CN104629245B - Exempt from spraying ABS compositions and its preparation method and application with special decorative effects - Google Patents
Exempt from spraying ABS compositions and its preparation method and application with special decorative effects Download PDFInfo
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- CN104629245B CN104629245B CN201310552379.2A CN201310552379A CN104629245B CN 104629245 B CN104629245 B CN 104629245B CN 201310552379 A CN201310552379 A CN 201310552379A CN 104629245 B CN104629245 B CN 104629245B
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Abstract
Exempt to spray ABS compositions and its preparation method and application, including following component with special decorative effects the invention discloses a kind of：The 98wt% of ABS resin 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 ABS resin, the compatibility of special-effect powder and ABS resin can be obviously improved, eliminate the product current mark that surface is formed in extrusion or injection moulding process and mitigate weld bond, the ABS 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
The invention belongs to polymeric material field, and in particular to a kind of to exempt to spray ABS 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 sprayed on material product and just progressively show its competition
Power, exempt from spraying aesthetic resin can replicate spray painting produce gorgeous colorful tone and pearly-lustre, flash effect, metallic luster and
The special-effects such as texture, so as to meet diversified, differential customer demand, and section can be really realized in process of production
Energy emission reduction, can be widely applied to the fields such as handicraft, toy, household electrical appliances, automobile, electronic product, sports goods and office appliance.
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 ABS 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 ABS compositions with special decorative effects
Method.
The present invention is achieved by the following technical solutions：
Exempt from spraying ABS compositions with special decorative effects, by weight percentage, including following component：
ABS resin 70-98wt%
Polymer overmold special-effect powder microballoon 1-25wt%
Compatilizer 0-10wt%
Antioxidant 0.1-1wt%
Processing aid 0.1-0.5wt%；
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 ABS resin is acrylonitrile-butadiene-styrene copolymer ABS, acrylonitrile-styrene-acrylic ester three
Membered copolymer ASA, MBS MBS, acrylonitrile-ethylene propylene diene rubber-styrene
Copolymer A ES, haloflex-acrylonitritrile-styrene resin ACS or one kind in acrylonitritrile-styrene resin SAN or
Several mixing.
The compatilizer includes ABS grafted maleic anhydrides, the sulfonate of polystyrene, SBS grafted maleic anhydrides, SEBS and connect
The one or more of branch maleic anhydride, SMA or acrylate copolymer.
The antioxidant is to include Hinered phenols antioxidant, phosphite kind antioxidant, amine antioxidants, thioether 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 aqueous polymer dispersion be selected from ABS emulsions, AS emulsions, ASA emulsions, MBS emulsions, polystyrene emulsion,
Styrene-acrylic emulsion, vinyl acetate emulsion, acrylic acid ester emulsion, butyronitrile emulsion, polyaminoester emulsion, polyurethane-acrylic ester emulsion and its change
The one or more of property thing.
The solid content of the aqueous polymer dispersion is 10-60wt%.
Described 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 be 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 aziridine and its derivative, amino resins, polyisocyanates and its oligomer, poly- carbonization two
The one or more of imines, organosiloxane.
Polymer overmold special-effect powder microballoon of the present invention can also according to be actually needed add other functions help
Agent, such as defoamer, dispersant, anti-settling agent, fire retardant, toughener, antistatic additive, reinforcing agent, filler, its dosage are used to be conventional
Amount.
The particle diameter of the polymer overmold special-effect powder microballoon is 10-1000 μm, preferably 10-300 μm；Wherein special effect
The weight percent content that fruit 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 ABS 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 different aesthetic effect exempt from spray ABS compositions can be in electronic apparatus, sports goods, office
It is used widely in articles for use, 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 ABS resin
In, the compatibility of special-effect powder and matrix resin can be obviously improved, improve special-effect powder endurance of cutting and its
Flowing uniformity in extrusion or injection moulding process with melt, so as to eliminate the current mark of product surface, mitigate weld bond, it is prepared
Exempt from spray ABS compositions there is obvious metal-like and special aesthetic effect, substantially increase and exempt from sprayed on material
Market 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 acrylic acid ester emulsion, and its solid content is 60wt%；Metal powder is through table
The flake copper of face processing, the content of Cu elements is 70wt% in copper powder, simultaneously containing Zn and Sn；Its particle diameter is 5 μm；Antioxygen delays
Erosion agent is phenylpropyl alcohol triazole；Curing agent is polycarbodiimide.
In embodiment 3：Aqueous polymer dispersion is polyurethane-acrylic ester emulsion, and its solid content is 40wt%；Pearly-lustre
Powder is silica-coating pearl essence, and its particle diameter is 20 μm；Curing agent is polyisocyanates.
In embodiment 4：Aqueous polymer dispersion is ABS emulsions, and its solid content is 50wt%；Pearl essence coats for mica
Pearl essence, its particle diameter are 200 μm；Curing agent is amino resins.
In embodiment 5：Aqueous polymer dispersion is styrene-acrylic emulsion, and its solid content is 30wt%；Special-effect powder is zinc powder
With the mixture of silica-coating pearl essence；Curing agent is aziridine.
In embodiment 6：Aqueous polymer dispersion is polystyrene emulsion, and its solid content is 20wt%；Special-effect powder is
The mixture of silver powder and mica coating pearl essence；Curing agent is organosiloxane.
Embodiment 7-13 has the preparation for exempting to spray ABS compositions of special decorative effects：
By the formula in table 2 by ABS resin, polymer overmold special-effect powder microballoon, compatilizer, antioxidant, plus
Work auxiliary agent is inserted high-speed mixer and is well mixed；Obtained mixture is inserted in double screw extruder and is kneaded, pelletizing after cooling,
Packaging, is produced.Acquired results are shown in Table 2：
Compatilizer is ABS grafted maleic anhydrides；
Antioxidant is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168；
Processing aid is oleamide.
Comparative example 1-6：Tradition is exempted to spray the preparation of ABS compositions：
ABS resin, special-effect powder, compatilizer, antioxidant, processing aid are inserted at a high speed by the formula in table 2
Mixer is well mixed；Obtained mixture is inserted in double screw extruder and is kneaded, pelletizing, packaging, are produced after cooling.Gained
It the results are shown in Table 2：
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 (21)
1. exempt from spraying ABS compositions with special decorative effects, by weight percentage, including following component：
ABS resin 70-98wt%
Polymer overmold special-effect powder microballoon 1-25wt%
Compatilizer 0-10wt%
Antioxidant 0.1-1wt%
Processing aid 0.1-0.5wt%；
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 antioxygen corrosion inhibiter is selected from phenylpropyl alcohol triazole, phytic acid, phytate, 8-hydroxyquinoline, organic phosphorus compound, phosphoric acid and its spread out
One or more of mixing in biology or pyrogallic acid.
2. according to claim 1 exempt from spraying ABS compositions with special decorative effects, it is characterised in that the ABS
Resinoid is acrylonitrile-butadiene-styrene copolymer ABS, acrylonitrile-styrene-acrylic ester terpolymer ASA, first
Base methylacrylate-butadiene-styrol copolymer MBS, acrylonitrile-ethylene propylene diene rubber-styrol copolymer AES, chlorination
One or more of mixing in polyethylene-propylene nitrile-styrol copolymer ACS or acrylonitritrile-styrene resin SAN.
3. according to claim 1 exempt from spraying ABS compositions with special decorative effects, it is characterised in that the phase
Holding agent includes ABS grafted maleic anhydrides, the sulfonate of polystyrene, SBS grafted maleic anhydrides, SEBS grafted maleic anhydrides, SMA
Or the one or more of acrylate copolymer；The antioxidant include Hinered phenols antioxidant, phosphite kind antioxidant,
One or more in amine antioxidants and thioether kind antioxidant；The processing aid is silicone series lubricant agent, amide-type lubrication
One or more in agent, stearic acid lubricant, TPO lubricant or ester lubricant.
4. according to claim 1 exempt from spraying ABS compositions with special decorative effects, it is characterised in that the water
Property polymer dispersion liquid be selected from ABS emulsions, AS emulsions, ASA emulsions, MBS emulsions, polystyrene emulsion, styrene-acrylic emulsion, the breast of second third
Liquid, acrylic acid ester emulsion, butyronitrile emulsion, polyaminoester emulsion, polyurethane-acrylic ester emulsion and its modifier it is a kind of or more
Kind；The solid content of the aqueous polymer dispersion is 10-60wt%.
5. according to claim 1 exempt from spraying ABS 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.
6. according to claim 5 exempt from spraying ABS 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 water-based special effect
The solid content of fruit powder slurry is 10-80wt%.
7. according to claim 6 exempt from spraying ABS compositions with special decorative effects, it is characterised in that the water
The solid content of property special-effect slurry material is 20-70wt%.
8. according to claim 6 exempt from spraying ABS 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.
9. according to claim 8 exempt from spraying ABS compositions with special decorative effects, it is characterised in that the aluminium
The particle diameter of powder is 5-100 μm.
10. according to claim 6 exempt from spraying ABS 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.
11. according to claim 10 exempt from spraying ABS compositions with special decorative effects, it is characterised in that described
The particle diameter of copper powder is 5-100 μm.
12. according to claim 5 exempt from spraying ABS 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.
13. according to claim 12 exempt from spraying ABS compositions with special decorative effects, it is characterised in that described
The particle diameter of pearl essence is 5-200 μm.
14. according to claim 1 exempt from spraying ABS compositions with special decorative effects, it is characterised in that described solid
Agent is selected from aziridine and its derivative, amino resins, polyisocyanates and its oligomer, polycarbodiimide, organic silica
The one or more of alkane.
15. according to claim 1 exempt from spraying ABS 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%.
16. according to claim 15 exempt from spraying ABS 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%.
17. according to claim 1 exempt from spraying ABS 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.
18. exempt from spraying ABS 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 150-300 DEG C, air outlet temperature 50-
130℃。
19. exempt from spraying ABS compositions with special decorative effects described in claim 18, 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℃。
20. the preparation method for exempting to spray ABS compositions with special decorative effects described in claim any one of 1-19, 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.
21. exempt to spray ABS compositions in electronic apparatus, body with special decorative effects described in claim any one of 1-19
Educate the application in articles for use, office appliance, traffic and transport field.
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| CN201310552379.2A CN104629245B (en) | 2013-11-06 | 2013-11-06 | Exempt from spraying ABS compositions and its preparation method and application with special decorative effects |
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| CN105524399B (en) * | 2015-12-29 | 2018-08-31 | 银禧工程塑料（东莞）有限公司 | A kind of polymer material of 3D printing and preparation method thereof |
| CN105802116A (en) * | 2016-04-29 | 2016-07-27 | 上汽通用五菱汽车股份有限公司 | Spraying-free high-metal-gloss transparent ABS material and preparation method |
| CN108623983A (en) * | 2017-03-26 | 2018-10-09 | 合肥杰事杰新材料股份有限公司 | A kind of spraying-free metal effect improves the acrylonitrile-butadiene-styrene (ABS) composition and preparation method thereof of current mark |
| CN108250662A (en) * | 2018-01-12 | 2018-07-06 | 北京慧缘有限责任公司 | Colorful is exempted to spray ABS compositions and its production technology and ABS safety caps |
| CN108912478B (en) * | 2018-05-03 | 2021-04-30 | 安徽古驰智能环保家居有限公司 | Accessory for gondola water faucet |
| CN109776950A (en) * | 2018-12-11 | 2019-05-21 | 广东波斯科技股份有限公司 | A kind of polyolefine material of spraying-free metal effect and its preparation method and application |
| CN109880280B (en) * | 2019-03-27 | 2021-03-16 | 金旸（厦门）新材料科技有限公司 | Spraying-free ABS material with 3D pearlescent effect and preparation method thereof |
| CN111187501A (en) * | 2020-02-18 | 2020-05-22 | 江苏博云塑业股份有限公司 | Spraying-free PC/PBT alloy material and preparation method thereof |
| CN111793317A (en) * | 2020-07-27 | 2020-10-20 | 五行科技股份有限公司 | High-density spraying-free metal-like ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN113861236B (en) * | 2021-10-18 | 2023-09-05 | 山东寿光巨能金玉米开发有限公司 | Method for preparing calcium phytate by purifying phytic acid |
| CN114891311A (en) * | 2022-06-14 | 2022-08-12 | 深圳市富恒新材料股份有限公司 | Antibacterial weather-resistant ASA composite material and preparation method thereof |
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|---|---|---|---|---|
| CN102516700A (en) * | 2011-12-09 | 2012-06-27 | 上海锦湖日丽塑料有限公司 | Appearance-improving spraying-free aesthetic resin and its preparation method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516700A (en) * | 2011-12-09 | 2012-06-27 | 上海锦湖日丽塑料有限公司 | Appearance-improving spraying-free aesthetic resin and its preparation method |
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