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Plastic composition and surface selective metallization process thereof

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Publication number
CN101654564B
CN101654564B CN 200810141987 CN200810141987A CN101654564B CN 101654564 B CN101654564 B CN 101654564B CN 200810141987 CN200810141987 CN 200810141987 CN 200810141987 A CN200810141987 A CN 200810141987A CN 101654564 B CN101654564 B CN 101654564B
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composition
plastic
surface
process
selective
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CN 200810141987
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Chinese (zh)
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CN101654564A (en )
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刘倩倩
宫清
林信平
陈炎
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比亚迪股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS, COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/002Catalysts characterised by their physical properties
    • B01J35/004Photocatalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS, COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16Reducing
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22Roughening, e.g. by etching

Abstract

The invention provides a plastic composition and a surface selective metallization process thereof. The plastic composition comprises a high molecular polymer and a photocatalyst, wherein the mass ratio of the polymer to the photocatalyst is 1 to 100. The surface selective metallization process of the plastic composition comprises the following steps: performing laser etching on the surface of the plastic composition; putting the plastic composition after the laser etching into an aqueous solution containing a metal ion salt and a cavity sacrificial agent to perform photocatalysis reduction reaction so as to obtain a plastic composition with nanometer metal particles on the surface; and finally performing metal chemical plating. By adopting the plastic composition and the surface selective metallization process of the plastic composition, the bonding force of a plating layer and the chemical plating precision are very high.

Description

一种塑料组合物及其表面选择性金属化工艺 A plastic composition and the surface selective metallization process

【技术领域】 TECHNICAL FIELD

[0001] 本发明涉及一种塑料组合物及其表面选择性金属化工艺。 [0001] The present invention relates to a plastic composition and the surface selective metallization process. 【背景技术】 【Background technique】

[0002] 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。 [0002] Conventional electronic industry, information industry preparation circuit depends chemical and photochemical methods, these methods in the initial routing process, must be photographic film, exposure, development and etching and other processes to complete. 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。 With the rapid development of the electronics industry, product design and development time, cost, small-scale production capacity we have put forward higher requirements. 而传统的技术显示出工序过多、周期过长的缺点。 The traditional techniques exhibit excessive step, long cycle disadvantages.

[0003] 因此,电子工业中的激光直写技术应运而生。 [0003] Thus, the electronics industry in laser direct writing technology came into being. LPKF公司发明了一种激光直接成型(Laser Direct Structuring-LDS)技术,采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。 LPKF invented a laser direct structuring (Laser Direct Structuring-LDS) technology, the use of plastic added with some non-conductive metal organic compound as the raw material, the laser beam is projected directly on the surface of the molded part is irradiated portion may be a metal plating deposition. 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。 The plastic art without specially roughened, sensitization, activation, electroless plating can be carried out directly after the laser irradiation, and short process, simple operation and large production of high flexibility, line width, line spacing accuracy. 但是采用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。 But using LDS techniques must be used with a plastic LDS properties, some of the non-conductive plastic containing organometallic complexes, laser irradiation is performed while the plastic member, only the surface portion of the plating requires activation occurs through laser light irradiation, other non-activated portion of the laser irradiation does not occur, thus unactivated plastic organometallic complexes have not been utilized, resulting in great waste.

[0004] CN1772949A中公开了一种激光诱导选择性化学镀方法,该方法采用聚乙烯吡咯烷酮/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。 In [0004] CN1772949A discloses a laser-induced selective chemical plating method polyvinylpyrrolidone / silver colloids coated on a substrate, selective irradiation with ultraviolet laser beams, colloidal silver silver ions in the radiation region in the It is reduced to metallic silver particles embedded in the matrix and, the non-irradiated area of ​​colloidal silver is washed away, and then electroless plating on the substrate to obtain micron-scale patterning the plating layer. 但采用该方法进行选择性化学镀,涉及到银污染问题。 However, this method for selective chemical plating, silver involving pollution problems. 由于该专利中使用的硝酸银、甲酸银、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,最后化学镀时镀层结合力较差。 Since silver nitrate used in this patent, silver formate, silver acetate, silver propionate, silver butyrate readily decompose under sunlight and heated, so in actual operation, likely to cause a non-laser radiation silver stain area, even cleaning, it is difficult to completely remove, after the copper plating, a non-laser radiation will have a surface area of ​​the base portion of the coating; Further, by coating the silver colloid polyvinylpyrrolidone info / and laser irradiation silver particles embedded in a matrix, poor coating adhesion final plating.

【发明内容】 [SUMMARY]

[0005] 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。 [0005] The present invention addresses the deficiencies of the prior art proposes a plastic composition and the surface selective metallization process.

[0006] 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。 [0006] The present invention provides a plastic composition comprising a polymer, a photocatalyst, wherein the polymer mass ratio of the photocatalyst 1~100.

[0007] 本发明还提供了一种本发明所提供的塑料组合物表面选择性金属化工艺方法,包含以下步骤: [0007] The present invention further provides a process for surface metalized plastic composition of the present invention is provided, comprising the steps of:

[0008] (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;[0009] (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。 [0008] (a) laser etching the plastic surface of the composition, the plastic composition was placed after the laser etching aqueous solution containing a metal ion salt and a hole in the sacrificial agent, the light irradiation, the laser etching the exposed portion occurs due to metal ion photocatalytic reduction reaction, the plastic composition is deposited selectively on the surface of the metal particles occurs; [0009] (b) for the selective deposition of the plastic composition of the metal particles occurs by chemical plating, to give plating.

[0010] 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裸露出来;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,裸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。 [0010] The concept of the present invention is: a plastic composition comprising a polymer and a photocatalyst under the laser irradiation conditions, the laser radiation region instantaneous temperature is high, above the glass transition temperature of the plastic composition of the plastic composition of high instantly softened polymer molecule sink, while the photocatalyst plastic composition is opposite from the float out of the polymer, such that the portion of the photocatalyst plastic composition expose; then, after laser etching plastic composition into an aqueous solution containing a metal ion salt, a hole in the sacrificial agent, under irradiation conditions can excite the photocatalyst, the photocatalyst exposed surface of the plastic composition of the metal ions in solution may be reduced to give metal nano-particles; Finally, the metal plating.

[0011] 采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: [0011] The plastic composition and the surface selective metallization process provided by the present invention has the following advantages over the prior art:

[0012] (1)光催化剂分布在塑料组合物内部,激光照射条件下裸露出部分光催化剂,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; [0012] (1) In the light distribution of the catalyst inside the plastic composition, the exposed portion of the laser irradiation conditions photocatalyst is deposited on this surface of nano metal particles and plating, high coating adhesion;

[0013] (2)选择性金属化工艺时,只在裸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。 [0013] (2) When the selective metallization process, only the exposed surface of the photocatalyst is deposited out of the nano metal particles, nano metal particles and then plating the active center, very high precision.

【具体实施方式】 【detailed description】

[0014] 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。 [0014] The present invention provides a plastic composition comprising a polymer, a photocatalyst, wherein the polymer mass ratio of the photocatalyst 1~100.

[0015] 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。 [0015] The plastic composition of the present invention is provided, wherein the polymer well known to those skilled in the art for a variety of plastic polymer art. 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、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯、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、聚对亚甲基苯、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、聚苯硫醚、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、聚甲醛、聚苯醚、聚砜、醋酸纤维素、醋酸丁酸纤维素、赛璐珞、玻璃纸、脲甲醛、三聚氰胺甲醛、三聚氰胺脲甲醛、聚醚砜、聚苯砜、聚氨基双马来酰胺、聚三嗪中的一种或几种。 In the present invention, the polymer comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate poly benzoate , polyamide, polycarbonate, acrylonitrile - butadiene - styrene copolymer, polyimide, polyamide - imide, polybenzimidazole, polyurethanes, polypyrrole, polythiophene, polyaniline, methylene benzene, styrene - acrylonitrile copolymer, a phenol resin, urea resin, polyoxymethylene, polyether ether ketone, polyether ketone, polyether sulfone, polyphenylene sulfide, chlorinated polyethylene, styrene - butadiene alkenyl - styrene block polymers, styrene - ethylene - butadiene - styrene block polymers, polytetrafluoroethylene, epoxy resins, polyoxymethylene, polyphenylene oxide, polysulfone, cellulose acetate, acetate butyrate acid cellulose, celluloid, cellophane, urea formaldehyde, melamine formaldehyde, melamine urea-formaldehyde, polyether sulfone, polyphenyl sulfone, polyamino bismaleimide, one or more poly-triazines. 本发明实施例中均优选采用ABS,但不局限于此。 Embodiments of the present invention are preferably used ABS, but is not limited thereto.

[0016] 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。 [0016] The photocatalyst at various photon excitation can be a catalytic species. 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(&02),硫化镉(CdS)等多种氧化物硫化物半导体。 Common titanium dioxide photocatalyst (Titania and), zinc oxide (ZnO), tin oxide (Sn02), zirconium dioxide (& 02), cadmium sulfide (CdS) and other oxides sulfide semiconductor. 本发明中,所述光催化剂选自Ti02、Cu20、Fe203>Zn0, ZnS^Nb2O5, MoO3> CdS> In203> SnO2> Ta2O5^ WO3> Bi203> BaTiO3^ SrTiO3^ CaTiO3^ MgTi03、PbTi03、BaSnO3^ CaSnO3, InSnO3, CaSnO3, NiSnO3, PbSnO3, LiNbO3, KNbO3, BaSb2O6, PbSb2O6, MgSb2O6, NaTaO3, KTaO3, Ba5Ta4O15, Ca6Bi6O15、钨酸钠、钨酸钾、钼酸锂、钼酸钠、钼酸铵、钼酸锌、钼酸钙中的一种或几种。 In the present invention, the photocatalyst is selected from Ti02, Cu20, Fe203> Zn0, ZnS ^ Nb2O5, MoO3> CdS> In203> SnO2> Ta2O5 ^ WO3> Bi203> BaTiO3 ^ SrTiO3 ^ CaTiO3 ^ MgTi03, PbTi03, BaSnO3 ^ ​​CaSnO3, InSnO3, CaSnO3, NiSnO3, PbSnO3, LiNbO3, KNbO3, BaSb2O6, PbSb2O6, MgSb2O6, NaTaO3, KTaO3, Ba5Ta4O15, Ca6Bi6O15, sodium tungstate, potassium tungstate, lithium molybdate, sodium molybdate, ammonium molybdate, zinc molybdate, one or more of calcium molybdate. 本发明实施例中均优选采用二氧化钛,但不局限于此。 Embodiments of the present invention are preferably used titanium oxide, but is not limited thereto.

[0017] 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: [0017] The present invention further provides a process for the surface of the selective metallization of a plastic composition, comprising the steps of:

[0018] (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; [0018] (a) laser etching the plastic surface of the composition, the plastic composition was placed after the laser etching aqueous solution containing a metal ion salt and a hole in the sacrificial agent, the light irradiation, the laser etching the exposed portion occurs due to photocatalytic reduction reaction of metal ions, the composition selectively deposited plastic surface of the metal particles occurs;

4[0019] (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。 4 [0019] (b) for the selective deposition of the plastic composition of the metal particles occurs by chemical plating, to give plating.

[0020] 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裸露出来。 [0020] The method of the present invention is provided, wherein said laser etching is: a substrate placed in the plastic composition to laser irradiation, since the region instantaneous temperature of the laser radiation is very high, higher than the glass transition temperature of the plastic composition , plastic polymer in the composition to soften the moment sink, while the photocatalyst plastic composition is opposite from the float in the polymer, so that part of the plastic composition expose the photocatalyst. 而未经激光辐射的区域,表面无明显变化。 No significant change in the area of ​​the laser radiation without surface. 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。 Thus, after the laser irradiation, the surface of a substrate selective distribution of the plastic composition photocatalyst.

[0021] 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1〜60KHz,中间延时0〜30ms,填充间距彡0. 01mm,刻蚀时间1〜60s。 [0021] wherein the conditions of the laser etching known to those skilled in the art: the current mark 0~24A, frequency 1~60KHz, intermediate delay 0~30ms, gap distance San 0. 01mm, the etching time is 1 ~ 60s. 所述激光刻蚀所采用的激光波长为200〜1064nm,本发明实施例中均优选为1064nm,但不局限于此。 The laser wavelength of the laser used for etching 200~1064nm, embodiments of the present invention are preferably 1064nm, but is not limited thereto.

[0022] 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,在裸露出的光催化剂表面沉积金属粒子。 Aqueous [0022] The laser-etched into the plastic composition containing a metal ion salt and a hole in the sacrificial agent, photocatalytic reduction reaction of metal ions in the light conditions, the deposited metal particles are exposed out of the surface of the photocatalyst.

[0023] 其中,所述金属离子盐所采用的金属包含Cu、Au、Ni、Co、Fe、ai、Pd、Pt、Ru、Rh、Re、 Os、Ir中的一种或几种。 [0023] wherein the metal of the metal ion salt used comprising Cu, one or more of Au, Ni, Co, Fe, ai, Pd, Pt, Ru, Rh, Re, Os, Ir in.

[0024] 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。 [0024] The cavity sacrificial agent, also known as the organic electron donor, is used to capture photogenerated holes cause a species of carrier separation, improve the photocatalytic efficiency. 本发明中,所述空穴牺牲剂选自甲醇、亚硫酸盐、有机染料中的一种或几种。 In the present invention, the hole sacrificial agent is selected from methanol, sulfites, organic dye is one or several. 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。 Wherein the organic dyes well-known to the skilled various dyes, 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.

[0025] 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。 [0025] The method of the present invention is provided, wherein the mass of metal ion salt and the hole ratio of the sacrificial agent is 0. 1 ~ 100.

[0026] 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(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。 [0026] In the photocatalyst so that certain wavelengths of light irradiation molecular orbital electrons leaving the valence band (Valence band) the transition to the conduction band (conduction band), to generate electron - hole pairs, the electrons in the metal ions to give photocatalytic reduction reaction, the hole sacrificial agent provides electrons, eliminating holes. 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180〜lOOOnm。 In the present invention, the main light source of the catalytic metal ion reduction reaction employed emission wavelength 180~lOOOnm.

[0027] 经过光催化还原反应,金属粒子沉积于光催化剂表面。 [0027] The light passing through the catalytic reduction reaction, the metal particles are deposited on the surface of the photocatalyst. 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。 In the active center in the metal particles, conventional chemical plating, to give the desired plating. 所述化学镀技术为本领域技术人员所公知,优选为还原性不强于金属粒子的金属镀层。 The plating techniques known to those skilled in known, preferably not stronger than a reducing metal plating metal particles. 本发明所提供的实施例中,均优选化学镀铜,但不局限于此。 Embodiment, the electroless copper plating of the present invention are preferably provided, but is not limited thereto.

[0028] 所述金属粒子为纳米级,平均粒径为10〜lOOnm。 [0028] The nanoscale metal particles, an average particle diameter 10~lOOnm.

[0029] 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。 [0029] In the present invention, the plastic composition prior to laser etching, the need for pretreatment. 所述前处理, 其技术为本领域技术人员所公知。 The pretreatment, which techniques are known to those skilled in the art. 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。 The present invention has no special requirements on the method of pretreatment, in general, the pretreatment composition comprises the surface of a plastic substrate sequentially degreasing and roughening.

[0030] 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。 Degreasing pretreatment of the [0030], in order to remove oxides and grease compositions plastic substrate surface. 除油的方法为本领域技术人员所公知的各种方法。 Various methods are known degreasing method for those skilled in the art. 本发明中采用:将塑料组合物基材浸泡至含有NaOHlmol. I71、Na2CO3Imol. Γ1、十二烷基磺酸钠0. lmol. Γ1的溶液中5〜lOmin,溶液温度为50〜60°C。 Used in the present invention: the substrate is immersed into the plastic composition containing NaOHlmol I71, Na2CO3Imol Γ1, sodium dodecyl sulfate solution of 0. lmol Γ1 5~lOmin, a solution temperature of 50~60 ° C.. 取出后用水清洗,浸泡至lmol.厂1的磷酸溶液中5〜lOmin,然后取出用水清洗。 After removing the washing water, soaked to lmol. Plant phosphoric acid solution 1 5~lOmin, washed with water and then removed.

[0031] 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。 The [0031] Pretreatment roughened purpose is to make the surface of the plastic composition to produce a sponge-like microvoids and hydrophilic properties, coating adhesion strength of the metal to meet the force requirements. 粗化的方法为本领域技术人员所公知的各种方法。 The present method of roughening a variety of methods known to those skilled in the art. 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。 Used in the present invention: chromic anhydride, sulfuric acid, CrCl3 · 6H20 solution soaking plastic composition containing substrate 10~15min, a solution temperature of 60~70 ° C, washed with water and taken out. 也可采用含Na0H、KMn04的溶液浸泡塑料组合物基材10〜 15min,溶液温度为60〜70°C。 It may also be employed including Na0H, KMn04 solution soaking plastic substrate composition 10~ 15min, a solution temperature of 60~70 ° C. 然后在40〜50°C下用稀盐酸浸洗5〜8min。 Then at 40~50 ° C immersion 5~8min with dilute hydrochloric acid. 取出后用水清洗。 Washed with water after removal.

[0032] 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,优选情况下,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。 [0032] In the present invention, the degreasing and washing step roughening process, the number of water washing is not particularly limited as long as the surface treatment liquid composition of the plastic substrate can be washed sufficiently removed, Preferably, in the washing times is performed after said degreasing ~ 3 times; the number of times washed with water after the roughening is 4 ~ 6 times. 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,本发明优选为去离子水。 The water washing step is prior art various kinds of water, such as municipal tap water, deionized water, distilled water, purified water or mixtures thereof, the present invention is preferably deionized water.

[0033] 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。 [0033] The method of the present invention is provided, prior to plating, the need for the plastic composition-impregnated substrate an aqueous solution of metal ion salt and the sacrificial agent contains a hole cleaning. 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。 Cleaning the skilled artisan is well known, there are no special requirements of the present invention, which is not repeated herein.

[0034] 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。 [0034] In the present invention, the non-irradiated area by laser light without a catalyst, without deposition of metal particles, the metal plating layer does not occur, and thus high precision plating.

[0035] 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。 [0035] By the following detailed description of specific embodiments of the present invention, the plastic composition is provided and its surface selective metallization process. 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。 The following examples serve only to further illustrate the invention, but not limit the scope of the present invention.

[0036][实施例1] [0036] [Example 1]

[0037] 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。 [0037] The present examples serve to illustrate the present invention provides compositions and plastic surface selective metallization process.

[0038] (1)塑料组合物的制备:称取IkgABS塑料颗粒(东莞同鑫工程塑料有限公司, C2950)和Ikg 二氧化钛粉末,混合均勻,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 14. 5cm的ABS塑料组合物基材,记为ABS-I。 [0038] (1) Preparation of plastic composition: Weigh IkgABS plastic particles (Dongguan Xin Engineering Plastics Co., C2950) and Ikg titania powder, mixing, using an extruder (Nanjing New Era Electromechanical Co., XSD-35) was pressed and then using an injection molding machine (Haitian plastic Machinery Co., HTF60W1) injection, ABS plastic composition to obtain a substrate 4. 5cmX 14. 5cm, denoted as ABS-I.

[0039] (2)基材前处理:将步骤(1)制得的ABS-I 放入含NaOHlmol. Γ1、Na2CO3Imol. Γ1、 0. Imol. Γ1十二烷基硫酸钠的溶液中,50°C下浸洗lOmin,取出后用去离子水清洗,然后放入含磷酸lmol. Γ1的溶液中浸洗lOmin,取出后用去离子水清洗。 [0039] (2) Pretreatment of the substrate: step (1) was prepared containing the ABS-I into NaOHlmol Γ1, Na2CO3Imol Γ1, 0. Imol Γ1 sodium lauryl sulfate solution, 50 °... dipping the C lOmin, rinsed with deionized water taken out, and then placed in phosphate-containing lmol. Γ1 lOmin immersion solution, washed with deionized water after removal. 将清洗后的ABS-I放入含H2S04200ml. Γ1、Cr034mol. Γ1、CrCl3 · 6Η200. 02mol. Γ1 的溶液中,溶液温度为70°C,浸泡时间lOmin。 The ABS-I after cleaning into the containing H2S04200ml. Γ1, Cr034mol. Γ1, CrCl3 · 6Η200. 02mol. Γ1 solution, a solution temperature of 70 ° C, soaking time lOmin. 取出后用去离子水清洗。 After removal washed with deionized water.

[0040] (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的甲醇(AR级),加去离子水配制成200ml金属离子-空穴牺牲剂水溶液。 [0040] (3) was prepared: copper sulfate was added 3. 2g in 200ml of water, 2ml of formaldehyde, 6gEDTA_ 2Na, 4g of sodium potassium tartrate, and adjusting the PH value of water bath at 12. 5,50 ° C with NaOH, to give an electroless plating bath; copper nitrate said taking 3g of methanol and 20mL (grade AR), deionized water 200ml formulated as metal ions - an aqueous solution of sacrificial agent hole.

[0041] (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。 [0041] (4) laser etching: step (2) ABS-I obtained after washing was dried perpendicularly affixed to the glass wall. 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。 Use Ted Laser Marking Machine (Shenzhen Ted Laser Technology Co., DPY-M50) on the ABS-I is etched, laser wavelength of 1064nm, specific power 50W. 刻蚀条件:标记电流13. 0A,频率5KHZ,步长如nit,中间延时100 μ s,填充间距0. 05mm,刻蚀时间10s。 Etching conditions: current mark 13. 0A, frequency 5KHZ, steps such as nit, intermediate delay 100 μ s, a gap distance of 0. 05mm, the etching time 10s.

[0042] (5)光催化还原反应:将经过步骤的ABS-I放入(3)所配制的金属离子-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lOmin。 [0042] (5) photocatalytic reduction reaction: After the step into the ABS-I (3) of the formulated metal ion - in an aqueous solution of sacrificial agent hole, placed in an ultra high pressure mercury lamp (Shenzhen Boli Da Optoelectronics Technology Co., Ltd. , the irradiation wavelength of 365 nm), the irradiation time of lOmin.

[0043] (6)化学镀铜:将经过光催化还原反应的ABS-I放入IOOmL去离子水中清洗;取出后,放入步骤⑶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 [0043] (6) electroless copper plating: the light passing through the catalytic reduction of ABS-I into IOOmL washed in deionized water; taken out and put into the chemical plating step ⑶ formulated electroless copper plating bath, 50 ° C water bath, taken after 15min, to obtain

6到镀件Al。 6 to the plating Al.

[0044][实施例2] [0044] [Example 2]

[0045] 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。 [0045] The present examples serve to illustrate the present invention provides compositions and plastic surface selective metallization process.

[0046] 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^gABS塑料颗粒(东莞同鑫工程塑料有限公司,以950) 和20g 二氧化钛粉末。 [0046] The same method of one pair of surfaces of the plastic ABS-I composition selective electroless metal plating a substrate in Example except that: in step (1) was weighed ^ gABS plastic particles (plastic Dongguan Xin Co., Ltd., 950), and 20g titanium dioxide powder. 制备得到的ABS塑料组合物基材记为ABS-II。 ABS plastic composition prepared was referred to as a substrate ABS-II.

[0047] 按照上述方法得到镀件,记为A2。 [0047] The plating obtained by the above method, referred to as A2.

[0048][实施例3] [0048] [Example 3]

[0049] 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。 [0049] The present examples serve to illustrate the present invention provides compositions and plastic surface selective metallization process.

[0050] 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(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中所采用的紫外灯,照射时间为lOmin。 [0050] The selective metal plating on the surface of the plastic ABS-I compositions with a substrate of the same method as in Example 1, except that: in step (5) with infrared light (Shenzhen Hongda Technology Co., PHILIPS infrared lamp iN R95E, wavelength 850nm) UV lamp replaced employed in Example 1 embodiment, the irradiation time of lOmin.

[0051] 按照上述方法得到镀件,记为A3。 [0051] The plating obtained by the above method, referred to as A3.

[0052][实施例4] [0052] [Example 4]

[0053] 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。 [0053] The present examples serve to illustrate the present invention provides compositions and plastic surface selective metallization process.

[0054] 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(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2中所采用的紫外灯,照射时间为lOmin。 [0054] the same manner as ABS-II two pairs of surfaces of the plastic base composition of metal plating and selective embodiment, except that: in step (5) with infrared light (Shenzhen Hongda Technology Co., PHILIPS infrared lamp iN R95E, wavelength 850nm) alternative employed in Example 2 ultraviolet lamp, the irradiation time of lOmin.

[0055] 按照上述方法所得镀件,记为A4。 [0055] According to the above method resulting plating, referred to as A4.

[0056][实施例5] [0056] [Example 5]

[0057] 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。 [0057] The present examples serve to illustrate the present invention provides compositions and plastic surface selective metallization process.

[0058] 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。 [0058] the same manner as the substrate 1 ABS-I selective surface of the plastic composition and the metal plating embodiment, except that: in step (3), said palladium chloride alternative embodiment taken in Example 1 2g of copper nitrate to prepare a metal ion - hole sacrificial agent solution.

[0059] 按照上述方法得到镀件,记为A5。 [0059] The plating obtained by the above method, referred to as A5.

[0060][实施例6] [0060] [Example 6]

[0061] 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。 [0061] The present examples serve to illustrate the present invention provides compositions and plastic surface selective metallization process.

[0062] 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。 [0062] the same manner as ABS-II two pairs of surfaces of the plastic base composition of metal plating and selective embodiment, except that: in step (3), said palladium chloride alternative embodiment of Example 2 taken 2g of copper nitrate to prepare a metal ion - hole sacrificial agent solution.

[0063] 按照上述方法得到镀件,记为A6。 [0063] The plating obtained by the above method, referred to as A6.

[0064][实施例7] [0064] [Example 7]

[0065] 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。 [0065] The present examples serve to illustrate the present invention provides compositions and plastic surface selective metallization process.

[0066] 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⑶中,称取20mg有机染料N3替换实施例1中的20mL的甲醇,力口去离子水配制成200mL的金属离子-空穴牺牲剂水溶液。 [0066] The selective metal plating on the surface of the plastic substrate ABS-I compositions with the same method as in Example 1, except that: in step ⑶, said organic dye is taken 20mg N3 alternative embodiment 20 mL 1 methanol, deionized water port force formulated into 200mL of metal ions - an aqueous solution of sacrificial agent hole.

[0067] 按照上述方法得到镀件,记为A7。 [0067] The plating obtained by the above method, referred to as A7.

[0068][实施例8] [0068] [Example 8]

[0069] 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。 [0069] The present examples serve to illustrate the present invention provides compositions and plastic surface selective metallization process. [0070] 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20mg有机染料N3替换实施例2中的20mL的甲醇,力口去离子水配制成200mL的金属离子-空穴牺牲剂水溶液。 [0070] the same manner as ABS-II two pairs of surfaces of the plastic base composition of metal plating and selective embodiment, except that: in step (3), the organic dye was weighed 20mg N3 alternative embodiment of Example 2 20mL of methanol, deionized water port force formulated into 200mL of metal ions - an aqueous solution of sacrificial agent hole.

[0071] 按照上述方法得到镀件,记为A8。 [0071] The plating obtained by the above method, referred to as A8.

[0072][对比例1] [0072] [Comparative Example 1]

[0073] 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^gABS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IkgABS塑料颗粒和Ikg 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。 [0073] The same method common in the art of surface plastic substrate in Example 1 selective metal plating, except that: in step (1), directly weighed ^ gABS plastic particles (Dongguan Xin engineering plastics Co., C2950) substituted IkgABS plastic particles in Example 1 and the titanium dioxide powder Ikg, compression molded ABS plastic substrate 4. 5cmX 14. 5cm, denoted as ABS-III. 采用与实施例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。 Pretreated using ABS-III of the same method as in Example 1, laser etching, and the photocatalytic reduction reaction of the electroless copper plating step, the resulting plating denoted Dl.

[0074][对比例2] [0074] [Comparative Example 2]

[0075] 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。 [0075] CN1772949A disclosed technical solution to the surface of a plastic substrate by selective metal plating.

[0076] 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。 [0076] ABS plastic substrate ABS-III prepared in Comparative Example 1 and ABS-III employed for pretreating the same method as in Example 1.

[0077] 称取0. IOg硝酸银,加入IOml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;采用旋转涂布器(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/银胶体均勻涂布在经过前处理后的ABS-III上,自然晾干。 [0077] Weigh 0. IOg silver nitrate, IOml ethanol was added, at 20 ° C with stirring to dissolve before adding 0. 2g of polyvinylpyrrolidone, stirring is continued until all dissolved at 20 ° C, to give polyvinylpyrrolidone / silver colloids; resulting polyvinylpyrrolidone / silver colloid using a spin coater (Guangzhou Shenghua Chemical Technology Co., 1110N / 1112N) was uniformly coated on the ABS-III before and after the treatment, the dry naturally.

[0078] 采用与实施例1相同的方法对涂布了聚乙烯吡咯烷酮/银胶体的ABS-III进行紫外激光选择性辐射和化学镀铜。 [0078] The same method as in Example 1 embodiment the coated polyvinylpyrrolidone / silver colloid ABS-III ultraviolet laser radiation and selective copper plating. 所得镀件记为D2。 The resulting plating referred to as D2.

[0079] 性能测试: [0079] Performance Testing:

[0080] 样品镀层结合力测试,简称划格法: [0080] The coating adhesion test sample, referred to as the cross-hatch:

[0081] 采用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Al〜 A8和Dl〜D2进行结合力测试:将试样Al〜A8和Dl〜D2涂于样板上,待干透后,采用具有6个切割面的多刀片切割器的划格测试器(德国BI公司,511系列)平行拉动3〜km, 切刀间隙为1mm,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。 [0081] The disclosed embodiments of the method GB9286-88 1~8 and Comparative Examples 1~2 resulting plated Al~ A8 and embodiment Dl~D2 binding Test: A sample was applied Al~A8 and Dl~D2 of the model to be dry, using the cross hatch test device having a multi-blade cutters 6 cut surface (BI German company, 511 series) parallel to the pulling 3~km, blade gap of 1mm, there are six cuts, should cut through the paint film; then the same manner as the former vertically, six cuts; thus formed many small squares. 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。 With a soft brush from a diagonal direction of the brush 5 or taped on the grid and quickly opened by cutting the coating surface inspection test 4 times the magnifying glass and compared to determine coating adhesion level. 0级附着力最佳,一般超过2 级在防腐涂料中就认为附着力达不到要求。 0 best adhesion, generally more than level 2 in the anti-corrosion coating adhesion is considered below standard.

[0082] 0级切割边缘完全平滑,无一格脱落; [0082] 0 a cutting edge completely smooth, without shedding a grid;

[0083] 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5% ; [0083] In stage 1 the intersection of the cut-sheet coating is slightly separated, but the crosscut area affected significantly less than 5%;

[0084] 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% ; [0084] 2-stage coating or cut edges at the intersection off significantly greater than 5%, but not more than 15% affected;

[0085] 3级涂层沿边缘部分或全部以大碎片脱落,在15%〜35%之间。 [0085] Level 3 along the edge portion or all of the coating in large fragments falling between 15% ~ 35%.

[0086] 实验结果如下表1所示。 [0086] The results are shown in Table 1.

[0087] 表1 [0087] TABLE 1

[0088] [0088]

Figure CN101654564BD00081
Figure CN101654564BD00091

[0089] 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。 [0089] As can be seen from the test results in Table 1, and Comparative Example 1~8 1~2 Comparative seen, the coating adhesion of plating the technical solution provided by the present invention is significantly better than the prior art obtained embodiment .

[0090] 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优选方案即金属离子盐与空穴牺牲剂的质量比为0.1〜100时,所得到的镀层结合力高。 [0090] As can be seen from the embodiments 1~6 Comparative Examples and results of Examples 7~8 embodiment, using the preferred embodiment of the present invention provides a mass of metal ion salt i.e., the hole ratio of 0.1~100 sacrificial agent, the resulting high coating adhesion.

[0091] 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夕卜,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。 [0091] It was found by comparison of Comparative Example 1, due to the absence of the photocatalyst, there is no deposition of nano metal plating layer did not form a chemical plating; plating obtained in Comparative Example 2, except that the laser etching Bu Xi region coating without laser etching region of the coating also exist, does not meet the requirements of the circuit board pattern. 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,使激光未刻蚀区域受到银污染,最后造成镀件精度很差。 Since before and after laser etching, even at room temperature, the silver salt is also easy to see the light, thermal decomposition, laser unetched regions by silver stain, finally resulting in poor plating accuracy. 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Al〜A8,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。 And the technical solution provided by the present invention obtained in Example 1~8 plating Al~A8, since the laser unetched area of ​​the surface of the absence of the photocatalyst, there is no deposition of nano metal particles, so copper plating after the plating surface pattern of clear-cut, high accuracy.

Claims (9)

1. 一种塑料组合物表面选择性金属化工艺方法,包含以下步骤:(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;(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;所述塑料组合物,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。 A process for surface metalized plastic composition, comprising the steps of: (a) laser etching the plastic surface of the composition, the plastic composition after laser etching comprises metal ion salt was placed in the hole and the sacrificial agent an aqueous solution, the light irradiation, the laser etching the exposed portion occurs due to photocatalytic reduction reaction of the metal ion, the plastic surface of the composition occurs selectively deposited metal particles; (b) a plastic composition undergoes selective deposition of metal particles is plating, plating obtained; the plastic composition, comprising a polymer, a photocatalyst, wherein the polymer, the mass ratio of the photocatalyst is 1~100.
2.根据权利要求1所述的方法,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、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯、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、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、聚苯硫醚、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、聚苯醚、聚砜、醋酸纤维素、醋酸丁酸纤维素、赛璐珞、玻璃纸、脲甲醛、三聚氰胺甲醛、三聚氰胺脲甲醛、聚氨基双马来酰胺、聚三嗪中的一种或几种。 2. The method according to claim 1, wherein: said polymer comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate alcohol esters, polyethylene glycol benzoic acid ester, polyamide, polycarbonate, acrylonitrile - butadiene - styrene copolymer, polyimide, polyamide - imide, polybenzimidazole, polyurethanes, polypyrrole, polythiophene, polyaniline, styrene - acrylonitrile copolymer, a phenol resin, urea resin, polyoxymethylene, polyether ether ketone, polyether ketone, polyphenylene sulfide, chlorinated polyethylene, styrene - butadiene alkenyl - styrene block polymers, styrene - ethylene - butadiene - styrene block polymers, polytetrafluoroethylene, epoxy resin, polyphenylene oxide, polysulfone, cellulose acetate, cellulose acetate butyrate , celluloid, cellophane, urea formaldehyde, melamine formaldehyde, melamine urea formaldehyde, polyamino bismaleimide, polytriazine of one or more.
3.根据权利要求1所述的方法,其特征在于:所述光催化剂包含Ti02、Cu20、Fe203、ai0、 ZnS、Nb2O5, MoO3> CdS, In2O3> SnO2, Ta2O5, WO3> Bi203、BaTiO3> SrTiO3> CaTiO3> MgTiO3> PbTi03、 BaSnO3, CaSnO3, InSnO3, NiSnO3, PbSnO3, LiNbO3, KNbO3, BaSb2O6, PbSb2O6, MgSb2O6, NaTaO3, KTaO3, Ba5Ta4O15, Ca6Bi6O15、钨酸钠、钨酸钾、钼酸锂、钼酸钠、钼酸铵、钼酸锌、钼酸钙中的一种或几种。 3. The method according to claim 1, wherein: said photocatalyst comprises Ti02, Cu20, Fe203, ai0, ZnS, Nb2O5, MoO3> CdS, In2O3> SnO2, Ta2O5, WO3> Bi203, BaTiO3> SrTiO3> CaTiO3> MgTiO3> PbTi03, BaSnO3, CaSnO3, InSnO3, NiSnO3, PbSnO3, LiNbO3, KNbO3, BaSb2O6, PbSb2O6, MgSb2O6, NaTaO3, KTaO3, Ba5Ta4O15, Ca6Bi6O15, sodium tungstate, potassium tungstate, lithium molybdate, sodium molybdate, ammonium molybdate, zinc molybdate, calcium molybdate is one or several.
4.根据权利要求1所述的方法,其中(a)步骤所述激光刻蚀所采用的激光波长为200 〜1064nm。 4. The method according to claim 1, wherein step (a) the wavelength of the laser used for the laser etching 200 ~1064nm.
5.根据权利要求1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 〜IOOOnm0 The method according to claim 1, wherein the primary light source (a) said step of catalytic reduction employed in the light emission wavelength was 180 ~IOOOnm0
6.根据权利要求1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。 6. The method according to claim 1, wherein the metal employed metal ion salt comprising a Cu, Au, Ni, Co, Fe, Zn, Pd, Pt, Ru, Rh, Re, Os, Ir in one or several.
7.根据权利要求1所述的方法,其中(a)步骤所述空穴牺牲剂选自甲醇、亚硫酸盐、有机染料中的一种或几种。 7. The method according to claim 1, wherein step (a) the hole sacrificial agent is selected from methanol, sulfites, organic dye is one or several.
8.根据权利要求1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。 8. The method according to claim 1, wherein step (a) in the solution, the mass ratio of metal ion salt and the hole sacrificial agent is 0. 1~100.
9.根据权利要求1所述的方法,其特征在于:所述金属粒子的平均粒径为10〜lOOnm。 9. The method according to claim 1, wherein: the average particle diameter of the metal particles 10~lOOnm.
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