A plastic composition according to the present invention, wherein the high molecular weight polymer is a polymer which is well known to those skilled in the art for use in the plastics field. In the present invention, the high molecular polymer comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate, butylene terephthalate. Ester, polyamide, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyimide, polyamide-imide, polybenzimidazole, polyurethane, polypyrrole, polythiophene, polyaniline, poly P-menthylene, styrene-acrylonitrile copolymer, phenolic resin, urea-formaldehyde resin, polyoxymethylene ether, polyetheretherketone, polyether ketone, polyether sulfone, polyphenylene ether, chlorinated polyethylene, styrene-butyl Diene-styrene block polymer, styrene-ethylene-butadiene-styrene block polymer, polytetrafluoroethylene, epoxy resin, polyfurfural, polyphenylene ether, polysulfone, cellulose acetate, One or more of cellulose acetate butyrate, cellophane, cellophane, urea furfural, melamine furfural, melamine urea furfural, polyethersulfone, polyphenylsulfone, polyaminobismaleamide, polytriazine. According to an embodiment of the present invention, ABS is used, but is not limited thereto.
所述光催化剂， 为各种在光子的激发下能够起催化作用的一类物质。 常见 的光催化剂有二氧化钛 (Ti02)，氧化锌 (ZnO)，氧化锡 (Sn02)，二氧化锆 (Zr02), 硫化镉 (CdS)等多种氧化物硫化物半导体。本发明中， 所述光催化剂选自 Ti02、 Cu20、 Fe203、 ZnO、 ZnS、 Nb205、 Mo03、 CdS, ln203、 Sn02、 Ta205、 W03、 Bi203、 BaTi03、 SrTi03、 CaTi03、 MgTi03、 PbTi03、 BaSn03、 CaSn03、 InSn03、 CaSn03、 MSn03、 PbSn03、 Li 03、 KN 03、 BaSb206、 PbSb206、 MgSb206、 NaTa03、 KTa03、 Ba5Ta4015、 Ca6Bi6015、 钨酸钠、 钨酸钾、 钼酸锂、 鉬酸钠、 钼酸按、 钼酸锌、 钼酸钙中的一种或几种。 本发明实施例中均釆用二氧化钛， 但是需要说明的是， 这只是为了说明的目的而不是为了限制本发明的保护范 围。 The photocatalyst is a class of substances which can catalyze under the excitation of photons. Common photocatalysts include titanium oxide (Ti02), zinc oxide (ZnO), tin oxide (Sn02), zirconium dioxide (ZrO2), cadmium sulfide (CdS) and other oxide sulfide semiconductors. In the present invention, the photocatalyst is selected from the group consisting of Ti0 2 , Cu 2 0, Fe 2 0 3 , ZnO, ZnS, Nb 2 0 5 , Mo0 3 , CdS, ln 2 0 3 , Sn0 2 , Ta 2 0 5 , W0. 3 , Bi 2 0 3 , BaTi0 3 , SrTi0 3 , CaTi0 3 , MgTi0 3 , PbTi0 3 , BaSn0 3 , CaSn0 3 , InSn0 3 , CaSn0 3 , MSn0 3 , PbSn0 3 , Li 0 3 , KN 0 3 , BaSb 2 0 6 , PbSb 2 0 6 , MgSb 2 0 6 , NaTa0 3 , KTa0 3 , Ba 5 Ta40 15 , Ca 6 Bi 6 0 15 , sodium tungstate, potassium tungstate, lithium molybdate, sodium molybdate, molybdic acid One or more of zinc molybdate and calcium molybdate. Titanium dioxide is used in the examples of the present invention, but it should be noted that this is for illustrative purposes only and is not intended to limit the scope of the present invention.
本发明还提供了一种所述塑料组合物表面选择性金属化工艺方法，包含以 下步骤：  The invention also provides a surface selective metallization process for the plastic composition, comprising the steps of:
(a)激光刻蚀塑料组合物表面，将激光刻蚀后的塑料组合物置于含有金属离 子盐和空穴牺牲剂的水溶液中， 光源照射下， 在激光刻蚀造成的棵露部分发生  (a) laser etching the surface of the plastic composition, placing the laser-etched plastic composition in an aqueous solution containing a metal ion salt and a hole sacrificial agent, and irradiating the light source to cause a dew portion caused by laser etching
3 PIDM090739P 金属离子光催化还原反应， 使塑料组合物表面发生选择性沉积金属粒子；3 PIDM090739P Photocatalytic reduction of metal ions to selectively deposit metal particles on the surface of the plastic composition;
(b)对发生选择性沉积金属粒子的塑料组合物进行化学镀， 得到镀件。 根据本发明所提供的方法， 其中所述激光刻蚀为： 将塑料组合物基材放置 于激光下进行照射， 由于激光辐射的区域瞬间温度很高， 高于塑料组合物玻璃 化温度， 塑料组合物中的高分子聚合物瞬间软化下沉， 而塑料组合物中的光催 化剂则相对的从高分子聚合物中浮出来，使得塑料组合物中的部分光催化剂棵 露出来。 而未经激光辐射的区域， 表面无明显变化。 因而， 经过激光照射后， 塑料组合物基材表面选择性分布有光催化剂。 (b) Electroless plating of a plastic composition in which metal particles are selectively deposited to obtain a plated member. According to the method provided by the present invention, the laser etching is: placing the plastic composition substrate under laser irradiation, because the instantaneous temperature of the laser irradiation region is high, higher than the glass transition temperature of the plastic composition, the plastic combination The high molecular polymer in the material instantaneously softens and sinks, and the photocatalyst in the plastic composition relatively floats out of the high molecular polymer, so that part of the photocatalyst in the plastic composition is exposed. In the area without laser radiation, there is no significant change in the surface. Thus, after laser irradiation, a photocatalyst is selectively distributed on the surface of the substrate of the plastic composition.
其中， 所述激光刻蚀的条件为本领域技术人员所公知： 标记电流 0~24A, 频率 l~60KHz, 中间延时 0~30ms, 填充间 ≥0.01mm, 刻蚀时间 l~60s。 所 述激光刻蚀所采用的激光波长为 200~1064nm, 才艮据本发明的一个实施例， 该 激光波长为 1064nm, 但不局限于此。  The conditions of the laser etching are known to those skilled in the art: the marking current is 0~24A, the frequency is l~60KHz, the intermediate delay is 0~30ms, the filling interval is ≥0.01mm, and the etching time is l~60s. The laser light used in the laser etching is 200 to 1064 nm, and according to an embodiment of the present invention, the laser wavelength is 1064 nm, but is not limited thereto.
将经过激光刻蚀的塑料组合物放入含有金属离子盐和空穴牺牲剂的水溶 液中，金属离子在光照条件下发生光催化还原反应， 在棵露出的光催化剂表面 沉积金属粒子。  The laser-etched plastic composition is placed in an aqueous solution containing a metal ion salt and a hole sacrificial agent, and the metal ion undergoes a photocatalytic reduction reaction under light conditions to deposit metal particles on the exposed photocatalyst surface.
其中， 所述金属离子盐所釆用的金属包含 Cu、 Au、 M、 Co、 Fe、 Zn、 Pd、 Pt、 Ru、 Rh、 Re、 Os、 Ir中的一种或几种。  Wherein, the metal used for the metal ion salt comprises one or more of Cu, Au, M, Co, Fe, Zn, Pd, Pt, Ru, Rh, Re, Os, Ir.
所述空穴牺牲剂， 又称有机电子给体， 是用来捕获光生空穴促使载流子分 离的一类物质， 提高光催化效率。 本发明中， 所述空穴牺牲剂选自曱醇、 亚硫 酸盐、 有机染料中的一种或几种。 其中， 所述有机染料为本领域技术所公知的 各种染料， 如 N3、 N719、 N621、 N712、 N749、 Z235、 N773、 N790、 N820, N823、 N845、 N886、 N945、 K8、 K9、 K19、 K23、 K27、 K29、 K51、 K60、 K66、 K69、 K73、 K77、 Z316、 Z907、 Z910。  The hole sacrificial agent, also known as an organic electron donor, is a type of substance used to trap photogenerated holes to promote carrier separation, thereby improving photocatalytic efficiency. In the present invention, the hole sacrificing agent is one or more selected from the group consisting of decyl alcohol, sulfite, and organic dye. Wherein the organic dye is various dyes well known in the art, such as N3, N719, N621, N712, N749, Z235, N773, N790, N820, N823, N845, N886, N945, K8, K9, K19, K23, K27, K29, K51, K60, K66, K69, K73, K77, Z316, Z907, Z910.
根据本发明所提供的方法，其中所述金属离子盐与空穴牺牲剂的质量比为 0.1-100: 1。  According to the method of the present invention, the mass ratio of the metal ion salt to the hole sacrificial agent is from 0.1 to 100:1.
所述光催化剂在一定波长的光线照射下使分子轨道中的电子离开价带 The photocatalyst leaves electrons in the molecular orbital away from the valence band under illumination of a certain wavelength of light
(Valence band)跃迁至导带 (conduction band)， 生成电子-空穴对， 所述金属离子 得到电子发生光催化还原反应， 所述空穴牺牲剂提供电子， 消除空穴。 本发明 中， 所述金属离子的光催化还原反应所采用的光源的主发射波长为 The (Valence band) transitions to a conduction band to generate an electron-hole pair which is subjected to a photocatalytic reduction reaction of electrons, the hole sacrificial agent providing electrons and eliminating holes. In the present invention, the main emission wavelength of the light source used in the photocatalytic reduction reaction of the metal ion is
4 PIDM090739P 180〜1000nm。 4 PIDM090739P 180~1000nm.
经过光催化还原反应，金属粒子沉积于光催化剂表面。 以所述金属粒子为 活性中心， 进行常规化学镀， 即可得所需镀件。 所述化学镀技术为本领域技术 人员所公知， 可以为还原性不强于金属粒子的金属镀层。 本发明所提供的实施 例中， 均优选化学镀铜， 但不局限于此。  After photocatalytic reduction, metal particles are deposited on the surface of the photocatalyst. With the metal particles as an active center, conventional electroless plating is performed to obtain desired plating parts. The electroless plating technique is well known to those skilled in the art and may be a metal plating layer which is less reducible than metal particles. In the examples provided by the present invention, electroless copper plating is preferred, but is not limited thereto.
所述金属粒子为纳米级， 平均粒径为 10~100nm。  The metal particles are of a nanometer order and have an average particle diameter of 10 to 100 nm.
本发明中， 对所述塑料组合物进行激光刻蚀之前， 还需进行前处理。 所述 前处理， 其技术为本领域技术人员所公知。 本发明对前处理的方法没有特殊要 求， 一般情况下， 前处理包括将塑料组合物基材表面依次进行除油和粗化。  In the present invention, pretreatment is required before the plastic composition is subjected to laser etching. The pretreatment, the techniques of which are known to those skilled in the art. The present invention has no particular requirements for the method of pretreatment. In general, the pretreatment comprises sequentially degreasing and roughening the surface of the substrate of the plastic composition.
所述前处理中的除油， 目的是除去塑料组合物基材表面的油脂及其氧化 物。 除油的方法为本领域技术人员所公知的各种方法。 本发明中采用： 将塑料 组合物基材浸泡至含有 NaOH lmol.！ 1、 Na2C03 lmol. L 、 十二烷基磺酸钠 0.1 mol. L 的溶液中 5~10min， 溶液温度为 50~60°C。 取出后用水清洗， 浸泡 至 lmol. L"1的磷酸溶液中 5~10min, 然后取出用水清洗。 The purpose of degreasing in the pretreatment is to remove grease and its oxides from the surface of the substrate of the plastic composition. Methods of degreasing are various methods known to those skilled in the art. In the present invention, the substrate of the plastic composition is soaked to contain NaOH lmol. 1 , Na 2 C0 3 lmol. L, sodium dodecyl sulfate 0.1 mol. L solution in 5 ~ 10min, the solution temperature is 50 ~ 60 ° C. After taking out, it is washed with water, soaked in 1 mol. L" 1 phosphoric acid solution for 5 to 10 min, and then taken out and washed with water.
所述前处理中的粗化，目的是使塑料组合物表面产生海绵状微孔洞和亲水 性能， 满足金属镀层结合力强度的要求。粗化的方法为本领域技术人员所公知 的各种方法。 本发明中采用： 用含铬酐、 硫酸、 CrCl3*6H20 的溶液浸泡塑料 组合物基材 10~15min， 溶液温度为 60~70°C， 取出后用水清洗。 也可釆用含 NaOH, KMn04的溶液浸泡塑料组合物基材 10~15min， 溶液温度为 60~70°C。 然后在 40~50°C下用稀盐酸浸洗 5~8min。 取出后用水清洗。 The purpose of the roughening in the pretreatment is to produce sponge-like micropores and hydrophilic properties on the surface of the plastic composition, and to meet the requirements of the strength of the metal plating adhesion. The method of roughening is various methods known to those skilled in the art. In the present invention, the substrate of the plastic composition is immersed in a solution containing chromic anhydride, sulfuric acid, CrCl 3 *6H 2 0 for 10-15 minutes, the temperature of the solution is 60-70 ° C, and it is taken out and washed with water. The plastic composition substrate may also be immersed in a solution containing NaOH and KMn0 4 for 10-15 minutes, and the solution temperature is 60-70 °C. Then, it is immersed in dilute hydrochloric acid at 40~50 °C for 5~8min. After taking out, wash with water.
本发明中， 所述除油和粗化过程中的水洗工序， 水洗次数没有特别限制， 只要将塑料组合物基材表面的处理液充分去除洗净即可，根据本发明的一个实 施例，在所述除油后进行的水洗次数为 1~3次； 在所述粗化之后进行的水洗次 数为 4~6次。 水洗工序所用的水为现有技术中的各种水， 如市政自来水、 去离 子水、 蒸馏水、 纯净水或者它们的混合物， 根据本发明的一个实施例， 本发明 中釆用去离子水。  In the present invention, in the water washing step in the degreasing and roughening process, the number of times of washing is not particularly limited as long as the treatment liquid on the surface of the plastic composition substrate is sufficiently removed and washed, according to an embodiment of the present invention, The number of times of washing after the degreasing is 1 to 3 times; the number of washings performed after the roughening is 4 to 6 times. The water used in the water washing step is various waters of the prior art, such as municipal tap water, deionized water, distilled water, purified water or a mixture thereof. According to an embodiment of the present invention, deionized water is used in the present invention.
根据本发明所提供的方法， 在化学镀之前，还需对浸过含有金属离子盐和 空穴牺牲剂水溶液的塑料组合物基材进行清洗。所述清洗为本领域技术人员所 公知， 本发明没有特殊要求， 在此不赘述。  According to the method provided by the present invention, it is also necessary to clean the substrate of the plastic composition impregnated with the aqueous solution containing the metal ion salt and the hole sacrificial agent before the electroless plating. The cleaning is well known to those skilled in the art, and the present invention has no special requirements and will not be described herein.
5 PIDM090739P 本发明中， 非激光辐射区域表面没有光催化剂， 不会沉积金属粒子， 也不 会产生金属镀层， 因而化学镀精度很高。 以下通过具体实施例来详细说明本发明所提供的塑料组合物及其表面选 择性金属化工艺。 以下的实施例仅用于进一步说明本发明， 而不是限制本发明 的范围。 5 PIDM090739P In the present invention, the surface of the non-laser radiation region has no photocatalyst, metal particles are not deposited, and a metal plating layer is not generated, so that the electroless plating precision is high. The plastic composition provided by the present invention and its surface selective metallization process are described in detail below by way of specific examples. The following examples are merely illustrative of the invention and are not intended to limit the scope of the invention.
[实施例 11 [Example 11
本实施例用于说明本发明提供的塑料组合物及其表面选择性金属化工艺。 This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process.
(1)塑料组合物的制备： 称取 lkgABS塑料颗粒 (东莞同鑫工程塑料有限公 司， C2950)和 lkg二氧化钛粉末， 混合均匀， 使用挤压机 (南京新时代机电工 贸有限公司， XSD-35)进行挤压， 然后采用注塑机 (海天塑料机械有限公司， HTF60W1)进行注射， 得到 4.5cmx l4.5cm 的 ABS 塑料组合物基材， 记为 ABS- I 。 (1) Preparation of plastic composition: Weigh lkgABS plastic granules (Dongguan Tongxin Engineering Plastics Co., Ltd., C2950) and lkg titanium dioxide powder, mix evenly, use extruder (Nanjing New Times Machine Electric Co., Ltd., XSD-35 The extrusion was carried out, and then injection molding was carried out using an injection molding machine (Haitian Plastic Machinery Co., Ltd., HTF60W1) to obtain a 4.5 cm x 14.5 cm ABS plastic composition substrate, which was designated as ABS-I.
(2)基材前处理： 将步骤 (1)制得的 ABS- I放入含 NaOH lmol. L"\ Na2C03 lmol. L"\ O.lmol. I 1十二烷基硫酸钠的溶液中， 50°C下浸洗 10min， 取出后 用去离子水清洗， 然后放入含磚酸 lmol. I 1的溶液中浸洗 10min， 取出后用去 离子水清洗。 将清洗后的 ABS- I放入含 H2SO4200ml. ΐ Cr034mol. ΐΛ CrCl3-6H20 0.02mol. I/1的溶液中， 溶液温度为 70°C , 浸泡时间 10min。 取出 后用去离子水清洗。 (2) Pretreatment of the substrate: The ABS-I obtained in the step (1) is placed in a NaOH containing 1 mol of L.\Na 2 C0 3 lmol. L"\O.lmol. I 1 sodium lauryl sulfate. In the solution, it was immersed for 10 min at 50 ° C, taken out and washed with deionized water, then immersed in a solution containing 1 mol of silicic acid for 1 min, taken out and rinsed with deionized water. The washed ABS-I was placed in a solution containing H 2 SO 4 200 ml. ΐ Cr0 3 4 mol. ΐΛ CrCl 3 -6H 2 0 0.02 mol. I/ 1 , the solution temperature was 70 ° C, and the soaking time was 10 min. After removal, rinse with deionized water.
(3)溶液配制： 在 200ml水中加入 3.2g硫酸铜， 2ml甲醛， 6gEDTA-2Na, 4g酒石酸钾钠， 并用 NaOH调节 PH值为 12.5， 50°C下水浴恒温， 得到化学 镀镀液； 称取 3g 的硝酸铜和 20mL的曱醇 (AR级)， 加去离子水配制成 200ml 金属离子 -空穴牺牲剂水溶液。 (3) was prepared: 2 00ml of water was added in 3.2g of copper sulfate, formaldehyde 2ml, 6gEDTA-2Na, 4g potassium sodium tartrate, water bath and adjust the PH value of 12.5, 50 ° C with NaOH, to give an electroless plating bath; said Take 3 g of copper nitrate and 20 mL of decyl alcohol (AR grade), and add deionized water to prepare 200 ml of metal ion-hole sacrificial solution.
(4)激光刻蚀： 将步骤 (2)所得清洗后的 ABS- I干燥后垂直贴于玻璃壁上。 使用泰德激光打标机 (深圳市泰德激光科技有限公司， DPY-M50)对 ABS- I进 行刻蚀， 激光波长为 1064nm， 特定功率 50W。 刻蚀条件： 标记电流 13.0A, 频率 5KHZ， 步长 4unit， 中间延时 ΙΟΟμβ, 填充间距 0.05mm， 刻蚀时间 10s。 (4) Laser etching: The cleaned ABS-I obtained in the step (2) is dried and then vertically attached to the glass wall. The ABS-I was etched using a Ted laser marking machine (Shenzhen Ted Laser Technology Co., Ltd., DPY-M50) with a laser wavelength of 1064 nm and a specific power of 50 W. Etching conditions: Marking current 13.0A, frequency 5KH Z , step size 4unit, intermediate delay ΙΟΟμβ, filling pitch 0.05mm, etching time 10s.
(5)光催化还原反应： 将经过步骤 (4) 的 ABS- I放入 (3)所配制的金属离子-  (5) Photocatalytic reduction reaction: ABS-I subjected to step (4) is placed in (3) prepared metal ions -
6 PIDM090739P 空穴牺牲剂水溶液中， 置于紫外高压汞灯 (深圳博利达光电科技有限公司， 波 长 365nm)下照射， 照射时间为 10min。 6 PIDM090739P In the aqueous solution of the hole sacrificial agent, it was irradiated under ultraviolet high pressure mercury lamp (Shenzhen Bolida Optoelectronics Technology Co., Ltd., wavelength 365 nm), and the irradiation time was 10 min.
(6)化学镀铜：将经过光催化还原反应的 ABS- I放入 lOOmL去离子水中清 洗； 取出后， 放入步骤 (3)所配制的化学镀镀液中进行化学镀铜， 50°C水浴恒 温， 15min后取出， 即得到镀件 Al。  (6) Electroless copper plating: ABS-I subjected to photocatalytic reduction reaction is washed in 100 mL of deionized water; after being taken out, it is placed in the electroless plating solution prepared in the step (3) for electroless copper plating, 50 ° C The water bath was kept at a constant temperature and taken out after 15 minutes to obtain a plated Al.
[实施例 2j [Example 2j
本实施例用于说明本发明提供的塑料组合物及其表面选择性金属化工艺。 采用与实施例 1相同的方法对塑料组合物基材 ABS- I表面进行选择性金 属化学镀， 不同之处在于： 步骤 (1)中称取 2kgABS塑料颗粒 (东莞同鑫工程塑 料有限公司， C2950)和 20g二氧化钛粉末。 制备得到的 ABS塑料组合物基材 记为 ABS- II 。  This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process. The surface of the plastic composition substrate ABS-I was subjected to selective metal electroless plating in the same manner as in Example 1, except that: 2 kg of ABS plastic granules were weighed in step (1) (Dongguan Tongxin Engineering Plastic Co., Ltd., C2950) And 20 g of titanium dioxide powder. The prepared ABS plastic composition substrate was designated as ABS-II.
按照上述方法得到镀件， 记为 A2。  The plated member was obtained in the above manner and was designated as A2.
[实施例 3] [Embodiment 3]
本实施例用于说明本发明提供的塑料组合物及其表面选择性金属化工艺。 釆用与实施例 1相同的方法对塑料组合物基材 ABS- I表面进行选择性金 属化学镀， 不同之处在于： 步骤 (5)中用红外灯 (深圳市安宏达科技有限公司， PHILIPS红外线灯管 IN R95E， 波长 850nm)替换实施例 1中所釆用的紫外灯， 照射时间为 10min。  This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process. The surface of the plastic composition substrate ABS-I was subjected to selective metal electroless plating in the same manner as in Example 1, except that: Infrared lamp was used in step (5) (Shenzhen Anhongda Technology Co., Ltd., PHILIPS infrared The lamp IN R95E, wavelength 850 nm) was replaced with the UV lamp used in Example 1, and the irradiation time was 10 min.
按照上述方法得到镀件， 记为 A3。  The plated member was obtained in the above manner and was designated as A3.
[实施例 4] [Embodiment 4]
本实施例用于说明本发明提供的塑料组合物及其表面选择性金属化工艺。 釆用与实施例 2相同的方法对塑料组合物基材 ABS- II表面进行选择性金 属化学镀， 不同之处在于： 步骤 (5)中用红外灯 (深圳市安宏达科技有限公司， PHILIPS红外线灯管 IN 95E, 波长 850nm)替换实施例 2中所采用的紫外灯， 照射时间为 10min。  This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process. The surface of the plastic composition substrate ABS-II was subjected to selective metal electroless plating in the same manner as in Example 2, except that: Infrared lamp was used in step (5) (Shenzhen Anhongda Technology Co., Ltd., PHILIPS infrared The lamp IN 95E, wavelength 850 nm) was replaced with the UV lamp used in Example 2, and the irradiation time was 10 min.
按照上述方法所得镀件， 记为 A4。  The plated member obtained according to the above method was designated as A4.
7 PIDM090739P [实施例 5】 7 PIDM090739P [Example 5]
本实施例用于说明本发明提供的塑料组合物及其表面选择性金属化工艺。 采用与实施例 1相同的方法对塑料组合物基材 ABS- I表面进行选择性金 属化学镀， 不同之处在于： 步骤 (3)中， 称取 2g 的氯化钯替换实施例 1中的硝 酸铜， 配制成金属离子 -空穴牺牲剂水溶液。  This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process. The surface of the plastic composition substrate ABS-1 was subjected to selective metal electroless plating in the same manner as in Example 1, except that: in the step (3), 2 g of palladium chloride was weighed to replace the nitric acid in Example 1. Copper is formulated as an aqueous metal ion-hole sacrificial solution.
按照上述方法得到镀件， 记为 A5。  The plated member was obtained in the above manner and was designated as A5.
[实施例 6】 [Embodiment 6]
本实施例用于说明本发明提供的塑料组合物及其表面选择性金属化工艺。 采用与实施例 2相同的方法对塑料组合物基材 ABS- II表面进行选择性金 属化学镀， 不同之处在于： 步骤 (3)中， 称取 2g 的氯化钯替换实施例 2中的硝 酸铜， 配制成金属离子 -空穴牺牲剂水溶液。  This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process. The surface of the plastic composition substrate ABS-II was subjected to selective metal electroless plating in the same manner as in Example 2 except that: in the step (3), 2 g of palladium chloride was weighed to replace the nitric acid in Example 2. Copper is formulated as an aqueous metal ion-hole sacrificial solution.
按照上述方法得到镀件， 记为 A6。  The plated member was obtained in the above manner and was designated as A6.
[实施例 7】 [Embodiment 7]
本实施例用于说明本发明提供的塑料组合物及其表面选择性金属化工艺。 釆用与实施例 1相同的方法对塑料组合物基材 ABS- I表面进行选择性金 属化学镀， 不同之处在于： 步骤 (3)中， 称取 20mg有机染料 N3替换实施例 1 中的 20mL的曱醇，加去离子水配制成 200mL 的金属离子-空穴牺牲剂水溶液。  This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process. The surface of the plastic composition substrate ABS-1 was subjected to selective metal electroless plating in the same manner as in Example 1, except that in the step (3), 20 mg of the organic dye N3 was weighed and replaced with 20 mL of the Example 1. The sterol was added to deionized water to prepare a 200 mL aqueous metal ion-hole sacrificial solution.
按照上述方法得到镀件， 记为 A7。  The plated member was obtained in the above manner and was designated as A7.
[实施例 8] [Embodiment 8]
本实施例用于说明本发明提供的塑料组合物及其表面选择性金属化工艺。 釆用与实施例 2相同的方法对塑料组合物基材 ABS- II表面进行选择性金 属化学镀， 不同之处在于： 步骤 (3)中， 称取 20mg有机染料 N3替换实施例 2 中的 20mL的曱醇，加去离子水配制成 200mL 的金属离子-空穴牺牲剂水溶液。  This example is intended to illustrate the plastic composition provided by the present invention and its surface selective metallization process. The surface of the plastic composition substrate ABS-II was subjected to selective metal electroless plating in the same manner as in Example 2 except that: in the step (3), 20 mg of the organic dye N3 was weighed and replaced with 20 mL of the Example 2. The sterol was added to deionized water to prepare a 200 mL aqueous metal ion-hole sacrificial solution.
按照上述方法得到镀件， 记为 A8。  The plated member was obtained in the above manner and was designated as A8.
8 PIDM090739P [对比例 1] 8 PIDM090739P [Comparative Example 1]
采用与实施例 1 中相同的方法对现有技术中常用的塑料基材表面进行选 择性金属化学镀， 不同之处在于： 步骤 (1)中， 直接称取 2kgABS塑料颗粒 (东 莞同鑫工程塑料有限公司， C2950)取代实施例 1中的 lkgABS塑料颗粒和 1kg 二氧化钛粉末， 压塑成 4.5cmx 14.5cm的 ABS工程塑料基材， 记为 ABS-III。 釆用与实施例 1相同的方法对 ABS-III进行前处理、 激光刻蚀、 光催化还原反 应和化学镀铜步骤， 所得镀件记为 Dl。  The surface of the plastic substrate commonly used in the prior art was subjected to selective metal electroless plating in the same manner as in Example 1, except that: In the step (1), 2 kg of ABS plastic particles were directly weighed (Dongguan Tongxin Engineering Plastics) Co., Ltd., C2950), in place of the lkgABS plastic pellets of Example 1 and 1 kg of titanium dioxide powder, was compression molded into a 4.5 cm x 14.5 cm ABS engineering plastic substrate, designated ABS-III. The ABS-III was subjected to pretreatment, laser etching, photocatalytic reduction reaction and electroless copper plating in the same manner as in Example 1, and the obtained plated member was designated as D1.
[对比例 2] [Comparative Example 2]
采用 CN1772949A 中公开的技术方案对塑料基材表面进行选择性金属化 学镀。  Selective metallization of the surface of the plastic substrate is carried out using the technical solution disclosed in CN1772949A.
采用对比例 1中制备的 ABS工程塑料基材 ABS-III, 然后采用与实施例 1 相同的方法对 ABS-III进行前处理。  The ABS engineering plastic substrate ABS-III prepared in Comparative Example 1 was used, and then ABS-III was pretreated in the same manner as in Example 1.
称取 0.10g硝酸银， 加入 10ml乙醇中， 在 20°C下搅拌溶解后再加入 0.2g 聚乙烯吡咯烷酮， 继续在 20 °C下搅拌至全部溶解， 得到聚乙烯吡咯烷酮 /银胶 体； 釆用旋转涂布器 (广州市盛华化工科技有限公司， 1110N/1112N)将所得聚 乙烯吡咯烷酮 /银胶体均勾涂布在经过前处理后的 ABS-ΙΠ上， 自然晾干。  Weigh 0.10g of silver nitrate, add 10ml of ethanol, stir and dissolve at 20 ° C, then add 0.2g of polyvinylpyrrolidone, continue to stir at 20 ° C until all dissolved, to obtain polyvinylpyrrolidone / silver colloid; The applicator (Guangzhou Shenghua Chemical Technology Co., Ltd., 1110N/1112N) coats the obtained polyvinylpyrrolidone/silver colloid on the pretreated ABS-ΙΠ and naturally dries.
釆用与实施例 1相同的方法对涂布了聚乙烯吡咯烷酮 /银胶体的 ABS-ΠΙ进 行紫外激光选择性辐射和化学镀铜。 所得镀件记为 D2。 性能测试：  The polyvinylpyrrolidone/silver colloid-coated ABS-rhenium was subjected to ultraviolet laser selective irradiation and electroless copper plating in the same manner as in Example 1. The resulting plated member was designated as D2. Performance Testing:
样品镀层结合力测试， 简称划格法：  Sample coating adhesion test, referred to as the cross-cut method:
釆用 GB9286-88所公开的方法对实施例 1~8以及对比例 1~2所得镀件  Using the methods disclosed in GB9286-88 for the plating parts obtained in Examples 1 to 8 and Comparative Examples 1 to 2
A1 A8和 D1~D2进行结合力测试： 将试样 A1 A8和 D1~D2涂于样板上， 待干透 后， 釆用具有 6个切割面的多刀片切割器的划格测试器 (德国 BYK公司， 511 系歹 ' 平行拉动 3 ~ 4cm， 切刀间隙为 lmm, 有六道切痕， 应切穿漆膜； 然后用 同样的方法与前者垂直， 切痕六道； 这样形成许多小方格。 用软刷从对角方向 刷 5次或用胶带粘于格子上并迅速拉开， 用 4倍放大镜检查试验涂层的切割表 面， 并进行对比确定镀层结合力级。 0级附着力最佳， 一般超过 2级在防腐涂料 A1 A8 and D1~D2 were tested for binding force: Samples A1 A8 and D1~D2 were applied to the sample plate, and after drying, a cross-cut tester with a multi-blade cutter with 6 cutting faces was used (BYK, Germany) The company, 511 system 歹' parallel pull 3 ~ 4cm, cutter gap is lmm, there are six cut marks, should be cut through the paint film; then the same method is used to perpendicular to the former, six cut; thus forming many small squares. The soft brush is brushed 5 times from the diagonal direction or taped to the grid and quickly pulled open. The cut surface of the test coating is inspected with a 4x magnifying glass, and the adhesion level of the coating is determined by comparison. The 0-level adhesion is the best, generally More than 2 grades in anti-corrosion coating
9 PIDM090739P 中就认为附着力达不到要求。 9 PIDM090739P In the middle, it is considered that the adhesion does not meet the requirements.
0级 切割边缘完全平滑， 无一格脱落；  Level 0 The cutting edge is completely smooth, without a single drop;
1级 在切口交叉处涂层有少许薄片分离， 但划格区受影响明显不超过 Level 1 There is a slight separation of the coating at the intersection of the incisions, but the cross-cut area is obviously not affected.
5%; 5%;
2级 切口边缘或交叉处涂层脱落明显大于 5%, 但受影响不大于 15%; 3级 涂层沿边缘部分或全部以大碎片脱落， 在 15% ~ 35%之间。  Level 2 The thickness of the coating at the edge or intersection of the cut is significantly greater than 5%, but is affected by no more than 15%; the level 3 coating is partially or completely peeled off along the edge, between 15% and 35%.
实验结果如下表 1所示。  The experimental results are shown in Table 1 below.
表 1  Table 1
从表 1的测试结果可以看出， 实施例 1〜8与对比例 1〜2比较看出，采用本 发明所提供的技术方案得到的镀件的镀层结合力明显优于现有技术。 As can be seen from the test results of Table 1, the comparison of Examples 1 to 8 with Comparative Examples 1 to 2 shows that the plating adhesion of the plated member obtained by the technical solution provided by the present invention is significantly superior to the prior art.
从实施例 1〜6与实施例 7〜8的结果比较可以看出，采用本发明所提供的方 案即金属离子盐与空穴牺牲剂的质量比为 0.1〜： 100: 1 时， 所得到的镀层结合 力高。  It can be seen from the comparison between the results of Examples 1 to 6 and Examples 7 to 8 that the mass ratio of the metal ion salt to the hole sacrificial agent is 0.1 to: 100:1 by the solution provided by the present invention. The coating has a high bonding strength.
通过比较实验结果发现， 对比例 1中， 由于没有光催化剂的存在， 所以没 有纳米金属的沉积， 化学镀时根本形成不了镀层； 对比例 2中得到的镀件， 除 激光刻蚀的区域有镀层外， 未经激光刻蚀的区域也有镀层存在， 不满足电路板 图案的要求。 因为在激光刻蚀前后， 即使在室温下，银盐也易见光、 受热分解，  By comparing the experimental results, it was found that in Comparative Example 1, since there was no photocatalyst, there was no deposition of nano metal, and no plating was formed at the time of electroless plating; the plated part obtained in Comparative Example 2 was coated except for the laser etched region. In addition, the areas not laser etched are also coated, which does not meet the requirements of the board pattern. Because before and after laser etching, even at room temperature, silver salts are easy to see light, decompose by heat,
10 PIDM090739P 使激光未刻蚀区域受到银污染， 最后造成镀件精度很差。 而采用本发明所提供 的技术方案得到的实施例 1~8中镀件 Α1~Α8 , 由于激光未刻蚀区域表面没有 光催化剂的存在， 没有纳米金属粒子的沉积， 故化学镀铜后镀件表面图案清晰 分明， 精度很高。 10 PIDM090739P The unetched areas of the laser are contaminated with silver, which ultimately results in poor precision of the plated parts. In the first to eighth embodiments obtained by the technical solution provided by the present invention, the plating members Α1 to Α8, because there is no photocatalyst on the surface of the laser unetched region, there is no deposition of nano metal particles, so the electroless copper plating after plating The surface pattern is clear and precise.
11 PIDM090739P 11 PIDM090739P

Claims

权 利 要 求 书 Claim
1、 一种塑料组合物， 包含高分子聚合物和光催化剂， 其中高分子聚合物 和光催化剂的质量比为 1〜100： 1。 A plastic composition comprising a high molecular polymer and a photocatalyst, wherein the mass ratio of the high molecular polymer to the photocatalyst is from 1 to 100:1.
2、 根据权利要求 1所述的塑料组合物， 其特征在于： 所述高分子聚合物 包含聚乙烯、 聚丙烯、 聚苯乙烯、 聚氯乙烯、 聚曱基丙烯酸曱酯、 聚对苯二曱 酸乙二醇酯、 聚对苯甲酸丁二醇酯、 聚酰胺、 聚碳酸酯、 丙烯腈-丁二烯 -苯乙 烯共聚物、 聚酰亚胺、 聚酰胺-酰亚胺、 聚苯并咪唑、 聚氨酯、 聚吡咯、 聚噻 吩、 聚苯胺、 聚对亚曱基苯、 苯乙烯-丙烯腈共聚体、 酚酸树脂、 脲醛树脂、 聚曱醛、 聚醚醚酮、 聚醚酮、 聚醚砜、 聚苯^醚、 氯化聚乙烯、 苯乙烯 -丁二 烯-苯乙烯嵌段聚合物、 苯乙烯-乙烯-丁二烯-苯乙烯嵌段聚合物、 聚四氟乙烯、 环氧树脂、 聚曱醛、 聚苯酸、 聚砜、 醋酸纤维素、 醋酸丁酸纤维素、 赛璐珞、 玻璃纸、 脲曱醛、 三聚氰胺曱醛、 三聚氰胺脲曱醛、 聚醚砜、 聚苯砜、 聚氨基 双马来酰胺、 聚三嗪中的一种或几种。  2. The plastic composition according to claim 1, wherein: the high molecular polymer comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, polydecyl methacrylate, polyparaphenylene difluoride. Acid ethylene glycol ester, polybutylene terephthalate, polyamide, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyimide, polyamide-imide, polybenzimidazole , polyurethane, polypyrrole, polythiophene, polyaniline, polyparaphenylene benzene, styrene-acrylonitrile copolymer, phenolic resin, urea resin, polyfurfural, polyetheretherketone, polyetherketone, polyethersulfone , polyphenylene ether, chlorinated polyethylene, styrene-butadiene-styrene block polymer, styrene-ethylene-butadiene-styrene block polymer, polytetrafluoroethylene, epoxy resin, Polyacetal, polyphenylene, polysulfone, cellulose acetate, cellulose acetate butyrate, cellophane, cellophane, urea furfural, melamine furfural, melamine urea furfural, polyethersulfone, polyphenylsulfone, polyaminos One of an amide or a polytriazine or Species.
3、 根据权利要求 1所述的塑料组合物， 其特征在于： 所述光催化剂包含 金属氧化物、 金属硫化物、 钨酸盐、 钼酸盐的一种或几种。  The plastic composition according to claim 1, wherein the photocatalyst comprises one or more of a metal oxide, a metal sulfide, a tungstate, and a molybdate.
4、 根据权利要求 3 所述的塑料组合物， 其特征在于： 所述金属氧化物包 含 Ti02、 Cu20、 Fe203、 ZnO、 205、 Mo03、 ln203、 Sn02、 Ta205、 W03、 Bi203、 BaTi03、 SrTi03、 CaTi03、 MgTi03、 PbTi03、 BaSn03、 CaSn03、 InSn03、 CaSn03、 NiSn03、 PbSn03、 Li b03、 KNb03、 BaSb206、 PbSb206、 MgSb206、 NaTa03、 KTa03、 Β&5Τ 015、 Ca6Bi6015中的至少一个。 4. The plastic composition according to claim 3, wherein: said metal oxide comprises Ti0 2, Cu 2 0, Fe 2 0 3, ZnO, 2 0 5, Mo0 3, ln 2 0 3, Sn0 2 , Ta 2 0 5 , W0 3 , Bi 2 0 3 , BaTi0 3 , SrTi0 3 , CaTi0 3 , MgTi0 3 , PbTi0 3 , BaSn0 3 , CaSn0 3 , InSn0 3 , CaSn0 3 , NiSn0 3 , PbSn0 3 , Li b0 3 , at least one of KNb0 3 , BaSb 2 0 6 , PbSb 2 0 6 , MgSb 2 0 6 , NaTa0 3 , KTa0 3 , Β & 5 Τ 0 15 , and Ca 6 Bi 6 0 15 .
5、 根据权利要求 3 所述的塑料组合物， 其特征在于： 所述金属硫化物包 含 ZnS 和 CdS中的至少一个。  The plastic composition according to claim 3, wherein the metal sulfide contains at least one of ZnS and CdS.
6、 根据权利要求 3 所述的塑料组合物， 其特征在于： 所述钨酸盐包含钨 酸钠和钨酸钾中的至少一个。  6. The plastic composition according to claim 3, wherein: the tungstate comprises at least one of sodium tungstate and potassium tungstate.
7、 根据权利要求 3所述的塑料组合物， 其特征在于： 所述鉬酸盐包含钼 酸锂、 钼酸钠、 钼酸铵、 钼酸锌和钼酸钙中的至少一个。  The plastic composition according to claim 3, wherein the molybdate comprises at least one of lithium molybdate, sodium molybdate, ammonium molybdate, zinc molybdate and calcium molybdate.
8、 一种塑料组合物的表面选择性金属化方法， 所述塑料组合物包含高分 子聚合物和光催化剂， 其中高分子聚合物和光催化剂的质量比为 1~100 : 1 ,  8. A surface selective metallization method for a plastic composition, wherein the plastic composition comprises a polymer polymer and a photocatalyst, wherein a mass ratio of the polymer to the photocatalyst is from 1 to 100:1.
12 PIDM090739P 所述方法包括以下步骤： 12 PIDM090739P The method includes the following steps:
(a) 用刻蚀法处理塑料组合物表面， 将刻蚀后的塑料组合物置于含有金属 离子盐和空穴牺牲剂的水溶液中， 在光源照射的条件下， 在刻蚀造成的裸露部 分发生金属离子光催化还原反应， 使塑料组合物表面发生选择性沉积金属粒 子； 以及  (a) treating the surface of the plastic composition by etching, placing the etched plastic composition in an aqueous solution containing a metal ion salt and a hole sacrificial agent, and exposing the bare portion caused by the etching under the irradiation of the light source Metal ion photocatalytic reduction reaction to selectively deposit metal particles on the surface of the plastic composition;
(b) 对发生选择性沉积金属粒子的塑料组合物进行化学镀， 得到镀件。 (b) Electroless plating of a plastic composition in which selective deposition of metal particles occurs to obtain a plated member.
9、 根据权利要求 8所述的方法， 其中 (a)步骤所述刻蚀法为激光刻蚀法。9. The method according to claim 8, wherein the etching method in the step (a) is a laser etching method.
10、 根据权利要求 9 所述的方法， 所述激光刻蚀法所采用的激光波长为 200〜1064匪。 10. The method according to claim 9, wherein the laser etching method uses a laser having a wavelength of 200 to 1064 Å.
11、根据权利要求 8所述的方法，其中（a)步骤所述光催化还原所采用的光 源主发射波长为 180~1000nm。  The method according to claim 8, wherein the photocatalytic reduction used in the step (a) employs a light source having a main emission wavelength of 180 to 1000 nm.
12、根据权利要求 8所述的方法， 其中所述金属离子盐所采用的金属包含 Cu、 Au、 Ni、 Co、 Fe、 Zn、 Pd、 Pt、 Ru、 Rh、 Re、 Os、 Ir中的一种或几种。  The method according to claim 8, wherein the metal used for the metal ion salt comprises one of Cu, Au, Ni, Co, Fe, Zn, Pd, Pt, Ru, Rh, Re, Os, Ir Kind or several.
13、 根据权利要求 8所述的方法， 其中 (a)步骤所述空穴牺牲剂选自醇类、 亚硫酸盐、 有机染料中的一种或几种。  13. The method according to claim 8, wherein the hole sacrificing agent in (a) is selected from one or more of an alcohol, a sulfite, and an organic dye.
14、 根据权利要求 13所述的方法， 所述醇类包含曱醇。  14. The method of claim 13 wherein the alcohol comprises decyl alcohol.
15、根据权利要求 8所述的方法， 其中 (a)步骤所述溶液中， 金属离子盐与 空穴牺牲剂的质量比为 0.1-100： 1。  The method according to claim 8, wherein in the solution of the step (a), the mass ratio of the metal ion salt to the hole sacrificial agent is from 0.1 to 100:1.
16、 根据权利要求 8所述的方法， 其特征在于： 所述金属粒子的平均粒径 为 10~100匪。  The method according to claim 8, wherein the metal particles have an average particle diameter of 10 to 100 Å.
13 PIDM090739P  13 PIDM090739P
PCT/CN2009/073466 2008-08-23 2009-08-24 Plastic composition and method of selective metallization on the surface thereof WO2010022641A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200810141987.3 2008-08-23
CN2008101419873A CN101654564B (en) 2008-08-23 2008-08-23 Plastic composition and surface selective metallization process thereof

Publications (1)

Publication Number Publication Date
WO2010022641A1 true WO2010022641A1 (en) 2010-03-04

Family

ID=41709026

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2009/073466 WO2010022641A1 (en) 2008-08-23 2009-08-24 Plastic composition and method of selective metallization on the surface thereof

Country Status (2)

Country Link
CN (1) CN101654564B (en)
WO (1) WO2010022641A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100155218A1 (en) * 2008-12-12 2010-06-24 University Of South Carolina Novel Photocatalysts that Operate Under Visible Light
WO2012022255A1 (en) * 2010-08-19 2012-02-23 Byd Company Limited Method of metalizing surface of plastic substrate and plastic article made therefrom
US8920936B2 (en) 2010-01-15 2014-12-30 Byd Company Limited Metalized plastic articles and methods thereof
US9080052B2 (en) 2011-03-10 2015-07-14 Battelle Energy Alliance, Llc Precursor polymer compositions comprising polybenzimidazole
US9103020B2 (en) 2010-02-26 2015-08-11 Byd Company Limited Metalized plastic articles and methods thereof
CN106362803A (en) * 2016-08-26 2017-02-01 江苏大学 Ag-PANI embedded imprinting CdS/Fe3O4/C of Z-like heterojunction and preparation method of Ag-PANI embedded imprinting CdS/Fe3O4/C
US10059852B2 (en) 2013-04-02 2018-08-28 Shenzhen Byd Auto R&D Company Limited Metal compound, method for preparing the same, selective metallization of surface of substrate with the metal compound
CN113912976A (en) * 2021-10-11 2022-01-11 四川大学 Application of molybdenum-containing sensitization auxiliary agent in preparation of resin composition capable of being selectively metallized through laser activation

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102071412B (en) * 2010-04-14 2012-03-07 比亚迪股份有限公司 Plastic product and preparation method thereof
CN101873766B (en) * 2010-06-02 2011-07-27 上海律图表面处理有限公司 Method for manufacturing conductor track structure
CN102492940B (en) * 2010-08-19 2013-01-09 比亚迪股份有限公司 Preparation method of plastic product and plastic product
CN102806789A (en) * 2011-06-03 2012-12-05 上海安费诺永亿通讯电子有限公司 Method for forming metal pattern on surface of insulator
CN102516645B (en) * 2011-11-23 2013-07-24 安徽宜万丰电器有限公司 Automotive engine harness guard plate and manufacturing method thereof
EP2639334A1 (en) * 2012-03-15 2013-09-18 Atotech Deutschland GmbH Method for metallising non-conductive plastic surfaces
EP2639332A1 (en) * 2012-03-15 2013-09-18 Atotech Deutschland GmbH Method for metallising non-conductive plastic surfaces
CN106519740B (en) 2012-10-26 2019-01-11 比亚迪股份有限公司 White coating composition, the method for insulating substrate surface selective metallization and composite article
CN103111288A (en) * 2013-03-24 2013-05-22 桂林理工大学 Visible-light responsive tungstenic composite oxide photocatalyst Li2WO4 and preparation method thereof
TW201445006A (en) * 2013-05-23 2014-12-01 Byd Co Ltd A method of selective metallizing a surface of a polymer article and a polymer article obtained thereof
CN103539444B (en) * 2013-09-29 2015-11-25 桂林理工大学 Low-temperature sintered microwave dielectric ceramic Ca 2bi 2o 5and preparation method thereof
CN106634214B (en) * 2013-12-31 2020-03-20 比亚迪股份有限公司 Ink composition and surface selective metallization method
CN105400360A (en) * 2015-11-14 2016-03-16 合肥标兵凯基新型材料有限公司 Antibacterial anti-corrosion two-component coating specially used for pop can
CN106967965B (en) * 2016-01-13 2019-10-11 比亚迪股份有限公司 The method of plastic products and plastic basis material surface selective metallization
US9850578B1 (en) * 2016-09-13 2017-12-26 Rohm And Haas Electronic Materials Llc Shielding coating for selective metallization
US9797043B1 (en) * 2016-09-13 2017-10-24 Rohm And Haas Electronic Materials Llc Shielding coating for selective metallization
CN106399980B (en) * 2016-10-13 2019-06-14 北京工业大学 A method of high bond strength silver electrode is prepared on flexible substrate using laser writing technology
CN107012450A (en) * 2017-04-21 2017-08-04 中国科学院深圳先进技术研究院 A kind of method of polymeric substrate surface metallization and application thereof
CN107293672A (en) * 2017-07-25 2017-10-24 芜湖华力五星电源科技有限公司 A kind of lead-acid accumulator for motorcycle
CN107474518A (en) * 2017-08-03 2017-12-15 吕素慧 A kind of fiberglass reinforced polyphenylene oxide composite material and preparation method thereof
CN109385067A (en) * 2017-08-03 2019-02-26 吕素慧 A kind of fiberglass reinforced polyphenylene oxide composite material and preparation method thereof
CN108441843B (en) * 2018-03-13 2020-02-18 北京科技大学 Laser direct-writing preformed photocatalytic plating preparation method for metal patterns on surface of material
CN109856708B (en) * 2018-12-30 2021-07-30 瑞声光学解决方案私人有限公司 Lens extinction process
CN112779561A (en) * 2019-11-10 2021-05-11 青岛农业大学 Preparation of laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode
CN113831589A (en) * 2021-10-11 2021-12-24 四川大学 Application of tungsten-containing sensitization auxiliary agent in preparation of resin composition capable of being selectively metallized through laser activation
CN113956605B (en) * 2021-12-03 2023-10-24 四川大学 Application of oxide in preparation of resin composition capable of being selectively metallized by laser activation
CN114392392A (en) * 2022-02-15 2022-04-26 西南科技大学 Preparation method of personalized and customized polyether-ether-ketone implanted prosthesis with high biological activity
CN114505086A (en) * 2022-03-04 2022-05-17 重庆第二师范学院 Heterojunction photocatalyst BaSb2O6/g-C3N4Preparation method of (2)
CN115160623A (en) * 2022-07-11 2022-10-11 深圳原驰三维技术有限公司 Method for selectively adsorbing metal ions on surface area of polycarbonate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524611A (en) * 2003-09-18 2004-09-01 武汉理工大学 Composite material comprising photocatalyst and phenolic resin group active carbon and preparation method thereof
CN1886030A (en) * 2006-07-06 2006-12-27 复旦大学 Printed circuit board wiring technique based on nanometer TiO2 photocatalysis property
US20070014975A1 (en) * 2005-07-14 2007-01-18 Fuji Photo Film Co., Ltd. Method of manufacturing wiring substrate, and wiring substrate
CN1927939A (en) * 2006-09-27 2007-03-14 李向阳 Non-contact non-printing consumable material laser direct printing nano material and printing method thereof
CN101418091A (en) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 Laser marked plastic and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4615907A (en) * 1984-11-23 1986-10-07 Phillips Petroleum Company Plating poly(arylene sulfide) surfaces

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524611A (en) * 2003-09-18 2004-09-01 武汉理工大学 Composite material comprising photocatalyst and phenolic resin group active carbon and preparation method thereof
US20070014975A1 (en) * 2005-07-14 2007-01-18 Fuji Photo Film Co., Ltd. Method of manufacturing wiring substrate, and wiring substrate
CN1886030A (en) * 2006-07-06 2006-12-27 复旦大学 Printed circuit board wiring technique based on nanometer TiO2 photocatalysis property
CN1927939A (en) * 2006-09-27 2007-03-14 李向阳 Non-contact non-printing consumable material laser direct printing nano material and printing method thereof
CN101418091A (en) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 Laser marked plastic and preparation method thereof

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100155218A1 (en) * 2008-12-12 2010-06-24 University Of South Carolina Novel Photocatalysts that Operate Under Visible Light
US10392708B2 (en) 2010-01-15 2019-08-27 Byd Company Limited Metalized plastic articles and methods thereof
US9435035B2 (en) 2010-01-15 2016-09-06 Byd Company Limited Metalized plastic articles and methods thereof
US8920936B2 (en) 2010-01-15 2014-12-30 Byd Company Limited Metalized plastic articles and methods thereof
US9103020B2 (en) 2010-02-26 2015-08-11 Byd Company Limited Metalized plastic articles and methods thereof
US8846151B2 (en) 2010-08-19 2014-09-30 Byd Company Limited Metalized plastic articles and methods thereof
US8841000B2 (en) 2010-08-19 2014-09-23 Byd Company Limited Metalized plastic articles and methods thereof
US9770887B2 (en) 2010-08-19 2017-09-26 Byd Company Limited Metalized plastic articles and methods thereof
WO2012022255A1 (en) * 2010-08-19 2012-02-23 Byd Company Limited Method of metalizing surface of plastic substrate and plastic article made therefrom
US9080052B2 (en) 2011-03-10 2015-07-14 Battelle Energy Alliance, Llc Precursor polymer compositions comprising polybenzimidazole
US10059852B2 (en) 2013-04-02 2018-08-28 Shenzhen Byd Auto R&D Company Limited Metal compound, method for preparing the same, selective metallization of surface of substrate with the metal compound
CN106362803A (en) * 2016-08-26 2017-02-01 江苏大学 Ag-PANI embedded imprinting CdS/Fe3O4/C of Z-like heterojunction and preparation method of Ag-PANI embedded imprinting CdS/Fe3O4/C
CN113912976A (en) * 2021-10-11 2022-01-11 四川大学 Application of molybdenum-containing sensitization auxiliary agent in preparation of resin composition capable of being selectively metallized through laser activation

Also Published As

Publication number Publication date
CN101654564B (en) 2012-05-30
CN101654564A (en) 2010-02-24

Similar Documents

Publication Publication Date Title
WO2010022641A1 (en) Plastic composition and method of selective metallization on the surface thereof
CN101634018A (en) Selective chemical plating method for plastic base material
KR100759069B1 (en) Resin substrate having a resin-metal composite layer and method for manufacturing thereof
CN101654775B (en) Chemical plating material and preparation method thereof
JP3399434B2 (en) Method for forming plating of polymer molding material, circuit forming part, and method for manufacturing this circuit forming part
CN109844178B (en) Method for forming conductive trace on surface of polymer product
JP3486864B2 (en) Method for forming copper wiring on substrate and substrate on which copper wiring is formed
JP4135459B2 (en) Method for pretreatment of electroless plating material and method for manufacturing plating coated member
KR100883726B1 (en) Method of plating nonconductor product
JP4930804B2 (en) Method for producing electroless plating material
SE508280C2 (en) A method of increasing the adhesiveness of conductive materials to polymeric surface layers
JP4918123B2 (en) Method for producing electroless plating material
JP2007231362A (en) Electroless plating method of resin product
Akamatsu et al. Site-selective direct photochemical deposition of copper on glass substrates using TiO2 nanocrystals
US20040101665A1 (en) Direct patterning method
Ng et al. Ultra-violet direct patterning of metal on polyimide
JP4445711B2 (en) Metal oxide pattern forming method and metal wiring pattern forming method
CN111112643B (en) Nano silver wire preparation method for nanosecond laser-assisted thermal decomposition of silver nitrate, nano silver wire and application
JP3742872B2 (en) Electroless plating method using light-fixed fine particles as catalyst
JP5083005B2 (en) Resin substrate having a precious metal fixed on the surface layer, its manufacturing method, circuit board, and its manufacturing method
KR101891222B1 (en) Preparing method of metal nanotube for transparent electrode using electrospinning
JP2006526889A (en) Method of structured metallization of polymer and ceramic support materials and activatable compounds used in the method
CN112921309A (en) Method for preparing electrode based on laser
WO2007043380A1 (en) Catalyst treatment method, electroless plating method, and method for formation of circuit by using the electroless plating method
JP4145884B2 (en) Electroless plating method of printed circuit board using photocatalyst

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09809226

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09809226

Country of ref document: EP

Kind code of ref document: A1