CN112094134A - Natural stone containing antibacterial agent prepared by zinc replacement process and preparation process thereof - Google Patents
Natural stone containing antibacterial agent prepared by zinc replacement process and preparation process thereof Download PDFInfo
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- CN112094134A CN112094134A CN202011071973.6A CN202011071973A CN112094134A CN 112094134 A CN112094134 A CN 112094134A CN 202011071973 A CN202011071973 A CN 202011071973A CN 112094134 A CN112094134 A CN 112094134A
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- Prior art keywords
- antibacterial
- antibacterial agent
- natural stone
- zinc
- silver
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 109
- 239000004575 stone Substances 0.000 title claims abstract description 97
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000011701 zinc Substances 0.000 title claims abstract description 56
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 40
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 176
- 230000001681 protective effect Effects 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 56
- 239000000084 colloidal system Substances 0.000 claims abstract description 35
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 67
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 58
- 239000010949 copper Substances 0.000 claims description 39
- 229910052709 silver Inorganic materials 0.000 claims description 39
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 39
- 239000004332 silver Substances 0.000 claims description 38
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 35
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 35
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 29
- 239000011787 zinc oxide Substances 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 22
- 239000007853 buffer solution Substances 0.000 claims description 17
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- -1 phosphate ester Chemical class 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 15
- 229940007718 zinc hydroxide Drugs 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000000845 anti-microbial effect Effects 0.000 claims description 8
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 8
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 5
- 239000004599 antimicrobial Substances 0.000 claims description 5
- 150000001282 organosilanes Chemical class 0.000 claims description 5
- 125000005375 organosiloxane group Chemical group 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 230000000474 nursing effect Effects 0.000 claims description 4
- 239000012466 permeate Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000010438 granite Substances 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002969 artificial stone Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004579 marble Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
- C04B41/4535—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension
-
- 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
- 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
- A01N59/20—Copper
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Dentistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a natural stone containing an antibacterial agent prepared by a zinc replacement process and a preparation process thereof. The surface of the natural stone is coated with antibacterial protective liquid, the antibacterial protective liquid comprises an antibacterial agent, the antibacterial agent comprises silver-copper simple substance colloid, and the silver-copper simple substance colloid is prepared by adopting a zinc replacement preparation process. The invention also provides a preparation process of the natural stone containing the antibacterial agent prepared by the zinc replacement process, which comprises an antibacterial agent preparation step, an antibacterial protective solution preparation step and an antibacterial protective solution coating step. The zinc replacement preparation process of the antibacterial agent has the advantages of simple components, few impurities, high and controllable reduction efficiency, high raw material utilization rate, no heavy metal emission, environmental protection and safety. The prepared antibacterial protective liquid is pure and transparent, and is particularly suitable for natural stone materials with original color and texture. The prepared natural stone containing the antibacterial agent prepared by the zinc replacement process has antibacterial performance and antibacterial durability meeting the requirements of JC/T897-2014 standard.
Description
Technical Field
The invention relates to the technical field of antibacterial agents and stones, in particular to a natural stone containing an antibacterial agent prepared by a zinc replacement process and a preparation process thereof.
Background
The protection of the natural stone in the prior art is to distribute and solidify some protective agents on the surface of the stone by adopting methods such as brushing, spraying, coating, rolling, spraying, soaking and the like, so as to form a surface protective layer which can prolong the service life of the stone and has antibacterial or wear-resisting properties.
The formed surface protection layer isolates the original surface of the natural stone from direct contact with a user, reduces the texture and touch of the original natural texture of the natural stone, and has poor use experience effect.
The stone protective agent in the prior art improves the antibacterial effect by adding the silver-carrying antibacterial agent containing silver ions, the carried silver is directly prepared by dipping silver nitrate in a silver nitrate solution and adsorbing the silver nitrate and then drying, when the silver ions in the aqueous solution are easy to dissolve and run off, the preservation and slow release effects of the antibacterial agent are not understood, and the antibacterial durability effect is poor.
Disclosure of Invention
The invention provides a natural stone containing an antibacterial agent prepared by a zinc replacement process and a preparation process thereof, and the prepared natural stone has a good antibacterial effect, clear surface textures of the stone and no visible film layer, and has good texture and touch.
In order to achieve the purpose, the invention adopts the following technical scheme:
the natural stone containing the antibacterial agent prepared by the zinc replacement process is characterized in that the surface of the natural stone is coated with antibacterial protection liquid, the antibacterial protection liquid comprises the antibacterial agent, the antibacterial agent comprises silver-copper simple substance colloid, and the silver-copper simple substance colloid is prepared by the zinc replacement preparation process.
Preferably, the antibacterial agent further comprises zinc oxide nanoparticles; the molar content ratio of the silver simple substance to the copper simple substance to the zinc oxide nano-particles in the antibacterial agent is 0.2:1: 1.5.
Specifically, the content of the antibacterial agent in the antibacterial protective liquid is 0.5-1.5 wt%; the antibacterial protective liquid also comprises a waterproof agent or an oil-proof agent, and the dosage of the antibacterial protective liquid used for natural stone nursing is 30-45 g/square meter.
Furthermore, the invention also provides a preparation process of the natural stone containing the antibacterial agent prepared by the zinc replacement process, which is used for preparing the natural stone containing the antibacterial agent prepared by the zinc replacement process and comprises an antibacterial agent preparation step, an antibacterial protective solution preparation step and an antibacterial protective solution coating step;
wherein, the antibacterial agent preparation step comprises the following steps:
s1) adding blue vitriol into distilled water to obtain blue vitriol solution;
s2) adding zinc powder into the copper sulfate solution, stirring at a high speed for 1 hour, and filtering and cleaning the precipitate to obtain a mixture A containing copper simple substance colloid and zinc hydroxide;
s3) preparing a silver nitrate aqueous solution, and adding EDTA to prepare a silver nitrate buffer solution;
s4) adding the mixture A into the silver nitrate buffer solution, stirring in a constant-temperature water bath for 30 minutes, adding zinc powder, stirring in a constant-temperature water bath for 30 minutes, and filtering and cleaning the precipitate to obtain a mixture B containing silver-copper simple substance colloid and zinc hydroxide;
s5) placing the mixture B into a high-temperature baking furnace to bake for 30 minutes to obtain the antibacterial agent containing silver-copper simple substance colloid and zinc oxide nanoparticles.
It may be implemented that, in the step S1), the copper sulfate content in the copper sulfate solution is 1 to 3.5 mol;
in the step S2), the mole content ratio of copper sulfate to zinc powder in the copper sulfate solution is 1: 1.1;
in the step S3), the content of silver nitrate in the silver nitrate buffer solution is 0.2 time of the content of copper sulfate, and the molar content ratio of silver nitrate to EDTA is 1:1.
Specifically, in the step S4), the constant temperature of the constant temperature water bath is 50 ℃, and the molar content of the added zinc powder is 2 times of the silver nitrate content; in step S5), the baking temperature is 150-380 ℃.
The preparation method of the antibacterial protective solution comprises the following steps:
p1) adding the antibacterial agent into an aqueous solution containing a surfactant, uniformly stirring, and adding into the stone protective liquid to obtain the protective liquid containing the antibacterial agent.
Specifically, in the step P1), the surfactant is one or two of surfactants of organosilane, organosiloxane and sodium methyl silicate, or one or two of surfactants of titanate and phosphate; the weight part ratio of the antibacterial agent to the surfactant to the water is 2:1: 2; in step P1), the antimicrobial agent is present in an amount of 0.5 to 1.5 wt% based on the weight of the antimicrobial protective solution.
Optionally, the step of applying the antimicrobial protective solution comprises:
q1) polishing the processed natural stone with edible baking soda powder to remove surface stains;
q2) coating the antibacterial protection solution on the surface of the cleaned natural stone according to the using amount of 30-45 g/square meter, standing for 8 hours until the antibacterial protection solution permeates into the surface layer of the natural stone, and thus obtaining the natural stone containing the antibacterial agent prepared by the zinc replacement process.
The invention has the beneficial effects that: the invention provides a natural stone containing an antibacterial agent prepared by a zinc replacement process and a preparation process thereof.
The antibacterial agent is prepared by adopting a zinc replacement preparation process, has the advantages of simple components, less impurities, high and controllable reduction efficiency, high utilization rate of heavy metal in the prepared raw materials, no heavy metal emission, environmental protection and safety.
The prepared antibacterial protective liquid is pure and transparent, is particularly suitable for natural stone with the appearance requirement of keeping the original color and the texture of a plate, and the coated stone has a lasting and broad-spectrum antibacterial effect.
The antibacterial performance and the antibacterial durability of the prepared natural stone containing the antibacterial agent prepared by the zinc replacement process can meet the standard requirements of JC/T897-2014 antibacterial ceramic product antibacterial performance.
The whole of the antibacterial artificial stone in the prior art contains the antibacterial agent, the dosage is large, the cost is high, the antibacterial protective liquid is only used on the surface layer, the effect is good, the dosage is small, and the coating production efficiency is high, and the cost is low. The antibacterial protective liquid can be used for artificial stones and natural stones, and has a wider application range.
The invention solves the problems of isolation of original natural textures, poor texture, touch and use experience effects of the antibacterial natural stone in the prior art; also solves the problems that the preservation and the slow release effect of the antibacterial agent are not understood and the antibacterial durability effect is poor.
Detailed Description
The technical solution of the present invention is further described below in specific embodiments.
The natural stone containing the antibacterial agent prepared by the zinc replacement process is characterized in that the surface of the natural stone is coated with antibacterial protection liquid, the antibacterial protection liquid comprises the antibacterial agent, the antibacterial agent comprises silver-copper simple substance colloid, and the silver-copper simple substance colloid is prepared by the zinc replacement preparation process.
The natural stone containing the antibacterial agent prepared by the zinc replacement process adopts the antibacterial protection liquid as a permeable protective agent, the active ingredients of the natural stone are completely permeated into the natural stone through capillary holes after coating, and no visible film layer exists on the surface of the natural stone.
The antibacterial action principle of the antibacterial agent is as follows:
when the simple substance silver is contacted with a humid environment containing oxygen, such as water, acid and alkaline solution, the silver atoms of the simple substance silver are oxidized into silver ions, and the antibacterial capability is realized. When the simple substance silver and the simple substance copper exist simultaneously, the silver atom of the simple substance silver is oxidized into silver ions, the electrode potential of the silver ions/silver is 0.80 volt, the electrode potential of the copper ions/copper is 0.34 volt, and due to the existence of the potential difference of the electrode potentials, gold is generatedThe silver ions in the colloid can oxidize copper atoms into copper ions, and the silver ions are reduced into silver atoms, and the chemical reaction formula is 2Ag++Cu＝2Ag+Cu++Potential difference E thereof0＝ψAg+/Ag-ψCu++0.80-0.34-0.46 volt, the copper atom of simple substance copper in colloid is converted into Cu with bactericidal and antibacterial properties++Ions.
The antibacterial protection solution comprises an antibacterial substance of silver-copper elementary substance colloid, the antibacterial substance of the silver-copper elementary substance colloid is not easy to run off, has good slow release performance, and has good antibacterial effect.
The antibacterial protective liquid is smeared on the surface of the natural stone, and an antibacterial surface layer with lasting, broad-spectrum antibacterial and good slow-release effect can be obtained on the surface of the natural stone after drying treatment.
Preferably, the antibacterial agent further comprises zinc oxide nanoparticles; the molar content ratio of the silver simple substance to the copper simple substance to the zinc oxide nano-particles in the antibacterial agent is 0.2:1: 1.5.
The zinc oxide is an antibacterial agent with good antibacterial effect and has photosensitive bactericidal performance.
The zinc oxide can protect the silver film under the alkaline environment from being alkalized and prevent the silver film from being converted into silver hydroxide to be separated out, so that the conversion rate of converting a copper simple substance into copper ions is reduced, and the reduction of the antibacterial performance of the antibacterial protective solution can be avoided. Only after the zinc oxide is consumed by the reaction, the silver film is converted into silver hydroxide by alkalization and is separated out.
Therefore, the antibacterial protective liquid has the performance of avoiding silver precipitation and discoloration, and a coated product can have a better color or transparent effect.
The chemical reaction mechanism is as follows.
Silver ions react with basic groups in alkaline environment to generate silver hydroxide precipitate
Ag++OH-AgOH ↓ (white)
Unstable decomposition of silver hydroxide precipitate to silver oxide precipitate
2AgOH＝Ag2O ↓ (dark brown) + H2O
When zinc oxide and silver oxide coexist, the chemical reaction activity of the zinc oxide under the alkaline environment is higher than that of the silver oxide, and the zinc oxide firstly reacts with basic groups to delay and prevent the precipitation of the silver oxide.
ZnO++2OH-＝Zn(OH)2↓ (white)
The zinc oxide is selected as the stabilizer of silver ions, so that the stability of the antibacterial performance of the antibacterial protective liquid can be improved, and the alkali corrosion resistance of the antibacterial protective liquid can be widened by increasing the using amount and proportion of the zinc oxide.
The molar content ratio of the silver simple substance, the copper simple substance and the zinc oxide nanoparticles in the antibacterial agent is 0.2:1:1.5, wherein the zinc oxide nanoparticles are larger than the sum of the contents of the silver simple substance and the copper simple substance, so that silver ions and copper ions in the replacement process are completely reduced, the pollution of silver and copper heavy metals can be reduced, the utilization rate of raw materials can be improved, and the antibacterial agent has better manufacturing cost.
Specifically, the content of the antibacterial agent in the antibacterial protective liquid is 0.5-1.5 wt%; the antibacterial protective liquid also comprises a waterproof agent or an oil-proof agent, and the dosage of the antibacterial protective liquid used for natural stone nursing is 30-45 g/square meter.
The antibacterial protective liquid contains 0.5-1.5 wt% of the antibacterial agent, so that the antibacterial performance and the antibacterial durability of the natural stone coated with the antibacterial protective liquid can meet the requirements of JC/T897-2014 antibacterial ceramic product standard, the antibacterial performance index below 0.5% does not reach the standard, and the resource is wasted due to the mass surplus of more than 1.5%.
The antibacterial protective liquid also comprises a waterproof agent or an oil-proof agent, so that the antibacterial protective liquid has a more universal use effect, and the applicability of the antibacterial protective liquid is improved.
The invention further provides a preparation process of the natural stone containing the antibacterial agent prepared by the zinc replacement process, which is used for preparing the natural stone containing the antibacterial agent prepared by the zinc replacement process and comprises an antibacterial agent preparation step, an antibacterial protective solution preparation step and an antibacterial protective solution coating step;
wherein, the antibacterial agent preparation step comprises the following steps:
s1) adding blue vitriol into distilled water to obtain blue vitriol solution;
s2) adding zinc powder into the copper sulfate solution, stirring at a high speed for 1 hour, and filtering and cleaning the precipitate to obtain a mixture A containing copper simple substance colloid and zinc hydroxide;
s3) preparing a silver nitrate aqueous solution, and adding EDTA to prepare a silver nitrate buffer solution;
s4) adding the mixture A into the silver nitrate buffer solution, stirring in a constant-temperature water bath for 30 minutes, adding zinc powder, stirring in a constant-temperature water bath for 30 minutes, and filtering and cleaning the precipitate to obtain a mixture B containing silver-copper simple substance colloid and zinc hydroxide;
s5) placing the mixture B into a high-temperature baking furnace to bake for 30 minutes to obtain the antibacterial agent containing silver-copper simple substance colloid and zinc oxide nanoparticles.
The preparation process of the natural stone containing the antibacterial agent prepared by the zinc replacement process has the advantages of simple process, simple equipment, small occupied area and investment and low manufacturing cost.
The principle of the zinc replacement preparation process is as follows:
the standard electrode potential of Ag is 0.8V, the standard electrode potential of Cu is 0.337V, and the standard electrode potential of Zn is-0.76V. So Zn + Cu++——Zn++The standard electrode potential difference of + Cu is; 1.10V, the replacement reaction can be carried out; zn +2Ag+——Zn++The standard electrode potential difference of +2Ag is; 1.56V, the displacement reaction can be carried out; cu +2Ag+——Cu++The standard electrode potential difference of +2Ag is; 0.463V, the metathesis reaction proceeded.
Therefore, Zn simple substance can reduce Cu + + ions and Ag + ions, and Cu simple substance can reduce Ag + ions.
Firstly, replacing copper ions in copper salt with metal zinc powder to form copper colloid, and then partially replacing silver ions with the copper colloid in silver salt solution to form simple substance silver film on the surface of the copper colloid, so that the copper colloid absorbed with the metal silver film has better oxidation resistance and corrosion resistance, and the metal zinc powder is replaced with zinc hydroxide and left in the precipitate. And then the volatile matters and impurities are removed through baking, and the antibacterial agent containing the copper-silver bimetallic simple substance colloid and the zinc oxide nanoparticles is prepared.
The process of the displacement chemical reaction of copper sulfate and zinc is as follows:
zn and Cu++In the solution, a displacement reaction firstly occurs, copper particles which are initially precipitated are fine and black, and then become brownish red along with the gradual coarsening of the Cu particles. The chemical reaction formula is as follows:
Zn+Cu++＝Zn+++ Cu ↓ (red brown)
2. As the Zn powder is deposited with the metal Cu, a Zn-Cu primary battery is formed, so that hydrogen atoms contained in water obtain electrons at a positive electrode (Cu electrode) to generate H2And simultaneously generate OH-，Cu++And H2And OH-Reaction to form Cu+，Cu+Is very unstable in aqueous solution and rapidly undergoes disproportionation reaction Cu+Disproportionating into Cu and Cu++The chemical reaction formula is as follows:
Zn+2H2O＝H2↑+Zn+++2OH-
2Cu+++H2+2OH-＝2Cu++2H2O
2Cu+＝Cu+++ Cu ↓ (red brown)
3. As the reaction proceeds, Cu in solution++Is completely reduced and replaced by deposited Cu, zinc powder is continuously dissolved, OH-The concentration is increased continuously to make the solution alkaline, and Zn in the solution++And OH-Combine to form Zn (OH)2White precipitate.
Zn+++2OH-＝Zn(OH)2↓ (white)
The replacement chemical reaction process of the elemental copper and the silver nitrate buffer solution is as follows:
cu and Ag+The replacement reaction is firstly carried out in the solution, the separated silver Ag particles are adsorbed on the surface of the copper simple substance colloid, and a silver film is formed along with the accumulation of the Ag particles. The chemical reaction formula is as follows:
Cu+2Ag+＝Cu+++2Ag ↓ (silver)
The antibacterial agent can be uniformly dispersed into waterproof and oil-proof stone panel protective liquid after surface activation, and silver-copper elementary substance colloid contained in the antibacterial agent is activated and converted into silver-copper ions when contacting with aqueous solution; therefore, the prepared antibacterial protective solution has good antibacterial activity, stable antibacterial substance adsorption, difficult loss and good slow release performance.
Optionally, step S2) further includes, before the suction filtration and cleaning of the precipitate, adding 0.1mol/L sodium hydroxide aqueous solution dropwise into the copper sulfate solution until no precipitate appears, and then performing suction filtration and cleaning;
step S4), before the precipitate is filtered and cleaned, 0.2mol/L sodium hydroxide aqueous solution is dripped into the silver nitrate buffer solution until no precipitate appears, and then the precipitate is filtered and cleaned.
It is worth further explaining that no precipitation is confirmed by dripping 0.1mol/L sodium hydroxide aqueous solution, so that zinc ions in the solution are completely converted into zinc hydroxide, the utilization rate of the zinc powder is improved, and the emission pollution of heavy metal zinc can be reduced.
Specifically, in the step S1), the copper sulfate content in the copper sulfate solution is 1-3.5 mol; in the step S2), the mole content ratio of copper sulfate to zinc powder in the copper sulfate solution is 1: 1.1; in the step S3), the content of silver nitrate in the silver nitrate buffer solution is 0.2 time of the content of copper sulfate, and the molar content ratio of silver nitrate to EDTA is 1:1.
The molar concentration ratio of copper sulfate to zinc powder in the copper sulfate solution is 1:1.1, and the molar content of the zinc powder is higher than that of the copper sulfate, so that the copper sulfate can be completely reduced and replaced.
EDTA is added into silver nitrate solution to prepare buffer solution, so that the reduction speed of silver ions is slower and more effective when the silver ions and copper atoms carry out redox reaction, the reduced silver atoms can be captured by copper colloid in sufficient time to form a silver film, and the oxidation resistance and corrosion resistance of the antibacterial protective solution are improved.
Specifically, in the step S4), the constant temperature of the constant temperature water bath is 50 ℃, and the molar content of the added zinc powder is 2 times of the silver nitrate content; in step S5), the baking temperature is 150-380 ℃.
The constant temperature is 50 ℃, which is more beneficial to improving the adsorption stability of the silver film generated by the silver mirror reaction; the molar content of the zinc powder is 2 times of the silver nitrate content, so that the oxidized part of copper ions can be completely reduced and replaced again, and the precipitated zinc hydroxide is baked to generate oxidizing nanoparticles with an antibacterial effect, so that the antibacterial performance of the antibacterial protective solution can be improved.
Baking at 150-380 deg.C to remove all water and oxidize zinc hydroxide into zinc oxide; the temperature exceeding 380 ℃ can cause the copper simple substance to be oxidized into copper oxide; the conversion rate of zinc hydroxide to zinc oxide is low below 150 ℃.
The antibacterial agent is prepared by adopting a zinc replacement preparation process, has the advantages of simple components, less impurities, high and controllable reduction efficiency, high utilization rate of heavy metal in the prepared raw materials, no heavy metal emission, environmental protection and safety.
Specifically, the preparation steps of the antibacterial protective liquid comprise:
p1) adding the antibacterial agent into an aqueous solution containing a surfactant, uniformly stirring, and adding into the stone protective liquid to obtain the protective liquid containing the antibacterial agent.
Specifically, in the step P1), the surfactant is one or two of surfactants of organosilane, organosiloxane and sodium methyl silicate, or one or two of surfactants of titanate and phosphate; the weight part ratio of the antibacterial agent to the surfactant to the water is 2:1: 2; in step P1), the antimicrobial agent is present in an amount of 0.5 to 1.5 wt% based on the weight of the antimicrobial protective solution.
The addition of the surfactant can ensure that the antibacterial agent is dispersed in the antibacterial protective solution more uniformly, and reduce the deposition phenomenon;
titanate or phosphate surfactant is adopted to enhance the surface bonding strength of the antibacterial agent and marble (calcium carbonate and magnesium) natural stone; for silicate granite stone, surface active agents of organic silane, organic siloxane and methyl sodium silicate are adopted to enhance the surface bonding strength of the antibacterial agent and the granite natural stone. The prepared antibacterial protective liquid is pure and transparent, is particularly suitable for natural stone with the appearance requirement of keeping the original color and the texture of a plate, and the coated stone has a lasting and broad-spectrum antibacterial effect.
Optionally, the step of applying the antimicrobial protective solution comprises:
q1) polishing the processed natural stone with edible baking soda powder to remove surface stains;
q2) coating the antibacterial protection solution on the surface of the cleaned natural stone according to the using amount of 30-45 g/square meter, standing for 8 hours until the antibacterial protection solution permeates into the surface layer of the natural stone, and thus obtaining the natural stone containing the antibacterial agent prepared by the zinc replacement process.
The usage amount of the natural stone surface protection after the natural stone surface protection is coated and cleaned according to the usage amount of the antibacterial protection liquid of 30-45 g/square meter is that the antibacterial performance and the antibacterial durability of the prepared natural stone containing the antibacterial agent prepared by the zinc replacement process can be ensured to meet the requirements of JC/T897-2014 'antibacterial ceramic product antibacterial performance' standard, the antibacterial performance index below 30 g/square meter does not reach the standard, and the resource is wasted if the mass is more than 45 g/square meter.
The natural stone processed and cleaned by the polishing of the edible baking soda dry powder can not only remove surface stains, but also neutralize acid substances on the surface of the stone, reduce the adverse effect of processing residues on the antibacterial effect, and is more favorable for improving the processing effect and the antibacterial effect of the antibacterial protective liquid.
Examples and comparative examples
1. A natural stone containing an antibacterial agent prepared by a zinc replacement process, wherein the surface of the natural stone is coated with an antibacterial protection liquid, the antibacterial protection liquid comprises the antibacterial agent, the antibacterial agent comprises silver-copper simple substance colloid, and the silver-copper simple substance colloid is prepared by the zinc replacement preparation process;
the antibacterial agent also comprises zinc oxide nano-particles; the molar content ratio of the silver simple substance to the copper simple substance to the zinc oxide nano particles in the antibacterial agent is 0.2:1: 1.5;
the content of the antibacterial agent in the antibacterial protective liquid is 0.5-1.5 wt%; the antibacterial protective liquid also comprises a waterproof agent or an oil-proof agent, and the dosage of the antibacterial protective liquid used for natural stone nursing is 30-45 g/square meter.
2. The preparation process of the natural stone containing the antibacterial agent prepared by the zinc replacement process comprises an antibacterial agent preparation step, an antibacterial protective solution preparation step and an antibacterial protective solution coating step;
wherein, the antibacterial agent preparation step comprises the following steps:
s1) adding blue vitriol into distilled water to obtain blue vitriol solution;
s2) adding zinc powder into the copper sulfate solution, stirring at a high speed for 1 hour, and filtering and cleaning the precipitate to obtain a mixture A containing copper simple substance colloid and zinc hydroxide;
s3) preparing a silver nitrate aqueous solution, and adding EDTA to prepare a silver nitrate buffer solution;
s4) adding the mixture A into the silver nitrate buffer solution, stirring in a constant-temperature water bath for 30 minutes, adding zinc powder, stirring in a constant-temperature water bath for 30 minutes, and filtering and cleaning the precipitate to obtain a mixture B containing silver-copper simple substance colloid and zinc hydroxide;
s5) placing the mixture B into a high-temperature baking furnace to bake for 30 minutes to obtain the antibacterial agent containing silver-copper simple substance colloid and zinc oxide nanoparticles;
step S2), before the suction filtration and cleaning of the precipitate, 0.1mol/L sodium hydroxide aqueous solution is dripped into the copper sulfate solution until no precipitate appears, and then suction filtration and cleaning are carried out; step S4), before the precipitate is filtered and cleaned, 0.2mol/L sodium hydroxide aqueous solution is dripped into the silver nitrate buffer solution until no precipitate appears, and then the precipitate is filtered and cleaned.
In the step S1), the content of copper sulfate in the copper sulfate solution is 1-3.5 mol; in the step S2), the mole content ratio of copper sulfate to zinc powder in the copper sulfate solution is 1: 1.1; in the step S3), the content of silver nitrate in the silver nitrate buffer solution is 0.2 time of the content of copper sulfate, and the molar content ratio of silver nitrate to EDTA is 1:1.
In the step S4), the constant temperature of the constant temperature water bath is 50 ℃, and the molar content of the added zinc powder is 2 times of the silver nitrate content; in step S5), the baking temperature is 150-380 ℃.
The preparation steps of the antibacterial protective liquid comprise:
p1) adding the antibacterial agent into an aqueous solution containing a surfactant, uniformly stirring, and adding into a stone protective liquid to prepare a protective liquid containing the antibacterial agent;
in the step P1), the surfactant is one or two of organosilane, organosiloxane and sodium methyl silicate, or one or two of titanate and phosphate ester; the weight part ratio of the antibacterial agent to the surfactant to the water is 2:1: 2; in step P1), the antimicrobial agent is present in an amount of 0.5 to 1.5 wt% based on the weight of the antimicrobial protective solution.
The coating step of the antibacterial protective liquid comprises the following steps:
q1) polishing the processed natural stone with edible baking soda powder to remove surface stains;
q2) coating the antibacterial protection solution on the surface of the cleaned natural stone according to the using amount of 30-45 g/square meter, standing for 8 hours until the antibacterial protection solution permeates into the surface layer of the natural stone, and thus obtaining the natural stone containing the antibacterial agent prepared by the zinc replacement process.
3. The natural stone materials of the respective examples and comparative examples were prepared according to the above procedure, and the contents and ratios of the specific raw material components and the parameters of the respective examples are shown in table 1, and the contents and ratios of the specific raw material components and the parameters of the respective ratios are shown in table 2.
4. The samples are taken according to JC/T897-2014 antibacterial ceramic product antibacterial performance standard, and relevant antibacterial performance antibacterial rate and antibacterial durability antibacterial rate are tested, the test results of each example are shown in Table 1, and the test results of each proportion are shown in Table 2.
TABLE 1 data and test results for the examples
TABLE 2 comparative data and test results
The following is an analytical description based on the cases and test results of the above examples and comparative examples:
1. according to the standard requirement of JC/T897-2014 antibacterial ceramic product antibacterial performance, the antibacterial rate (%) of the antibacterial performance is more than or equal to 90 percent and the antibacterial rate (%) of the antibacterial durability is more than or equal to 85 percent; example 7 in table 1 shows that the control sample without the antibacterial protective solution had failed to measure the antibacterial performance and antibacterial durability.
2. Examples 1-6 were analyzed according to the above test results and related data: examples 1 to 6 are granite or marble natural stone, and the antibacterial rate (%) of the antibacterial property and the antibacterial durability (%) of examples 1 to 6 are both acceptable; in examples 1 to 6, the copper sulfate content in the copper sulfate solution in step S1) was 1 to 3.5 mol; in the step S2), the mole content ratio of copper sulfate to zinc powder in the copper sulfate solution is 1: 1.1; in the step S3), the content of silver nitrate in the silver nitrate buffer solution is 0.1mol, and the molar content ratio of the silver nitrate to EDTA is 1: 1; in the step S4), the constant temperature of the constant temperature water bath is 50 ℃, and the molar content of the added zinc powder is 0.2 mol; in the step S5), the baking temperature is 150-380 ℃; in the step P1), the surfactant is one or two of organosilane, organosiloxane and sodium methyl silicate, or one or two of titanate and phosphate ester; the weight part ratio of the antibacterial agent to the surfactant to the water is 2:1: 2; the weight percentage of the antibacterial agent in the antibacterial protective liquid is 0.5-1.5 wt%; the preparation process of the natural stone containing the antibacterial agent prepared by the zinc replacement process is effective, and the prepared antibacterial agent, the antibacterial protective liquid and the natural stone containing the antibacterial agent prepared by the zinc replacement process have good antibacterial effect and durability.
2. Comparative examples 1 and 2 were analyzed in comparison with example 3, the differences between comparative examples 1 and 2 being: the antimicrobial protective solutions added in comparative examples 1 and 2 were used in different amounts of 28 and 48g/m, respectively2Out of the defined 30-45g/m2The usage amount; the results of the tests of the antibacterial performance and antibacterial durability (%) of comparative example 1 were all unqualified; the results of the tests of antibacterial performance and antibacterial durability (%) of comparative example 2 were all more satisfactory than those of example 3, but the improvement in comparison with example 6 was limited, and the results of the tests of antibacterial performance and antibacterial durability (%) of example 6 were all very excellent, so that the amount of the antibacterial protecting liquid used was set to 30 to 45g/m2It is more suitable.
3. Comparative examples 3 and 4 were analyzed in comparison with example 3, the differences of comparative examples 3 and 4 being: step P1), the weight percentages of the antimicrobial agent in the antimicrobial protective solution are different, respectively 0.3 wt% and 1.8 wt%, outside the defined range of 0.5-1.5 wt%; the results of the tests of the antibacterial performance and antibacterial durability (%) of comparative example 3 were all unqualified; the results of the tests of the antibacterial performance antibacterial rate and the antibacterial durability antibacterial rate (%) of comparative example 4 were all more satisfactory than those of example 3, but the improvement in comparison with example 6 was limited, and the results of the tests of the antibacterial performance antibacterial rate and the antibacterial durability antibacterial rate (%) of example 6 were excellent, so that it was appropriate to set the weight percentage of the antibacterial agent in the antibacterial protecting liquid to 0.5 to 1.5 wt%.
4. Comparative examples 5 and 6 were analyzed in comparison with example 3, the differences between comparative examples 5 and 6 being: in the step S5), the baking temperatures are different, wherein the baking temperature of the comparative example 5 is 130 ℃, the baking temperature of the comparative example 6 is 400 ℃, and the baking temperature exceeds 150-380 ℃; the baking temperature of comparative example 5 is 130 ℃ lower than the lower limit of 150 ℃, the conversion rate of zinc hydroxide in the antibacterial agent prepared in comparative example 5 is not enough, so that the content of zinc oxide in the antibacterial protective solution prepared in comparative example 5 is low, and zinc hydroxide which is not converted into zinc oxide is easy to run off during test flushing after being coated on granite, so that the antibacterial effect and antibacterial durability of comparative example 5 are reduced, and the detection results of the antibacterial performance and antibacterial durability antibacterial rate (%) of comparative example 5 are both unqualified; the baking temperature of the comparative example 6 is 400 ℃, the baking temperature exceeds the upper limit of 380 ℃, so that a copper simple substance in the antibacterial protective liquid prepared in the comparative example 6 is oxidized into copper oxide, and the copper oxide is easy to run off during test flushing after being coated on granite, so that the antibacterial effect and the antibacterial durability of the comparative example 6 are reduced, and the detection results of the antibacterial performance and the antibacterial durability antibacterial rate (%) of the comparative example 6 are not qualified; therefore, the baking temperature in step S5 is preferably set to 150-380 ℃.
In conclusion, the antibacterial performance and antibacterial durability of the antibacterial protection liquid prepared by the preparation process of the natural stone containing the antibacterial agent prepared by the zinc replacement process have excellent antibacterial rate and antibacterial durability (%) detection results. The preparation process is simple, the equipment requirement is low, and the manufacturing cost is low.
The antibacterial protective solution contains 0.5-1.5% of the antibacterial agent, and has a concentration of 30-45g/m2The antibacterial ceramic coating is coated on natural stone, and the antibacterial performance and the antibacterial durability can meet the standard requirements of JC/T897-2014 antibacterial ceramic product antibacterial performance.
The antibacterial stone protective liquid contains silver-copper simple substance colloid and zinc oxide nanoparticles, is convenient to store, is not easy to run off, has the characteristics of good heat resistance, broad-spectrum antibacterial property, excellent slow release property and the like, is suitable for various natural stones, and has a wide application range.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. The natural stone containing the antibacterial agent prepared by the zinc replacement process is characterized in that the surface of the natural stone is coated with antibacterial protection liquid, the antibacterial protection liquid comprises the antibacterial agent, the antibacterial agent comprises silver-copper simple substance colloid, and the silver-copper simple substance colloid is prepared by the zinc replacement preparation process.
2. The natural stone containing the antibacterial agent prepared by the zinc substitution process as claimed in claim 1, wherein the antibacterial agent further comprises zinc oxide nanoparticles; the molar content ratio of the silver simple substance to the copper simple substance to the zinc oxide nano-particles in the antibacterial agent is 0.2:1: 1.5.
3. The natural stone material containing the antibacterial agent prepared by the zinc substitution process as claimed in claim 2, wherein the antibacterial agent content in the antibacterial protection solution is 0.5-1.5 wt%; the antibacterial protective liquid also comprises a waterproof agent or an oil-proof agent, and the dosage of the antibacterial protective liquid used for natural stone nursing is 30-45 g/square meter.
4. A preparation process of natural stone containing an antibacterial agent prepared by a zinc replacement process is characterized in that the preparation process is used for preparing the natural stone containing the antibacterial agent prepared by the zinc replacement process according to any one of claims 1 to 3, and comprises an antibacterial agent preparation step, an antibacterial protective solution preparation step and an antibacterial protective solution coating step;
wherein, the antibacterial agent preparation step comprises the following steps:
s1) adding blue vitriol into distilled water to obtain blue vitriol solution;
s2) adding zinc powder into the copper sulfate solution, stirring at a high speed for 1 hour, and filtering and cleaning the precipitate to obtain a mixture A containing copper simple substance colloid and zinc hydroxide;
s3) preparing a silver nitrate aqueous solution, and adding EDTA to prepare a silver nitrate buffer solution;
s4) adding the mixture A into the silver nitrate buffer solution, stirring in a constant-temperature water bath for 30 minutes, adding zinc powder, stirring in a constant-temperature water bath for 30 minutes, and filtering and cleaning the precipitate to obtain a mixture B containing silver-copper simple substance colloid and zinc hydroxide;
s5) placing the mixture B into a high-temperature baking furnace to bake for 30 minutes to obtain the antibacterial agent containing silver-copper simple substance colloid and zinc oxide nanoparticles.
5. The process for preparing natural stone containing antibacterial agent prepared by zinc substitution process as claimed in claim 4, wherein in step S1), copper sulfate content in said copper sulfate solution is 1-3.5 mol; in the step S2), the mole content ratio of copper sulfate to zinc powder in the copper sulfate solution is 1: 1.1; in the step S3), the content of silver nitrate in the silver nitrate buffer solution is 0.2 time of the content of copper sulfate, and the molar content ratio of silver nitrate to EDTA is 1:1.
6. The process for preparing natural stone containing antibacterial agent prepared by zinc substitution process as claimed in claim 4, wherein in step S4), the thermostatic temperature of the thermostatic waterbath is 50 ℃, and the molar content of the added zinc powder is 2 times of the silver nitrate content; in step S5), the baking temperature is 150-380 ℃.
7. The process for preparing natural stone containing an antibacterial agent prepared by a zinc substitution process according to claim 4, wherein the antibacterial protection solution preparation step comprises:
p1) adding the antibacterial agent into an aqueous solution containing a surfactant, uniformly stirring, and adding into the stone protective liquid to obtain the protective liquid containing the antibacterial agent.
8. The process for preparing natural stone materials containing antibacterial agents prepared by zinc substitution process as claimed in claim 7, wherein in step P1), the surfactant is one or two of organosilane, organosiloxane and sodium methyl silicate, or one or two of titanate and phosphate ester surfactants; the weight part ratio of the antibacterial agent to the surfactant to the water is 2:1: 2; in step P1), the antimicrobial agent is present in an amount of 0.5 to 1.5 wt% based on the weight of the antimicrobial protective solution.
9. The process for preparing natural stone containing an antibacterial agent prepared by zinc substitution process according to claim 4, wherein said antibacterial protection solution coating step comprises:
q1) polishing the processed natural stone with edible baking soda powder to remove surface stains;
q2) coating the antibacterial protection solution on the surface of the cleaned natural stone according to the using amount of 30-45 g/square meter, standing for 8 hours until the antibacterial protection solution permeates into the surface layer of the natural stone, and thus obtaining the natural stone containing the antibacterial agent prepared by the zinc replacement process.
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| CN1262043A (en) * | 2000-01-01 | 2000-08-09 | 华东理工大学 | Bimetal Cu-Ag colloid as antibacterial agent and its preparing process |
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| CN104312396A (en) * | 2014-10-10 | 2015-01-28 | 东莞市长安东阳光铝业研发有限公司 | Penetration type nano stone protecting agent and preparation method thereof |
| CN109819979A (en) * | 2019-03-15 | 2019-05-31 | 尚蒙科技无锡有限公司 | Nano silver copper bimetallic colloid/liquid of high anti-microbial property and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1262043A (en) * | 2000-01-01 | 2000-08-09 | 华东理工大学 | Bimetal Cu-Ag colloid as antibacterial agent and its preparing process |
| CN1539898A (en) * | 2003-11-03 | 2004-10-27 | 吉林省纳米技术应用工程（集团）股份 | Method of producing Nano Functional agent for protecting stone surface and water proof, soil repellent and antibacterial dimension stone |
| CN104312396A (en) * | 2014-10-10 | 2015-01-28 | 东莞市长安东阳光铝业研发有限公司 | Penetration type nano stone protecting agent and preparation method thereof |
| CN109819979A (en) * | 2019-03-15 | 2019-05-31 | 尚蒙科技无锡有限公司 | Nano silver copper bimetallic colloid/liquid of high anti-microbial property and preparation method thereof |
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Application publication date: 20201218 |
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| RJ01 | Rejection of invention patent application after publication |