CN114920888A - Hydroxy acrylic ester emulsion for bi-component anti-doodling finishing varnish and preparation method thereof - Google Patents
Hydroxy acrylic ester emulsion for bi-component anti-doodling finishing varnish and preparation method thereof Download PDFInfo
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- CN114920888A CN114920888A CN202210192523.5A CN202210192523A CN114920888A CN 114920888 A CN114920888 A CN 114920888A CN 202210192523 A CN202210192523 A CN 202210192523A CN 114920888 A CN114920888 A CN 114920888A
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- acrylate
- graffiti
- sodium
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- 239000000839 emulsion Substances 0.000 title claims abstract description 64
- 239000002966 varnish Substances 0.000 title claims abstract description 26
- -1 Hydroxy acrylic ester Chemical class 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000004132 cross linking Methods 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 64
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 38
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 32
- 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 29
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 29
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 29
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 238000004321 preservation Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 19
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 19
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 19
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 18
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 18
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 12
- 235000010350 erythorbic acid Nutrition 0.000 claims description 12
- 229940026239 isoascorbic acid Drugs 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000004318 erythorbic acid Substances 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-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 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 229940001607 sodium bisulfite Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 21
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000004925 Acrylic resin Substances 0.000 abstract description 2
- 229920000178 Acrylic resin Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000000576 coating method Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 10
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001804 emulsifying effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a hydroxyl acrylic ester emulsion for a double-component anti-doodling finishing varnish, which comprises 100-600 parts of hydroxyl acrylic resin monomer; 500-1500 parts of vinyl-containing monomer; 1-10 parts of a crosslinking monomer; 50-110 parts of an emulsifier; 5-20 parts of an initiator; 0.5-2 parts of a reducing agent; 0-3 parts of a neutralizing agent; 2500-3600 parts of deionized water, and the emulsion has the advantages that the reactive emulsifier is adopted, so that the emulsion is higher in reactivity and better in water resistance; the hydroxyl content of the polymer is increased by a low-solid content mode; the high hydroxyl content emulsion can improve the crosslinking degree of the final paint film, so that the paint film has higher hardness, water resistance, solvent resistance and graffiti resistance.
Description
Technical Field
The invention relates to the field of coatings, in particular to a hydroxyl acrylate emulsion for a bi-component anti-doodling finishing varnish and a preparation method thereof.
Background
The anti-doodling finishing varnish paint is a functional surface treatment paint. Has high crosslinking density and hardness. The paint film has the characteristics of high hardness, good solvent resistance, smooth surface and self-cleaning, and common white board pens, water-based color pens, crayons and lipstick graffiti have the effect of being easy to erase on the paint film. According to market research and demand feedback of a plurality of customers. In the decoration process of some kindergartens, nursery houses, theme parks of children and the like, some special scenes hope to use some environment-friendly coating or finishing varnish with scrawling resistance to coat the wall so as to prevent the children from scrawling the wall in a classroom.
The solvent-based anti-graffiti coating contains a large amount of small molecular compounds and volatile organic solvents which are harmful to human bodies. The damage to constructors and the environment is caused during construction; in the using process, a paint film can slowly release a large amount of small molecular compounds, volatile organic solvents and other harmful substances for a long time, so that the paint film can cause great harm to people and environment. With the increasing environmental protection requirements, solvent-based coatings are gradually eliminated. The coating varnish prepared from the conventional acrylate emulsion is not compact enough in coating and poor in solvent resistance, and common color paste of a color pen and a white board pen contains an organic solvent, so that the common coating varnish coating is corroded and damaged, and the color paste permeates into the coating to cause the coating to be incapable of being scrubbed.
The water-based bi-component scrawling-resistant finishing varnish has the advantages of convenient construction, small smell and small environmental pollution. Due to the adoption of a bi-component crosslinking system, compared with a common clear paint film, the paint film has the advantages of high hardness, more compact paint film and better solvent resistance. Therefore, the bi-component anti-graffiti paint film has excellent anti-graffiti effect.
Patent CN105219247A mentions an anti-doodling double-component transparent varnish and a preparation method thereof, wherein a hydroxy acrylic emulsion and a water-based isocyanate curing agent are subjected to a cross-linking reaction, and a wax emulsion is added in a formula to reduce surface tension and achieve a certain anti-doodling effect.
Patent CN111763287A mentions that a preparation method of a hydroxyl acrylic emulsion for an aqueous anti-graffiti anti-sticking coating adopts a core-shell polymerization process and adds an organic silicon monomer and a hydroxyl monomer to achieve the effect, compared with the method of the invention, the production process is complex, the raw material cost is high, and the practicability of the application scene is greatly influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provide the hydroxyl acrylate emulsion for the double-component scrawling-resistant finishing varnish with stronger practicability and simpler operation process, and prepare the double-component scrawling-resistant finishing varnish by matching the hydroxyl acrylate emulsion with a water-based isocyanate curing agent. The paint film has the characteristics of high hardness, high compactness, high solvent resistance and the like so as to achieve good anti-graffiti effect.
The invention provides a hydroxy acrylate emulsion for double-component scrawling-resistant finishing varnish and a preparation method thereof, and in order to achieve the aim and the effect, the invention adopts the following technology:
the hydroxyl acrylic ester emulsion for the bi-component scrawling-resistant finishing varnish is prepared by introducing abundant hydroxyl groups into the surface layer of emulsion particles and using 100-600 parts by mass of hydroxyl acrylic resin monomer; 500-1500 parts of vinyl-containing monomer; 1-10 parts of a crosslinking monomer; 50-110 parts of an emulsifier; 5-20 parts of an initiator; 0.5-2 parts of a reducing agent; 0-3 parts of a neutralizing agent; 2500-3600 parts of deionized water.
One or more of hydroxyethyl acrylate mono (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and N-methylolacrylamide, preferably one of hydroxyethyl acrylate and hydroxybutyl acrylate, are used in the present invention.
The vinyl-containing monomer is selected from one or more of styrene, methyl (meth) acrylate, butyl (meth) acrylate, isooctyl acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, itaconic acid, allyloxy hydroxy sodium sulfonate and 2-acrylamide-2-methylpropanesulfonic acid. Two or more of styrene, (meth) acrylic acid, butyl acrylate, isooctyl acrylate, methyl methacrylate are preferred.
The crosslinking monomer is selected from one or more of vinyltriethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane and carbodiimide. One of vinyltrimethoxysilane and glycidoxypropyltrimethoxysilane is preferred.
The emulsifier is selected from one or more of alkyl propenyl phenoxy polyether sulfate, allyl-containing alkyl alcohol ether sulfate, fatty alcohol ether sulfate, branched alkyl alcohol ether phosphate ammonium salt and isomeric alcohol polyoxyethylene ether. Preferably one or more of allyl-containing alkyl alcohol ether sulfate, fatty alcohol ether sulfate and isomeric alcohol polyoxyethylene ether
The initiator is selected from one of sodium persulfate, ammonium persulfate, potassium persulfate and tert-butyl hydroperoxide. Preferably one or more of sodium persulfate, ammonium persulfate and tert-butyl hydroperoxide.
The reducing agent is selected from one or more of sodium metabisulfite, isoascorbic acid, sodium bisulfite and FF 6M. One or more of sodium metabisulfite, erythorbic acid, FF6M are preferred.
The neutralizing agent is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia water, AMP-95, triethylamine, sodium bicarbonate and triethanolamine. Preferably one or more of sodium hydroxide, ammonia water, AMP-95, and sodium bicarbonate.
The invention relates to a preparation method of hydroxyl acrylic ester emulsion for double-component anti-doodling finishing varnish, which comprises the following steps:
step one, preparing a pre-emulsion: preparing the deionized water, the emulsifier, the vinyl-containing monomer, the hydroxyl acrylate monomer and the crosslinking monomer into pre-emulsion in an emulsion bottle;
step two, preparing a reaction bottle bottom solution: the deionized water and the emulsifier are arranged in a reaction bottle and stirred and heated to 80-86 ℃;
step three, reaction process: adding a primary initiator, beginning to simultaneously dropwise add the pre-emulsion and the initiator for 180-240 minutes, adding the crosslinking monomer into the pre-emulsion when the pre-emulsion is left 1/3, and keeping the temperature for 1 hour after dropwise adding;
step four, post-treatment process: after the heat preservation is finished, cooling to 55-60 ℃, adding post-treatment, dropwise adding an oxidant and a reducing agent for 30-60 minutes after the post-treatment, and preserving the heat for 30-60 minutes after the post-treatment is finished; and (5) after heat preservation, cooling, neutralizing, filtering and packaging.
The invention adopts a semi-continuous polymerization process, the reaction process is simple and controllable, and the raw materials and reagents used in the invention are commercially available;
compared with the prior art, the invention has the beneficial effects that: the invention has the advantages that the reactivity of the emulsion is higher and the water resistance is better by adopting the reactive emulsifier; the hydroxyl content of the polymer is increased by a low-solid content mode; the high hydroxyl content emulsion can improve the crosslinking degree of the final paint film, so that the paint film has higher hardness, water resistance, solvent resistance and graffiti resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present patent and are not intended to limit the present invention.
The invention is further described below by means of specific examples.
Example 1
In this example, the raw materials include, by weight, 320 parts of styrene, 8 parts of acrylic acid, 456 parts of butyl acrylate, 324 parts of hydroxyethyl acrylate, 100 parts of methyl methacrylate, 72 parts of allyl-containing alkyl alcohol ether sulfate, 3.1 parts of isomeric alcohol polyoxyethylene ether, 5.1 parts of sodium bicarbonate, 12.8 parts of sodium persulfate, 1.6 parts of tert-butyl hydroperoxide, FF6M1.6 parts of sodium persulfate, and 3500 parts of deionized water.
The polymerization process comprises the following steps:
adding 28 parts of allyl-containing alkyl alcohol ether sulfate, 3.1 parts of isomeric alcohol polyoxyethylene ether, 1.1 parts of sodium bicarbonate and 1340 parts of deionized water into a reaction kettle, stirring and heating;
adding 44 parts of allyl-containing alkyl alcohol ether sulfate, 4 parts of sodium bicarbonate and 1860 parts of deionized water into an emulsifying cylinder, starting stirring and dispersing for more than 15 minutes, and then preparing 320 parts of styrene, 8 parts of acrylic acid, 456 parts of butyl acrylate, 324 parts of hydroxyethyl acrylate and 100 parts of methyl methacrylate into a pre-emulsion in sequence;
adding 50 parts of aqueous solution of sodium persulfate into the reaction kettle when the temperature of the reaction kettle is raised to 85 ℃, then simultaneously dropwise adding the pre-emulsion and 163 parts of aqueous solution of sodium persulfate for 210 minutes, and preserving the temperature for 60 minutes;
after the heat preservation is finished, cooling to 70 ℃, simultaneously dripping 40 parts of tert-butyl hydroperoxide and 40 parts of FF6M aqueous solution for 45 minutes, and preserving the heat for 30 minutes after finishing dripping;
after the heat preservation is finished, cooling to room temperature, adding ammonia water to adjust the pH value to 7-9, and then filtering and packaging.
Example 2
The acrylic acid-butyl acrylate copolymer is prepared from the following raw materials, by weight, 10 parts of acrylic acid, 125 parts of butyl acrylate, 525 parts of hydroxybutyl acrylate, 750 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 100 parts of allyl-containing alkyl alcohol ether sulfate, 2.5 parts of vinyl trimethoxy silane, 5 parts of isomeric alcohol polyoxyethylene ether, 5 parts of sodium bicarbonate, 13 parts of sodium persulfate, 1.5 parts of tert-butyl hydroperoxide, FF6M1.5 parts of deionized water and 2225 parts of deionized water.
The polymerization process comprises the following steps:
25 parts of allyl-containing alkyl alcohol ether sulfate, 5 parts of isomeric alcohol polyoxyethylene ether, 2.5 parts of sodium bicarbonate and 1250 parts of deionized water are added into a reaction kettle, and stirring and heating are started; adding 75 parts of allyl-containing alkyl alcohol ether sulfate, 2.5 parts of sodium bicarbonate and 700 parts of deionized water into an emulsifying cylinder, starting stirring and dispersing for more than 15 minutes, and then sequentially preparing 10 parts of acrylic acid, 125 parts of butyl acrylate, 525 parts of hydroxybutyl acrylate, 750 parts of methyl methacrylate, 100 parts of isooctyl acrylate and 2.5 parts of vinyl trimethoxy silane into a pre-emulsion; adding 50 parts of aqueous solution of sodium persulfate into the reaction kettle when the temperature of the reaction kettle rises to 85 ℃, then simultaneously dropwise adding the pre-emulsion and 104 parts of aqueous solution of sodium persulfate for 210 minutes, and preserving the temperature for 60 minutes;
after the heat preservation is finished, cooling to 70 ℃, simultaneously dropwise adding 50 parts of tert-butyl hydroperoxide and 50 parts of FF6M aqueous solution for 45 minutes, and preserving the heat for 30 minutes after dropwise adding;
after the heat preservation is finished, cooling to room temperature, adding ammonia water to adjust the PH value to 7-9, and then filtering and packaging.
Example 3
In this example, the raw materials include, by weight, 320 parts of styrene, 8 parts of acrylic acid, 456 parts of butyl acrylate, 324 parts of hydroxyethyl acrylate, 100 parts of methyl methacrylate, 2 parts of vinyltrimethoxysilane, 72 parts of allyl-containing alkyl alcohol ether sulfate, 3.1 parts of isomeric alcohol polyoxyethylene ether, 5.1 parts of sodium bicarbonate, 12.8 parts of sodium persulfate, 1.6 parts of tert-butyl hydroperoxide, 0.8 part of erythorbic acid, and 3500 parts of deionized water.
The polymerization process comprises the following steps:
adding 28 parts of allyl-containing alkyl alcohol ether sulfate, 3.1 parts of isomeric alcohol polyoxyethylene ether, 1.1 parts of sodium bicarbonate and 1340 parts of deionized water into a reaction kettle, stirring and heating;
adding 44 parts of allyl-containing alkyl alcohol ether sulfate, 4 parts of sodium bicarbonate and 1860 parts of deionized water into an emulsifying cylinder, starting stirring and dispersing for more than 15 minutes, and then preparing 320 parts of styrene, 8 parts of acrylic acid, 456 parts of butyl acrylate, 324 parts of hydroxyethyl acrylate, 100 parts of methyl methacrylate and 2 parts of vinyl trimethoxy silane into a pre-emulsion;
adding 50 parts of aqueous solution of sodium persulfate into the reaction kettle when the temperature of the reaction kettle is raised to 85 ℃, then simultaneously dropwise adding the pre-emulsion and 163 parts of aqueous solution of sodium persulfate for 210 minutes, and preserving the temperature for 60 minutes;
after the heat preservation is finished, cooling to 55 ℃, simultaneously dripping 40 parts of tert-butyl hydroperoxide and 40 parts of isoascorbic acid aqueous solution for 45 minutes, and preserving the heat for 30 minutes after dripping;
after the heat preservation is finished, the temperature is reduced to room temperature, sodium hydroxide is added to adjust the pH value to 3.5-4.5, and then filtration and packaging are carried out.
Example 4
The acrylic acid-butyl acrylate copolymer is prepared from the following raw materials, by weight, 10 parts of acrylic acid, 125 parts of butyl acrylate, 525 parts of hydroxybutyl acrylate, 750 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 100 parts of allyl-containing alkyl alcohol ether sulfate, 2.5 parts of vinyl trimethoxy silane, 5 parts of isomeric alcohol polyoxyethylene ether, 5 parts of sodium bicarbonate, 13 parts of sodium persulfate, 1.5 parts of tert-butyl hydroperoxide, 0.75 part of isoascorbic acid, and 2225 parts of deionized water.
The polymerization process comprises the following steps:
adding 25 parts of allyl-containing alkyl alcohol ether sulfate, 5 parts of isomeric alcohol polyoxyethylene ether, 2.5 parts of sodium bicarbonate and 1250 parts of deionized water into a reaction kettle, stirring and heating; adding 75 parts of allyl-containing alkyl alcohol ether sulfate, 2.5 parts of sodium bicarbonate and 700 parts of deionized water into an emulsifying cylinder, starting stirring and dispersing for more than 15 minutes, and then sequentially preparing 10 parts of acrylic acid, 125 parts of butyl acrylate, 525 parts of hydroxybutyl acrylate, 750 parts of methyl methacrylate, 100 parts of isooctyl acrylate and 2.5 parts of vinyl trimethoxy silane into a pre-emulsion; adding 50 parts of aqueous solution of sodium persulfate into the reaction kettle when the temperature of the reaction kettle rises to 85 ℃, then simultaneously dropwise adding the pre-emulsion and 104 parts of aqueous solution of sodium persulfate for 210 minutes, and preserving the temperature for 60 minutes;
after the heat preservation is finished, cooling to 55 ℃, simultaneously dropwise adding 50 parts of tert-butyl hydroperoxide and 50 parts of isoascorbic acid aqueous solution for 45 minutes, and preserving the heat for 30 minutes after dropwise adding; after the heat preservation is finished, the temperature is reduced to room temperature, sodium hydroxide is added to adjust the pH value to 3.5-4.5, and then filtration and packaging are carried out.
Example 5
In the embodiment, the raw materials include, by weight, 320 parts of styrene, 8 parts of acrylic acid, 456 parts of butyl acrylate, 324 parts of hydroxyethyl acrylate, 100 parts of methyl methacrylate, 2 parts of vinyl trimethoxy silane, 72 parts of allyl-containing alkyl alcohol ether sulfate, 3.1 parts of isomeric alcohol polyoxyethylene ether, 5.1 parts of sodium bicarbonate, 12.8 parts of sodium persulfate, 1.6 parts of tert-butyl hydroperoxide, 0.8 part of isoascorbic acid, and 3500 parts of deionized water.
The polymerization process comprises the following steps:
adding 28 parts of allyl-containing alkyl alcohol ether sulfate, 3.1 parts of isomeric alcohol polyoxyethylene ether, 1.1 parts of sodium bicarbonate and 1340 parts of deionized water into a reaction kettle, stirring and heating;
adding 44 parts of allyl-containing alkyl alcohol ether sulfate, 4 parts of sodium bicarbonate and 1860 parts of deionized water into an emulsifying cylinder, starting stirring and dispersing for more than 15 minutes, and then sequentially preparing 320 parts of styrene, 8 parts of acrylic acid, 456 parts of butyl acrylate, 324 parts of hydroxyethyl acrylate, 100 parts of methyl methacrylate and 2 parts of vinyl trimethoxy silane into a pre-emulsion;
adding 100 parts of pre-emulsion and 50 parts of aqueous solution of sodium persulfate into the reaction kettle when the temperature of the reaction kettle is raised to 85 ℃ for reaction for 5 minutes, then simultaneously dropwise adding the pre-emulsion and 163 parts of aqueous solution of sodium persulfate for 210 minutes, and keeping the temperature for 60 minutes;
after the heat preservation is finished, cooling to 55 ℃, simultaneously dripping 40 parts of tert-butyl hydroperoxide and 40 parts of isoascorbic acid aqueous solution for 45 minutes, and preserving the heat for 30 minutes after dripping;
after the heat preservation is finished, the temperature is reduced to room temperature, sodium hydroxide is added to adjust the pH value to 3.5-4.5, and then filtration and packaging are carried out.
Example 6
The acrylic acid-butyl acrylate copolymer is prepared from the following raw materials, by weight, 10 parts of acrylic acid, 125 parts of butyl acrylate, 525 parts of hydroxybutyl acrylate, 750 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 100 parts of allyl-containing alkyl alcohol ether sulfate, 2.5 parts of vinyl trimethoxy silane, 5 parts of isomeric alcohol polyoxyethylene ether, 5 parts of sodium bicarbonate, 13 parts of sodium persulfate, 1.5 parts of tert-butyl hydroperoxide, 0.75 part of isoascorbic acid, and 2225 parts of deionized water.
The polymerization process comprises the following steps:
25 parts of allyl-containing alkyl alcohol ether sulfate, 5 parts of isomeric alcohol polyoxyethylene ether, 2.5 parts of sodium bicarbonate and 1250 parts of deionized water are added into a reaction kettle, and stirring and heating are started; adding 75 parts of allyl-containing alkyl alcohol ether sulfate, 2.5 parts of sodium bicarbonate and 700 parts of deionized water into an emulsifying cylinder, starting stirring and dispersing for more than 15 minutes, and then sequentially preparing 10 parts of acrylic acid, 125 parts of butyl acrylate, 525 parts of hydroxybutyl acrylate, 750 parts of methyl methacrylate, 100 parts of isooctyl acrylate and 2.5 parts of vinyl trimethoxy silane into a pre-emulsion; adding 100 parts of pre-emulsion and 50 parts of aqueous solution of sodium persulfate into the reaction kettle when the temperature of the reaction kettle is raised to 85 ℃ for reaction for 5 minutes, then simultaneously dropwise adding the pre-emulsion and 104 parts of aqueous solution of sodium persulfate for 210 minutes, and preserving the temperature for 60 minutes;
after the heat preservation is finished, cooling to 55 ℃, simultaneously dropwise adding 50 parts of tert-butyl hydroperoxide and 50 parts of isoascorbic acid aqueous solution for 45 minutes, and preserving the heat for 30 minutes after dropwise adding; after the heat preservation is finished, the temperature is reduced to room temperature, sodium hydroxide is added to adjust the pH value to 3.5-4.5, and then filtration and packaging are carried out.
Comparative example 1
The comparative example is prepared from 384 parts by weight of styrene, 8 parts by weight of acrylic acid, 656 parts by weight of butyl acrylate, 10 parts by weight of hydroxyethyl acrylate, 150 parts by weight of methyl methacrylate, 72 parts by weight of allyl-containing alkyl alcohol ether sulfate, 3.1 parts by weight of isomeric alcohol polyoxyethylene ether, 5.1 parts by weight of sodium bicarbonate, 12.8 parts by weight of sodium persulfate, 1.6 parts by weight of tert-butyl hydroperoxide, FF6M1.6 parts by weight of deionized water, and 3500 parts by weight of deionized water.
The polymerization process comprises the following steps:
adding 28 parts of allyl-containing alkyl alcohol ether sulfate, 3.1 parts of isomeric alcohol polyoxyethylene ether, 1.1 parts of sodium bicarbonate and 1340 parts of deionized water into a reaction kettle, stirring and heating;
adding 44 parts of allyl-containing alkyl alcohol ether sulfate, 4 parts of sodium bicarbonate and 1860 parts of deionized water into an emulsifying cylinder, starting stirring and dispersing for more than 15 minutes, and then preparing 320 parts of styrene, 8 parts of acrylic acid, 456 parts of butyl acrylate, 324 parts of hydroxyethyl acrylate and 100 parts of methyl methacrylate into a pre-emulsion in sequence;
adding 50 parts of aqueous solution of sodium persulfate into the reaction kettle when the temperature of the reaction kettle is raised to 85 ℃, then simultaneously dropwise adding the pre-emulsion and 163 parts of aqueous solution of sodium persulfate for 210 minutes, and preserving the temperature for 60 minutes;
after the heat preservation is finished, cooling to 70 ℃, simultaneously dripping 40 parts of tert-butyl hydroperoxide and 40 parts of FF6M aqueous solution for 45 minutes, and preserving the heat for 30 minutes after finishing dripping;
after the heat preservation is finished, the temperature is reduced to room temperature, ammonia water is added to adjust the PH value to 3.5-4.5, and then filtration and packaging are carried out.
Comparative example 2
The comparative example is prepared from the following raw materials, by weight, 10 parts of acrylic acid, 450 parts of butyl acrylate, 10 parts of hydroxybutyl acrylate, 740 parts of methyl methacrylate, 300 parts of isooctyl acrylate, 100 parts of allyl-containing alkyl alcohol ether sulfate, 2.5 parts of vinyl trimethoxy silane, 5 parts of isomeric alcohol polyoxyethylene ether, 5 parts of sodium bicarbonate, 13 parts of sodium persulfate, 1.5 parts of tert-butyl hydroperoxide, FF6M1.5 parts of and 2225 parts of deionized water.
The polymerization process comprises the following steps:
adding 25 parts of allyl-containing alkyl alcohol ether sulfate, 5 parts of isomeric alcohol polyoxyethylene ether, 2.5 parts of sodium bicarbonate and 1250 parts of deionized water into a reaction kettle, stirring and heating; adding 75 parts of allyl-containing alkyl alcohol ether sulfate, 2.5 parts of sodium bicarbonate and 700 parts of deionized water into an emulsifying cylinder, starting stirring and dispersing for more than 15 minutes, and then sequentially preparing 10 parts of acrylic acid, 125 parts of butyl acrylate, 525 parts of hydroxybutyl acrylate, 750 parts of methyl methacrylate, 100 parts of isooctyl acrylate and 2.5 parts of vinyl trimethoxy silane into a pre-emulsion; adding 50 parts of aqueous solution of sodium persulfate into the reaction kettle when the temperature of the reaction kettle rises to 85 ℃, then simultaneously dropwise adding the pre-emulsion and 104 parts of aqueous solution of sodium persulfate for 210 minutes, and preserving the temperature for 60 minutes;
after the heat preservation is finished, cooling to 70 ℃, simultaneously dropwise adding 50 parts of tert-butyl hydroperoxide and 50 parts of FF6M aqueous solution for 45 minutes, and preserving the heat for 30 minutes after dropwise adding;
after the heat preservation is finished, the temperature is reduced to the room temperature, ammonia water is added to adjust the PH value to 3.5-4.5, and then filtration and packaging are carried out.
The above examples and comparative examples were each formulated as an aqueous two-component anti-graffiti coating (component a) having the following formulation (parts by mass):
TABLE 1 coating formulations
The prepared component A coating and the component B curing agent are prepared into the scrawling-resistant finishing varnish according to the mass ratio of 5: 1. The paint testing method is based on type B in the national standard requirement of the anti-doodling and anti-sticking paint for JG/T304-: and (4) carrying out plate making test on the scrawling-proof type. The pencil hardness, solvent rub resistance, adhesion, anti-graffiti (marker) performance were tested separately. The test results of examples and comparative examples are shown in the following table.
TABLE 2 test results
| Test items | Hardness of pencil | Solvent resistance wiping | Adhesion force | Anti-doodling character (Mark pen) |
| National standard requirements | ≥2H | Bottom not exposed for 100 times | ≤1 | ≤3 |
| Example 1 | 2H | ＞100 | 0 | 4 |
| Example 2 | 2H | ＞100 | 0 | 4 |
| Example 3 | 2H | ＞100 | 0 | 3 |
| Example 4 | 2H | ＞100 | 0 | 2 |
| Example 5 | 2H | ＞100 | 0 | 3 |
| Example 6 | 2H | ＞100 | 0 | 3 |
| Comparative example 1 | 2B | 7 | 7 | Can not be removed |
| Comparative example 2 | B | 10 | 4 | Can not be removed |
The combination of the above experimental results shows that: the invention uses the reactive anionic emulsifier and the low solid content polymerization mode to polymerize the hydroxy acrylic emulsion for the two-component finishing varnish with high hydroxyl content and high reactivity. It can be seen from the results of the experiments in examples 1, 3 and 2, 4 that neutralization of the emulsion has a negative effect on the properties of the final paint film, while low pH values are more favourable for the properties of the final paint film after crosslinking. The experimental results of examples 3 and 4 show that the hydroxyl monomer with stronger hydrophobicity has better performance on faster crosslinking speed of the paint film. The invention adopts a reactive emulsifier and a hydroxyl monomer with stronger hydrophobicity; obtaining a hydroxyl acrylate emulsion with high hydroxyl content by using a low solid content polymerization mode; the crosslinking reaction between the hydroxyl emulsion and the curing agent is stronger by controlling the pH value, so that the paint film has more excellent performance. The test data in the table above shows that the oil-based marking pen in example 4 has a remarkable erasing effect and a good anti-graffiti effect.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as can be conceived and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention.
The invention is not limited to the specific embodiments described above, but rather only to the specific embodiments described above. The embodiments of the present invention have been described in detail, but the embodiments are only examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (9)
1. The hydroxyl acrylate emulsion for the double-component scrawling-resistant finishing varnish is characterized in that abundant hydroxyl groups are introduced into the surface layer of emulsion particles, and the hydroxyl emulsion is prepared from the following raw materials in parts by mass, namely 100-600 parts of hydroxyl propylene resin monomer; 500-1500 parts of vinyl-containing monomer; 1-10 parts of a crosslinking monomer; 50-110 parts of an emulsifier; 5-20 parts of an initiator; 0.5-2 parts of a reducing agent; 0-3 parts of a neutralizing agent; 2500-3600 parts of deionized water.
2. The hydroxyacrylate emulsion for two-component graffiti-resistant finishing varnish according to claim 1, wherein one or more of the hydroxyacrylate mono (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, N-methylol acrylamide.
3. The hydroxyacrylate emulsion for a two-component graffiti-resistant overcoat varnish according to claim 1, wherein the vinyl-containing monomer is selected from one or more of styrene, methyl (meth) acrylate, butyl (meth) acrylate, isooctyl acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, itaconic acid, sodium allyloxy hydroxysulfonate, 2-acrylamido-2-methylpropanesulfonic acid. Two or more of styrene, (meth) acrylic acid, butyl acrylate, isooctyl acrylate, methyl methacrylate are preferred.
4. The hydroxyacrylate emulsion for a two-component graffiti-resistant overcoat varnish according to claim 1, wherein the crosslinking monomer is selected from one or more of vinyltriethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane, and carbodiimide.
5. A hydroxyacrylate emulsion for a two-component graffiti-resistant finishing varnish according to claim 1, wherein the emulsifier is selected from one or more of the group consisting of an alkyl propenyl phenoxy polyether sulfate, an allyl-containing alkyl alcohol ether sulfate, a fatty alcohol ether sulfate, a branched alkyl alcohol ether phosphate ammonium salt, and an isomeric alcohol polyoxyethylene ether.
6. The hydroxyacrylate emulsion for a two-component anti-graffiti topcoat varnish according to claim 1, wherein the initiator is one selected from the group consisting of sodium persulfate, ammonium persulfate, potassium persulfate, and t-butyl hydroperoxide. Preferably one or more of sodium persulfate, ammonium persulfate and t-butyl hydroperoxide.
7. The hydroxyacrylate emulsion for a two-component anti-graffiti overcoat varnish according to claim 1, wherein the reducing agent is selected from one or more of sodium metabisulfite, erythorbic acid, sodium bisulfite, FF 6M. One or more of sodium metabisulfite, erythorbic acid, FF6M are preferred.
8. The hydroxyacrylate emulsion for a two-component anti-graffiti topcoat varnish according to claim 1, wherein the neutralizing agent is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, AMP-95, triethylamine, sodium bicarbonate, triethanolamine. Preferably one or more of sodium hydroxide, ammonia water, AMP-95, and sodium bicarbonate.
9. The process for preparing a hydroxy acrylate emulsion for a two-component graffiti-resistant overcoat varnish according to claim 1, comprising the steps of:
step one, preparing a pre-emulsion: preparing the deionized water, the emulsifier, the vinyl-containing monomer, the hydroxyl acrylate monomer and the crosslinking monomer into pre-emulsion in an emulsion bottle;
step two, preparing a reaction bottle bottom solution: the deionized water and the emulsifier are arranged in a reaction bottle, stirred and heated to 80-86 ℃;
step three, reaction process: adding a primary initiator, beginning to simultaneously dropwise add the pre-emulsion and the initiator for 180-240 minutes, adding the crosslinking monomer into the pre-emulsion when the pre-emulsion is left 1/3, and keeping the temperature for 1 hour after dropwise adding;
step four, post-treatment process: after the heat preservation is finished, cooling to 55-60 ℃, adding post-treatment, dropwise adding an oxidant and a reducing agent for 30-60 minutes after the post-treatment, and preserving the heat for 30-60 minutes after the post-treatment;
and step five, finishing heat preservation, cooling, neutralizing, filtering and packaging.
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| PCT/CN2022/101248 WO2023165057A1 (en) | 2022-03-01 | 2022-06-24 | Hydroxyacrylate emulsion for two-component anti-doodling finishing varnish and preparation method therefor |
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| CN105254800A (en) * | 2015-11-05 | 2016-01-20 | 浩力森涂料（上海）有限公司 | Acrylate emulsion used for water-based metallic paint and preparation method thereof |
| CN110511388A (en) * | 2019-08-23 | 2019-11-29 | 湖北双键精细化工有限公司 | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing |
| CN111763287A (en) * | 2019-04-02 | 2020-10-13 | 万华化学集团股份有限公司 | Hydroxyl acrylic emulsion for water-based double-component anti-doodling and anti-sticking coating and preparation method thereof |
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| CN102101960B (en) * | 2010-12-24 | 2013-06-05 | 大连工业大学 | High-hydroxy silicon-acrylate aqueous glass coating emulsion and synthesis method thereof |
| CN105061665B (en) * | 2015-07-31 | 2018-06-22 | 华南理工大学 | A kind of hydroxy polyacrylate lotion and preparation method and application |
| TWI610992B (en) * | 2016-11-22 | 2018-01-11 | 南亞塑膠工業股份有限公司 | Water-based environmental protection coating with high hardness and high density characteristic and manufacturing method thereof |
| CN108440704B (en) * | 2018-02-28 | 2021-03-12 | 中山市巴德富化工科技有限公司 | Boiling water resistant high-adhesion double-component acrylate emulsion and preparation method thereof |
| CN110615875B (en) * | 2019-10-16 | 2022-10-25 | 佛山市顺德区巴德富实业有限公司 | Quick-drying anti-bulging hydroxyl emulsion for exterior wall coating and preparation method thereof |
| CN113308180B (en) * | 2021-05-24 | 2022-08-23 | 上海保立佳新材料有限公司 | Bi-component water-based hydroxyl acrylic polyurethane finish emulsion and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254800A (en) * | 2015-11-05 | 2016-01-20 | 浩力森涂料（上海）有限公司 | Acrylate emulsion used for water-based metallic paint and preparation method thereof |
| CN111763287A (en) * | 2019-04-02 | 2020-10-13 | 万华化学集团股份有限公司 | Hydroxyl acrylic emulsion for water-based double-component anti-doodling and anti-sticking coating and preparation method thereof |
| CN110511388A (en) * | 2019-08-23 | 2019-11-29 | 湖北双键精细化工有限公司 | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing |
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