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Número de publicaciónCN101654564 B
Tipo de publicaciónConcesión
Número de solicitudCN 200810141987
Fecha de publicación30 May 2012
Fecha de presentación23 Ago 2008
Fecha de prioridad23 Ago 2008
También publicado comoCN101654564A, WO2010022641A1
Número de publicación200810141987.3, CN 101654564 B, CN 101654564B, CN 200810141987, CN-B-101654564, CN101654564 B, CN101654564B, CN200810141987, CN200810141987.3
Inventores刘倩倩, 宫清, 林信平, 陈炎
Solicitante比亚迪股份有限公司
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos:  SIPO, Espacenet
Plastic composition and surface selective metallization process thereof
CN 101654564 B
Resumen
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.
Reclamaciones(9)  traducido del chino
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。 1. A plastic composition metallization process for the selective surface, comprising the steps of: (a) laser etching the plastic surface of the composition, the plastic composition is laser etched into a salt containing metal ions and holes sacrificial agent aqueous solution, the light irradiation, laser etching the exposed portion of the metal ions occur due to photocatalytic reduction reaction, the plastic surface of the composition occurs selectively deposited metal particles; (b) of the plastic composition of the metal particles occurs selectively deposited was subjected to electroless plating, plating obtained; the plastic composition, comprising polymer, a photocatalyst, wherein the polymer, the mass ratio of the photocatalyst 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. A method according to claim 1, characterized in that: said polymer comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate alcohol esters, polyethylene, polybutylene terephthalate acid, polyamides, polycarbonates, acrylonitrile - butadiene - styrene copolymer, polyimide, polyamide - imide, polybenzimidazole, polyurethane, polypyrrole, polythiophene, polyaniline, styrene - acrylonitrile copolymer, phenol resin, urea resin, polyoxymethylene, polyether ether ketone, polyether ketone, polyphenylene sulfide, chlorinated polyethylene, styrene - butadiene ene - styrene block polymers, styrene - ethylene - butadiene - styrene block polymers, polytetrafluoroethylene, epoxy resin, polyphenylene ether, polysulfone, cellulose acetate, cellulose acetate butyrate , celluloid, cellophane, urea formaldehyde, melamine formaldehyde, melamine urea formaldehyde, polyamino bismaleimide amide, poly-triazine 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, molybdate, zinc molybdate, calcium in 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 of 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 5. The method of claim 1, wherein the primary light source (a) said step of catalytic reduction used in the optical 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 of claim 1, wherein the metal used in the metal ion salt comprises Cu, Au, Ni, Co, Fe, Zn, Pd, Pt, Ru, Rh, Re, Os, Ir in a 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 dyes of one or more.
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 of 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, characterized in that: the average particle diameter of the metal particles is 10~lOOnm.
Descripción  traducido del chino

一种塑料组合物及其表面选择性金属化工艺 A plastic composition and 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 surface selective metallization process. 【背景技术】 BACKGROUND OF THE INVENTION

[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] The traditional electronic industry, circuit prepared information industry is mainly dependent chemical and photochemical methods that early in the routing process, you must go through photographic film, exposure, developing and etching and other procedures 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, the product design and development time, cost, small-scale production capacity 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 process technology exhibits excessive disadvantage long period.

[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 the laser direct writing technology is introduced. 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 company invented a LDS (Laser Direct Structuring-LDS) technology, by adding some kind of non-conductive plastic organic metal complexes as raw materials, direct the laser beam onto the surface of the molded parts were irradiated part can be chemically deposited metal plating. 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 art of plastic parts without specially roughened, sensitization, activation, direct laser irradiation can be carried out after plating, and the short process, simple operation, high production flexibility large, 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 LDS performance plastic, the plastic contains some non-conductive organic metal complex, while the laser irradiation plastic parts, only the surface portion needs to electroless plating occurs by activating the laser irradiation, other activation site without 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。 [0004] CN1772949A discloses a laser-induced selective plating method using PVP / silver colloid is coated on a substrate, selective irradiation with ultraviolet laser beams in the radiation area of colloidal silver in the silver ion is reduced to metallic silver particles embedded in the matrix and the non-irradiated areas of the colloidal silver is washed, electroless plating is then performed to obtain the base body micron patterned electroless plating. 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 of selective plating involves silver 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 the patent used silver nitrate, formic acid, silver acetate, propionate, silver butyrate silver in the sunlight and heat are liable to break down, so in actual operation, likely to cause pollution of the non-silver laser radiation area, even cleaning, it is difficult to completely remove, after electroless copper plating, the substrate surface area there will be a non-laser radiation coating portion; Further, by applying polyvinylpyrrolidone / silver colloid way, the use of laser radiation and the silver particles embedded in a matrix, coating adhesion is poor final plating.

【发明内容】 SUMMARY OF THE INVENTION

[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, it proposes a plastic composition and 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 plastics composition comprising a high molecular polymer, a photocatalyst, wherein the polymer, the 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 also provides a surface selective metallization process for the 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 surface of the plastic composition of the plastic composition is laser etched into an aqueous solution containing a salt of a metal ion and a hole in the sacrificial agent, under light irradiation, laser etching the exposed portion caused by the occurrence of Metal ion photocatalytic reduction reaction, the plastic surface of the composition occurs selectively deposited metal particles; [0009] (b) of the plastic composition of the metal particles occurs selectively deposited was subjected to chemical plating, get 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] idea of the invention is: a plastic composition containing polymer and a photocatalyst under laser irradiation conditions, the temperature of the laser radiation region instant high, higher than the glass transition temperature of the plastic composition, the plastic composition of the high instantly softens the polymer molecules sink, and the plastic composition of the photocatalyst is relatively floating out from polymer such that the composition of the plastic part photocatalyst exposed out; then the plastic composition is laser etched into an aqueous solution containing metal ion salts, sacrificial agents in the hole, the light can excite the photocatalyst under the irradiation conditions, exposed to the surface of the photocatalyst plastic composition may be a solution of the metal ions are reduced to give the nanoscale metal particles; Finally, 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 surface selective metallization process provided by the present invention, as compared with the prior art has the following advantages:

[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) photocatalyst distributed in plastic compositions inside the laser irradiation conditions bare part photocatalyst nano metal particles deposited on this surface and electroless 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) the selective metallization process, only the bared photocatalyst nano metal particles deposited on the surface, and then the nano metal particles are active center for chemical plating, accuracy is very high.

【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 plastics composition comprising a high molecular polymer, a photocatalyst, wherein the polymer, the 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 known to those skilled in the various known for polymer plastics sector. 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 , polyamides, polycarbonates, acrylonitrile - butadiene - styrene copolymer, polyimide, polyamide - imide, polybenzimidazole, polyurethane, polypyrrole, polythiophene, polyaniline, poly methylene benzene, styrene - acrylonitrile copolymer, phenol resin, urea resin, polyoxymethylene, polyether ether ketone, polyether ketone, polyether sulfone, polyphenylene sulfide, chlorinated polyethylene, styrene - butadiene ene - 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, polyphenylene sulfone, amide polyamino bismaleimide, triazine polymerization of one or more. 本发明实施例中均优选采用ABS,但不局限于此。 Embodiments of the invention are preferably used in ABS, but is not limited to this.

[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 under various excitation photon can play 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 photocatalyst titania (Ti02), zinc oxide (ZnO), tin oxide (Sn02), zirconia (& 02), cadmium sulfide (CdS), and other semiconductor oxides sulfides. 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。 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, calcium molybdate one or several. 本发明实施例中均优选采用二氧化钛,但不局限于此。 In embodiments of the invention are preferably used titanium oxide, but 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 also provides a composition of the plastic surface selective metallization process method, 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 surface of the plastic composition of the plastic composition is laser etched into an aqueous solution containing a salt of a metal ion and a hole in the sacrificial agent, under light irradiation, laser etching the exposed portion caused by the occurrence of Metal ion photocatalytic reduction reaction, the plastic surface of the composition occurs selectively deposited metal particles;

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) of the plastic composition of the metal particles occurs selectively deposited was subjected to chemical plating, get 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 according to the present invention there is provided, wherein said laser etching is: The substrate is placed in the plastic composition is irradiated with laser light, due to the high temperature region of the laser radiation instantaneously, higher than the glass transition temperature of the plastic composition plastic composition polymers soften moment sink, and the plastic composition of the photocatalyst is relatively floating out from polymer such that the composition of the plastic part photocatalyst bared. 而未经激光辐射的区域,表面无明显变化。 The area without the laser radiation, the surface no significant change. 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 the plastic substrate selectivity composition distribution 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 laser etching conditions known to those skilled known: Mark current 0~24A, frequency 1~60KHz, intermediate delay 0~30ms, fill spacing San 0. 01mm, the etching time 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, the embodiment 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 solution [0022] The plastic composition through laser etching was placed in a salt containing metal ions and holes sacrificial agent, the metal ions photocatalytic reduction in light conditions, in light of bare metal particles deposited on the catalyst surface.

[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 ions used in the metal salt comprises Cu, Au, Ni, Co, Fe, ai, Pd, Pt, Ru, Rh, Re, Os, Ir one or several.

[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 hole sacrificial agent, also known as organic electron donor, is used to capture the photo-generated carriers in separate holes prompted a class of substances, 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。 The present invention, the cavity sacrificial agent selected from methanol, sulfites, organic dye in 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 dye skilled various known 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 according to the present invention there is provided, wherein said metal ion salt mass sacrificial agent with a hole ratio of 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] The photocatalyst when exposed to light of a certain wavelength of the molecule orbital electrons leave the valence band (Valence band) transition to the conduction band (conduction band), to generate electron - hole pairs, the metal ions are electrons photocatalytic reduction reaction, the hole sacrificial agent provides electronic, 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。 The present invention, the main light catalytic reduction reaction of the metal ion source used in emission wavelength of 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] After the photocatalytic reduction reaction, metal particles 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 metal particles as an active center for conventional chemical plating, to obtain 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 the known, and preferably not strong reduction of the metal coating 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。 , Electroless copper plating of the present invention are preferably provided in the embodiment, 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 metal nano-particles, the average particle diameter of 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 invention, the plastic composition before laser etching, the need for pre-treatment. 所述前处理, 其技术为本领域技术人员所公知。 The pre-treatment, its technology 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 requires no special pre-treatment method, under normal circumstances, the pre-treatment composition comprising a plastic substrate surface was washed degreasing and coarsening.

[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。 Pretreatment of oil [0030], the purpose is to remove grease and oxide plastic composition of the substrate surface. 除油的方法为本领域技术人员所公知的各种方法。 Degreasing methods are known to those skilled in the various known methods. 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。 The present invention is used: the plastic composition containing a substrate to soak NaOHlmol I71, Na2CO3Imol Γ1, sodium dodecyl sulfate solution 0. lmol Γ1 5~lOmin, the solution temperature was 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 with water to soak lmol. Phosphoric acid plant 1 5~lOmin, and then remove the water clean.

[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。 [0031] The pre-treatment of roughening the aim is to make the plastic composition of the surface of the sponge-like micro pores and hydrophilic properties, coating adhesion strength of the metal to meet the requirements. 粗化的方法为本领域技术人员所公知的各种方法。 Roughening methods known to those skilled in the various known methods. 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。 The present invention uses: containing chromic anhydride, sulfuric acid, CrCl3 · 6H20 was soaked plastic composition substrate 10~15min, the solution temperature was 60~70 ° C, washing with water removal. 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 used containing Na0H, KMn04 solution soaking plastic compositions substrate 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 40~50 ° C under 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] The present invention, the crude oil and the process of washing process, washing times is not particularly limited as long as the treatment liquid plastic composition of the substrate surface can be washed sufficiently removed, Preferably, in the washing cycles performed for degreasing later ~ 3 times; washing cycles performed 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 of the prior art for the various 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 according to the present invention there is provided, prior to plating, the need for soaking the plastic composition containing a substrate metal ion salt and a hole at the expense of an aqueous solution of 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。 Those skilled in the washing well known, the present invention has no special requirements, this does not repeat.

[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-laser irradiation region of the surface without a photocatalyst, the metal particles are not deposited, it does not produce metal plating, electroless plating and thus high accuracy.

[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 provides a plastic composition of matter 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 are intended to further illustrate the present invention without limiting the scope of the 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。 Examples are illustrative embodiment of the present invention provides a plastic composition and surface selective metallization process [0037] The present.

[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] Production of plastic composition (1): Weigh IkgABS plastic particles (Dongguan Xin Engineering Plastics Co., C2950) and Ikg titanium dioxide powder, mix well, using an extruder (Nanjing new era of Electrical and Mechanical Services Ltd., XSD-35) squeezed, then an injection molding machine (Haitian Plastics Machinery Co., HTF60W1) injection, ABS plastic composition to obtain a substrate 4. 5cmX 14. 5cm, denoted by 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) a substrate pre-treatment: Step (1) obtained by ABS-I into containing NaOHlmol Γ1, Γ1, 0. Imol Γ1 solution of sodium lauryl sulfate Na2CO3Imol in, 50 °... Dip C under lOmin, washed with deionized water after removing, and then into contain phosphoric acid lmol. Γ1 solution immersion lOmin, after removing the deionized water. 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。 After the cleaning of ABS-I into containing H2S04200ml. Γ1, Cr034mol. Γ1, CrCl3 · 6Η200. 02mol. Γ1 solution, the solution temperature was 70 ° C, soaking time lOmin. 取出后用去离子水清洗。 After removing the 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 formulated: 3. 2g in 200ml of water was added copper sulfate, 2ml formaldehyde, 6gEDTA_ 2Na, 4g potassium sodium tartrate, and the PH value is adjusted with NaOH 12. 5,50 ° C water bath, the plating obtained bath; 3g weighed copper nitrate and 20mL methanol (AR grade), deionized water 200ml formulated as metal ion - water hole sacrificial agent.

[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) was obtained after washing dried ABS-I vertical 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) of the ABS-I is etched, laser wavelength of 1064nm, a 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: Flag current 13. 0A, frequency 5KHZ, step such as nit, intermediate delay 100 μ s, fill spacing 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: it will go through the steps of ABS-I into (3) the preparation of metal ion - water hole sacrificial agent, placed in an ultra high pressure mercury lamp (Shenzhen Boli Da Optoelectronics Technology Co., Ltd. wavelength 365nm) irradiation, irradiation time was 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) Copper Plating: light passing through the catalytic reduction of ABS-I put IOOmL deionized water cleaning; remove and put it into step ⑶ formulated chemical plating bath in the copper, 50 ° C water bath, 15min after the removal, that was

6到镀件Al。 6 to 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。 Examples are illustrative embodiment of the present invention provides a plastic composition and surface selective metallization process [0045] The present.

[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 as in Example 1 for plastic compositions substrate surface ABS-I selective metal plating, except that: step (1) Weigh ^ gABS plastic particles (with plastic Dongguan Xin Limited to 950) and titanium dioxide powder 20g. 制备得到的ABS塑料组合物基材记为ABS-II。 ABS plastic composition prepared substrate was referred to as ABS-II.

[0047] 按照上述方法得到镀件,记为A2。 [0047] According to the above method to obtain plating, 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] This example illustrates the plastic composition of the present invention provides a selective metallization process and its surface.

[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 method of Example 1 with the same composition of the base material for the plastic ABS-I surface for selective metal plating, except that: step (5) with infrared light (Shenzhen Hongda Technology Co., PHILIPS infrared lamp IN R95E, wavelength 850nm) used in Example 1 was replaced with ultraviolet lamps embodiment, the irradiation time of lOmin.

[0051] 按照上述方法得到镀件,记为A3。 [0051] According to the above method to obtain plating, 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] This example illustrates the plastic composition of the present invention provides a selective metallization process and its surface.

[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 method as in Example 2 plastic compositions substrate surface ABS-II selective metal plating, except that: step (5) with infrared light (Shenzhen Hongda Technology Co., PHILIPS infrared lamp IN R95E, wavelength 850nm) in Example 2 to replace the use of ultraviolet light irradiation time was lOmin.

[0055] 按照上述方法所得镀件,记为A4。 [0055] The plating obtained in the above method, 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。 Examples are illustrative embodiment of the present invention provides a plastic composition and surface selective metallization process [0057] The present.

[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] using the same method as in Example 1 for plastic compositions substrate surface ABS-I selective metal plating, except that: in step (3), weighed 2g of Example 1 was replaced with palladium chloride copper nitrate to prepare a metal ion - water hole sacrificial agent.

[0059] 按照上述方法得到镀件,记为A5。 [0059] According to the above method to obtain plating, 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] This example illustrates the plastic composition of the present invention provides a selective metallization process and its surface.

[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] using the same method as in Example 2 to plastic compositions substrate surface ABS-II selective metal plating, except that: in step (3), weighed 2g alternative embodiment of palladium chloride 2 copper nitrate to prepare a metal ion - water hole sacrificial agent.

[0063] 按照上述方法得到镀件,记为A6。 [0063] According to the above method to obtain plating, 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。 Examples are illustrative embodiment of the present invention provides a plastic composition and surface selective metallization process [0065] The present.

[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 method of Example 1 with the same composition of the base material for the plastic ABS-I surface for selective metal plating, except that: step ⑶, the weighed 20mg organic dye N3 alternative embodiment in Example 1 20mL methanol, force mouth 200mL deionized water into a metal ion - water hole sacrificial agent.

[0067] 按照上述方法得到镀件,记为A7。 [0067] According to the above method to obtain plating, 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] This example illustrates the plastic composition of the present invention provides a selective metallization process and its surface. [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 method as in Example 2 plastic compositions substrate surface ABS-II selective metal plating, except that: step (3), weighed 20mg organic dye N3 replacement Example 2 The 20mL of methanol, force mouth 200mL deionized water into a metal ion - water hole sacrificial agent.

[0071] 按照上述方法得到镀件,记为A8。 [0071] According to the above method to obtain plating, 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] Example 1 using the same method used in the prior art plastic substrate surface for selective metal plating, except that: step (1), the direct weighed ^ gABS plastic particles (Dongguan Xin Engineering Plastics Co., C2950) replace IkgABS plastic particles in Example 1 and Ikg titanium dioxide powder, compression molded ABS plastic substrate 4. 5cmX 14. 5cm, denoted by 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。 Using the same method as in Example 1 on the ABS-III pre-treatment, laser etching, light catalytic reduction and chemical plating step, the resulting plating denoted as 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] The technical solution disclosed CN1772949A plastic substrate surface 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] Comparative Example 1 was prepared using ABS plastic base material ABS-III, and then using the same method as in Example 1 on the ABS-III pretreatment.

[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, added IOml ethanol, in the dissolved with stirring at 20 ° C and then added 0. 2g polyvinylpyrrolidone, and continue stirring until completely dissolved in at 20 ° C to obtain PVP / silver colloid; using a spin coater (Guangzhou Shenghua Chemical Technology Co., 1110N / 1112N) and the resulting PVP / silver colloid uniformly applied before and after treatment on ABS-III through, air dry.

[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 manner as in Example 1 on the coated PVP / silver colloids ABS-III UV laser radiation and selective electroless 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] sample coating adhesion test, referred to as grid method:

[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 method disclosed GB9286-88 Example 1 ~ 8 and Comparative Examples 1 to 2 obtained plating Al~ A8 and Dl~D2 binding force test: A sample was applied Al~A8 and Dl~D2 the model to be dry, the use of multi-blade cutter has six cutting surface of cross-cut tester (Germany BI company, 511 series) parallel pulling 3~km, knife gap of 1mm, there are six cuts, should cut through the film; then, in the same way as the former vertical incisions six; so the formation of 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。 Use a soft brush from the brush diagonally 5 or taped on the grid and quickly opened, with four times the magnifying glass to check the test coating cutting surface, 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, usually over two 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 cutting edge is 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] an incision at the intersection of coating a little sheet separation, but the cross-cut 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 at the intersection of the cut edge or coating off significantly greater than 5%, but by no more than 15%;

[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] 3 coating along the edge portion or all of the large fragments falling, between 15% ~ 35%.

[0086] 实验结果如下表1所示。 [0086] The results are shown below 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 ~ 2 Comparative seen plating of coating adhesion using technology provided by the present invention was significantly better than the prior technical implementation .

[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] From Example 1~6 and Comparative Examples 7~8 results can be seen, the use of a preferred embodiment of the present invention provides a metal ion salt, i.e., the quality of the hole ratio of 0.1~100 sacrificial agent, the resulting The coating adhesion is high.

[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] By comparing the results found in Comparative Example 1, since there is no presence of the photocatalyst, so there is no nanocrystalline metal plating can not simply be formed when plating; plating obtained in Comparative Example 2, except that the laser etching Regional Xi Bu plated without laser etching of a region also has the presence of the coating, the board does not meet the requirements of the 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。 Because before and after laser etching, even at room temperature, silver is also easy to see the light, thermal decomposition, laser etched area not contaminated by silver, and finally result in poor precision plating. 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。 The embodiment uses technology provided by the present invention obtained 1 ~ 8 in plating Al~A8, since the laser unetched region of the surface of the photocatalyst does not exist, no deposition of nano metal particles, so after electroless copper plating surface pattern of clear-cut, high precision.

Citas de patentes
Patente citada Fecha de presentación Fecha de publicación Solicitante Título
US461590723 Nov 19847 Oct 1986Phillips Petroleum CompanyPlating poly(arylene sulfide) surfaces
Otras citas
Referencia
1Hilmar Esrom.Fast selective metal deposition on polymers by using IR and excimer VUV photons.《Applied Surface Science》.2000,第168卷1-4.
2JP特开2003-192905A 2003.07.09
3T. J. Hirsch,et al..Selective-area electroless copper plating on polyimide employing laser patterning of a catalytic film.《Appl. Phys. Lett.》.1990,第57卷(第13期),1357-1359.
Clasificaciones
Clasificación internacionalC23C18/31, C08K3/24, C08K3/30, C08K3/22, C08L101/00, C23C18/20
Clasificación cooperativaC23C18/22, B01J35/004, B01J37/16
Clasificación europeaB01J37/16, C23C18/22, B01J35/00D6
Eventos legales
FechaCódigoEventoDescripción
24 Feb 2010C06Publication
21 Jul 2010C10Request of examination as to substance
30 May 2012C14Granted