Matt ASA material and preparation method thereof

Abstract

The invention relates to the technical field of matte ASA material processing, and discloses a matte ASA material and a preparation method thereof, the matte ASA resin comprises, by mass, 66.7-89.5 parts of styrene-acrylonitrile resin, 10-30 parts of an ASA graft copolymer, 0.5-3 parts of a matte auxiliary agent, and 0.05-0.3 part of an antioxidant. The preparation method comprises the following steps: mixing the raw materials, and carrying out twin-screw extrusion granulation. According to the technical scheme, the glossiness of the resin is reduced by introducing the matte additive, so that the problem that the toughness of the material is reduced while the glossiness is reduced by adopting BMAT and filler traditionally is avoided; besides, the ASA rubber powder is effectively dispersed by adopting a strong shearing screw combination, so that the phenomenon that the color and luster are not uniform during injection molding of a material produced by common shearing is avoided; the matte ASA material prepared by the method has low glossiness, soft surface gloss, small influence on mechanical properties, especially toughness, simple preparation method and low cost.

Description

Technical Field

[0001] The invention relates to the technical field of matte ASA material modification, and in particular to a matte ASA material and a preparation method thereof. Background Art

[0002] ASA material is a ternary polymer composed of acrylonitrile, styrene and acrylic rubber. The structure and performance of ASA material are similar to those of acrylonitrile-butadiene-styrene (ABS), and it retains the excellent mechanical and physical properties of ABS as an engineering plastic. Because acrylate does not contain the unsaturated C=C structural characteristics of polybutadiene rubber, ASA has very outstanding weather resistance. According to test results, its weather resistance is about 10 times that of ABS material; and ASA material also has excellent mechanical properties and molding processing performance.

[0003] For the sake of driving safety, the selection and design of car interiors must pay attention to the reflective effect of the surface, minimize glare, and prevent the dashboard from forming a reflected image on the front windshield, which interferes with the driver's vision. Therefore, the surface of the dashboard must be matte or matte treated to obtain a comfortable and safe driving experience. Therefore, for car interior materials, the material is required to have matte or low gloss properties.

[0004] At present, there are several methods in the field to reduce the surface gloss of ABS: one is to add SBS resin with low gloss; the second is to add mineral fillers; the third is to add incompatible components, such as cross-linked styrene-acrylonitrile powder. Although the above methods can also reduce the gloss when used in ASA, some methods are more expensive, some methods reduce the toughness of the material, and some methods have low surface gloss but lack a comfortable and soft surface effect. Therefore, the development of a new type of matte ASA material and its preparation method is of great significance in the industry. Summary of the invention

[0005] The present invention aims to provide a matte ASA material and a preparation method thereof, so as to solve the problem in the prior art that the toughness and comfort of the material cannot be taken into account when reducing the surface gloss of the ASA material.

[0006] To achieve the above purpose, the present invention adopts the following technical scheme: a matte ASA material, calculated by mass, includes 68-89.5 parts of styrene-acrylonitrile resin, 10-30 parts of ASA graft copolymer, 0.5-2 parts of matte additive, and 0.05-0.3 parts of antioxidant.

[0007] Preferably, as an improvement, the melt index of the styrene-acrylonitrile resin at 220° C. and 10 kg is 10-50 g / 10 min.

[0008] Preferably, as an improvement, the ASA graft copolymer is a ternary graft copolymer with butyl acrylate rubber as the core and styrene-acrylonitrile as the shell.

[0009] Preferably, as an improvement, the rubber content of the ASA graft copolymer is 40-60 wt%.

[0010] Preferably, as an improvement, the matte auxiliary agent is one or more of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer or tetrapolymer, polymethylsilsesquioxane spherical silicone resin, and cross-linked high molecular weight methyl methacrylate copolymer.

[0011] Preferably, as an improvement, the antioxidant is one or more of hindered phenol antioxidants, phosphite antioxidants, and thioester antioxidants.

[0012] Preferably, as an improvement, a method for preparing a matte ASA material is provided, wherein the raw materials are mixed and then granulated by twin-screw extrusion, and the screw combination is a strong shear combination.

[0013] Preferably, as an improvement, the extrusion conditions of the twin-screw are: screw diameter 40 mm, main engine speed 300-600 rpm, main engine current 40-50 A, vacuum degree > 0.06, processing temperature 220-240° C., and feeding section temperature 60-80° C.

[0014] The principle and advantage of this scheme are: in practical application, in this technical scheme, the components and preparation process of matte ASA resin are optimized as a whole in view of the problem that the gloss and material mechanical properties (toughness) cannot be taken into account in the preparation of matte ASA materials in the prior art. In the existing technical reports, traditional ABS materials are mostly treated with BMAT (cross-linked styrene-acrylonitrile) to reduce their gloss, but the surface gloss is stiff and not soft, and the toughness of the material is reduced; in addition, the method of using fillers to reduce gloss is inefficient, and the amount of fillers added is large, which also has a great negative impact on the toughness of the material; in addition, there are attempts to use SBS treatment in the prior art, but its cost is high, and because it contains butadiene double bonds, its weather resistance is poor. Based on this, this scheme reduces the gloss of the resin by introducing a matte additive, avoiding the problem that the traditional use of BMAT and fillers to reduce gloss while reducing material toughness, and can take into account gloss and material mechanical properties. With regard to the preparation process, the present invention uses a strong shear screw combination to effectively disperse the ASA rubber powder, avoiding the uneven color phenomenon of injection molding of materials produced by ordinary shearing methods. In addition, the present technical solution creatively uses two different particle sizes of ASA rubber powder (graft copolymer) for treatment, and the results show that it has a more prominent effect compared with the single particle size treatment method. In the process of preparing ASA materials, the use of transparent AS and rubber powder to prepare ASA materials is prone to pearlescent phenomenon, which is manifested as uneven color on a macro scale. The use of strong shearing method with different particle size rubber powders can effectively solve the pearlescent phenomenon generated when transparent materials and rubber powder are blended.

[0015] Through testing, it is found that the matte ASA material prepared by this method has low gloss, soft surface gloss, and little effect on mechanical properties, especially toughness. The preparation method is simple and the cost is low, which is very suitable for promotion and application in the industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a microscopic observation picture of the material of Example 1 of the present invention (magnified 100 times).

[0017] Figure 2 This is a microscopic observation picture of the material of Example 2 of the present invention (magnified 100 times).

[0018] Figure 3 This is a microscopic observation picture of the material of Comparative Example 2 of the present invention (magnified 100 times).

[0019] Figure 4 This is a microscopic observation picture of the material of comparative example 3 of the present invention (magnified 100 times). DETAILED DESCRIPTION

[0020] The following is further described in detail through specific implementations, but the implementation of the present invention is not limited thereto. Unless otherwise specified, the technical means used in the following implementations are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; the materials, reagents, etc. used can all be obtained from commercial channels.

[0021] Program Overview

[0022] A matte ASA material comprises, by weight, 68-89.5 parts of styrene-acrylonitrile resin, 10-30 parts of ASA graft copolymer, 0.5-2 parts of matte auxiliary agent and 0.05-0.3 parts of antioxidant.

[0023] Among them, the melt index of styrene-acrylonitrile (St-AN) resin at 220°C and 10kg is 10-50g / 10min.

[0024] ASA graft copolymer (ASA rubber powder) is a ternary graft copolymer with butyl acrylate rubber (PBA) as the core and styrene-acrylonitrile (St-AN) as the shell, and the ASA graft copolymer has a high rubber content of 40wt-60wt%.

[0025] The matte additive is one or more of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer or tetrapolymer, polymethylsilsesquioxane spherical silicone resin, and cross-linked high molecular weight methyl methacrylate copolymer.

[0026] The antioxidant is one or more of hindered phenol antioxidants, phosphite antioxidants, and thioester antioxidants.

[0027] A method for preparing a matte ASA material comprises the following steps: uniformly mixing various components according to a proportion, extruding and granulating through a twin-screw, wherein the screws adopt a strong shear combination to obtain the matte ASA material.

[0028] In this embodiment, the strong shear combination of the screw is: feeding port, 48×3, 32, 22×2, K48×30°, 22, K32×45°, K22×60°, K22×60°, 22, K32×45°, K22×60°, 32, K32×90°, 11L, 48×3, 32, 22, K32×90°, K22×60°, 22, K32×45°, K22×60°, 22, K32×45°L, 22, K32×45°, K22×60°, 22, K32×90°, 11L, 48×4, 32×4, 22×3, and screw head.

[0029] Example 1

[0030] A matte ASA material comprises, by weight, 75 parts of styrene-acrylonitrile resin, 25 parts of ASA graft copolymer, 1 part of matte auxiliary agent and 0.2 part of antioxidant.

[0031] The melt index of styrene-acrylonitrile (St-AN) resin at 220° C. and 10 kg is 10 g / 10 min.

[0032] The ASA graft copolymer (ASA rubber powder) is a ternary graft copolymer with butyl acrylate rubber (PBA) as the core and styrene-acrylonitrile (St-AN) as the shell, and the ASA graft copolymer has a high rubber content, and the rubber content is 60wt%.

[0033] The matte additive is a terpolymer of ethylene-acrylate-glycidyl methacrylate.

[0034] The antioxidant is a hindered phenol antioxidant.

[0035] A method for preparing a matte ASA material comprises the following steps: uniformly mixing various components according to a proportion, extruding and granulating through a twin-screw, wherein the screws adopt a strong shear combination to obtain the matte ASA material.

[0036] In this embodiment, the strong shear combination of the screw is: feeding port, 48×3, 32, 22×2, K48×30°, 22, K32×45°, K22×60°, K22×60°, 22, K32×45°, K22×60°, 32, K32×90°, 11L, 48×3, 32, 22, K32×90°, K22×60°, 22, K32×45°, K22×60°, 22, K32×45°L, 22, K32×45°, K22×60°, 22, K32×90°, 11L, 48×4, 32×4, 22×3, and screw head.

[0037] Example 2

[0038] A matte ASA material comprises, by weight, 75 parts of styrene-acrylonitrile resin, 25 parts of ASA graft copolymer, 2 parts of matte auxiliary agent and 0.2 parts of antioxidant.

[0039] The melt index of styrene-acrylonitrile (St-AN) resin at 220° C. and 10 kg is 10 g / 10 min.

[0040] The ASA graft copolymer (ASA rubber powder) is a ternary graft copolymer with butyl acrylate rubber (PBA) as the core and styrene-acrylonitrile (St-AN) as the shell, and the ASA graft copolymer has a high rubber content, and the rubber content is 60wt%.

[0041] The matte additive is polymethylsilsesquioxane (PMSQ) spherical silicone resin.

[0042] The antioxidant is a hindered phenol antioxidant.

[0043] A method for preparing a matte ASA material comprises the following steps: uniformly mixing various components according to a proportion, extruding and granulating through a twin-screw, wherein the screws adopt a strong shear combination to obtain the matte ASA material.

[0044] In this embodiment, the strong shear combination of the screw is: feeding port, 48×3, 32, 22×2, K48×30°, 22, K32×45°, K22×60°, K22×60°, 22, K32×45°, K22×60°, 32, K32×90°, 11L, 48×3, 32, 22, K32×90°, K22×60°, 22, K32×45°, K22×60°, 22, K32×45°L, 22, K32×45°, K22×60°, 22, K32×90°, 11L, 48×4, 32×4, 22×3, and screw head.

[0045] Examples 1-7 are examples of the present invention, and comparative examples 1-4 are comparative examples of the present invention. The difference between each example and the comparative example is the composition and addition amount of the raw materials. The specific design is detailed in Table 1, where " / " means no addition; the particle size of ASA rubber powder 1 is 112μm; the particle size of ASA rubber powder 2 is 60μm. SAN 3027 is styrene-acrylonitrile resin; ASA rubber powder 1 and ASA rubber powder 2 are both ASA graft copolymers; BMAT is a cross-linked styrene-acrylonitrile polymer; RAS-302 is a compatibilizer; AX 8900, SL-200M, and BS110 are all matte additives; 1076 is antioxidant 1076.

[0046] Table 1

[0047]

[0048] Experimental Example 1 Glossiness and Mechanical Properties Testing

[0049] The glossiness and mechanical properties of the matte ASA materials prepared in the above embodiments and comparative examples were tested, and the test indicators and test methods are as follows:

[0050] 1. Glossiness test: Use a handheld gloss meter to measure the glossiness of the material at 60°, measured in accordance with JIS-Z-8741.

[0051] 2. Mechanical properties testing: Test the tensile strength according to ISO 527 and the notched impact strength according to ISO 180.

[0052] The experiment was repeated three times for each group, and the results are shown in Table 2.

[0053] Table 2

[0054]

[0055]

[0056] It can be seen from Table 2 that when the technical solution of the present invention is adopted, the glossiness of the obtained ASA material is reduced to varying degrees compared with Comparative Example 1, and has a comfortable and soft surface effect; although Comparative Example 2 has low glossiness, its surface effect is not good, and the toughness is reduced; Comparative Example 4 has low glossiness, but the toughness is greatly reduced. From Examples 1, 4, and 5, AX8900 can effectively reduce the glossiness of the system. From Examples 1 and 6, compounding high-rubber powder can also reduce the glossiness of the material. From Examples 2, 4, and 7, compounding matte additives can further reduce the glossiness of the material.

[0057] Experimental Example 2 Microscopic Observation

[0058] The materials prepared in Examples 1-2 and Comparative Examples 2-3 of the present invention were observed under a microscope. Figure 1-4 As shown, it can be seen from the results that the surface of the comparative example presents a large gully-like structure, while the surface of this embodiment is a uniform and dense structure.

[0059] The above is only an embodiment of the present invention, and the common knowledge such as the known specific technical solutions and / or characteristics in the solution is not described in detail here. It should be pointed out that for those skilled in the art, without departing from the technical solution of the present invention, several modifications and improvements can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicality of the patent. The scope of protection required by this application shall be based on the content of its claims, and the specific implementation methods and other records in the specification can be used to interpret the content of the claims.

Claims

1. A matte ASA material, characterized by: Calculated by weight, the composition comprises 66.7-89.5 parts of styrene-acrylonitrile resin, 10-30 parts of ASA graft copolymer, 0.5-3 parts of matte additive and 0.05-0.3 parts of antioxidant.

2. A matte ASA material according to claim 1, characterized in that: The melt index of the styrene-acrylonitrile resin at 220° C. and 10 kg is 10-50 g / 10 min.

3. A matte ASA material according to claim 2, characterized in that: The ASA graft copolymer is a ternary graft copolymer with butyl acrylate rubber as the core and styrene-acrylonitrile as the shell.

4. A matte ASA material according to claim 3, characterized in that: The rubber content of the ASA graft copolymer is 40-60 wt %.

5. A matte ASA material according to claim 4, characterized in that: The matte additive is one or more of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer or tetrapolymer, polymethylsilsesquioxane spherical silicone resin, and cross-linked high molecular weight methyl methacrylate copolymer.

6. A matte ASA material according to claim 5, characterized in that: The antioxidant is one or more of a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant.

7. A method for preparing a matte ASA material according to any one of claims 1 to 6, characterized in that: The raw materials are mixed and then granulated by twin-screw extrusion, and the screw combination is a strong shear combination.

8. The method for preparing a matte ASA material according to claim 7, characterized in that: The twin-screw extruder has a screw diameter of 40 mm, a main engine speed of 300-600 rpm, a main engine current of 40-50 A, a vacuum degree>0.06, a processing temperature of 220-240° C., and a feeding section temperature of 60-80° C.

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