CN106349432B - A kind of polyurethane-modified silicone acrylic emulsion and the preparation method and application thereof - Google Patents
A kind of polyurethane-modified silicone acrylic emulsion and the preparation method and application thereof Download PDFInfo
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- CN106349432B CN106349432B CN201610804966.XA CN201610804966A CN106349432B CN 106349432 B CN106349432 B CN 106349432B CN 201610804966 A CN201610804966 A CN 201610804966A CN 106349432 B CN106349432 B CN 106349432B
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- China
- Prior art keywords
- polyurethane
- modified silicone
- acrylic emulsion
- silicone acrylic
- preparation
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- 239000000839 emulsion Substances 0.000 title claims abstract description 65
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920003023 plastic Polymers 0.000 claims abstract description 18
- 239000004033 plastic Substances 0.000 claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- -1 hydroxyl acrylic ester Chemical class 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 3
- LQNMMOSUQPOUTQ-UHFFFAOYSA-N henicosane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCCCCC(O)O LQNMMOSUQPOUTQ-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims 4
- 229940074391 gallic acid Drugs 0.000 claims 2
- 235000004515 gallic acid Nutrition 0.000 claims 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 2
- 239000006071 cream Substances 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 150000002527 isonitriles Chemical class 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000009835 boiling Methods 0.000 abstract description 15
- 238000004945 emulsification Methods 0.000 abstract description 5
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 238000007639 printing Methods 0.000 description 9
- 239000002985 plastic film Substances 0.000 description 7
- 229920006255 plastic film Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention belongs to water-based polyurethane ink technical field, a kind of polyurethane-modified silicone acrylic emulsion and the preparation method and application thereof is disclosed.The preparation method is that: the dihydroxy compounds with Long carbon chain is dissolved in polyvalent alcohol, add di-isocyanate reaction, after-NCO base content reaches certain value, hydrophilic chain extender is added to be reacted, then hydroxyl acrylic ester monomer is added to be reacted, adding acrylic ester monomer and organic silicon monomer reduces the viscosity of reactant, obtains base polyurethane prepolymer for use as；Then it is added after neutralizer is ionized and carries out water dispersion emulsification, initiator is added and causes unsaturated monomer progress Raolical polymerizable, obtains polyurethane-modified silicone acrylic emulsion.The polyurethane-modified silicone acrylic emulsion of gained of the invention has good adhesion strength to polyolefin plastics (OPP, PE) film, and water resistance and boiling resistance can be good.
Description
Technical field
The invention belongs to water-based polyurethane ink technical fields, and in particular to a kind of polyurethane-modified silicone acrylic emulsion and its system
Preparation Method and application.
Background technique
Water-based ink is one of current printing ink the most environmentally friendly and currently the only recommended and approved by U.S. FDA
, can be used for printing ink variety with direct food contact.Relative to solvent-based ink, water-based ink, which has, does not pollute atmosphere
The features such as environment, low toxicity, safe low-resource energy consumption and operating environment.In China, paper printing is market-oriented with water-based ink,
But due to the not absorption characteristics and low-surface-energy characteristic of plastic film, package plastics of food film printing water-based ink also in
Study the starting stage.Currently, the printing of polyolefin plastics film packaging substantially uses solvent type ink used for plastic, this is because
Polyolefin plastics film surface energy is low, hydrophobicity is strong, not for the active group of reaction, and general waterborne polymeric is difficult to soak
Its surface simultaneously obtains good adhesion strength.According to the adhesion mechanism on polyolefin plastics surface, the polarity of ink adhesive and poly-
Olefin plastics surface polarity is closer, and ink is better in polyolefin plastics wettability of the surface, adhesion strength；Ink adhesive
Molecular structure is more similar to polyolefin plastics molecular structure, and molecular force is bigger between the two.Application No. is
201310338763.2 patent report is a kind of suitable for the water-soluble self-crosslinking acrylic tree for printing compound oil ink in OPP
Rouge, primary raw material are acrylic acid and its derivative, non-acrylic compounds carboxylic monomer, utilize the lower polarity of acrylate polymer
And carboxylic group obtains good adhesive strength in OPP, PET base material, but acrylate polymer it is heated easily return it is viscous, gloss compared with
Low and scrub performance is poor.
Aqueous polyurethane has fabulous wearability, marresistance and good low as novel environment-friendly material
Warm nature energy, Gloss Retention etc. have broad application prospects in water-based ink field.But aqueous polyurethane contains a large amount of polar groups
Group, to the poor adhesive force of non-polar polyolefinic plastic film.Currently, improving water-based ink polyurethane binder in polyolefin plastics
The method of adhesive force is mainly by two kinds on film.First is that addition chloridized polyolefin adhesion promoter.But the master of chloridized polyolefin
Wanting solvent is toluene, not only endangers greatly environment and construction personnel, and be easy to remain in ink layer, endangers food safety,
Meanwhile chlorine atom is reactive group in chloridized polyolefin, meets high temperature or is illuminated by the light chlorine atom for a long time and is easy to fall off, ink layer is tough
Property and durability are poor.Second is that introducing acrylate polymer in aqueous polyurethane.Utilize the lower table of acrylate polymer
Face polarity adjusts the surface property of aqueous polyurethane, and similar to the molecular structure of polyolefin plastics using acrylate polymer
Property, make it that there is good adhesion strength on polyolefin plastics.Application No. is 201010190353.4 patent reports one
Kind there is the integrated plastic gravure alcohol-soluble water aqueous composite ink resin of good adhesion to all types of plastic film substrate, be with can
Polymerizable polyurethane polymeric monomer, (methyl) acrylate, vinylacetate and active function monomer are raw material, pass through Solution Free Radical
Copolymerization is made.But the preparation process of the resin is complex, is unfavorable for industrialized production.
Summary of the invention
In order to solve the disadvantage that the above prior art and shortcoming, the primary purpose of the present invention is that providing a kind of poly- ammonia
The preparation method of ester modified silicone acrylic emulsion.
Another object of the present invention is to provide a kind of polyurethane-modified silicone acrylic emulsions being prepared by the above method.
A further object of the present invention is to provide above-mentioned polyurethane-modified silicone acrylic emulsions in polyolefin plastics film ink
Application.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of polyurethane-modified silicone acrylic emulsion, including following preparation step:
It (1) will be with C12~18The dihydroxy compounds of Long carbon chain is dissolved in polyvalent alcohol at 60~80 DEG C, adds two
End-NCO base the performed polymer with double bond is made in isocyanates, 60~90min of prepolymerization reaction at 70~85 DEG C；
(2) it is added hydrophilic chain extender obtained by the step (1) in the end-NCO base performed polymer with double bond, it is anti-at 70~85 DEG C
60~90min is answered, hydroxyl acrylic ester monomer is added, reacts 15~30min, is then cooled to 40~60 DEG C, is added
Acrylic ester monomer and organic silicon monomer adjust viscosity, and base polyurethane prepolymer for use as is made；
(3) neutralizer is added in the performed polymer obtained by step (2) and carries out 3~5min of ionization, then pass through shearing moisture
5~10min of emulsification is dissipated, aqueous polyurethane emulsion is obtained；
(4) initiator is added in aqueous polyurethane emulsion obtained by the step (3), react 60 at 75~85 DEG C~
120min obtains the polyurethane-modified silicone acrylic emulsion.
The band C12~18The dihydroxy compounds of Long carbon chain is preferably dihydroxypropyl octadecane acid esters, 1,2- hexadecane
At least one of glycol, 2,3- dihydroxy propyl alcohol dodecanoate；Band C12~18The additional amount of the dihydroxy compounds of Long carbon chain accounts for
The 2%~8% of solids quality in the final polyurethane-modified silicone acrylic emulsion of gained.
The polyvalent alcohol is preferably poly-epsilon-caprolactone glycol, dimer (fatty acid) yl esterdiol, at least one in polypropylene glycol
Kind；The additional amount of polyvalent alcohol accounts for 29%~33% of solids quality in the final polyurethane-modified silicone acrylic emulsion of gained.
The diisocyanate is preferably isophorone diisocyanate, hexamethylene diisocyanate, 4,4 '-two hexamethylenes
At least one of dicyclohexylmethane diisocyanate；The additional amount of diisocyanate accounts in the final polyurethane-modified silicone acrylic emulsion of gained
The 9%~16% of solids quality.
Hydrophilic chain extender described in step (2) be preferably 2,2- dihydromethyl propionic acid, in dimethylolpropionic acid at least
It is a kind of；The additional amount of hydrophilic chain extender accounts for 2%~4% of solids quality in the final polyurethane-modified silicone acrylic emulsion of gained.
The hydroxyl acrylic ester monomer is preferably at least one of hydroxypropyl acrylate, hydroxy-ethyl acrylate；
The additional amount of hydroxyl acrylic ester monomer account for solids quality in the final polyurethane-modified silicone acrylic emulsion of gained 0.3%~
1%.
The acrylic ester monomer is preferably butyl acrylate, butyl methacrylate, methyl acrylate, metering system
At least one of sour methyl esters；The additional amount of acrylic ester monomer accounts for solids in the final polyurethane-modified silicone acrylic emulsion of gained
The 45%~48% of quality.
The organic silicon monomer is preferably γ-methacryloxypropyl trimethoxy silane, vinyl trimethoxy
At least one of silane, vinyl silane triisopropoxide；Preferentially use vinyl silane triisopropoxide；Organic silicon monomer
The additional amount accounted for accounts for 2%~4% of solids quality in the final polyurethane-modified silicone acrylic emulsion of gained.
Neutralizer described in step (3) is preferably at least one of triethylamine, ammonium hydroxide, sodium hydroxide, with degree of neutralization
100% amount addition.
Initiator described in step (4) is preferably at least one of ammonium persulfate, potassium peroxydisulfate；The addition of initiator
Amount accounts for the 0.5%~0.7% of acrylic ester monomer and organic silicon monomer gross mass.
A kind of polyurethane-modified silicone acrylic emulsion, is prepared by the above method.
Application of the above-mentioned polyurethane-modified silicone acrylic emulsion in polyolefin plastics film ink.
The principle of the present invention is using band Long carbon chain (C12~18) dihydroxy compounds modified polyurethane, then with modified
Polyurethane-modified siloxane-acrylate copolymer.- the OH of dihydroxy compounds with Long carbon chain (12~18C) and-NCO of polyisocyanates
Group reacts, and the aqueous polyurethane emulsion of belt length carbon chain branches is made, then be modified siloxane-acrylate copolymer with it.On the one hand, long
Carbon chain branches can reduce the polarity of polyurethane, it, which is shared with the organosilicon with low-surface-energy, can further improve polymer and exist
Wetability on non-polar polyolefinic plastic film, meanwhile, the structure of Long carbon chain branch is similar to polyolefin plastics molecular structure,
When the two intermolecular distance is sufficiently small, stronger intermolecular force can provide good adhesion strength between the two, and organic
Silicon have improve polymer wetability on low surface energy substrates, shorten polymer molecule between substrate molecule at a distance from work
With.On the other hand, the hydrophobicity of Long carbon chain branch and organosilicon can be improved polyurethane-modified polyacrylate lotion water resistance and
Boiling resistance.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) present invention will be with Long carbon chain (C12~18) dihydroxy compounds modified polyurethane and organosilicon-modified acrylic
Two systems of ester combine, the common wetability for improving waterborne polymeric on non-polar polyolefinic plastic film, contracting
Short polymer molecule between substrate molecule at a distance from；
(2) polyurethane-modified silicone acrylic emulsion prepared by the present invention due in its molecule the structure of certain segments and polyolefin it is poly-
Adduct molecule structure is similar, and intermolecular dispersion force is stronger, has polymer molecule on non-polar polyolefinic plastic film substrate
There is good adhesion strength, can be used as water-based ink binder, without adding adhesion promoter；
(3) during the present invention prepares polyurethane-modified silicone acrylic emulsion, any catalyst is not used, and with Long carbon chain
(C12~18) dihydroxy compounds be mostly non-toxic and safe compound, therefore the polyurethane-modified silicone acrylic emulsion be suitable for food packaging
Ink adhesive.
Detailed description of the invention
Fig. 1 is contact angle test result figure of the polyurethane-modified silicone acrylic emulsion on OPP film obtained by the embodiment of the present invention.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
(1) 40g polypropylene glycol is added in the 500ml four-hole boiling flask that blender, thermometer, reflux condensing tube are housed
(PPG, molecular weight 2000), 2.7g dihydroxypropyl octadecane acid esters stir 10min at 65 DEG C.Then heat to 78.5
DEG C, it is added 18.7g isophorone diisocyanate (IPDI), reacts 70min, end-NCO base performed polymer is made.
(2) 2.7g dihydromethyl propionic acid (DMPA) is dissolved in 5g acetone, is added in above-mentioned end-NCO base performed polymer, in
70min is reacted at 78.5 DEG C, 0.7g hydroxy-ethyl acrylate is then added, and reacts 20min；It has reacted and has been cooled to 40 DEG C, be added
65.5g unsaturated monomer (27g butyl acrylate, 34.5g methyl methacrylate, 4g vinyl silane triisopropoxide) is adjusted
Base polyurethane prepolymer for use as is made in viscosity.
(3) above-mentioned base polyurethane prepolymer for use as is moved in dispersion tank, 2.1g triethylamine (TEA), 5g water is added, in 1000r/
5min is ionized under min mixing speed；140g water is added on one side and is dispersed to 7000r/min for another edge height mixing speed
Emulsification obtains aqueous polyurethane emulsion after emulsifying 10min.
(4) it is added in aqueous polyurethane emulsion after 0.4g potassium peroxydisulfate being dissolved in 10g water, is carried out freely at 80 DEG C
Base polymerization, reaction time 90min are cooled to 40 DEG C after reaction, discharge to get polyurethane-modified silicone acrylic emulsion.
Embodiment 2
(1) 40g polypropylene glycol is added in the 500ml four-hole boiling flask that blender, thermometer, reflux condensing tube are housed
(PPG, molecular weight 2000), 5.3g 1,2- hexadecane diol stir 10min at 65 DEG C.78.5 DEG C are then heated to, is added
Enter 15.7g isophorone diisocyanate (IPDI), react 70min, end-NCO base performed polymer is made.
(2) 3g dihydromethyl propionic acid (DMPA) is dissolved in 5g acetone, is added in above-mentioned end-NCO base performed polymer, in
70min is reacted at 78.5 DEG C, 0.7g hydroxy-ethyl acrylate is then added, and reacts 20min；It has reacted and has been cooled to 55 DEG C, be added
65.5g unsaturation is adjusted to monomer (27g butyl acrylate, 34.5g methyl methacrylate, 4g vinyl silane triisopropoxide)
Viscosity is saved, base polyurethane prepolymer for use as is made.
(3) above-mentioned base polyurethane prepolymer for use as is moved in dispersion tank, 2.2g triethylamine (TEA), 5g water is added, in 1000r/
5min is ionized under min mixing speed；140g water is added on one side and is dispersed to 7000r/min for another edge height mixing speed
Emulsification obtains aqueous polyurethane emulsion after emulsifying 10min.
(4) it is added in aqueous polyurethane emulsion after 0.4g potassium peroxydisulfate being dissolved in 10g water, is carried out freely at 80 DEG C
Base polymerization, reaction time 90min are cooled to 40 DEG C after reaction, discharge to get polyurethane-modified silicone acrylic emulsion.
Embodiment 3
(1) 40g polypropylene glycol is added in the 500ml four-hole boiling flask that blender, thermometer, reflux condensing tube are housed
(PPG, molecular weight 2000), 7.9g 2,3- dihydroxy propyl alcohol dodecanoate, stir 10min at 65 DEG C.It then heats to
It 78.5 DEG C, is added 12.9g isophorone diisocyanate (IPDI), reacts 70min, end-NCO base performed polymer is made
(2) 3.1g dihydromethyl propionic acid (DMPA) is dissolved in 5g acetone, is added in above-mentioned end-NCO base performed polymer, in
70min is reacted at 78.5 DEG C, 0.7g hydroxy-ethyl acrylate is then added, and reacts 20min；It has reacted and has been cooled to 60 DEG C, be added
65.5g unsaturation is adjusted to monomer (27g butyl acrylate, 34.5g methyl methacrylate, 4g vinyl silane triisopropoxide)
Viscosity is saved, base polyurethane prepolymer for use as is made.
(3) above-mentioned base polyurethane prepolymer for use as is moved in dispersion tank, 2.3g triethylamine (TEA), 5g water is added, in 1000r/
5min is ionized under min mixing speed；140g water is added on one side and is dispersed to 7000r/min for another edge height mixing speed
Emulsification obtains aqueous polyurethane emulsion after emulsifying 10min.
(4) it is added in aqueous polyurethane emulsion after 0.4g potassium peroxydisulfate being dissolved in 10g water, is carried out freely at 80 DEG C
Base polymerization, reaction time 90min are cooled to 40 DEG C after reaction, discharge to get polyurethane-modified silicone acrylic emulsion.
Properties of product test:
1. surface tension and contact angle:
It is obtained polyurethane-modified using the JC2000 type surface tension tester test of upper marine morning Numerical Technologies Inc
The surface tension of silicone acrylic emulsion and the contact angle on OPP film, as a result as Fig. 1 (by left-to-right respectively embodiment 1, is implemented
Example 2 and embodiment 3) and table 1 shown in.
The table tension and the contact angle on OPP film of the polyurethane-modified silicone acrylic emulsion of 1 Examples 1 to 3 of table preparation
By Fig. 1 and table 1 as it can be seen that with C12~18The addition of the dihydroxy compounds and organosilicon composition of Long carbon chain reduces poly-
The surface tension of the modified silicone acrylic emulsion of urethane and the contact angle on OPP film.The introducing of Long carbon chain side chain provides aqueous poly-
The hydrophobicity of urethane molecule, so that polyurethane molecular amphipathic property is more obvious, and on side chain, freedom of movement,
Lipophilic group is easier to towards air when water surface adsorbs.With the increase of Long carbon chain content, water surface saturated extent of adsorption by
Cumulative big, surface tension gradually decreases therewith.The reduction of polyurethane-modified silicone acrylic emulsion surface tension improves it in OPP film
On wetability so that its contact angle on OPP film gradually becomes smaller.
2. peel strength test:
Polyurethane-modified silicone acrylic emulsion film obtained is dried on OPP, PE film using printing ink intaglio printing proof press
Gluing (the solvent type glue of resistance to boiling) is carried out on it after dry, it is compound after the volatilization of its surface solvent, then with the progress of CPP film,
Measure its 90 ° of peel strengths after curing 48h, rate of extension 300mm/min, test result is as shown in table 2:
The peel strength of the polyurethane-modified silicone acrylic emulsion of 2 Examples 1 to 3 of table preparation
As can be seen from Table 2, the peel strength of all embodiments is higher.This is because the molecule of polyurethane-modified silicone acrylic emulsion
The Long carbon chain branch and organosilicon chain link of middle introducing reduce the surface tension of aqueous polyurethane, keep it thin in OPP and PE plastics
There is good wetability on film, meanwhile, the structure of Long carbon chain branch is similar to OPP and PE molecular structure, and stronger point between the two
Active force provides good adhesion strength between son.
3. boiling and boiling test:
By taking embodiment 2 as an example, by the polyurethane-modified silicone acrylic emulsion film of synthesis on OPP, PE film, at it after drying
Upper progress gluing (the solvent type glue of resistance to boiling), after its surface solvent volatilization after, then with CPP film carry out it is compound, then according to
People's Republic of China's light industry standard " water-base gravure plastic film table printing ink " (QBT 4103-2010), carries out respectively
Whether 100 DEG C of boilings and 121 DEG C of boiling tests, observation sample wrinkle, rupture.
After boiling, boiling, sample is not wrinkled, is not ruptured, shows the water boiling resistance of polyurethane-modified silicone acrylic emulsion obtained
It is good with boiling resistance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of polyurethane-modified silicone acrylic emulsion, it is characterised in that including following preparation step:
It (1) will be with C12~18The dihydroxy compounds of Long carbon chain is dissolved in polyvalent alcohol at 60~80 DEG C, adds two isocyanides
End-NCO base the performed polymer with double bond is made in acid esters, 60~90min of prepolymerization reaction at 70~85 DEG C；
(2) hydrophilic chain extender is added in the end-NCO base performed polymer with double bond obtained by step (1), reacts 60 at 70~85 DEG C
~90min adds hydroxyl acrylic ester monomer, reacts 15~30min, is then cooled to 40~60 DEG C, and propylene is added
Esters of gallic acid monomer and organic silicon monomer adjust viscosity, and base polyurethane prepolymer for use as is made；
(3) neutralizer is added in the performed polymer obtained by step (2) and carries out 3~5min of ionization, then pass through shearing water dispersion cream
Change 5~10min, obtains aqueous polyurethane emulsion；
(4) initiator is added in the aqueous polyurethane emulsion obtained by step (3), 60~120min is reacted at 75~85 DEG C, is obtained
To the polyurethane-modified silicone acrylic emulsion.
2. a kind of preparation method of polyurethane-modified silicone acrylic emulsion according to claim 1, it is characterised in that: the band
C12~18The dihydroxy compounds of Long carbon chain is dihydroxypropyl octadecane acid esters, 1,2- hexadecane diol, 2,3- dihydroxy propyl alcohol
At least one of dodecanoate；Band C12~18It is polyurethane-modified that the additional amount of the dihydroxy compounds of Long carbon chain accounts for final gained
The 2%~8% of solids quality in silicone acrylic emulsion.
3. a kind of preparation method of polyurethane-modified silicone acrylic emulsion according to claim 1, it is characterised in that: described poly- more
First alcohol is at least one of poly-epsilon-caprolactone glycol, dimer (fatty acid) yl esterdiol, polypropylene glycol；The additional amount of polyvalent alcohol accounts for
The 29%~33% of solids quality in the final polyurethane-modified silicone acrylic emulsion of gained.
4. a kind of preparation method of polyurethane-modified silicone acrylic emulsion according to claim 1, it is characterised in that: described two is different
Cyanate is isophorone diisocyanate, in hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates
It is at least one；The additional amount of diisocyanate account for solids quality in the final polyurethane-modified silicone acrylic emulsion of gained 9%~
16%.
5. a kind of preparation method of polyurethane-modified silicone acrylic emulsion according to claim 1, it is characterised in that: step (2)
Described in hydrophilic chain extender be at least one of 2,2- dihydromethyl propionic acid, dimethylolpropionic acid；Hydrophilic chain extender
Additional amount accounts for 2%~4% of solids quality in the final polyurethane-modified silicone acrylic emulsion of gained.
6. a kind of preparation method of polyurethane-modified silicone acrylic emulsion according to claim 1, it is characterised in that: the band hydroxyl
Base acrylic ester monomer is at least one of hydroxypropyl acrylate, hydroxy-ethyl acrylate；Hydroxyl acrylic ester monomer
Additional amount account for 0.3%~1% of solids quality in the final polyurethane-modified silicone acrylic emulsion of gained.
7. a kind of preparation method of polyurethane-modified silicone acrylic emulsion according to claim 1, it is characterised in that: the propylene
Esters of gallic acid monomer is at least one of butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate；
The additional amount of acrylic ester monomer accounts for 45%~48% of solids quality in the final polyurethane-modified silicone acrylic emulsion of gained；Institute
It is different for γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxysilane, vinyl three to state organic silicon monomer
At least one of npropoxysilane；The additional amount of organic silicon monomer accounts for solids in the final polyurethane-modified silicone acrylic emulsion of gained
The 2%~4% of quality.
8. a kind of preparation method of polyurethane-modified silicone acrylic emulsion according to claim 1, it is characterised in that: step (3)
Described in neutralizer be at least one of triethylamine, ammonium hydroxide, sodium hydroxide, added with the amount of degree of neutralization 100%；Step
(4) initiator described in is at least one of ammonium persulfate, potassium peroxydisulfate；The additional amount of initiator accounts for esters of acrylic acid list
The 0.5%~0.7% of body and organic silicon monomer gross mass.
9. a kind of polyurethane-modified silicone acrylic emulsion, it is characterised in that: prepared by method according to any one of claims 1 to 8
It obtains.
10. application of the polyurethane-modified silicone acrylic emulsion as claimed in claim 9 in polyolefin plastics film ink.
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| CN102433052A (en) * | 2011-09-10 | 2012-05-02 | 中国十七冶集团有限公司 | Waterborne polyurethane modified silicone-acrylate multifunctional waterproof heat-insulation elastic coating and preparation method thereof |
| CN104804492A (en) * | 2015-04-08 | 2015-07-29 | 牛无畏 | A scratch-resistant high-performance waterborne wood coating |
| CN105566607A (en) * | 2016-02-29 | 2016-05-11 | 深圳市姿彩科技有限公司 | Modified polyurethane acrylate and preparation method thereof |
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| CN102433052A (en) * | 2011-09-10 | 2012-05-02 | 中国十七冶集团有限公司 | Waterborne polyurethane modified silicone-acrylate multifunctional waterproof heat-insulation elastic coating and preparation method thereof |
| CN104804492A (en) * | 2015-04-08 | 2015-07-29 | 牛无畏 | A scratch-resistant high-performance waterborne wood coating |
| CN105566607A (en) * | 2016-02-29 | 2016-05-11 | 深圳市姿彩科技有限公司 | Modified polyurethane acrylate and preparation method thereof |
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