WO2015066910A1 - 易电镀的电镀pc/abs合金材料及其制备方法 - Google Patents

易电镀的电镀pc/abs合金材料及其制备方法 Download PDF

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WO2015066910A1
WO2015066910A1 PCT/CN2013/086827 CN2013086827W WO2015066910A1 WO 2015066910 A1 WO2015066910 A1 WO 2015066910A1 CN 2013086827 W CN2013086827 W CN 2013086827W WO 2015066910 A1 WO2015066910 A1 WO 2015066910A1
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resin
abs
electroplated
alloy material
abs alloy
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PCT/CN2013/086827
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English (en)
French (fr)
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柏莲桂
辛敏琦
罗明华
李强
李文强
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上海锦湖日丽塑料有限公司
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Priority to US15/034,530 priority Critical patent/US9834674B2/en
Publication of WO2015066910A1 publication Critical patent/WO2015066910A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
    • B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention belongs to the field of polymer blending and polymer molding processing, and particularly relates to an electroplatable PC/ABS alloy material which is easy to electroplating and a preparation method thereof.
  • Electroplated PC/ABS alloy materials are widely used in automotive interior and exterior parts due to their excellent heat resistance, toughness and fatigue strength and plating properties, such as interior and exterior door handles, car nameplates, wheel covers, grilles, trim strips. Wait. In the electroplating process, the roughening process is closely related to the properties of the material.
  • PC/ABS is not as easy to plate as ABS because it cannot be plated.
  • PC/ABS is thicker than electroplated ABS, which affects the electroplating efficiency of PC/ABS.
  • This combination method is a method of physical bonding, and the bonding force is low.
  • the roughening liquid is mainly composed of concentrated sulfuric acid and chromic acid, and has strong oxidizing property.
  • the material is changed from hydrophobic to hydrophilic, and the contact angle of the surface is lowered to make the roughening liquid on the surface. It is capable of spreading, evenly etching the rubber B on the surface of the material, which is improved by the plating solution to improve the hydrophilicity of the material surface.
  • PE0 is a hydrophilic resin widely used in the fields of medicine and cosmetics. Because PE0 is highly hydrophilic, it may cause the material to have high hygroscopicity and increase the water content. While PC materials are sensitive to moisture, it may cause degradation of PC materials, which has made PE0 rarely used in the field of modified PC.
  • An object of the present invention is to provide an electroplated PC/ABS alloy material which is easy to electroplate.
  • the electroplatable electroplated PC/ABS alloy material of the present invention has the characteristics of easy electroplating and high plating adhesion.
  • Another object of the present invention is to provide a method of preparing the alloy material.
  • the electroplatable electroplated PC/ABS alloy material of the present invention comprises components having the following parts by weight:
  • PC polycarbonate
  • ABS acrylonitrile-styrene-butadiene copolymer
  • the optimum content of the above PE0 resin ranges from 5 to 10 parts; when the PE0 content is less than 5 parts, the influence on the surface contact angle of the PC/ABS alloy is small, and the electroplating performance is not achieved, and when the PE0 content is higher than 10 parts, the moisture absorption Strong, it has a great influence on the physical properties of materials, resulting in reduced impact performance.
  • the PC resin has a relative molecular weight of 17,000 to 30000 g/mol and a glass transition temperature of 140 to 150 °C.
  • the PC resin is a phosgene-synthesized PC resin.
  • the preferred reason is that the PC of the phosgene method is excellent in thermal stability.
  • the ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and has a relative molecular weight of 100,000 to 180,000 g/mol, wherein the weight percentage of butadiene is 30 to 55%, and the weight of acrylonitrile The percentage content is 15 to 32%, and the styrene weight percentage is 30 to 60%.
  • the ABS resin has a relative molecular weight of from 15,000 to 180,000 g/mol, wherein the butadiene is present in an amount of from 45 to 55% by weight, the acrylonitrile is present in an amount of from 15 to 32% by weight, and the styrene is present in an amount of from 30 to 60% by weight.
  • the preferred ABS has a high butadiene content and is excellent in improving the impact properties of the PC/ABS alloy material of the present invention.
  • the PE0 resin has a relative molecular weight of 10,000 to 20,000.
  • the molecular weight of PE0 is between 10,000 and 20,000, which is the most obvious reduction in the contact angle of PC/ABS, which makes the PC/ABS alloy material easy to electroplating.
  • the antioxidant is diethylene glycol bis[ ⁇ _(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], four [ ⁇ _ (3, 5 -di-tert-butyl 4-hydroxyphenyl)propionic acid] one of pentaerythritol ester, tris(2,4-di-tert-butylphenyl) phosphite, dioctadecyl alcohol pentaerythritol diphosphite or A mixture of several.
  • the lubricant is a mixture of one or more of a silane polymer, a solid paraffin, a liquid paraffin, a fatty acid salt, a fatty acid amide, calcium stearate, zinc stearate, and stearic acid amide.
  • the stearic acid amide is one or both of methyl bis stearic acid amide and hydrazine, hydrazine-ethylene bis stearic acid amide.
  • the invention also relates to the aforementioned method of electroplating a PC/ABS alloy material, comprising the steps of:
  • step a The mixture obtained in the step a is blended and granulated by a twin-screw extruder to obtain an electroplatable electroplated PC/ABS. Alloy particles.
  • the extruder has a barrel temperature of 200 to 260 ° C and a screw rotation speed of 200 to 600 rpm.
  • the invention has the beneficial effects that: the method of the invention is simple and easy, and the surface of the PC/ABS is hydrophilic due to the presence of the PE0 resin, and the roughening liquid is more likely to infiltrate the surface during the roughening of the electroplating. It makes the roughening easier.
  • the hydrophilic group and the metal binding force on the surface of PE0 are high, and in addition to the physical bonding, there is a chemical bond bonding effect, and the two aspects work together to improve the plating effect of the PC/ABS alloy material.
  • the mechanism of action of the present invention is: by using a phosgene-synthesized PC, by adding a suitable proportion of ABS, the impact property of the material is improved, and the influence of the hygroscopicity of PE0 on the material properties is reduced; by selecting a suitable molecular weight of PE0, moisture absorption Low in nature, significantly lowering the PC/ABS contact angle and improving surface hydrophilicity. Since the PE0 resin is hydrophilic, it can lower the contact angle of the PC/ABS surface, making the roughening liquid spread better and making the roughening easier. At the same time, the surface of the PE0 resin contains a large amount of hydroxyl groups, which can be very dense with the metal plating. A good combination, better bonding of the coating by chemical bonding.
  • Examples 1 to 4 relate to an electroplatable electroplated PC/ABS alloy material, and the components and contents of the PC/ABS alloy material are shown in Table 1; wherein the PC resin is selected from PC1250WP of Japan Teijin Co., Ltd. (relative number average molecular weight) It is 22 000 g/mol, the glass transition temperature is 140 ° C); ABS resin is selected from Korea Kumho Petrochemical P/D190 (relative weight average molecular weight is 120 000 g / mol, of which the weight percentage of butadiene) At 50%, the acrylonitrile content is 15% by weight and the styrene weight percentage is 35%.
  • the PC resin is selected from PC1250WP of Japan Teijin Co., Ltd. (relative number average molecular weight) It is 22 000 g/mol, the glass transition temperature is 140 ° C); ABS resin is selected from Korea Kumho Petrochemical P/D190 (relative weight average molecular weight is 120 000 g / mol
  • PE0 resin is selected from PEG-10000 of Hunan Petrochemical Co., Ltd. (the number average molecular weight is 10,000 g/mol); the antioxidant is Irbaox 1076 and Irganox 168 of Ciba, the weight ratio is 1:1; Commercially available pentaerythritol stearic acid.
  • Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
  • This embodiment relates to an electroplatable PC/ABS alloy material which is easy to electroplate, and the preparation method thereof is as follows:
  • the PC resin has a relative molecular weight of 17,000 g/m O l and a glass transition temperature of 140 ° C, which is a PC resin synthesized by phosgene method;
  • the ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and has a relative molecular weight of 1000 ng/mol, wherein the butadiene content is 55% by weight, and the acrylonitrile is 15% by weight, benzene.
  • the ethylene content by weight is 30%;
  • the PE0 resin has a molecular weight of 20000 g/mol
  • the antioxidant is diethylene glycol bis[ ⁇ -(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; the lubricant is ruthenium, osmium-ethylene Bistearic acid amide.
  • This embodiment relates to an electroplatable PC/ABS alloy material which is easy to electroplate and which is prepared in the same manner as in Embodiment 5, except that: 30 parts of PC resin,
  • the PC resin has a relative molecular weight of 30,000 g / mol and a glass transition temperature of 150 ° C, which is a PC resin synthesized by phosgene method;
  • the ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and has a relative molecular weight of 180,000 g/mol, wherein the butadiene content is 30% by weight, and the acrylonitrile is 15% by weight, benzene.
  • the ethylene content by weight is 55%;
  • the PE0 resin has a molecular weight of 1000o/mol
  • the antioxidant is tetrakis[ ⁇ _ (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite;
  • the lubricant is a mixture of methyl bis-stearic acid amide and hydrazine, hydrazine-ethylene bis stearic acid amide.
  • the electroplatable electroplated PC/ABS alloy material prepared in the above Examples 1 to 6 was injection molded into a 140 mm*90 mm*3 hidden high-light plate and electroplated in an electroplating factory in Shanghai.
  • the concentration of concentrated sulfuric acid and chromic acid was 400 g/L, and the roughening temperature was 68 °C.
  • the contact angle test was carried out in accordance with the ISO 15989 standard and the test liquid was secondary deionized water.
  • the plating adhesion was carried out in accordance with the GMW14668-2010 standard, with a tensile speed of 100 mm/min and an angle of 90.
  • the notched impact strength is in accordance with ASTM D256 and the temperature is 23 V.
  • the PE0 resin is added to make the surface of the PC/ABS hydrophilic, and the roughening liquid is easier when the plating is roughened.
  • the surface is wetted to make the roughening easier.
  • the hydrophilic group and the metal bonding force on the surface of PE0 are high.
  • there is a chemical bond which improves the plating effect of the PC/ABS alloy material.
  • this comparative example is to study the effect of the amount of PE0 resin on the properties of the electroplated PC/ABS alloy material of the present invention; this comparative example is to adjust the amount of PE0 on the basis of Example 3 to be 3, 4, 5, 10, 11 respectively. 12 parts by weight, and the performance of the obtained PC/ABS alloy material was tested by the method of Example 7. The results are shown in Table 3 below:
  • the optimum content of the PE0 resin is in the range of 5 to 10 parts, and when the PE0 content is less than 5 parts or more than 10 parts, the plating adhesion is decreased. This is because when the PE0 content is less than 5 parts, the influence on the surface contact angle of the PC/ABS alloy is small, and the electroplating performance is not achieved. When the PE0 content is higher than 10 parts, the hygroscopicity is strong, which has a great influence on the physical properties of the material, resulting in The impact performance is reduced.
  • This comparative example is based on the study of Comparative Example 1 to further study the effect of the relative molecular weight of the PE0 resin on the properties of the electroplated PC/ABS alloy material of the present invention; the composition and preparation method of the present comparative example are the same as those of the third embodiment. Therefore, the PE0 resin used is PEG-6000 (the number average molecular weight of 6,000 g/mol) and PEG-30000 (the number average molecular weight is 30,000 g/mol) of Hunan Petrochemical, Korea. The method of Example 7 was used to test the properties of the obtained PC/ABS alloy material. The results are shown in Table 4 below:
  • PC/ABS alloy material of Example 3 has the best electroplating performance; this is because the molecular weight of PE0 is 10,000 to 20,000, and the reduction of the contact angle of PC/ABS is most obvious, so that the PC/ABS alloy material is achieved. Easy to plate performance.
  • this comparative example is to further study the influence of the butadiene content in the ABS resin on the properties of the electroplated PC/ABS alloy material of the present invention on the basis of the studies of Comparative Examples 1 and 2; the present comparative example is adjusted on the basis of Example 3.
  • the weight percentage of butadiene in the ABS resin was 20%, 30%, 45%, 50%, 55%, 60%, respectively, and the performance of the obtained PC/ABS alloy material was tested by the method of Example 7, The results are shown in Table 5 below:
  • the content of butadiene in the ABS resin is 20%, and the addition of PE0 has a great influence on the impact, and when the content of butadiene is 60%, the roughening is easy to be excessive, resulting in a decrease in the binding force; that is, in the present invention.
  • the butadiene content of the medium ABS resin ranges from 30 to 55%. At the same time, when the butadiene content of the ABS resin is 45 to 55%, the impact performance of the PC/ABS alloy material is excellent.
  • the purpose of the comparative examples 4 and 5 is to further study the effect of the compounding action of PC resin and PE0 resin on the properties of the electroplated PC/ABS alloy material of the present invention on the basis of the studies of Comparative Examples 1, 2, and 3; this Comparative Example 4 is On the basis of Example 3, the PC resin was adjusted to PC201-22 of Korea LG-D0W (relative number average molecular weight was 20,000 g/mol, glass transition temperature was 140 ° C, and the resin was prepared by a transesterification method)
  • the PC resin used in Comparative Example 5 was the same as that in Example 3, which was a phosgene-synthesized PC resin, except that the amount of the PC resin was 20, 25, 65, and 70 parts by weight, respectively.
  • the method was applied to the performance test of the prepared PC/ABS alloy material. The results are shown in Table 6 below:
  • Comparative Example 4 employed a PC resin which was not phosgene, and its thermal stability was lower than that of Example 3, thereby affecting the plating adhesion of the electroplated PC/ABS alloy material.
  • the electroplating performance of the PC/ABS alloy material prepared in Comparative Example 5 was much lower than that in Example 3.
  • the PC fraction was higher than 65 parts, significant plating leakage occurred, indicating that there is a suitable relationship between PC resin and PE0 resin and other components. In the ratio, the components can exert the best synergistic effect, thereby achieving the overall improvement of the plating effect of the PC/ABS alloy material of the present invention.
  • the method of the present invention is simple and easy, and by using a phosgene-synthesized PC, by adding a suitable proportion of ABS, the impact property of the material is improved, and the influence of the hygroscopicity of PE0 on the material properties is reduced;
  • a suitable molecular weight of PE0 has low hygroscopicity, significantly lowers the PC/ABS contact angle, and improves surface hydrophilicity. Since the PE0 resin is hydrophilic, it can lower the contact angle of the PC/ABS surface, making the roughening liquid spread better and making the roughening easier.
  • the surface of the PE0 resin contains a large amount of hydroxyl groups, which can be very thick with the metal plating.
  • a good combination the bonding strength of the coating is better improved by the chemical bonding; the combination of the two effects achieves the electroplating effect of the PC/ABS alloy material of the present invention.

Abstract

一种易电镀的电镀PC/ABS合金材料及其制备方法；包含以下组分及重量份：PC树脂30〜70份，ABS树脂15〜65份，PEO树脂5〜10份，抗氧剂0.1〜1份，润滑剂0.1〜1份。制备时，将PC树脂、ABS树脂、PEO树脂、抗氧剂和润滑剂加入混合搅拌机中进行混合；将所得混合物通过双螺杆挤出机共混造粒，制得易电镀的电镀PC/ABS合金材料。该方法简单易行，由于PEO树脂的存在，使得PC/ABS表面亲水，在电镀粗化时粗化液更容易浸润表面，使粗化更加容易，PEO表面的亲水性基团和金属结合力高，除了物理结合以外还有化学键结合，通过这两点提高了PC/ABS合金材料的电镀效果。

Description

易电镀的电镀 PC/ABS合金材料及其制备方法 技术领域
本发明属于高分子共混、高分子成型加工领域，具体涉及一种易电镀的电镀 PC/ABS 合金材料及其制备方法。
背景技术
电镀 PC/ABS合金材料由于其优异的耐热性、 韧性和耐疲劳强度和电镀性能， 被广 泛应用与汽车内外饰部件上， 如内外门拉手、 汽车铭牌、 车轮壳罩、 格栅、 装饰条等。 电镀工艺中， 粗化过程和材料的性能息息相关。
对于 PC/ABS材料， 由于 PC是无法电镀的， PC/ABS的电镀容易能力不如 ABS。 同样 的粗化温度时， PC/ABS粗化的时间长于电镀 ABS , 影响 PC/ABS的电镀生产效率。 粗化 后，材料表面形成均匀分布的孔洞，化学镍通过这些孔洞来达到镀层和材料结合的作用。 这种结合方法是通过物理结合力的方法， 结合力较低。
传统电镀过程中， 粗化液主要由浓硫酸和铬酸组成， 具有强氧化性， 通过氧化材料 表面， 将材料由疏水性变成亲水性， 降低表面的接触角， 使粗化液在表面能够铺展， 均 匀的刻蚀材料表面分布的橡胶 B， 这是通过电镀液来改善材料表面亲水性。
PE0是一种亲水性树脂， 广泛的应用在医药和化妆品领域。 因为 PE0亲水性很强， 可能会造成材料吸湿性大， 含水率增加， 而 PC材料对于水分比较敏感， 可能会造成 PC 材料降解， 导致至今 PE0在改性 PC领域很少应用。
发明内容
本发明的目的在于提供一种易电镀的电镀 PC/ABS合金材料， 本发明的易电镀的电 镀 PC/ABS合金材料具有容易电镀、 电镀结合力高的特点。 本发明的另一目的在于提供 该合金材料的制备方法。
本发明的目的是通过以下的技术方案实现的， 本发明的易电镀的电镀 PC/ABS合金 材料包含具有以下重量份的组分：
PC (聚碳酸酯） 树脂 30〜60份，
ABS (丙烯腈 -苯乙烯-丁二烯共聚物)树脂 15〜55份， PEO树脂 5〜10份，
抗氧剂 0. 1〜1份，
润滑剂 0. 1〜1份。 上述 PE0树脂的最佳含量范围为 5〜10份； PE0含量低于 5份时，对于 PC/ABS合金 表面接触角影响小， 达不到易电镀的性能， PE0含量高于 10份时， 吸湿性强， 对于材料 的物性影响大， 造成冲击性能降低。
优选地， 所述 PC树脂的相对分子量为 17000〜30000g/mol， 其玻璃化温度为 140〜 150°C。
优选地， 所述 PC树脂为光气法合成的 PC树脂。优选原因在于， 光气法的 PC， 热稳 定性优异。
优选地， 所述 ABS树脂为丙烯腈-丁二烯-苯乙烯组成的接枝共聚物， 其相对分子量 为 100000〜180000g/mol， 其中丁二烯重量百分比含量为 30〜55%， 丙烯腈重量百分比 含量为 15〜32%， 苯乙烯重量百分比含量为 30〜60 %。 更优选 ABS树脂的相对分子量为 15000〜180000 g/mol， 其中丁二烯重量百分比含量为 45〜55%， 丙烯腈重量百分比含量 为 15〜32%， 苯乙烯重量百分比含量为 30〜60%。 优选的 ABS中丁二烯含量高， 对于提 高本发明的 PC/ABS合金材料冲击性能表现优异。
优选地，所述 PE0树脂的相对分子量为 10000〜20000。PE0分子量在 10000〜20000， 对于 PC/ABS接触角的降低最明显， 从而使得 PC/ABS合金材料达到易电镀的性能。
优选地， 所述抗氧剂为二縮三乙二醇双 [ β _ (3-叔丁基 -4-羟基 -5-甲基苯基)丙酸 酯]、 四 [ β _ (3， 5-二叔丁基 4-羟基苯基)丙酸]季戊四醇酯、 三 (2， 4-二叔丁基苯基) 亚磷酸酯、 双十八烷基醇季戊四醇二亚磷酸酯中的一种或几种的混合。
优选地， 所述润滑剂为硅烷聚合物、 固体石蜡、液体石蜡、脂肪酸盐、脂肪酸酰胺、 硬脂酸钙、 硬脂酸锌、 硬脂酸酰胺中的一种或几种的混合。
优选地， 所述硬脂酸酰胺为甲撑双硬脂酸酰胺和 Ν， Ν-乙撑双硬脂酸酰胺中的一种 或两种。
第二方面， 本发明还涉及前述易电镀的电镀 PC/ABS合金材料的方法， 包括如下步 骤：
( a) 将所述 PC树脂、 ABS树脂、 PE0树脂、 抗氧剂和润滑剂加入混合搅拌机中进 行混合；
(b ) 将步骤 a所得混合物通过双螺杆挤出机共混造粒， 得到易电镀的电镀 PC/ABS 合金粒子。
优选地， 所述挤出机的机筒温度为 200〜260°C， 螺杆转速为 200〜600rpm。
与现有技术相比， 本发明具有的有益效果为： 本发明的方法简单易行， 由于 PE0树 脂的存在， 使得 PC/ABS表面亲水， 在电镀粗化时粗化液更容易浸润表面， 使粗化更加 容易， 同时， PE0表面的亲水性基团和金属结合力高， 除了物理结合以外还有化学键结 合作用， 两方面共同作用从而提高了 PC/ABS合金材料的电镀效果。
本发明的作用机理在于： 通过使用光气法合成的 PC， 通过添加合适比例的 ABS， 提 高了材料的冲击性能， 减少了 PE0的吸湿性对于材料性能的影响； 通过选择合适分子量 的 PE0, 吸湿性低， 明显降低 PC/ABS接触角， 改善表面亲水性。 由于 PE0树脂是亲水性 的， 可以降低 PC/ABS表面的接触角， 使得粗化液更好的铺展， 让粗化变得容易； 同时， PE0树脂表面含有大量的羟基， 可以和金属镀层很好的结合， 通过化学键结合的方式更 好的提高镀层结合力。
具体实施方式
下面结合具体实施例对本发明进行详细说明。 以下实施例将有助于本领域的技术人 员进一步理解本发明， 但不以任何形式限制本发明。 应当指出的是， 对本领域的普通技 术人员来说， 在不脱离本发明构思的前提下， 还可以做出若干变形和改进。 这些都属于 本发明的保护范围。
实施例 1〜4
实施例 1〜4涉及易电镀的电镀 PC/ABS合金材料， 该 PC/ABS合金材料包含的各组 分及含量如表 1所示； 其中， PC树脂选用日本帝人公司的 PC1250WP (相对数均分子量 为 22, 000 g/mol,玻璃化转变温度为 140°C )； ABS树脂选用韩国锦湖石油化学的 P/D190 (相对重均分子量为 120, 000 g/mol, 其中丁二烯重量百分比含量为 50%， 丙烯腈重量 百分比含量为 15%， 苯乙烯重量百分比含量为 35%。
； PE0树脂选用韩国湖南石化的 PEG-10000 (其数均相对分子量为 10, 000 g/mol )； 抗氧剂为 Ciba公司的 Irganox 1076和 Irganox 168， 其重量比为 1 : 1 ; 润滑剂为市售 的季戊四醇硬脂酸。
表 1 组分及重量份
实施例 1 实施例 2 实施例 3 实施例 4
PC 60 30 50 50
ABS 15 55 40 42
PE0 5 5 10 8 抗氧剂 0. 1 0. 4 0. 4 1 润滑剂 0. 1 0. 3 0. 3 1 制备方法如下：
( a) 首先将 PC树脂、 ABS树脂、 PE0树脂、 抗氧剂和润滑剂混合搅拌机中进行混 合.
(b )然后将混合物通过双螺杆挤出机共混造粒， 制得易电镀的电镀 PC/ABS合金粒 子， 挤出机的机筒温度为 200〜260°C， 螺杆转速为 200〜600rpm。
实施例 5
本实施例涉及一种易电镀的电镀 PC/ABS合金材料， 其制备方法如下：
a、 按以下组分及重量份备料：
PC树脂 60份，
ABS树脂 15份，
PE0树脂 5份，
抗氧剂 0. 5份，
润滑剂 0. 5份。
b、首先将 PC树脂、 ABS树脂、 PE0树脂、抗氧剂和润滑剂混合搅拌机中进行混合; c、然后将混合物通过双螺杆挤出机共混造粒，制得易电镀的电镀 PC/ABS合金粒子， 挤出机的机筒温度为 200〜260°C， 螺杆转速为 200〜600rpm。
所述 PC树脂的相对分子量为 17000g/mOl， 其玻璃化温度为 140°C， 为光气法合成 的 PC树脂；
所述 ABS 树脂为丙烯腈-丁二烯-苯乙烯组成的接枝共聚物， 其相对分子量为 lOOOOOg/mol , 其中丁二烯重量百分比含量为 55%， 丙烯腈重量百分比含量为 15%， 苯乙 烯重量百分比含量为 30%;
所述 PE0树脂分子量为 20000 g/mol ;
所述抗氧剂为二缩三乙二醇双 [ β - (3-叔丁基 -4-羟基 -5-甲基苯基)丙酸酯]； 所述润滑剂为 Ν， Ν-乙撑双硬脂酸酰胺。
实施例 6
本实施例涉及一种易电鍍的电鍍 PC/ABS合金材料，其制备方法同实施例 5，所不同 之处在于： PC树脂 30份，
ABS树脂 55份，
PE0树脂 5份，
抗氧剂 0. 1份，
润滑剂 0. 1份。
所述 PC树脂的相对分子量为 30000g/mol， 其玻璃化温度为 150°C， 为光气法合成 的 PC树脂；
所述 ABS 树脂为丙烯腈-丁二烯-苯乙烯组成的接枝共聚物， 其相对分子量为 180000g/mol , 其中丁二烯重量百分比含量为 30%， 丙烯腈重量百分比含量为 15%， 苯乙 烯重量百分比含量为 55%;
所述 PE0树脂分子量为 lOOOOg/mol ;
所述抗氧剂为四 [ β _ (3， 5-二叔丁基 4-羟基苯基)丙酸]季戊四醇酯和三 (2， 4-二 叔丁基苯基)亚磷酸酯；
所述润滑剂为甲撑双硬脂酸酰胺和 Ν， Ν-乙撑双硬脂酸酰胺的混合。
实施例 7、 实施效果
将以上实施例 1〜6制备的易电镀的电镀 PC/ABS合金材料注塑成 140mm*90mm*3隱 的高光板， 在上海某电镀厂电镀。 电镀的粗化液中， 浓硫酸和铬酸的浓度均为 400g/L， 粗化温度为 68 °C。
接触角测试按照 ISO 15989标准进行， 检测液体为二次去离子水。
电镀结合力按照 GMW14668-2010标准进行，拉伸速度为 100 mm/mi n，角度为 90 。 ； 缺口冲击强度按照 ASTM D256标准进行， 温度为 23 V。
测试结果如表 2所示：
表 2 实施例 1〜6的产品粗化时间和测试结果
Figure imgf000006_0001
由表 2可知， 加入 PE0树脂， 使得 PC/ABS表面亲水， 在电镀粗化时粗化液更容易 浸润表面， 使粗化更加容易， PE0表面的亲水性基团和金属结合力高， 除了物理结合以 外还有化学键结合， 通过这两点提高了 PC/ABS合金材料的电镀效果。
对比例 1
本对比例的目的在于研究 PE0树脂的用量对本发明的电镀 PC/ABS合金材料性能的 影响； 本对比例是在实施例 3的基础上调整 PE0的用量分别为 3、 4、 5、 10、 11、 12重 量份， 并采用实施例 7的方法对制得的 PC/ABS合金材料进行性能测试， 结果如下表 3:
表 3
Figure imgf000007_0001
由表 3可知， PE0树脂的最佳含量范围为 5〜10份， 当 PE0含量低于 5份或是高于 10份时， 电镀结合力下降。 这是由于 PE0含量低于 5份时， 对于 PC/ABS合金表面接触 角影响小， 达不到易电镀的性能， PE0含量高于 10份时， 吸湿性强， 对于材料的物性影 响大， 造成冲击性能降低。
对比例 2
本对比例是在对比例 1的研究基础上进一步研究 PE0树脂的相对分子量对本发明的 电镀 PC/ABS合金材料性能的影响；本对比例的组分及制备方法同实施例 3，所不同之处 在于， 采用的 PE0树脂分别为韩国湖南石化的 PEG-6000 (其数均相对分子量为 6, 000 g/mol ) 和 PEG-30000 (其数均相对分子量为 30, 000 g/mol ) 同样采用实施例 7的方法 对制得的 PC/ABS合金材料进行性能测试， 结果如下表 4:
表 4
对比例 2
实施例 3
(PEG6000) (PEG-30000) 接触角 65. 4 70 68 粗化时间 11 13 13 电镀结合力 (N/cm) 9. 8 4. 0 3. 2 由表 4可知， 实施例 3的 PC/ABS合金材料的易电镀性能最佳； 这是由于 PE0分子 量在 10000〜20000，对于 PC/ABS接触角的降低最明显，从而使得 PC/ABS合金材料达到 易电镀的性能。
对比例 3
本对比例的目的是在对比例 1、 2的研究基础上进一步研究 ABS树脂中丁二烯含量 对本发明的电镀 PC/ABS合金材料性能的影响；本对比例是在实施例 3的基础上调整 ABS 树脂中丁二烯的重量百分比含量分别为 20%、 30%、 45%、 50%、 55%、 60%, 并采用实施例 7的方法对制得的 PC/ABS合金材料进行性能测试， 结果如下表 5 :
表 5
Figure imgf000008_0001
由表 5可知， ABS树脂中丁二烯含量为 20%， PE0的加入对于冲击影响大， 丁二烯含 量为 60%时， 粗化易过度， 造成结合力下降； 也就是说， 在本发明中 ABS树脂中丁二烯 含量范围为 30〜55%。 同时， ABS树脂中丁二烯含量为 45〜55%时， PC/ABS合金材料冲 击性能表现优异。
对比例 4、 5
本对比例 4、 5的目的是在对比例 1、 2、 3的研究基础上进一步研究 PC树脂与 PE0 树脂的复配作用对本发明的电镀 PC/ABS合金材料性能的影响；本对比例 4是在实施例 3 的基础上调整 PC树脂为韩国 LG-D0W的 PC201-22 (相对数均分子量为 20, 000 g/mol,玻 璃化转变温度为 140°C，该树脂是采用酯交换方法制备而得的； 对比例 5采用的 PC树脂 同实施例 3， 是光气法合成的 PC树脂， 不同之处在于， PC树脂的用量分别为 20、 25、 65、 70重量份。 同样采用实施例 7的方法对制得的 PC/ABS合金材料进行性能测试， 结 果如下表 6 :
表 6
对比例 5 ( PC用量）
实施例 3 对比例 4
20 25 65 70 接触角 65. 4 65. 4 64. 2 64. 4 66. 2 68 粗化时间 11 11 11 11 11 11 电镀结合力 (N/cm) 9. 8 6 3 4 2 1. 5 由表 6可知，对比例 4采用非光气法的 PC树脂， 其热稳定性低于实施例 3， 从而影 响电鍍 PC/ABS合金材料的电镀结合力。对比例 5制得的 PC/ABS合金材料的电镀性能远 低于实施例 3, PC份数高于 65份时， 出现明显漏镀现象， 说明 PC树脂与 PE0树脂以及 其他组分之间存在合适的配比关系， 在该配比下， 各组分能够发挥最佳协同作用， 从而 实现全面提升本发明的 PC/ABS合金材料的电镀效果。
综上所述， 本发明的方法简单易行， 通过使用光气法合成的 PC, 通过添加合适比例 的 ABS， 提高了材料的冲击性能， 减少了 PE0的吸湿性对于材料性能的影响； 通过选择 合适分子量的 PE0， 吸湿性低， 明显降低 PC/ABS接触角， 改善表面亲水性。 由于 PE0 树脂是亲水性的， 可以降低 PC/ABS表面的接触角， 使得粗化液更好的铺展， 让粗化变 得容易； 同时， PE0树脂表面含有大量的羟基， 可以和金属镀层很好的结合， 通过化学 键结合的方式更好的提高镀层结合力； 两种作用相结合实现了提高本发明的 PC/ABS合 金材料的电镀效果。
以上对本发明的具体实施例进行了描述。 需要理解的是， 本发明并不局限于上述特 定实施方式， 本领域技术人员可以在权利要求的范围内做出各种变形或修改， 这并不影 响本发明的实质内容。

Claims

权 利 要 求 书
1、 一种易电镀的电镀 PC/ABS合金材料， 其特征在于， 包含具有以下重量份的各组 分：
PC树脂 30〜60份，
ABS树脂 15〜55份，
PE0树脂 5〜10份，
抗氧剂 0. 1〜1份，
润滑剂 0. 1〜1份。
2、 根据权利要求 1所述的易电镀的电镀 PC/ABS合金材料， 其特征在于， 所述 PC 树脂的相对分子量为 17000〜30000g/mol， 其玻璃化温度为 140〜150°C。
3、 根据权利要求 1所述的易电镀的电镀 PC/ABS合金材料， 其特征在于， 所述 PC 树脂为光气法合成的 PC树脂。
4、 根据权利要求 1所述的易电镀的电镀 PC/ABS合金材料， 其特征在于， 所述 ABS 树脂为丙烯腈-丁二烯-苯乙烯组成的接枝共聚物， 所述 ABS 树脂的相对分子量为 100000〜 180000 g/mol , 其中丁二烯重量百分比含量为 30〜55%， 丙烯腈重量百分比含 量为 15〜32%， 苯乙烯重量百分比含量为 30〜60%。
5、 根据权利要求 1所述的易电镀的电镀 PC/ABS合金材料， 其特征在于， 所述 PE0 树脂的相对分子量为 10000〜20000。
6、 根据权利要求 1所述的易电镀的电镀 PC/ABS合金材料， 其特征在于， 所述抗氧 剂为二縮三乙二醇双 [ β _ (3-叔丁基 -4-羟基 -5-甲基苯基)丙酸酯]、 四 [ β _ (3， 5-二叔 丁基 4-羟基苯基)丙酸]季戊四醇酯、 三 (2， 4-二叔丁基苯基)亚磷酸酯、 双十八烷基醇 季戊四醇二亚磷酸酯中的一种或几种的混合。
7、 根据权利要求 1所述的易电镀的电镀 PC/ABS合金材料， 其特征在于， 所述润滑 剂为硅烷聚合物、 固体石蜡、 液体石蜡、 脂肪酸盐、 硬脂酸钙脂肪酸酰胺、 硬脂酸钙、 硬脂酸锌、 硬脂酸酰胺中的一种或几种的混合。
8、 根据权利要求 7所述的易电镀的电镀 PC/ABS合金材料， 其特征在于， 所述硬脂 酸酰胺为甲撑双硬脂酸酰胺和 N， N-乙撑双硬脂酸酰胺中的一种或两种。
9、 一种制备权利要求 1所述易电镀的电镀 PC/ABS合金材料的方法， 其特征在于， 包括如下步骤：
a、 将所述 PC树脂、 ABS树脂、 PE0树脂、 抗氧剂和润滑剂加入混合搅拌机中进行 混合；
b、 将步骤 a所得混合物通过双螺杆挤出机共混造粒， 得到易电镀的电镀 PC/ABS合 金粒子。
10、 根据权利要求 9所述的制备方法， 其特征在于， 所述双螺杆挤出机的机筒温度 为 200〜260°C， 螺杆转速为 200〜600rpm。
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