Ultralow-glossiness, ultralow-temperature resistant ASA resin composition and preparation method thereof

Abstract

The present disclosure provides an ultralow-glossiness, ultralow-temperature resistant ASA resin composition and preparation method thereof. The composition includes the following components in parts by weight: 20˜60 parts of an acrylonitrile-styrene-acrylate graft copolymer, 40˜80 parts of an acrylonitrile-styrene copolymer, 1˜20 parts of an ultralow-glossiness, low temperature resistant modifier, and 0.1˜5 parts of a processing aid. The ultralow-glossiness, low temperature resistant modifier includes a carrier copolymer, a fluorinated copolymer, a low-temperature flexibilizer, a coupling agent, fumed silica and an assistant. The ASA resin composition prepared by the present disclosure has an ultralow-glossiness, can be used to replace mold processing technology such leather marking and texturing, which greatly saves mold cost and processing production cost; and meanwhile it also has excellent low temperature resistance and can be applied in cases having requirements on low temperature resistance and low glossiness such as automobile parts, outdoor profiles, building materials and electrical appliances.

Claims

1. An ultralow-glossiness, ultralow-temperature resistant ASA resin composition, wherein the composition comprises the following components in parts by weight: 20˜60 parts of an acrylonitrile-styrene-acrylate graft copolymer, 40˜80 parts of an acrylonitrile-styrene copolymer, 1˜20 parts of an ultralow-glossiness, low temperature resistant modifier, and 0.1˜5 parts of a processing aid, wherein the ultralow-glossiness, low temperature resistant modifier comprises the following components in a weight percentage: 10˜70 wt % of a carrier copolymer, 10˜70 wt % of a fluorinated copolymer, 5˜50 wt % of a flexibilizer, 5˜25 wt % of a coupling agent, 1˜5 wt % of fumed silica, and 0.1˜5 wt % of an assistant.

2. The ultralow-glossiness, ultralow-temperature resistant ASA resin composition according to claim 1, wherein in the acrylonitrile-styrene-acrylate graft copolymer, acrylate has a weight percentage of 30˜80 wt %, acrylate has a number average particle size of 0.1˜4.0 μm; and the acrylonitrile-styrene-acrylate graft copolymer has a weight-average molecular weight of 100,000˜300,000.

3. The ultralow-glossiness, ultralow-temperature resistant ASA resin composition according to claim 1, wherein the acrylonitrile-styrene copolymer has a weight-average molecular weight of 100,000˜500,000, wherein acrylonitrile has a weight percentage of 15˜40 wt %.

4. The ultralow-glossiness, ultralow-temperature resistant ASA resin composition according to claim 1, wherein the carrier copolymer is selected from at least one of the groups consisting of poly(methyl methacrylate), polystyrene, poly(α-alkyl)styrene, maleic anhydride modified styrene polymer, styrene/maleic anhydride copolymer, maleimide modified styrene polymer, styrene-N arylmaleimide copolymer, styrene/acrylonitrile compolyer, (α-alkyl)styrene/acrylonitrile copolymer, styrene/(α-alkyl)styrene/acrylonitrile copolymer, styrene/acrylonitrile/methyl methacrylate copolymer, styrene/(α-alkyl)styrene/acrylonitrile/methyl methacrylate copolymer, and (α-alkyl)styrene/acrylonitrile/methyl methacrylate copolymer.

5. The ultralow-glossiness, ultralow-temperature resistant ASA resin composition according to claim 1, wherein the fluorinated copolymer is poly(fluorinated alkene), selected from at least one of the groups consisting of polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, tetrafluoroethylene/perfluoroalkyl ether copolymer, polyvinyl fluoride, chlorotrifluoroethylene/ethylene copolymer, and poly(chlorotrifluoroethylene).

6. The ultralow-glossiness, ultralow-temperature resistant ASA resin composition according to claim 1, wherein the flexibilizer is a core-shell structure copolymer formed by taking any one of silicone rubber, acrylic rubber, and silicon/acrylate composite rubber as a core, and taking any one of acrylonitrile-styrene graft copolymer, alkyl acrylate copolymer, epoxy modified alkyl acrylate copolymer as a shell.

7. The ultralow-glossiness, ultralow-temperature resistant ASA resin composition according to claim 1, wherein the coupling agent is a silane coupling agent, comprises one or more of an amino functional silane coupling agent, a vinyl functional silane coupling agent, an epoxy functional silane coupling agent, and a methacryloyl functional silane coupling agent.

8. The ultralow-glossiness, ultralow-temperature resistant ASA resin composition according to claim 1, wherein a preparation method of the ultralow-glossiness, low temperature resistant modifier comprises steps of: weighing components in parts by weight, after a thorough and uniformly mixing, extruding and granulating by a twin-screw extruder to obtain the ultralow-glossiness, low temperature resistant modifier.

9. A method for preparing the ultralow-glossiness, ultralow-temperature resistant ASA resin composition according to claim 1, wherein the method comprises steps of: step 1: preparing raw materials based on the following components in parts by weight: 20˜60 parts of an acrylonitrile-styrene-acrylate graft copolymer, 40˜80 parts of an acrylonitrile-styrene copolymer, 1˜20 parts of an ultralow-glossiness, low temperature resistant modifier, and 0.1˜5 parts of a processing aid; step 2: stirring and mixing the raw material prepared in step 1 in a high speed mixer, extruding and granulating by the twin-screw extruder to obtain the ultralow-glossiness, ultralow-temperature resistant ASA resin composition.

Description

DETAILED DESCRIPTION

(1) The present disclosure will be described in detail with reference to specific examples. The following examples are intended to further understand the present disclosure, but are not intended to limit the present disclosure in any way. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the present disclosure. These are all within the protect scope of the present disclosure.

Example 1 Preparation of the Ultralow-Glossiness, Low Temperature Resistant Modifier

(2) The components and weight percentage contents of the ultralow-glossiness, low temperature resistant modifier (E) are shown in Table 1. A carrier copolymer (A), a fluorinated copolymer (B), a low temperature toughening agent (C), a coupling agent (D), fumed silica, 0.7 phr of a lubricant EBS and 0.3 phr of an antioxidant IG-1076 are stirred and mixed in a high-speed mixer, and fed into a twin-screw extruder through a metering device, under a conveying, shearing and mixing of the screws, the above materials are melted and compounded, and then extruded, drawn, cooled and granulated, to obtain an ultra-low glossiness, low temperature resistance modifier E1˜E8 with uniform particle size.

(3) Where, the twin-screw extruder has a screw length-diameter ratio of 40, the twin-screw extruder has an extrusion temperature of 200˜300° C., and a screw rotation speed is 200˜500 r/min.

(4) TABLE-US-00001 TABLE 1 Preparation of the ultralow-glossiness, low temperature resistant modifier (E) Formulation component E1 E2 E3 E4 E5 E6 E7 E8 Component A-1 28 / 28 28 70 31 57 57 Component A-2 / 28 / / / / / / Component B-1 29 29 / 29 29 29 29 / Component B-2 / / 29 / / / / / Component C-1 29 29 29 / / 29 / 29 Component C-2 / / / 29 / / / / Component D-1 10 10 10 10 / 10 10 10 Fumed silica 3 3 3 3 / / 3 3 lubricant 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 antioxidant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Appearance of Even Even Even Even uneven uneven Even uneven the modifier and and and and and and and and matte matte matte matte matte matte matte specular In table 1: Component A-1: styrene/acrylonitrile copolymer, has a weight-average molecular weight of 250,000 Component A-2: poly(methyl methacrylate), has a weight-average molecular weight of 250,000. Component B-1: polytetrafluoroethylene, has a weight-average molecular weight of 200,000. Component B-2: polyvinylidene fluoride, has a weight-average molecular weight of 200,000. Component C-1: a core-shell structure copolymer having an acrylate rubber as a core and an acrylonitrile-styrene craft copolymer as a shell layer. Component C-2: a core-shell structure copolymer of silicon/acrylate composite rubber as a core, and epoxy modified methyl methacrylate as a shell. Component D-1: silane coupling agent, KH-550.

(5) From the appearance results of the modifier of table 1, it can be seen that by using a cross-linking reaction of three components compounded of the core-shell structure copolymer, the fluoropolymer and the silane coupling agent, an ultra-low glossiness, low temperature resistant modifier (E) having a uniform appearance can be prepared, and the matt effect is evenly distributed. It can be seen from E5, E6 and E7 that the addition of the coupling agent and fumed silica has a great influence on the uniformity of the matte effect, and only in the case where both two components are present at the same time, the cross-linking reaction of the coupling agent and promotion of dispersion of fumed silica can achieve a soft and uniform matte effect on the surface. It is known from E1, E3 and E8 that the fluoropolymer can significantly reduce the glossiness of the ASA resin.

Examples 2˜9 Preparation of the Ultralow-Glossiness, Ultralow-Temperature Resistant ASA Resin Composition

(6) Examples 2 to 9 provide an ultralow-glossiness, ultralow-temperature resistant ASA resin composition and a preparation method thereof, the components and the weight percentages of the ultralow-glossiness, ultralow-temperature resistant ASA resin composition as shown in table 2. The method include the steps of: An acrylonitrile-styrene-acrylate graft copolymer, an acrylonitrile-styrene copolymer, an ultralow-glossiness, low temperature resistant modifier (E), 0.6 phr of a lubricant EBS and 0.3 phr of an antioxidant IG-1076 are stirred and mixed in a high-speed mixer, and fed into a twin-screw extruder through a metering device, under a conveying, shearing and mixing of the screws, the above components are melted and compounded, and then extruded, drawn, cooled and granulated, to obtain the ultralow-glossiness, ultralow-temperature resistance ASA resin composition.

(7) Where, the twin-screw extruder has a screw length-diameter ratio of 40, the twin-screw extruder has an extrusion temperature of 200˜300° C., and a screw rotation speed is 200˜500 r/min.

Comparative Examples 1˜6

(8) Comparative examples 1˜6 provide an ultralow-glossiness, ultralow-temperature resistant ASA resin composition and a preparation method thereof, the components and the weight percentages of the ultralow-glossiness, ultralow-temperature resistant ASA resin composition as shown in table 2. The method include the steps of: An acrylonitrile-styrene-acrylate graft copolymer, an acrylonitrile-styrene copolymer, an ultralow-glossiness, low temperature resistant modifier (E), 0.6 phr of a lubricant EBS and 0.3 phr of an antioxidant IG-1076 are stirred and mixed in a high-speed mixer, and fed into a twin-screw extruder through a metering device, under a conveying, shearing and mixing of the screws, the above components are melted and compounded, and then extruded, drawn, cooled and granulated, to obtain the ultralow-glossiness and ultralow-temperature resistance ASA resin composition.

(9) Where, the twin-screw extruder has a screw length-diameter ratio of 40, the twin-screw extruder has an extrusion temperature of 200˜300° C., and a screw rotation speed is 200˜500 r/min.

(10) TABLE-US-00002 TABLE 2 material formulation of the examples and the comparative examples Formulation component Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 acrylonitrile-styrene- 40 40 40 40 40 40 60 20 acrylate graft copolymer acrylonitrile-styrene 60 60 60 60 60 60 40 80 copolymer E1 10 / / / / / / / E2 / 10 / / / / / / E3 / / 10 / / / / / E4 / / / 10 1 20 10 10 E5 / / / / / / / / E6 / / / / / / / / E7 / / / / / / / / E8 / / / / / / / / Processing aid 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Formulation Comparative Comparative Comparative Comparative Comparative Comparative component example 1 example 2 example 3 example 4 example 5 example 6 acrylonitrile-styrene- 40 40 40 40 40 40 acrylate graft copolymer acrylonitrile-styrene 60 60 60 60 60 60 copolymer E1 / / / / / / E2 / / / / / / E3 / / / / / / E4 / 30 / / / / E5 / / 1.0 / / / E6 / / / 10 / / E7 / / / / 10 / E8 / / / / / 10 Processing aid 0.9 0.9 0.9 0.9 0.9 0.9

(11) The above examples and the comparative examples relate to the components and features are as follows:

(12) The acrylonitrile-styrene-acrylate graft copolymer is prepared by taking acrylate as a soft core, grafted acrylonitrile and styrene to form a core-shell structure, where the acrylate has a weight percentage of 45˜60 wt %, acrylate has a number average particle size of 0.5˜2.0 um, and the acrylonitrile-styrene-acrylate graft copolymer has a weight-average molecular weight of 100,000˜300,000.

(13) The acrylonitrile-styrene copolymer has a weight-average molecular weight of 200,000˜400,000, acrylonitrile has a weight percentage of 25˜35 wt %.

(14) The processing aid is 0.6 phr of a lubricant EBS and 0.3 phr of an antioxidant IG-1076.

(15) The ASA resin composition prepared according to the examples 2˜9 and the comparative example 1˜5, a test sample strip is prepared by the same injection molding conditions, the specific mechanical property and the glossiness evaluation tests are as follows:

(16) Tensile strength: tested according to the ISO 527 standard, a testing speed is 50 mm/min;

(17) Bending strength: tested according to the ISO 178 standard, a testing speed is 2 mm/min;

(18) Bending modulus: tested according to the ISO 178 standard, a testing speed is 1 mm/min;

(19) Notched izod impact strength at 23° C.: tested according to the ISO 180 standard, a thickness of the sample strip is 4 mm;

(20) Notched izod impact strength at −40° C.: tested according to the ISO 180 standard, a thickness of the sample strip is 4 mm, and a test condition is −40° C./4 h;

(21) Heat distortion temperature: tested according to the ISO 75 standard, a test condition is 0.45 MPa;

(22) Melt flow rate: tested according to the ISO 1183 standard, a test condition is 220° C./10 kg;

(23) Glossiness: the surface glossiness of a common color plate with a thickness of 3 mm and K31 matte leather color plate is tested according to ASTM D523 at 60° C. by using Garden Gloss Meter, and recorded in units of gloss units (GU), where the glossiness of a standard black glass sheet is 100 GU.

(24) The test results are shown in table 3.

(25) TABLE-US-00003 TABLE 3 Performance comparison between the examples and the comparative examples Material performance example 2 example 3 example 4 example 5 example 6 example 7 example 8 example 9 Tensile strength 44 47 45 47 49 46 37 57 Bending modulus 2205 2350 2223 2320 2368 2270 1890 2610 (MPa) Notched izod 12.6 13.6 13.3 14.5 11.4 16.1 20.7 8.3 impact strength at 23° C. (KJ/m.sup.2) Notched izod 40 5.2 4.7 5.5 2.2 7.6 6.5 3.0 impact strength at −40° C. (KJ/m.sup.2) Heat distortion 100.9 100.5 99.8 100.1 101.6 99.4 94.2 104.9 temperature (° C.) Melt flow rate 5.4 4.2 4.6 5.0 5.2 35 2.8 9.3 (g/10 min) Glossiness of 30 28 34 31 82 22 27 41 common color plate Glossiness of 2.2 1.7 2.4 2.2 73 1.1 2.0 3.3 K31 leather color plate Material Comparative Comparative Comparative Comparative Comparative Comparative performance example 1 example 2 example 3 example 4 example 5 example 6 Tensile strength 51 45 50 49 49 48 Bending modulus 2190 2202 2150 2120 2130 2182 (MPa) Notched izod 10.9 25.5 9.8 12.9 10.8 12.0 impact strength at 23° C. (KJ/m.sup.2) Notched izod 1.8 8.5 1.4 4.2 1.7 3.8 impact strength at −40° C. (KJ/m.sup.2) Heat distortion 101.5 98.0 100.8 100.6 100.7 100.3 temperature (° C.) Melt flow rate 6.2 1.7 5.5 5.0 4.9 5.5 (g/10 min) Glossiness of 98 18 54 46 45 92 common color plate Glossiness of 8.9 0.8 4.3 4.0 3.9 8.1 K31 leather color plate

(26) From the test results of the examples and the comparative examples in table 3, it can be seen that from the examples 2˜7, the glossiness of the ASA resin of the present disclosure is greatly reduced, and a low temperature toughness of the material is greatly improved, while the influence on other mechanical properties is not obvious. From example 1, examples 5˜9 and the comparative example 1, it is known that an increase in the rubber content can increase a normal temperature impact toughness of the material, and contribute little to a low temperature toughness; in addition, it also has a great influence on the strength and heat resistance of the material; while an increase of the content of the ultralow-glossiness, low temperature modifier (E) can effectively improve the low temperature impact toughness of the material and effectively reduce the glossiness of the material. In contrast, the influence on other mechanical properties is very small. It can be seen from the comparative example 2 that the content of the ultralow-glossiness, low temperature modifier (E) is not as good as possible. When the mass fraction is 30 parts, its influence on heat resistance and fluidity is large, and the melt flow rate is greatly reduced, which directly affects the processability of the ASA resin. Therefore, it is not too high to control the proper addition amount. From the comparative examples 5 to 6, it is known that the fluorinated copolymer has a great effect on lowering the glossiness, and the core-shell structure copolymer a remarkable effect on improving the low temperature toughness, and further comparison of the examples 2 to 9 and the comparative examples 5 to 6, it is known that the fluorinated copolymer and the core-shell structure copolymer have synergistic effects on reducing the glossiness of the material and improving the low temperature toughness, and finally prepared the ASA resin composition has excellent ultralow-glossiness and excellent low temperature resistance, and can be applied to outdoor products such as building materials, sports equipment, communication equipment casings and automobile parts and soon on.

(27) In conclusion, the present disclosure adopts a cross-linking reaction of a core-shell structure copolymer, a fluoropolymer and a silane coupling agent to prepare an ultralow-glossiness, low temperature resistance modifier (E) with uniform appearance, and further prepare an ultralow-glossiness, ultralow-temperature resistant ASA resin composition, the obtained ASA resin composition has ultralow surface glossiness and excellent low temperature resistance toughness. The present disclosure solves the problem that low glossiness and low temperature toughness of the ASA resin in the existing technologies are difficult to balance. The ASA resin composition prepared by the present disclosure has high low temperature toughness, and the Notched izod impact strength at −40° C. can reach 7 KJ/m.sup.2 or more, which is equivalent to the low temperature toughness of the ABS resin, and can meet the low temperature storage requirement of the automobile parts article, and the heat resistance of the ASA resin composition is high, which also can meet the high temperature storage requirements of the article. In addition, the ASA resin prepared by the present disclosure has a soft and uniform matte effects, and also has a ultralow surface glossiness, can be well applied to some occasions with low gloss requirements, and can even try to replace the mold processing techniques such as leather marking and texturing, which greatly saves mold cost and processing production cost.

(28) There are many specific application paths of the present disclosure, and the above description is only preferred examples of the present disclosure. It should be noted that the above examples are merely illustrative of the present disclosure but not intended to limit the protect scope of the present disclosure. A number of modifications may be made by those skilled in the art without departing from the principles of the present disclosure, and such modifications are also should be considered to be within the protection scope of the present disclosure.