Semi-transparent electroplated ABS material having high light transmittance, preparation method therefor, and use thereof

Abstract

The present invention relates to a semi-transparent electroplated ABS material having high light transmittance, a preparation method therefor, and a use thereof. The material comprises the following components in parts by weight: 25-35 parts of ABS high-rubber powder, 40-60 parts of MAS copolymer resin, 5-10 parts of transparent ABS resin, 5-10 parts of a dispersing agent, 0.1-0.4 parts of an antioxidant, and 0.1-0.3 parts of a lubricant. Compared with the existing technology, the electroplated ABS material prepared by the present invention has high light transmittance performance, and is suitable for electroplated articles having optical requirements.

Description

High-transmittance semi-permeable electroplating ABS material, preparation method and application thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and relates to a high-transmittance semi-permeable electroplating ABS material, a preparation method and application thereof. BACKGROUND

[0002] Nowadays, with the development of the new energy automobile market, consumers have put forward more demands for the personalization of automobiles on the premise of pursuing the functionality of automobiles. In automobile design, in addition to the appearance and color, some detailed decorative parts also play an important role, among which the light-emitting decorative part with a unique light design can improve the modernity, sense of technology and seniority of the vehicle, and increase the recognition and visual attraction.

[0003] The electroplated parts such as buttons and emblems can also achieve the light-emitting effect. After the electroplated material and the transparent material are double-injection molded, the electroplated layer is removed together with the electroplated material by laser engraving, the transparent material layer is exposed, and the light-emitting effect can be achieved after the lamp beads are added inside the part. However, on the one hand, the complex injection molding process limits the structure design of the part; on the other hand, the material layer with a thickness of 1-2 mm needs to be laser engraved at the same time, the laser energy is high and difficult to control, and if a complex pattern is laser engraved, the edge will be rough, affecting the clarity of the pattern, so the complex pattern design cannot be performed.

[0004] Xu Lu et al. mentioned in the document "Research Progress of Transparent ABS Resin" that there are two ways to make ABS resin transparent: one is to match the refractive indexes of the rubber dispersed phase and the base resin phase, reduce the light scattering effect to make the transparent ABS resin; the other is to make the rubber particle size smaller than the visible light wavelength, at which time the dispersed and continuous two phases are close to uniform in optics, and the ABS resin can also be transparent. In order to reduce the refractive index of the SAN resin phase, the refractive index of polymethyl methacrylate (1.492) and polybutyl acrylate (1.524) with lower refractive index can be introduced as refractive index adjusters for adjustment, and finally the refractive index difference between the two phases of the dispersed phase and the continuous phase is less than 0.009, and the ABS resin can be transparent.

[0005] However, reducing the size of the rubber phase in the electroplated ABS resin will reduce the toughness of the material, causing the risk of fracture of the electroplated part, and introducing excessive third phase (MMA) that cannot be coarsened will seriously reduce the coarsening performance of the electroplated material, resulting in insufficient coarsening and causing the electroplated part to be plated.

[0006] Therefore, it is necessary to develop an electroplated ABS material specially used for light-transmitting electroplated parts to meet the demand for light-transmitting electroplated materials in the market fields of automobiles, lighting products, household appliances and the like. SUMMARY

[0007] The present application aims at overcoming the defects of the prior art, and provides a semi-permeable electroplating ABS material with high light transmittance, and a preparation method and application thereof.

[0008] The object of the present application can be achieved by the following technical solutions.

[0009] In the first aspect, the present application provides a semi-permeable electroplating ABS material with high light transmittance, comprising the following raw material components in parts by weight:

[0010] Further, the content of butadiene in the ABS high rubber powder is 25-60wt%, and the number average molecular weight is 100-150 thousand.

[0011] Further, the ABS high rubber powder is ABS with a butadiene rubber content of more than 40%, and the crosslinking degree is 60-80wt%, and the particle size of the contained butadiene rubber is preferably 100-300nm, and more preferably 100-150nm.

[0012] Further, the transparent ABS resin has a refractive index of 1.51-1.54, a melt flow rate (under the condition of 220℃*10kg) of 10-20g / min, is grafted with MMA groups, and the grafting rate is 20-30%.

[0013] Further, the MAS copolymer resin is methyl methacrylate-styrene-acrylonitrile, and the proportion of MMA is 30-40wt%.

[0014] Further, the dispersing aid is one or more of maleic anhydride type graft copolymers containing styrene.

[0015] Further, the dispersing aid is one or a combination of styrene-g-maleic anhydride and styrene-acrylonitrile-g-maleic anhydride. Preferably, the content of maleic anhydride groups is 7-20wt%.

[0016] Further, the semi-permeable electroplating ABS material further comprises the following raw material components in parts by weight: antioxidant 0.1-0.4 parts; lubricant 0.1-0.3 parts.

[0017] Further, the antioxidant is one or several of polyphenol antioxidants and phosphate antioxidants.

[0018] Further, the lubricant is one or several of vinyl bis-stearamide and pentaerythritol stearate lubricants.

[0019] In the second aspect, the application provides a preparation method of a semi-permeable electroplating ABS material with high light transmittance, comprising the following steps:

[0020] (1) proportionally weigh each raw material component, mix uniformly to obtain a mixed raw material;

[0021] (2) add the mixed raw material into a double-screw extruder, control the rotating speed at 400-600 rpm, the feeding section temperature at 210-220℃, the plasticizing section temperature at 220℃-230℃, the extrusion temperature at 230-240℃, and the pressure at 2-4 MPa; after melt blending, the extruded strip is cooled in a water tank and then cut into particles to obtain the product.

[0022] In the third aspect, the application further provides an application of the semi-permeable electroplating ABS material with high light transmittance in a light-transmitting electroplating part.

[0023] Compared with the prior art, the application has the following advantages:

[0024] 1. The ABS material has excellent electroplating performance and high light transmittance, and is suitable for light-transmitting electroplating decorative strips of automobiles, lighting products and household appliances.

[0025] 2. The ABS resin used in the application has a low molecular weight and a crosslinking degree of 60-80%, which is helpful for the uniform dispersion of the rubber powder in the base material and the roughening of the rubber powder.

[0026] 3. The ABS resin used in the application is grafted with part of MMA groups, which reduces the comprehensive refractive index of the grafted ABS and makes the refractive index of the ABS closer to that of the MSA resin, thereby increasing the light transmittance and improving the compatibility of the ABS and the MSA.

[0027] 4. The maleic anhydride type graft copolymer containing styrene used in the application greatly improves the dispersion performance of the rubber powder, and the rubber powder is more easily roughened by the roughening liquid.

[0028] 5. The semi-permeable electroplating ABS material with high light transmittance has low cost and simple production process, and has high cost performance. DETAILED DESCRIPTION

[0029] The application will be described in detail below with specific examples. The examples are implemented on the premise of the technical solution of the application, and detailed implementation modes and specific operation processes are given, but the protection scope of the application is not limited to the examples below.

[0030] Raw materials used in the following examples and comparative examples:

[0031] ABS resin 1: P / D181, Korean Kumho Petrochemical Co., Ltd., containing butadiene rubber with a particle size of 370 nm; ABS resin 2: P / D192, Korean Kumho Petrochemical Co., Ltd., containing butadiene rubber with a particle size of 100 nm; ABS resin 3: WD132, Shandong Wanda Chemical Co., Ltd., containing butadiene rubber with a particle size of 300 nm; MAS resin: W1822, Donghai Plastic Industry Co., Ltd.; transparent aid (i.e. transparent ABS resin): PA758, Zhenjiang Qimei Chemical Co., Ltd.; dispersion aid 1: SMA1440, Crevillant (Guangzhou) Chemical Co., Ltd., styrene grafted maleic anhydride copolymer; dispersion aid 2: SAG001, Shanghai Rizhisheng Technology Co., Ltd., styrene-acrylonitrile-glycidyl methacrylate copolymer; hindered phenolic antioxidant: IG-1076, BASF SE; phosphoric acid ester antioxidant: Ultranox 626, Ciba Specialty Chemicals; lubricant: P861, Imerys Oleochemicals.

[0032] Table 1 Composition of semi-permeable electroplated ABS composition

[0033] Comparative examples 1-4 and examples 1-6

[0034] The ABS resin was dried at 90-100°C for 2-3h and then used; the MAS resin was dried at 90-100°C for 4-6h and then used.

[0035] 1) The ABS resin, MAS resin, transparent ABS resin, dispersion aid, antioxidant and lubricant were weighed according to the weight ratio in Table 1 and then mixed uniformly;

[0036] 2) The mixed raw materials of step 1) were blended and granulated by a twin-screw extruder, the rotation speed of the extruder was 600 rpm, the temperature of the feeding section was 210°C, the temperature of the plasticizing section was 230°C, the extrusion temperature was 245°C, the pressure was 3 MPa, after melt blending, the extruded strip was cooled in a water tank and then cut into particles to obtain the product.

[0037] The length-diameter ratio of the extruder screw used in the twin-screw extruder was 44:1.

[0038] The above product was dried in a blast oven at 85°C for 5 hours, and then injection molded into a standard light plate (150 mm*100 mm*3 mm) using a plastic injection molding machine at an injection temperature of 250°C.

[0039] The above standard light plate was roughened, with a roughening liquid temperature of 70°C and a roughening time of 10 min.

[0040] The above roughened standard light plate was electroplated, with a copper layer thickness of 21±1 μm and a chromium layer thickness of 15±1 μm.

[0041] The materials prepared in Comparative Example 1 and Examples 1-6 were subjected to performance testing, and the test results are shown in Table 2.

[0042] Transmittance test: The transmittance test was performed on the roughened 3.0 mm standard light plate according to the ASTM D1003-13 standard.

[0043] Electroplating adhesion test: The electroplated standard light plate was cut into a 10 mm*150 mm*3 mm sample according to the DIN EN 1464 standard, and the electroplating adhesion test was performed.

[0044] Heat resistance test: The electroplated standard light plate was placed in a 100°C oven for 6H for the heat resistance test according to the TL528 electroplated ABS heat resistance standard.

[0045] Cross-hatch performance after heat aging: The heat-aged standard light plate was subjected to the cross-hatch test, and the marks that did not fall off were marked as OK, and the marks that fell off were marked as NG.

[0046] Table 2 Performance of semi-transparent electroplated ABS

[0047] From the transmittance test results, it can be seen that in Comparative Examples 3 and 4 and Examples 1-6, which added transparent ABS resin, the transparency was higher than that of Comparative Examples 1-2, which did not add transparent ABS resin. In addition, in Examples 1-3, which added different amounts of ABS resin 2 under the same total glue amount, the higher the proportion of small particle size ABS resin 2, the higher the transparency. Among them, in Examples 3 and 5, which added different amounts of dispersing aids, the transparency of Example 5, which had a higher content of dispersing aids, was higher, indicating that the dispersing aid containing a maleic anhydride group (MAH) structure and the small particle size rubber powder had a synergistic effect on improving the transparency of the transparent ABS material.

[0048] From the results of the electroplating adhesion experiment, in Comparative Example 2 and Examples 1-6 with the addition of dispersing aids, the electroplating adhesion is higher than that of Comparative Examples 1 and 3 without the addition of dispersing aids; among Examples 3 and 5 with the addition of dispersing aids in different amounts, the higher the content of dispersing aids, the higher the electroplating adhesion; in addition, from Examples 1-3, it can be seen that the addition of ABS resin 2 reduces the average particle size of rubber in the material, and the smaller the particle size of rubber, the easier the material is to be roughened, and the higher the electroplating adhesion.

[0049] Comparative Example 4 is substantially the same as Example 5, except that a dispersing aid containing glycidyl methacrylate (GMA) is introduced, and the addition of the dispersing aid slightly improves the transparency of the material, but due to the lack of MAH structure, there is no synergistic effect, and the electroplating performance is poor, the adhesion is comparable to that of Comparative Example 3, and the cross-hatch test after heat aging is NG.

[0050] The roughening conditions are a roughening liquid temperature of 70°C and a roughening time of 10 min. In this roughening process, the rubber on the ABS resin is etched by the roughening liquid to produce dovetail hole structures of appropriate size. In the present application, the polar maleic anhydride groups in the dispersing aid containing MAH structure can interact with ABS having weak polarity, preventing the agglomeration and entanglement of ABS powder, allowing the powder to disperse more uniformly, and having a synergistic effect with small particle size rubber, further reducing the domain size of ABS island phase; on the one hand, the domain size is reduced to below the wavelength of visible light (880-380 nm), which affects the propagation of light, produces a diffraction effect, and allows light to partially bypass the powder, increasing the light transmittance or blurring the transparent feeling in visual effect; on the other hand, the specific surface area increases after the domain size is reduced, making it easier to be etched by the roughening liquid, forming more hollow structures, reducing the reduction of the roughening performance of MMA, and increasing the electroplating adhesion of the material.

[0051] In addition, the transmittance, electroplating performance, and heat resistance of Examples 5 and 6 are comparable, indicating that the addition or non-addition of processing aids has no effect on the transmittance, electroplating performance, and heat resistance of the material.

[0052] The above description of the examples is to facilitate the understanding and use of the invention by those skilled in the art. Those skilled in the art can easily make various modifications to these examples, and apply the general principles described herein to other examples without having to undergo creative labor. Therefore, the present application is not limited to the above examples, and improvements and modifications made by those skilled in the art without departing from the scope of the present application should be within the scope of protection of the present application.

Claims

1. A semi-permeable electroplating ABS material with high light transmittance, characterized in that, The raw material components include the following parts by weight:

2. The semi-permeable electroplating ABS material with high light transmittance according to claim 1, characterized in that, The ABS high glue powder has a butadiene content of 25-60wt%, and a weight average molecular weight of 100-150 thousand; The ABS high glue powder is ABS with a butadiene rubber content of more than 40%, a crosslinking degree of 60-80%, and butadiene rubber particles with a size of 100-300nm.

3. The semi-permeable electroplating ABS material with high light transmittance according to claim 1, characterized in that, The transparent ABS resin has a refractive index of 1.51-1.54, a melt flow rate of 10-20g / min, is grafted with MMA groups, and has a grafting rate of 20-30%.

4. The semi-permeable electroplating ABS material with high light transmittance according to claim 1, characterized in that, The MAS copolymer resin is methyl methacrylate-styrene-acrylonitrile, wherein the proportion of MMA is 30-40wt%.

5. The semi-permeable electroplating ABS material with high light transmittance according to claim 1, characterized in that, The dispersing aid is one or more of styrene-containing maleic anhydride type graft copolymers.

6. The semi-permeable electroplating ABS material with high light transmittance according to claim 5, characterized in that, The dispersing aid is a combination of one or both of styrene-g-maleic anhydride and styrene-acrylonitrile-g-maleic anhydride.

7. The semi-permeable electroplating ABS material with high light transmittance according to claim 1, characterized in that, The following raw material components are also included: Antioxidant 0.1-0.4 parts; Lubricant 0.1-0.3 parts.

8. The semi-permeable electroplating ABS material with high light transmittance according to claim 7, characterized in that, The antioxidant is one or more of polyphenol antioxidants and phosphate antioxidants; The lubricant is one or more of vinyl bis-stearamide and pentaerythritol stearate lubricants.

9. The method for preparing a high-transmittance semi-transparent electroplated ABS material as described in any one of claims 1-8, characterized in that, The following steps are included: (1) Weighing each raw material component according to the weight ratio, mixing uniformly to obtain a mixed raw material; (2) Adding the mixed raw material into a double-screw extruder, controlling the rotation speed at 400-600rpm, the feeding section temperature at 210-220℃, the plasticizing section temperature at 220-230℃, the extrusion temperature at 230-240℃, the pressure at 2-4MPa, and after melt blending, the extruded strip is cooled in a water tank and then cut into particles to obtain the product.

10. Use of the high-transparency semi-permeable electroplating ABS material of any one of claims 1-8 in a light-transmitting electroplated part.

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