Low-gloss heat-resistant abs resin composition and its preparation method

Abstract

The present invention relates to a low-gloss heat-resistant ABS resin composition and its preparation method. The low-gloss heat-resistant ABS resin composition includes following components by weight: 100 parts of acrylonitrile-butadiene-styrene (ABS) resin, 5-30 parts of heat-resistant agent, 1-5 parts of matte masterbatch D, 0.2-1.0 parts of light stabilizer, and 0.5-2.0 parts of other additives. The preparation method includes steps of: stirring and fully mixing the above-mentioned raw materials in a high-speed mixer, and then feeding the raw materials into a twin-screw extruder through a metering device; melting and compounding the materials under the conveying, shearing and mixing of the screws, and then extruding, pulling, cooling and granulating, and finally obtaining the low-gloss heat-resistant ABS resin composition. The resin composition provided by the present invention not only has excellent mechanical properties, but also has an ultra-low gloss; therefore, it is very suitable for use in the field of automotive interior parts.

Claims

1. A low-gloss heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition, comprising following components in part by weight of: TABLE-US-00007 acrylonitrile-butadiene-styrene resin 100, heat-resistant agent   5-30, matte masterbatch D   1-5, light stabilizer 0.2-1.0, and additives 0.5-2.0.

2. The low-gloss heat-resistant ABS resin composition according to claim 1, wherein the ABS resin has a weight-average molecular weight of 80,000 to 150,000; a weight content of butadiene rubber in the ABS resin is 10-17%.

3. The low-gloss heat-resistant ABS resin composition according to claim 1, wherein the heat-resistant agent is N-phenylmaleimide-styrene-maleic anhydride copolymer or a-methylstyrene-acrylonitrile copolymer.

4. The low-gloss heat-resistant ABS resin composition according to claim 1, wherein the matte masterbatch D comprises processing aids and components by following weight percentages of: TABLE-US-00008 resin A containing maleic anhydride functional group  15-40%, resin B containing glycidyl methacrylate functional  20-50%, group polyolefin-alkyl acrylate copolymer C  20-60%, fumed silica   1-5%, and hydrated zinc borate 0.5-3%.

5. The low-gloss heat-resistant ABS resin composition according to claim 4, wherein the matte masterbatch D is obtained from a preparation method comprising following steps of: (S1) preparing materials according to the following components and contents of: TABLE-US-00009 the resin A containing maleic anhydride functional group  15-40%, the resin B containing glycidyl methacrylate functional  20-50%, group the polyolefin-alkyl acrylate copolymer C  20-60%, the fumed silica   1-5%, and the hydrated zinc borate 0.5-3%; and (S2) fully and uniformly mixing the resin A containing maleic anhydride functional group, the resin B containing glycidyl methacrylate functional group, the polyolefin-alkyl acrylate copolymer C, the fumed silica, the hydrated zinc borate and the processing aids, and then extruding and granulating through a twin-screw extruder, and finally obtaining the matte masterbatch D.

6. The low-gloss heat-resistant ABS resin composition according to claim 1, wherein the light stabilizer is at least one member selected from a group consisting of salicylate, benzophenone UV absorbent, triazine UV absorbent, benzotriazole UV absorbent and hindered amine radical scavenger.

7. The low-gloss heat-resistant ABS resin composition according to claim 1, wherein the additives are at least one member selected from a group consisting of silane coupling agent, titanate coupling agent, hindered phenolic antioxidant, phosphite antioxidant, ethylene bisstearamide, pentaerythritol stearate, magnesium stearate and calcium stearate.

8. A preparation method of the low-gloss heat-resistant ABS resin composition according to claim 1, comprising steps of: (S1) preparing materials according to the following components and parts by weight: 100 parts of the ABS resin, 5-30 parts of the heat-resistant agent, 1-5 parts of the matte masterbatch D, 0.2-1.0 parts of the light stabilizer and 0.5-2.0 parts of the additives; and (S2) stirring and mixing the ABS resin, the heat-resistant agent, the matte masterbatch D, the light stabilizer and the additives in a high-speed mixer, and then extruding and granulating through a twin-screw extruder, and finally obtaining the low-gloss heat-resistant ABS resin composition.

9. The preparation method of the low-gloss heat-resistant ABS resin composition according to claim 8, wherein in the step of (S2), the twin-screw extruder has a screw length-diameter ratio of 36-44; the twin-screw extruder comprises a temperature controlling device and a vacuum device.

10. The preparation method of the low-gloss heat-resistant ABS resin composition according to claim 8, wherein in the step of (S2), an extrusion temperature of the twin-screw extruder is 190-240° C., and a screw speed thereof is 200-500 rpm.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0035] The present invention is described in detail as follows with reference to specific embodiments. The following embodiments will be conductive to further understanding of the present invention for those skilled in the art, and not in any way limit the present invention. It should be noted that several variants and improvements can be made without departing from concept of the present invention for ordinary persons skilled in the art. All these fall within the protection scope of the present invention.

First Embodiment

[0036] The first embodiment relates to a low-gloss heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition and its preparation method, as described below.

[0037] 1. Preparation of matte masterbatch D (components and weight contents are shown in Table 1):

[0038] Stirring and fully mixing resin A containing maleic anhydride (MAH) functional group, resin B containing glycidyl methacrylate (GMA) functional group, polyolefin-alkyl acrylate copolymer C, fumed silica, hydrated zinc borate, as well as antioxidant B900 0.3 phr and lubricant EBS 1.0 phr in a high-speed mixer to obtain a mixture, feeding the mixture into a twin-screw extruder through a metering device; melting and compounding the mixture under conveying, shearing and mixing of screws, and then extruding, pulling, cooling and granulating, and finally obtaining matte masterbatches D1-D8 with uniform particle size.

[0039] A length-diameter ratio of the screws of the twin-screw extruder is 40; a temperature at a front section of the screws is 200-230° C.; a temperature at a middle section thereof is 240-260° C.; a head extrusion temperature is 250° C.; and a screw speed is 300 rpm.

TABLE-US-00004 TABLE 1 Preparation of Matte Masterbatch D Component/g D1 D2 D3 D4 D5 D6 D7 D8 A1 15 30 20 20 30 30 A2 40 B1 30 30 26 30 30 B2 50 50 C1 53.5 36 30 23 23 39 40 36 SiO.sub.2 1 3 2 5 5 3 2ZnO•3B.sub.2O.sub.3•7H.sub.2O 0.5 1 2 2 1 1 Zn(AC).sub.2•2H.sub.2O 2 Nylon 6 30 Polypropylene- 30 methacrylate copolymer (PP-g-AA) Appearance of matte Even Even Even Even Even Uneven Uneven Even masterbatch

[0040] In Table 1, the resin Al containing maleic anhydride (MAH) functional group: styrene-maleic anhydride copolymer (SMA), Polyscope SZ23110;

[0041] The resin A2 containing maleic anhydride (MAH) functional group: ethylene-octene-maleic anhydride copolymer (POE-g-MAH), Nantong Rizhisheng 5805SL;

[0042] The resin B1 containing glycidyl methacrylate (GMA) functional group: styrene-acrylonitrile-glycidyl methacrylate copolymer (SAN-g-GMA), Nantong Rizhisheng SAG002;

[0043] The resin B2 containing glycidyl methacrylate (GMA) functional group: ethylene-methyl methacrylate-glycidyl methacrylate copolymer (EMA-g-GMA), Arkema Lotader AX8900;

[0044] Polyolefin-alkyl acrylate copolymer C1: ethylene-methyl methacrylate (EMA): Arkema Lotader 29MA03;

[0045] Fumed SiO.sub.2: Degussa Evonik TS100.

[0046] 2. Preparation of low-gloss heat-resistant ABS resin composition (components and weight contents are shown in Table 3):

[0047] Stirring and fully mixing ABS resin, heat-resistant agent, matte masterbatch D, light stabilizer and other additives in a high-speed mixer to obtain a mixture, feeding the mixture into a twin-screw extruder through a metering device; melting and compounding the mixture under conveying, shearing and mixing of screws, and then extruding, pulling, cooling and granulating, and finally obtaining a low-gloss resin composition which can be used for automotive interior parts;

[0048] wherein: a length-diameter ratio of the screws of the twin-screw extruder is 40; a temperature at a front section of the screws is 190-210° C.; a temperature at a middle section thereof is 220-240° C.; a head extrusion temperature is 235° C.; and a screw speed is 300 rpm.

Second, Third, Fourth, Fifth and Sixth Embodiments

[0049] The second, third, fourth, fifth and sixth embodiments relate to the preparation of low-gloss heat-resistant ABS resin composition; the preparation method is the same as that mentioned in the first embodiment. The components and contents in part by weight of the low-gloss heat-resistant ABS resin composition corresponding to the second, third, fourth, fifth and sixth embodiments are shown in Table 3.

FIRST, SECOND, THIRD, FOURTH, FIFTH AND SIXTH COMPARATIVE EXAMPLES

[0050] The first, second, third, fourth, fifth and sixth comparative examples relate to the preparation of low-gloss heat-resistant ABS resin composition; the preparation method is the same as that mentioned in the first embodiment. The components and contents in part by weight of the ABS resin composition corresponding to the first, second, third, fourth, fifth and sixth comparative examples are shown in Table 3.

[0051] The mechanical properties of the low-gloss heat-resistant ABS resin composition prepared in the embodiments and comparative examples are tested according to the ASTM standard (see Table 2). The gloss test is carried out by using the ASTM D2457 method and Multigloss 268 Glossmeter of Konica Minolta; the test angle on the injection molding color plate is 60°.

TABLE-US-00005 TABLE 2 Physical properties Test method Tensile strength (50 mm/min) ASTM D638 Bending strength (3 mm/min) ASTM D790 Bending modulus (3 mm/min) ASTM D790 IZOD notched impact strength (3.2 mm) ASTM D256 Vicat (5 kg, 50° C./h) ASTM D1525

TABLE-US-00006 TABLE 3 The Components and Parts by Weight of the ABS Resin Composition in the first, second, third, fourth, fifth and sixth embodiments and the first, second, third, fourth, fifth and sixth comparative examples Embodiment Comparative example Component 1 2 3 4 5 6 1 2 3 4 5 6 ABS ABS1 100 resin ABS2 100 100 100 100 ABS3 100 100 ABS4 100 100 ABS5 100 ABS6 100 ABS7 100 Heat-resistant α-SAN 30 15 20 15 15 15 15 agent N-PMI-St- 5 10 10 10 10 MAH Matte D1 1 masterbatch D2 3 D D3 5 3 D4 3 2 D5 3 D6 3 D7 3 D8 3 Light Tinuvin 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 stabilizer 770 (bis (2,2,6,6- tetramethyl- 4-piperidyl) sebacate) Miscellaneous Irganox 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 B900 Auxiliaries EBS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 ASTM Tensile strength/Mpa 47 46 45 43 46 45 49 38 42.5 46 46 46 Bending strength/Mpa 68 66 65 62 65 65 70 58 63 65 66 66 Bending modulus/Mpa 2420 2315 2300 2130 2350 2250 2550 1950 2215 2300 2320 2325 Impact strength/J/m 325 275 285 185 256 260 280 315 190 268 280 278 Vicat softening point/° C. 102 99 99.5 102.8 100 103 104 103 99.6 99.3 99.5 99.6 Gloss/60° 6.2 4.3 3.1 3.5 3.8 3.6 20.6 8.0 9.6 7.2 9.5 10.6

[0052] The components and characteristics involved in the above-mentioned embodiments and comparative examples are as follows:

[0053] ABS resin ABS1: a content of butadiene rubber is 17%; a particle size is 0.6 μm; a weight-average molecular weight is 80,000;

[0054] ABS resin ABS2: the content of butadiene rubber is 15%; the particle size is 1.0 μm; the weight-average molecular weight is 100,000;

[0055] ABS resin ABS3: the content of butadiene rubber is 15%; the particle size is 1.5 μm; the weight-average molecular weight is 120,000;

[0056] ABS resin ABS4: the content of butadiene rubber is 10%; the particle size is 2.5 μm; the weight-average molecular weight is 140,000;

[0057] ABS resin ABSS: the content of butadiene rubber is 13%; the particle size is 0.8 μm; the weight-average molecular weight is 150,000;

[0058] ABS resin ABS6: the content of butadiene rubber is 15%; the particle size is 0.4 μm; the weight-average molecular weight is 120,000;

[0059] ABS resin ABS7: the content of butadiene rubber is 13%; the particle size is 4.5 μm; the weight-average molecular weight is 120,000;

[0060] Heat-resistant agent: a-methylstyrene-acrylonitrile copolymer (α-SAN), BASF KR2556;

[0061] Heat-resistant agent: N-phenylmaleimide-styrene-maleic anhydride copolymer (N-PMI-St-MAH) is electrochemical MSNH.

[0062] According to the preparation of matte masterbatch D in Table 1 and the embodiments and comparative examples in Table 3, the matte masterbatch with uniform appearance and low-gloss heat-resistant ABS resin composition can be prepared by using the crosslinking reaction between the resin containing glycidyl methacrylate (GMA) functional group and polyolefin-alkyl acrylate copolymer under catalysis of hydrated zinc borate; the matte effect is distributed uniformly. According to the second, third, fourth, fifth and sixth embodiments, the present invention has high efficiency for reducing the gloss of ABS resin, can maintain the excellent mechanical properties and meet the application of automotive interior parts. According to the second comparative example, the mechanical properties of ABS resin with large rubber particle size will be greatly reduced, which is not conducive to the actual use of the product. In the third comparative example, when zinc acetate hydrate is used as a crosslinking catalyst, water loss may occur due to the ultra-low thermal decomposition temperature, thereby reducing the catalytic cross-linking effect, so that the efficiency of reducing the gloss of ABS resin is greatly reduced. In the fourth comparative example and the fifth comparative example, there is no fumed SiO.sub.2, the overall gloss of the heat-resistant ABS resin will be improved, and the gloss uniformity will be deteriorated. It can be seen in the fifth comparative example that the effect of hydrated zinc borate on the promotion of gloss reduction is significant. In the sixth comparative example, the effect of reducing the gloss by using the crosslinking reaction between the amide group of PA6 and methacrylic acid is relatively limited.

[0063] It should be noted that the light stabilizer is not limited to the above-mentioned Tinuvin 770 (bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate); the benzophenone UV absorbent, e.g., Cyasorb UV-53, the triazine UV absorbent, e.g., Cyasorb UV-1164, the benzotriazole UV absorbent, such as Tinuvin 326 and Cyasorb UV-5411, the hindered amine radical scavenger, e.g., Cyasorb UV-3346, can be used as a light stabilizer to achieve the present invention.

[0064] Specific embodiments of the present invention are described above. It shall be understood that the present invention is not limited to the above-mentioned specific embodiments, and those skilled in the art can make different variants and modifications within the scope of the claims, and it shall not affect the substance of the present invention.