CN113416372B - Spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material and preparation method thereof - Google Patents
Spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material and preparation method thereof Download PDFInfo
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- CN113416372B CN113416372B CN202110737509.4A CN202110737509A CN113416372B CN 113416372 B CN113416372 B CN 113416372B CN 202110737509 A CN202110737509 A CN 202110737509A CN 113416372 B CN113416372 B CN 113416372B
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
Abstract
The invention discloses a spraying-free metallic-texture high-gloss high-weather-resistance PMMA/ASA alloy material and a preparation method thereof. The PMMA/ASA alloy material with metal texture, high gloss and high weather resistance provided by the invention can be directly injected without paint spraying treatment, and can realize a colorful appearance effect without spraying, so that the cost is reduced, the environment is protected, the production process is simple, the product yield is improved, the application prospect is very wide, and the PMMA/ASA alloy material has good use value.
Description
Technical Field
The invention belongs to the technology of automobile materials, and particularly relates to a spraying-free metal-texture high-gloss high-weather-resistance PMMA/ASA alloy material.
Background
ASA resin is prepared by acrylonitrile (A), styrene (S) and acrylate (A) ternary graft copolymer (also called AAS), and is widely applied to the fields of electronic and electric appliances, automobile industry, outdoor products and the like. Along with the improvement of aesthetic appearance of people, the pursuit of different colors is different, and the ASA material can be dyed into colorful colors without fading due to the good weather resistance and colorability of the ASA material, and can be directly processed and injected into a product with tens of colors without paint spraying and plating, so that the ASA material can be used as an outdoor product. The PMMA material is one of the directions of high-gloss extruded products, so that the high-gloss high-surface-hardness ASA material can be prepared by adding PMMA in a proper proportion. The key technology of the metal-containing high-gloss high-weather-resistance modified ASA resin lies in the selection and proportioning scheme of rubber, resin, processing aid and the like, and different formulas bring different technical effects.
CN112409738A discloses a spray-free material, which comprises the following components in percentage by mass: 80-95% of matrix resin, 0.1-3% of effect toner, 0.1-3% of base toner, 1-3% of auxiliary agent master batch and 0-20% of filler; can realize the color effect of multiple difference, has better toughness simultaneously, still discloses a manufacturing approach of spraying-free gadget for automotive interior, utilizes double-colored forming die to avoid producing flow mark and weld line defect. CN109401161A relates to a PMMA material which is free of spraying, high in weather resistance and scratch resistance and a preparation method thereof; the PMMA material comprises the following raw materials in parts by mass: 40-60 parts of PMMA resin; 30-40 parts of an impact modifier; 5-20 parts of a scratch-resistant agent; 0.5-1 part of antioxidant; 0.5-1 part of ultraviolet absorbent; 2-4 parts of modified pigment; the scratch-resistant agent is prepared from fluororesin and silicone powder according to the weight ratio of (95-98): and (2) to (5), has excellent weather resistance and scratch resistance, and can meet the quality requirements of automobile exterior parts on weather resistance and scratch resistance. CN109320873A discloses a paint-free lamp plastic with a metal effect and a preparation method thereof, wherein the paint-free lamp plastic comprises the following components in parts by mass: 95-105 parts of plastic, 0.5-1 part of silver powder, 1-2.5 parts of pearl powder, 0.7-1.5 parts of toner, 0.2-0.5 part of dispersant and 0.3-0.5 part of anti-flow agent, and directly injection-molding the required lamp and lamp decoration product shells through an injection molding machine after stirring, mixing, dehumidifying and drying processes. CN107778750A provides a scratch-resistant and weather-resistant blending material with high-brightness metal texture, which comprises the following components in parts by weight: 40-60 parts of ASA resin, 40-60 parts of PMMA resin, 20-40 parts of SAN resin, 0.2-1 part of metal pigment, 0.2-1 part of processing aid, 2-5 parts of compatilizer, 0.1-1 part of antioxidant and 0.2-1 part of weather-resistant agent. CN106519530A discloses a composite material and a preparation method thereof, wherein the composite material comprises the following raw materials in parts by mass: ASA resin: 10-50 parts; PMMA resin: 50-80 parts; compatible toughening agent: 5-20 parts of a solvent; color master batch: 2-6 parts; pearl powder: 0.1-2 parts; lubricant: 0.5-2 parts; antioxidant: 0.2-0.6 part; the composite material is prepared by blending, melting and granulating the raw materials in parts by weight. CN111978673A relates to a high-gloss high-surface-hardness spraying-free ABS composite material and a preparation method thereof, wherein the high-gloss high-surface-hardness spraying-free ABS composite material comprises the following components in parts by weight: 100 parts of ABS, 8-30 parts of cycloolefin copolymer, 5-12 parts of compatilizer I, 5-15 parts of spraying-free effect pigment master batch, 0.3-0.5 part of antioxidant, 0.3-0.6 part of light stabilizer and 0.3-0.8 part of dispersant I. CN110938276A discloses a spraying-free ABS plastic raw material, which comprises the following components in percentage by mass: 60% of ABS resin, 23% of SAN resin, 10% of PMMA resin, 5% of assistant and 2% of silver powder.
In addition, for the metal texture spraying-free plastic alloy, the appearance flow mark is a production defect which is difficult to overcome all the time, and in the prior art, the effect of reducing the flow mark is realized by utilizing a compatilizer (coupling agent) and adopting a method of composite metal powder/pearl powder. At present, the PMMA/ASA alloy material with metallic texture, high glossiness and high weather resistance is contained at home and abroad, the spraying (priming paint spraying, baking, color paint spraying, baking, finish paint spraying and baking) is mainly carried out, in order to ensure that the surface of the product has metallic texture, a large amount of pearl powder or metal powder is sprayed, the requirements of the environmental protection aspect and the product qualification rate are difficult to meet, and the existing method for overcoming the flow marks is not good for improving the spraying-free metallic texture high gloss alloy, so the problem that the technical need is broken through is solved.
Disclosure of Invention
The PMMA/ASA alloy material with metal texture, high gloss and high weather resistance provided by the invention can be directly injected without paint spraying treatment, and can realize a colorful appearance effect without spraying, so that the cost is reduced, the environment is protected, the production process is simple, the product yield is improved, the application prospect is very wide, and the PMMA/ASA alloy material has good use value.
The invention adopts the following technical scheme:
a spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material comprises AS resin, PMMA resin, ASA rubber powder, glass powder, pigment and an auxiliary agent; the glass powder is in a polyhedral structure. Preferably, the spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material consists of AS resin, PMMA resin, ASA rubber powder, glass powder, pigment and an auxiliary agent.
The invention discloses a preparation method of the spraying-free metallic-texture high-gloss high-weather-resistance PMMA/ASA alloy material.
The invention also discloses a spraying-free metallic high-gloss high-weather-resistance PMMA/ASA injection molding piece, which is obtained by injection molding of the spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material; the preparation method comprises the steps of mixing AS resin, PMMA resin, ASA rubber powder, glass powder, pigment and an auxiliary agent, adding the mixture into a screw extruder, extruding to obtain a spraying-free metallic-texture high-gloss high-weather-resistance PMMA/ASA alloy material, and then injecting the spraying-free metallic-texture high-gloss high-weather-resistance PMMA/ASA alloy material to obtain a spraying-free metallic-texture high-gloss high-weather-resistance PMMA/ASA injection molding piece.
In the invention, the glass powder is in a polyhedral structure, and the particle size is 1-200 mu m, preferably 10-100 mu m; the invention discloses a polyhedral glass powder for preparing a spraying-free alloy material for the first time, which is combined with a resin formula to avoid appearance flow marks and solves the defect that the flow marks can be avoided only by a coupling agent compatilizer and the like in the prior art.
According to the invention, the sum of the weight of AS resin, PMMA resin and ASA rubber powder is 100%, the weight of AS resin is 20-40%, the weight of PMMA resin is 30-50%, the weight of ASA rubber powder is the rest, the weight of glass powder is 0.5-2%, the weight of pigment is 0.5-2%, and the weight of auxiliary agent is 0.8-2%. Preferably, the sum of the weight of the AS resin, the PMMA resin and the ASA rubber powder is 100%, the weight of the AS resin is 25-35%, the weight of the PMMA resin is 35-45%, the weight of the ASA rubber powder is the rest, the weight of the glass powder is 0.8-1.5%, the weight of the pigment is 0.8-1.2%, and the weight of the auxiliary agent is 0.9-1.5%.
In the invention, the pigment is a single-component pigment or a multi-component pigment. For example, the pigment is a red pigment, may be a single red pigment, or may be a composite red pigment, preferably a composite red pigment, more preferably a composite of an organic red pigment and an organic orange pigment, and most preferably, the weight ratio of the organic red pigment to the organic orange pigment is 1: (2-3), preferably 2: 5.
In the invention, the auxiliary agent is an antioxidant and an anti-ultraviolet agent, and is a conventional auxiliary agent in the field.
In the invention, the resin is the existing product, wherein:
the AS resin is acrylonitrile-styrene copolymer, and the melt index is 20-50 g/10 min;
the PMMA resin is polymethyl methacrylate, and the melt index is 5-20 g/10 min;
the ASA rubber powder is core-shell copolymer of butyl acrylate, methyl methacrylate, acrylonitrile and styrene, wherein the content of butyl acrylate is 40-70%.
The preparation method comprises the steps of mixing AS resin, PMMA resin, ASA rubber powder, glass powder, pigment and an auxiliary agent, adding the mixture into a screw extruder, and extruding to obtain the spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material. Specifically, AS resin, PMMA resin, ASA rubber powder, glass powder, pigment and an auxiliary agent are mixed in a high-speed mixer, then the mixture is directly added into a double-screw extruder, and the spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material is obtained through the working procedures of melting plasticization, extrusion, cooling, grain cutting, drying and the like. Screw extrusion is a conventional process. For example, the processing temperature of the extruder is 160-200 ℃ in one-five zones; 200-220 ℃ from six areas to ten areas; eleven to thirteen zones 230 ℃. The rotating speed of the screw is set to be 320-350 r/min, and the rotating speed of the main feeding screw is set to be 30-35 r/min.
According to the invention, polyhedral glass powder is combined with the composite red pigment, so that the obtained injection molding part has no flow mark, is bright in appearance, saturated in metal texture and high in glossiness without modification of a coupling agent, and can meet the requirements of automobile ornaments on weather resistance, glossiness and appearance quality. In particular, the invention takes AS resin and PMMA resin AS matrixes, ASA rubber powder is added, the low temperature resistance is improved, and the weather resistance and the glossiness of the product are obviously improved by combining polyhedral glass powder and composite red pigment.
Drawings
FIG. 1 shows injection molded parts of different formulations of pigments;
FIG. 2 is a photograph of a prior art painted product;
FIG. 3 is a formulation injection molded part of example 1;
FIG. 4 shows the formulation injection molded part of example 1 and the formulation injection molded part of example 4;
FIG. 5 shows a formulation injection molded part of comparative example 1.
Detailed Description
The raw materials of the invention are all commercial products.
AS resin SAN-PN 2200; PMMA resin, Mitsubishi yang VH 5-001; ASA gelatine powder is Mitsubishi yang ASA-S2001; ASA resin BADALAC, ASA 30; the glass powder is GW050 of Yingrong technology, the particle size is 10-100 mu m, and the glass powder is polyhedral; the mica pearl powder is PW153 of Yingrong technology, and the particle size is 10-100 mu m; the metal powder is PE5501DSS with strength and the particle size of 55 mu m (D50); the particle size of the glass beads is 10-30 μm.
The test methods or technical requirements of the present invention are conventional in the art:
melt index: according to ISO 1133, 220 ℃, 10 kg; and (3) judging standard: MFR is more than or equal to 10 g/10 min;
impact strength: cone swinging according to ISO 179-1eA 4J; DW-50 low-temperature test chamber: -30 ℃/4 h; and (3) judging standard: not less than 4 kj/m2；
Xenon lamp aging (weathering resistance): SAE J2527 Total energy 2500kj/m2(ii) a And (3) judging standard: the sample piece has no crack, DE ≦ 3.0, gray scale: at least 4 grades, no cracks, slight changes in color and gloss;
gloss: an angle of 20 degrees is required to be more than or equal to 78 degrees;
a color difference meter: 10 degree/D65, which is required to be consistent with the A value of the existing spraying product color (note: the A value is within +/-1 of the standard);
tensile strength: universal tensile testing machine ISO 527, tensile speed 50mm/min, gauge length 50mm, determination standard: not less than 44 MPa.
Note: r orange, C16H9Cl2N2NaO4S; the composite pigment is pigment R orange and pigment solvent red 135 with the weight ratio of 2: 5.
The invention provides a spraying-free alloy material for replacing the existing paint spraying product, and creatively realizes the technical effects of good appearance (similar to or even slightly superior to the existing paint spraying product), no flow mark, consistent color with the existing paint spraying product and good weather resistance.
The examples and comparative formulations are shown in table 1, and the preparation methods are as follows: adding AS resin, ASA rubber powder, PMMA resin, glass powder, an antioxidant 1076, an antioxidant 9228, an anti-UV agent 2020, an anti-UV agent UV234 and all pigments into a high-speed mixer and conventionally mixing for 7 min; and melting and plasticizing the uniformly mixed materials by a double-screw extruder, extruding, cooling and granulating, drying the obtained composite granules in a drying box at the temperature of 100 ℃ for 5 hours to obtain the metallic high-gloss high-weather-resistance ASA alloy granules, which is a spraying-free red metallic high-gloss high-weather-resistance PMMA/ASA alloy material. If a component is omitted from the example, it is not added; if the component is replaced, the component is replaced and added. The processing temperature of the extruder is 160-200 ℃ in one-five areas; 200-220 ℃ from six areas to ten areas; eleven to thirteen zones 230 ℃. The screw speed was set at 350r/min and the main feed screw speed was 30 r/min.
The PMMA/ASA alloy materials in the embodiment and the proportion are subjected to injection molding (the injection molding temperature is 220-260 ℃, and the mold temperature is 70-80 ℃) to obtain an injection molding piece, and the performance test is carried out, wherein the results are shown in Table 2.
The composite pigment of the example 1 is replaced by other conventional pigments with the same weight, the rest of the pigments are unchanged, and injection molding is carried out to obtain injection molding parts with different colors (blue, red, yellow, gray and the like) through the same granulation and injection molding, and the injection molding parts are good in appearance, free of flow marks and 78-80 in glossiness (20-degree angle) as shown in figure 1.
FIG. 2 is a photograph of a prior art painted product (painted comparative) and FIG. 3 is a view of an injection molded article according to example 1 of the present invention, showing that the present invention is an alternative in appearance to the prior art painted product and the improvement in gloss is remarkable.
FIG. 4 shows the injection-molded articles of example 1 (left) and example 4 (right), and it can be seen that the products of the present invention have high gloss, excellent appearance, and no flow marks.
Fig. 5 shows the injection-molded part of comparative example 1, in which the flow marks are evident in comparison with fig. 3.
Comparative example 6
On the basis of example 1, the AS resin and the ASA rubber powder were all replaced by the same amount of ASA resin, and the balance was unchanged, so that the glossiness (20-degree angle) was reduced to 79, and the low-temperature performance was not satisfactory.
Example 5
The amount of the glass frit was adjusted to 1.5Kg in addition to example 1, and the balance was unchanged, the gloss (20 ° angle) was 80, and the weather resistance was lowered, DE × = 3.0.
Based on example 1, the amount of glass frit was adjusted to 2.0Kg, and the balance was unchanged, the gloss (20 ° angle) was 78, and the weather resistance was decreased, DE × = 3.5.
Example 6
In addition to example 1, the glass powder was replaced with mica pearl powder, and the balance was unchanged, the appearance was free from flow marks, the gloss (20 ° angle) was reduced to 80, and the weather resistance was reduced, DE × = 3.3.
Example 7
Based on the example 1, the antioxidant 1076 was replaced with the antioxidant 1010, and the balance was unchanged, the appearance was free from flow marks, the gloss (20 ℃ angle) was 83, and the weather resistance was satisfactory.
Example 8
In addition to example 1, the UV inhibitor 2020 was replaced with Tinuvin770, and the balance was unchanged, so that the coating had no flow mark on the appearance, had a gloss (20 ° angle) of 82, and satisfied weather resistance.
Claims (7)
1. A spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material is characterized by comprising AS resin, PMMA resin, ASA rubber powder, glass powder, pigment and an auxiliary agent, wherein a coupling agent is not included; the particle size of the glass powder is 1-200 mu m; the glass powder is in a polyhedral structure; the weight sum of the AS resin, the PMMA resin and the ASA rubber powder is 100%, the weight sum of the AS resin is 25-35%, the weight sum of the PMMA resin is 35-45%, the weight sum of the ASA rubber powder is the rest, the weight sum of the glass powder is 0.8-1.5%, the weight sum of the pigment is 0.8-1.2%, and the weight sum of the auxiliary agent is 0.9-1.5%.
2. The preparation method of the spraying-free metallic-sense high-gloss high-weather-resistance PMMA/ASA alloy material AS claimed in claim 1, which is characterized by comprising the following steps of mixing AS resin, PMMA resin, ASA rubber powder, glass powder, pigment and auxiliary agents, adding the mixture into a screw extruder, and extruding to obtain the spraying-free metallic-sense high-gloss high-weather-resistance PMMA/ASA alloy material.
3. The preparation method of the spray-free metal-textured high-gloss high-weather-resistance PMMA/ASA alloy material as claimed in claim 2, characterized in that the pigment is a single-component pigment or a multi-component pigment.
4. A spraying-free metallic high-gloss high-weather-resistance PMMA/ASA injection molding part is characterized by being obtained by injection molding of the spraying-free metallic high-gloss high-weather-resistance PMMA/ASA alloy material of claim 1.
5. The preparation method of the spraying-free metallic-sense high-gloss high-weather-resistance PMMA/ASA injection molding piece AS claimed in claim 4, which is characterized by comprising the following steps of mixing AS resin, PMMA resin, ASA rubber powder, glass powder, pigment and an auxiliary agent, adding the mixture into a screw extruder, extruding to obtain a spraying-free metallic-sense high-gloss high-weather-resistance PMMA/ASA alloy material, and then injecting the spraying-free metallic-sense high-gloss high-weather-resistance PMMA/ASA alloy material to obtain a spraying-free metallic-sense high-gloss high-weather-resistance PMMA/ASA injection molding piece.
6. The use of the spray-free, metallic, high-gloss, weather-resistant PMMA/ASA alloy material of claim 1 in the preparation of spray-free, high-gloss plastics.
7. Use according to claim 6, characterized in that the high gloss is at an angle of 20 ° or more and 78.
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| CN114516994B (en) * | 2022-02-25 | 2023-07-07 | 江苏金发科技新材料有限公司 | Light aging resistant red PMMA/ASA alloy and preparation method and application thereof |
| CN114773757A (en) * | 2022-05-31 | 2022-07-22 | 四川朗迪新材料有限公司 | Spraying-free metal weather-resistant PMMA/ASA alloy material |
| CN115011054A (en) * | 2022-07-03 | 2022-09-06 | 四川朗迪新材料有限公司 | High-black high-brightness spraying-free scratch-resistant super-weather-resistant PMMA/ASA alloy material |
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