CN116716029B - Long-acting antibacterial and antiviral polyester finishing paint and preparation method thereof - Google Patents
Long-acting antibacterial and antiviral polyester finishing paint and preparation method thereof Download PDFInfo
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- CN116716029B CN116716029B CN202310825466.4A CN202310825466A CN116716029B CN 116716029 B CN116716029 B CN 116716029B CN 202310825466 A CN202310825466 A CN 202310825466A CN 116716029 B CN116716029 B CN 116716029B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- 239000003973 paint Substances 0.000 title claims abstract description 49
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 48
- 229920000728 polyester Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920001225 polyester resin Polymers 0.000 claims abstract description 50
- 239000004645 polyester resin Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- -1 tertiary amine compounds Chemical class 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 239000003443 antiviral agent Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 6
- 239000000049 pigment Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920003180 amino resin Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000000845 anti-microbial effect Effects 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- SZCWBURCISJFEZ-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)COC(=O)C(C)(C)CO SZCWBURCISJFEZ-UHFFFAOYSA-N 0.000 claims description 6
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 6
- CVNPKVXQUCOSOI-UHFFFAOYSA-N 3-ethylheptane-2,3-diol Chemical compound CCCCC(O)(CC)C(C)O CVNPKVXQUCOSOI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- FTPAHNNMUYOHOB-UHFFFAOYSA-N 3-(bromomethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(CBr)=C1 FTPAHNNMUYOHOB-UHFFFAOYSA-N 0.000 claims description 2
- PBSUMBYSVFTMNG-UHFFFAOYSA-N 3-(chloromethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(CCl)=C1 PBSUMBYSVFTMNG-UHFFFAOYSA-N 0.000 claims description 2
- CQQSQBRPAJSTFB-UHFFFAOYSA-N 4-(bromomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CBr)C=C1 CQQSQBRPAJSTFB-UHFFFAOYSA-N 0.000 claims description 2
- OITNBJHJJGMFBN-UHFFFAOYSA-N 4-(chloromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CCl)C=C1 OITNBJHJJGMFBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 12
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000036541 health Effects 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 4
- 206010011409 Cross infection Diseases 0.000 abstract description 3
- 206010029803 Nosocomial infection Diseases 0.000 abstract description 3
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 208000015181 infectious disease Diseases 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000295 complement effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004321 preservation Methods 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002987 primer (paints) Substances 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 241000700605 Viruses Species 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical group CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 230000029812 viral genome replication Effects 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- 229920003275 CYMEL® 325 Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of paint, and in particular relates to a long-acting antibacterial and antiviral polyester finish paint and a preparation method thereof, wherein the finish paint comprises 20-35 parts of structural modified polyester resin, 3-10 parts of branched polyester resin, 6-10 parts of curing agent, 20-35 parts of pigment and filler, 1-3 parts of antibacterial and antiviral agent, 1-2 parts of auxiliary agent and 15-30 parts of solvent, and the structural modified polyester resin is formed by sequentially carrying out chemical reaction on polyester resin with hydroxyl groups, alpha-halogenated carboxylic acid and tertiary amine compounds. The polyester finishing paint disclosed by the invention combines the advantages of the additive type antibacterial and antiviral paint and has high antibacterial and antiviral efficiency, broad spectrum, stability and durability through the synergistic effect and complementary advantages; meanwhile, the paint film can be endowed with excellent chemical resistance and stain resistance, can be widely applied to the fields of household appliances and building materials, reduces the probability of cross infection and contact infection, and provides health and safety protection.
Description
Technical Field
The invention belongs to the technical field of paint, and in particular relates to a long-acting antibacterial and antiviral polyester finish paint and a preparation method thereof.
Background
With the improvement of living standard and the progress of science and technology, the fields of disease prevention, sanitation and safety, living environment and other microorganisms related to human health attract the eyes of more and more scientific researchers. Meanwhile, the industry is developed at a high speed, the living environment of human beings is further deteriorated, and bacteria, viruses and the like seriously threaten the health of human beings. There is a need for antimicrobial and antiviral activity in many areas of facilities, tools, buildings, etc. that people are exposed to in their daily life. The antibacterial and antiviral coating has antibacterial and antiviral functions on the surface of the coating and can prevent bacteria and microorganisms from growing, and the use of the antibacterial and antiviral coating is one of the most effective methods for realizing environmental pollution-free, antibacterial and bactericidal effects and antiviral effects, so that the antibacterial and antiviral coating is favored by all countries in the world in research and application, and becomes a new hot spot in the current scientific field. Development of a coating having antibacterial and antiviral functions is one of the directions of development of the coating industry.
The existing antibacterial and antiviral coating is generally realized by adopting an additive means, such as an inorganic antibacterial antiviral agent and a small molecular organic antibacterial antiviral agent. The antibacterial and antiviral coating prepared by the method has the defects of poor heat resistance, easy exudation, easy decomposition, easy migration, no washing resistance and short service life because the antibacterial and antiviral agent is in a free state, so that the antibacterial and antiviral agent is easy to migrate to the surface of the coating, and the use effect of the antibacterial and antiviral coating is reduced over time.
Meanwhile, for the paint applied to public areas where people gather in hospitals and the like, a large amount of chemical agents are required to be sprayed and scrubbed on the surface of the paint to realize disinfection, so that the environment is maintained. The disinfectant often has strong oxidizing property, is easy to cause irreversible erosion to the coating, and the severe use condition further tests the durability of the coating. Conventional coatings on the market at present cannot effectively block corrosion of the disinfectant to the coating and the substrate. It is therefore important to develop a coating that effectively prevents corrosion of the coating and substrate by the disinfectant.
Disclosure of Invention
In order to solve the technical problems, the invention provides a long-acting antibacterial and antiviral polyester finishing paint, which comprises the following components in parts by weight:
Wherein the structural modified polyester resin is formed by sequentially carrying out chemical reaction on polyester resin with hydroxyl-terminated groups and alpha-halogenated carboxylic acid and tertiary amine compounds.
As preferable: the polyester resin with terminal hydroxyl groups is obtained by esterification reaction of dihydric alcohol and dibasic acid, wherein the dihydric alcohol comprises one or a combination of more than one of neopentyl glycol hydroxypivalate monoester, ethyl butyl propylene glycol BEPD and 2, 4-trimethyl-1, 3-pentanediol, wherein the sum of the mole numbers of the neopentyl glycol hydroxypivalate monoester, the ethyl butyl propylene glycol BEPD and the 2, 4-trimethyl-1, 3-pentanediol and the total mole number of the dihydric alcohol is 0.05-0.15: 1.
In addition, the dihydric alcohol can also comprise one or a combination of more of neopentyl glycol, methyl propylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol and 3-methyl-1, 5-pentanediol.
In addition, the dibasic acid is one or a combination of a plurality of adipic acid, hexahydrophthalic anhydride, 1, 4-cyclohexanedicarboxylic acid and 1, 2-cyclohexanedicarboxylic acid.
Further: the ratio of the mol number of hydroxyl groups contained in the dihydric alcohol to the mol number of carboxyl groups contained in the dibasic acid is 1.1-1.3: 1.
As preferable: the ratio of the number of moles of hydroxyl groups of the polyester resin having terminal hydroxyl groups to the number of moles of carboxyl groups of the α -halogenated carboxylic acid was 1:0.05 to 0.15, the mole ratio of the tertiary amine compound and the alpha-halogenated carboxylic acid is 1.05 to 1.5:1.
As preferable: the alpha-halogenated carboxylic acid is one or a combination of a plurality of 3- (chloromethyl) benzoic acid, 4- (chloromethyl) benzoic acid, 3- (bromomethyl) benzoic acid and 4- (bromomethyl) benzoic acid.
As preferable: the tertiary amine compound has long alkyl chain with carbon number not less than 14 in molecular structure and is one or several of tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, bisdodecyl tertiary amine and docosyl dimethyl tertiary amine.
As preferable: when the structural modified polyester resin is formed by chemical reaction, the mixture of dihydric alcohol, dibasic acid and esterification catalyst is heated to 140 ℃ at the speed of 10 ℃/h under the continuous stirring state for reflux reaction for 1-2 hours, then heated to 200 ℃ for heat preservation reaction for 1-2 hours, and then heated to 230 ℃ for heat preservation reaction until the acid value of the reaction system is stable; cooling to 200 ℃, adding alpha-halogenated carboxylic acid, heating to 230 ℃ for heat preservation reaction until the acid value of a reaction system is stable, cooling to 180 ℃, adding tertiary amine compound, continuing heat preservation reaction for 1-2 hours, cooling, and filtering to obtain filtrate, namely the structural modified polyester resin, wherein the esterification catalyst is monobutyl tin oxide.
As preferable: the branched polyester resin is a branched saturated polyester resin with terminal hydroxyl groups, the acid value of the branched saturated polyester resin is 0-8 mgKOH/G, the number average molecular weight is 2000-4500, the hydroxyl value is 35-100 mgKOH/G, such as the commercially available big desert new material types CL271, CL151, CL150, C7621, G9630, CB226, CD426, and Korean SK company type ES710 and ES 750.
As preferable: the curing agent is a combination of blocked polyisocyanate resin and amino resin, and the amino resin is at least one of full methyl ether amino resin and high imino amino resin, such as commercial resin products with the model numbers of CYMEL303, CYMEL325 and the model numbers of Resimene-747 and Resimene-717 of Cyanum company; the blocked polyisocyanate resin is a trimeric isocyanate and may be selected from DESMODUR BL3175 available from Bayer, B1358 available from Evonik or similar blocked isocyanate resins available from the market.
As preferable: the pigment and filler is one or a combination of more of titanium white, carbon black, iron oxide red and iron oxide yellow.
As preferable: the antibacterial antiviral agent is silver-carrying phosphate substances, and the phosphate used as carrier comprises degradable calcium phosphate substances such as tricalcium phosphate, tetracalcium phosphate, hydroxyapatite, etc.
As preferable: the auxiliary agent is at least one of dispersing agent, defoaming agent, leveling agent and curing catalyst,
The dispersing agent is at least one selected from AFCONA-4010, AFCONA-4017, AFCONA-4060, AFCONA-4070, AFCONA-4080,
The defoaming agent is a non-silicon defoaming agent, is at least one of BYK-054, BYK-352 and BYK-057,
The leveling agent is a non-silicon leveling agent, and is at least one selected from the group consisting of model numbers AFCONA-3700, AFCONA-3750, AFCONA-3773, AFCONA-3775, AFCONA-3777 and AFCONA-3779,
The curing catalyst comprises an acid catalyst selected from at least one of NACURE1419, NACURE1051, NACURE2500, NACURE 5225.
As preferable: the solvent is at least one of butanol, propylene glycol methyl ether acetate, S-100# aromatic hydrocarbon solvent, S-150# aromatic hydrocarbon solvent and dibasic ester DBE.
The invention also provides a preparation method of the long-acting antibacterial and antiviral polyester finishing paint, which comprises the following steps:
(1) Mixing 30-50% of structural modified polyester resin with a dispersing agent and pigment and filler, adding 30-50% of solvent, and grinding to obtain slurry;
(2) Adding the rest structural modified polyester resin, branched polyester resin, antibacterial antiviral agent and the rest auxiliary agent except the dispersing agent into the slurry obtained in the step (1), mixing, then adding the curing agent and the rest solvent, and mixing to obtain the long-acting antibacterial antiviral polyester finish paint.
The invention has the beneficial effects that:
The structural modified polyester resin in the polyester finishing paint component is prepared by the reaction (Menschutkin reaction) of alpha-halogenated carboxylic acid, tertiary amine compound and linear polyester resin with terminal hydroxyl, so that antibacterial and antiviral functional groups are generated, the steric hindrance density of a resin chain can be improved, and the steric hindrance is higher.
On the one hand, the generated quaternary ammonium salt group with antibacterial and antiviral functions is combined with polyester resin chemical bonds, and the slow-release antibacterial and antiviral application is realized through the functional groups, so that the defects of unstable performance and short service life of the traditional antibacterial and antiviral coating can be avoided. The antimicrobial and antiviral factors in the finish paint are combined with amide bonds and sulfhydryl groups on protein peptide bonds to inhibit virus replication, kill viruses and bacteria at the same time, destroy living environments of the bacteria, and achieve dual effects of antimicrobial and antiviral, and the finish paint combines the advantages of the additive type antimicrobial and antiviral coating, and shows high efficiency, broad spectrum, stability and lasting antimicrobial and antiviral performance through synergistic effect and advantage complementation of the two;
Meanwhile, glycol serving as a repeating unit of the linear polyester resin, neopentyl glycol hydroxypivalate monoester, ethyl butyl propylene glycol and 2, 4-trimethyl-1, 3-pentanediol all have a side group distribution structure with strong stereoscopicity and appear in the form of a repeating unit, and two methyl groups and one long-chain alkyl group are simultaneously connected to a polar quaternary ammonium salt group generated by reaction on the linear polyester resin, so that the terminal branching effect of the linear polyester resin is endowed, the steric hindrance density of a structural modified polyester resin chain is improved together, the structural modified polyester resin chain has higher steric hindrance, and the finishing paint is endowed with excellent chemical resistance and stain resistance. Therefore, the polyester finishing paint is particularly suitable for being applied to base materials with chemical corrosion risks besides broad-spectrum antibacterial application, such as places where people gather, such as hospitals, and the like, equipment and building material surfaces of the polyester finishing paint can be sprayed and scrubbed with corrosive chemical agents very frequently, so that ideal chemical resistance can ensure long-term existence of finishing paint coatings in the places, and the antibacterial and antiviral coating effects are exerted.
The curing agent of the finish paint adopts the combination of the closed polyisocyanate resin and the amino resin, so that the effective balance of the hardness and the flexibility of a paint film is realized, the paint film simultaneously has ideal processability and hardness, and the finish paint can be used as coiled material paint: after the finish paint is formed into a film, the coating can be prevented from cracking and falling off in the process of being processed together with the base material. Meanwhile, the quaternary ammonium salt group in the paint film can better and longer exert the antibacterial and antiviral effects.
The polyester finish paint has simple preparation method, meets the production requirements of green and environment protection, and is easy for mass production. The coating can be widely applied to coil coating in the fields of household appliances and building materials, reduces the probability of cross infection and contact infection, provides health and safety protection, and meets the requirements of diversification and functionalization.
Detailed Description
The structurally modified polyester resins a to V in table 1 were prepared as follows (both structurally modified polyester resins U and V are adjustments made on the basis of structurally modified polyester resin L):
(1) Adding dihydric alcohol (II in table 1), dibasic acid (I in table 1), monobutyl tin oxide 0.25g and dimethylbenzene 80g into a clean reaction bottle provided with a stirrer, a thermometer, a water separator, a condenser pipe and an inert gas inlet, continuously stirring and protecting the inert atmosphere, heating the materials to 140 ℃ at a speed of 10 ℃/h for reflux reaction for 1 hour after the components are fully mixed, heating to 200 ℃ for heat preservation reaction for 2 hours, heating to 230 ℃ for heat preservation reaction until the acid value of a reaction system is stable, and obtaining the linear polyester resin with terminal hydroxyl groups, and cooling the materials to 200 ℃;
(2) And (3) maintaining the stirring and inert atmosphere protection state of the step (1), adding alpha-halogenated carboxylic acid (III in table 1) into the reaction system obtained in the step (1), heating to 230 ℃ for heat preservation reaction until the acid value of the reaction system is stable, cooling to 180 ℃, adding tertiary amine compound (IV in table 1), continuing heat preservation reaction for 2 hours, cooling, and filtering to obtain filtrate, namely the structural modified polyester resin.
The specific choices of the reactants are shown in table 1:
TABLE 1
Based on each of the structurally modified polyester resins in table 1, a long-acting antimicrobial and antiviral polyester topcoat was formulated separately (comparative example 1 and comparative example 2 each had structural modified polyester resin adjusted based on example 12, the remaining components unchanged; comparative example 3 and comparative example 3 each had curing agent adjusted based on example 38, the remaining components unchanged), the formulation procedure was as follows:
(1) Firstly, 50% by weight of structural modified polyester resin, a dispersing agent and pigment and filler are mixed, then 50% by weight of solvent is added, grinding and mixing are carried out fully to obtain slurry, wherein the slurry is ground to below 15 mu m;
(2) Adding the rest of the structural modified polyester resin, the branched polyester resin, the antibacterial antiviral agent and the rest of the auxiliary agent into the slurry in the step (1) and mixing; then adding the curing agent and the residual solvent, mixing thoroughly, and filtering to obtain the long-acting antibacterial and antiviral polyester finishing paint.
The specific selection and weight portions of the components are shown in Table 2:
TABLE 2
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The description is as follows: comparative example 1 on the basis of example 12, neopentyl glycol hydroxypivalate monoester, ethylbutyl propylene glycol BEPD or 2, 4-trimethyl-1, 3-pentanediol were not contained in the synthesis of the structurally modified polyester resin, and thus are not within the scope of the present invention; comparative example 2 on the basis of example 12, the process of synthesizing the structurally modified polyester resin does not contain quaternary ammonium salt groups and is therefore not within the scope of the present invention; comparative example 3 on the basis of example 38, the curing agent was only an amino resin and therefore was not within the scope of the present invention; comparative example 4 the curing agent was only a blocked polyisocyanate resin based on example 38 and therefore was not within the scope of the present invention.
The coating film forming process comprises the following steps: primer + topcoat
And (3) primer coating and film forming: the HY-JD-101 white primer manufactured by Changzhou environmental protection paint Co., ltd., china sea oil is coated on a pretreated galvanized steel sheet with the thickness of 12cm multiplied by 15cm multiplied by 0.5mm by a wire rod, and the steel sheet is baked in an oven at 300 ℃ for 40s, and the temperature PMT of the steel sheet is as follows: 224 ℃ to obtain a primer layer with the film thickness of 8-10 mu m;
and (3) finishing paint coating to form a film: the long-acting antibacterial and antiviral polyester finishing paint prepared in each example and comparative example is respectively coated on the surface of the primer layer by a wire rod roller, and then the primer layer is baked for 40 seconds in a baking oven at 300 ℃, and the steel plate temperature PMT is as follows: 224℃and a topcoat layer with a film thickness of 14-16. Mu.m.
The finish paint layers formed by the long-acting antibacterial and antiviral polyester finish paint of the examples 1 to 40 through the operation are detected to meet various quality standards, and the quality standards are shown in the table 3:
TABLE 3 Table 3
The performance of the finish paint layers formed by the long-acting antibacterial and antiviral polyester finish paint of comparative examples 1 to 4 through the above operation is shown in the following table 4:
TABLE 4 Table 4
As can be seen from tables 3 and 4 above:
(1) The high-performance polyester finishing paint prepared by the invention grafts the groups with antibacterial and antiviral functions on the polymer chain of the base resin in a chemical bond form, adopts a slow-release antibacterial and antiviral technology, inhibits virus replication through the complexation of an antiviral factor with an amide bond and a sulfhydryl group on a protein peptide bond, kills bacteria while killing the viruses, destroys the living environment of the bacteria, and achieves the dual effects of resisting bacteria and viruses; the advantages of the additive type antibacterial and antiviral coating and the structural type antibacterial and antiviral coating are combined, and the synergistic effect and the advantage complementation of the additive type antibacterial and antiviral coating can be widely applied to the fields of household appliances and building materials, the probability of cross infection and contact infection is reduced, and health safety protection is provided. The base material carrying the finishing paint has a double-layer super-resistant barrier layer (one layer is the chemical resistance guarantee of a resin structure in the finishing paint, and the other layer is the chemical resistance guarantee provided by a final paint film after curing), has excellent chemical resistance and stain resistance, has antibacterial and antiviral properties with high efficiency, broad spectrum, stability and durability, and has excellent antibacterial and antiviral effects.
(2) In the structurally modified polyester resin of comparative example 1, the repeating unit having a structure of a distribution of a steric side group is not contained, and thus the steric hindrance effect of the polyester resin chain is weak, resulting in poor chemical resistance.
(3) Comparative example 2, which does not contain quaternary ammonium salt groups, is not the structural modified polyester resin of the present invention, resulting in weakening of antibacterial and antiviral durability; the resin structure loses the terminal branching effect brought by the polar quaternary ammonium salt group, so that the steric hindrance effect is also influenced, and the performance of hydrogen peroxide resistance is poor.
(4) In comparative example 3, the curing agent contained only an amino resin, the flexibility of the paint film was deteriorated as compared with example 38, and the crosslinked structure formed by only an amino resin greatly hindered migration of the additive type antibacterial antiviral agent inside the paint film to the surface of the paint film, and thus the antiviral property was poor.
(5) In comparative example 4, the curing agent contained only the blocked polyisocyanate resin, the paint film was soft, the degree of crosslinking was insufficient, and the hardness was insufficient.
It should be understood that the above examples are only preferred embodiments of the present application and are intended to illustrate specific embodiments of the technical solution of the present application, but not to limit the scope of the present application. It should be noted that: modifications and equivalents may be made by those skilled in the art after reading the present application without departing from the principles of the application, and such modifications and equivalents fall within the scope of the application as defined in the claims.
Claims (3)
1. A long-acting antibacterial and antiviral polyester finishing paint is characterized in that: the finishing paint comprises the following components in parts by weight
Structural modified polyester resin 20-35 parts
3-10 Parts of branched polyester resin
6-10 Parts of curing agent
Pigment and filler 20-35 parts
1-3 Parts of antibacterial antiviral agent
1-2 Parts of auxiliary agent
15-30 Parts of a solvent,
Wherein the structural modified polyester resin is formed by chemical reaction of polyester resin with hydroxyl end groups and alpha-halogenated carboxylic acid and tertiary amine compounds in sequence,
The polyester resin with hydroxyl ends is obtained by esterification reaction of dihydric alcohol and dibasic acid, wherein the dihydric alcohol comprises one or a combination of more than one of neopentyl glycol hydroxypivalate monoester, ethyl butyl propylene glycol BEPD and 2, 4-trimethyl-1, 3-pentanediol, wherein the sum of the mole numbers of the neopentyl glycol hydroxypivalate monoester, the ethyl butyl propylene glycol BEPD and the 2, 4-trimethyl-1, 3-pentanediol is 0.05-0.15: 1,
The alpha-halogenated carboxylic acid is one or a combination of a plurality of 3- (chloromethyl) benzoic acid, 4- (chloromethyl) benzoic acid, 3- (bromomethyl) benzoic acid and 4- (bromomethyl) benzoic acid,
The tertiary amine compound is one or a combination of more of tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, bisdodecyl tertiary amine and docosyl dimethyl tertiary amine,
The ratio of the number of moles of hydroxyl groups of the polyester resin having hydroxyl groups at the end to the number of moles of carboxyl groups of the α -halogenated carboxylic acid is 1:0.05 to 0.15, wherein the molar ratio of the tertiary amine compound to the alpha-halogenated carboxylic acid is 1.05 to 1.5:1,
The branched polyester resin is branched saturated polyester resin with terminal hydroxyl, the acid value is 0-8 mgKOH/g, the number average molecular weight is 2000-4500, the hydroxyl value is 35-100 mgKOH/g,
The curing agent is a combination of a closed polyisocyanate resin and an amino resin,
The auxiliary agent is at least one of dispersing agent, defoaming agent, leveling agent and curing catalyst.
2. The long-acting antimicrobial antiviral polyester topcoat as set forth in claim 1, wherein: the ratio of the mole number of hydroxyl groups contained in the dihydric alcohol to the mole number of carboxyl groups contained in the dibasic acid is 1.1-1.3: 1.
3.A method for preparing the long-acting antibacterial and antiviral polyester finishing paint as claimed in claim 1, which is characterized in that: comprises the following steps of the method,
(1) Mixing 30-50% of the structural modified polyester resin with a dispersing agent and the pigment and filler, adding 30-50% of the solvent, and grinding to obtain slurry;
(2) Adding the rest of the structural modified polyester resin, the branched polyester resin, the antibacterial antiviral agent and the rest of the auxiliary agent except the dispersing agent into the slurry obtained in the step (1), mixing, then adding the curing agent and the rest of the solvent, and mixing to obtain the long-acting antibacterial antiviral polyester finishing paint.
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| CN114437612A (en) * | 2020-11-05 | 2022-05-06 | 立邦工业涂料(上海)有限公司 | Deep embossing resistant antibacterial/antiviral coating composition and application |
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| BR112013024482A2 (en) * | 2011-03-25 | 2017-02-14 | Dsm Ip Assets Bv | resin compositions for thermosetting powder coating compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107434950A (en) * | 2017-08-31 | 2017-12-05 | 浙江天女集团制漆有限公司 | A kind of colored steel coil coating polyurethane primer |
| CN108070077A (en) * | 2017-11-14 | 2018-05-25 | 湖州南浔嘉骏化工有限公司 | A kind of high durable saturated polyester resin and preparation method |
| CN114437612A (en) * | 2020-11-05 | 2022-05-06 | 立邦工业涂料(上海)有限公司 | Deep embossing resistant antibacterial/antiviral coating composition and application |
| CN112646159A (en) * | 2020-12-21 | 2021-04-13 | 浙江光华科技股份有限公司 | Preparation method of quaternary ammonium salt modified polyester resin for antibacterial powder coating |
| CN113604137A (en) * | 2021-04-03 | 2021-11-05 | 中海油常州涂料化工研究院有限公司 | Scratch-resistant epoxy modified polyester back paint for coiled material with high coating rate and preparation method thereof |
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