WO2015154502A1 - 在塑料表面形成选择性金属线路的方法及塑料部件 - Google Patents

在塑料表面形成选择性金属线路的方法及塑料部件 Download PDF

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WO2015154502A1
WO2015154502A1 PCT/CN2014/093499 CN2014093499W WO2015154502A1 WO 2015154502 A1 WO2015154502 A1 WO 2015154502A1 CN 2014093499 W CN2014093499 W CN 2014093499W WO 2015154502 A1 WO2015154502 A1 WO 2015154502A1
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plastic substrate
plastic
activation
roughening
chemical
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PCT/CN2014/093499
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English (en)
French (fr)
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王咏
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深圳市泛友科技有限公司
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    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the invention relates to the manufacture of conductor structures, in particular to a method for forming selective metal lines on plastic surfaces and plastic parts.
  • LDS Laser Direct Structuring
  • the Chinese Patent No. 02812609 describes a conductor track structure and its manufacturing method.
  • the conductor track structure is composed of a metal crystal core and a subsequent metallization layer coated on the metal crystal core.
  • the conductor track structure is located on a non-conductive carrier material, and the carrier material is mixed with a non-conductive metal compound.
  • the area on the carrier material where the conductor track structure is to be produced is irradiated by electromagnetic radiation, and the non-conductive metal compound incorporated therein separates the heavy metal nuclei, and then the area is chemically reduced and metalized; while the unirradiated area remains unchanged. This makes it possible to produce a conductor track structure on a non-conductive carrier material.
  • the disclosed method is costly.
  • the non-conductive metal compound incorporated in the non-conductive carrier material is highly thermally stable, stable and insoluble in aqueous acidic or alkaline metallization electrolytes, and is non-conductive. Based on higher-order oxides of spinel or simple d-metal oxides with a structure similar to spinel or mixtures thereof, it can be seen that the non-conductive metal compound has higher performance and structure requirements and is expensive; secondly, it can The cost of the carrier material doped with the above-mentioned non-conductive metal compound is relatively high, which also causes certain restrictions.
  • the LDS process requires special materials, and the metal compounds necessary for the LDS process are added to this material. Due to the large proportion of addition, the modified material has thermal stability and compatibility with the metal compound and the plastic substrate. , Plasticization stability, electrical performance stability and other aspects have a greater impact, which increases the cost but also limits the scope of application of the material.
  • the purpose of the present invention is to provide a method for forming selective metal lines on plastic surfaces and plastic parts, so that the plastic substrate does not require special materials when selecting materials, the cost is low, the application range of the materials is significantly expanded, and the metalized wiring is fine at the same time.
  • the radium carving surface on the surface of the plastic substrate can form a strong adsorption zone, which is conducive to absorbing more active substances.
  • the embodiment of the present invention discloses a method for forming a selective metal circuit on a plastic surface, which includes the following steps:
  • the activated plastic substrate is put into a chemical reduction solution for electroless plating, so that a plating layer is selectively deposited on the surface of the plastic substrate to form a metalized circuit.
  • the embodiment of the present invention also discloses a plastic part with a metal circuit on the surface.
  • the metal circuit is formed on the plastic part by using the above-mentioned method of forming a selective metal circuit on the plastic surface. To Formed on the surface.
  • the double-roughening scheme combining laser roughening and chemical roughening makes the material requirements of the plastic substrate significantly reduced when selecting materials, no special materials are required, low cost and suitable for materials
  • the scope is significantly expanded; in addition, combining laser roughening and chemical roughening, on the one hand, laser roughening can make the wiring fine, and on the other hand, chemical roughening can make the radium carving surface of the plastic substrate form a strong adsorption zone. Conducive to the absorption of more active substances.
  • the plastic substrate of the present invention does not need to add the metal compound necessary for the LDS process, and the cost is low and the application range of the material is significantly expanded.
  • a suitable roughening chemical solution and roughing operation process are selected to control the chemical roughening intensity, which can achieve good selective chemical roughening.
  • dual activation helps the substrate to absorb enough active materials, avoids the problem of missing plating or uneven plating, and achieves good selective plating.
  • the combination of double roughening and double activation can not only achieve good selective plating, but also more effectively ensure the conduction functionality at structures such as vias and micro vias;
  • the metal line can carry a larger current to meet the needs of more application scenarios.
  • FIG. 1 is a schematic flow chart of a method for forming selective metal lines on a plastic surface in the first embodiment of the present invention
  • Figure 2 is an effect diagram of electroless plating of different materials after laser roughening only
  • Fig. 3 is an effect diagram of plating with different degrees of roughening in the first embodiment of the present invention.
  • Fig. 4 is a comparison diagram of the plating effect between dual activation and single activation in the second embodiment of the present invention.
  • FIG. 7 is a comparison diagram of 100 grid test results of the PC substrate in the second embodiment of the present invention after electroplating in four different types of roughening and activation methods;
  • FIG. 8 is a description diagram of the adhesion level of the hundred grid test in the second embodiment of the present invention.
  • FIG. 9 is a schematic flowchart of a method for forming selective metal lines on a plastic surface in the second embodiment of the present invention.
  • the first embodiment of the present invention relates to a method for forming a selective metal circuit on a plastic surface.
  • FIG. 1 is a schematic flow chart of the method for forming a selective metal circuit on a plastic surface.
  • the method for forming selective metal lines on the plastic surface includes the following steps:
  • step 101 laser is used to perform line laser engraving on the surface of the molded plastic substrate to realize laser roughening of the surface.
  • laser roughening is to etch the surface of the plastic part with a laser to form fine microscopic pits so that the active material can be adsorbed and filled to form a catalytic center for electroless plating.
  • Laser roughening can be understood as physical roughening. In the experiment, it was found that the areas roughened by laser are more likely to be chemically roughened, which promotes selective chemical roughening. However, if only laser roughening is implemented, no matter whether the post-process is single activation or double activation, it is difficult to ensure the adsorption of active materials, especially for multiple plastics.
  • Figure 2 shows the effect of electroless plating of different materials after only laser roughening. As shown in Figure 2, PC materials cannot be plated even with dual activation, while PP materials can be partially plated, PC/ABS materials The lack of plating also exists.
  • the plastic substrate includes one of the following or any combination thereof:
  • Polycarbonate acrylonitrile-styrene-butadiene copolymer, mixture of polycarbonate and acrylonitrile-butadiene-styrene copolymer, polyamide or nylon, polypropylene, liquid crystal polymer, polyoxymethylene Resin, polyimide, polyethylene terephthalate. among them,
  • PC Polycarbonate
  • COCl2 carbon oxychloride
  • ABS material is acrylonitrile (Acrylonitrile), 1,3-butadiene (Butadiene), styrene (Styrene) three kinds of monomers Body graft copolymer;
  • PC/ABS Polycarbonate and acrylonitrile-butadiene-styrene copolymers and mixtures
  • Polyamide or nylon polyamides, "PA” for short), the basic constituent material of which is an aliphatic polyamide connected by an amide bond—[NHCO]—;
  • Liquid crystal polymer liquid crystal polymer, referred to as "LCP"
  • liquid crystal polymer industrialized liquid crystal polymer, etc.
  • Polyoxymethylene polyoxymethylene, "POM” for short
  • POM plastic Saigang material, etc., milky white opaque crystalline linear thermoplastic resin
  • PI Polyimide
  • PAI polyamide-imide
  • PEI polyetherimine
  • PET Polythylene terephthalate
  • polyester resin is a milky white or yellowish highly crystalline polymer
  • the formulation of ordinary plastics is that compared with the special materials required by the LDS process, the materials are added with the metal compounds necessary for the process, and the doping ratio is 3% to 10%. Due to the large proportion of addition, the modification The material has a greater impact on the thermal stability, compatibility, plasticization stability, and electrical stability of the metal compound and the plastic substrate, which increases the cost and limits the scope of application of the material.
  • the plastic substrate of the present invention does not need to add the metal compounds necessary for the LDS process, the cost is low, and the application range of the material is significantly expanded.
  • a suitable roughing chemical solution and roughing operation process are selected to control the chemical roughening intensity, and a good selective chemical roughening can be realized.
  • the plastic substrate includes the above-mentioned materials To But it is not limited to this.
  • step 102 is performed to clean the plastic substrate after laser roughening.
  • step 103 is entered, and the cleaned plastic substrate is placed in a chemical agent for chemical roughening.
  • Chemical roughening is to etch the surface of the plastic substrate through chemical action to produce chemical bond breaks.
  • the surface of the plastic substrate becomes polar and forms a good hydrophilic effect. At the same time, it forms a dense uniform due to chemical etching. The matt microscopic pits.
  • Chemical roughening produces surface polarity, which makes it easier to adsorb active substances than lasers.
  • selective electroplating cannot be achieved by only chemical roughening.
  • the currently commonly used method is: After activation, all the metal is plated on the surface of the substrate, and then the yellow light contrast method is used to achieve partial etching to form lines, resulting in its selectivity The metallization process is more complicated and expensive.
  • step 103 In order to perform selective chemical roughening for the laser roughened surface, according to different material characteristics, it is necessary to control a certain chemical roughening intensity through a suitable roughening chemical solution and roughening operation process.
  • this step 103 Preferably, in this step 103:
  • the chemical agent is preferably potassium permanganate
  • the concentration of the agent is preferably 20-120g/L
  • the roughening time of chemical roughening is preferably 5-50min
  • the roughening temperature is preferably 25-80°C. .
  • FIG 3 shows the effect of plating with different degrees of roughening.
  • excessive roughening for example, the roughening time of the chemical roughening of the PC material is greater than 50min, and the roughening temperature is greater than 80°C
  • the coarsening Insufficient roughening for example, the roughening time of the chemical roughening of the PC material is less than 5min, and the roughening temperature is less than 25°C
  • the roughening strength is appropriate (For example, the roughening time of the chemical roughening of the PC material is 5-50 minutes, and the roughening temperature is 25-80°C), the plating can be uniform.
  • step 104 is performed to reduce and clean the chemically roughened plastic substrate.
  • the chemical solution used for reduction and cleaning is hydrogen peroxide.
  • the chemical solution used for reduction and cleaning is not limited to hydrogen peroxide, and may also be other chemical solutions, such as sodium hypophosphite solution or dilute sulfuric acid.
  • step 105 is entered to place the plastic substrate in the activator for activation.
  • the plastic substrate is immersed in the activator for chemical activation treatment, so that a part of the area adsorbs the metal atoms in the activator.
  • step 106 is entered, and the activated plastic substrate is put into a chemical reduction solution for electroless plating, so that a plating layer is selectively deposited on the surface of the plastic substrate to form a metalized circuit.
  • the method further includes the following steps:
  • the plating layer on the surface of the plastic substrate is thickened by chemical reduction or electrolysis as required.
  • the thickened plating layer is an electroless copper plating layer
  • the thickness of the electroless copper plating is 1-50um
  • the copper sinking rate is preferably 2.0-3.5u/h
  • the electroless copper plating temperature is preferably 30-70°C.
  • the method of forming selective metal lines on the plastic surface combines the dual roughening scheme of laser roughening and chemical roughening, so that the material requirements for the plastic substrate are significantly reduced when selecting materials, and no special materials are required. The cost is low and the scope of application of the material is significantly expanded.
  • laser roughening can make the wiring fine
  • chemical roughening can make the radium carving surface on the surface of the plastic substrate form a strong adsorption area, which is conducive to more absorption. Active substance.
  • the second embodiment of the present invention relates to a method for forming selective metal lines on a plastic surface.
  • the second embodiment is an improvement on the basis of the first embodiment.
  • the main improvement lies in the fact that the plastic substrate is placed in the activation
  • activation is double activation, including the following sub-steps:
  • the plastic substrate is placed in the second activator for the second activation.
  • the first activator and the second activator are two different activating solutions.
  • the first activator and the second activator can be colloidal palladium solution or ionic palladium and other palladium ion-containing activation solutions, silver ammonia or other silver ion-containing activation solutions, or colloidal copper or other copper ion-containing activation solutions liquid.
  • the first activator and the second activator are each one of them.
  • the first activator is preferably a colloidal palladium solution
  • the activation time is preferably 1-10 min
  • the activation temperature is preferably 25-50°C
  • the second activator is preferably silver ammonia activation solution.
  • the time is preferably 1-10 min
  • the activation temperature is preferably 25-50°C.
  • FIG. 4 shows the comparison of double activation and single activation plating effects. As shown in the figure, the inventor found that double activation helps the substrate to absorb enough active materials to avoid missing plating or uneven plating. Problem, to achieve good selective plating.
  • double roughening combined with double activation can not only achieve good selective plating, but also:
  • Figure 5 shows the comparison of electroplating effects of dual activation and single activation on vias and micro vias.
  • Figures 5 (A) and 5 (C) show the effects of dual activation on vias and micro vias. The plating effect is that the vias are evenly plated, and the micro vias are connected;
  • Figures 5(B) and 5(D) are the electroless plating effects of single activation on the vias and micro vias. The vias are poorly plated and the micro vias are Poor electroplating via holes.
  • Figures 5A, 5C, 5B, and 5D are Figures 5(A) and 5(C) respectively To Enlarged views of 5(B) and 5(D).
  • Figure 6 is a comparison diagram of electroless plating effects under 6 groups of different laser parameters.
  • Figures 6(a) and 6(b) are the effects after laser engraving and electroless plating respectively.
  • the 6 groups of laser parameters are shown in Table 1 below. .
  • 6 groups of laser parameters with large differences can all obtain better selective electroplating results.
  • Figure 7 is a comparison diagram of 100 grid test results of PC substrates after electroplating in four different types of roughening and activation methods. Hundred grid test is a universal method to test the surface adhesion of materials. The test steps include:
  • Figure 8 shows the description of the adhesion level of the 100 grid test. It will be attached according to the peeling condition of the metal layer. To The level of focus is divided into 0B ⁇ 5B.
  • the criterion for passing the 100-grid test is: grade 4B or higher (see FIG. 8), that is, the drop-off range is less than 5% of the test area.
  • Double roughening combined with double activation can achieve very good coating adsorption effect, see Figure 7, as shown in Figure 7, comparing single roughening + single activation, single roughening + double activation, double roughing + single activation, etc. ,
  • the double roughening + double activation method not only achieves the selective plating well, but also basically does not fall off in the 100-grid test, indicating that its adhesion is very good and guarantees a good coating adsorption.
  • FIG. 9 a schematic flow diagram of the method for forming selective metal lines on the plastic surface is shown in FIG. 9.
  • the specific implementation steps of the preferred embodiment are as follows:
  • the common substrate is formed by injection molding or other methods
  • the laser equipment used in the above process can also be a gas laser or a liquid laser, or other solid-state lasers; the power of the equipment is 3-50W, preferably 10-25W; the laser wavelength can be 200-1064nm, preferably 1064nm ;
  • the laser carving parameters are preferably the parameters in Table 1;
  • step s3 immerse the substrate roughened by the laser in a degreaser for cleaning, and remove the attachments generated during the laser roughening process;
  • step s4 immerse the insulator in a chemical roughening solution for chemical roughening, select different chemical roughening according to the characteristics of the material, and control a certain chemical roughening strength;
  • the PC substrate is preferably potassium permanganate Coarse
  • the concentration of the chemical solution is 20 ⁇ 120g/L
  • the coarsening time is 5 ⁇ 50min
  • the coarsening temperature is 25 ⁇ 80°C;
  • the substrate needs to be reduced and cleaned;
  • the reducing and cleaning solution is, for example, hydrogen peroxide, or sodium hypophosphite solution, or dilute sulfuric acid, etc.
  • step s6 immerse the above-mentioned substrate in the activator 1 for the first activation; for example, the roughened PC substrate is preferably immersed in a colloidal palladium solution to complete the first activation, and the activation time To 1 ⁇ 10min, activation temperature 25 ⁇ 50°C;
  • step s7 immerse the above-mentioned substrate in the activator 2 for the second activation; for example, the PC substrate after the first activation is preferably immersed in the silver ammonia activation solution to complete the second activation, and the activation time is 1-10 min.
  • Activation temperature 25 ⁇ 50°C;
  • step s8 immerse the activated substrate in an electroless copper plating solution or an electroless nickel plating solution with a certain activity, for example, the copper plating rate of electroless copper plating is 2.5 ⁇ 4.0 u/h; A copper layer is formed on the surface of the material;
  • step s9 is entered, and the above-mentioned substrate may continue to be electroless thickened or electroplated thickened.
  • the thickness of the electroless copper plating is 1-50um
  • the copper sinking rate is 2.0-3.5u/h
  • the electroless copper plating temperature is 30-70°C; subsequent plating of silver, gold and other metal coatings can also be selected.
  • the third embodiment of the present invention relates to a plastic part with a metal circuit on the surface.
  • the metal circuit of the plastic part is formed on the surface of the plastic part by using any one of the methods of the first and second embodiments.
  • the present invention provides a simple, low-cost method for forming selective metal lines on the surface of ordinary plastics and plastic parts with metal lines on the surface, and has the following technical advantages:
  • the combination of double roughening and double activation can be applied to the circuit surface formed by different laser laser engraving parameters, and has a wide range of adaptability to laser processing.

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Abstract

一种在塑料表面形成选择性金属线路的方法，包括步骤：使用激光对成型的塑料基材表面线路镭雕，实现激光粗化；将塑料基材进行清洗；将塑料基材置于化学药剂中进行化学粗化；化学粗化后进行还原和清洗；将塑料基材置入活化剂中进行活化；进行化学镀，使塑料基材表面选择性沉积镀层，形成金属化线路。及一种表面具有金属线路的塑料部件，该金属线路是采用上述方法在塑料部件表面形成的。

Description

在塑料表面形成选择性金属线路的方法及塑料部件 技术领域
本发明涉及导体结构制造，特别涉及在塑料表面形成选择性金属线路的方法及塑料部件。
背景技术
激光直接成型(Laser Direct Structuring，简称“LDS”)技术是目前实现立体电路的方法之一，其工艺流程为利用特殊的材料做成结构件(该材料可以被激光活化以实现选择性化镀)，通过激光将所需的图形打标到工件表面，然后化镀上金属层形成电路。
专利号为02812609的中国专利中描述了一种导体轨道结构及其制造方法。该导体轨道结构由金属晶核以及后续在金属晶核上涂覆的金属化层构成。导体轨道结构位于不导电的承载材料上，承载材料中掺入了不导电金属化合物。承载材料上要产生导体轨道结构的区域由电磁射线照射，其掺入的不导电金属化合物分离出重金属晶核，然后该区域再被化学还原金属化；而未照射的区域则保持不变。由此实现了在不导电的承载材料上制造导体轨道结构。但是，所公开的方法成本较高。首先，为了制造导体轨道结构，在不导电承载材料中所掺入的不导电金属化合物，是高度热稳定的、在含水的酸性或碱性金属化电解液中稳定且不溶解的、不导电的基于尖晶石的较高阶氧化物或者结构类似尖晶石的简单的d-金属氧化物或其混合物，由此可知，该不导电金属化合物的性能结构要求较高，价格昂贵；其次，能够掺入上述不导电金属化合物的承载材料成本较大，也造成了一定的限制。
由此可见，LDS工艺需要特殊材料，且该材料中添加了LDS工艺所必需的金属化合物，由于添加的比例较大，该改性材料对金属化合物与塑料基材的热稳定性，相容性，塑化稳定性，电性能稳定性等方面产生较大的影响，使成本提高的同时也限制了材料的适用范围。
因此，如何实现一种由普通低成本材料制造形成选择性金属线路的简单可靠且生产效率高的方法是目前迫切需要解决的技术问题。
发明内容
本发明的目的在于提供一种在塑料表面形成选择性金属线路的方法及塑料部件，使得在选材时塑料基材不需要特殊材料，成本低廉且材料的适用范围明显扩大，金属化布线精细的同时塑料基材表面的镭雕面能够形成较强的吸附区，有利于吸收更多的活性物质。
为解决上述技术问题，本发明的实施方式公开了一种在塑料表面形成选择性金属线路的方法，包括以下步骤：
使用激光对成型后的塑料基材的表面进行线路镭雕，实现表面激光粗化；
将激光粗化后的塑料基材进行清洗；
将清洗后的塑料基材置于化学药剂中进行化学粗化；
对经化学粗化后的塑料基材进行还原和清洗；
将塑料基材置入活化剂中进行活化；
将经活化的塑料基材放入化学还原溶液中进行化镀，使塑料基材表面选择性沉积镀层，形成金属化线路。
本发明的实施方式还公开了一种表面具有金属线路的塑料部件，该金属线路是采用上文提及的在塑料表面形成选择性金属线路的方法在塑料部件 表面形成的。
本发明实施方式与现有技术相比，主要区别及其效果在于：
在塑料表面形成选择性金属线路的方法中结合激光粗化和化学粗化的双粗化方案，使得在选材时对塑料基材的材料要求明显降低，不需要特殊材料，成本低廉且材料的适用范围明显扩大；此外，结合激光粗化和化学粗化，一方面激光粗化可以使布线精细，另一方面化学粗化又可以使塑料基材表面的镭雕面形成较强的吸附区，有利于吸收更多的活性物质。
进一步地，相较于LDS工艺所需的特殊材料，本发明中的塑料基材并不需要添加了LDS工艺所必需的金属化合物，成本低廉且材料的适用范围明显扩大。
进一步地，化学粗化的步骤中根据不同的基材材料特性，选择合适的粗化药液和粗化操作工艺来控制化学粗化强度，能够实现良好的选择性化学粗化。
进一步地，双活化有助于基材吸附足够多的活性物质，避免漏镀或者上镀不均匀的问题，实现良好的选择性上镀。
进一步地，结合双粗化和双活化，不仅能够实现良好的选择性上镀，还能更有效地在过孔、微过孔等构造处保证其导通功能性；
进一步地，结合双粗化和双活化，适用于更广的激光镭雕参数加工，对激光加工有广泛的适应性；
进一步地，结合双粗化和双活化，在对激光加工有广泛适应性的同时，还保证了良好的镀层吸附力。
进一步地，通过加镀层，可以使金属线路能够承载更大的电流，以符合更多应用场景的需要。
附图说明
图1是本发明第一实施方式中一种在塑料表面形成选择性金属线路的方法的流程示意图；
图2是不同材料仅经过激光粗化后的化镀效果图；
图3是本发明第一实施方式中不同粗化程度的上镀效果图；
图4是本发明第二实施方式中双活化与单活化上镀效果对比图；
图5是本发明第二实施方式中双活化与单活化在过孔与微过孔上的化镀效果对比图；
图6是本发明第二实施方式中6组区别较大的激光参数下化镀效果对比图；
图7是本发明第二实施方式中PC基材在四种不同类型的粗化和活化方式下化镀后的百格测试结果对比图；
图8是本发明第二实施方式中百格测试的附着力等级描述图；
图9是本发明第二实施方式中一种在塑料表面形成选择性金属线路的方法的流程示意图。
具体实施方式
在以下的叙述中，为了使读者更好地理解本申请而提出了许多技术细节。但是，本领域的普通技术人员可以理解，即使没有这些技术细节和基于以下各实施方式的种种变化和修改，也可以实现本申请各权利要求所要求保护的技术方案。
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图对本发明的实施方式作进一步地详细描述。
本发明第一实施方式涉及一种在塑料表面形成选择性金属线路的方法，图1是该在塑料表面形成选择性金属线路的方法的流程示意图。
具体地说，如图1所示，该在塑料表面形成选择性金属线路的方法包括以下步骤：
在步骤101中，使用激光对成型后的塑料基材的表面进行线路镭雕，实现表面激光粗化。
此外，可以理解，激光粗化是用激光将塑件表面刻蚀形成细密的显微凹坑，以便活性物质的吸附和填充，形成化学镀的催化中心。激光粗化可以理解为物理粗化，在实验中发现激光粗化过的地区也更易被化学粗化，从而促进了选择性化学粗化。但是，如果仅实施激光粗化，无论后制程是单活化还是双活化，都很难保证活性物质的吸附，特别是针对多种塑料时。如图2所示为不同材料仅经过激光粗化后的化镀效果图，如图2所示，PC材料即使采用双活化也无法上镀，而PP材料可以部份上镀，PC/ABS材料同样存在缺镀现象。
在使用激光对成型后的塑料基材的表面进行线路镭雕，实现表面激光粗化的步骤101中，塑料基材包括以下之一或其任意组合：
聚碳酸酯，丙烯腈-苯乙烯-丁二烯共聚物，聚碳酸酯和丙烯腈-丁二烯-苯乙烯共聚物的混合物，聚酰胺或尼龙，聚丙烯，液晶高分子聚合物，聚甲醛树脂，聚酰亚胺，聚对苯二甲酸乙二醇酯。其中，
聚碳酸酯(polycarbonate，简称“PC”)可由双酚A和氧氯化碳(COCl2)合成；
丙烯腈-苯乙烯-丁二烯共聚物(acrylonitrile butadiene styrene，简称“ABS”)，ABS材料是丙烯腈(Acrylonitrile)、1，3-丁二烯(Butadiene)、苯乙烯(Styrene)三种单体的接枝共聚物；
聚碳酸酯和丙烯腈-丁二烯-苯乙烯共聚物和混合物(PC/ABS)，是由 聚碳酸酯和聚丙烯腈合金而成的热可塑性塑胶；
聚酰胺或尼龙(polyamides，简称“PA”)，其基本组成物质是通过酰胺键—[NHCO]—连接起来的脂肪族聚酰胺；
聚丙烯(polypropylene，简称“PP”)，是一种高聚物，单体是丙烯CH2＝CH－CH3；
液晶高分子聚合物(liquid crystal polymer，简称“LCP”)或称液晶聚合物，工业化液晶聚合物等，是一种新型高性能特种工程塑料
聚甲醛树脂(polyoxymethylene，简称“POM”)，或称POM塑料、赛钢料等，乳白色不透明结晶性线性热塑性树脂；
聚酰亚胺(polyimide，简称“PI”)，是分子结构含有酰亚胺基链节的芳杂环高分子化合物，可分为均苯型PI，可溶性PI，聚酰胺-酰亚胺(PAI)和聚醚亚胺(PEI)四类
聚对苯二甲酸乙二醇酯(polythylene terephthalate，简称“PET”)(俗称涤纶树脂)，是乳白色或前黄色高度结晶性的聚合物
普通塑料的提法是相较于LDS工艺所需的特殊材料，该材料中添加了该工艺所必需的金属化合物，掺杂比例在3％～10％，由于添加的比例较大，该改性材料对金属化合物与塑料基材的热稳定性，相容性，塑化稳定性，电性能稳定性等方面产生较大的影响，使成本提高的同时也限制了材料的适用范围。
相较于LDS工艺所需的特殊材料，本发明中的塑料基材并不需要添加了LDS工艺所必需的金属化合物，成本低廉且材料的适用范围明显扩大。化学粗化的步骤中根据不同的基材材料特性，选择合适的粗化药液和粗化操作工艺来控制化学粗化强度，能够实现良好的选择性化学粗化。
此外，可以理解，在本发明的其他实施方式中，塑料基材包括上述材料 但并不局限于此。
此后进入步骤102，将激光粗化后的塑料基材进行清洗。
此后进入步骤103，将清洗后的塑料基材置于化学药剂中进行化学粗化。
化学粗化是通过化学作用对塑料基材表面刻蚀，产生化学断键，一方面使得塑料基材表面变成极性，形成良好的亲水性效果，同时也由于化学蚀刻形成致密的的均匀的无光泽的显微凹坑。化学粗化由于产生表面极性，比激光更易吸附活性物质。但是仅实施化学粗化是无法实现选择性化镀的，目前普遍采用的方法是：活化后在基材表面全部镀上金属，然后再黄光造影的方法实现局部蚀刻形成线路，导致其选择性金属化工艺较为复杂且昂贵。
为了针对激光粗化表面做选择性化学粗化，根据不同的材料特性，需通过合适的粗化药液和粗化操作工艺来控制一定的化学粗化强度。优选地，在此步骤103中：
当塑料基材的材料为聚碳酸酯时，化学药剂优选高锰酸钾，药剂的浓度优选20～120g/L，化学粗化的粗化时间优选5～50min，粗化温度优选25～80℃。
粗化强度不足，将导致不上镀或者上镀不均匀；粗化过度则会导致满镀。如图3所示为不同粗化程度的上镀效果图。如图3(a)所示，粗化过度时(例如，PC材料化学粗化的粗化时间大于50min，粗化温度大于80℃)会导致满镀；如图3(b)所示，粗化不足时(例如，PC材料化学粗化的粗化时间小于5min，粗化温度小于25℃)会导致不上镀或者上镀不均匀；如图3(c)所示，粗化强度合适时(例如，PC材料化学粗化的粗化时间为5～50min，粗化温度为25～80℃)则能够上镀均匀。
此后进入步骤104，对经化学粗化后的塑料基材进行还原和清洗。
优选地，在此步骤中，还原和清洗所使用的药液为双氧水。
此外，可以理解，在本发明的其他实施方式中，还原和清洗所使用的药液并不局限于双氧水，也可以为其他药液，例如次磷酸钠溶液或稀硫酸等。
此后进入步骤105，将塑料基材置入活化剂中进行活化。
将塑料基材浸泡在活化剂中进行化学活化处理，使部分区域吸附该活化剂中的金属原子。
此后进入步骤106，将经活化的塑料基材放入化学还原溶液中进行化镀，使塑料基材表面选择性沉积镀层，形成金属化线路。
优选地，在将经活化的塑料基材放入化学还原溶液中进行化镀，使塑料基材表面选择性沉积镀层，形成金属化线路的步骤106之后，还包括步骤：
根据需要通过化学还原法或电解法将塑料基材表面的镀层增厚。
优选地，在此步骤中，增厚的镀层为化学镀铜层，化学镀铜增厚厚度为1～50um，沉铜速率优选2.0～3.5u/h，化学镀铜温度优选30～70℃。
此外，可以理解，在本发明的其他实施方式中，后续还可选择镀银、金等其他金属镀层。
在本实施方式中，在塑料表面形成选择性金属线路的方法中结合激光粗化和化学粗化的双粗化方案，使得在选材时对塑料基材的材料要求明显降低，不需要特殊材料，成本低廉且材料的适用范围明显扩大。此外，结合激光粗化和化学粗化，一方面激光粗化可以使布线精细，另一方面化学粗化又可以使塑料基材表面的镭雕面形成较强的吸附区，有利于吸收更多的活性物质。
本发明第二实施方式涉及一种在塑料表面形成选择性金属线路的方法，第二实施方式在第一实施方式的基础上进行了改进，主要改进之处在于，在将塑料基材置入活化剂中进行活化的步骤中，活化为双活化，包括以下子步骤：
将塑料基材置入第一活化剂中进行第一次活化；
对塑料基材进行清洗；
将塑料基材置入第二活化剂中进行第二次活化。
第一活化剂和第二活化剂是两种不同的活化溶液。
第一活化剂和第二活化剂可以是胶体钯溶液或离子钯等含钯离子的活化液，可以是银氨或其它含银离子的活化液，可以是或胶体铜或者其它含铜离子的活化液。第一活化剂和第二活化剂分别是其中的一种。
此外，在浸入活化剂进行活化操作时，对于不同材料，将选择合适的操作工艺，例如常温浸泡方式，或是水浴升温浸泡等
优选地，当塑料基材的材料为聚碳酸酯时，第一活化剂优选胶体钯溶液，活化时间优选1～10min，活化温度优选25～50℃，第二活化剂优选银氨活化液，活化时间优选1～10min，活化温度优选25～50℃。
可以理解，尽管双粗化后基材镭雕图形表面吸附活性的能力较好，但仅实施单活化，还是很难保证基材吸附足够多的活性物质，不能完全避免漏镀或者上镀不均匀的问题。如图4所示为双活化与单活化上镀效果对比图，如图所示，提供实验发明人发现双活化有助于基材吸附足够多的活性物质，避免漏镀或者上镀不均匀的问题，实现良好的选择性上镀。
制程中，发明人还发现双粗化结合双活化，不仅能实现良好的选择性上镀，还能够：
1、更有效地在过孔、微过孔等构造处保证其导通功能性。如图5所示为双活化与单活化在过孔与微过孔上的化镀效果对比图，其中图5(A)、5(C)为双活化在过孔与微过孔上的化镀效果，其过孔均匀上镀，微过孔导通；图5(B)、5(D)为单活化在过孔与微过孔上的化镀效果，过孔化镀不良，且微过孔化镀不良。图5A、5C、5B、5D分别是图5(A)、5(C) 5(B)、5(D)的放大图。
2、结合双粗化和双活化，适用于更广的激光镭雕参数加工，对激光加工有广泛的适应性。图6为6组区别较大的激光参数下化镀效果对比图，图6(a)、6(b)分别是镭雕后和化镀后的效果，其中6组激光参数如下表1所示。如图6所示，6组区别较大的激光参数都可以得到较好的选择性化镀结果。
编号 功率 频率/kHz 速度/mm/s
1 90％ 25 2500
2 70％ 25 2500
3 65％ 65 3000
4 65％ 28 1500
5 80％ 65 3500
6 65％ 65 3500
表1
3、结合双粗化和双活化，在对激光加工有广泛适应性的同时，还保证了良好的镀层吸附力。图7为PC基材在四种不同类型的粗化和活化方式下化镀后的百格测试结果对比图。百格测试是一种通用的测试材料表面附着力的方法，其测试步骤包括：
先以乙醇(95％)擦拭镀层表面，然后用百格刀/美工刀切割100个方格(每个方格的规格为1mm*1mm)，必需将表面金属层切断；接着用3M#610胶带黏贴百格区后，以棉布或橡皮擦拭抹平后放置90秒，抓取胶带一端瞬间垂直拉起，在同一位置如此重复3次上述动作，然后查看金属层的脱落情况。
图8所示是百格测试的附着力等级描述图，根据金属层的脱落情况将附 着力的等级划分为0B～5B。本实施方式中百格测试合格的判断标准是：等级4B以上(参见图8)，即脱落范围小于测试区域的5％。
双粗化结合双活化，能够取得非常好的镀层吸附力效果，参见图7，如图7所示，对比单粗化+单活化、单粗化+双活化、双粗化+单活化等方式，双粗化+双活化方式不仅很好地实现了选择性上镀，而且百格测试上基本没有脱落，说明其附着力非常好，保证了良好的镀层吸附力。
作为本实施方式的优选例，在塑料表面形成选择性金属线路的方法的流程示意图如图9所示，优选实施例的具体实施步骤如下：
在步骤s1中，普通基材通过注塑等方式成型；
此后进入步骤s2，使用一定波长激光在基材表面进行局部线路镭雕，形成表面激光粗化；使用深圳市泛友科技有限公司生产的三维打标机(型号为：QM3D1H)将线路图形镭雕到结构件上，上述工艺所用的激光设备还可以是气体激光器或液体激光器，或是其它的固体激光器；设备功率是3～50W，优选10～25W；激光波长可以是200～1064nm，优选是1064nm；镭雕参数优选表1中的参数；
此后进入步骤s3，将被激光粗化的基材浸入除油剂中清洗，清除激光粗化过程中所产生的附着物；
此后进入步骤s4，将该绝缘体浸在化学粗化药液中进行化学粗化，根据材料的特性选择不同的化学粗化，并控制一定的化学粗化强度；例如PC基材优选高锰酸钾粗化，药液浓度20～120g/L,粗化时间5～50min，粗化温度25～80℃；
此后进入步骤s5，粗化后，基材需做还原和清洗；还原和清洗药液例如是双氧水，或次磷酸钠溶液，或稀硫酸等
此后进入步骤s6，将上述基材浸入活化剂1中进行第一次活化；例如粗化后的PC基材，优选浸入胶体钯溶液方式完成第一次活化，活化时间 1～10min，活化温度25～50℃；
此后进入步骤s7，将上述基材浸入活化剂2中做第二次活化；例如第一次活化后的PC基材，优选浸入银氨活化液中完成第二次活化，活化时间1～10min，活化温度25～50℃；
此后进入步骤s8，将经活化的基材浸入在具有一定活性的化学镀铜液或者化学镀镍液中，例如化学镀铜的沉铜速率为2.5～4.0u/h；经化学反应，在基材表面形成一层铜层；
此后进入步骤s9，上述基材可以继续化学镀加厚或者电镀加厚镀层。例如化学镀铜增厚厚度为1～50um，沉铜速率2.0～3.5u/h，化学镀铜温度为30～70℃；后续还可选择镀银、金等其他金属镀层。
本发明第三实施方式涉及一种表面具有金属线路的塑料部件，该塑料部件的金属线路是采用第一、二实施方式中任一项的方法在塑料部件表面形成的。
综合上述，本发明提供了一种工艺简单、成本低的在普通塑料表面形成选择性金属线路的方法以及表面具有金属线路的塑料部件，具备如下技术优势：
1、适用于普通塑料，无需添加有机金属化合物进行改性，节省制作和加工成本；
2、包括但不限于PC、PC+ABS、PA、PP、LCP、POM、PI、PET等等普通塑料基材，适用范围广；
3、双粗化和双活化的结合，在顺利实现上镀的同时，还具备优秀的图形精度；
4、双粗化和双活化的结合，有效解决了“附着力”、选择性的问题；
5、双粗化和双活化的结合，有效解决了过孔、微过孔等构造处的导通 功能性；
6、双粗化和双活化的结合，可以适用于不同激光镭雕参数加工形成的线路表面，对激光加工有广泛的适应性。
需要说明的是，在本专利的权利要求和说明书中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
虽然通过参照本发明的某些优选实施方式，已经对本发明进行了图示和描述，但本领域的普通技术人员应该明白，可以在形式上和细节上对其作各种改变，而不偏离本发明的精神和范围。

Claims (9)

  1. 一种在塑料表面形成选择性金属线路的方法，其特征在于，包括以下步骤：
    使用激光对成型后的塑料基材的表面进行线路镭雕，实现表面激光粗化；
    将激光粗化后的塑料基材进行清洗；
    将清洗后的塑料基材置于化学药剂中进行化学粗化；
    对经所述化学粗化后的塑料基材进行还原和清洗；
    将所述塑料基材置入活化剂中进行活化；
    将经活化的塑料基材放入化学还原溶液中进行化镀，使所述塑料基材表面选择性沉积镀层，形成金属化线路。
  2. 根据权利要求1所述的在塑料表面形成选择性金属线路的方法，其特征在于，在所述使用激光对成型后的塑料基材的表面进行线路镭雕，实现表面激光粗化的步骤中，所述塑料基材包括以下之一或其任意组合：
    聚碳酸酯，丙烯腈-苯乙烯-丁二烯共聚物，聚碳酸酯和丙烯腈-丁二烯-苯乙烯共聚物的混合物，聚酰胺或尼龙，聚丙烯，液晶高分子聚合物，聚甲醛树脂，聚酰亚胺，聚对苯二甲酸乙二醇酯。
  3. 根据权利要求1所述的在塑料表面形成选择性金属线路的方法，其特征在于，在所述将清洗后的塑料基材置于化学药剂中进行化学粗化的步骤中：
    当所述塑料基材的材料为聚碳酸酯时，所述化学药剂优选高锰酸钾，药剂的浓度优选20～120g/L，所述化学粗化的粗化时间优选5～50min，粗化温度优选25～80℃。
  4. 根据权利要求1所述的在塑料表面形成选择性金属线路的方法，其特征在于，在所述将塑料基材置入活化剂中进行活化的步骤中，所述活化为双活化，包括以下子步骤：
    将所述塑料基材置入第一活化剂中进行第一次活化；
    对所述塑料基材进行清洗；
    将所述塑料基材置入第二活化剂中进行第二次活化；
    所述第一活化剂和所述第二活化剂是两种不同的活化溶液。
  5. 根据权利要求4所述的在塑料表面形成选择性金属线路的方法，其特征在于，在所述双活化的步骤中：
    当所述塑料基材的材料为聚碳酸酯时，所述第一活化剂优选胶体钯溶液，活化时间优选1～10min，活化温度优选25～50℃；
    所述第二活化剂优选银氨活化液，活化时间优选1～10min，活化温度优选25～50℃。
  6. 根据权利要求1所述的在塑料表面形成选择性金属线路的方法，其特征在于，在所述对经化学粗化后的塑料基材进行还原和清洗的步骤中，所述还原和清洗所使用的药液为双氧水。
  7. 根据权利要求1所述的在塑料表面形成选择性金属线路的方法，其特征在于，在所述将经活化的塑料基材放入化学还原溶液中进行化镀，使所述塑料基材表面选择性沉积镀层，形成金属化线路的步骤之后，还包括步骤：
    根据需要通过化学还原法或电解法将所述塑料基材表面的镀层增厚。
  8. 根据权利要求7所述的在塑料表面形成选择性金属线路的方法，其特征在于，在所述根据需要通过化学还原法或电解法将所述塑料基材表面的镀层增厚的步骤中，所述增厚的镀层为化学镀铜层，化学镀铜增厚厚度为1～50um，沉铜速率优选2.0～3.5u/h，化学镀铜温度优选30～70℃。
  9. 一种表面具有金属线路的塑料部件，其特征在于，该金属线路是采用权利要求1至8中任一项所述的方法在塑料部件表面形成的。
PCT/CN2014/093499 2014-04-11 2014-12-10 在塑料表面形成选择性金属线路的方法及塑料部件 WO2015154502A1 (zh)

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