CN116649363A - Antibacterial composition and preparation method thereof, protective coating finish paint and preparation method thereof - Google Patents
Antibacterial composition and preparation method thereof, protective coating finish paint and preparation method thereof Download PDFInfo
- Publication number
- CN116649363A CN116649363A CN202310520070.9A CN202310520070A CN116649363A CN 116649363 A CN116649363 A CN 116649363A CN 202310520070 A CN202310520070 A CN 202310520070A CN 116649363 A CN116649363 A CN 116649363A
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- Prior art keywords
- parts
- protective coating
- rosin
- paint
- antibacterial composition
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- 239000003973 paint Substances 0.000 title claims abstract description 78
- 239000011253 protective coating Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 43
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 39
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 39
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims description 33
- 229920000647 polyepoxide Polymers 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 16
- 239000002562 thickening agent Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 12
- 229910000278 bentonite Inorganic materials 0.000 claims description 12
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 12
- 229910021485 fumed silica Inorganic materials 0.000 claims description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- 230000000845 anti-microbial effect Effects 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims 3
- 239000004927 clay Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 20
- 238000005336 cracking Methods 0.000 abstract description 13
- 244000005700 microbiome Species 0.000 abstract description 11
- 230000007774 longterm Effects 0.000 abstract description 7
- 241000894006 Bacteria Species 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 19
- 239000002519 antifouling agent Substances 0.000 description 17
- 239000004952 Polyamide Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical group CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 4
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000004901 spalling Methods 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 3
- 230000003588 decontaminative effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- -1 silver ions Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses an antibacterial composition and a preparation method thereof, protective coating finish paint and a preparation method thereof, wherein the preparation method of the antibacterial composition comprises the following steps: taking a proper amount of rosin, dividing the rosin into two parts, dissolving one part of rosin in an alcohol solvent, adding the solution into a mixed solution of silver nitrate and an alkaline slow-release agent, heating to 100-110 ℃, further cooling to room temperature, washing, drying, and uniformly mixing with the rest part of rosin to obtain the antibacterial composition. The protective coating finishing paint containing the antibacterial composition has good gloss, effectively improves the weather resistance, heat resistance and water resistance of the protective coating finishing paint, reduces the phenomena of peeling, cracking and chalking of a paint film, can inhibit microorganisms and fouling organisms in a humid environment from adhering to nuclear power plant equipment, inhibits the growth of microorganisms and bacteria, reduces the moisture absorption phenomenon of a coating, and enables the protective coating paint film to adapt to the working environment of the nuclear power plant with long-term irradiation and high temperature.
Description
Technical Field
The invention particularly relates to an antibacterial composition and a preparation method thereof, and protective coating finishing paint containing the antibacterial composition and a preparation method thereof.
Background
The nuclear power plant can realize the transformation of the fission energy into the electric energy, and generates heat energy through fission to generate power or generate power and supply heat, and the containment is the central part of the nuclear power plant. The presence of large amounts of radioactive and high-emissivity materials in the nuclear power plant environment can create intense radiation that can accelerate the aging and damage of equipment materials, reducing the functionality of the containment system.
The surface of concrete and steel structures in the containment of a nuclear power plant can be coated with a protective coating to form a protective coating for the life-time aging relief and corrosion protection. The radioactive irradiation can cause spalling, cracking and pulverization of the protective coating, so that a large amount of residues enter the total emergency cooling liquid of the reactor in the containment, and the blockage of equipment such as pipelines, nozzles, pumps and the like is caused, thereby bringing about serious safety accidents. Thus, protective coatings are required to meet the requirements of radiation resistance, ageing resistance and stain removal.
The common matched protective paint is formed by combining oily epoxy primer and epoxy finish paint, so that the protective paint and a base material can be kept to have good adhesive force, but the traditional epoxy finish paint is poor in weather resistance and heat resistance, and a paint film is easy to appear in the phenomena of peeling, cracking and pulverization of powder under the working environment of long-term irradiation and high temperature of a nuclear power plant; in addition, the traditional finishing paint is easy to absorb moisture, bacteria are easy to grow in a humid environment for a long time, and the base material is damaged, so that the traditional coating finishing paint is difficult to adapt to long-term service maintenance requirements in a containment vessel of a nuclear power plant.
Disclosure of Invention
In view of the above, in order to overcome the defects of the prior art, the invention aims to provide an antibacterial composition and a preparation method thereof, and a protective coating finish containing the antibacterial composition and a preparation method thereof, which are used for improving the weather resistance and heat resistance of the protective coating finish, enhancing the antibacterial performance of a coating and reducing the phenomenon of moisture absorption of the coating.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an object of the present invention is to provide a method for preparing an antibacterial composition, comprising the steps of:
taking a proper amount of rosin, dividing the rosin into two parts, dissolving one part of rosin in an alcohol solvent, adding the solution into a mixed solution of silver nitrate and an alkaline slow-release agent, heating to 100-110 ℃, further cooling to room temperature, washing, drying, and uniformly mixing with the rest part of rosin to obtain the antibacterial composition.
The abietic acid is contained in the rosin, silver ions in the silver nitrate can be reduced to form nano silver, so that microorganisms and fouling organisms in a humid environment are inactivated, and the adhesion and propagation of the microorganisms on the surface of a paint film are inhibited. And the generated nano silver can be stably protected by fatty acid in rosin, so that the phenomenon that the nano silver is agglomerated in a coating system is reduced, and the nano silver is promoted to be uniformly dispersed in the coating system. The protective effect of the rosin on the nano silver can lead the antibacterial performance of the nano silver to have a certain slow release effect, and lead the antibacterial and anti-fouling performance of the paint to be longer.
According to some preferred embodiments of the invention, the mass of the rosin is equal for both parts.
According to some preferred embodiments of the invention, the alkaline slow-release agent is aqueous ammonia.
It is another object of the present invention to provide an antibacterial composition prepared by the above-mentioned preparation method of an antibacterial composition.
The invention also aims to provide a protective coating finishing paint which comprises a component A and the antibacterial composition, wherein the component A comprises the following raw material components in parts by weight: 30-40 parts of waterborne phenolic epoxy resin and 3-8 parts of silane coupling agent;
the antibacterial composition comprises the following raw material components: 3-8 parts of rosin, 3-8 parts of silver nitrate, 2-3 parts of an alkaline slow-release agent and 8-10 parts of an alcohol solvent.
The water-based phenolic epoxy resin is adopted as the main raw material to replace phenolic epoxy resin used in the prior art, and the water-based phenolic epoxy resin has excellent adhesive force and good impact resistance of the epoxy resin, and also has good water resistance, ageing resistance and solvent resistance. The paint finish paint formed by taking the aqueous phenolic epoxy resin as the main raw material also has outstanding antirust effect and dimensional stability, and improves the problem of film shrinkage. On the other hand, the waterborne phenolic epoxy resin also has excellent heat resistance and weather resistance, so that the problem that the common epoxy resin is easy to pulverize is solved, the heat resistance of the protective coating is improved, and the waterborne phenolic epoxy resin can be better adapted to the working environment with long-term high temperature. Because rosin has a unique honeycomb structure, the rosin is added into the waterborne phenolic epoxy resin, so that the formed paint film has certain viscoelasticity and luster, and the film forming performance of the rosin is good, so that a layer of protective film is formed on the surface of the paint film, the water resistance of the paint film is improved, and the phenomenon of moisture absorption of the paint film of the protective paint is reduced; the abietic acid is contained in the rosin, so that silver ions in the silver nitrate can be reduced to form nano silver, and the nano silver can inactivate microorganisms and fouling organisms in a humid environment and inhibit the microorganisms from adhering and propagating on the surface of a paint film. And the generated nano silver can be stably protected by fatty acid in rosin, so that the phenomenon that the nano silver is agglomerated in a coating system is reduced, and the nano silver is promoted to be uniformly dispersed in a water-based phenolic epoxy resin system. The protective effect of the rosin on the nano silver can lead the antibacterial performance of the nano silver to have a certain slow release effect, and lead the antibacterial and anti-fouling performance of the paint to be longer.
Further, the thickener can improve the fluidity of the aqueous phenolic epoxy resin system, enhance the viscosity of the aqueous phenolic epoxy resin system, promote the protective coating finishing paint to form a good paint film, and further reduce the cracking and peeling phenomena of the coating. The anti-flash rust agent has corrosion inhibition performance, and can reduce the flash rust phenomenon generated when the protective coating is solidified on nuclear power plant equipment. The anti-settling agent is beneficial to introducing loose network thixotropic structure into a paint finish paint system, and promotes the components of pigment, thickener and the like of the finish paint to suspend but not settle, so that the finish paint has excellent leveling property, thereby improving the weather resistance of the paint and enabling the paint to be better suitable for the working environment of a nuclear power plant. The silane coupling agent can promote the compatibility of filler, water-based phenolic epoxy resin and other components in the paint, enhance the adhesive force between the protective paint finish and the primer and between the protective paint finish and the base material, reduce the peeling and cracking phenomena of the protective paint film, and improve the water resistance, weather resistance and wear resistance of the protective paint finish.
According to some preferred embodiments of the present invention, the raw material of the component A further comprises 0.5-1 part of a thickener, 0.5-1 part of a flash rust inhibitor, 1-3 parts of an anti-settling agent, 5-20 parts of a filler and 1-3 parts of radiation resistant particles in parts by weight. The radiation-resistant particles are added into the raw materials of the protective coating finish paint, so that the coating has better radiation-resistant performance, and the influence of radioactive and high-radiation substances in a nuclear power plant on the coating is reduced, thereby reducing the phenomena of spalling, cracking and pulverization of the protective coating, and enabling the protective coating to be better suitable for the high-radiation working environment.
According to some preferred embodiments of the invention, the filler is a mixture of at least two of talc, barium sulfate and mica. The barium sulfate has excellent chemical corrosion resistance and weather resistance, can promote the coating to keep good glossiness, has certain reflectivity, and improves the ageing resistance of a paint film. The talcum powder is not easy to sink, and can absorb the expansion stress of the coating, thereby reducing cracks and gaps generated by the coating and improving the weather resistance of the protective coating finish paint. The mica powder can improve the toughness and heat resistance of the coating, and meanwhile, the mica powder and talcum powder also have excellent radiation resistance, corrosion resistance and decontamination capability, so that the radiation resistance, ageing resistance and decontamination capability of the protective coating are improved, and nuclear power plant equipment is better protected.
According to some preferred embodiments of the invention, the anti-settling agent is a mixture of fumed silica and bentonite.
According to some preferred embodiments of the invention, the mass ratio of fumed silica to bentonite is 0.1-5:1.
According to some preferred embodiments of the invention, the fumed silica has a particle size of 30-40nm and the bentonite has a particle size of 150-250 mesh. The fumed silica has small particle size, has the excellent performances of large specific surface area, strong surface adsorption force, large surface energy and the like, has good dispersibility, can generate a certain adsorption effect with the filler, and promotes the filler particles to be better dispersed. The bentonite has good thixotropic property, dispersibility and suspension property, can reduce the phenomenon of layering and precipitation of the paint finish, and further reduces chalking of the protective coating.
According to some preferred embodiments of the present invention, the protective coating top coat further comprises a curing agent in parts by weight, and the mass ratio of the component A to the curing agent is 2.5-4:1. In some embodiments of the invention, the curing agent is polyamide curing agent, and the polyamide curing agent is used as the curing agent in the aqueous phenolic epoxy resin system, so that the curing efficiency of the paint finishing paint can be accelerated, the adhesive force between the paint finishing paint and the substrate can be enhanced, and the corrosion resistance and impact resistance of a paint film can be improved.
Further, the raw material component of the component A also comprises 0.5-1 part of solvent, wherein the solvent is propylene glycol monobutyl ether or ethylene glycol butyl ether. The propylene glycol monobutyl ether or ethylene glycol butyl ether is added into the water-based phenolic epoxy resin, so that the water-based phenolic epoxy resin and the curing agent have a certain solubilization function, the crosslinking density of the water-based phenolic epoxy resin and the curing agent can be promoted, the surface tension of a paint film can be reduced, the wettability of the paint finishing paint is improved, the better combination of the protective paint finishing paint, a primer and a base material is further promoted, and the phenomena of spalling and cracking of the paint film are reduced. Specifically, in some embodiments of the present invention, component A comprises, by weight, 30-40 parts of an aqueous novolac epoxy resin, 0.5-1 part of a thickener, 0.5-1 part of an anti-flash rust agent, 1-3 parts of an anti-settling agent, 3-8 parts of a silane coupling agent, 20-30 parts of water, 5-20 parts of a filler, 1-3 parts of anti-radiation particles, and 0.5-1 part of a solvent.
The invention also aims to provide a preparation method of the protective coating finishing paint, which comprises the following steps:
(1) Preparation of an antibacterial composition: taking a proper amount of rosin, equally dividing the rosin into two parts, dissolving a part of rosin in an alcohol solvent, adding the solution into a mixed solution of silver nitrate and an alkaline slow-release agent, stirring at a speed of 200-400r/min, heating to 100-110 ℃, stopping heating when the color of the solution becomes brown, continuing stirring for 10-30min, further cooling to room temperature, washing by using the alcohol solvent, centrifugally separating to obtain solid particles, and drying to obtain nano silver particles; and uniformly mixing the prepared nano silver particles with the rest of rosin to obtain the antibacterial composition.
(2) Mixing water, filler and radiation-resistant particles, stirring at 700-900r/min for 10-30min, grinding by a grinder until the granularity of the mixture is 25-35 mu m, adding a thickening agent, an anti-settling agent and an anti-flash rust agent while stirring, stirring at 300-500r/min for 10-20min, adding aqueous phenolic epoxy resin, a solvent and a silane coupling agent to obtain a component A, adding an antibacterial composition into the component A, and stirring at 300-500r/min for 3-5min to uniformly mix the mixture;
(3) And (3) adding a curing agent into the mixture obtained in the step (2), and stirring to uniformly mix the curing agent and the mixture, so that the protective coating finishing paint can be prepared.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the raw material of the protective paint finishing paint adopts the water-based phenolic epoxy resin, has excellent impact resistance, dimensional stability and acid and alkali resistance, has stronger adhesive force with a base material, has better heat resistance and weather resistance, can reduce the phenomena of peeling, cracking and chalking of a protective paint film, and promotes the protective paint film to better adapt to the working environment of long-term irradiation and high temperature of a nuclear power plant;
2. the antibacterial composition is prepared from rosin and silver nitrate, so that the waterproof performance of the protective coating is improved, the moisture absorption phenomenon of the coating is reduced, and the gloss of a paint film of the protective coating is also improved; the nano silver obtained by taking silver nitrate as a raw material and abietic acid in rosin as a reducing agent can play an antibacterial role in coating finishing paint, inhibit microorganisms and fouling organisms in a humid environment from adhering to nuclear power plant equipment, inhibit the growth of the microorganisms and bacteria, and enhance the protective effect of protective coating finishing paint on a substrate.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The preparation method of the protective coating finishing paint in the embodiment comprises the following steps:
(1) Preparation of an antibacterial composition: taking 5 parts of rosin according to parts by weight, equally dividing the 5 parts of rosin into two parts, wherein each part contains 2.5 parts of rosin, dissolving 2.5 parts of rosin in 9 parts of ethanol solvent, adding the solution into a mixed solution of 5 parts of silver nitrate and 3 parts of ammonia water, heating to 110 ℃ while stirring at the speed of 300r/min, stopping heating when the color of the solution becomes brownish yellow, continuing stirring for 20min, cooling to room temperature, washing by using the ethanol solvent, centrifuging to obtain solid particles, and drying to obtain nano silver particles; and uniformly mixing the prepared nano silver particles with the rest 2.5 parts of rosin to prepare the antibacterial composition.
(2) According to parts by weight, 25 parts of water, 4 parts of talcum powder, 4 parts of barium sulfate, 4 parts of mica and 2 parts of radiation-resistant particles are mixed, stirred at a speed of 800r/min for 20min, then ground by a grinder until the granularity of the mixture is 25-35 mu m, then 0.8 part of thickener, 1 part of fumed silica, 1 part of bentonite and 0.8 part of flash rust inhibitor are added while stirring, stirred at a speed of 400r/min for 15min, then 35 parts of water-based phenolic epoxy resin, 0.8 part of propylene glycol monobutyl ether and 5 parts of silane coupling agent are added to obtain a component A, and then the antibacterial composition prepared in the step (1) is fully added into the component A, and stirred at a speed of 400r/min for 5min to uniformly mix the mixture.
(3) And (3) adding a polyamide curing agent into the mixture obtained in the step (2) and stirring to uniformly mix the polyamide curing agent and the polyamide curing agent, wherein the mass ratio of the polyamide curing agent to the component A is 3:1.
Example 2
This example differs from example 1 in that 8 parts by weight of silver nitrate was added in step (1), and the remaining steps and parameters were the same.
Example 3
This example differs from example 1 in that 3 parts by weight of silver nitrate was added in step (1), and the remaining steps and parameters were the same.
Comparative example 1
The preparation method of the protective coating finishing paint in the comparative example comprises the following steps:
according to parts by weight, 25 parts of water, 4 parts of talcum powder, 4 parts of barium sulfate, 4 parts of mica and 2 parts of radiation-resistant particles are mixed, stirred at a speed of 800r/min for 20min, then ground by a grinding machine until the granularity is 25-35 mu m, then 0.8 part of thickener, 1 part of fumed silica, 1 part of bentonite and 0.8 part of anti-flashing agent are added while stirring, stirring at a speed of 400r/min for 15min, 35 parts of water-based phenolic epoxy resin, 0.8 part of propylene glycol monobutyl ether and 5 parts of silane coupling agent are added, stirring at a speed of 400r/min for 5min, so that the component A is prepared, and finally the component A and polyamide curing agent are mixed at a mass ratio of 3:1, so that the protective paint finishing paint is obtained.
Comparative example 2
The preparation method of the protective coating finishing paint in the comparative example comprises the following steps:
according to parts by weight, 25 parts of water, 4 parts of talcum powder, 4 parts of barium sulfate, 4 parts of mica and 2 parts of radiation-resistant particles are mixed, stirred at a speed of 800r/min for 20min, then ground by a grinder until the granularity is 25-35 mu m, then 0.8 part of thickener, 1 part of fumed silica, 1 part of bentonite and 0.8 part of anti-flashing agent are added while stirring, stirring at a speed of 400r/min for 15min, 35 parts of water-based phenolic epoxy resin, 0.8 part of propylene glycol monobutyl ether and 5 parts of silane coupling agent are added to prepare a component A, then 5 parts of rosin is added to the component A, stirring at a speed of 400r/min for 5min to uniformly mix the mixture, and then polyamide curing agent is added to the mixture and stirred to uniformly mix the mixture, so that the protective paint is prepared, wherein the mass ratio of the polyamide curing agent to the component A is 3:1.
Comparative example 3
This comparative example differs from example 1 in that 35 parts by weight of the aqueous epoxy novolac resin in example 1 was replaced with 35 parts by weight of the aqueous epoxy resin in step (2), and the remaining steps and parameters were the same. Wherein the aqueous epoxy resin is selected from Shanghai Jide chemical Co., ltd, and has the brand number of EW-5120.
Comparative example 4
This comparative example differs from example 1 in that 35 parts by weight of the aqueous phenolic resin in example 1 was replaced with 35 parts by weight of the aqueous phenolic resin in step (2), and the remaining steps and parameters were the same. Wherein the aqueous phenolic resin is selected from the group consisting of Variosen, with the brand of EP-5003.
Comparative example 5
This comparative example differs from example 1 in that in step (2), no thickener and silane coupling agent were added, and the remaining steps and parameters were the same.
Comparative example 6
The comparative example differs from example 1 in that no anti-settling agent, i.e., fumed silica and bentonite, was added in step (2), and the remaining steps and parameters were the same.
Comparative example 7
The comparative example differs from example 1 in that in step (2), the commercial anti-settling agent of the type basf EFKA@RM 1463 was used instead of the anti-settling agent obtained by mixing fumed silica and bentonite in example 1, and the remaining steps and parameters were the same.
In the above examples 1 to 3 and comparative examples 1 to 7, the raw materials used were respectively: the thickener is associated polyurethane, and the molecular weight of the thickener is 15000; the water-based phenolic epoxy resin is selected from Bass synthetic New Material Co., ltd, with the brand BS-2155F; the flash rust inhibitor is selected from Hechuan chemical industry, with the brand ZT-709; KH-550 is selected as the silane coupling agent; polyamide curing agents were selected from Xuzhou Ming's scientific and technical industries, inc., trade name ZY-140.
Example 4 results and discussion
The protective coating topcoats prepared in examples 1 to 3 and comparative examples 1 to 7 were coated on the epoxy primer-coated substrates to test their adhesion, temperature resistance and antibacterial properties, respectively, by the following methods: according to the standard of GB/T5210-2006 adhesion test of colored paint and varnish pulling-off method, coating protective coating finishing paint on a base material coated with epoxy primer as a sample, and detecting the adhesion of the sample; referring to the standard of GB/T1735-2009 "determination of heat resistance of color paint and varnish", coating protective paint top-coat on a base material coated with epoxy primer as a sample, wherein the experimental condition is 120 ℃ for 200 hours, and detecting whether a sample paint film has cracking, chalking and flaking phenomena and the adhesive force of a sample after the test; reference GJB150.10A-2009 "laboratory environmental test method for military equipment", section 10: the standard of mould test is that protective coating top coats are coated on a base material coated with epoxy primer as a sample, and the mould proof grade of a paint film of the sample is detected. The mildew-proof grade is 0-4 grade, wherein grade 0 represents no mildew growth on the surface of the sample; grade 1 represents minimal growth, with scattered, rare or very localized mold growth on the sample surface; grade 2 represents light growth, intermittent mold spread or loose colony distribution on the sample surface; grade 3 represents moderate growth, and the surface of the sample has a large amount of mould growth; grade 4 represents severe growth, with thick mold growth on the surface of the sample. The specific test results are shown in table 1 below.
It should be noted that before the above adhesion, temperature resistance and antibacterial performance tests were performed, three major nuclear grade paint proprietary tests including a simulated DBA test, a radiation resistance test and a decontamination test have been performed on the protective paint topcoats prepared in examples 1 to 3 and comparative examples 1 to 7, all of which meet the national NB/T energy qualification standards.
TABLE 1 Performance test results of protective coating topcoats prepared in examples 1-3 and comparative examples 1-7
The results in Table 1 show that the protective coating topcoats of examples 1-3 are superior to comparative examples 1-7 in adhesion, temperature resistance and antimicrobial properties. Compared with comparative examples 1-2, in examples 1-3, the aqueous phenolic epoxy resin is used in the raw material components of the protective coating finish, and rosin and silver nitrate are added, so that the protective coating finish has excellent impact resistance, dimensional stability and acid-base resistance, has stronger adhesive force with a substrate, has better heat resistance and weather resistance, and can reduce the phenomena of peeling, cracking and chalking of a protective paint film; and abietic acid in the rosin reduces silver ions in silver nitrate into nano silver, so that microorganisms and bacteria are inactivated, and the bacteria are inhibited from adhering to the surface of a paint film, so that the antibacterial performance of the protective paint finish paint is obviously improved. In comparative example 3, the conventional aqueous epoxy resin was used instead of the aqueous novolac epoxy resin, and the epoxy resin paint film exhibited the phenomena of chalking and cracking under a long-term high-temperature environment. This is probably because the epoxy resin is degraded by the interaction of radiation and oxygen, which promotes separation between the resin and filler particles, thereby causing pulverization and cracking; in comparative example 4, the traditional aqueous phenolic resin is used for replacing the aqueous phenolic epoxy resin, the curing time of the protective coating finish paint is slowed, and the paint film is peeled off and cracked, which is probably because the adhesive force between the finish paint and the substrate is greatly reduced, and the phenolic resin has the characteristic of high volume shrinkage rate, thereby causing the phenomenon that the paint film is easy to peel off and crack in severe environment; in comparative example 5, the protective coating top coat was cracked without using a thickener and a silane coupling agent, and the protective coating top coat was easily embrittled and hardened at a high temperature for a long period of time due to the absence of the thickener and the silane coupling agent, and the adhesiveness between particles in the coating top coat system was deteriorated, and the adhesion on the substrate was deteriorated; in comparative example 6, the combination property of the protective coating top coat was lowered without using an anti-settling agent, and in actual operation, the protective coating top coat was layered; in comparative example 7, a general commercial anti-settling agent was used, and although the protective coating top coat did not show delamination and sagging, the gloss of the protective coating top coat was significantly reduced, probably because the general commercial anti-settling agent easily caused diffuse reflection during the drying of the paint film, thereby affecting the gloss of the paint film.
In conclusion, the protective coating finishing paint disclosed by the invention can effectively improve the weather resistance, heat resistance and water resistance of the protective coating finishing paint, reduce the phenomena of spalling, cracking and chalking of a paint film, reduce the moisture absorption phenomenon of a coating, inhibit microorganisms and fouling organisms in a humid environment from adhering to nuclear power plant equipment, inhibit the growth of microorganisms and bacteria, and promote the protective coating film to better adapt to the working environment of the nuclear power plant under long-term irradiation and high temperature.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (13)
1. A method of preparing an antimicrobial composition comprising the steps of:
taking a proper amount of rosin, dividing the rosin into two parts, dissolving one part of rosin in an alcohol solvent, adding the solution into a mixed solution of silver nitrate and an alkaline slow-release agent, heating to 100-110 ℃, further cooling to room temperature, washing, drying, and uniformly mixing with the rest part of rosin to obtain the antibacterial composition.
2. The method of preparing an antimicrobial composition according to claim 1, wherein the mass of the rosin is equal in both parts.
3. The method of preparing an antimicrobial composition according to claim 1, wherein the alkaline slow-release agent is aqueous ammonia.
4. An antibacterial composition prepared by the method of any one of claims 1 to 3.
5. The protective coating finishing paint is characterized by comprising a component A and the antibacterial composition of claim 4, wherein the component A comprises the following raw material components in parts by weight: 30-40 parts of waterborne phenolic epoxy resin and 3-8 parts of silane coupling agent;
the antibacterial composition comprises the following raw material components: 3-8 parts of rosin, 3-8 parts of silver nitrate, 2-3 parts of an alkaline slow-release agent and 8-10 parts of an alcohol solvent.
6. The protective coating top-coat paint according to claim 5, wherein the raw material components of the component A further comprise 0.5-1 part of a thickener, 0.5-1 part of a flash rust inhibitor, 1-3 parts of an anti-settling agent, 5-20 parts of a filler and 1-3 parts of radiation resistant particles in parts by weight.
7. The protective coating topcoat of claim 6 wherein the filler is a mixture of at least two of talc, barium sulfate and mica.
8. The protective coating topcoat of claim 6 wherein the anti-settling agent is a mixture of fumed silica and bentonite clay.
9. The protective coating top coat of claim 8, wherein the mass ratio of fumed silica to bentonite is from 0.1 to 5:1.
10. The protective coating topcoat as recited in claim 8 wherein the fumed silica has a particle size of 30-40nm and the bentonite has a particle size of 150-250 mesh.
11. The protective coating top coat according to claim 5, further comprising a curing agent in parts by weight, wherein the mass ratio of component a to curing agent is 2.5-4:1.
12. A method for preparing a protective coating topcoat as claimed in any one of claims 5 to 11, comprising the steps of:
and uniformly mixing and grinding water, filler and radiation-resistant particles, adding a thickening agent, an anti-settling agent and an anti-flash rust agent, uniformly stirring, adding water-based phenolic epoxy resin, a solvent and a silane coupling agent to obtain a component A, adding the antibacterial composition into the component A, stirring, adding a curing agent into the component A, and uniformly mixing to obtain the protective coating finishing paint.
13. The method of claim 12, wherein the water, filler and radiation resistant particles are mixed uniformly and ground to a particle size of 25-35 μm.
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