Chemical coarsening and metallization process method of LCP plastic
阅读说明：本技术 Lcp塑料的化学粗化及金属化工艺方法 (Chemical coarsening and metallization process method of LCP plastic ) 是由 邢洪滨 徐晨阳 于 2021-03-18 设计创作，主要内容包括：本发明公开了一种LCP塑料的化学粗化及金属化工艺方法,包括以下步骤：(1)第一次粗化：使用蚀刻液对产品进行浸泡；(2)第二次粗化：调整浸泡温度和时间继续浸泡,使得所述产品表面出现一层均匀的孔洞；(3)活化：使用离子催化剂对所述产品进行活化,将所述产品放置在所述离子催化剂中浸泡；(4)还原：使用离子钯还原剂对所述产品进行浸泡还原；(5)化学铜：使用高速化学铜溶液对所述产品进行沉铜；(6)电镀铜：使用高速高整平性酸性镀铜对所述产品电镀铜；(7)化学镍：使用光亮中磷高温化学镍溶液对所述产品进行沉镍。其本粗化工艺对LCP塑料工件有着良好的粗化效果,具有浸泡时间短,易于操作等特点。(The invention discloses a chemical coarsening and metallization process method of LCP (liquid crystal polymer) plastics, which comprises the following steps of: (1) coarsening for the first time: soaking the product by using an etching solution; (2) and (3) coarsening for the second time: adjusting the soaking temperature and time to continue soaking so that a layer of uniform holes appears on the surface of the product; (3) and (3) activation: activating the product by using an ionic catalyst, and soaking the product in the ionic catalyst; (4) reduction: soaking and reducing the product by using an ionic palladium reducing agent; (5) chemical copper: using a high-speed chemical copper solution to carry out copper deposition on the product; (6) copper electroplating: electroplating copper on the product by using high-speed high-leveling acid copper plating; (7) chemical nickel: and (3) using a bright medium-phosphorus high-temperature chemical nickel solution to carry out nickel precipitation on the product. The coarsening process has good coarsening effect on LCP plastic workpieces, and has the characteristics of short soaking time, easy operation and the like.)
1. A chemical coarsening and metallization process method of LCP plastic is characterized by comprising the following steps:
(1) coarsening for the first time: soaking the product by using an etching solution;
(2) and (3) coarsening for the second time: adjusting the soaking temperature and time to continue soaking so that a layer of uniform holes appears on the surface of the product;
(3) and (3) activation: activating the product by using an ionic catalyst, and soaking the product in the ionic catalyst;
(4) reduction: soaking and reducing the product by using an ionic palladium reducing agent;
(5) chemical copper: using a high-speed chemical copper solution to carry out copper deposition on the product;
(6) copper electroplating: electroplating copper on the product by using high-speed high-leveling acid copper plating;
(7) chemical nickel: and (3) using a bright medium-phosphorus high-temperature chemical nickel solution to carry out nickel precipitation on the product.
2. The chemical roughening and metallization process for LCP plastic as claimed in claim 1, wherein said etching solution is LCP ETCH product of Ma De Mei technology (Suzhou) Co., Ltd, said ionic Catalyst is MID Catalyst 100 series product of Ma De Mei technology (Suzhou) Co., Ltd, said ionic palladium reducing agent is MID Reducer series product of Ma De Mei technology (Suzhou) Co., Ltd, said high speed chemical copper solution is MID Cu XD series product of Ma De Mei technology (Suzhou) Co., Ltd, said high speed high leveling acid copper plating is SYSTEK BMP-LP8 series product of Ma De Mei technology (Suzhou) Co., Ltd, and said bright MID-phosphorus high temperature chemical nickel solution is MID Ni200 MID-phosphorus series product of Ma De Mei technology (Suzhou) Co., Ltd.
3. The chemical roughening and metallization process for LCP plastic as claimed in claim 1, wherein the soaking temperature for the first roughening in step (1) is 65-75 ℃; the soaking temperature for the second coarsening in the step (2) is 70-80 ℃; the activating soaking temperature in the step (3) is 40-50 ℃; the soaking temperature for reduction in the step (4) is 40-50 ℃; the soaking temperature of the chemical copper in the step (5) is 45-55 ℃; the electroplating temperature in the step (6) is 40-50 ℃; the soaking temperature of the chemical nickel in the step (7) is 80-90 ℃.
4. The chemical roughening and metallization process for LCP plastic as claimed in claim 1, wherein the soaking time for the first roughening in step (1) is 5-10 min; soaking for 10-30min for the second coarsening in the step (2); the activating soaking time in the step (3) is 5-15 min; the soaking time for reduction in the step (4) is 5-10 min; the soaking time of the chemical copper in the step (5) is 15-30 min.
5. The chemical roughening and metallization process for LCP plastic of claim 1, wherein the current density of step (6) is 2-3 ASD.
6. The chemical roughening and metallization process for LCP plastic of claim 1, wherein the operating concentrations of the etching solution are: 300ml/L (step (1)) and 500ml/L (step (2)); the operating concentration of the ionic catalyst was 60 ppm; the operation concentration of the ionic palladium reducing agent is 50 ml/L.
7. The chemical roughening and metallization process for LCP plastic of claim 1, wherein the composition of the high speed chemical copper solution is: 0.10mol/L complexing agent, 3.0g/L copper ions, 5.0g/L sodium hydroxide and 4.0g/L formaldehyde;
the components of the high-speed high-leveling acidic copper plating are 100g/L copper sulfate, 200g/L sulfuric acid, 2ml/L copper plating gloss agent and 12.5ml/L leveling agent;
the operating concentration of the chemical nickel is Part A50 ml/L and Part B150 ml/L.
Technical Field
The invention relates to the field of metallization processing, in particular to a chemical coarsening and metallization process method of LCP (liquid crystal polymer) plastics.
Background
LCP plastic, also known as liquid crystal polymer, is a novel polymer material, has excellent acid and alkali corrosion resistance, heat resistance and forming processability, and is mainly applied to the aspects of electronics, electrics, printed circuit boards, artificial satellite electronic components, jet engine parts, automobile mechanical parts, medical treatment and the like.
LCP plastic has high acid and alkali resistance, and the surface is difficult to coarsen by a common chemical method; the surface is not easy to coarsen, and the general plating layer has large internal stress, so that the adhesive force can not be ensured; the LCP plastic surface is very rough after chemical roughening, and the subsequent plating layer can not effectively fill up the pores, so that the appearance of the plating layer of the workpiece is poor.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a chemical roughening and metallization process method for LCP plastics, which can enable uniform pores to be generated on the surface of the LCP plastics and can obtain a flat and uniform metal plating layer.
In order to achieve the purpose, the embodiment of the application discloses a chemical coarsening and metallization process method of LCP plastics, which comprises the following steps:
(1) coarsening for the first time: soaking the product by using an etching solution;
(2) and (3) coarsening for the second time: adjusting the soaking temperature and time to continue soaking so that a layer of uniform holes appears on the surface of the product;
(3) and (3) activation: activating the product by using an ionic catalyst, and soaking the product in the ionic catalyst;
(4) reduction: soaking and reducing the product by using an ionic palladium reducing agent;
(5) chemical copper: using a high-speed chemical copper solution to carry out copper deposition on the product;
(6) copper electroplating: electroplating copper on the product by using high-speed high-leveling acid copper plating;
(7) chemical nickel: and (3) using a bright medium-phosphorus high-temperature chemical nickel solution to carry out nickel precipitation on the product.
Preferably, the etching solution is an LCP ETCH product of Midame technology (Suzhou) limited, the ionic Catalyst is an MID Catalyst 100 series product of the Midame technology (Suzhou) limited, the ionic palladium reducing agent is an MID Reducer series product of the Midame technology (Suzhou) limited, the high-speed chemical copper solution is an MID Cu XD series product of the Midame technology (Suzhou) limited, the high-speed high-leveling acid copper plating is a SYSTEM BMP-LP8 series product of the Midame technology (Suzhou) limited, and the bright medium-phosphorus high-temperature chemical nickel solution is an MID Ni200 medium-phosphorus series product of the Midame technology (Suzhou) limited.
Preferably, the soaking temperature of the first coarsening in the step (1) is 65-75 ℃; the soaking temperature for the second coarsening in the step (2) is 70-80 ℃; the activating soaking temperature in the step (3) is 40-50 ℃; the soaking temperature for reduction in the step (4) is 40-50 ℃; the soaking temperature of the chemical copper in the step (5) is 45-55 ℃; the electroplating temperature in the step (6) is 40-50 ℃; the soaking temperature of the chemical nickel in the step (7) is 80-90 ℃.
Preferably, the soaking time for the first coarsening in the step (1) is 5-10 min; soaking for 10-30min for the second coarsening in the step (2); the activating soaking time in the step (3) is 5-15 min; the soaking time for reduction in the step (4) is 5-10 min; the soaking time of the chemical copper in the step (5) is 15-30 min.
Preferably, the current density of step (6) is 2-3 ASD.
Preferably, the operating concentration of the etching solution is: 300ml/L (step (1)) and 500ml/L (step (2)); the operating concentration of the ionic catalyst was 60 ppm; the operation concentration of the ionic palladium reducing agent is 50 ml/L.
Preferably, the high-speed chemical copper solution comprises the following components: 0.10mol/L complexing agent, 3.0g/L copper ions, 5.0g/L sodium hydroxide and 4.0g/L formaldehyde;
the components of the high-speed high-leveling acidic copper plating are 100g/L copper sulfate, 200g/L sulfuric acid, 2ml/L copper plating gloss agent and 12.5ml/L leveling agent;
the operating concentration of the chemical nickel is Part A50 ml/L and Part B150 ml/L.
The invention has the following beneficial effects:
1. the process flow can enable uniform pores to be generated on the surface of LCP plastic, and is beneficial to the subsequent metallization flow;
2. the process flow uses low internal stress electro-coppering and chemical nickel liquid medicine, so that the adhesive force of the plating layer is more guaranteed;
3. the copper electroplating process used in the process flow can effectively fill up the pores and pits generated by chemical coarsening on the surface of the plastic, can obtain a smooth and uniform metal coating, and greatly improves the appearance performance of the workpiece.
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "bottom", "inner", "outer", and the like indicate orientations or positional relationships only for the convenience of describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature.
Example 1
(1) Coarsening for the first time: soaking the product in etching solution at 70 deg.C for 8 min;
(2) and (3) coarsening for the second time: adjusting the soaking temperature and time to continue soaking to enable a layer of uniform holes to appear on the surface of the product, and soaking for 15min at 75 ℃;
(3) and (3) activation: activating the product by using an ionic catalyst, and soaking the product in the ionic catalyst at the soaking temperature of 45 ℃ for 10 min;
(4) reduction: soaking and reducing the product by using an ionic palladium reducing agent at the soaking temperature of 45 ℃ for 8 min;
(5) chemical copper: using a high-speed chemical copper solution to carry out copper deposition on the product, wherein the soaking temperature is 50 ℃, and the soaking time is 20 min;
(6) copper electroplating: electroplating copper on the product by using high-speed high-leveling acid copper plating, wherein the soaking temperature is 45 ℃, the current density is 2-3ASD, and the electroplating time is determined according to the thickness required by a customer;
(7) chemical nickel: and (3) using a bright medium-phosphorus high-temperature chemical nickel solution to carry out nickel precipitation on the product, wherein the soaking temperature is 85 ℃, and the soaking time is determined according to the nickel thickness required by a customer.
Wherein, the operating concentration of the etching solution is respectively as follows: 300ml/L (step (1)) and 500ml/L (step (2)); the operating concentration of the ionic catalyst is 60 ppm; the operation concentration of the ionic palladium reducing agent is 50ml/L respectively; the components of the high-speed chemical copper solution are 0.10mol/L complexing agent, 3.0g/L copper ions, 5.0g/L sodium hydroxide and 4.0g/L formaldehyde; the components of the high-speed high-leveling acidic copper plating are 100g/L copper sulfate, 200g/L sulfuric acid, 2ml/L copper plating gloss agent and 12.5ml/L leveling agent; the operating concentration of the chemical nickel is Part A50 ml/L and Part B150 ml/L.
Example 2
(1) Coarsening for the first time: soaking the product in etching solution at 65 deg.C for 5 min;
(2) and (3) coarsening for the second time: adjusting the soaking temperature and time to continue soaking so that a layer of uniform holes appears on the surface of the product, wherein the soaking temperature is 70 ℃, and the soaking time is 10 min;
(3) and (3) activation: activating the product by using an ionic catalyst, and soaking the product in the ionic catalyst at the soaking temperature of 45 ℃ for 10 min;
(4) reduction: soaking and reducing the product by using an ionic palladium reducing agent at the soaking temperature of 45 ℃ for 8 min;
(5) chemical copper: using a high-speed chemical copper solution to carry out copper deposition on the product, wherein the soaking temperature is 50 ℃, and the soaking time is 20 min;
(6) copper electroplating: electroplating copper on the product by using high-speed high-leveling acid copper plating, wherein the soaking temperature is 45 ℃, the current density is 2-3ASD, and the electroplating time is determined according to the thickness required by a customer;
(7) chemical nickel: and (3) using a bright medium-phosphorus high-temperature chemical nickel solution to carry out nickel precipitation on the product, wherein the soaking temperature is 85 ℃, and the soaking time is determined according to the nickel thickness required by a customer.
Wherein the operating concentrations of the etching solution, the ionic catalyst and the ionic palladium reducing agent are respectively as follows: 300ml/L (first coarsening), 500ml/L (second coarsening), 60ppm of ionic palladium and 50ml/L of reducing agent; the components of the high-speed chemical copper solution are 0.10mol/L complexing agent, 3.0g/L copper ions, 5.0g/L sodium hydroxide and 4.0g/L formaldehyde; the components of the high-speed high-leveling acidic copper plating are 100g/L copper sulfate, 200g/L sulfuric acid, 2ml/L copper plating gloss agent and 12.5ml/L leveling agent; the operating concentrations of chemical nickel were Part A50 ml/L and Part B150 ml/L.
Example 3
(1) Coarsening for the first time: soaking the product in etching solution at 75 deg.C for 5 min;
(2) and (3) coarsening for the second time: adjusting the soaking temperature and time to continue soaking so that a layer of uniform holes appears on the surface of the product, wherein the soaking temperature is 80 ℃, and the soaking time is 10 min;
(3) and (3) activation: activating the product by using an ionic catalyst, and soaking the product in the ionic catalyst at the soaking temperature of 45 ℃ for 10 min;
(4) reduction: soaking and reducing the product by using an ionic palladium reducing agent at the soaking temperature of 45 ℃ for 8 min;
(5) chemical copper: using a high-speed chemical copper solution to carry out copper deposition on the product, wherein the soaking temperature is 50 ℃, and the soaking time is 20 min;
(6) copper electroplating: electroplating copper on the product by using high-speed high-leveling acid copper plating, wherein the soaking temperature is 45 ℃, the current density is 2-3ASD, and the electroplating time is determined according to the thickness required by a customer;
(7) chemical nickel: and (3) using a bright medium-phosphorus high-temperature chemical nickel solution to carry out nickel precipitation on the product, wherein the soaking temperature is 85 ℃, and the soaking time is determined according to the nickel thickness required by a customer.
Wherein the operating concentration of the etching solution is 300ml/L (step (1)), 500ml/L (step (2)), the operating concentration of the ionic catalyst is 60ppm, and the operating concentrations of the ionic palladium reducing agent are respectively 50 ml/L;
the components of the high-speed chemical copper solution are 0.10mol/L complexing agent, 3.0g/L copper ions, 5.0g/L sodium hydroxide and 4.0g/L formaldehyde; the components of the high-speed high-leveling acidic copper plating are 100g/L copper sulfate, 200g/L sulfuric acid, 2ml/L copper plating gloss agent and 12.5ml/L leveling agent; the operating concentration of the chemical nickel is Part A50 ml/L and Part B150 ml/L.
Comparative example 1
The difference from the embodiment 3 is only that the etching solution in the step (1) is replaced by NaOH, so that the obtained LCP plastic workpiece has a poor appearance, the surface of the LCP plastic workpiece cannot be effectively roughened, and the adhesion of the subsequent plating layer is poor.
Comparative example 2
The only difference from example 3 is that the ionic catalyst in step (3) is replaced by colloidal palladium, and the obtained LCP plastic workpiece has rough plating layer, poor appearance and unsatisfactory plating layer roughness.
Comparative example 3
The difference from the embodiment 3 is only that, by replacing the etching solution in the step (1) with KOH, the obtained LCP plastic workpiece has a poor appearance, the surface of the LCP plastic workpiece cannot be effectively roughened, and the adhesion of the subsequent plating layer is poor.
Comparative example 4
The only difference from example 3 is that the soaking temperature for the first roughening in step (1) is 80 ℃.
Comparative example 5
The only difference from example 3 is that the soaking temperature for the second roughening in step (2) was 85 ℃.
Comparative example 6
The only difference from example 3 is that the soaking temperature for activation in step (3) is 51 ℃.
Comparative example 7
The only difference from example 3 is that the soaking temperature for the reduction in step (4) is 51 ℃.
Comparative example 8
The only difference from example 3 is that the immersion temperature of the chemical copper in step (5) is 56 ℃.
Comparative example 9
The only difference from example 3 is that the immersion temperature for the plating in step (6) was 51 ℃.
Comparative example 10
The only difference from example 3 is that the soaking temperature for the reduction in step (7) was 91 ℃.
Adhesion test
Test 1: marking a cross grid shape on the surface of a product by using a hundred grid cutter, counting 100 grids (1mm multiplied by 1mm), slightly sweeping the cut to a base material by using a soft brush along each diagonal line of the cross grid for several times, then sweeping forwards and backwards for several times, pulling 3 times by using 3M 600# adhesive tape, observing the conditions of respective areas, counting the percentage of the area without falling to the total area, and obtaining the following table 1:
TABLE 1
Examples of the invention
Non-shedding area ratio (%)
Example 1
100
Example 2
100
Example 3
100
Comparative example 1
80
Comparative example 2
90
Comparative example 3
75
Comparative example 4
70
Comparative example 5
90
Comparative example 6
80
Comparative example 7
50
Comparative example 8
60
Comparative example 9
50
Comparative example 10
60
As can be seen from table 1, after the tape was scratched with a hundred-grid knife, the tape was pulled 3 times using 3M 600# tape, and no peeling occurred on the surfaces of the products in examples 1 to 3, indicating that the surfaces of the products in the present invention have excellent adhesion. Comparing the comparative examples with example 3, it is found that when the etching solution in the roughening step is replaced or the operating concentrations of the substances are changed, the size and uniformity of the holes on the surface of the product are affected, which further affects the adhesion of the subsequent coating to the surface of the product and obviously reduces the adhesion. When the operating concentration of various working solutions is changed in other steps, the adhesion of the coating is also affected to a certain extent due to the change of properties such as the surface electrical property of the product, and the corresponding reduction is further caused.
The principle and the implementation mode of the invention are explained by applying specific embodiments in the invention, and the description of the embodiments is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.