CN104629343A - Spraying-free TPU composition having special aesthetic effects and preparation method and application thereof - Google Patents
Spraying-free TPU composition having special aesthetic effects and preparation method and application thereof Download PDFInfo
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- CN104629343A CN104629343A CN201310544206.6A CN201310544206A CN104629343A CN 104629343 A CN104629343 A CN 104629343A CN 201310544206 A CN201310544206 A CN 201310544206A CN 104629343 A CN104629343 A CN 104629343A
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Abstract
The invention discloses a spraying-free TPU composition having special aesthetic effects and a preparation method and an application thereof. The spraying-free TPU composition comprises the following components: 70-98 wt% of TPU 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 TPU resin, so that the compatibility of the special-effect powder and the TPU 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 TPU 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
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of there is special decorative effects exempt from spraying TPU composition and method of making the same and application.
Background technology
Along with people environmental problem more and more paid attention to and pay close attention to, exempt from spraying special-effect material product and just progressively demonstrate its competitive power, exempt from spraying aesthetic resin and can copy the special-effect such as gorgeous colorful tone and pearly-lustre, flash effect, metalluster and texture of spraying paint and producing, thus meet variation, differential customer demand, and really can realize energy-saving and emission-reduction in process of production, the fields such as artwork, toy, household electrical appliances, automobile, electronic product, sports goods and office appliance can be widely used in.
At present, exempt from the comparatively common preparation method of spraying resin in resin material, add the effect powder that metal powder, pearlescence etc. have particular color and gloss.By special-effect powder is distributed in matrix resin, interconnection between special-effect powder, form the film of continuous print special-effect, hide base material, present special-effect texture, although by special-effect powder is directly added in resin binder, the effect of special gloss can be realized, but the poor compatibility of matrix resin and special-effect powder, to extrude or under the strong pressure of injection moulding and Strong shear condition, it is consistent that special-effect powder and base resin material are difficult to reach mobility, particularly baroque goods, special-effect powder along flow direction orientation occurs and occurs that melt flow turns to, flow velocity is unstable, the phenomenons such as melt converges, cause special-effect powder skewness in the melt, easily form the defect such as current mark and weld bond at product surface, serious prevention and limit such marketing of exempting from spray material and application.
Summary of the invention
In order to the shortcoming overcoming prior art is with not enough, primary and foremost purpose of the present invention be to provide a kind of without current mark, light weld bond have special decorative effects exempt from spray TPU composition.
Another object of the present invention is to provide the above-mentioned preparation method exempting to spray TPU composition with special decorative effects.
The present invention is achieved by the following technical solutions:
What have special decorative effects exempts from spraying TPU composition, by weight percentage, comprises following component:
TPU resin 70-98wt%
Polymer overmold special-effect powder microballoon 1-25wt%
Oxidation inhibitor 0.1-1wt%
Processing aid 0.1-5wt%;
Wherein, described polymer overmold special-effect powder microballoon, by weight percentage, comprises following component:
Aqueous polymer dispersion 18-90wt%
Antioxygen inhibiter 0-5wt%
Special-effect powder, or water-based special-effect powder slurry 5-80wt%
Solidifying agent 0.2-10wt%.
Described aqueous polymer dispersion is one or more of polyaminoester emulsion, polyurethane-acrylic ester emulsion and modifier thereof;
The solid content of described aqueous polymer dispersion is 10-60wt%.
Described oxidation inhibitor be comprise Hinered phenols antioxidant, phosphite kind antioxidant, amine antioxidants, containing one or more in sulfur type antioxidant or metallic salt oxidation inhibitor;
Described processing aid is one or more in silicone lubricant, amides lubricant, stearic acid lubricant, polyolefins lubricant or ester lubricant.
Described antioxygen inhibiter is selected from the mixing of one or more in phenylpropyl alcohol triazole, phytic acid, phytate, oxine, Organophosphorous compounds, phosphoric acid and derivative thereof or pyrogallol.
Described special-effect powder comprise in metal powder or pearlescence one or more.
Described metal powder is selected from one or more in aluminium powder, copper powder, bronze, silver powder, zinc powder, glass putty, iron powder, nickel powder;
Described water-based special-effect powder slurry adds water and water-soluble solvent in special-effect powder, and as Virahol, ethanol etc. and other auxiliary agents, its solid content is 10-80wt%, preferred 20-70wt%.
In described aluminium 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 element one or more simultaneously; The shape of described aluminium powder be spherical, petal, dendriform, snowflake shape, corn flakes shape, silver dollar shape or half silver dollar shape one or more; Its particle diameter is 3-200 μm, preferred 5-100 μm.
In order to avoid aluminium powder explosive in the course of processing, oxidizable, the defects such as bad Ball milling, the present invention's aluminium powder used adds surface treatment agent if lubricant etc. is through surface treatment, then the flake aluminum that becomes of ball milling.
In described copper 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 element one or more simultaneously; The shape of described copper powder is spherical, dendroid or sheet, and its particle diameter is 3-200 μm, preferred 5-100 μm.
Its transverse section of described pearlescence has the physical structure being similar to pearl, kernel is the material of low optical specific refractory power, being coated on outer field is the metal oxide of high refractive index, and its kind specifically comprises one or more in mica coating pearlescence, pearl white crystallization pearlescence, silica-coating pearlescence, aluminium silicate salt coating pearlescence, aluminum borate salt coating pearlescence, bismuth oxide coating pearlescence; At least coated layer of metal oxide compound in described pearlescence surface, described metal oxide is one or more of aluminum oxide, tindioxide, titanium dioxide, ferric oxide, weisspiessglanz or zinc oxide; The particle diameter of described pearlescence is 5-500 μm, is preferably 5-200 μm.
The present invention adds pearlescence can make the metal-like of frosting more obvious, this is because pearlescence has special physical structure, when being subject to irradiate light, pearl effect can be revealed by multipath reflection and interference solid, making the reflected light of material surface closer to metal-like.
Described solidifying agent be selected from polyisocyanates and oligopolymer, aminoresin, organo-siloxane, aziridine and derivative thereof, polycarbodiimide one or more.
Polymer overmold special-effect powder microballoon of the present invention can also add other auxiliary agents according to actual needs, and as defoamer, dispersion agent, anti-settling agent etc., its consumption is conventional amount used.
The particle diameter of described polymer overmold special-effect powder microballoon is 10-1000 μm, preferred 10-300 μm; The weight percent content that wherein metal powder/special aesthstic powder accounts for microballoon is 5-80wt%, preferred 5-50wt%.
The preparation method of polymer overmold special-effect powder microballoon of the present invention, specifically comprises the following steps:
A) first, in aqueous polymer dispersion, add antioxygen inhibiter under normal temperature, dispersed with stirring 10-30min, obtain dispersion liquid; Under agitation, special-effect powder is slowly added in dispersion liquid, or water-based special-effect powder slurry, then solidifying agent is added while stirring, and continue to stir 30-120min, special-effect powder is fully disperseed and coated by dispersion liquid, finally the composite dispersion liquid of obtained polymer overmold special-effect powder;
B) by composite dispersion liquid drying treatment, polymer overmold special-effect powder microballoon is obtained.
Preferably, the drying wherein described in step (b) is spraying dry, and the intake air temperature of described spray-drying process is 150-300 DEG C, preferred 170-250 DEG C, and air outlet temperature is 50-130 DEG C, preferred 70-100 DEG C.
The preparation method exempting to spray TPU composition with special decorative effects of the present invention, comprises the steps: that each raw material is inserted high-speed mixer according to the above ratio to be mixed; Insert in twin screw extruder mixing by the mixture obtained, pelletizing after cooling, packaging, to obtain final product.
Of the present invention have exempting from spraying TPU composition and can being used widely in electronic apparatus, sports goods, office appliance, traffic and transport field of special decorative effects.
The present invention compared with prior art, has following beneficial effect:
The present invention by redispersion after special-effect powder use polymer dispersion liquid is overmolding to microballoon in TPU resin, obviously can improve the consistency of special-effect powder and TPU resin, improve special-effect powder endurance of cutting and extrude or in injection moulding process with the flowing consistence of melt, thus eliminate product surface current mark, alleviate weld bond, the spraying TPU composition of exempting from prepared has obvious metal-like or special aesthetic effect, substantially increases the market range of application exempting from spray material.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
the preparation of embodiment 1-6 polymer overmold special-effect powder microballoon:
By the formula in table 1, first, in aqueous polymer dispersion, add antioxygen inhibiter under normal temperature, dispersed with stirring 15min, obtain dispersion liquid; Under agitation, special-effect powder is slowly added in dispersion liquid, or water-based special-effect powder slurry, then solidifying agent is added while stirring, and continue to stir 30-120min, special-effect powder is fully disperseed and coated by dispersion liquid, finally the composite dispersion liquid of obtained polymer overmold special-effect powder; By composite dispersion liquid spray drying treatment, obtain polymer overmold special-effect powder microballoon, the intake air temperature of spray-drying process is 150-300 DEG C, and air outlet temperature is 50-130 DEG C.
The concrete proportioning (wt%) that table 1 embodiment 1 ~ 6 respectively forms
In embodiment 1: aqueous polymer dispersion is polyaminoester emulsion, its solid content is 10wt%; 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; Antioxygen inhibiter is pyrogallol; Solidifying agent is polyisocyanates.
In embodiment 2: aqueous polymer dispersion is polyurethane-acrylic ester emulsion, its solid content is 60wt%; 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; Antioxygen inhibiter is phenylpropyl alcohol triazole; Solidifying agent is polycarbodiimide.
In embodiment 3: aqueous polymer dispersion is polyaminoester emulsion, its solid content is 40wt%; Special-effect powder is silica-coating pearlescence, and its particle diameter is 20 μm; Solidifying agent is aziridine.
In embodiment 4: aqueous polymer dispersion is polyaminoester emulsion, its solid content is 50wt%; Special-effect powder is mica coating pearlescence, and its particle diameter is 200 μm; Solidifying agent is polyisocyanates.
In embodiment 5: aqueous polymer dispersion is polyaminoester emulsion, its solid content is 30wt%; Special-effect powder is the mixture of zinc powder and silica-coating pearlescence; Solidifying agent is aminoresin.
In embodiment 6: aqueous polymer dispersion is polyurethane-acrylic ester emulsion, its solid content is 20wt%; Special-effect powder is the mixture of silver powder and mica coating pearlescence; Solidifying agent is organo-siloxane.
embodiment 7-13 has the preparation exempting to spray TPU composition of special decorative effects:
By in table 2 formula by TPU resinoid, polymer overmold special-effect powder microballoon, compatilizer, oxidation inhibitor,
Processing aid is inserted high-speed mixer and is mixed; Insert in twin screw extruder mixing by the mixture obtained, pelletizing after cooling, packaging, to obtain final product.Acquired results is in table 2:
Oxidation inhibitor is hindered phenol antioxygen 1010;
Processing aid is calcium stearate.
comparative example 1-6: tradition exempts from the preparation spraying TPU composition:
By in table 2 formula TPU resinoid, golden special-effect powder, compatilizer, oxidation inhibitor, processing aid are inserted high-speed mixer and are mixed; Insert in twin screw extruder mixing by the mixture obtained, pelletizing after cooling, packaging, to obtain final product.Acquired results is in table 2:
In comparative example 1: metal powder is surface treated flake aluminum, 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, 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, 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 pearlescence, its particle diameter is 20 μm;
In comparative example 5: special-effect powder is mica coating pearlescence;
In comparative example 6: special-effect powder is the mixture of zinc powder and silica-coating pearlescence.
The concrete proportioning (wt%) respectively formed in table 2 embodiment 7-13 and comparative example 1-6 and test performance result thereof
Note :+more multilist show that current mark is more
Zero more multilist show that weld bond is more serious
-represent there is not current mark or weld bond, or not obvious
As can be seen from the Comparative result in upper table 2, when ensureing that other components are substantially identical with content, embodiment 7-13 adopts polymer overmold special-effect powder microballoon to mix with matrix resin, in comparative example 1-6, special-effect powder is directly joined in matrix resin, comparing embodiment 7-12 and comparative example 1-6, find to use polymer-coated metal powder and the microballoon of pearlescence and the product surface of matrix resin mixing gained substantially without current mark, weld bond is comparatively light, and has better aesthetic effect.
Claims (15)
1. what have special decorative effects exempts from spraying TPU composition, by weight percentage, comprises following component:
TPU resin 70-98wt%
Polymer overmold special-effect powder microballoon 1-25wt%
Oxidation inhibitor 0.1-1wt%
Processing aid 0.1-5wt%;
Wherein, described polymer overmold special-effect powder microballoon, by weight percentage, comprises following component:
Aqueous polymer dispersion 18-90wt%
Antioxygen inhibiter 0-5wt%
Special-effect powder, or water-based special-effect powder slurry 5-80wt%
Solidifying agent 0.2-10wt%.
2. according to claim 1 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, described aqueous polymer dispersion is one or more of polyaminoester emulsion, polyurethane-acrylic ester emulsion and modifier thereof; The solid content of described aqueous polymer dispersion is 10-60wt%.
3. according to claim 1 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, described oxidation inhibitor be comprise Hinered phenols antioxidant, phosphite kind antioxidant, amine antioxidants, containing one or more in sulfur type antioxidant or metallic salt oxidation inhibitor; Described processing aid is one or more in silicone lubricant, amides lubricant, stearic acid lubricant, polyolefins lubricant or ester lubricant.
4. according to claim 1 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, described antioxygen inhibiter is selected from the mixing of one or more in phenylpropyl alcohol triazole, phytic acid, phytate, oxine, Organophosphorous compounds, phosphoric acid and derivative thereof, pyrogallol.
5. according to claim 1 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, described special-effect powder comprise in metal powder or pearlescence one or more.
6. according to claim 5 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, described metal powder is selected from one or more in aluminium powder, copper powder, bronze, silver powder, zinc powder, glass putty, iron powder, nickel powder;
The solid content of the special powder slurry of described water-based is 10-80wt%, preferred 20-70wt%.
7. according to claim 6 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, in described aluminium 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 element one or more simultaneously; The shape of described aluminium powder be spherical, petal, dendriform, snowflake shape, corn flakes shape, silver dollar shape or half silver dollar shape one or more; Its particle diameter is 3-200 μm, preferred 5-100 μm.
8. according to claim 6 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, in described copper 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 element one or more simultaneously; The shape of described copper powder is spherical, dendroid or sheet, and its particle diameter is 3-200 μm, preferred 5-100 μm.
9. according to claim 5 there is metal effect/special decorative effects exempt from spraying TPU composition, it is characterized in that, described pearlescence comprises one or more in mica coating pearlescence, pearl white crystallization pearlescence, silica-coating pearlescence, aluminium silicate salt coating pearlescence, aluminum borate salt coating pearlescence, bismuth oxide coating pearlescence; At least coated layer of metal oxide compound in described pearlescence surface, described metal oxide is one or more of aluminum oxide, tindioxide, titanium dioxide, ferric oxide, weisspiessglanz or zinc oxide; The particle diameter of described pearlescence is 5-500 μm, is preferably 5-200 μm.
10. according to claim 1 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, described solidifying agent be selected from polyisocyanates and oligopolymer, aminoresin, organo-siloxane, aziridine and derivative thereof, polycarbodiimide one or more.
11. according to claim 1 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, the particle diameter of described polymer overmold special-effect powder microballoon is 10-1000 μm, preferred 10-300 μm; Wherein special-effect powder accounts for the weight percent content of microballoon is 5-80wt%, preferred 5-50wt%.
12. according to claim 1 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, the preparation method of described polymer overmold special-effect powder microballoon, specifically comprises the following steps:
A) first, in aqueous polymer dispersion, add antioxygen inhibiter under normal temperature, dispersed with stirring 10-30min, obtain dispersion liquid; Under agitation, special-effect powder is slowly added in dispersion liquid, or water-based special-effect powder slurry, then solidifying agent is added while stirring, and continue to stir 30-120min, special-effect powder is fully disperseed and coated by dispersion liquid, finally the composite dispersion liquid of obtained polymer overmold special-effect powder;
B) by composite dispersion liquid drying treatment, polymer overmold special-effect powder microballoon is obtained.
13. according to claim 12 there is special decorative effects exempt from spraying TPU composition, it is characterized in that, drying described in step (b) is spraying dry, the intake air temperature of described spray-drying process is 150-300 DEG C, preferred 170-250 DEG C, air outlet temperature is 50-130 DEG C, preferred 70-100 DEG C.
The preparation method exempting to spray TPU composition with special decorative effects described in 14. any one of claim 1-13, is characterized in that, comprise the steps: that each raw material is inserted high-speed mixer according to the above ratio to be mixed; Insert in twin screw extruder mixing by the mixture obtained, pelletizing after cooling, packaging, to obtain final product.
Described in 15. any one of claim 1-13 there is special decorative effects exempt from the spraying application of TPU composition in electronic apparatus, sports goods, office appliance, traffic and transport field.
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Cited By (4)
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| CN107541043A (en) * | 2017-09-01 | 2018-01-05 | 品诚塑胶科技（上海）有限公司 | High glaze exempts to spray PC/ABS alloy materials and preparation method thereof |
| CN107840976A (en) * | 2017-05-05 | 2018-03-27 | 东莞市正程新材料有限公司 | A kind of TPU film and preparation method thereof |
| CN107868439A (en) * | 2016-09-27 | 2018-04-03 | 湖北创鑫聚氨酯材料有限公司 | A kind of compound polyurethane material |
| CN109971157A (en) * | 2019-03-27 | 2019-07-05 | 金旸（厦门）新材料科技有限公司 | A kind of TPU composite material and preparation method of alternative plating and coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107541043A (en) * | 2017-09-01 | 2018-01-05 | 品诚塑胶科技（上海）有限公司 | High glaze exempts to spray PC/ABS alloy materials and preparation method thereof |
| CN109971157A (en) * | 2019-03-27 | 2019-07-05 | 金旸（厦门）新材料科技有限公司 | A kind of TPU composite material and preparation method of alternative plating and coating |
| CN109971157B (en) * | 2019-03-27 | 2021-04-16 | 金旸（厦门）新材料科技有限公司 | TPU composite material capable of replacing electroplating and coating and preparation method thereof |
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