CN104629343B - Exempt from spraying TPU compositions and its preparation method and application with special decorative effects - Google Patents
Exempt from spraying TPU compositions and its preparation method and application with special decorative effects Download PDFInfo
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- CN104629343B CN104629343B CN201310544206.6A CN201310544206A CN104629343B CN 104629343 B CN104629343 B CN 104629343B CN 201310544206 A CN201310544206 A CN 201310544206A CN 104629343 B CN104629343 B CN 104629343B
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Abstract
Exempt to spray TPU compositions and its preparation method and application, including following component with special decorative effects the invention discloses a kind of：The 98wt% of TPU resins 70；The 25wt% of polymer overmold special-effect powder microballoon 1；The 10wt% of compatilizer 0；The 1wt% of antioxidant 0.1；The 0.5wt% of processing aid 0.1；The present invention is by redisperse after special-effect powder is overmolding into microballoon with aqueous polymer dispersion into TPU resins, the compatibility of special-effect powder and TPU resins can be obviously improved, eliminate the product current mark that surface is formed in extrusion or injection moulding process and mitigate weld bond, the TPU compositions of exempting to spray being prepared have the special aesthetic effects such as obvious metal-like, pearly-lustre flicker, substantially increase the market application for exempting from sprayed on material.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of to exempt to spray TPU combinations with special decorative effects
Thing and its preparation method and application.
Background technology
As people increasingly pay attention to and paid close attention to environmental problem, exempt from spraying special-effect material product and just progressively show
Its competitiveness, gorgeous colorful tone and pearly-lustre, flash effect, metal that spray painting is produced can be replicated by exempting from spraying aesthetic resin
The special-effect such as gloss and texture, so as to meet diversified, differential customer demand, and in process of production can be real
Energy-saving and emission-reduction are realized, can be widely applied to handicraft, toy, household electrical appliances, automobile, electronic product, sports goods and office appliance etc.
Field.
At present, it is that the tool such as metal powder, pearl essence is added in resin material to exempt to spray the more common preparation method of resin
There is the effect powder of particular color and gloss.By the way that special-effect powder is distributed in matrix resin, between special-effect powder mutually
Connection, forms the film of continuous special-effect, has covered base material, show special-effect texture, although by by special-effect
Powder is directly added into 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 extruded or be molded, special-effect powder is extremely difficult to mobility with base resin material
Unanimously, particularly baroque product, occur along the special-effect powder of flow direction orientation and melt flows steering occur,
Phenomena such as flow velocity is unstable, and melt converges, causes special-effect powder skewness in the melt, easily formed in product surface
The defects of current mark and weld bond, seriously prevent and limit such marketing and application for exempting from sprayed on material.
The content of the invention
The shortcomings that in order to overcome prior art and deficiency, primary and foremost purpose of the invention are that provide one kind melts without current mark, gently
Wiring exempts from spraying TPU compositions with special decorative effects.
It is still another object of the present invention to provide the above-mentioned preparation side for exempting to spray TPU compositions with special decorative effects
Method.
The present invention is achieved by the following technical solutions：
Exempt from spraying TPU compositions with special decorative effects, by weight percentage, including following component：
TPU resins 70-98wt%
Polymer overmold special-effect powder microballoon 1-25wt%
Antioxidant 0.1-1wt%
Processing aid 0.1-5wt%；
Wherein, described polymer overmold special-effect powder microballoon, by weight percentage, including following component：
Aqueous polymer dispersion 18-90wt%
Antioxygen corrosion inhibiter 0-5wt%
Special-effect powder, or water-based special-effect slurry material 5-80wt%
Curing agent 0.2-10wt%.
The aqueous polymer dispersion is one kind of polyaminoester emulsion, polyurethane-acrylic ester emulsion and its modifier
It is or a variety of；
The solid content of the aqueous polymer dispersion is 10-60wt%.
The antioxidant is to include Hinered phenols antioxidant, phosphite kind antioxidant, amine antioxidants, sulfur-bearing class antioxygen
One or more in agent or metallic salt antioxidant；
The processing aid is silicone series lubricant agent, acid amides series lubricant agent, stearic acid lubricant, TPO lubricant
Or the one or more in ester lubricant.
The antioxygen corrosion inhibiter be selected from phenylpropyl alcohol triazole, phytic acid, phytate, 8-hydroxyquinoline, organic phosphorus compound, phosphoric acid and
One or more of mixing in its derivative or pyrogallic acid.
The special-effect powder includes the one or more in metal powder or pearl essence.
One or more of the metal powder in aluminium powder, copper powder, bronze, silver powder, zinc powder, glass putty, iron powder, nickel powder；
The water-based special-effect slurry material is that water and water-soluble solvent are added in special-effect powder, such as isopropanol, second
Alcohol etc. and other auxiliary agents, its solid content are 10-80wt%, preferably 20-70wt%.
The content of Al elements is no less than 60wt% in the aluminium powder, simultaneously containing Zn, Sn, Ni, Pb, Fe, Mg, Si, Mn, Be,
Cu, Ti or rare earth element one or more；Being shaped as the aluminium powder is spherical, petal, dendriform, snowflake shape, cornflakes
The one or more of shape, silver dollar shape or half silver dollar shape；Its particle diameter is 3-200 μm, preferably 5-100 μm.
It is oxidizable in order to avoid aluminium powder explosive in process, the defects of bad ball milling disperses, used in the present invention
Aluminium powder is to add surface conditioning agent such as lubricant etc. by surface treatment, then ball milling into flake aluminum.
The content of Cu elements is no less than 60wt% in the copper powder, simultaneously containing Zn, Sn, Ni, Be, Al, Mn, Fe, Pb, Si,
P, the one or more of B, Ti or rare earth element；Being shaped as the copper powder is spherical, dendroid or sheet, its particle diameter are 3-200 μ
M, preferably 5-100 μm.
Its cross section of the pearl essence has the physical arrangement similar to pearl, 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 mica coating pearl essence, bismoclite 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 in light powder；The pearl essence surface at least coats layer of metal oxide, and the metal oxide is oxidation
Aluminium, tin ash, titanium dioxide, iron oxide, the one or more of antimony oxide or zinc oxide；The particle diameter of the pearl essence is 5-
500 μm, preferably 5-200 μm.
The present invention, which adds pearl essence, can make the metal-like of frosting more obvious, because pearl essence has spy
Different physical arrangement, when being irradiated by light, pearl effect can be embodied by multipath reflection and interference so that material surface
Reflected light closer to metal-like.
The curing agent is selected from polyisocyanates and its oligomer, amino resins, organosiloxane, aziridine and its derivative
The one or more of thing, polycarbodiimide.
Polymer overmold special-effect powder microballoon of the present invention can also add other auxiliary agents according to being actually needed, such as
Defoamer, dispersant, anti-settling agent etc., its dosage are conventional amount used.
The particle diameter of the polymer overmold special-effect powder microballoon is 10-1000 μm, preferably 10-300 μm；Wherein metal
The weight percent content that powder/special aesthstic powder accounts for microballoon is 5-80wt%, preferably 5-50wt%.
The preparation method of polymer overmold special-effect powder microballoon of the present invention, specifically includes following steps：
a）First, antioxygen corrosion inhibiter is added under normal temperature in aqueous polymer dispersion, 10-30min is dispersed with stirring, obtains
Dispersion liquid；Under agitation, special-effect powder, or water-based special-effect slurry material are slowly added into dispersion liquid, then
Curing agent is added while stirring, and continues to stir 30-120min, is made special-effect powder fully dispersed and is coated by dispersion liquid, most
The composite dispersion liquid of polymer overmold special-effect powder is made afterwards；
b）By composite dispersion liquid drying process, polymer overmold special-effect powder microballoon is obtained.
Preferably, wherein step（b）Described in drying for spray drying, the intake air temperature of the 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.
Preparation method of the present invention that exempt to spray TPU compositions with special decorative effects, comprises the following steps：
Each raw material is inserted into high-speed mixer according to the above ratio to be well mixed；Obtained mixture is inserted in double screw extruder and mixed
Refining, pelletizing, packaging, are produced after cooling.
It is of the present invention with special decorative effects exempt to spray TPU compositions 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 passes through redisperse after special-effect powder is overmolding into microballoon with aqueous polymer dispersion to TPU resins
In, the compatibility of special-effect powder and TPU resins can be obviously improved, the endurance of cutting of special-effect powder is improved and its is squeezing
Go out or injection moulding process in flowing uniformity with melt, so as to eliminate the current mark of product surface, mitigate weld bond, be prepared
Exempting from spraying TPU compositions has obvious metal-like or special aesthetic effect, substantially increases the city for exempting from sprayed on material
Field application.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
The preparation of embodiment 1-6 polymer overmold special-effect powder microballoons：
By the formula in table 1, first, antioxygen corrosion inhibiter is added under normal temperature in aqueous polymer dispersion, is dispersed with stirring
15min, obtain dispersion liquid；Under agitation, special-effect powder, or water-based special-effect powder are slowly added into dispersion liquid
Slurry, curing agent is then added while stirring, and continue to stir 30-120min, make special-effect powder fully dispersed and disperseed
Liquid coats, and the composite dispersion liquid of polymer overmold special-effect powder is finally made；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, air outlet temperature 50-
130℃。
The specific proportioning that the embodiment 1 ~ 6 of table 1 respectively forms（wt%）
In embodiment 1：Aqueous polymer dispersion is polyaminoester emulsion, and its solid content is 10wt%；Metal powder is through surface
The flake aluminum of processing, the content of Al elements is 60wt% in aluminium powder, simultaneously containing Zn and Sn；Its particle diameter is 100 μm；Antioxygen delays
Erosion agent is pyrogallic acid；Curing agent is polyisocyanates.
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 the content of Cu elements is 70wt% in copper powder, simultaneously containing Zn and Sn；Its particle diameter is 5 μ
m；Antioxygen corrosion inhibiter is phenylpropyl alcohol triazole；Curing agent is polycarbodiimide.
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 are 20 μm；Curing agent is aziridine.
In embodiment 4：Aqueous polymer dispersion is polyaminoester emulsion, and its solid content is 50wt%；Special-effect powder is cloud
Mother's coating pearl essence, its particle diameter are 200 μm；Curing agent is polyisocyanates.
In embodiment 5：Aqueous polymer dispersion is polyaminoester emulsion, and its solid content is 30wt%；Special-effect powder is zinc
The mixture of powder and silica-coating pearl essence；Curing agent is amino resins.
In embodiment 6：Aqueous polymer dispersion is polyurethane-acrylic ester emulsion, and its solid content is 20wt%；It is special
Effect powder is the mixture that silver powder and mica coat pearl essence；Curing agent is organosiloxane.
Embodiment 7-13 has the preparation for exempting to spray TPU compositions of special decorative effects：
By the formula in table 2 by TPU resinoids, polymer overmold special-effect powder microballoon, compatilizer, antioxidant,
Processing aid is inserted high-speed mixer and is well mixed；Obtained mixture is inserted in double screw extruder and is kneaded,
Pelletizing, packaging, are produced after cooling.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 TPU compositions：
TPU resinoids, golden special-effect powder, compatilizer, antioxidant, processing aid are inserted into height by the formula in table 2
Fast mixer is well mixed；Obtained mixture is inserted in double screw extruder and is kneaded, pelletizing, packaging, are produced after cooling.Institute
2 must be the results are shown in Table：
In comparative example 1：Metal powder is surface treated flake aluminum, and the content of Al elements is 60wt% in aluminium powder, simultaneously
Contain Zn and Sn；Its particle diameter is 100 μm；
In comparative example 2：Metal powder is surface treated flake aluminum, and the content of Al elements is 60wt% in aluminium powder, simultaneously
Contain Zn and Sn；Its particle diameter is 100 μm；
In comparative example 3：Metal powder is surface treated flake copper, and the content of Cu elements is 70wt% in copper powder, simultaneously
Contain 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 is that mica coats pearl essence；
In comparative example 6：Special-effect powder is the mixture of zinc powder and silica-coating pearl essence.
The specific proportioning respectively formed in the embodiment 7-13 of table 2 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 that current mark or weld bond, or unobvious are not present
It can be seen from the Comparative result in upper table 2 in the case where ensureing that other components and content are essentially identical, implement
Example 7-13 is mixed using polymer overmold special-effect powder microballoon with matrix resin, in comparative example 1-6 that special-effect powder is direct
It is added in matrix resin, comparing embodiment 7-12 and comparative example 1-6, finds micro- with polymer-coated metal powder and pearl essence
Ball mixes the product surface of gained with matrix resin substantially without current mark, and weld bond is lighter, and has more preferable aesthetic effect.
Claims (20)
1. exempt from spraying TPU compositions with special decorative effects, by weight percentage, including following component：
TPU resins 70-98wt%
Polymer overmold special-effect powder microballoon 1-25wt%
Antioxidant 0.1-1wt%
Processing aid 0.1-5wt%；
Wherein, described polymer overmold special-effect powder microballoon, by weight percentage, including following component：
Aqueous polymer dispersion 18-90wt%
Antioxygen corrosion inhibiter 0-5wt%
Special-effect powder, or water-based special-effect slurry material 5-80wt%
Curing agent 0.2-10wt%;
The content of the antioxygen corrosion inhibiter is not 0, selected from phenylpropyl alcohol triazole, phytic acid, phytate, 8-hydroxyquinoline, organic phosphatization
One or more of mixing in thing, phosphoric acid and its derivative, pyrogallic acid.
2. according to claim 1 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the water
Property polymer dispersion liquid be polyaminoester emulsion, polyurethane-acrylic ester emulsion and its modifier one or more；The water
The solid content of property polymer dispersion liquid is 10-60wt%.
3. according to claim 1 exempt from spraying TPU compositions with special decorative effects, it is characterised in that described anti-
Oxygen agent is to include Hinered phenols antioxidant, phosphite kind antioxidant, amine antioxidants, resist containing sulfur type antioxidant or metallic salt
One or more in oxygen agent；The processing aid is silicone series lubricant agent, acid amides series lubricant agent, stearic acid lubricant, poly-
One or more in alkene series lubricant agent or ester lubricant.
4. according to claim 1 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the spy
Special effect fruit powder includes the one or more in metal powder or pearl essence.
5. according to claim 4 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the gold
Belong to one or more of the powder in aluminium powder, copper powder, bronze, silver powder, zinc powder, glass putty, iron powder, nickel powder；
The solid content of the water-based special slurry material is 10-80wt%.
6. according to claim 5 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the water
The solid content of the special slurry material of property is 20-70wt%.
7. according to claim 5 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the aluminium
The content of Al elements is no less than 60wt% in powder, simultaneously containing Zn, Sn, Ni, Pb, Fe, Mg, Si, Mn, Be, Cu, Ti or rare earth member
The one or more of element；Being shaped as the aluminium powder is spherical, petal, dendriform, snowflake shape, cornflakes shape, silver dollar shape or half
The one or more of silver dollar shape；Its particle diameter is 3-200 μm.
8. according to claim 7 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the aluminium
The particle diameter of powder is 5-100 μm.
9. according to claim 5 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the copper
The content of Cu elements is no less than 60wt% in powder, simultaneously containing Zn, Sn, Ni, Be, Al, Mn, Fe, Pb, Si, P, B, Ti or rare earth member
The one or more of element；Being shaped as the copper powder is spherical, dendroid or sheet, its particle diameter are 3-200 μm.
10. according to claim 9 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the copper
The particle diameter of powder is 5-100 μm.
11. according to claim 4 exempt from spraying TPU compositions with special decorative effects, it is characterised in that the pearl
Light powder includes mica coating pearl essence, bismoclite crystallization pearl essence, silica-coating pearl essence, aluminium silicate salt coating pearly-lustre
One or more in powder, boric acid aluminium salt coating pearl essence, bismuth oxide coating pearl essence；The pearl essence surface at least coats one
Layer metal oxide, the metal oxide are aluminum oxide, tin ash, titanium dioxide, iron oxide, antimony oxide or zinc oxide
It is one or more of；The particle diameter of the pearl essence is 5-500 μm.
12. according to claim 11 exempt from spraying TPU compositions with special decorative effects, it is characterised in that described
The particle diameter of pearl essence is 5-200 μm.
13. according to claim 1 exempt from spraying TPU compositions with special decorative effects, it is characterised in that described solid
Agent is selected from polyisocyanates and its oligomer, amino resins, organosiloxane, aziridine and its derivative, the poly- Asia of carbonization two
The one or more of amine.
14. according to claim 1 exempt from spraying TPU compositions with special decorative effects, it is characterised in that described poly-
The particle diameter of compound cladding special-effect powder microballoon is 10-1000 μm；Wherein special-effect powder accounts for the weight percent content of microballoon
For 5-80wt%.
15. according to claim 14 exempt from spraying TPU compositions with special decorative effects, it is characterised in that described
The particle diameter of polymer overmold special-effect powder microballoon is 10-300 μm；Wherein special-effect powder accounts for the weight percent content of microballoon
For 5-50wt%.
16. according to claim 1 exempt from spraying TPU compositions with special decorative effects, it is characterised in that described poly-
Compound coats the preparation method of special-effect powder microballoon, specifically includes following steps：
a）First, antioxygen corrosion inhibiter is added under normal temperature in aqueous polymer dispersion, 10-30min is dispersed with stirring, is disperseed
Liquid；Under agitation, special-effect powder, or water-based special-effect slurry material are slowly added into dispersion liquid, then side is stirred
Mix side and add curing agent, and continue to stir 30-120min, make special-effect powder fully dispersed and coated by dispersion liquid, finally made
Obtain the composite dispersion liquid of polymer overmold special-effect powder；
b）By composite dispersion liquid drying process, polymer overmold special-effect powder microballoon is obtained.
17. exempt from spraying TPU compositions with special decorative effects described in claim 16, it is characterised in that step（b）In
Described drying is spray drying, and the intake air temperature of the spray-drying process is 150-300 DEG C, air outlet temperature 50-
130℃。
18. exempt from spraying TPU compositions with special decorative effects described in claim 17, it is characterised in that step（b）In
Described drying is spray drying, and the intake air temperature of the spray-drying process is 170-250 DEG C, air outlet temperature 70-
100℃。
19. the preparation method for exempting to spray TPU compositions with special decorative effects described in claim any one of 1-18, its
It is characterised by, comprises the following steps：Each raw material is inserted into high-speed mixer according to the above ratio to be well mixed；The mixture that will be obtained
Insert in double screw extruder and be kneaded, pelletizing, packaging, are produced after cooling.
20. exempt to spray TPU compositions in electronic apparatus, body with special decorative effects described in claim any one of 1-18
Educate the application in articles for use, office appliance, traffic and transport field.
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| 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 |
| CN107840976B (en) * | 2017-05-05 | 2021-08-10 | 东莞市正程新材料有限公司 | TPU film and preparation method thereof |
| CN107541043B (en) * | 2017-09-01 | 2019-09-06 | 品诚塑胶科技（上海）有限公司 | High glaze exempts to spray PC/ABS alloy material and preparation method thereof |
| 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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| CN1764691A (en) * | 2003-01-23 | 2006-04-26 | 通用电气公司 | Polymer encapsulation of high aspect ratio materials and methods of making same |
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| CN102020918B (en) * | 2011-01-11 | 2012-07-25 | 深圳市广田环保涂料有限公司 | Polyurethane paint as well as preparation method and use method thereof |
| 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 |
| CN103571266B (en) * | 2012-08-06 | 2014-12-24 | 上海麟多祈化工科技有限公司 | Water-based hand-feeling gravure ink |
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