CN111500042B - Matte PC/ABS alloy material and preparation method thereof - Google Patents
Matte PC/ABS alloy material and preparation method thereof Download PDFInfo
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- CN111500042B CN111500042B CN202010217335.4A CN202010217335A CN111500042B CN 111500042 B CN111500042 B CN 111500042B CN 202010217335 A CN202010217335 A CN 202010217335A CN 111500042 B CN111500042 B CN 111500042B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a matte PC/ABS alloy material and a preparation method thereof. According to the invention, the material is endowed with matte performance by adopting a special organic matte agent and matching with a treated inorganic matte agent, the influence on the mechanical performance of the material is small, and the material does not depend on high ABS content; even under a mold without skin lines, the PC/ABS alloy can be molded into matte, so that the PC/ABS alloy has higher heat-resistant temperature, and is particularly suitable for occasions with higher requirements on use environments, particularly the fields of indoor household appliances, illumination and other products without skin lines on the surfaces.
Description
Technical Field
The invention belongs to the field of engineering plastics, and particularly relates to a matte PC/ABS alloy material and a preparation method thereof.
Background
Polycarbonate resins are general-purpose engineering plastics, have various advantages such as transparency, impact resistance, heat resistance and dimensional stability, and are industrially widely used as materials in the fields of automobiles, office equipment such as printers, and electric and electronic fields such as mobile phones because of the excellent characteristics. PC/ABS is one of the main alloys, has the heat resistance and toughness of PC and the processability of ABS, and has wide influence on the industries of electronics, electrical appliances, household appliances and the like. In recent years, in the household appliance and lighting industry, in order to meet the brand-new modeling requirement and reduce the visual fatigue of indoor personnel on the appliances, higher and higher requirements are put on the matte of the plastic shell. Unlike the requirements in the automotive interior field, it is necessary to achieve matte finish on the basis of a fine-grain or skinless mold. The common method for reducing the surface gloss of the plastic comprises the steps of reducing the compatibility of PC/ABS, adding matte resin, reactive resin or inorganic filler and the like, matching with different types of dermatoglyphs of automobile interiors, and realizing matte effect, but when the mold has no dermatoglyphs, the matte effect is very unobvious, and in addition, the defects of uneven gloss effect or serious reduction of the mechanical property of the material exist, and the like, so that the requirements of customers cannot be met.
In addition, aiming at the household appliance or lighting industry, heat release exists in the actual working condition, so that the heat resistance is higher, the heat deformation temperature is generally required to be more than 100 ℃, the toughness requirement cannot be reduced, and the ISO notch impact strength is required to be more than 50kJ/m 2 To cope with accidental violent damage. Therefore, the proportion of ABS in the PC/ABS alloy cannot be too high, otherwise, the problems of deformation and the like can occur, however, the addition of less ABS sets greater difficulty for achieving the matte purpose.
Disclosure of Invention
The invention aims to solve the technical problem of providing a matte PC/ABS alloy material and a preparation method thereof, and the alloy material overcomes the defects of uneven gloss effect or serious reduction of mechanical properties of the material and the like while achieving a matte effect in the prior art.
The invention provides a matte PC/ABS alloy material which comprises the following components in parts by mass:
preferably, the matte PC/ABS alloy material comprises the following components in parts by mass:
the polycarbonate resin is a thermoplastic aromatic polycarbonate polymer or copolymer with a branched chain, which is obtained by reacting an aromatic hydroxyl compound with phosgene or a carbonic diester, or reacting the aromatic hydroxyl compound and a small amount of a polyhydroxy compound with phosgene or a carbonic diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and conventionally known techniques such as a phosgene method (interfacial polymerization method) and a melting method (transesterification method) can be used. In the present invention, the molecular weight of the polycarbonate resin is appropriately selected for improving the appearance and the flowability of the molded article, and is at least one of aromatic polycarbonates having a viscosity average molecular weight of 10000 to 40000. The viscosity-average molecular weight [ Mv ] obtained by converting the solution viscosity is usually 10000 or more, preferably 12000 or more, and usually 40000 or less, preferably 30000 or less, and more preferably 25000 or less. By setting the viscosity average molecular weight within the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be ensured, and the polycarbonate resin composition is more preferable when used for applications requiring high mechanical strength, and high fluidity in thin wall molding can be ensured.
The toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic ester-glycidyl methacrylate terpolymer, maleic anhydride functionalized ethylene-vinyl acetate copolymer, acrylic toughening agent and organic silicon rubber graft toughening agent. More preferably, the toughening agent is a methyl methacrylate-butadiene-styrene copolymer toughening agent, wherein the volume average particle size of the rubber component in the toughening agent is 180-2000 nm, preferably 230-1400 nm, more preferably 300-1200 nm, and further preferably 330-700 nm. By setting the volume average particle diameter of the rubber component within the range of 330 to 700nm, good impact resistance can be obtained.
The organic matte agent is at least one of amide copolymer, SEBS, gelled SAN and glycidyl methacrylate copolymer. The organic matte agent is MH2030 which is originally an antistatic agent, and the organic matte agent has better compatibility with matrix resin and more uniform matte effect.
The inorganic matte agent is subjected to surface treatment. The inorganic matte agent is at least one of barium sulfate, calcium carbonate, silicon dioxide, kaolin and talcum powder. Preferably, the inorganic matte agent is talcum powder. The particle size D50 of the preferred talcum powder is 0.5-3.5 μm, and the specific surface area of the talcum powder is 15-40m 2 (ii)/g; more preferably a particle size D50 of 0.5 to 2.5 μm and a particle size D95 thereof<8 μm and a specific surface area of 12 to 25m 2 (ii) talc powder per gram.
The surface treatment method comprises the following steps:
drying talcum powder in an electric heating forced air drying oven at 100 deg.C for 3h; after cooling, transferring the powder into a high-speed mixer, and spraying and adding a diluent with 20% of the mass fraction of a silane coupling agent (hexadecyl trimethoxy silane) under stirring at the rotating speed of 1000 r/min; heating to 110 deg.C, stirring for 0.5h, drying at 110 deg.C for 4h, sealing, and using.
The antioxidant is a main antioxidant and an auxiliary antioxidant with the mass ratio of 1.0-1.0 or only the main antioxidant is added into the antioxidant.
The primary and secondary antioxidants may include the following classes of antioxidants:
acrylates, which may include, but are not limited to, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate;
phosphite antioxidants, which may include, but are not limited to, tris (nonylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite;
alkylated monophenols or polyphenols, alkylated reaction products of polyphenols with dienes, such as butylated reaction products of tetrakis [ methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, p-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ether; an alkylidene bisphenol; a benzyl compound; esters of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono-or polyhydric alcohols; esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono-or polyhydric alcohols; esters of thioalkyl or thioaryl compounds, such as distearylthiopropionate, dilaurylthiopropionate, tricosylthiodipropionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl 4-hydroxyphenyl) propionate; amides of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid.
Preferably, the primary antioxidant is Chinox 1076 and the secondary antioxidant is THANOX 168.
The other auxiliary agent is a lubricant and/or an anti-dripping agent.
The lubricant used in the invention is glyceryl stearate, and the anti-dripping agent is PTFE coated by AS.
The invention also provides a preparation method of the matte PC/ABS alloy material, which comprises the following steps:
(1) Weighing the raw materials according to the formula, and sequentially putting the raw materials into a mixer to be uniformly blended to obtain a premix;
(2) And (2) putting the premix prepared in the step (1) into a double-screw extruder, and carrying out melt mixing and extrusion granulation in the double-screw extruder to obtain the premix.
The length-diameter ratio of a screw of the double-screw extruder in the step (2) is 40-45, the temperature of a screw cylinder is 250-280 ℃, and the rotating speed of the screw is 400-500 rpm.
The invention also provides an application of the matte PC/ABS alloy material.
Advantageous effects
The special organic matte agent is added into the PC, so that the glossiness of the PC can be greatly reduced, and the PC does not depend on the excessively high rubber content in the ABS; meanwhile, the processed inorganic matte agent is matched, so that the glossiness of the PC/ABS alloy is further reduced while the mechanical property of the material is hardly reduced, and the glossiness effect is uniform. Because the PC/ABS alloy does not depend on high rubber content, the heat-resistant temperature of the obtained PC/ABS alloy is higher, and the high toughness property of the PC is also maintained, so that the PC/ABS alloy is particularly suitable for occasions with higher requirements on the use environment, particularly the field without skin lines on the surfaces of products such as indoor household appliances, illumination and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The raw materials used in the specific examples and comparative examples are as follows:
PC resin is PC S-2000F (Mitsubishi, japan) with viscosity average molecular weight of 22000; the toughening agent is Japanese Kochia's M-701; the organic matte agent is MH2030 (French Dokema), and other organic matte agents are BMAT (commercially available); the inorganic matte agent is Jetfine 3CA (IMERY, france). The antioxidant is Chinox 1076, namely beta- (3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (CAS No.: 2082-79-3); the lubricant of other adjuvants is UNISTER-M9676 (Japanese daily oil).
Weighing polycarbonate resin, ABS resin, a toughening agent, an organic matte agent, an inorganic matte agent, an antioxidant and other auxiliaries according to the use amounts of the raw materials in the formula shown in Table 1, and sequentially putting the raw materials into a mixer to blend uniformly to obtain a premix; and then putting the premix into a double-screw extruder for melt mixing and extrusion granulation to prepare the matte PC/ABS alloy material. Wherein the length-diameter ratio of a screw of the double-screw extruder is 40, the temperature of a screw cylinder is 260-280 ℃, and the rotating speed of the screw is 400-500 rpm.
The prepared matte PC/ABS alloy material is respectively tested for the notch cantilever beam impact strength, the heat resistance and the 60-degree gloss, and the reference standard or the method for testing is as follows.
(1) The method for measuring the cantilever beam impact strength comprises the following steps: notched izod impact strength was measured using a 4.0mm thick molded notched izod impact bar. Notched Izod impact strength measured in kJ/m according to ISO 180 2 The results were recorded and the test was performed at room temperature (23 ℃).
(2) Heat resistance: expressed using Heat Deflection Temperature (HDT), higher temperatures indicate better heat resistance. HDT was determined according to the test standard ISO75-1, lying flat on bars of 4.0mm thickness under a load of 1.82MPa, the results being recorded at ℃ C.
(3) Method for measuring 60 ° gloss: the obtained material is injected and molded at 250 ℃ to form a square plate with the thickness of 2mm multiplied by 100mm, the surface of the mold is smooth and has no skin marks, and the temperature of the mold is 30 ℃. The gloss of the square panels was tested using a 60 ℃ gloss meter according to standard GB/T8807.
(4) The matte uniformity degree determination method comprises the following steps: the obtained material is injected and molded at 250 ℃ to form a square plate with the thickness of 2mm multiplied by 100mm, the surface of the mold is smooth and has no skin marks, and the temperature of the mold is 30 ℃. The surface of the square plate is observed by naked eyes and judged to be uniform or non-uniform
The results of the above tests are shown in Table 1.
TABLE 1 amounts (unit: parts by weight) and performance test results of examples 1 to 5 and comparative examples 1 to 6
It can be seen that the composite phases obtained in examples 1 to 5 and comparative examples 1 to 6In comparison, the comparative example 1 only adds the organic matte agent, the glossiness on the optical plate is 46, and the occasions with high matte requirements cannot be met; the conventional BMAT matte agent used in the comparative example 2 brings matte and greatly reduces the heat-resistant temperature of the material, and the surface gloss uniformity of the material is poor; in the comparison ratio 3, only the inorganic matte agent is used, so that the reduction of the glossiness is limited; comparative example 4 is a formula without any matte agent, has higher heat resistance, toughness and other properties, but cannot be used in the field with matte requirement; comparative example 5 is a material whose gloss can be reduced by using a conventional BMAT matte agent, but the heat-resistant temperature of the material is seriously reduced due to its low heat-resistant temperature, and in addition, the gloss uniformity is poor; comparative example 6, the untreated inorganic matte agent was used, and the dispersion was not uniform, the impact on the toughness of the material was large, and the reduction in gloss was not satisfactory; the matte effect required by the surface of the product without the skin texture and the high heat resistance (the heat resistance temperature is more than 100 ℃) in special use environment can not be satisfied at the same time. Different from comparative examples 1 to 6, the matte PC/ABS alloy material prepared by the embodiment of the invention uses a special organic matte agent, has small influence on PC heat resistance, can achieve uniform glossiness, can further reduce the glossiness with the help of special surface-treated inorganic matte powder, even achieves the super-matte effect below 10, can still maintain the mechanical property at a high degree, and has the ISO notch impact strength of 50kJ/m 2 Above, the heat distortion temperature exceeds 100 ℃.
The matte PC/ABS alloy material product prepared by the invention can be widely applied to household appliances, wall switches, kitchen appliances, housing materials, automobile materials, materials for manufacturing parts in other industrial fields and the like, and is particularly suitable for the harsh application fields with visual requirements and high heat resistance requirements of indoor household appliances, lighting appliances and the like.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (7)
1. A matte PC/ABS alloy material is characterized in that: the composite material comprises the following components in parts by mass:
70.0-90.0 parts of polycarbonate resin;
5.0-35.0 parts of ABS resin;
0.1-10.0 parts of a toughening agent;
2.0-15.0 parts of organic matte agent;
1.0-6.0 parts of inorganic matte agent;
0.01-2.0 parts of antioxidant;
0.01-1.2 parts of other auxiliary agents;
wherein the organic matte agent is MH2030; the inorganic matte agent is talcum powder subjected to surface treatment.
2. The alloy material of claim 1, wherein: the polycarbonate resin is at least one of aromatic polycarbonates with viscosity average molecular weight of 10000-40000.
3. The alloy material of claim 1, wherein: the toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic ester-glycidyl methacrylate terpolymer, maleic anhydride functionalized ethylene-vinyl acetate copolymer and organic silicon rubber graft toughening agent.
4. The alloy material of claim 1, wherein: the antioxidant is a main antioxidant and an auxiliary antioxidant which are in a mass ratio of 1.0-1.0 or only the main antioxidant is added.
5. The alloy material of claim 1, wherein: the other auxiliary agent is a lubricant and/or an anti-dripping agent.
6. A method of preparing the matte PC/ABS alloy material of claim 1, comprising: (1) Weighing the raw materials according to the formula, and sequentially putting the raw materials into a mixer to be uniformly blended to obtain a premix; (2) And (2) putting the premix prepared in the step (1) into a double-screw extruder, and carrying out melt mixing and extrusion granulation in the double-screw extruder to obtain the premix.
7. Use of the matte PC/ABS alloy material according to claim 1 in household appliances, wall switches, residential materials, automotive materials.
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Families Citing this family (5)
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| CN112375362B (en) * | 2020-11-06 | 2022-03-22 | 金发科技股份有限公司 | PC/ABS composition and preparation method and application thereof |
| CN114773820B (en) * | 2022-03-31 | 2023-11-03 | 金发科技股份有限公司 | PC/ABS copolymer and preparation method thereof |
| CN115286743A (en) * | 2022-08-17 | 2022-11-04 | 中山大简科技有限公司 | Photocuring resin for high-precision matte 3D printing and preparation method thereof |
| CN115521602A (en) * | 2022-10-21 | 2022-12-27 | 苏州旭光聚合物有限公司 | Low-glossiness PC-ABS resin and preparation method thereof |
| CN115895227A (en) * | 2022-11-17 | 2023-04-04 | 湖北合聚高分子材料有限公司 | Low-gloss PC/ABS flame-retardant material and preparation method thereof |
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