CN115746651A - Water-based acrylic resin for water-based single-component plastic silver paint and preparation method thereof - Google Patents
Water-based acrylic resin for water-based single-component plastic silver paint and preparation method thereof Download PDFInfo
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- CN115746651A CN115746651A CN202211393970.3A CN202211393970A CN115746651A CN 115746651 A CN115746651 A CN 115746651A CN 202211393970 A CN202211393970 A CN 202211393970A CN 115746651 A CN115746651 A CN 115746651A
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- Prior art keywords
- water
- parts
- vinyl monomer
- acrylic resin
- sodium
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000003973 paint Substances 0.000 title claims abstract description 74
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000004332 silver Substances 0.000 title claims abstract description 67
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 67
- 229920003023 plastic Polymers 0.000 title claims abstract description 59
- 239000004033 plastic Substances 0.000 title claims abstract description 59
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 52
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 123
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 85
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 85
- 239000008367 deionised water Substances 0.000 claims abstract description 53
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 53
- 239000003999 initiator Substances 0.000 claims abstract description 44
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 20
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000003254 radicals Chemical class 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 239000012966 redox initiator Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 9
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- XOCSLJFIGMLQLF-UHFFFAOYSA-N butyl 2-sulfanylpropanoate Chemical compound CCCCOC(=O)C(C)S XOCSLJFIGMLQLF-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 6
- -1 sodium alkyl sulfate Chemical class 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- BCHLLOWWPPBMNK-UHFFFAOYSA-N 2-hydroperoxy-2-methylpropane;sodium Chemical compound [Na].CC(C)(C)OO BCHLLOWWPPBMNK-UHFFFAOYSA-N 0.000 claims description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- ORDRGXFSRBRQQG-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)C(C)S ORDRGXFSRBRQQG-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 18
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 12
- 230000001804 emulsifying effect Effects 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 230000007717 exclusion Effects 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 229920006942 ABS/PC Polymers 0.000 description 1
- WUVDKNZNAHKSJS-UHFFFAOYSA-L S([O-])[O-].C=O.[Na+].C(C)(C)(C)OO.[Na+] Chemical compound S([O-])[O-].C=O.[Na+].C(C)(C)(C)OO.[Na+] WUVDKNZNAHKSJS-UHFFFAOYSA-L 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The embodiment of the application discloses a water-based acrylic resin for a water-based single-component plastic silver paint and a preparation method thereof. The water-based acrylic resin provided by the embodiment of the application adopts a two-step dropping method to design a core-shell structure in the preparation process, controls the silver draining effect, the adhesive force to a base material and the alcohol-rub resistance of a paint film of the prepared water-based acrylic resin by adjusting the proportion of a hydrophilic vinyl monomer, a molecular weight regulator and a self-crosslinkable vinyl monomer in the shell structure design, and is mainly prepared from the following components in parts by weight: 33.0-38.0 parts of hydrophobic vinyl monomer, 1.0-3.0 parts of hydrophilic vinyl monomer, 1.0-4.0 parts of self-crosslinking vinyl monomer, 0.1-0.3 part of molecular weight regulator, 0.1 part of free radical initiator, 0.2-0.4 part of emulsifier, 0.4-0.6 part of neutralizer and 59-61 parts of deionized water.
Description
Technical Field
The application relates to the field of water-based single-component plastic silver paint, in particular to water-based acrylic resin for water-based single-component plastic silver paint and a preparation method thereof.
Background
Plastic substrates, such as commonly used butadiene-Acrylonitrile-Styrene copolymers (ABS), polycarbonate resins (PC), polyvinyl chloride PVC, polyvinyl chloride), high Impact Polystyrene (HIPS), ABS/PC composite resins, are widely used in automobiles, home appliances, toys, and 3C products due to their advantages of light weight, good processability, and low price. In order to beautify and improve the durability of the substrate, silver paint is generally sprayed on the surface of the substrate of the plastic parts. However, at present, plastic silver paint mainly uses oil paint with high VOC (Volatile Organic Compounds) content, which neither meets the requirement of people on environmental protection, but runs counter to the carbon neutralization goal in our country.
The water-based plastic silver paint uses water as a dispersant, so that the water-based plastic silver paint has the advantages of low VOC (volatile organic compounds) emission, no toxicity and friendly construction environment in the using process, and has attracted extensive attention. The water-based resin for the water-based single-component plastic silver paint mainly comprises water-based polyurethane and water-based acrylic acid. The aqueous polyurethane resin has poor adhesion to ABS base materials, and the application of the aqueous polyurethane resin is limited. Therefore, the market mainly uses the water-based acrylic resin, but the research and the production of the water-based acrylic resin produced in China are in the beginning stage, and the water-based acrylic resin cannot completely meet the requirements of customers on adhesive force, alcohol wiping resistance and silver row effect. Therefore, the domestic middle-high application field is mainly monopolized by imported products abroad. With the proposal of national carbon neutralization targets and the gradual improvement of environmental protection consciousness of people, the usage amount of the water-based single-component plastic silver paint is bound to be larger and larger, and the water-based single-component plastic silver paint can gradually and comprehensively replace the oil-based plastic silver paint. However, the current economic globalization is subject to strong headwind, and trade barriers and advanced technical blockages between countries have gradually come up with the signs of greatly increasing the risk of continued acquisition of these imported materials. Based on the backgrounds, the development of the waterborne acrylic resin for the water-based single-component plastic silver paint, which has good adhesive force, good alcohol wiping resistance and excellent silver row effect, has stronger urgency and higher economic benefit.
Disclosure of Invention
The invention aims to provide the water-based acrylic resin for the water-based single-component plastic silver paint, which is prepared by designing a core-shell structure by adopting a two-step dropping method in the preparation process and adjusting the proportion of a hydrophilic vinyl monomer, a molecular weight regulator and a self-crosslinkable vinyl monomer in the shell structure design, has a good silver-lined effect, has excellent adhesive force to various plastic substrates and strong alcohol wiping resistance and is used for solving the technical problems in the background.
In a first aspect, an embodiment of the application provides an aqueous acrylic resin for an aqueous single-component plastic silver paint, which comprises the following components in parts by weight: 33.0-38.0 parts of hydrophobic vinyl monomer, 1.0-3.0 parts of hydrophilic vinyl monomer, 1.0-4.0 parts of self-crosslinking vinyl monomer, 0.1-0.3 part of molecular weight regulator, 0.1 part of free radical initiator, 0.2-0.4 part of emulsifier, 0.4-0.6 part of neutralizer and 59-61 parts of deionized water.
In a preferred embodiment, the vinyl monomers include hydrophobic vinyl monomers, hydrophilic vinyl monomers, and self-crosslinkable vinyl monomers; the hydrophobic vinyl monomer comprises at least one of methyl methacrylate, styrene, alpha-methyl styrene, n-butyl acrylate, isooctyl acrylate, lauryl acrylate, cyclohexyl acrylate, allyl methacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol diacrylate and pentaerythritol triacrylate; the hydrophilic vinyl monomer comprises at least one of acrylic acid, methacrylic acid and itaconic acid; the self-crosslinkable vinyl monomer comprises at least one of glycidyl methacrylate, N-methylol acrylamide, diacetone acrylamide, ethylene glycol acetoacetate methacrylate, trimethoxy vinyl silane, triethoxy vinyl silane, gamma-methacryloxypropyl trimethoxy silane and gamma-methacryloxypropyl triethoxy silane.
In a preferred embodiment, the molecular weight regulator comprises at least one of dodecyl mercaptan, mercaptopropionic acid, n-butyl mercaptopropionate, isooctyl mercaptopropionate, mercaptoethanol, and a-methylstyrene linear dimer.
In a preferred embodiment, the free radical initiator comprises a thermal initiator and a redox initiator; the thermal initiator comprises at least one of ammonium persulfate and sodium persulfate; the redox initiator comprises at least one of ammonium persulfate-sodium bisulfite, ammonium persulfate-sodium metabisulfite, sodium persulfate-sodium bisulfite, sodium persulfate-sodium metabisulfite, tert-butyl hydroperoxide-formaldehyde sodium sulfite and tert-butyl hydroperoxide-sodium ascorbate.
In a preferred embodiment, the emulsifier comprises at least one of a sodium salt of an alkyl sulfate, a sodium salt of an alkyl sulfonate, and a sodium salt of an alcohol ether sulfate. Further, the emulsifier comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and C12-14 fatty alcohol ether sodium sulfate.
In a preferred embodiment, the neutralizing agent comprises at least one of ammonia, N-dimethylethanolamine, triethanolamine, and AMP-95.
In a second aspect, the embodiment of the application also provides a preparation method of the water-based acrylic resin for the water-based single-component plastic silver paint, which comprises the following steps:
s1, dissolving an emulsifier by using deionized water, and adding a vinyl monomer to obtain a monomer emulsion E1;
s2, synchronously dripping the monomer emulsion E1 and the thermal initiator aqueous solution into deionized water at the temperature of 80-90 ℃ for 1-3h, and preserving heat for 0.5-1h at the temperature of 80-90 ℃ after finishing dripping.
S3, dissolving an emulsifier by using deionized water, and then adding a vinyl monomer and a molecular weight regulator to obtain a monomer emulsion E2;
s4, synchronously dropwise adding the monomer emulsion E2 and the thermal initiator aqueous solution into the material obtained in the step S2 for 1-3h, and preserving heat for 0.5-1h at the temperature of 80-90 ℃ after dropwise adding;
and S5, cooling the material obtained in the step S4 to 60-65 ℃, adding a redox initiator, keeping the temperature at 60-65 ℃ for 0.5-1h, and finally cooling to below 50 ℃, adding a neutralizer to adjust the pH =7.5-8.5.
In a preferred embodiment, the hydrophilic vinyl monomer in S1 accounts for 2-5% of the total mass of the vinyl monomers in the step, the hydrophobic vinyl monomer accounts for 90-97% of the total mass of the vinyl monomers in the step, and the self-crosslinkable vinyl monomer accounts for 1-5% of the total mass of the vinyl monomers in the step; in S3, the hydrophilic vinyl monomer accounts for 5-12% of the total mass of the vinyl monomers in the step, the hydrophobic vinyl monomer accounts for 73-87% of the total mass of the vinyl monomers in the step, and the self-crosslinkable vinyl monomer accounts for 8-15% of the total mass of the vinyl monomers in the step.
The technical scheme of the invention has the beneficial effects that:
according to the invention, a two-step dropping method is adopted to design a core-shell structure in the preparation process, and the proportion of the hydrophilic vinyl monomer, the molecular weight regulator and the self-crosslinkable vinyl monomer in the shell structure design is adjusted to control the silver exclusion effect, the adhesion to a base material and the alcohol wiping resistance of a paint film of the prepared water-based acrylic resin for the single-component plastic silver paint. Specifically, the method comprises the following steps: 1. the core-shell structure is designed through a two-step dropping method, so that hydrophilic groups are enriched in a shell layer, the adhesive force to a base material is improved, and the coating and dispersing capacity of resin to silver powder is improved, so that the silver bar effect is improved; 2. the relative molecular weight of a shell polymer is reduced by using a molecular weight regulator in the shell preparation process, so that the wetting and penetrating abilities of the resin to microstructures such as holes on the uneven surface of a base material are improved, the anchoring effect between a paint film and the base material is increased, and the effect of improving the adhesion force is achieved; 3. by combining the use of the self-crosslinkable vinyl monomer, the anchoring effect of the holes on the uneven surface between paint film molecules and a base material is cured in the drying process of the paint film, so that the adhesive force is enhanced, the crosslinking density of the paint film is improved, and the alcohol wiping resistance of the paint film is enhanced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The embodiments of the present invention have been presented for purposes of illustration and description, and are not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to practitioners skilled in this art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following specifically describes the water-based acrylic resin for the water-based single-component plastic silver paint and the preparation method thereof in the embodiment of the present application.
The water-based acrylic resin for the water-based single-component plastic silver paint is formed by a two-step dropping method, and the latex particles with the shell-core structure can be formed by the two-step dropping method, so that the components in the shell-core structure can be adjusted respectively, and the performance of the product can be conveniently adjusted.
The technical scheme of the invention provides a water-based acrylic resin for water-based single-component plastic silver paint, which comprises the following components in parts by weight: 33.0-38.0 parts of hydrophobic vinyl monomer, 1.0-3.0 parts of hydrophilic vinyl monomer, 1.0-4.0 parts of self-crosslinking vinyl monomer, 0.1-0.3 part of molecular weight regulator, 0.1 part of free radical initiator, 0.2-0.4 part of emulsifier, 0.4-0.6 part of neutralizer and 59-61 parts of deionized water.
The specific types of the components are as follows:
the vinyl monomer comprises hydrophobic vinyl monomer, hydrophilic vinyl monomer and self-crosslinkable vinyl monomer; the hydrophobic vinyl monomer comprises at least one of methyl methacrylate, styrene, alpha-methyl styrene, n-butyl acrylate, isooctyl acrylate, lauryl acrylate, cyclohexyl acrylate, allyl methacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol diacrylate and pentaerythritol triacrylate; the hydrophilic vinyl monomer comprises at least one of acrylic acid, methacrylic acid and itaconic acid; the self-crosslinkable vinyl monomer comprises at least one of glycidyl methacrylate, N-methylol acrylamide, diacetone acrylamide, ethylene glycol acetoacetate methacrylate, trimethoxy vinyl silane, triethoxy vinyl silane, gamma-methacryloxypropyl trimethoxy silane and gamma-methacryloxypropyl triethoxy silane.
The molecular weight regulator comprises at least one of dodecyl mercaptan, mercaptopropionic acid, n-butyl mercaptopropionate, isooctyl mercaptopropionate, mercaptoethanol, and a-methyl styrene linear dimer.
Free radical initiators include thermal initiators and redox initiators; the thermal initiator comprises at least one of ammonium persulfate and sodium persulfate; the redox initiator comprises at least one of ammonium persulfate-sodium bisulfite, ammonium persulfate-sodium metabisulfite, sodium persulfate-sodium bisulfite, sodium persulfate-sodium metabisulfite, tert-butyl hydroperoxide-sodium formaldehyde sulfoxylate and tert-butyl hydroperoxide-sodium ascorbate.
The emulsifier comprises at least one of alkyl sodium sulfate salt, alkyl sulfonic acid sodium salt and alcohol ether sodium sulfate salt. Further, the emulsifier comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and C12-14 fatty alcohol ether sodium sulfate.
The neutralizer comprises at least one of ammonia, N-dimethylethanolamine, triethanolamine and AMP-95.
The preparation of the water-based acrylic resin for the water-based one-component plastic silver paint is carried out by four examples within the range specified by the components and the component ratio. Meanwhile, two comparative examples are provided outside the specified ranges of the component ratios of the present application. Finally, the water-based acrylic resin for the water-based single-component plastic silver paint prepared in the four embodiments and the two comparative examples is prepared into the water-based plastic silver paint under the same formula conditions, and corresponding index detection is carried out.
Table 1 examples and comparative examples the amounts of main raw materials used
Example 1
The water-based acrylic resin for the water-based single-component plastic silver paint comprises the following components in parts by weight: 40 parts of vinyl monomer (1.5 parts of hydrophilic vinyl monomer, 36.5 parts of hydrophobic vinyl monomer and 2.0 parts of self-crosslinking vinyl monomer), 0.1 part of molecular weight regulator, 0.1 part of free radical initiator, 0.2 part of emulsifier, 0.5 part of neutralizer and 59 parts of deionized water.
The water-based acrylic resin for the water-based single-component plastic silver paint is prepared according to the components and the component proportion, and comprises the following steps:
(1) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 0.4 part of methacrylic acid, 19.4 parts of styrene and 0.3 part of allyl methacrylate, and stirring to obtain a monomer emulsion E1; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution A.
(2) Adding 36 parts of deionized water into a reaction kettle, heating to 80-90 ℃, starting to synchronously dropwise add the monomer emulsion E1 and the initiator aqueous solution A for 2 hours, and controlling the reaction temperature to be 80-90 ℃; after the dripping is finished, the temperature is kept for 0.5h at the temperature of 80-90 ℃.
(3) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 1.1 part of methacrylic acid, 1.8 parts of butyl acrylate, 15.0 parts of styrene, 2.0 parts of diacetone acrylamide and 0.1 part of n-butyl mercaptopropionate, and stirring to obtain a monomer emulsion E2; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution B.
(4) Synchronously dropwise adding the monomer emulsion E2 and the initiator aqueous solution B into the material obtained in the step (2) for 2h, controlling the reaction temperature to be 80-90 ℃, and preserving heat for 0.5h at the temperature of 80-90 ℃ after dropwise adding. Then the temperature is reduced to 60-65 ℃, redox initiator (0.09 part of tert-butyl hydroperoxide is dissolved in 1 part of deionized water, 0.06 part of sodium formaldehyde sulfoxylate is dissolved in 2 parts of deionized water) is added, and the temperature is kept for 0.5h to eliminate residual monomers. And (3) cooling to 50 ℃, adding 0.6 part of 20% ammonia water to adjust the pH =7.5, and finally adding 0.93 part of adipic dihydrazide to obtain the water-based acrylate resin for the water-based single-component plastic silver paint.
Example 2
The water-based acrylic resin for the water-based single-component plastic silver paint comprises the following components in parts by weight: 40 parts of vinyl monomer (2.5 parts of hydrophilic vinyl monomer, 35.5 parts of hydrophobic vinyl monomer and 2.0 parts of self-crosslinking vinyl monomer), 0.1 part of molecular weight regulator, 0.1 part of free radical initiator, 0.2 part of emulsifier, 0.5 part of neutralizer and 59 parts of deionized water.
The water-based acrylic resin for the water-based single-component plastic silver paint is prepared according to the components and the component proportion, and comprises the following steps:
(1) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 0.4 part of methacrylic acid, 19.4 parts of styrene and 0.3 part of allyl methacrylate, and stirring to obtain a monomer emulsion E1; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution A.
(2) Adding 36 parts of deionized water into a reaction kettle, heating to 80-90 ℃, starting to synchronously dropwise add the monomer emulsion E1 and the initiator aqueous solution A for 2 hours, and controlling the reaction temperature to be 80-90 ℃; after the dripping is finished, the temperature is kept for 0.5h at the temperature of 80-90 ℃.
(3) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 2.1 parts of methacrylic acid, 1.4 parts of butyl acrylate, 14.4 parts of styrene, 2 parts of diacetone acrylamide and 0.1 part of n-butyl mercaptopropionate, and stirring to obtain a monomer emulsion E2; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution B.
(4) Synchronously dropwise adding the monomer emulsion E2 and the initiator aqueous solution B into the material obtained in the step (2), wherein the dropwise adding time is 2h, the reaction temperature is controlled to be 80-90 ℃, and the temperature is kept for 0.5h at the temperature of 80-90 ℃ after the dropwise adding is finished. Then the temperature is reduced to 60 to 65 ℃, redox initiator (0.09 part of tert-butyl hydroperoxide is dissolved in 1 part of deionized water, 0.06 part of sodium formaldehyde sulfoxylate is dissolved in 2 parts of deionized water) is added, and the temperature is kept for 0.5h to eliminate residual monomers. And (3) cooling to 50 ℃, adding 0.6 part of 20% ammonia water to adjust the pH =7.5, and finally adding 0.93 part of adipic dihydrazide to obtain the water-based acrylic resin for the water-based single-component plastic silver paint.
Example 3
The water-based acrylic resin for the water-based single-component plastic silver paint comprises the following components in parts by weight: 40 parts of vinyl monomer (2.5 parts of hydrophilic vinyl monomer, 35.5 parts of hydrophobic vinyl monomer and 2.0 parts of self-crosslinking vinyl monomer), 0.25 part of molecular weight regulator, 0.1 part of free radical initiator, 0.2 part of emulsifier, 0.6 part of neutralizer and 59 parts of deionized water.
The water-based acrylic resin for the water-based single-component plastic silver paint is prepared according to the components and the component proportion, and comprises the following steps:
(1) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 0.4 part of methacrylic acid, 19.4 parts of styrene and 0.3 part of allyl methacrylate, and stirring to obtain a monomer emulsion E1; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution A.
(2) Adding 36 parts of deionized water into a reaction kettle, heating to 80-90 ℃, starting to synchronously dropwise add the monomer emulsion E1 and the initiator aqueous solution A for 2 hours, and controlling the reaction temperature to be 80-90 ℃; after the dripping is finished, the temperature is kept for 0.5h at the temperature of 80-90 ℃.
(3) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 2.1 parts of methacrylic acid, 1.4 parts of butyl acrylate, 14.4 parts of styrene, 2 parts of diacetone acrylamide and 0.25 part of n-butyl mercaptopropionate, and stirring to obtain a monomer emulsion E2; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution B.
(4) Synchronously dropwise adding the monomer emulsion E2 and the initiator aqueous solution B into the material obtained in the step (2), wherein the dropwise adding time is 2h, the reaction temperature is controlled to be 80-90 ℃, and the temperature is kept for 0.5h at the temperature of 80-90 ℃ after the dropwise adding is finished. Then the temperature is reduced to 60-65 ℃, redox initiator (0.09 part of tert-butyl hydroperoxide is dissolved in 1 part of deionized water, 0.06 part of sodium formaldehyde sulfoxylate is dissolved in 2 parts of deionized water) is added, and the temperature is kept for 0.5h to eliminate residual monomers. And (3) cooling to 50 ℃, adding 0.6 part of 20% ammonia water to adjust the pH =7.5, and finally adding 0.93 part of adipic dihydrazide to obtain the water-based acrylic resin for the water-based single-component plastic silver paint.
Example 4
The water-based acrylic resin for the water-based single-component plastic silver paint comprises the following components in parts by weight: 40 parts of vinyl monomer (2.5 parts of hydrophilic vinyl monomer, 34.0 parts of hydrophobic vinyl monomer and 3.5 parts of self-crosslinking vinyl monomer), 0.25 part of molecular weight regulator, 0.1 part of free radical initiator, 0.2 part of emulsifier, 0.6 part of neutralizer and 59 parts of deionized water.
The water-based acrylic resin for the water-based single-component plastic silver paint is prepared according to the components and the component proportion, and comprises the following steps:
(1) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 0.4 part of methacrylic acid, 19.4 parts of styrene and 0.3 part of allyl methacrylate, and stirring to obtain a monomer emulsion E1; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution A.
(2) Adding 36 parts of deionized water into a reaction kettle, heating to 80-90 ℃, starting to synchronously dropwise add the monomer emulsion E1 and the initiator aqueous solution A for 2 hours, and controlling the reaction temperature to be 80-90 ℃; after the dripping is finished, the temperature is kept for 0.5h at the temperature of 80-90 ℃.
(3) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 2.1 parts of methacrylic acid, 1.3 parts of butyl acrylate, 13.0 parts of styrene, 3.5 parts of diacetone acrylamide and 0.25 part of n-butyl mercaptopropionate, and stirring to obtain a monomer emulsion E2; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution B.
(4) Synchronously dropwise adding the monomer emulsion E2 and the initiator aqueous solution B into the material obtained in the step (2), wherein the dropwise adding time is 2h, the reaction temperature is controlled to be 80-90 ℃, and the temperature is kept for 0.5h at the temperature of 80-90 ℃ after the dropwise adding is finished. Then the temperature is reduced to 60-65 ℃, redox initiator (0.09 part of tert-butyl hydroperoxide is dissolved in 1 part of deionized water, 0.06 part of sodium formaldehyde sulfoxylate is dissolved in 2 parts of deionized water) is added, and the temperature is kept for 0.5h to eliminate residual monomers. And (3) cooling to 50 ℃, adding 0.6 part of 20% ammonia water to adjust the pH =7.5, and finally adding 1.62 parts of adipic dihydrazide to obtain the waterborne acrylic resin for the waterborne single-component plastic silver paint.
Comparative example 1
The hydrophilic vinyl monomer, the hydrophobic vinyl monomer, the self-crosslinkable vinyl monomer, the molecular weight regulator and the reaction temperature are in the same proportion as those in the example 4, and a monomer dropping process is not carried out in two steps, so that the water-based acrylic resin for the core-shell structure-free particle water-based single-component plastic silver paint is obtained.
The preparation method of the water-based acrylic resin for the water-based single-component plastic silver paint comprises the following steps:
(1) Dissolving 1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 2.5 parts of methacrylic acid, 32.4 parts of styrene, 1.3 parts of n-butyl acrylate, 0.3 part of allyl methacrylate, 3.5 parts of diacetone acrylamide and 0.25 part of n-butyl mercaptopropionate, and stirring to obtain the monomer emulsion E1. 0.1 part of ammonium persulfate and 8 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution A.
(2) Adding 36 parts of deionized water into a reaction kettle, heating to 80-90 ℃, starting to synchronously dropwise add the monomer emulsion E1 and the initiator aqueous solution A for 2 hours, controlling the reaction temperature to 80-90 ℃, and preserving the heat for 0.5 hour at the temperature of 80-90 ℃ after dropwise addition. The temperature is reduced to 60 to 65 ℃, redox initiator (0.09 part of tert-butyl hydroperoxide is dissolved in 1 part of deionized water-0.06 part of sodium formaldehyde sulfoxylate is dissolved in 2 parts of deionized water) is added, and the temperature is kept for 0.5h to eliminate residual monomers. And (3) cooling to 50 ℃, adding 6 parts of 20% ammonia water to adjust the pH =7.5, and finally adding 1.62 parts of adipic dihydrazide to obtain the aqueous acrylic resin for the aqueous single-component plastic silver paint.
Comparative example 2
Example 4 an aqueous acrylic resin for an aqueous one-component plastic silver paint was prepared under the same process conditions without using a molecular weight regulator.
The water-based acrylic resin for the water-based single-component plastic silver paint comprises the following components in parts by weight: 40 parts of vinyl monomer (2.5 parts of hydrophilic vinyl monomer, 34.0 parts of hydrophobic vinyl monomer and 3.5 parts of self-crosslinking vinyl monomer), 0 part of molecular weight regulator, 0.1 part of free radical initiator, 0.2 part of emulsifier, 0.6 part of neutralizer and 59 parts of deionized water.
The water-based acrylic resin for the water-based single-component plastic silver paint is prepared according to the components and the component proportion, and comprises the following steps:
(1) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 0.4 part of methacrylic acid, 19.4 parts of styrene and 0.3 part of allyl methacrylate, and stirring to obtain a monomer emulsion E1; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution A.
(2) Adding 36 parts of deionized water into a reaction kettle, heating to 80-90 ℃, starting to synchronously dropwise add the monomer emulsion E1 and the initiator aqueous solution A for 2 hours, and controlling the reaction temperature to be 80-90 ℃; after the dripping is finished, the temperature is kept for 0.5h at the temperature of 80-90 ℃.
(3) Dissolving 0.1 part of emulsifier sodium dodecyl sulfate in 6 parts of deionized water in an emulsifying kettle, adding 2.1 parts of methacrylic acid, 1.3 parts of butyl acrylate, 13.0 parts of styrene and 3.5 parts of diacetone acrylamide, and stirring to obtain a monomer emulsion E2; 0.05 part of ammonium persulfate and 4 parts of deionized water are mixed and dissolved to obtain an initiator aqueous solution B.
(4) Synchronously dropwise adding the monomer emulsion E2 and the initiator aqueous solution B into the material obtained in the step (2), wherein the dropwise adding time is 2h, the reaction temperature is controlled to be 80-90 ℃, and the temperature is kept for 0.5h at the temperature of 80-90 ℃ after the dropwise adding is finished. Then the temperature is reduced to 60 to 65 ℃, redox initiator (0.09 part of tert-butyl hydroperoxide is dissolved in 1 part of deionized water, 0.06 part of sodium formaldehyde sulfoxylate is dissolved in 2 parts of deionized water) is added, and the temperature is kept for 0.5h to eliminate residual monomers. And (3) cooling to 50 ℃, adding 0.6 part of 20% ammonia water to adjust the pH =7.5, and finally adding 1.62 parts of adipic dihydrazide to obtain the waterborne acrylic resin for the waterborne single-component plastic silver paint.
To illustrate the performance of the water-based acrylic resin for the water-based one-component plastic silver paint of the examples and comparative examples, the following formulation was used to prepare the one-component water-based silver paint. 56 parts of water-based acrylic resin for the water-based single-component plastic silver paint, 7 parts of silver powder, 5 parts of dipropylene glycol butyl ether, 7 parts of diethylene glycol butyl ether, 0.1 part of neutralizer, 5 parts of wax emulsion, 0.1 part of defoamer, 0.4 part of wetting agent, 0.2 part of rheological additive, 0.3 part of dispersant and 15.4 parts of pure water. All the materials are calculated by mass.
And then respectively spraying the single-component water-based silver paint on clean ABS, PC and HIPS base materials, controlling the thickness of a dry paint film to be 10-20 mu m, baking the paint film at 70 ℃ for 30min, standing the paint film at room temperature for 3 days, and testing the adhesive force and the alcohol rub resistance according to the following methods.
Silver bar effect: with naked eye observation, grade 0 is the worst and grade 5 is the best.
Adhesion force: the test was carried out according to the national Standard GB/T9286-1998 test for marking test on paint and varnish films, with grade 0 being the best and grade 5 being the worst.
Alcohol rub resistance: the test is carried out according to the national standard GB/T23989-2009 method for measuring the solvent resistance of the coating, the test solvent is absolute ethyl alcohol, the load weight is 500g, and the exposed bottom of a paint film is taken as the test termination standard.
The test results are shown in the following table.
TABLE 2 results of Performance test of examples 1 to 4 and comparative examples 1 to 2
By comparatively analyzing the silver exclusion effect, the adhesion force and the alcohol rub resistance of the water-based acrylic resin for the water-based single-component plastic silver paint, example 1, example 2, example 3, example 4, comparative example 1 and comparative example 2, it is found that the larger the amount of the hydrophilic vinyl monomer in the amount range of the application, the better the silver exclusion effect of the water-based acrylic resin for the water-based single-component plastic silver paint; the adhesion of the paint film to each base material can be obviously improved by increasing the using amount of the molecular weight regulator; under the condition of the same structure, the dosage of the self-crosslinkable vinyl is in positive correlation with the alcohol wiping resistance of the paint film.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by one of ordinary skill in the art and related arts based on the embodiments of the present invention without any creative effort, shall fall within the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.
Claims (10)
1. The water-based acrylic resin for the water-based single-component plastic silver paint is characterized by comprising the following components in parts by weight: 33.0 to 38.0 portions of hydrophobic vinyl monomer, 1.0 to 3.0 portions of hydrophilic vinyl monomer, 1.0 to 4.0 portions of self-crosslinking vinyl monomer, 0.1 to 0.3 portion of molecular weight regulator, 0.1 portion of free radical initiator, 0.2 to 0.4 portion of emulsifier, 0.4 to 0.6 portion of neutralizer and 59 to 61 portions of water.
2. The waterborne acrylic resin for the waterborne one-component plastic silver paint of claim 1, wherein the hydrophilic vinyl monomer comprises at least one of acrylic acid, methacrylic acid and itaconic acid.
3. The waterborne acrylic resin for the waterborne one-component plastic silver paint of claim 1, wherein the self-crosslinkable vinyl monomer comprises at least one of glycidyl methacrylate, N-methylolacrylamide, diacetone acrylamide, ethylene glycol acetoacetate methacrylate, trimethoxyvinylsilane, triethoxyvinylsilane, gamma-methacryloxypropyltrimethoxysilane and gamma-methacryloxypropyltriethoxysilane.
4. The waterborne acrylic resin for the waterborne one-component plastic silver paint of claim 1, wherein the hydrophobic vinyl monomer comprises at least one of methyl methacrylate, styrene, alpha-methyl styrene, n-butyl acrylate, isooctyl acrylate, lauryl acrylate, cyclohexyl acrylate, allyl methacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol diacrylate and pentaerythritol triacrylate.
5. The waterborne acrylic resin for the waterborne one-component plastic silver paint of claim 1, wherein the molecular weight regulator comprises at least one of dodecyl mercaptan, mercaptopropionic acid, n-butyl mercaptopropionate, isooctyl mercaptopropionate, mercaptoethanol, and a-methyl styrene linear dimer.
6. The waterborne acrylic resin for the waterborne one-component plastic silver paint of claim 1, wherein the neutralizing agent comprises at least one of ammonia, N-dimethylethanolamine, triethanolamine and AMP-95.
7. The water-based acrylic resin for the water-based single-component plastic silver paint as claimed in claim 1, wherein the emulsifier comprises at least one of sodium alkyl sulfate, sodium alkyl sulfonate and sodium alcohol ether sulfate; further, the emulsifier comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and C12-C14 fatty alcohol ether sodium sulfate.
8. The waterborne acrylic resin for the waterborne one-component plastic silver paint of claim 1, wherein the free radical initiator comprises a thermal initiator and a redox initiator, and the thermal initiator comprises at least one of ammonium persulfate and sodium persulfate; the redox initiator comprises at least one of ammonium persulfate-sodium bisulfite, ammonium persulfate-sodium metabisulfite, sodium persulfate-sodium bisulfite, sodium persulfate-sodium metabisulfite, tert-butyl hydroperoxide-formaldehyde sodium hydrosulfite and tert-butyl hydroperoxide-sodium ascorbate.
9. The preparation method of the water-based acrylic resin for the water-based single-component plastic silver paint, which is disclosed by claim 1, is characterized by comprising the following steps of:
s1, dissolving an emulsifier by using deionized water, and adding a vinyl monomer to obtain a monomer emulsion E1;
s2, synchronously dripping the monomer emulsion E1 and the thermal initiator aqueous solution into deionized water at the temperature of 80-90 ℃ for 1-3h, and preserving heat for 0.5-1h at the temperature of 80-90 ℃ after finishing dripping;
s3, dissolving an emulsifier by using deionized water, and then adding a vinyl monomer and a molecular weight regulator to obtain a monomer emulsion E2;
s4, synchronously dropwise adding the monomer emulsion E2 and the thermal initiator aqueous solution into the material obtained in the step S2 for 1-3h, and preserving heat for 0.5-1h at the temperature of 80-90 ℃ after dropwise adding;
and S5, cooling the material obtained in the step S4 to 60-65 ℃, adding a redox initiator, keeping the temperature at 60-65 ℃ for 0.5-1h, and finally cooling to below 50 ℃, adding a neutralizer to adjust the pH =7.5-8.5.
10. The method for preparing the water-based acrylic resin for the water-based single-component plastic silver paint as claimed in claim 9, wherein the vinyl monomers in the monomer emulsion E1 comprise, by weight, 2-5 parts of the hydrophilic vinyl monomer, 90-97 parts of the hydrophobic vinyl monomer, and 1-5 parts of the self-crosslinkable vinyl monomer; in the monomer emulsion E2, the vinyl monomers comprise, by weight, 5-12 parts of the hydrophilic vinyl monomers, 73-87 parts of the hydrophobic vinyl monomers and 8-15 parts of the self-crosslinkable vinyl monomers.
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| CN111333783A (en) * | 2020-04-12 | 2020-06-26 | 常熟巴德富科技有限公司 | Preparation method of hydroxyl acrylate emulsion for water-based wood paint |
| CN112321774A (en) * | 2020-11-03 | 2021-02-05 | 湖北双键精细化工有限公司 | Waterborne polyurethane/acrylate composite emulsion for single-component plastic silver paint and preparation method thereof |
| CN114149542A (en) * | 2021-11-18 | 2022-03-08 | 南雄西顿化工有限公司 | Water-based acrylic resin for high-developability printing ink and preparation method thereof |
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