CN117777365A - Modified hydroxy acrylic emulsion for two-component one-plastic-coated paint and preparation method thereof - Google Patents
Modified hydroxy acrylic emulsion for two-component one-plastic-coated paint and preparation method thereof Download PDFInfo
- Publication number
- CN117777365A CN117777365A CN202311813503.6A CN202311813503A CN117777365A CN 117777365 A CN117777365 A CN 117777365A CN 202311813503 A CN202311813503 A CN 202311813503A CN 117777365 A CN117777365 A CN 117777365A
- Authority
- CN
- China
- Prior art keywords
- monomer
- parts
- emulsion
- component
- plastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 69
- 239000003973 paint Substances 0.000 title claims abstract description 66
- 239000004033 plastic Substances 0.000 title claims abstract description 45
- 229920003023 plastic Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 14
- -1 hydroxy acrylic ester Chemical class 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 125000003368 amide group Chemical group 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 3
- 239000011258 core-shell material Substances 0.000 claims description 20
- 239000012792 core layer Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000009775 high-speed stirring Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 7
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical class OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- 238000001914 filtration Methods 0.000 claims description 4
- 239000006174 pH buffer Substances 0.000 claims description 4
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- RQAVKYPVSDCFJQ-UHFFFAOYSA-N 2-methyl-n-(2-methylpropoxy)prop-2-enamide Chemical compound CC(C)CONC(=O)C(C)=C RQAVKYPVSDCFJQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-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
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- WFVZQYQWGBYJRH-UHFFFAOYSA-N but-1-ene;2-methylprop-2-enamide;urea Chemical compound CCC=C.NC(N)=O.CC(=C)C(N)=O WFVZQYQWGBYJRH-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 18
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 7
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZHNZXPCKMAJBQQ-UHFFFAOYSA-N 2-methyl-n-[2-(2-oxoimidazolidin-1-yl)ethyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCCN1CCNC1=O ZHNZXPCKMAJBQQ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000013022 formulation composition Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241000238367 Mya arenaria Species 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to the field of fine chemicals and preparation methods thereof, in particular to a modified hydroxyl acrylic emulsion for a two-component one-plastic-coated paint and a preparation method thereof, and the modified hydroxyl acrylic emulsion at least comprises the following raw materials in parts by weight: 50-60 parts of deionized water; 0.8 to 1.2 portions of compound emulsifier; 0.04-0.06 part of pH buffering agent; 0.09 to 0.15 portion of persulfate; 0.1 to 3 parts of carboxyl functional monomer; 25-32 parts of acrylate monomer; 6-7 parts of hydroxy acrylic ester monomer; 3-5 parts of cyclic methacrylate monomer; 1-3 parts of ureido or amido-containing acrylic acid monomer; 0.1 to 0.3 part of difunctional acrylic monomer; 0.1 to 0.3 part of molecular weight regulator; the amine neutralizer 0.1-0.5 parts, and the bi-component plastic paint prepared by the amine neutralizer not only has excellent adhesive force, water resistance and chemical resistance, but also has good appearance, is convenient to construct, and can meet the construction requirement of one-step coating.
Description
Technical Field
The invention relates to the field of fine chemicals and preparation methods thereof, in particular to a modified hydroxy acrylic emulsion for a two-component one-plastic-coated paint and a preparation method thereof.
Background
The one-step coating construction method is simple, has high efficiency, has advantages in the aspects of VOC emission and energy consumption, and can avoid the problems of undercut, bloom, poor composite coating performance and the like caused by the mismatch between the primer and the finish paint possibly existing in the multi-step construction. Therefore, the coating is increasingly popular in the plastic part coating of electronic products, two-wheelers and small household appliances. The single-component plastic paint does not need to additionally add a curing agent, has low use cost, does not have a pot life and has high drying speed, but has poor hardness, water resistance and chemical resistance of a paint film due to the fact that a cross-linked structure is not present or the cross-linked density is very low, and can only be applied to some low-end fields. The bi-component plastic paint is formed by matching the main paint with the curing agent, can form a compact crosslinked structure in the film forming process, and has excellent comprehensive performance.
The existing two-component plastic paint for one-step coating is mainly a solvent product, and the water-based two-component plastic paint for one-step coating has a plurality of problems that only a few low-hydroxyl resins can be used for improving the drying speed and the adhesive force, so that the crosslinking density is insufficient, the paint film performance is not ideal, and the adhesive force of the paint film on a plastic substrate is unstable due to the overlarge cohesive force although the paint film performance is excellent.
For example, chinese patent application (publication No. CN 104673020 a) discloses a single-coating high-gloss boiling-resistant plastic paint and a preparation method thereof, wherein high-hydroxyl acrylic resin is used as a main body, low-hydroxyl resin with higher glass transition temperature is used as an auxiliary resin, and the prepared plastic paint has better gloss and boiling-resistant performance. The adhesive force problem is solved through the compounding of the high-hydroxyl resin and the low-hydroxyl resin, and the paint film performance is better, but the solvent-based resin is used, the VOC content is high, and the environment protection requirement is not met. Chinese patent application (CN 115873485A) discloses a water-based low-temperature double-component polyurethane primer-topcoat silver paint and a preparation method thereof, wherein the prepared silver paint can meet the performance requirement of the pen-powered computer silver paint by matching low-hydroxyl acrylic acid secondary dispersion with medium-high-hydroxyl acrylic acid secondary dispersion. The hydroxyl acrylic acid secondary dispersion used in the invention is water-based resin, but still contains organic solvent, and because of the limitation of the secondary dispersion preparation process, the molecular weight is smaller, the dryness is poorer, and more silver discharging auxiliary agent is needed to improve the silver powder arrangement.
In summary, most of the two-component one-coat plastic paints disclosed in the prior art use oily or two-stage dispersion as film-forming resins, so that VOC cannot be radically eliminated, and in addition, high-hydroxyl resin and low-hydroxyl resin are adopted for mixing and splicing in order to balance the adhesive force and performance, so that the use is difficult.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the modified hydroxy acrylic emulsion for one-step coating of the bi-component plastic paint, and the bi-component plastic paint prepared by using the modified hydroxy acrylic emulsion not only has excellent adhesive force, water resistance and chemical resistance, but also has good appearance, is convenient to construct and can meet the construction requirement of one-step coating.
The invention provides a modified hydroxy acrylic emulsion for a two-component one-plastic-coated paint, which at least comprises the following raw materials in parts by weight: 50-60 parts of deionized water; 0.8 to 1.2 portions of compound emulsifier; 0.04-0.06 part of pH buffering agent; 0.09 to 0.15 portion of persulfate; 0.1 to 3 parts of carboxyl functional monomer; 25-32 parts of acrylate monomer; 6-7 parts of hydroxy acrylic ester monomer; 3-5 parts of cyclic methacrylate monomer; 1-3 parts of ureido or amido-containing acrylic acid monomer; 0.1 to 0.3 part of difunctional acrylic monomer; 0.1 to 0.3 part of molecular weight regulator; 0.1-0.5 part of amine neutralizer.
As a preferable technical scheme, the compound emulsifier is a combination of a nonionic reactive emulsifier and an anionic reactive emulsifier, and the mass ratio of the combination of the nonionic reactive emulsifier and the anionic reactive emulsifier is (5-10): (1-5), preferably (7-8): (3-4), most preferably 7.5:3.5; preferably, the nonionic reactive emulsifier and the anionic reactive emulsifier both contain allyl reactive functionalities and neither contain nonylphenol. Preferably, the nonionic reactive emulsifier has an EO added mole number of 10-40, and the anionic reactive emulsifier has an EO added mole number of 10-20. Preferably, the compound emulsifier is a combination of SR-10 (Ai Dike) and ER-20 (Ai Dike), and both reactive emulsifiers do not contain nonylphenol.
As a preferred embodiment, the pH buffer is selected from at least one of carbonate or phosphate, preferably sodium bicarbonate.
As a preferable technical scheme, the persulfate is at least one of ammonium persulfate, sodium persulfate and potassium persulfate, and is preferably ammonium persulfate.
As a preferred technical scheme, the carboxyl functional monomer is acrylic acid or methacrylic acid.
As a preferable technical scheme, the acrylic ester monomer is one or a combination of a plurality of methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, n-butyl acrylate and isooctyl acrylate.
As a preferable technical scheme, the hydroxy acrylic monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
As a preferable embodiment, the cyclic methacrylate monomer is at least one selected from isobornyl methacrylate and cyclohexyl methacrylate.
As a preferable technical scheme, the ureido-or amido-containing acrylic monomer is at least one of methacrylamide ethyl ethylene urea, N-methylol acrylamide and N- (isobutoxy) methacrylamide.
As a preferable technical scheme, the difunctional acrylic monomer is at least one of 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate and triethylene glycol diacrylate.
As a preferable technical scheme, the molecular weight regulator is at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan and alpha-methyl styrene dimer.
As a preferable technical scheme, the amine neutralizer is at least one of ammonia water, triethylamine and dimethylethanolamine.
The invention also provides a preparation method of the modified hydroxyl acrylic emulsion for the two-component one-plastic-coated paint, which at least comprises the following steps: according to parts by weight, deionized water, a compound emulsifier, persulfates, a pH buffer agent, a carboxyl functional monomer, an acrylic ester monomer, a hydroxyl acrylic ester monomer, a cyclic methacrylic ester monomer, an ureido or amido acrylic ester monomer, a bifunctional acrylic acid monomer and a molecular weight regulator are respectively prepared into a core-shell emulsion and a shell emulsion through a high-speed dispersion emulsification process, the core-shell emulsion and the shell emulsion are prepared into a core-shell emulsion through a core-shell emulsion polymerization process, and then an amine neutralizer is added for neutralization until the pH value is 7-9, and the core-shell emulsion is obtained after filtration.
Preferably, the preparation process of the core layer emulsion comprises the following steps: 8 to 12 parts of deionized water, 0.3 to 0.5 part of compound emulsifier and 0.03 to 0.05 part of persulfate are stirred until the mixture is fully dissolved, then 14 to 18 parts of acrylate monomer, 0.05 to 0.3 part of carboxyl functional monomer, 1.5 to 2 parts of hydroxy acrylate monomer, 0.5 to 1.5 parts of ureido or amido acrylate monomer, 0.1 to 0.3 part of difunctional acrylic acid monomer and 1 to 3 parts of cyclic methacrylate monomer are sequentially added under high-speed stirring, and the high-speed stirring is continued for 20 to 60 minutes to obtain the core layer emulsion.
Preferably, the preparation process of the shell emulsion comprises the following steps: 8 to 12 parts of deionized water, 0.3 to 0.5 part of compound emulsifier and 0.03 to 0.05 part of persulfate are stirred until the mixture is fully dissolved, then 11 to 15 parts of acrylate monomer, 0.4 to 0.8 part of carboxyl functional monomer, 4 to 6 parts of hydroxy acrylate monomer, 0.5 to 1.5 parts of ureido or amido acrylate monomer, 1 to 3 parts of cyclic methacrylate monomer and 0.1 to 0.3 part of molecular weight regulator are sequentially added under high-speed stirring, and the high-speed stirring is continued for 20 to 60 minutes to obtain the shell emulsion.
Preferably, the core-shell emulsion polymerization process specifically comprises the following steps: adding 20-40 parts of deionized water, 0.1-0.3 part of compound emulsifier and 0.04-0.06 part of pH buffer agent into a reaction kettle in sequence, stirring until the mixture is fully dissolved to obtain emulsion dispersion, adding 0.02-0.05 part of initiator when the temperature is raised to 40-60 ℃, continuously raising the temperature to 70-90 ℃, adding 3-8 wt% of core emulsion, keeping the temperature for 20-30 min, uniformly dripping the rest of core emulsion into the reaction kettle within 1-2 h, keeping the temperature for 30min after the dripping, uniformly dripping the shell emulsion into the reaction kettle within 1-2 h, keeping the temperature of the material at 80-85 ℃, keeping the temperature for 1 h after the dripping is finished, keeping the temperature at 85-90 ℃, and then cooling to below 50 ℃.
The modified hydroxyl acrylic emulsion is prepared by adopting a core-shell emulsion polymerization process, the emulsion particles are designed into a core-shell structure, the hydroxyl content of a core layer is designed to be lower, the Tg value is properly improved, the hydroxyl content of a shell layer is designed to be higher, and the Tg value is designed to be lower; therefore, the shell layer is more hydrophilic than the core layer, a regular core-shell structure is formed more favorably, the high Tg low hydroxyl content of the core layer part is helpful to improve the adhesive force and the drying speed, the silver powder arrangement is improved, the low Tg high hydroxyl content of the shell layer part can improve film forming and increase the crosslinking density, and the paint film has better water resistance and chemical resistance. Specifically, a proper amount of difunctional monomers are added in the polymerization stage of the core layer to crosslink the polymer part of the core layer so as to increase the molecular weight of the polymer, so that the drying speed can be further improved; the molecular weight regulator is added in proper amount in the polymerization stage of the shell layer to ensure that the molecular weight of the shell polymer is not too large and has narrower molecular weight distribution, thereby solving the problem of poor adhesive force caused by too large crosslinking density. Furthermore, by introducing the ureido-containing or amido-containing acrylate monomer, the ureido-containing or amido-containing acrylate monomer forms strong hydrogen bond with the hydroxyl monomer and the carboxyl monomer, the adhesion to a substrate and the arrangement of silver powder are improved, and the drying speed and the water resistance are improved by matching with the introduction of the cyclic methacrylate monomer.
The emulsion provided by the invention has a core-shell structure with hard core/soft shell, high core/low shell molecular weight and low core/high shell hydroxyl content, can give consideration to the dryness, the adhesive force and the chemical resistance, and meets the use requirement of a coating process.
The modified hydroxyl acrylic emulsion of the double-component plastic paint for one-step coating provided by the invention does not use an organic solvent in the synthesis process, compared with a secondary dispersion paint, the double-component plastic paint prepared by the modified hydroxyl acrylic emulsion completely eradicates the problem of organic solvent residue from the source, has long pot life and good drying property, has higher crosslinking density, also has good adhesive force on a common plastic substrate, can be packaged in a lower line after being dried for 30 minutes at 40-50 ℃, can achieve the level of 0 in adhesive force test, has the hardness of more than H and can be boiled for more than two hours at the temperature of 100 ℃, and in addition, has very excellent wear resistance, solvent resistance and aging resistance, and can achieve the effect of traditional multi-step coating after being coated.
Advantageous effects
(1) The invention provides a modified hydroxy acrylic emulsion for one-step coating of a double-component plastic paint, and the double-component plastic paint prepared by the modified hydroxy acrylic emulsion has excellent adhesive force, water resistance and chemical resistance, good appearance and convenient construction, and can meet the construction requirement of one-step coating.
(2) The modified hydroxyl acrylic emulsion is prepared by adopting a core-shell emulsion polymerization process, the emulsion particles are designed into a core-shell structure, the hydroxyl content of a core layer is designed to be lower, the Tg value is properly improved, the hydroxyl content of a shell layer is designed to be higher, and the Tg value is designed to be lower; therefore, the shell layer is more hydrophilic than the core layer, a regular core-shell structure is formed more favorably, the high Tg low hydroxyl content of the core layer part is helpful to improve the adhesive force and the drying speed, the silver powder arrangement is improved, the low Tg high hydroxyl content of the shell layer part can improve film forming and increase the crosslinking density, and the paint film has better water resistance and chemical resistance.
(3) The drying speed can be further improved by adding a proper amount of difunctional monomers into the core layer polymerization stage to crosslink the core layer polymer part and increase the molecular weight of the polymer; the molecular weight regulator is added in proper amount in the polymerization stage of the shell layer to ensure that the molecular weight of the shell polymer is not too large and has narrower molecular weight distribution, thereby solving the problem of poor adhesive force caused by too large crosslinking density.
(4) By introducing the ureido or amido-containing acrylate monomer, the hydroxyl monomer and the carboxyl monomer form strong hydrogen bond action, the adhesion to a substrate and the arrangement of silver powder are improved, and the drying speed and the water resistance are improved by matching with the introduction of the cyclic methacrylate monomer.
(5) The modified hydroxyl acrylic emulsion of the double-component plastic paint for one-step coating provided by the invention does not use an organic solvent in the synthesis process, compared with a secondary dispersion paint, the double-component plastic paint prepared by the modified hydroxyl acrylic emulsion completely eradicates the problem of organic solvent residue from the source, has long pot life and good drying property, has higher crosslinking density, also has good adhesive force on a common plastic substrate, can be packaged in a lower line after being dried for 30 minutes at 40-50 ℃, can achieve the level of 0 in adhesive force test, has the hardness of more than H and can be boiled for more than two hours at the temperature of 100 ℃, and in addition, has very excellent wear resistance, solvent resistance and aging resistance, and can achieve the effect of traditional multi-step coating after being coated.
Drawings
FIG. 1 is a graph showing the alignment of silver powder of example 3 and comparative example 4 according to the present invention, wherein the left side corresponds to example 3 and the right side corresponds to comparative example 4
Detailed Description
In the embodiment, the comparative example and the performance test of the invention, the rotating speed of high-speed stirring is 2000r/min, and the rotating speed of medium-speed stirring is 800r/min.
Example 1
Example 1 of the present invention provides a modified hydroxy acrylic emulsion for a two-component one-coat plastic paint, the formulation composition of which is shown in Table 2 in parts by weight.
The preparation method of the modified hydroxyl acrylic emulsion for the two-component one-plastic-coated paint specifically comprises the following steps:
(1) 10 parts of deionized water, 0.3 part of SR-10, 0.1 part of ER-20 and 0.04 part of APS are stirred until the components are fully dissolved, then 14.2 parts of MMA, 3 parts of BA, 0.1 part of MAA, 1.7 parts of HEMA, 1 part of MAEEU, 0.2 part of HDDA and 0 part of cyclic methacrylate monomer are sequentially added under high-speed stirring, and high-speed stirring is continued for 30 minutes to obtain the core-layer emulsion. Similarly, 10 parts of deionized water, 0.3 part of SR-10, 0.1 part of ER-20 and 0.04 part of APS are stirred until the components are fully dissolved, then 6.7 parts of MMA, 6.6 parts of BA, 0.6 part of MAA, 5.1 parts of HEMA, 1 part of MAEEU, 0 part of cyclic methacrylate monomer and 0.2 part of AMSD are sequentially added under high-speed stirring, and high-speed stirring is continued for 30 minutes to obtain a shell emulsion.
(2) Adding 30 parts of deionized water, 0.15 part of SR-10, 0.1 part of ER-20 and 0.05 part of sodium bicarbonate into a reaction kettle in sequence, stirring until the mixture is fully dissolved to obtain emulsion dispersion, adding 0.04 part of APS when the temperature is raised to 50 ℃, continuously raising the temperature to 80 ℃, adding 5% of core layer emulsion, and preserving the heat for 30min to obtain blue light semitransparent seed emulsion. And (3) uniformly dripping the residual core layer emulsion into the reaction kettle within 2 hours, keeping the material temperature at 80 ℃, keeping the temperature for 30 minutes after dripping, uniformly dripping the shell layer emulsion into the reaction kettle within 2 hours, and keeping the material temperature at 80 ℃ after dripping.
(3) After the dripping is finished, preserving the temperature for 1 hour at 85 ℃, then cooling to below 50 ℃, adding amine neutralizer to adjust the emulsion to pH=7, and filtering to obtain the modified hydroxyl acrylic emulsion for the two-component one-plastic-coated paint.
The amine neutralizer is 20wt% ammonia water.
Examples 2 to 4
Examples 2-4 were prepared according to the procedure of example 1 and the formulation composition is shown in Table 2.
Comparative examples 1 to 4
Comparative examples 1-4 were prepared in the same manner as in example 1 and the formulation compositions are shown in Table 2. Wherein, the names and abbreviations of the raw materials in the examples and comparative examples are shown in Table 1.
Table 1 names and abbreviations of raw materials
Table 2 specific formulations of examples and comparative examples
Performance testing
(1) The modified hydroxyl acrylic emulsion prepared in the example and the comparative example is prepared into the water-based double-component plastic paint according to the formula shown in the table 3, the raw materials are sequentially added in sequence under medium-speed stirring according to the following formula, then the mixture is stirred at a high speed for 20min, and the water-based double-component plastic paint is obtained after filtration.
Table 3 aqueous two-component Plastic silver paint
The component A and the component B are uniformly mixed according to the ratio of n (-NCO)/n (-OH) =1.5:1, water-based double-component plastic paint is sprayed on a clean ABS plastic plate, the mixture is baked for 30min at 50 ℃, then the mixture is dried at room temperature (25 ℃) for 3 days to obtain a paint film with the thickness of 17+/-1 mu m, and the following adhesive force, boiling resistance, solvent resistance, RCA, artificial aging resistance test and flash index test are carried out, wherein the test results are shown in table 5.
(1) Hardness: the hardness of the paint film is measured according to the national standard GB/T6739-2006 "paint and varnish pencil method".
(2) Adhesion force: the test was carried out according to the national standard GB/T9286-1998 "cross-cut test of paint and varnish films".
(3) Boiling resistance: and (3) placing the sample into a water bath kettle, boiling the sample for 2 hours at the temperature of 100 ℃ and observing whether the sample plate turns white, changes color, bubbles and wrinkles.
(4) Solvent resistance: the test was performed according to national standard GB/T23989-2009 "solvent rub resistance assay", wherein the test solvent was ethanol, with > 500 times being noted as excellent, > 300 times (< 500 times) being noted as good, and < 300 times being noted as poor.
(5) RCA: and (3) testing by using a paper tape wear-resistant tester, loading 175g, and taking the paint film penetrating bottom as a termination standard, wherein more than 100 times are marked as qualified, and less than or equal to 100 times are marked as unqualified.
(6) Artificial aging resistance test: testing according to national standard GB/T1865-2009 'artificial weathering of color paints and varnishes and exposure of artificial radiation to filtered xenon arc radiation', if the light loss is less than 20% over 1000 hours, marking the color paint and varnish as qualified without chalking or obvious discoloration, otherwise marking the color paint and varnish as unqualified.
(7) Flash Index (FI): the test is carried out by adopting an X-Rite MA68II multi-angle color difference meter.
(8) Pot life: the component A and the component B are mixed and then placed in an environment of 25 ℃ to take the viscosity increase to the end point that normal spraying cannot be carried out or the paint film performance is obviously changed.
(9) Silver powder arrangement: the appearance of the paint film was observed, and the results are shown in FIG. 1 and Table 5.
TABLE 5 test results for examples 1-4 and comparative examples 1-4
Comparative examples 1,2 and 3 show that the addition of the high Tg cyclic methacrylate monomer can obviously improve the hardness of a paint film and the early hardness increasing speed, and can meet the requirement of low-temperature short-time baking and then can be taken off line for packaging. The adhesion of the IOBMA in both cyclic monomers will be better.
As is clear from comparative examples 3, 4 and 2, the addition of urea-containing MAEEU and amide-containing NMA significantly improves the adhesion to plastic substrates, and in addition, the addition of these monomers greatly aids the alignment of silver powder because they form strong hydrogen bonds with hydroxyl and carboxyl groups to impart some thixotropic properties to the emulsion.
Comparative example 3 and comparative example 1 show that the dry speed and adhesion can be effectively improved by controlling the molecular weight of the core/shell two layers.
As can be seen from comparative example 3 and comparative examples 3 and 4, the core-shell structure has higher designability, can change the two-phase hydroxyl distribution and different Tg, and the design of the core-shell is soft, and the core with low hydroxyl content and high hydroxyl content can lead to the emulsion having more excellent comprehensive properties.
In conclusion, the bi-component plastic paint prepared from the modified hydroxyl acrylic emulsion with the optimal scheme has good adhesive force before and after water boiling, silver powder is well arranged, and the fully cured paint film has excellent hardness, wear resistance, chemical resistance and weather resistance, long service life and quick drying speed, can be used for a quick production process, and basically can meet the construction requirement of one-step coating.
Claims (10)
1. The modified hydroxy acrylic emulsion for the two-component one-plastic-coated paint is characterized by at least comprising the following raw materials in parts by weight: 50-60 parts of deionized water; 0.8 to 1.2 portions of compound emulsifier; 0.04-0.06 part of pH buffering agent; 0.09 to 0.15 portion of persulfate; 0.1 to 3 parts of carboxyl functional monomer; 25-32 parts of acrylate monomer; 6-7 parts of hydroxy acrylic ester monomer; 3-5 parts of cyclic methacrylate monomer; 1-3 parts of ureido or amido-containing acrylic acid monomer; 0.1 to 0.3 part of difunctional acrylic monomer; 0.1 to 0.3 part of molecular weight regulator; 0.1-0.5 part of amine neutralizer.
2. The modified hydroxyl acrylic emulsion for the two-component one-plastic-coated paint according to claim 1, wherein the compound emulsifier is a combination of a nonionic reactive emulsifier and an anionic reactive emulsifier, and the mass ratio of the combination of the nonionic reactive emulsifier and the anionic reactive emulsifier is (5-10): (1-5), the nonionic reactive emulsifier and the anionic reactive emulsifier both contain allyl reactive functionalities and both do not contain nonylphenol.
3. The modified hydroxyl acrylic emulsion for the two-component plastic-coated paint according to claim 1, wherein the acrylic acid ester monomer is one or a combination of a plurality of methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, n-butyl acrylate and isooctyl acrylate.
4. The modified hydroxyacrylic acid emulsion for the two-component one-plastic-coated paint according to claim 1, wherein the hydroxyacrylic acid monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
5. The modified hydroxyacrylic acid emulsion for two-component one-coat plastic paint according to claim 1, wherein the cyclic methacrylate monomer is at least one selected from isobornyl methacrylate and cyclohexyl methacrylate.
6. The modified hydroxyacrylic emulsion for two-component one-part plastic-coated paint according to claim 1, wherein the ureido-or amido-containing acrylic monomer is at least one of methacrylamide ethyl ethylene urea, N-methylolacrylamide, N- (isobutoxy) methacrylamide.
7. The modified hydroxyacrylic acid emulsion for two-component one-coat plastic paint according to claim 1, wherein the difunctional acrylic monomer is at least one of 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate and triethylene glycol diacrylate.
8. A process for the preparation of a modified hydroxyacrylic emulsion for two-component one-coat plastic paints according to any one of claims 1-7, characterized in that it comprises at least the following steps: according to parts by weight, deionized water, a compound emulsifier, persulfates, a pH buffer agent, a carboxyl functional monomer, an acrylic ester monomer, a hydroxyl acrylic ester monomer, a cyclic methacrylic ester monomer, an ureido or amido acrylic ester monomer, a bifunctional acrylic acid monomer and a molecular weight regulator are respectively prepared into a core-shell emulsion and a shell emulsion through a high-speed dispersion emulsification process, the core-shell emulsion and the shell emulsion are prepared into a core-shell emulsion through a core-shell emulsion polymerization process, and then an amine neutralizer is added for neutralization until the pH value is 7-9, and the core-shell emulsion is obtained after filtration.
9. The method for preparing the modified hydroxyl acrylic emulsion for the two-component plastic-coated paint according to claim 8, wherein the preparation process of the core layer emulsion is as follows: 8 to 12 parts of deionized water, 0.3 to 0.5 part of compound emulsifier and 0.03 to 0.05 part of persulfate are stirred until the mixture is fully dissolved, then 14 to 18 parts of acrylate monomer, 0.05 to 0.3 part of carboxyl functional monomer, 1.5 to 2 parts of hydroxy acrylate monomer, 0.5 to 1.5 parts of ureido or amido acrylate monomer, 0.1 to 0.3 part of difunctional acrylic acid monomer and 1 to 3 parts of cyclic methacrylate monomer are sequentially added under high-speed stirring, and the high-speed stirring is continued for 20 to 60 minutes to obtain the core layer emulsion.
10. The method for preparing the modified hydroxyl acrylic emulsion for the two-component one-plastic-coated paint according to claim 8, wherein the preparation process of the shell emulsion is as follows: 8 to 12 parts of deionized water, 0.3 to 0.5 part of compound emulsifier and 0.03 to 0.05 part of persulfate are stirred until the mixture is fully dissolved, then 11 to 15 parts of acrylate monomer, 0.4 to 0.8 part of carboxyl functional monomer, 4 to 6 parts of hydroxy acrylate monomer, 0.5 to 1.5 parts of ureido or amido acrylate monomer, 1 to 3 parts of cyclic methacrylate monomer and 0.1 to 0.3 part of molecular weight regulator are sequentially added under high-speed stirring, and the high-speed stirring is continued for 20 to 60 minutes to obtain the shell emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311813503.6A CN117777365A (en) | 2023-12-26 | 2023-12-26 | Modified hydroxy acrylic emulsion for two-component one-plastic-coated paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311813503.6A CN117777365A (en) | 2023-12-26 | 2023-12-26 | Modified hydroxy acrylic emulsion for two-component one-plastic-coated paint and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117777365A true CN117777365A (en) | 2024-03-29 |
Family
ID=90397646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311813503.6A Pending CN117777365A (en) | 2023-12-26 | 2023-12-26 | Modified hydroxy acrylic emulsion for two-component one-plastic-coated paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117777365A (en) |
-
2023
- 2023-12-26 CN CN202311813503.6A patent/CN117777365A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101077954B (en) | Automobile metal sparkling paint and preparation method thereof | |
| US9012027B2 (en) | Aqueous emulsion | |
| CN113105571B (en) | Low-temperature self-crosslinking waterborne epoxy modified acrylic resin and preparation method and application thereof | |
| CN110511388B (en) | Modified hydroxyl acrylic emulsion for water-based metal decorating paint and preparation method thereof | |
| CN113088153B (en) | Chlorinated polypropylene/acrylate hybrid aqueous dispersion as well as preparation method and application thereof | |
| JP6329258B2 (en) | Use of 2-octyl acrylate polymers as binders in coating compositions | |
| CN109503738B (en) | Phosphoric acid modified polyisoprene rubber, polyisoprene rubber modified acrylate resin dispersion, preparation method and application | |
| CN111333783A (en) | Preparation method of hydroxyl acrylate emulsion for water-based wood paint | |
| CN107406557A (en) | Aqueous polymer emulsion | |
| US9169380B2 (en) | Use of aqueous polymer dispersions for improving resistance to chemical influences | |
| US5063091A (en) | Method for use of aqueous elastomeric coatings | |
| CA2022316A1 (en) | Aqueous compositions based on acid-functional acrylic silanol polymers | |
| MX2014008953A (en) | Polyurethane coating composition. | |
| CN109456442B (en) | Low-solvent room-temperature quick-drying type hydroxyl acrylic acid dispersion and preparation method thereof | |
| CN117777365A (en) | Modified hydroxy acrylic emulsion for two-component one-plastic-coated paint and preparation method thereof | |
| JPS60221469A (en) | Aqueous composition for coating | |
| CN115124657A (en) | Acrylate emulsion with core-shell structure and preparation method thereof | |
| CN114230717A (en) | Preparation process of water-based acrylic resin | |
| CN114316160A (en) | Acrylic emulsion polymer and preparation method of water-based paint based on polymer | |
| CN112961604A (en) | High-hardness overglaze and preparation method thereof | |
| CN115851065B (en) | Modified acrylic emulsion for single-component primer matched with UV finishing paint and preparation method thereof | |
| CN112538128B (en) | Acrylate emulsion and preparation method and application thereof | |
| JPS5927969A (en) | Water-base coating composition | |
| CA2658753C (en) | Emulsion polymer blend coating compositions and methods for increasing chalky substrate adhesion | |
| KR101052333B1 (en) | Non-Aqueous Dispersion Acrylic Resin for Paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |