CN104629088A - Pearl essence coated polymer microspheres and preparation method and application thereof - Google Patents
Pearl essence coated polymer microspheres and preparation method and application thereof Download PDFInfo
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- CN104629088A CN104629088A CN201310544147.2A CN201310544147A CN104629088A CN 104629088 A CN104629088 A CN 104629088A CN 201310544147 A CN201310544147 A CN 201310544147A CN 104629088 A CN104629088 A CN 104629088A
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Abstract
The invention discloses pearl essence coated polymer microspheres. The microspheres comprise the following components: 5-80wt% of pearl essence / aqueous pearl essence paste, 18-90 wt% of an aqueous polymer dispersion liquid and 0.2-10 wt% of a curing agent. A preparation method includes the steps of: a) slowly adding the pearl essence / aqueous pearl essence paste subjected to surface treatment into the aqueous polymer dispersion liquid at room temperature, stirring while adding the curing agent, and continuing stirring for 30-120 min to obtain a pearl essence coated polymer composite dispersion liquid; and b) conducting spray drying on the composite dispersion liquid, subjecting the pearl essence coated polymer droplets formed by spray to curing crosslinking reaction through the curing agent, so as to obtain the pearl essence coated polymer microspheres. The prepared pearl essence coated polymer microspheres can improve the compatibility between pearl essence and the matrix resin, improve the flow uniformity of pearl essence with a melt in an extrusion or injection molding process and, thereby eliminating flow mark on the surface of the product, and reduce the weld bond. Therefore, the invention can be used in the preparation of free-spraying materials.
Description
Technical field
The present invention relates to field of high polymer material modification, be specifically related to microballoon of polymer overmold pearlescence and preparation method thereof and application.
Background technology
For improving outward appearance, the prolongation product life of plastics, usually spray treatment need be carried out to surface of plastic products.But spraying coating process exists shortcomings: cost is high, Production Flow Chart is long, efficiency is low, defective products rate is high; Not environmentally, contaminate environment, the harm physical and mental health of operator, security risk are large; Lacquer painting easily comes off, and causes product appearance bad, affects product specification; Product and defective products reclaim difficulty.Along with people environmental problem more and more paid attention to and pay close attention to, exempting from spray material product and just progressively demonstrate its competitive power, artwork, toy, household electrical appliances, automobile, electronic product, sports goods and office appliance etc. can be widely used in.
In order to make goods have special pearl effect, normally in matrix resin, add pearlescence, interconnection between pearlescence and pearlescence, form the film of continuous print pearlescence effect, hidden base material, presented pearly-lustre texture; But by directly being added in matrix resin by pearlescence, the poor compatibility of matrix resin and pearlescence, is extruding or under the strong pressure of injection moulding and Strong shear condition, it is consistent that pearlescence and base resin material are difficult to reach mobility, easily occurs current mark; Particularly baroque goods, pearlescence along flow direction orientation turns in generation melt flow, flow velocity is unstable, during the phenomenons such as melt converges, cause pearlescence skewness in the melt, even form the defect such as current mark and weld bond at product surface, seriously limit the marketing and application of exempting from spray material.
Up to the present, polymer overmold pearlescence microballoon is formed by spraying dry and crosslinking reaction after pearlescence being coated on aqueous polymer dispersion, again the microballoon of this polymer overmold pearlescence and matrix resin are made by blending extrusion and exempt from spray material, thus the spray material of exempting from finally made without current mark, light weld bond rarely has report.
Summary of the invention
The primary and foremost purpose of invention aims to provide a kind ofly can improve the consistency of pearlescence and matrix resin, improve the microballoon of the conforming polymer overmold pearlescence of flowing of pearlescence and melt.
Another object of the present invention is the preparation method of the microballoon providing above-mentioned polymer overmold pearlescence.
The present invention is achieved by the following technical solution:
A microballoon for polymer overmold pearlescence, by weight percentage, comprises following component:
Pearlescence
/water-soluble pearlescent powder slurry 5-80wt%
Aqueous polymer dispersion 18-90wt%
Solidifying agent 0.2-10wt%.
The physical structure of the microballoon of described polymer overmold pearlescence is the pearlescence kernel containing particle diameter 3-500 μm, is coated with at the outside surface of pearlescence kernel the polymer shell that thickness is 5-800 μm.
The transverse section of described pearlescence has the physical structure being similar to pearl, and kernel is the material of low optical specific refractory power, and being coated on outer field is the metal oxide of high refractive index; Described pearlescence be selected from mica coating pearlescence, pearl white crystallization pearlescence, silica-coating pearlescence, aluminium silicate salt coating pearlescence, aluminum borate salt coating pearlescence, bismuth oxide coating pearlescence one or more.
The surface coated metal oxide of described pearlescence is selected from one or more of titanium oxide, chromium sesquioxide, titanium dioxide, ferric oxide, weisspiessglanz or zinc oxide; The particle diameter of described pearlescence is 3 μm-500 μm, is preferably 5-200 μm.
The solid content of described water-soluble pearlescent powder slurry is 10-80wt%, is preferably 20-70wt%.
The solid content of described aqueous polymer dispersion is 10-60wt%, be selected from polyaminoester emulsion, organic silicon emulsion, organic fluorine emulsion, epoxy resin latex, polyacrylate dispersion, benzene emulsion, organosilicon crylic acid latex, modified ABS resin emulsion, the modified-cellulose aqueous solution, polyvinyl alcohol and the condenses aqueous solution thereof, the polyacrylic acid aqueous solution, water-based urea-formaldehyde resin, aqueous melamine and etherified resin thereof, resol resins, aqueous alkide resin, aqueous polyester resin, aqueous polyvinyl acetate emulsion, ethene improved-vinyl acetate emulsion, nature rubber latex, styrene-butadiene emulsion, butyronitrile emulsion, one or more mixtures of vinyl acetate emulsion and mixture and modifier.
Described solidifying agent comprises aliphatic polyamine, aromatic polyamine, alicyclic polyamine, ammonium chloride, Resorcinol, aziridine and derivative thereof, ammonium chloride, zinc oxide, zinc salt, Dyhard RU 100, liquid polyamide, aromatic amine, aminoresin, polyisocyanates and oligopolymer, polycarbodiimide, organo-siloxane, the complex compound of boracic, one or more mixtures of epoxy based curing agent.
The microballoon of described polymer overmold pearlescence also comprises other auxiliary agent of 0-3wt%, and other auxiliary agents described comprise defoamer, dispersion agent and/or anti-settling agent; The wherein preferred silicone antifoam agent of defoamer; Dispersion agent is preferably polycarboxylate dispersant.
A preparation method for the microballoon of polymer overmold pearlescence, comprises the steps:
A) in aqueous polymer dispersion, surface-treated pearlescence/water-soluble pearlescent powder slurry is slowly added under normal temperature, add solidifying agent and/or other auxiliary agents while stirring, continue to stir 30-120min, pearlescence is fully disperseed and coated by aqueous polymer dispersion, obtain the composite dispersion liquid of polymer overmold pearlescence;
B) composite dispersion liquid step a) obtained carries out spraying dry, and in spray-drying process, the small droplets of the polymer overmold pearlescence that spraying is formed is cured crosslinking reaction by solidifying agent, obtains the microballoon of polymer overmold pearlescence.
Described spray-dired intake air temperature is 150-300 DEG C, is preferably 170-250 DEG C; Air outlet temperature is 50-130 DEG C, is preferably 70-100 DEG C.
The application of microballoon in thermoplasticity and thermosetting material of the polymer overmold pearlescence that the preparation method of the microballoon of described polymer overmold pearlescence prepares.
Compared with prior art, beneficial effect is as follows in the present invention:
The present invention by slowly adding pearlescence/water-soluble pearlescent powder slurry in aqueous polymer dispersion, make the microballoon of the polymer overmold pearlescence be prepared from can improve the consistency of pearlescence and matrix resin, improve pearlescence 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, can be widely used in preparing without current mark, light weld bond exempt from spraying thermoplastic 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.
embodiment 1-6 and comparative example 1-3:
By the formula of embodiment 1-6 in table 1 and comparative example 1-2, in aqueous polymer dispersion, surface-treated pearlescence/water-soluble pearlescent powder slurry is slowly added under normal temperature, add solidifying agent and/or other auxiliary agents while stirring, continue to stir 30-120min, pearlescence is fully disperseed and coated by aqueous polymer dispersion, obtain the composite dispersion liquid of polymer overmold pearlescence; The composite dispersion liquid obtained is carried out spraying dry, and in spray-drying process, the small droplets of the polymer overmold pearlescence that spraying is formed is cured crosslinking reaction by solidifying agent, obtains the microballoon of polymer overmold pearlescence; The intake air temperature of spray-drying process is 150-300 DEG C, and air outlet temperature is 50-130 DEG C.
Table 1
Embodiment 1: pearlescence is mica coating pearlescence, and its surface coated metal oxide is titanium oxide; Particle diameter is 5 μm; Aqueous polymer dispersion is polyacrylate dispersion, and its solid content is 10wt%; Solidifying agent is aminoresin.
Embodiment 2: pearlescence is pearl white crystallization pearlescence, and its surface coated metal oxide is titanium dioxide and chromium sesquioxide; Particle diameter is 100 μm; Aqueous polymer dispersion is polyaminoester emulsion, and its solid content is 50wt%; Solidifying agent is polyisocyanates, and other auxiliary agent is 0.4wt% silicone antifoam agent and 0.4wt% polycarboxylate dispersant.
Embodiment 3: pearlescence is silica-coating pearlescence, its surface coated metal oxide is ferric oxide; Particle diameter is 160 μm; Aqueous polymer dispersion is epoxy resin latex, and its solid content is 20wt%; Solidifying agent is aziridine, and other auxiliary agent is 1wt% silicone antifoam agent and 2wt% polycarboxylate dispersant.
Embodiment 4: pearlescence is aluminium silicate salt coating pearlescence, and its surface coated metal oxide is ferric oxide and titanium dioxide; Particle diameter is 200 μm; Aqueous polymer dispersion is polyacrylate dispersion, and its solid content is 40wt%; Solidifying agent is 5wt% aziridine and 5wt% polyisocyanates.
Embodiment 5: pearlescence is aluminum borate salt coating pearlescence, and its surface coated metal oxide is ferric oxide and titanium dioxide; Particle diameter is 50 μm; Aqueous polymer dispersion is ethene improved-vinyl acetate emulsion, and its solid content is 80wt%; Solidifying agent is 5wt% aminoresin and 2wt% aziridine, and other auxiliary agent is 0.4wt% silicone antifoam agent and 0.6wt% polycarboxylate dispersant.
Embodiment 6: pearlescence is bismuth oxide coating pearlescence, and its surface coated metal oxide is titanium dioxide; Particle diameter is 20 μm; Aqueous polymer dispersion is water-based urea-formaldehyde resin, and its solid content is 10wt%; Solidifying agent is aminoresin, and other auxiliary agent is 0.5wt% silicone antifoam agent and 0.9wt% polycarboxylate dispersant.
Comparative example 1: pearlescence is mica coating pearlescence, and its surface coated metal oxide is titanium oxide; Particle diameter is 5 μm; Aqueous polymer dispersion is polyacrylate dispersion, and its solid content is 10wt%; Solidifying agent is aminoresin, and other auxiliary agent is 0.4wt% silicone antifoam agent and 0.6wt% polycarboxylate dispersant.
Comparative example 2: pearlescence is silica-coating pearlescence, its surface coated metal oxide is ferric oxide; Particle diameter is 160 μm; Aqueous polymer dispersion is polyaminoester emulsion, and its solid content is 50wt%; Solidifying agent is polyisocyanates, and other auxiliary agent is 0.4wt% silicone antifoam agent and 0.4wt% polycarboxylate dispersant.
Comparative example 3: do not carry out coated common pearlescence/water-soluble pearlescent powder slurry, wherein pearlescence is mica coating pearlescence, and its surface coated metal oxide is titanium oxide; Particle diameter is 30 μm.
embodiment 7-14:
By the formula in table 2, the microballoon of 1-25wt% polymer overmold pearlescence is inserted high-speed mixer mix with 70-98wt% thermoplastic resin, 0-10wt% compatilizer, 0.1-1wt% oxidation inhibitor, 0.1-0.5wt% processing aid; Insert mixing extrusion in forcing machine, pelletizing after cooling, the moulding material of obtained thermoplastic polymer.Equally, by the formula in table 2, the microballoon of 1-25wt% polymer overmold pearlescence is inserted mixing machine mix with 70-98wt% thermosetting resin, 0-10wt% compatilizer, 0.1-1wt% oxidation inhibitor, 0.1-0.5wt% processing aid; Then be placed in forcing machine fusion plastification, then injecting the mould of heat, there is cross-linking and curing reaction in material at high temperature under high pressure, the moulding material of obtained thermosetting polymer.Both are distinguished sample preparation, and test its performance, test result is in table 2.
comparative example 4-9:
Pearlescence/water-soluble pearlescent powder the slurry of the polymer overmold pearlescence microballoon of comparative example 4-7 and comparative example 8-9 is inserted mixing machine mix with matrix resin (thermoplastic resin, thermosetting resin), compatilizer, oxidation inhibitor, processing aid; Then insert fusion plastification in forcing machine, prepare the moulding material of thermoplasticity and thermosetting polymer respectively by dicing machine and die material, its performance is tested in sample preparation, and test result is in table 2.
Table 2
Embodiment 7: thermoplastic resin is PP resin, compatilizer is terpolymer EP rubber, and oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is organic silicone lubricant;
Embodiment 8: thermosetting resin is epoxy resin, oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is Zinic stearas;
Embodiment 9: thermoplastic resin is PC/ABS alloy, compatilizer is acrylate copolymer, and oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is erucicamide;
Embodiment 10: thermosetting resin is resol, oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is Zinic stearas;
Embodiment 11: thermoplastic resin is ABS resin, compatilizer is ABS grafted maleic anhydride, and oxidation inhibitor is amine antioxidants 445, and processing aid is amine hydroxybenzene;
Embodiment 12: thermosetting resin is melamine formaldehyde resin, oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is Zinic stearas;
Embodiment 13: thermoplastic resin is TPU resin, oxidation inhibitor is hindered phenol antioxygen 1010, and processing aid is calcium stearate;
Embodiment 14: thermosetting resin is urethane resin, oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is Zinic stearas;
Comparative example 4: thermoplastic resin is PP resin, compatilizer is terpolymer EP rubber, and oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is organic silicone lubricant;
Comparative example 5: thermoplastic resin is thermoplastic ABS resin, compatilizer is ABS grafted maleic anhydride, and oxidation inhibitor is amine antioxidants 445, and processing aid is amine hydroxybenzene;
Comparative example 6: thermoplastic resin is PC/ABS alloy, compatilizer is acrylate copolymer, and oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is erucicamide;
Comparative example 7: thermosetting resin is resol, oxidation inhibitor is hindered phenol antioxygen 1010, and processing aid is calcium stearate;
Comparative example 8: thermoplastic resin is PP resin, pearlescence is mica coating pearlescence, and its surface coated metal oxide is titanium oxide; Particle diameter is 30 μm; Compatilizer is terpolymer EP rubber, and oxidation inhibitor is hindered phenol antioxygen 1010 and phosphoric acid ester irgasfos 168, and processing aid is organic silicone lubricant;
Comparative example 9: thermosetting resin is epoxy resin, pearlescence is silica-coating pearlescence, and its surface coated metal oxide is ferric oxide; Particle diameter is 30 μm; Oxidation inhibitor is hindered phenol antioxygen 1010, and processing aid is calcium stearate.
Properties testing standard or method:
Particle diameter: adopt testing electronic microscope;
Current mark: range estimation, "-" indicates without current mark, and "+" represents to there is current mark, and "+" more multilist shows that current mark is more serious;
Weld bond: range estimation, "+" more multilist show weld bond more seriously, more obvious.
Can find out from the embodiment and comparative example of table 1, by pearlescence/water-soluble pearlescent powder slurry with water polymer dispersion liquid carries out coated, is conducive to the consistency improving pearlescence and matrix resin, can reduce the blackening degree of pearlescence; Can find out from the embodiment and comparative example of table 2, the microballoon of the polymer overmold pearlescence of 1-25wt% is adopted in embodiment 7-14, again with matrix resin blending extrusion, and pearlescence/water-soluble pearlescent powder slurry is directly added to blending extrusion in matrix resin by comparative example 8-9, ensureing under other components prerequisite consistent with content, exempting from obtained by embodiment 7-14 sprays thermoplasticity and thermosetting material and has technique effect without current mark, gently weld bond.
Claims (11)
1. a microballoon for polymer overmold pearlescence, is characterized in that: by weight percentage, comprises following component:
Pearlescence
/water-soluble pearlescent powder slurry 5-80wt%
Aqueous polymer dispersion 18-90wt%
Solidifying agent 0.2-10wt%.
2. the microballoon of polymer overmold pearlescence according to claim 1, is characterized in that, containing the pearlescence kernel of particle diameter 3-500 μm, is coated with at the outside surface of pearlescence kernel the polymer shell that thickness is 5-800 μm.
3. the microballoon of polymer overmold pearlescence according to claim 1, is characterized in that, the transverse section of described pearlescence has the physical structure being similar to pearl, and kernel is the material of low optical specific refractory power, and being coated on outer field is the metal oxide of high refractive index; Described pearlescence be selected from mica coating pearlescence, pearl white crystallization pearlescence, silica-coating pearlescence, aluminium silicate salt coating pearlescence, aluminum borate salt coating pearlescence, bismuth oxide coating pearlescence one or more.
4. polymer overmold pearlescence microballoon according to claim 3, is characterized in that, the surface coated metal oxide of described pearlescence is selected from one or more of titanium oxide, chromium sesquioxide, titanium dioxide, ferric oxide, weisspiessglanz or zinc oxide; The particle diameter of described pearlescence is 3 μm-500 μm, is preferably 5-200 μm.
5. the microballoon of polymer overmold pearlescence according to claim 1, is characterized in that, the solid content of described water-soluble pearlescent powder slurry is 10-80wt%, is preferably 20-70wt%.
6. the microballoon of polymer overmold pearlescence according to claim 1, it is characterized in that, the solid content of described aqueous polymer dispersion is 10-60wt%, be selected from polyaminoester emulsion, organic silicon emulsion, organic fluorine emulsion, epoxy resin latex, polyacrylate dispersion, benzene emulsion, organosilicon crylic acid latex, modified ABS resin emulsion, the modified-cellulose aqueous solution, polyvinyl alcohol and the condenses aqueous solution thereof, the polyacrylic acid aqueous solution, water-based urea-formaldehyde resin, aqueous melamine and etherified resin thereof, resol resins, aqueous alkide resin, aqueous polyester resin, aqueous polyvinyl acetate emulsion, ethene improved-vinyl acetate emulsion, nature rubber latex, styrene-butadiene emulsion, butyronitrile emulsion, one or more mixtures of vinyl acetate emulsion and mixture and modifier.
7. the microballoon of polymer overmold pearlescence according to claim 1, it is characterized in that, described solidifying agent comprises aliphatic polyamine, aromatic polyamine, alicyclic polyamine, ammonium chloride, Resorcinol, aziridine and derivative thereof, zinc oxide, zinc salt, Dyhard RU 100, liquid polyamide, aromatic amine, aminoresin, polyisocyanates and oligopolymer, polycarbodiimide, organo-siloxane, the complex compound of boracic, one or more mixtures of epoxy based curing agent.
8. the microballoon of polymer overmold pearlescence according to claim 1, is characterized in that, also comprises other auxiliary agent of 0-3wt%, and other auxiliary agents described comprise defoamer, dispersion agent and/or anti-settling agent; Be preferably silicone antifoam agent and/or polycarboxylate dispersant.
9. the preparation method of the microballoon of the polymer overmold pearlescence as described in any one of claim 1-8, is characterized in that, comprise the steps:
A) in aqueous polymer dispersion, surface-treated pearlescence/water-soluble pearlescent powder slurry is slowly added under normal temperature, add solidifying agent and/or other auxiliary agents while stirring, continue to stir 30-120min, pearlescence is fully disperseed and coated by aqueous polymer dispersion, obtain the composite dispersion liquid of polymer overmold pearlescence;
B) composite dispersion liquid step a) obtained carries out spraying dry, and in spray-drying process, the small droplets of the polymer overmold pearlescence that spraying is formed is cured crosslinking reaction by solidifying agent, obtains the microballoon of polymer overmold pearlescence.
10. the preparation method of the microballoon of polymer overmold pearlescence according to claim 9, is characterized in that, described spray-dired intake air temperature is 150-300 DEG C, is preferably 170-250 DEG C; Air outlet temperature is 50-130 DEG C, is preferably 70-100 DEG C.
The application of microballoon in thermoplasticity and thermosetting material of the polymer overmold pearlescence that the preparation method of the microballoon of 11. polymer overmold pearlescences as claimed in claim 9 prepares.
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| 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 |
| CN112812369A (en) * | 2020-12-31 | 2021-05-18 | 金发科技股份有限公司 | Polymer-coated composite hollow microsphere and preparation method and application thereof |
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Application publication date: 20150520 |