A high-metallic-texture spray-free ABS / PMMA composite material and its preparation method and application

Abstract

The present invention discloses a high-metallic-texture spray-free ABS / PMMA composite material and its preparation method and application. The high-metallic-texture spray-free ABS / PMMA composite material comprises the following components calculated by weight: 30 to 70 parts of acrylonitrile-butadiene-styrene terpolymer; 5 to 30 parts of polymethyl methacrylate; 10 to 35 parts of toughening agent; 1 to 8 parts of dispersant; 1 to 8 parts of metallic pigment; 0.1 to 4.5 parts of auxiliary agent; the dispersant is ethylene-acrylic acid zinc ionomer. The present invention greatly improves the dispersibility of the metallic pigment by adding an appropriate amount of ethylene-acrylic acid zinc ionomer as a dispersant, so that the prepared ABS / PMMA composite material has a higher metallic texture and better notched impact strength.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer composite materials, and more specifically, relates to a high-metal texture spray-free ABS / PMMA composite material and a preparation method and application thereof. Background Art

[0002] After surface treatment, metal materials have unique aesthetic effects and excellent hand feel, and are usually used in high-end products by various home appliances, laptops, and mobile phone brands. Spray-free metal texture plastics achieve a metal-like appearance by directly adding metal effect pigments during the plastic granulation process. Spray-free metal texture plastics can be formed in one step, with simple processes and high yields. They are also environmentally friendly and energy-saving, recyclable and reusable, with good color durability and not easy to fade during transportation and use. Metal texture plastics are deeply loved by people because of their beautiful appearance and good visual texture effects.

[0003] The prior art CN 110016199 A discloses a spray-free material with a metallic texture, but it is found that the metallic texture is weak during use, and the L value in the Lab value is still not high at the same amount of metallic pigment added. Therefore, it is necessary to provide a high metallic texture spray-free composite material with a higher L value, that is, a higher metallic texture. Summary of the invention

[0004] The purpose of the present invention is to overcome the technical problems existing in the prior art and provide a high-metallic-texture spray-free ABS / PMMA composite material with a higher L value. The ABS / PMMA composite material has a higher metallic texture, a significantly improved metallic effect of the appearance, and better notched impact strength.

[0005] Another object of the present invention is to provide a method for preparing the high metallic texture spray-free ABS / PMMA composite material.

[0006] Another object of the present invention is to provide the use of the high metallic texture spray-free ABS / PMMA composite material in the preparation of household appliances, toys, and automotive materials.

[0007] To achieve the above object, the present invention is implemented through the following technical solutions:

[0008] A high-metallic-texture spray-free ABS / PMMA composite material, comprising the following components calculated in parts by weight:

[0009]

[0010]

[0011] The dispersant is ethylene-acrylic acid zinc ionomer.

[0012] The inventors have found through research that by using acrylonitrile-butadiene-styrene terpolymer (i.e., non-cross-linked ABS resin) and polymethyl methacrylate (PMMA) as raw materials and adding an appropriate amount of ethylene-zinc acrylate ionomer as a dispersant, the dispersibility of the metallic pigment is greatly improved, so that the prepared ABS / PMMA composite material has a higher L value and the metallic texture of the material is enhanced.

[0013] Furthermore, the high metallic texture spray-free ABS / PMMA composite material comprises the following components calculated in parts by weight:

[0014]

[0015] Preferably, the content of the acrylonitrile-butadiene-styrene terpolymer in the high metallic texture spray-free ABS / PMMA composite material is not less than 40wt%.

[0016] Furthermore, the viscosity of the dispersant is 1900 to 6000 cpc.

[0017] Furthermore, the viscosity of the dispersant is determined by 304-OR-1, which is a custom test standard provided by a manufacturer of ethylene-zinc acrylic acid ionomer.

[0018] Furthermore, the viscosity of the dispersant is measured at a temperature of 190°C.

[0019] Furthermore, the toughening agent is a core-shell structure, the core layer is a copolymer of butadiene and styrene, and the shell layer is a copolymer of methyl methacrylate and styrene.

[0020] Although the increase in the amount of toughening agent will increase the notched impact strength, the inventors found that when the amount of toughening agent increases, the L value of the ABS / PMMA composite material will decrease. More preferably, the amount of the toughening agent is 15 to 25 parts.

[0021] Furthermore, the melt mass flow rate of the acrylonitrile-butadiene-styrene terpolymer is 20 to 45 g / 10 min.

[0022] Furthermore, the test standard for the melt mass flow rate of the acrylonitrile-butadiene-styrene terpolymer is ISO 1133-1:2011.

[0023] Further, the melt mass flow rate of the acrylonitrile-butadiene-styrene terpolymer is tested at a temperature of 220° C. and a weight of 10 kg.

[0024] Furthermore, the polymethyl methacrylate is in powder form.

[0025] Furthermore, the melt mass flow rate of the polymethyl methacrylate is 10 to 25 g / 10 min.

[0026] Furthermore, the test standard for the melt mass flow rate of the polymethyl methacrylate is ISO 1133-1:2011.

[0027] Furthermore, the test temperature of the melt mass flow rate of the polymethyl methacrylate is 230° C., and the test weight is 3.8 kg.

[0028] Furthermore, the metallic pigment is one or more of aluminum powder, copper powder, gold powder or silver powder.

[0029] Furthermore, the average particle size of the metallic pigment is 25 to 100 μm.

[0030] Furthermore, the auxiliary agent is a lubricant and / or an antioxidant.

[0031] The present invention can select lubricants in the prior art, such as but not limited to one or more of stearic acid amide, polyolefin wax or ethylene bis stearamide.

[0032] The present invention can select antioxidants in the prior art, such as but not limited to one or more of hindered phenol antioxidants, phosphite antioxidants or thiodipropionic acid diester antioxidants.

[0033] Specifically, the hindered phenol antioxidant is one or more of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide (Irganox 1098), pentaerythritol tetrakis[1093,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010), triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Iragnox 259), β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate n-octadecyl (Iragno 1076) or spiroethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (ADK AO-80).

[0034] The phosphite antioxidant is one or more of 2,4-di-tert-butylphenol (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite (PEP-36) or 627A.

[0035] The thiodipropionic acid diester antioxidant is one or more of the thioether antioxidants distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol dodecapropylthioate.

[0036] The method for preparing the high metallic texture spray-free ABS / PMMA composite material comprises the following steps:

[0037] S1. The acrylonitrile-butadiene-styrene terpolymer, toughening agent, dispersant and additive are mixed in proportion to obtain a first mixture;

[0038] S2. The polymethyl methacrylate and the metallic pigment are mixed in proportion to obtain a second mixture;

[0039] S3. The first mixed material and the second mixed material are melt-blended, extruded and granulated to obtain a high-metallic-texture spray-free ABS / PMMA composite material.

[0040] Furthermore, in step S3, the equipment used for melt blending is a twin-screw extruder.

[0041] Furthermore, in step S3, the first mixed material is fed through a main feeding port, and the second mixed material is fed through a side feeding port.

[0042] Furthermore, in step S3, the temperature of the melt blending is 180-230°C.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] The invention provides a high-metal texture spray-free ABS / PMMA composite material. The terpolymer of acrylonitrile-butadiene-styrene and polymethyl methacrylate are used as raw materials, and an appropriate amount of ethylene-zinc acrylic acid ionomer is added as a dispersant to greatly improve the dispersibility of a metal pigment. The prepared ABS / PMMA composite material has a higher metal texture and good toughness. A suitable amount of a toughening agent can make the ABS / PMMA composite material have good toughness and good metal texture, so that the composite material has a higher L value under the same amount of metal pigment. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 Schematic diagram of the appearance and color of the composite materials prepared in Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0046] The present invention is further described in detail below in conjunction with specific examples, which are only used to explain the present invention and are not used to limit the scope of the present invention. The test methods used in the following examples are conventional methods unless otherwise specified; the materials and reagents used are reagents and materials that can be obtained from commercial channels unless otherwise specified.

[0047] The raw materials used in each embodiment and comparative example are:

[0048] Acrylonitrile-butadiene-styrene terpolymer: ABS GP-35, BASF, melt flow rate 34g / 10min; test standard ISO 1133-1-2011, test conditions 220℃, 10kg;

[0049] Polymethyl methacrylate: PMMALG2, Sumitomo Chemical, Japan, melt flow rate: 16g / 10min; test standard: ISO 1133-1-2011, test conditions: 220℃, 10kg;

[0050] Dispersant 1: Ethylene-acrylic acid zinc ionomer, AClyn 201A, Honeywell, viscosity 5500 cpc;

[0051] Dispersant 2: ethylene-acrylic acid zinc ionomer, AClyn 285P, Honeywell, viscosity 80,000 cpc;

[0052] Dispersant 3: Dispersogen 2774, nonionic polymeric dispersant, Clariant;

[0053] Dispersant 4: Ethylene-acrylic acid zinc ionomer, AC 1172, Honeywell, viscosity 1900 cpc;

[0054] The viscosity data of dispersants 1, 2, and 4 were provided by the manufacturer, and the determination method was the manufacturer's custom determination method 304-OR-1, and the test temperature was 190°C;

[0055] Toughener 1: EM500, LG Chemical Co., Ltd.; core-shell structure, with the core layer being a copolymer of butadiene and styrene, and the shell layer being a copolymer of methyl methacrylate and styrene

[0056] Toughener 2: HR181, Kumho Petrochemical Co., Ltd.; styrene-acrylonitrile-butadiene rubber, core-shell polymer

[0057] Metallic pigment 1: aluminum powder, ZP 34-20C, average particle size 34 μm, Eckart;

[0058] Metallic pigment 2: copper powder, DOROLAN 35 / 1, average particle size 35 μm, Eckart;

[0059] Antioxidant: pentaerythritol tetrakis[1093,5-di-tert-butyl-4-hydroxyphenyl)propionate, Beijing Jiyi Co., Ltd.;

[0060] Lubricant: Ethylene bisstearamide, Hebei Tianyu Chemical Co., Ltd.;

[0061] The same reagents were used in the parallel experiments of the embodiments and comparative examples of the present invention.

[0062] In Examples 1 to 15 and Comparative Examples 1 to 3, the high metallic texture spray-free ABS / PMMA composite material is prepared by the following method, comprising the following steps:

[0063] S1. The dried acrylonitrile-butadiene-styrene terpolymer, toughening agent, dispersant, lubricant and antioxidant are mixed in proportion to obtain a first mixture;

[0064] S2. The polymethyl methacrylate and the metallic pigment are mixed in proportion to obtain a second mixture;

[0065] S3. The first mixed material is fed through the main feeding port of the twin-screw extruder, and the second mixed material is fed through the side feeding port of the twin-screw extruder. The mixture is melt-blended, extruded, and granulated at 180-230° C., and dried to obtain a high metallic texture spray-free ABS / PMMA composite material.

[0066] The component contents of each example are shown in Tables 1 to 3.

[0067] Table 1 Formula of high metallic texture spray-free ABS / PMMA composite material in Examples 1 to 9 (unit: parts by weight)

[0068]

[0069] Table 2 Formula of high metallic texture spray-free ABS / PMMA composite material in Examples 10 to 15 (unit: parts by weight)

[0070]

[0071]

[0072] The component contents of each comparative example are shown in Table 3.

[0073] Table 3 Formula of high metallic texture spray-free ABS / PMMA composite material in Comparative Examples 1 to 3 (unit: weight parts)

[0074] Comparative Example 1 Comparative Example 2 Comparative Example 3 Acrylonitrile-butadiene-styrene terpolymer 70 60 60 Polymethyl methacrylate 15 15 15 Toughener 1 5 15 15 Dispersant 1 3.5 - - Dispersant 3 - - 3.5 Metallic Pigment 1 5 5 5 Antioxidants 0.5 0.5 0.5 Lubricants 1 1 1

[0075] Performance Testing:

[0076] The high metallic texture spray-free ABS / PMMA composite materials of the above embodiment and comparative example were subjected to performance tests, and the specific test methods are as follows:

[0077] L value: The L value of high metallic texture spray-free ABS / PMMA composite material is measured under D65 light source;

[0078] Notched impact strength: The high metallic texture spray-free ABS / PMMA composite material was measured according to standard ISO 180-2019.

[0079] The measurement results of Examples 1 to 15 and Comparative Examples 1 to 3 are shown in Table 4.

[0080] Table 4 Test results of Examples 1 to 15 and Comparative Examples 1 to 3

[0081] L value <![CDATA[Notched impact strength (KJ / m 2 )]]> Example 1 78.3 10.4 Example 2 76.6 15.3 Example 3 75.5 15.5 Example 4 72.4 15.8 Example 5 67.8 15.9 Example 6 64.5 13.2 Example 7 73.5 14.3 Example 8 76.8 15.5 Example 9 76.0 13.9 Example 10 72.5 13.3 Embodiment 11 69.8 14.1 Example 12 66.5 9.6 Example 13 74.2 16.5 Embodiment 14 71.7 15.1 Embodiment 15 67.5 12.7 Comparative Example 1 64.4 6.0 Comparative Example 2 56.2 12.6 Comparative Example 3 57.3 10.8

[0082] It can be seen from Table 4 that the high metallic texture spray-free ABS / PMMA composite material prepared by the present invention has a high metallic texture, an L value of not less than 66.5, and a good notched impact strength of not less than 9.6 kJ / m 2 .

[0083] It can be seen from Examples 1 to 9 that when the amount of toughening agent is 15 to 25 parts and the amount of dispersant is 1.5 to 5 parts, the comprehensive performance of the high metallic texture spray-free ABS / PMMA composite material obtained is better, with better metallic texture and notched impact strength, the L value is not less than 72.4, and the notched impact strength is not less than 14.3 kJ / m 2 .

[0084] By comparing Example 2 and Example 10, it can be seen that when the toughening agent is a core-shell structure, the core layer is a copolymer of butadiene and styrene, and the shell layer is a copolymer of methyl methacrylate and styrene, the comprehensive performance of the obtained high metallic texture spray-free ABS / PMMA composite material is better.

[0085] Comparing Example 2 and Example 11, it can be seen that when the viscosity of the dispersant is ethylene-zinc acrylate ionomer of 1900-6000 cpc, the obtained high metallic texture spray-free ABS / PMMA composite material has a higher L value and an improved metallic effect; when the viscosity of the ethylene-zinc acrylate ionomer is high, the dispersion effect decreases and the L value decreases significantly. Figure 1 (a is the composite material prepared in Example 1, b is the composite material prepared in Comparative Example 1) It can be seen that when the amount of toughening agent is too small, the L value of the obtained high metallic texture spray-free ABS / PMMA composite material is only 64.4, and the notched impact strength is significantly reduced to only 6 kJ / m 2 This is because the particle size of aluminum powder is large. As a filler, when the amount of aluminum powder added is large, if the amount of toughening agent is too small, the cantilever beam notched impact strength of the system will be greatly reduced.

[0086] It can be seen from Comparative Example 2 that when no dispersant is added to the system, the L value of the obtained high metallic texture spray-free ABS / PMMA composite material is only 56.2. This is because the dispersant can well disperse the aluminum powder in the system, forming a higher gloss and L value. At the same time, the dispersant is wrapped on the surface of the aluminum powder, so that the bonding strength between the aluminum powder and the substrate is better, thereby improving the notched impact strength of the material.

[0087] It can be seen from Comparative Example 3 that when Dispersogen 2774 is used as a dispersant, the aluminum powder cannot be effectively dispersed, and the obtained spray-free ABS / PMMA composite material has a low L value and a low impact strength.

[0088] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A high metallic texture spray-free ABS / PMMA composite material, It is characterized in that The composition comprises the following components calculated by weight: 30-70 parts of acrylonitrile-butadiene-styrene terpolymer; 5-30 parts of polymethyl methacrylate; 10 to 35 parts of toughening agent; 1 to 8 parts of dispersant; 1 to 8 parts of metallic pigment; 0.1 to 4.5 parts of additives; The dispersant is ethylene-acrylic acid zinc ionomer; The toughening agent is a core-shell structure, the core layer is a copolymer of butadiene and styrene, and the shell layer is a copolymer of methyl methacrylate and styrene, or the toughening agent is HR181, Kumho Petrochemical Co., Ltd.; The average particle size of the metal pigment is 25 to 100 μm.

2. According to claim 1, the high metallic texture spray-free ABS / PMMA composite material, It is characterized in that The composition comprises the following components calculated by weight: 30-70 parts of acrylonitrile-butadiene-styrene terpolymer; 5-30 parts of polymethyl methacrylate; 15-25 parts of toughening agent; Dispersant 1.5-5 parts; 3-6 parts of metallic pigment; 0.1 to 4.5 parts of additives.

3. The high metallic texture spray-free ABS / PMMA composite material according to claim 1, It is characterized in that The melt mass flow rate of the acrylonitrile-butadiene-styrene terpolymer is 20-45 g / 10 min, the test standard is ISO1133-1-2011, and the test conditions are 220° C. and 10 kg.

4. The high metallic texture spray-free ABS / PMMA composite material according to claim 1, It is characterized in that The melt mass flow rate of the polymethyl methacrylate is 10-25 g / 10 min, the test standard is ISO 1133-1-2011, and the test conditions are 220° C. and 10 kg.

5. The high metallic texture spray-free ABS / PMMA composite material according to claim 1, It is characterized in that The auxiliary agent is a lubricant and / or an antioxidant.

6. The method for preparing the high metallic texture spray-free ABS / PMMA composite material according to any one of claims 1 to 5, It is characterized in that The steps include: S1. The acrylonitrile-butadiene-styrene terpolymer, toughening agent, dispersant and additive are mixed in proportion to obtain a first mixture; S2. The polymethyl methacrylate and the metallic pigment are mixed in proportion to obtain a second mixture; S3. The first mixed material and the second mixed material are melt-blended, extruded and granulated to obtain a high-metallic-texture spray-free ABS / PMMA composite material.

7. The preparation method according to claim 6, It is characterized in that In S3, the first mixed material is fed through the main feeding port, and the second mixed material is fed through the side feeding port.

8. Use of the high metallic texture spray-free ABS / PMMA composite material according to any one of claims 1 to 6 in the preparation of household appliances, toys and automotive materials.

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