ASA composite material and preparation method thereof as well as plastic decoration plate and preparation method thereof

Abstract

The invention relates to the technical field of injection molding, in particular to an ASA composite material and a preparation method thereof as well as a plastic decoration plate and a preparation method thereof, and the ASA composite material comprises the following components in percentage by weight: 80-85% of ASA resin, 8-10% of a flow promoter, 3-5% of a plasticizer, 1-3% of a stabilizer, 1-3% of a surface modifier and 1-2% of a lubricant; according to the ASA composite material, the flow promoter is added into the ASA resin, so that interaction force and entanglement among molecular chains can be weakened, and a lubricating layer is formed in a melt; meanwhile, the plasticizer is added, so that the combination of the ASA resin and the flow promoter is promoted, and the good toughness of the product is also ensured; and additives such as the stabilizer and the surface modifier are added to ensure the processing stability and synergistically improve the fluidity of the resin. According to the ASA composite material disclosed by the invention, the fluidity of ASA resin is remarkably improved, so that the resin can better infiltrate a mold, and the appearance problems of gas marks and fogging are avoided.

Description

Technical Field

[0001] This application relates to the field of injection molding technology, specifically to an ASA composite material and its preparation method.

[0002] This application also relates to plastic decorative panels and methods for preparing the same. Background Technology

[0003] ASA (acrylonitrile-styrene-acrylate) material is widely used in the injection molding field due to its good weather resistance, heat resistance and impact strength. For example, the Chinese invention patent with application number 202011367061.3 uses ASA material to injection mold household appliances and outdoor information equipment products.

[0004] However, ASA material has a low melt flow index (flowability) for injection molding, with an initial flowability of only about 5.1g / 10min to 6g / 10min. This insufficient flowability prevents gas from escaping from the mold cavity during injection molding of parts with air bubbles, resulting in surface air bubbles and fogging, affecting the product's aesthetics and quality. It also leads to incomplete material filling, affecting the product's integrity and performance, thus limiting its application in complex injection molded parts. Summary of the Invention

[0005] The technical problem to be solved by this application is to provide an ASA composite material and its preparation method that overcomes the appearance problems of air marks and fogging in products, and a plastic decorative panel and its preparation method.

[0006] To solve the above-mentioned technical problems, the technical solution adopted in this application is: an ASA composite material, which, by weight percentage, comprises the following components: 80%~85% ASA resin, 8%~10% flow aid, 3%~5% plasticizer, 1%~3% stabilizer, 1%~3% surface modifier and 1%~2% lubricant.

[0007] Furthermore, the molecular weight of ASA resin is 180,000~190,000 g / mol.

[0008] Furthermore, the flow aid is polyethylene glycol or silicone powder.

[0009] Furthermore, the plasticizer is dioctyl phthalate.

[0010] Furthermore, the stabilizer is antioxidant 1010.

[0011] Furthermore, the surface modifier is nano-silica or polyether-modified polydimethylsiloxane.

[0012] Furthermore, the lubricant is one or more of calcium stearate, zinc stearate, and barium stearate.

[0013] The second technical solution adopted in this application is: a method for preparing the above-mentioned ASA composite material, specifically including the following steps: S1: The components of the ASA composite material are mixed in proportion, then melt-extruded and granulated to obtain ASA injection molding granules; S2: Dry the ASA injection molding granules to obtain the ASA composite material.

[0014] Furthermore, the mixing temperature in S1 is 50~70℃, and the extrusion temperature of melt extrusion in S1 is 180~220℃.

[0015] The third technical solution adopted in this application is a method for preparing a plastic decorative panel, specifically: using the aforementioned ASA composite material, injection molding is performed under injection pressure of 130~160MPa and injection speed of 5~9mm / s to obtain a plastic decorative panel.

[0016] The fourth technical solution adopted in this application is to provide a plastic decorative panel, which is prepared by the aforementioned method for preparing plastic decorative panels.

[0017] The beneficial effects of this application are as follows: The ASA composite material of this application, by adding a flow aid to the ASA resin, can weaken the interaction forces and entanglement between molecular chains and form a lubricating layer in the melt; simultaneously, the addition of a plasticizer promotes the bonding between the ASA resin and the flow aid, and also ensures that the product has good toughness; the addition of stabilizers, surface modifiers, and other additives can ensure processing stability and synergistically improve resin flowability. The ASA composite material of this application significantly improves the flowability of ASA resin, allowing the resin to better wet the mold and avoiding appearance problems such as air bubbles and fogging. Attached Figure Description

[0018] Figure 1 A schematic diagram illustrating the appearance quality of the plastic decorative panel in the embodiments provided in this application; Figure 2 A schematic diagram illustrating the appearance quality of a comparative plastic decorative panel provided in this application. Detailed Implementation

[0019] To explain the technical content, objectives, and effects of this application in detail, the following description is provided in conjunction with the embodiments and accompanying drawings.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0021] This application provides an ASA composite material, which, by weight percentage, comprises the following components: 80%~85% ASA resin, 8%~10% flow aid, 3%~5% plasticizer, 1%~3% stabilizer, 1%~3% surface modifier, and 1%~2% lubricant.

[0022] As can be seen from the above description, the beneficial effects of this application are as follows: This application improves the fluidity of ASA material by adjusting the formulation of ASA material and adding a certain amount of flow aid, plasticizer, stabilizer and surface modifier to ASA resin, so that the melt can flow more smoothly and fill the mold during injection molding, avoiding the generation of surface air marks and fogging.

[0023] The polar groups of flow aids can interact with the molecular chains of ASA resin (styrene-acrylonitrile copolymer), weakening the interactions and entanglement between molecular chains; they can also form a lubricating layer in the melt, reducing frictional resistance between molecular chains, lowering shear force, and preventing melt fracture. Plasticizers can weaken the interactions between ASA resin molecular chains and ensure material toughness. Stabilizers can enhance processing stability and delay / prevent material aging and degradation. Surface modifiers can reduce the coefficient of friction.

[0024] Furthermore, the molecular weight of ASA resin is 180,000~190,000 g / mol.

[0025] As can be seen from the above description, flowability is strongly correlated with molecular weight. The larger the molecular weight, the weaker the flowability. Therefore, the molecular weight of ASA resin should be controlled at 180,000~190,000 g / mol.

[0026] Furthermore, the flow aid is polyethylene glycol or silicone powder.

[0027] As can be seen from the above description, polyethylene glycol or silicone powder is compatible with ASA, has high stability under high temperature processing conditions, and has a good effect on improving flowability.

[0028] Furthermore, the plasticizer is dioctyl phthalate.

[0029] Furthermore, the stabilizer is antioxidant 1010.

[0030] Furthermore, the surface modifier is nano-silica or polyether-modified polydimethylsiloxane.

[0031] As can be seen from the above description, nano-silica or polyether-modified polydimethylsiloxane has good compatibility with the ASA matrix and can also improve surface hardness, scratch resistance, weather resistance and other properties.

[0032] Furthermore, the lubricant is one or more of calcium stearate, zinc stearate, and barium stearate.

[0033] As can be seen from the above description, calcium stearate, zinc stearate, and barium stearate provide thermal stability and lubrication, which can reduce the friction between the melt and the mold and improve thermal stability.

[0034] Another technical solution adopted in this application is: the preparation method of the above-mentioned ASA composite material, which specifically includes the following steps: S1: Mix the components of the ASA composite material in proportion, then melt extrude and granulate to obtain ASA injection molding granules; S2: The ASA injection molding granules are dried to obtain the ASA composite material.

[0035] Furthermore, the mixing temperature in S1 is 50~70℃.

[0036] Furthermore, the mixing time in S1 is 5-10 minutes.

[0037] Furthermore, the extrusion temperature of melt extrusion in S1 is 180~220℃.

[0038] Furthermore, in S1, melt extrusion is carried out in a twin-screw extruder with a screw speed of 200~300 rpm.

[0039] Furthermore, the drying temperature in S1 is 80~100℃, and the drying time is 2~4h.

[0040] Another technical solution adopted in this application is: a method for preparing a plastic decorative panel, specifically: using the aforementioned ASA composite material, injection molding is performed under injection pressure of 130~160MPa and injection speed of 5~9mm / s to obtain a plastic decorative panel.

[0041] As can be seen from the above description, this application employs high injection pressure and low injection speed, ensuring that the air gap content of the plastic decorative panel prepared by the plastic method of this application is no higher than 1%. Figure 1 As shown in the figure, it can effectively improve the air mark problem on the surface of air mark products.

[0042] Another technical solution adopted in this application is: a plastic decorative panel prepared by the aforementioned method for preparing decorative panels.

[0043] Unless otherwise specified, the raw materials used in the following embodiments and comparative examples of this application are all obtained from commercial sources.

[0044] Examples 1-4 and Comparative Examples 1-8 each provide an ASA composite material, the composition and content of which are shown in Tables 1-2: Table 1

[0045] Table 2

[0046] The ASA composite materials in Examples 1-4 were prepared by the following steps: The components of the ASA composite material are mixed in proportion at 50~70℃. The uniformly mixed material is then fed into a twin-screw extruder. The extrusion temperature is set to 180-220℃ and the screw speed is set to 200-300 rpm for melt extrusion. The extruded melt is then granulated by an underwater pelletizer to obtain ASA injection molding granules.

[0047] The ASA injection molding granules are dried at a temperature of 80-100℃ for 2-4 hours.

[0048] The composite materials of Comparative Examples 1-8 can be prepared by referring to the above method.

[0049] As can be seen from the data in Tables 1 and 2, the molecular weight of ASA resin in Comparative Example 1 is too high, with a melt index of 14.5 g / 10 min, which is not conducive to improving fluidity. In Comparative Examples 2 and 3, the flow modifier was insufficient, and the melt index was 16.5 g / 10 min, which was not conducive to improving flowability. Comparative Example 4 lacked flow aids, with a melt index of 16 g / 10 min, which was not conducive to improving flowability.

[0050] In Comparative Examples 5 and 6, the molecular weight of ASA resin was too high and the flow modifier was insufficient, resulting in a melt index of 12 g / 10 min, which was not conducive to improving flowability.

[0051] Examples 1-4 and Comparative Examples 1-8 each provide a plastic decorative panel, the number of air bubbles of which is shown in Table 1 and Table 2; The plastic decorative panels are obtained by injection molding ASA composite material in an injection mold; As can be seen from Tables 1 and 2, comparative examples 1 to 6 have too low melt flow index, resulting in a plastic trim with ≥6% air bubbles, which cannot meet the requirement of ≤1% air bubbles.

[0052] In Comparative Examples 7 and 8, the injection pressure was too low and the injection speed too high during the injection molding process, resulting in a ≥5% number of air bubbles in the molded plastic decorative panels. This was detrimental to reducing air bubbles and could not meet the requirement of ≤1% air bubble count. Figure 2 The situation as shown.

[0053] I. Melt Flow Index Test: Determined in accordance with the test method provided by GB / T 3682.1-2018: Determination of melt mass-flow rate (MFR) and melt volume-flow rate (MVR) of thermoplastics; II. Detection of the number of air streaks: The detection of the proportion of air streaks on the plastic trim panel adopts the visual inspection method. The core requirement is that the proportion of the air streak coverage on the product appearance surface ≤ 1%; This detection shall be carried out in a standard environment with a light intensity of 800~1200 lx, no direct strong light, no shadow interference, and clean and dust-free. The inspectors shall have a naked eye vision ≥ 1.0 (or wear corrective glasses), no color blindness and color weakness qualifications, and be qualified after special training in defect identification. Auxiliary equipment includes a magnifying glass with a magnification of 5~10 times, a white dust-free cloth, and a marking pen. Before detection, first wipe the appearance surface of the plastic trim panel with a white dust-free cloth to remove interfering impurities such as dust and oil adhering to the surface; Subsequently, the inspector maintains an observation distance of 30~50 cm from the sample appearance surface and slowly rotates the sample at a 45° angle to comprehensively inspect the appearance surface, with a focus on high-incidence areas of air streaks such as around the injection molding gate and corners. The air streaks are defined as filamentous patterns, foggy traces, and tiny bubble tracks formed by incomplete discharge of gas during the injection molding process, and need to be clearly distinguished from other appearance defects such as scratches, sink marks, and color differences. Only air streaks with a length ≥ 0.5 mm, a width ≥ 0.1 mm, and clearly visible to the naked eye (or confirmed by a magnifying glass with a magnification of 5~10 times) are counted as valid air streaks; For suspected defects, further verification is carried out through a magnifying glass, and if necessary, cross-checking is performed by two or more qualified inspectors. Calculate the proportion of air streaks according to "total area of effective air streak coverage ÷ total area of the plastic trim panel appearance surface × 100%". When the proportion ≤ 1%, the detection is judged to be qualified; when the proportion > 1%, it is judged to be unqualified.

[0054] In summary, the formula of this application has a large melt index, good fluidity, excellent stability, and no problems such as precipitation. The formula of this application is combined with the molding process of high injection pressure and low injection speed, and finally the air streaks on the surface of the air streak parts are controlled within the proportion range of 0%~1%, making the product have good appearance quality. The melt index (fluidity) of the ASA injection molding plastic particles has been significantly improved from 5.1~6 g / 10 min of conventional materials to 18 g / 10 min~20 g / 10 min. At the same time, the method of this application also improves the processing performance and injection molding efficiency of the material, reduces the production cost, and has significant economic and social benefits.

[0055] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0056] The above-described embodiments are merely illustrative of several implementation methods of the present invention, facilitating a detailed understanding of the technical solutions of the present invention, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided by the present invention through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this invention patent should be determined by the content of the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. An ASA composite material, characterized in that, The ASA composite material comprises the following components by weight percentage: 80%~85% ASA resin, 8%~10% flow aid, 3%~5% plasticizer, 1%~3% stabilizer, 1%~3% surface modifier and 1%~2% lubricant.

2. The ASA composite material according to claim 1, characterized in that, The molecular weight of the ASA resin is 180,000~190,000 g / mol.

3. The ASA composite material according to claim 1, characterized in that, The flow aid is polyethylene glycol or silicone powder.

4. The ASA composite material according to claim 1, characterized in that, The plasticizer is dioctyl phthalate.

5. The ASA composite material according to claim 1, characterized in that, The stabilizer is antioxidant 1010.

6. The ASA composite material according to claim 1, characterized in that, The surface modifier is nano-silica or polyether-modified polydimethylsiloxane.

7. The ASA composite material according to claim 1, characterized in that, The lubricant is one or more of calcium stearate, zinc stearate, and barium stearate.

8. A method for preparing an ASA composite material, characterized in that, Specifically, the following steps are included: S1: Mix the components of the ASA composite material according to any one of claims 1 to 7 in proportion, and then melt extrude and granulate to obtain ASA injection molding granules; S2: Dry the ASA injection molding granules to obtain the ASA composite material.

9. The method for preparing the ASA composite material according to claim 8, characterized in that, The mixing temperature in S1 is 50~70℃, and the extrusion temperature of melt extrusion in S1 is 180~220℃.

10. A method for preparing a plastic decorative panel, characterized in that, Plastic decorative panels are obtained by injection molding using the ASA composite material described in any one of claims 1 to 7 under injection pressure of 130 to 160 MPa and injection speed of 5 to 9 mm / s.

11. A plastic decorative panel, characterized in that, The plastic decorative panel was prepared using the method described in claim 10.

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