CN104629206B - Spraying-free PVC composition having special aesthetic effects and preparation method and application thereof - Google Patents
Spraying-free PVC composition having special aesthetic effects and preparation method and application thereof Download PDFInfo
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- CN104629206B CN104629206B CN201310544196.6A CN201310544196A CN104629206B CN 104629206 B CN104629206 B CN 104629206B CN 201310544196 A CN201310544196 A CN 201310544196A CN 104629206 B CN104629206 B CN 104629206B
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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
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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
- C08K7/00—Use of ingredients characterised by shape
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08K2003/0806—Silver
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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
- C08K2003/0893—Zinc
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Abstract
The invention discloses a spraying-free PVC composition having special aesthetic effects and a preparation method and an application thereof. The spraying-free PVC composition comprises the following components: 70-98 wt% of PVC resin, 1-25 wt% of microspheres formed by coating a special-effect powder with a polymer, 0-10 wt% of a compatibilizer, 0.1-1 wt% of an antioxidant, and 0.1-0.5 wt% of a processing auxiliary agent. The special-effect powder is coated with a water-based polymer dispersion liquid to form the microspheres, and then the microspheres are dispersed to the PVC resin, so that the compatibility of the special-effect powder and the PVC resin can be significantly improved, flow marks formed on the surface of products in an extrusion or injection molding process are eliminated, and weld lines are reduced; and the prepared spraying-free PVC composition has relatively obvious metal texture, pearly flashing effects and other special aesthetic effects, and the market application range of spraying-free materials is greatly improved.
Description
The invention belongs to polymeric material field is and in particular to a kind of spraying PVC that exempts from special decorative effects combines
Thing and its preparation method and application.
Background technology
With people, environmental problem is increasingly paid attention to and pay close attention to, exempt from spraying special-effect material product and just progressively show
Its competitiveness, exempts from spraying aesthetic resin and can replicate gorgeous colorful tone and pearly-lustre, flash effect, the metal that spray painting is produced
The special-effect such as gloss and texture, thus meeting diversified, differential customer demand, and in process of production can be real
Realize energy-saving and emission-reduction, can be widely applied to artware, toy, household electrical appliances, automobile, electronic product, sports goods and office appliance etc.
Field.
At present, exempting to spray the more common preparation method of resin is to add the tool such as metal powder, pearl essence in resin material
There is the effect powder of particular color and gloss.By being distributed to special-effect powder in matrix resin, between special-effect powder mutually
Connect, form the film of continuous special-effect, covered base material, presented special-effect texture, although passing through special-effect
Powder is directly added in resin binder, it is possible to achieve the effect of special gloss, but the compatibility of matrix resin and special-effect powder
Difference, under the conditions of the strong pressure and Strong shear of extrusion or injection, special-effect powder and base resin material are extremely difficult to mobility
Unanimously, particularly baroque product, along flow direction orientation special-effect powder occur and occur melt flows turn to,
Flow velocity is unstable, the phenomenon such as melt converges, and causes special-effect powder skewness in the melt, is easily formed in product surface
The defect such as current mark and weld bond, seriously stops and limits marketing and the application that such exempts from sprayed on material.
Content of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention be to provide one kind no current mark, gently melt
Wiring have special decorative effects exempt from spray PVC composition.
It is still another object of the present invention to provide the above-mentioned preparation side exempting from spraying PVC composition with special decorative effects
Method.
The present invention is achieved by the following technical solutions：
Have special decorative effects exempts from spraying PVC composition, by weight percentage, including following component：
Polyvinyl chloride resin 70-98wt%
Polymer overmold special-effect powder microsphere 1-25wt%
Antioxidant 0.1-1wt%
Processing aid 0.1-5wt%；
Wherein, described polymer overmold special-effect powder microsphere, by weight percentage, including following component：
Aqueous polymer dispersion 18-90wt%
Antioxygen corrosion inhibiter 0-5wt%
Special-effect powder, or aqueouss special-effect slurry material 5-80wt%
Firming agent 0.2-10wt%.
Described aqueous polymer dispersion is selected from PVC emulsion, ABS emulsion, AS emulsion, ASA emulsion, MBS emulsion, phenylpropyl alcohol breast
Liquid, vinyl acetate emulsion, acrylic acid ester emulsion, butyronitrile emulsion, ethylene-vinyl acetate emulsion, Pioloform, polyvinyl acetal solution, polyurethane
Emulsion, polyurethane-acrylic ester emulsion and its modifier one or more；
The solid content of described aqueous polymer dispersion is 10-60wt%.
Described antioxidant is including Hinered phenols antioxidant, phosphite kind antioxidant, amine antioxidants, sulfur-bearing class antioxygen
One or more of agent or metallic salt antioxidant；
Described processing aid is silicone series lubricant agent, amide series lubricant agent, stearic acid lubricant, TPO lubricant
One or more of or ester lubricant.
Described antioxygen corrosion inhibiter be selected from phenylpropyl alcohol triazole, phytic acid, phytate, 8-hydroxyquinoline, organic phosphorus compound, phosphoric acid and
The mixing of one or more of its derivant or pyrogallic acid.
Described special-effect powder includes one or more of metal powder or pearl essence.
Described metal powder is selected from one or more of aluminium powder, copper powder, bronze, argentum powder, zinc powder, glass putty, iron powder, nikel powder；
Described aqueouss special-effect slurry material is to add water and water-soluble solvent, such as isopropanol, second in special-effect powder
Alcohol etc. and other auxiliary agents, its solid content is 10-80wt%, preferably 20-70wt%.
In described aluminium powder the content of Al element be no less than 60wt%, contain simultaneously Zn, Sn, Ni, Pb, Fe, Mg, Si, Mn, Be,
Cu, Ti or one or more of rare earth element；Being shaped as of described aluminium powder is spherical, petal, dendriform, snowflake shape, cornflakes
Shape, silver dollar shape or half silver dollar shape one or more；Its particle diameter is 3-200 μm, preferably 5-100 μm.
In order to avoid aluminium powder explosive in process, oxidizable, the defect such as bad ball milling dispersion, used by the present invention
Aluminium powder is to add surface conditioning agent such as lubricant etc. through surface treatment, the flake aluminum that then ball milling becomes.
In described copper powder the content of Cu element be no less than 60wt%, contain simultaneously Zn, Sn, Ni, Be, Al, Mn, Fe, Pb, Si,
P, B, Ti or one or more of rare earth element；Being shaped as of described copper powder is spherical, dendroid or lamellar, and its particle diameter is 3-200 μ
M, preferably 5-100 μm.
Its transverse section of described pearl essence has the physical arrangement similar to Margarita, and kernel is the material of low optical refractive index,
Be coated on outer layer is the metal-oxide of high index of refraction, and its species specifically includes Muscovitum coating pearl essence, bismuth oxychloride crystallization
Pearl essence, silica-coating pearl essence, aluminium silicate salt coating pearl essence, boric acid aluminium salt coating pearl essence, bismuth oxide coating pearl
One or more of light powder；Described pearl essence surface at least coats layer of metal oxide, and described metal-oxide is oxidation
Aluminum, tin ash, titanium dioxide, ferrum oxide, stibium oxide or zinc oxide one or more；The particle diameter of described pearl essence is 5-
500 μm, preferably 5-200 μm.
The present invention adds pearl essence the metal-like of frosting can be made to become apparent from, this is because pearl essence has spy
Different physical arrangement, when being irradiated by light, can embody pearl effect by multipath reflection and interference so that material surface
Reflected light closer to metal-like.
Described firming agent is selected from polyisocyanates and its oligomer, amino resins, organosiloxane, aziridine and its derives
Thing, polycarbodiimide, one of firming agent containing epoxy radicals or multiple.
Polymer overmold special-effect powder microsphere of the present invention can also add other auxiliary agents, such as according to actual needs
Defoamer, dispersant, anti-settling agent etc., its consumption is conventional amount used.
The particle diameter of described polymer overmold special-effect powder microsphere is 10-1000 μm, preferably 10-300 μm；Wherein special U.S.
The weight percent content that effect powder accounts for microsphere is 5-80wt%, preferably 5-50wt%.
The preparation method of polymer overmold special-effect powder microsphere of the present invention, specifically includes following steps：
a）First, add antioxygen corrosion inhibiter, dispersed with stirring 10-30min in aqueous polymer dispersion under room temperature, obtain
Dispersion liquid；Under agitation, it is slowly added to special-effect powder in dispersion liquid, or aqueouss special-effect slurry material, then
Add firming agent while stirring, and continue to stir 30-120min, make special-effect powder fully dispersed and coated by dispersion liquid,
The composite dispersion liquid of polymer overmold special-effect powder is obtained afterwards；
b）By composite dispersion liquid dried, obtain polymer overmold special-effect powder microsphere.
Preferably, wherein step（b）Described in drying be spray-dried, the intake air temperature of described spray-drying process
For 150-300 DEG C, preferably 170-250 DEG C, air outlet temperature is 50-130 DEG C, preferably 70-100 DEG C.
The preparation method exempting from spraying PVC composition with special decorative effects of the present invention, comprises the steps：
Each raw material is inserted high-speed mixer mix homogeneously according to the above ratio；The mixture obtaining is inserted mixed in double screw extruder
Refining, after cooling, pelletizing, packaging, obtain final product.
Of the present invention have special decorative effects exempt from spray PVC composition can in electronic apparatus, sports goods, do
It is used widely in utility, traffic and transport field.
The present invention compared with prior art, has the advantages that：
The present invention is by being overmolding to after microsphere redispersion to polyvinyl chloride resin by special-effect powder aqueous polymer dispersion
In, the compatibility of special-effect powder and polyvinyl chloride resin can be obviously improved, improve the endurance of cutting of special-effect powder and its squeezing
Go out or injection moulding process in flowing concordance with melt, thus eliminating the current mark of product surface, mitigating weld bond, prepare
Exempt from spraying PVC composition and there is obvious metal-like or special aesthetic effect, substantially increase the city exempting from sprayed on material
Field range of application.
Specific embodiment
To further illustrate the present invention below by specific embodiment, following examples are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiments.
The preparation of embodiment 1-6 polymer overmold special-effect powder microsphere：
By the formula in table 1, first, in aqueous polymer dispersion, under room temperature, add antioxygen corrosion inhibiter, dispersed with stirring
15min, obtains dispersion liquid；Under agitation, it is slowly added to special-effect powder in dispersion liquid, or aqueouss special-effect powder
Slurry, then adds firming agent while stirring, and continues to stir 30-120min, makes special-effect powder fully dispersed and is disperseed
Liquid coats, and the composite dispersion liquid of polymer overmold special-effect powder is finally obtained；By composite dispersion liquid spray drying treatment, obtain
Polymer overmold special-effect powder microsphere, the intake air temperature of spray-drying process is 150-300 DEG C, and air outlet temperature is 50-
130℃.
The concrete proportioning of each composition of table 1 embodiment 1 ~ 6（wt%）
In embodiment 1：Aqueous polymer dispersion is modified PVC emulsion, and its solid content is 10wt%；Metal powder is through table
The flake aluminum that face is processed, in aluminium powder, the content of Al element is 60wt%, contains Zn and Sn simultaneously；Its particle diameter is 100 μm；Antioxygen
Corrosion inhibiter is pyrogallic acid；Firming agent is polycarbodiimide.
In embodiment 2：Aqueous polymer dispersion is polyurethane-acrylic ester emulsion, and its solid content is 60wt%；Metal
Powder is surface treated flake copper, and in copper powder, the content of Cu element is 70wt%, contains Zn and Sn simultaneously；Its particle diameter is 5 μ
m；Antioxygen corrosion inhibiter is phenylpropyl alcohol triazole；Firming agent is polyisocyanates.
In embodiment 3：Aqueous polymer dispersion is polyaminoester emulsion, and its solid content is 40wt%；Special-effect powder is two
Silica-coated pearl essence, its particle diameter is 20 μm；Firming agent is polyisocyanates.
In embodiment 4：Aqueous polymer dispersion is polyacrylate dispersion, and its solid content is 50wt%；Special-effect powder
Coat pearl essence for Muscovitum, its particle diameter is 200 μm；Firming agent is aziridine.
In embodiment 5：Aqueous polymer dispersion is ASA emulsion, and its solid content is 30wt%；Special-effect powder is zinc powder
Mixture with silica-coating pearl essence；Firming agent is amino resins.
In embodiment 6：Aqueous polymer dispersion is vinyl acetate emulsion, and its solid content is 20wt%；Special-effect powder is argentum powder
Coat the mixture of pearl essence with Muscovitum；Firming agent is organosiloxane.
Embodiment 7-13 has the preparation exempting from spraying PVC composition of special decorative effects：
By in table 2 formula by PVC resinoid, polymer overmold special-effect powder microsphere, compatilizer, antioxidant,
Processing aid inserts high-speed mixer mix homogeneously；The mixture obtaining is inserted mixing in double screw extruder,
After cooling, pelletizing, packaging, obtain final product.Acquired results are shown in Table 2：
Antioxidant is hindered phenol antioxygen 1010；
Processing aid is calcium stearate.
Comparative example 1-6：Tradition is exempted to spray the preparation of PVC composition：
By in table 2 formula PVC resinoid, special-effect powder, compatilizer, antioxidant, processing aid are inserted at a high speed
Mixer mix homogeneously；The mixture obtaining is inserted mixing in double screw extruder, after cooling, pelletizing, packaging, obtain final product.Gained
The results are shown in Table 2：
In comparative example 1：Metal powder is surface treated flake aluminum, and in aluminium powder, the content of Al element is 60wt%, simultaneously
Containing Zn and Sn；Its particle diameter is 100 μm；
In comparative example 2：Metal powder is surface treated flake aluminum, and in aluminium powder, the content of Al element is 60wt%, simultaneously
Containing Zn and Sn；Its particle diameter is 100 μm；
In comparative example 3：Metal powder is surface treated flake copper, and in copper powder, the content of Cu element is 70wt%, simultaneously
Containing Zn and Sn；Its particle diameter is 5 μm；
In comparative example 4：Special-effect powder is silica-coating pearl essence, and its particle diameter is 20 μm；
In comparative example 5：Special-effect powder coats pearl essence for Muscovitum；
In comparative example 6：Special-effect powder is the mixture of zinc powder and silica-coating pearl essence.
The concrete proportioning of each composition in table 2 embodiment 7-13 and comparative example 1-6（wt%）And its test performance result
Note：+ more expression current marks are more
More than zero represents that weld bond is more serious
- represent there is not current mark or weld bond, or inconspicuous
Be can be seen that in the case that guarantee other components and content are essentially identical by the Comparative result in upper table 2, implement
Example 7-13 is mixed with matrix resin using polymer overmold special-effect powder microsphere, will be direct for special-effect powder in comparative example 1-6
It is added in matrix resin, comparing embodiment 7-12 and comparative example 1-6, find micro- with polymer-coated metal powder and pearl essence
The product surface of ball and matrix resin mixing gained no current mark substantially, weld bond is lighter, and has more preferable aesthetic effect.
Claims (18)
1. have special decorative effects exempts from spraying PVC composition, by weight percentage, including following component：
Polyvinyl chloride resin 70-98wt%
Polymer overmold special-effect powder microsphere 1-25wt%
Antioxidant 0.1-1wt%
Processing aid 0.1-5wt%；
Wherein, described polymer overmold special-effect powder microsphere, by weight percentage, including following component：
Aqueous polymer dispersion 18-90wt%
Antioxygen corrosion inhibiter 0-5wt%
Special-effect powder, or aqueouss special-effect slurry material 5-80wt%
Firming agent 0.2-10wt%；
Described antioxygen corrosion inhibiter is selected from phenylpropyl alcohol triazole, phytic acid, phytate, 8-hydroxyquinoline, organic phosphorus compound, phosphoric acid and its spreads out
The mixing of one or more of biology, pyrogallic acid；
Described special-effect powder includes one or more of metal powder or pearl essence；
Described aqueous polymer dispersion be selected from PVC emulsion, ABS emulsion, AS emulsion, ASA emulsion, MBS emulsion, styrene-acrylic emulsion,
Vinyl acetate emulsion, acrylic acid ester emulsion, butyronitrile emulsion, ethylene-vinyl acetate emulsion, Pioloform, polyvinyl acetal solution, polyurethane breast
Liquid, polyurethane-acrylic ester emulsion and its modifier one or more；
Described firming agent be selected from polyisocyanates and its oligomer, amino resins, organosiloxane, aziridine and its derivant,
Polycarbodiimide, one of firming agent containing epoxy radicals or multiple.
2. according to claim 1 have special decorative effects exempt from spray PVC composition it is characterised in that described water
Property polymer dispersion liquid solid content be 10-60wt%.
3. according to claim 1 there are special decorative effects exempt to spray PVC composition it is characterised in that described anti-
Oxygen agent is including Hinered phenols antioxidant, phosphite ester kind antioxidant, amine antioxidants, resists containing sulfur type antioxidant or metallic salt
One or more of oxygen agent；Described processing aid is silicone series lubricant agent, amide series lubricant agent, stearic acid lubricant, poly-
One or more of alkene series lubricant agent or ester lubricant.
4. according to claim 1 have special decorative effects exempt from spray PVC composition it is characterised in that described gold
Belong to powder and be selected from one or more of aluminium powder, copper powder, bronze, argentum powder, zinc powder, glass putty, iron powder, nikel powder；
The solid content of described aqueouss special-effect slurry material is 10-80wt%.
5. according to claim 4 have special decorative effects exempt from spray PVC composition it is characterised in that described water
The solid content of property special-effect slurry material is 20-70wt%.
6. according to claim 4 have special decorative effects exempt from spray PVC composition it is characterised in that described aluminum
In powder, the content of Al element is no less than 60wt%, contains Zn, Sn, Ni, Pb, Fe, Mg, Si, Mn, Be, Cu, Ti or rare earth unit simultaneously
One or more of element；Being shaped as of described aluminium powder is spherical, petal, dendriform, snowflake shape, cornflakes shape, silver dollar shape or half
Silver dollar shape one or more；Its particle diameter is 3-200 μm.
7. according to claim 6 have special decorative effects exempt from spray PVC composition it is characterised in that described aluminum
The particle diameter of powder is 5-100 μm.
8. according to claim 4 have special decorative effects exempt from spray PVC composition it is characterised in that described copper
In powder, the content of Cu element is no less than 60wt%, contains Zn, Sn, Ni, Be, Al, Mn, Fe, Pb, Si, P, B, Ti or rare earth unit simultaneously
One or more of element；Being shaped as of described copper powder is spherical, dendroid or lamellar, and its particle diameter is 3-200 μm.
9. according to claim 8 have special decorative effects exempt from spray PVC composition it is characterised in that described copper
The particle diameter of powder is 5-100 μm.
10. according to claim 1 have special decorative effects exempt from spray PVC composition it is characterised in that described pearl
Light powder includes Muscovitum coating pearl essence, bismuth oxychloride crystallization pearl essence, silica-coating pearl essence, aluminium silicate salt coating pearly-lustre
One or more of powder, boric acid aluminium salt coating pearl essence, bismuth oxide coating pearl essence；Described pearl essence surface at least coats one
Layer metal-oxide, described metal-oxide is aluminium oxide, tin ash, titanium dioxide, ferrum oxide, stibium oxide or zinc oxide
One or more；The particle diameter of described pearl essence is 5-500 μm.
11. according to claim 10 have special decorative effects exempt from spray PVC composition it is characterised in that described
The particle diameter of pearl essence is 5-200 μm.
12. according to claim 1 there are special decorative effects exempt to spray PVC composition it is characterised in that described poly-
The particle diameter that compound coats special-effect powder microsphere is 10-1000 μm；Wherein special-effect powder accounts for the weight percent content of microsphere
For 5-80wt%.
13. according to claim 12 have special decorative effects exempt from spray PVC composition it is characterised in that described
The particle diameter of polymer overmold special-effect powder microsphere is 10-300 μm；Wherein special-effect powder accounts for the weight percent content of microsphere
For 5-50wt%.
14. according to claim 1 there are special decorative effects exempt to spray PVC composition it is characterised in that described poly-
Compound coats the preparation method of special-effect powder microsphere, specifically includes following steps：
a）First, add antioxygen corrosion inhibiter, dispersed with stirring 10-30min in aqueous polymer dispersion under room temperature, disperseed
Liquid；Under agitation, it is slowly added to special-effect powder in dispersion liquid, or aqueouss special-effect slurry material, then side is stirred
Mix side and add firming agent, and continue to stir 30-120min, make special-effect powder fully dispersed and coated by dispersion liquid, finally make
Obtain the composite dispersion liquid of polymer overmold special-effect powder；
b）By composite dispersion liquid dried, obtain polymer overmold special-effect powder microsphere.
Described in 15. claim 14 have special decorative effects exempt from spray PVC composition it is characterised in that step（b）In
Described drying is to be spray-dried, and the intake air temperature of described spray-drying process is 150-300 DEG C, and air outlet temperature is 50-
130℃.
Described in 16. claim 15 have special decorative effects exempt from spray PVC composition it is characterised in that described spraying
The intake air temperature of dry run is 170-250 DEG C, and air outlet temperature is 70-100 DEG C.
The preparation method exempting from spraying PVC composition with special decorative effects described in 17. any one of claim 1-16, its
It is characterised by, comprise the steps：Each raw material is inserted high-speed mixer mix homogeneously according to the above ratio；By the mixture obtaining
Insert mixing in double screw extruder, after cooling, pelletizing, packaging, obtain final product.
Described in 18. any one of claim 1-16 have special decorative effects exempt from spray PVC composition in electronic apparatus, body
Educate articles for use, office appliance, the application in traffic and transport field.
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| CN106752710A (en) * | 2016-12-21 | 2017-05-31 | 钦州太平电子科技有限公司 | A kind of corrosion resistant coating of electronic elements |
| CN112852066A (en) * | 2019-11-26 | 2021-05-28 | 东莞市乐晟塑胶科技有限公司 | Plastic with metal texture |
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| US7479523B2 (en) * | 2001-11-08 | 2009-01-20 | Martin Paul | Metallic-colored thermoplastic molding compound |
| CN102516700B (en) * | 2011-12-09 | 2013-06-12 | 上海锦湖日丽塑料有限公司 | Appearance-improving spraying-free aesthetic resin and its preparation method |
| CN102643505B (en) * | 2012-03-19 | 2014-06-18 | 上海锦湖日丽塑料有限公司 | Spraying-free aesthetic resin composition with magnetism and preparation method thereof |
| CN102690474A (en) * | 2012-06-07 | 2012-09-26 | 芜湖创科塑料科技有限公司 | Weather-resistant coloured coextrusion special paint with metal decorating effect and preparation method thereof |
| CN103073829B (en) * | 2012-12-31 | 2015-07-29 | 青岛润兴塑料新材料有限公司 | It is material modified and preparation method thereof that one exempts from metallize texture PMMA |
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