CN112852086A - Spraying-free metal-like effect ASA resin for ASA/PVC double-color co-extrusion fabric and preparation method and application thereof - Google Patents
Spraying-free metal-like effect ASA resin for ASA/PVC double-color co-extrusion fabric and preparation method and application thereof Download PDFInfo
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- CN112852086A CN112852086A CN202011642283.1A CN202011642283A CN112852086A CN 112852086 A CN112852086 A CN 112852086A CN 202011642283 A CN202011642283 A CN 202011642283A CN 112852086 A CN112852086 A CN 112852086A
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention provides a spraying-free metal-imitating ASA resin for an ASA/PVC (acrylonitrile styrene acrylate/polyvinyl chloride) double-color co-extruded fabric, which comprises the following components in parts by weight: 55-80 parts of styrene-acrylonitrile-acrylic rubber terpolymer; 0.5-4.0 parts of metal effect pigment; 0.5-6.0 parts of pearlescent pigment; 20-45 parts of an impact modifier; 0.1-4.0 parts of a lubricant; 0.1-0.6 part of antioxidant; the thickness of the metal effect pigment is 1-5 mu m; the average particle size of the metal effect pigment is 5-90 mu m; the average particle size of the pearlescent pigment is 10-250 μm. The ASA resin has excellent visual effect and glossiness with metallic color texture.
Description
Technical Field
The invention relates to the technical field of high polymer composite materials, in particular to a spraying-free metal-effect-imitating ASA resin for ASA/PVC double-color co-extrusion fabric and a preparation method and application thereof.
Background
The metal appearance has unique aesthetic effect, is an important element in appearance design, and is one of the development directions of future consumer electronic products. Metals, especially aluminum alloys, are commonly used in high-end products by various home appliances, notebook computers, and mobile phone brands, and become excellent representatives of high-grade, technological content, and texture. Although product designs prefer to use metal, metal has the disadvantages of being heavy, difficult to form into complex shapes, inconvenient assembly, cumbersome and expensive post-processing techniques, and the advantages of plastic just compensate for this. Spraying-free metal-texture plastics, and directly adding metal pigment in the plastic particle granulation process to achieve the appearance of imitation metal. The method has the characteristics of one-step forming, simple process, high yield, environmental protection, energy conservation, recoverability, reutilization, good color durability, difficult fading in the transportation and use processes and the like. The metal texture plastic has beautiful appearance and good visual texture effect and is very popular with people. Meanwhile, the composite material can be directly molded by injection or extrusion, so that the overall cost is effectively reduced, and the efficiency of enterprises is greatly improved, and the composite material is widely applied to the fields of household appliances such as refrigerators, freezers, electric cookers, dust collectors and induction cookers and the field of automobile bumpers.
PVC has the advantages of flame retardance, electrical insulation, corrosion resistance and the like, and is widely applied to automobiles, packaging and building materials. The spraying-free metal-imitating plastic is co-extruded with PVC to prepare the section with good metal appearance. Based on different materials of the co-extrusion layer, the method can be divided into PMMA/PVC co-extrusion, ASA/PVC co-extrusion and PVC/PVC co-extrusion.
At present, PMMA/PVC co-extrusion resin is generally applied to the aspects of door frames of refrigerators, freezers and the like, so the main performance of the PMMA/PVC co-extrusion resin is high gloss and scratch resistance, the adopted color mainly adopts silver color and black color, and Chinese patent (CN111117130A) discloses a spraying-free metal-effect-imitated PMMA/PVC two-color co-extrusion fabric resin and a preparation method thereof, and in a PMMA/PVC system, the melt index of PMMA is generally 30-40 g/10min, the viscosity of the system is low, and the PMMA/PVC co-extrusion fabric resin can be applied to conventional metal effect pigments.
As for an ASA/PVC co-extrusion fabric resin system, the resin system is mainly applied to window frames and roof tiles, and the difference of the system and the application causes that the PMMA/PVC system can not be directly applied to ASA resin at present, and if the resin system is directly applied, the problems of poor metal effect, poor appearance and the like can be caused.
Therefore, the development of ASA/PVC co-extrusion fabric resin aiming at the spraying-free metal-like effect is urgently needed.
Disclosure of Invention
The invention provides a spraying-free metal-imitating ASA resin for ASA/PVC double-color co-extrusion fabric, aiming at overcoming the defect of poor metal-imitating effect of the ASA/PVC co-extrusion resin.
The invention also aims to provide a preparation method of the spraying-free metal-imitating ASA resin for the ASA/PVC double-color co-extrusion fabric.
The invention also aims to provide application of the spraying-free metal-effect-imitating ASA resin for the ASA/PVC double-color co-extrusion fabric.
In order to achieve the purpose, the invention adopts the technical scheme that:
a spraying-free metal-like effect ASA resin for ASA/PVC double-color co-extrusion fabric comprises the following components in parts by weight:
the thickness of the metal effect pigment is 1-5 mu m;
the average particle size of the metal effect pigment is 5-90 mu m; the average particle size of the pearlescent pigment is 10-250 μm.
In an ASA/PVC resin system, because the melt index of the styrene-acrylonitrile-acrylic rubber terpolymer is very low, the viscosity of the system is very high, and very strong shearing force is needed in the preparation process to co-extrude the styrene-acrylonitrile-acrylic rubber terpolymer, but the very strong shearing force can also damage the metal effect pigment, because the thickness of the conventional metal effect pigment is generally about 0.5 μm, the strong shearing force can damage, bend and deform the metal effect pigment, so that the metal effect is reduced, and the glossiness is reduced.
The thickness of the metallic effect pigment is selected to be 1-5 mu m, so that the metallic effect pigment can be prevented from being crushed, deformed and bent, and when the thickness of the metallic effect pigment is not more than 5 mu m, the resin dispersion performance is reduced due to too thick thickness, the glossiness is reduced, and the appearance is damaged.
And when the particle size of the metallic effect pigment is 5-90 mu m and the particle size of the pearlescent pigment is 10-250 mu m, the dispersibility of the metallic effect pigment and the pearlescent pigment can be ensured, and the visual effect of excellent metallic color texture is achieved.
Preferably, the thickness of the metal effect pigment is 2-3 μm.
The thickness of the metallic effect pigment refers to the thickness of the metallic effect pigment before injection molding.
When the thickness of the metal effect pigment is 2-3 mu m, the metal effect pigment has better appearance and glossiness.
Preferably, the average particle size of the metal effect pigment is 30-90 μm. When the particle size of the metal effect pigment is 30-90 mu m, the metal effect pigment has better appearance and glossiness.
Preferably, the average particle size of the pearlescent pigment is 40-150 μm. When the particle size of the pearlescent pigment is 40-150 mu m, the pearlescent pigment has better appearance and glossiness.
Preferably, the weight part ratio of the pearlescent pigment to the metal effect pigment is more than or equal to 4: 1.
preferably, the melt index of the styrene-acrylonitrile-acrylic rubber terpolymer at 220 ℃ under a load of 10Kg is 5-20 g/10 min.
The melt index is determined by heating and applying a load to a styrene-acrylonitrile-acrylic rubber terpolymer by means of a melt index tester according to the requirements of the test standard (ISO1133-1-2011) to measure the mass of the material melt flowing out of a die of a specified diameter within 10 minutes.
Preferably, the metallic effect pigment is an aluminium pigment.
The form of the aluminum pigment is generally silver element type or corn flower type.
Preferably, the pearlescent pigment is one or a mixture of two of natural mica titanium pearlescent pigment or artificial synthetic mica titanium pearlescent pigment.
Preferably, the impact modifier is of a core-shell structure, wherein the core layer is a copolymer of butadiene and styrene, and the shell layer is a copolymer of methyl methacrylate and styrene.
Preferably, the antioxidant is at least one of phosphite antioxidant or hindered phenol antioxidant.
The invention also provides a preparation method of the spraying-free metal-like effect ASA resin for the ASA/PVC double-color co-extrusion fabric, which comprises the following steps:
s1, weighing and uniformly mixing the dried styrene-acrylonitrile-acrylic rubber terpolymer, the metal effect pigment, the pearlescent pigment, the dried impact modifier, the lubricant and the antioxidant according to a proportion to obtain a premix;
s2, putting the premix obtained in the step S1 into a double-screw machine, extruding, cooling and granulating to obtain the spraying-free metal effect imitating ASA resin for the ASA/PVC double-color co-extrusion fabric.
The spraying-free metal-imitating ASA resin for the ASA/PVC double-color co-extrusion fabric is applied to the preparation of colorful plastic doors and windows, plastic profiles, furniture or home appliance appearance decoration.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a spraying-free metal effect imitating ASA resin for an ASA/PVC double-color co-extrusion fabric, wherein a metal effect pigment with the thickness of 1-5 mu m is selected from the ASA resin, the particle size of the metal effect pigment is 5-90 mu m, and the particle size of a pearlescent pigment is 10-250 mu m, so that the dispersibility of the metal effect pigment and the pearlescent pigment can be ensured, and the ASA resin has excellent visual effect and glossiness with metal color texture.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following examples and comparative examples employ the following starting materials:
styrene-acrylonitrile-acrylic rubber terpolymer: A600N, Japanese UMG
Metal effect pigment a: aluminum pigment having a thickness of 1 μm and an average particle diameter of 15 μm, commercially available;
metal effect pigment B: aluminum pigment having a thickness of 2 μm and an average particle diameter of 15 μm, commercially available;
metallic effect pigment C1: aluminum pigment having a thickness of 3 μm and an average particle diameter of 15 μm, commercially available;
metal effect pigment D: aluminum pigment having a thickness of 4 μm and an average particle diameter of 15 μm, commercially available;
metal effect pigment E: an aluminum pigment having a thickness of 5 μm and an average particle diameter of 15 μm, which is commercially available;
metal effect pigment F: aluminum pigment with a thickness of 0.5 μm, an average particle size of 15 μm, commercially available;
metal effect pigment G: aluminum pigment having a thickness of 7 μm and an average particle diameter of 15 μm, commercially available;
metallic effect pigment C2: aluminum pigment having a thickness of 3 μm and an average particle diameter of 5 μm, commercially available;
metallic effect pigment C3: aluminum pigment having a thickness of 3 μm and an average particle diameter of 30 μm, commercially available;
metallic effect pigment C4: aluminum pigment having a thickness of 3 μm and an average particle diameter of 90 μm, commercially available;
metallic effect pigment C5: aluminum pigment having a thickness of 3 μm and an average particle diameter of 1 μm, commercially available;
metallic effect pigment C6: aluminum pigment having a thickness of 3 μm and an average particle diameter of 150 μm, commercially available;
pearlescent pigment A: the average particle size is 10 μm, and is commercially available;
and (3) pearlescent pigment B: the average particle size was 40 μm, commercially available;
pearlescent pigment C: the average particle size is 90 μm, and is commercially available;
pearlescent pigment D: the average particle size is 150 μm, and is commercially available;
pearlescent pigment E: the average particle size is 250 μm, and is commercially available;
pearlescent pigment F: the average particle size was 5 μm, commercially available;
pearlescent pigment G: the average particle size is 300 μm, and is commercially available;
impact modifier: EM500, LG Chem;
lubricant: HILUB-50, PT. CMS Chemical Indonesia;
antioxidant: JYANOX-168, Beijing, very easily manufactured by chemical Co.
The present invention will be described in detail with reference to examples and comparative examples.
The ASA resin is prepared by the following method in the examples and comparative examples, and the components are weighed according to the weight ratio in the table 1-3, and the specific steps are as follows:
s1, weighing and uniformly mixing the dried styrene-acrylonitrile-acrylic rubber terpolymer, the metal effect pigment, the pearlescent pigment, the dried impact modifier, the lubricant and the antioxidant according to a proportion to obtain a premix;
s2, putting the premix obtained in the step S1 into a double-screw machine, extruding, cooling and granulating to obtain the spraying-free metal effect imitating ASA resin for the ASA/PVC double-color co-extrusion fabric.
Examples 1 to 8
TABLE 1 formulations of examples 1-8
Examples 9 to 18
TABLE 2 formulations (parts) of examples 9 to 18
Comparative examples 1 to 6
TABLE 3 formulations (parts) of comparative examples 1 to 6
The above examples and comparative examples were each tested for performance by the following method
Gloss: the measurement is carried out according to the national standard GB/T8807-1988 method for testing the specular gloss of plastics, and the reflection data at an angle of 60 ℃ are tested.
Appearance: the appearance evaluation is based on visual inspection, and the following evaluation criteria are adopted:
excellent-the glossiness is more than or equal to 90, the surface metal effect is good, and no flow marks exist;
good-the glossiness is more than or equal to 88, the surface metal effect is better, no flow mark;
generally, the glossiness is more than or equal to 86, the surface metal effect is better, and slight flow marks are allowed to exist;
poor-gloss less than 86, weak surface metallic effect, visually apparent flow marks;
each sample was evaluated by 5 persons separately, and the average was taken.
TABLE 4 data for examples and comparative examples
As can be seen from examples 1 to 5, the aluminum pigment having a particle size of 2 to 3 μm in thickness is most suitable, and can provide a good metallic texture while preventing deformation due to an excessively thin aluminum sheet.
As can be seen from examples 3 and 6 to 8, the metallic feeling of the aluminum pigment is the best at a constant thickness of 30 to 90 μm.
As can be seen from examples 9 to 16, the pearlescent pigment has good appearance and luster when the particle size is 40 to 150 μm.
As can be seen from comparative examples 1 to 5, the aluminum pigment with too small thickness (0.5 μm) is easy to deform during extrusion molding, while the aluminum pigment with too large thickness (7 μm) is poor in metallic feeling on the surface of the aluminum powder, and the obtained product is poor in metallic feeling and gloss. When the particle size of the metallic effect pigment or the particle size of the pearlescent pigment is too large or too small, the luster and the appearance are affected and do not meet the standard,
it should be understood that the above-described 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. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The spraying-free metal-like effect ASA resin for the ASA/PVC double-color co-extrusion fabric is characterized by comprising the following components in parts by weight:
the thickness of the metal effect pigment is 1-5 mu m;
the average particle size of the metal effect pigment is 5-90 mu m; the average particle size of the pearlescent pigment is 10-250 μm.
2. The spraying-free metal effect imitating ASA resin for the ASA/PVC bi-color co-extruded fabric as claimed in claim 1, wherein the thickness of the metal effect pigment is 2-3 μm.
3. The spraying-free metal effect imitating ASA resin for ASA/PVC bi-color co-extrusion fabric according to claim 1, wherein the weight part ratio of the pearlescent pigment to the metal effect pigment is more than or equal to 4: 1.
4. the spraying-free metal-like effect ASA resin for ASA/PVC bicolor co-extrusion fabric as claimed in claim 1, wherein the melt index of the styrene-acrylonitrile-acrylic rubber terpolymer at 220 ℃ under a load of 10Kg is 5-20 g/10 min.
5. The spraying-free metal-effect-imitated ASA resin for the ASA/PVC bi-color co-extrusion fabric as recited in claim 1, wherein the metal effect pigment is aluminum pigment.
6. The spraying-free metal-effect-imitated ASA resin for ASA/PVC bi-color co-extrusion lining as claimed in claim 1, wherein the pearlescent pigment is one or a mixture of natural mica titanium pearlescent pigment or synthetic mica titanium pearlescent pigment.
7. The spraying-free metal-effect-imitated ASA resin for ASA/PVC bicolor co-extrusion fabric as recited in claim 1, wherein the impact modifier is of a core-shell structure, wherein the core layer is a copolymer of butadiene and styrene, and the shell layer is a copolymer of methyl methacrylate and styrene.
8. The spraying-free metal-like effect ASA resin for ASA/PVC bicolor co-extrusion fabric as claimed in claim 1, wherein the antioxidant is at least one of phosphite antioxidant or hindered phenol antioxidant.
9. The preparation method of the spraying-free metal effect imitating ASA resin for the ASA/PVC bi-color co-extruded fabric according to any one of claims 1 to 8, which comprises the following steps:
s1, weighing and uniformly mixing the dried styrene-acrylonitrile-acrylic rubber terpolymer, the metal effect pigment, the pearlescent pigment, the dried impact modifier, the lubricant and the antioxidant according to a proportion to obtain a premix;
s2, putting the premix obtained in the step S1 into a double-screw machine, extruding, cooling and granulating to obtain the spraying-free metal effect imitating ASA resin for the ASA/PVC double-color co-extrusion fabric.
10. The application of the spraying-free metal-effect-imitating ASA resin for the ASA/PVC bi-color co-extrusion fabric as defined in any one of claims 1 to 8 in the preparation of color plastic doors and windows, plastic profiles, furniture or home appliance appearance decoration.
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| CN202011642283.1A CN112852086B (en) | 2020-12-31 | 2020-12-31 | Spraying-free metal-like effect ASA resin for ASA/PVC double-color co-extrusion fabric and preparation method and application thereof |
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| CN202011642283.1A CN112852086B (en) | 2020-12-31 | 2020-12-31 | Spraying-free metal-like effect ASA resin for ASA/PVC double-color co-extrusion fabric and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199294A (en) * | 2015-09-25 | 2015-12-30 | 银禧工程塑料（东莞）有限公司 | High-gloss spraying-free ABS (acrylonitrile butadiene styrene) composite material with special effect and preparation method thereof |
| CN105647047A (en) * | 2016-01-21 | 2016-06-08 | 天津中财型材有限责任公司 | Chemical modification ASA resin and preparation method and application thereof |
| CN107915944A (en) * | 2017-11-10 | 2018-04-17 | 中山长虹电器有限公司 | It is a kind of that there is bright pearly-lustre, high flowing, the translucent ABS material of high intensity |
| CN110437576A (en) * | 2019-07-27 | 2019-11-12 | 广东奇德新材料股份有限公司 | A kind of nanometer environmental protection exempts from sprayed on material and preparation method thereof |
-
2020
- 2020-12-31 CN CN202011642283.1A patent/CN112852086B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199294A (en) * | 2015-09-25 | 2015-12-30 | 银禧工程塑料（东莞）有限公司 | High-gloss spraying-free ABS (acrylonitrile butadiene styrene) composite material with special effect and preparation method thereof |
| CN105647047A (en) * | 2016-01-21 | 2016-06-08 | 天津中财型材有限责任公司 | Chemical modification ASA resin and preparation method and application thereof |
| CN107915944A (en) * | 2017-11-10 | 2018-04-17 | 中山长虹电器有限公司 | It is a kind of that there is bright pearly-lustre, high flowing, the translucent ABS material of high intensity |
| CN110437576A (en) * | 2019-07-27 | 2019-11-12 | 广东奇德新材料股份有限公司 | A kind of nanometer environmental protection exempts from sprayed on material and preparation method thereof |
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