CN111838183A - Composite metal colloid inorganic antibacterial agent, preparation method thereof and inorganic artificial stone thereof - Google Patents
Composite metal colloid inorganic antibacterial agent, preparation method thereof and inorganic artificial stone thereof Download PDFInfo
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- CN111838183A CN111838183A CN202010809268.5A CN202010809268A CN111838183A CN 111838183 A CN111838183 A CN 111838183A CN 202010809268 A CN202010809268 A CN 202010809268A CN 111838183 A CN111838183 A CN 111838183A
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- Prior art keywords
- silver
- copper
- antibacterial
- inorganic
- composite metal
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Links
- 239000000084 colloidal system Substances 0.000 title claims abstract description 114
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 100
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 92
- 239000002184 metal Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 239000002969 artificial stone Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 181
- 239000000843 powder Substances 0.000 claims abstract description 104
- DQBMWCJATVWEAH-UHFFFAOYSA-J P(=O)(OO)([O-])[O-].[Zr+4].OOP(=O)([O-])[O-] Chemical compound P(=O)(OO)([O-])[O-].[Zr+4].OOP(=O)([O-])[O-] DQBMWCJATVWEAH-UHFFFAOYSA-J 0.000 claims abstract description 80
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052709 silver Inorganic materials 0.000 claims abstract description 32
- 230000001954 sterilising effect Effects 0.000 claims abstract description 32
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 19
- 150000003378 silver Chemical group 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 148
- 239000011787 zinc oxide Substances 0.000 claims description 73
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 58
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 35
- 238000001179 sorption measurement Methods 0.000 claims description 35
- 229910001868 water Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 28
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 23
- 229910001923 silver oxide Inorganic materials 0.000 claims description 23
- 238000006722 reduction reaction Methods 0.000 claims description 21
- FFQJCVTUFKZOTA-UHFFFAOYSA-N [N+](=O)(O)[O-].[Zn].[Cu].[Ag] Chemical compound [N+](=O)(O)[O-].[Zn].[Cu].[Ag] FFQJCVTUFKZOTA-UHFFFAOYSA-N 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 claims description 10
- KAJXMBMHKRBHOW-UHFFFAOYSA-L P(=O)(OO)([O-])[O-].[Zr+4].[Na+] Chemical compound P(=O)(OO)([O-])[O-].[Zr+4].[Na+] KAJXMBMHKRBHOW-UHFFFAOYSA-L 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- AYKOTYRPPUMHMT-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag] AYKOTYRPPUMHMT-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XOPUACSFJCBKSC-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Zn+2].[Cu+2].[Ag+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Zn+2].[Cu+2].[Ag+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] XOPUACSFJCBKSC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 10
- 239000013543 active substance Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 39
- 239000000243 solution Substances 0.000 description 33
- 238000004659 sterilization and disinfection Methods 0.000 description 27
- 230000000694 effects Effects 0.000 description 22
- 239000004332 silver Substances 0.000 description 21
- 239000000126 substance Substances 0.000 description 20
- 238000001514 detection method Methods 0.000 description 17
- 241000222122 Candida albicans Species 0.000 description 16
- 229940095731 candida albicans Drugs 0.000 description 16
- -1 Silver ions Chemical class 0.000 description 13
- 241000191967 Staphylococcus aureus Species 0.000 description 13
- 229910021645 metal ion Inorganic materials 0.000 description 13
- 241000588724 Escherichia coli Species 0.000 description 12
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 230000003115 biocidal effect Effects 0.000 description 8
- 239000005751 Copper oxide Substances 0.000 description 7
- 229910000431 copper oxide Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005202 decontamination Methods 0.000 description 5
- 230000003588 decontaminative effect Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 231100000956 nontoxicity Toxicity 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QIRJMTNEXDJJHV-UHFFFAOYSA-J [Na+].P(=O)([O-])([O-])[O-].O[Zr+3] Chemical compound [Na+].P(=O)([O-])([O-])[O-].O[Zr+3] QIRJMTNEXDJJHV-UHFFFAOYSA-J 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000305071 Enterobacterales Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NYAWADGYOWCCLK-UHFFFAOYSA-N [Na].[Zr] Chemical compound [Na].[Zr] NYAWADGYOWCCLK-UHFFFAOYSA-N 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
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- 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
- A01N25/22—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 ingredients stabilising the active ingredients
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/67—Biocides
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
- C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2092—Resistance against biological degradation
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/54—Substitutes for natural stone, artistic materials or the like
- C04B2111/542—Artificial natural stone
Abstract
The invention discloses a composite metal colloid inorganic antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof. The composite metal colloid inorganic antibacterial agent comprises zirconium hydroxy phosphate micro powder, silver atoms, copper atoms and nano titanium dioxide; wherein, the silver atom and copper atom colloid are adsorbed on the surface micropores of the nano titanium dioxide, and the silver atom, copper atom and nano titanium dioxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder; the silver atoms are used as an activating agent, the copper atoms are used as an antibacterial agent to be activated, and the nano titanium dioxide is used as an ultraviolet sterilizing body. Under oxygen-containing humid environment, the copper atoms are oxidized into copper ions with antibacterial activity. The antibacterial active substance contained in the composite metal colloid inorganic antibacterial agent is not easy to lose. The inorganic artificial stone prepared by the composite metal colloid inorganic antibacterial agent has the characteristics of good heat resistance, broad-spectrum antibacterial property, excellent slow release property, low purchase cost and the like, and has better cost advantage.
Description
Technical Field
The invention relates to the technical field of antibacterial agents and artificial stones, in particular to a composite metal colloid inorganic antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof.
Background
The surface of the sodium zirconium hydroxyphosphate has a porous structure, a large specific surface area, strong adsorption capacity, good chemical stability and high temperature resistance, and has good binding force with the antibacterial metal ions adsorbed in the gaps, so that the slow release effect of the antibacterial metal ions can be improved. The sodium zirconium hydroxy phosphate structure has compatibility with various metal ions and can adsorb various metal ions simultaneously.
Silver ions carried by the antibacterial agent in the prior art can be quickly lost when meeting liquid with stronger acidity and alkalinity, and the slow release performance of the antibacterial agent is poor.
In the food processing industry, particularly the medical industry, in order to reduce the infection and transmission of bacteria, a workbench containing antibacterial substances is selected, but the workbench needs to be frequently cleaned, sometimes materials or medicaments with strong acidity or alkalinity need to be used, and common antibacterial agents contained in the workbench are easy to lose efficacy.
Silver ions are an antibacterial agent with excellent bactericidal properties, most of the raw materials are silver nitrate, and the purchase cost is high. And the silver nitrate belongs to strong oxidants, corrosive products and environmental pollutants, so that the use amount of the silver nitrate is reduced, and the method is more environment-friendly.
Therefore, it is necessary to develop an acid and alkali resistant antibacterial agent which can use other raw materials instead of silver ions to reduce the cost and can be prepared into an antibacterial agent having a good antibacterial effect and being less prone to loss, so as to meet the needs of the above industries.
Disclosure of Invention
The invention provides a composite metal colloid inorganic antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite metal colloid inorganic antibacterial agent comprises zirconium hydroxy phosphate micro powder, silver atoms, copper atoms and nano titanium dioxide; wherein the silver atom and copper atom colloid are adsorbed on the surface micropores of the nano titanium dioxide, and the silver atom, copper atom and nano titanium dioxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder; the silver atoms are used as an activating agent, the copper atoms are used as an antibacterial agent to be activated, and the nano titanium dioxide is used as an ultraviolet sterilizing body.
Preferably, the silver hydroxide solution further comprises zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on zirconium hydroxy phosphate micro powder, and the zinc oxide is used for delaying the alkalization of the silver oxide in an alkaline environment and avoiding the phenomenon that the silver oxide is firstly converted into silver hydroxide to be separated out, so that copper atoms cannot be converted into copper ions.
Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed on the zirconium hydroxy phosphate micro powder and the nano titanium dioxide are all reduced in sequence.
Preferably, the molar content ratio of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is 4:2:2: 1.
Further, the invention also provides a preparation method of the composite metal colloid inorganic antibacterial agent, which comprises the following specific steps:
s1) adding silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide into water, and stirring and mixing uniformly to obtain a silver-copper-zinc nitric acid solution;
s2) adding zirconium sodium hydroxy phosphate micro powder into silver-copper-zinc-nitric acid solution, adjusting the pH value by using dilute nitric acid and dilute sodium hydroxide solution, carrying out water bath at constant temperature, and rapidly and uniformly stirring to obtain zirconium hydroxy phosphate micro powder adsorption solution;
s3) putting the zirconium hydroxy phosphate micro powder adsorption solution into an oven for drying to prepare zirconium hydroxy phosphate micro powder adsorption dry powder;
s4) conveying the zirconium hydroxy phosphate micro powder adsorption dry powder into a reduction sintering furnace for heating and roasting;
s5) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain zirconium hydroxy phosphate micro powder adsorption baking powder;
s6) sieving the zirconium hydroxy phosphate micro powder adsorption baking powder to obtain the composite metal colloid inorganic antibacterial agent.
Further, in the step S1, the silver copper zinc nitric acid solution contains copper nitrate, nano titanium dioxide, zinc oxide, silver nitrate and water in a mixing molar ratio of 2.5:1:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the water bath temperature is 50 ℃, and the pH value is 3-4.
Further, in the step 3, the drying temperature is 100-; in the step S4, the roasting temperature is 500-600 ℃, and the roasting time is 3-4 hours.
Further, in the step S5, the pressure of adding the carbon monoxide is 0.1 to 0.15MPa, and the time of the reduction reaction is 0.8 to 1 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.
The invention further provides an inorganic artificial stone, which comprises the raw materials of an antibacterial bonding liquid, wherein the raw materials of the antibacterial bonding liquid comprise the composite metal colloid inorganic antibacterial agent, the antibacterial bonding liquid is used for bonding the solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
Further, the composite metal colloid inorganic antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
The invention has the beneficial effects that:
the composite metal colloid inorganic antibacterial agent is zirconium hydroxy phosphate micro powder loaded with silver, copper metal colloid, nano titanium dioxide and zinc oxide, and has the characteristics of good heat resistance, high-efficiency broad-spectrum antibacterial property, excellent slow release property, ultraviolet ray reinforced sterilization and the like. Compared with the silver-loaded zirconium hydroxyphosphate antibacterial agent, the composite metal colloid inorganic antibacterial agent has better cost advantage.
The composite metal colloid inorganic antibacterial agent contains double adsorption carriers and various antibacterial substances, has good broad-spectrum sterilization effect, is not easy to run off, is suitable for places with high antibacterial sterilization requirements, and is particularly suitable for the medical and food processing industries.
The nano titanium dioxide, zinc oxide and copper nitrate have wide raw material sources and low purchase cost, so that the composite metal colloid inorganic antibacterial agent has better cost advantage and more optimized slow release performance compared with the silver ion-loaded zirconium hydroxyphosphate antibacterial agent in the prior art.
The invention provides a preparation method of the composite metal colloid inorganic antibacterial agent, and the prepared inorganic antibacterial agent containing a double-carrier structure and multiple antibacterial substances is convenient to store and use.
The invention also provides an inorganic artificial stone using the composite metal colloid inorganic antibacterial agent, and the prepared inorganic artificial stone has excellent antibacterial performance and antibacterial durability.
Detailed Description
The technical solution of the present invention is further described below in specific embodiments.
A composite metal colloid inorganic antibacterial agent comprises zirconium hydroxy phosphate micro powder, silver atoms, copper atoms and nano titanium dioxide; wherein the silver atom and copper atom colloid are adsorbed on the surface micropores of the nano titanium dioxide, and the silver atom, copper atom and nano titanium dioxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder; the silver atoms are used as an activating agent, the copper atoms are used as an antibacterial agent to be activated, and the nano titanium dioxide is used as an ultraviolet sterilizing body.
In the composite metal colloid inorganic antibacterial agent, silver atoms are used as an activating agent, copper atoms are used as an antibacterial agent to be activated, and nano titanium dioxide is used as an ultraviolet sterilizing body; the nano titanium dioxide is anatase nano titanium dioxide.
The zirconium hydroxy phosphate micro powder is prepared from sodium zirconium hydroxy phosphate, has hydrophilic groups and has good compatibility with aqueous solution. The sodium zirconium hydroxy phosphate has large specific surface area and high surface energy, can be used as an ideal carrier of the bactericidal and antibacterial metal ions, can store a large amount of bactericidal and antibacterial metal colloid, can reduce the loss of the bactericidal and antibacterial metal colloid, and improves the release concentration and the sustained release capacity of the bactericidal and antibacterial metal ions.
The silver-copper metal colloid loaded on the zirconium phosphate hydroxyl micropowder and the nano titanium dioxide can release active silver atoms and copper atoms, and the metal atom colloid is less prone to being damped and lost than a metal ion colloid, so that the slow-release effective period of the antibacterial substance can be prolonged.
When silver atoms are in a humid environment containing oxygen, such as contact with water, acid or alkaline solution, the silver atoms are oxidized into silver ions; when silver atom, silver ion and copper atom exist simultaneously, the electrode potential of silver ion/silver is 0.80 volt, the electrode potential of copper ion/copper is 0.34 volt, and due to the potential difference of electrode potential, the silver ion in the metal colloid can oxidize the copper atom in the colloid into colloid copper ion, and the silver ion is reduced into silver atom, and the chemical reaction formula is 2Ag++Cu＝2Ag+Cu++The potential difference of which is released E0＝ψAg+/Ag-ψCu++0.80-0.34-0.46 volt, and the copper atom in colloid is converted into Cu with bactericidal and antibacterial activity++Ions.
When the composite metal colloid inorganic antibacterial agent is in an oxygen-containing humid environment, silver atoms are oxidized into silver ions, copper atoms in the silver ion oxidized colloid are colloid copper ions and are copper ions with antibacterial activity, and the antibacterial activity of the composite metal colloid inorganic antibacterial agent is activated. The dried inorganic antibacterial agent of the composite metal colloid has good stability, and antibacterial active substances are not easy to lose.
The nano titanium dioxide selected by the invention is anatase type nano titanium dioxide which is a white powdery substance, has stable chemical property, strong photocatalytic oxidation reduction capability, high chemical stability and no toxicity, can be excited by visible light below 380nm, has strong oxidation effect under the action of sunlight or ultraviolet light, and can oxidize and decompose harmful organic matters such as formaldehyde, methylamine, benzene, xylene, ammonia, TVOC and the like, pollutant odor, bacteria and the like into harmless carbon dioxide and water. Has the characteristics of bacteriostasis, sterilization, disinfection, pollutant removal, hydrophilicity, self-cleaning property and the like, and has the characteristics of low price, no toxicity, and good acid-base chemical stability.
The nano titanium dioxide has good bactericidal effect under the irradiation of ultraviolet rays, has catalytic effect on the oxidative decomposition of organic pollutants, and has good adsorption performance. Is very suitable for the daily working environment needing ultraviolet sterilization, can improve the sterilization and decontamination effects, and can assist the adsorbed antibacterial substances to improve the broad-spectrum sterilization efficiency.
The composite metal colloid inorganic antibacterial agent contains double adsorption carriers and various antibacterial substances, has good broad-spectrum sterilization effect, is not easy to run off, is suitable for places with high antibacterial sterilization requirements, and is particularly suitable for the medical and food processing industries.
Preferably, the silver hydroxide solution further comprises zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on zirconium hydroxy phosphate micro powder, and the zinc oxide is used for delaying the alkalization of the silver oxide in an alkaline environment and avoiding the phenomenon that the silver oxide is firstly converted into silver hydroxide to be separated out, so that copper atoms cannot be converted into copper ions.
The zinc oxide is an antibacterial agent with a good antibacterial effect, has photosensitive bactericidal performance, is wide in raw material source and low in purchase cost, and has superior cost advantage compared with silver nitrate powder because silver nitrate is a raw material of silver atoms.
The silver oxide colloid is adsorbed on the composite metal colloid inorganic antibacterial agent, has better stability and is not easy to lose, the composite metal colloid inorganic antibacterial agent contains various active antibacterial substances, has wider product application range and more comprehensive antibacterial effect, and has better finished product advantages while improving the slow release performance.
The zinc oxide adsorbed on the composite metal colloid inorganic antibacterial agent is used for protecting silver oxide from being alkalized in an alkaline environment and preventing the silver oxide from being separated out by being converted into silver hydroxide, so that the conversion rate of copper atoms into copper ions is reduced, and the antibacterial performance of the composite metal colloid inorganic antibacterial agent is reduced. Only after the zinc oxide is consumed by the reaction, the silver oxide is alkalized and converted into silver hydroxide to be separated out.
The zinc oxide has good activity, can improve the adverse effect of precipitation under the alkaline environment of silver ions, and has the following chemical reaction mechanism.
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 used as a stabilizer of silver ions, so that the stability of the antibacterial performance of the composite metal colloid inorganic antibacterial agent can be improved, and the alkaline application range of the composite metal colloid inorganic antibacterial agent can be widened by increasing the using amount and proportion of the zinc oxide.
Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed on the zirconium hydroxy phosphate micro powder and the nano titanium dioxide are all reduced in sequence.
Preferably, the molar content ratio of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is 4:2:2: 1.
The composite metal colloid inorganic antibacterial agent contains silver atoms in oxygen-containing humid environment, and can effectively convert copper atoms into copper ions. Under the condition of keeping the effect of converting copper ions of silver atoms, the using amount of silver nitrate in the raw materials is reduced, and the using amounts of copper nitrate and zinc oxide are increased, so that the cost advantage of the composite metal colloid inorganic antibacterial agent can be effectively improved, and the composite metal colloid inorganic antibacterial agent is more environment-friendly.
The molar content ratio of copper atoms, nano titanium dioxide, zinc oxide and silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is 4:2:2:1, so that the cost performance is better, the composite metal colloid inorganic antibacterial agent has a good antibacterial effect, and a better cost advantage can be obtained.
The nano titanium dioxide can have a bactericidal effect only under the irradiation of near ultraviolet rays and low-frequency visible light, and simultaneously serves as an adsorption carrier of part of antibacterial metal ions, so that the molar content ratio of the nano titanium dioxide in the total mass of copper atoms, the nano titanium dioxide, zinc oxide and silver atoms is not more than 25%, otherwise, the number of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed on the nano titanium dioxide is too large, and the adsorption rate of the copper atoms, the zinc oxide and the silver atoms in the zirconium hydroxy phosphate micro powder is relatively low. And the molar content ratio of the nano titanium dioxide in the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms is lower than 20%, so that the sterilizing rate under the ultraviolet irradiation is low, and the method is not suitable for the requirements of high-standard use places.
The molar content ratio of the zinc oxide to the silver atoms is 2:1, the probability that the silver oxide is firstly alkalized can be reduced, the conversion rate of converting copper atoms adsorbed by the zirconium hydroxy phosphate micro powder into copper ions can be improved, and the stability of the antibacterial performance of the composite metal colloid inorganic antibacterial agent can be ensured.
Further, the invention also provides a preparation method of the composite metal colloid inorganic antibacterial agent, which comprises the following specific steps:
s1) adding silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide into water, and stirring and mixing uniformly to obtain a silver-copper-zinc nitric acid solution;
s2) adding zirconium sodium hydroxy phosphate micro powder into silver-copper-zinc-nitric acid solution, adjusting the pH value by using dilute nitric acid and dilute sodium hydroxide solution, carrying out water bath at constant temperature, and rapidly and uniformly stirring to obtain zirconium hydroxy phosphate micro powder adsorption solution;
s3) putting the zirconium hydroxy phosphate micro powder adsorption solution into an oven for drying to prepare zirconium hydroxy phosphate micro powder adsorption dry powder;
s4) conveying the zirconium hydroxy phosphate micro powder adsorption dry powder into a reduction sintering furnace for heating and roasting;
s5) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain zirconium hydroxy phosphate micro powder adsorption baking powder;
s6) sieving the zirconium hydroxy phosphate micro powder adsorption baking powder to obtain the composite metal colloid inorganic antibacterial agent.
The preparation method of the composite metal colloid inorganic antibacterial agent comprises the steps of dipping the zirconium hydroxy phosphate micro powder in an aqueous solution of silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide, wherein the nano titanium dioxide is insoluble in a nitric acid solution, and when the concentrations of the silver nitrate, the copper nitrate and the zinc oxide are higher and higher than that of the nano titanium dioxide, part of Ag in the nano titanium dioxide is adsorbed on the surface of the nano titanium dioxide+、Cu++And Zn++Ions, remainder Ag+、Cu++And Zn++Ions are adsorbed on the zirconium hydroxy phosphate micro powder, and the zirconium hydroxy phosphate micro powder with larger specific surface area adsorbs the nano titanium dioxide on the surface of the zirconium hydroxy phosphate micro powder to form a double composite carrier. Therefore, the composite metal colloid inorganic antibacterial agent has more efficient and broad-spectrum antibacterial performance.
Because of the high temperature stability of the sodium zirconium hydroxy phosphate, after the antibacterial metal ion salt solution is adsorbed at normal temperature, the antibacterial metal ions are oxidized into oxides by baking at high temperature, so that the binding force of the antibacterial metal ions in the sodium zirconium hydroxy phosphate is enhanced, the metal ions are further reduced into metal atoms, the dissociated antibacterial metal atoms are controlled, the antibacterial metal elements in the carrier are ensured to generate good slow release effect, and the long-term antibacterial effect is achieved.
The metal ions adsorbed on the zirconium hydroxy phosphate micro powder and the nano titanium dioxide are Ag+、Cu++And Zn++Ion, nano titanium dioxide is adsorbed on zirconium hydroxy phosphate micro powder, and then the zirconium hydroxy phosphate micro powder is baked at high temperature after being dried, so that Ag is obtained+、Cu++And Zn++The ions are converted into silver oxide, copper oxide and zinc oxide, then the silver oxide and the copper oxide are reduced into silver atom colloid and copper atom colloid by carbon monoxide under high temperature vacuum, nano titanium dioxide and zinc oxide can not be reduced, and are still adsorbed on the surface of the zirconium hydroxy phosphate micro powder in a colloid form, and metal colloid and zinc oxide colloid containing silver and copper atoms are adsorbed on the surface of the zirconium hydroxy phosphate micro powder to form the zirconium hydroxy phosphate micro powder with antibacterial activity.
Common zinc oxide powder is dissolved into Zn++The ions are oxidized again to oxidize the zinc, and the formed colloid is adsorbed on the zinc oxide on the surface of the zirconium hydroxy phosphate micro powder, so the antibacterial agent has broad-spectrum antibacterial performance and good antibacterial effect on candida albicans.
The nano titanium dioxide is a white powdery substance, has stable chemical properties, strong photocatalytic oxidation reduction capability, high chemical stability and no toxicity, can be excited by visible light below 380nm, has extremely strong oxidation effect under the action of sunlight or ultraviolet light, and can oxidize and decompose harmful organic matters such as formaldehyde, methylamine, benzene, xylene, ammonia, TVOC and the like, pollutant odor, bacteria and the like into harmless carbon dioxide and water. Has the characteristics of bacteriostasis, sterilization, disinfection, pollutant removal, hydrophilicity, self-cleaning property and the like, and has the characteristics of low price, no toxicity and good chemical stability.
The nano titanium dioxide has good bactericidal effect under the irradiation of ultraviolet rays, has catalytic effect on the oxidative decomposition of organic pollutants, and also has better adsorption performance. The ultraviolet sterilization and decontamination agent is very suitable for the daily working environment requiring ultraviolet sterilization, can provide sterilization and decontamination effects, and can assist the adsorbed antibacterial substances to improve the broad-spectrum sterilization efficiency.
The nano titanium dioxide can adopt nano titanium dioxide, the zinc oxide adopts zinc oxide powder, the copper oxide adopts copper nitrate powder, the raw material source is wide, and the purchase cost is low.
Therefore, the composite metal colloid antibacterial agent is zirconium hydroxy phosphate micro powder loaded with silver atoms, copper atoms, nano titanium dioxide and zinc oxide, and has the characteristics of good heat resistance, high-efficiency broad-spectrum antibacterial property, excellent slow release property, ultraviolet ray reinforced sterilization and the like. Compared with the silver-loaded zirconium hydroxyphosphate antibacterial agent, the composite metal colloid antibacterial agent has better cost advantage.
Further, in the step S1, the silver copper zinc nitric acid solution contains copper nitrate, nano titanium dioxide, zinc oxide, silver nitrate and water in a mixing molar ratio of 2.5:1:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the water bath temperature is 50 ℃, and the pH value is 3-4.
The molar ratio of copper nitrate to nano titanium dioxide to zinc oxide to silver nitrate to water is 2.5:1:1:0.5:20, the total content of silver, copper and zinc ions and the nano titanium dioxide antibacterial active substance is high, and the adsorption efficiency of zirconium hydroxy phosphate can be improved.
The ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the concentration of the contained antibacterial active substance is high, and the composite metal colloid inorganic antibacterial agent has a good antibacterial effect and is convenient to store and use.
The water bath temperature is 50 ℃, the pH value is 3-4, and the dissolution and adsorption efficiency of silver ions can be improved.
Further, in the step 3, the drying temperature is 100-; in the step S4, the roasting temperature is 500-600 ℃, and the roasting time is 3-4 hours.
The drying temperature is not lower than 100 ℃, and the zirconium hydroxy phosphate micro powder can be fully dried to adsorb the water contained in the solution.
Silver nitrate and copper nitrate are roasted at high temperature to form silver oxide and copper oxide, and then the silver oxide and the copper oxide are reduced by carbon monoxide at high temperature under vacuum to form metal colloid, and the metal colloid of silver and copper is gathered on the surface of zirconium hydroxy phosphate micro powder to be condensed into zirconium hydroxy phosphate micro powder with antibacterial activity.
The decomposition temperature of the silver nitrate is 440 ℃, the silver nitrate can be completely decomposed and oxidized into silver oxide by roasting at the temperature of more than 500 ℃, the decomposition temperature of the copper nitrate is lower than that of the silver nitrate, and the decomposition and oxidation of the copper nitrate are more complete. The high-temperature treatment can also increase the adsorbed strength of silver ions and prolong the slow-release effective period of the antibacterial agent, the effect is better at the temperature of 500-600 ℃, and the activity of the silver ions can be destroyed when the temperature exceeds 600 ℃, so that the proportion of the silver ions to be separated out and reduced is influenced. Therefore, the composite metal colloid inorganic antibacterial agent has relatively stable antibacterial metal precipitation performance and silver discoloration resistance.
Further, in the step S5, the pressure of adding the carbon monoxide is 0.1 to 0.15MPa, and the time of the reduction reaction is 0.8 to 1 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.
When the roasting is carried out at 500 ℃, the reduction effective rate of the silver oxide and the copper oxide can be reduced when the pressure of the added carbon monoxide is lower than 0.1MPa, and resources are wasted when the pressure is higher than 0.15 MPa. The roasting temperature is 500-600 ℃, the temperature is higher than 440 ℃ and is maintained for 0.8-1 hour, so that the reduction rate of the silver oxide and the copper oxide reduced into silver-copper colloid can be improved. The reducing gas can also adopt hydrogen, and carbon monoxide is more convenient and lower in cost than hydrogen, so that the method has better economic benefit.
The smaller the particle size of the zirconium hydroxy phosphate micro powder is, the larger the surface area ratio of the zirconium hydroxy phosphate micro powder is, the higher the activity of the loaded silver-copper colloid is, the particle size of the conventional zirconium hydroxy phosphate micro powder is 325 meshes, and the bonded composite metal colloid inorganic antibacterial agent with overlarge particle size can be removed by filtering with a 400-mesh filter sieve, so that the bad appearance of particles with uneven distribution is avoided when the zirconium hydroxy phosphate micro powder is used.
The invention further provides an inorganic artificial stone, which comprises the raw materials of an antibacterial bonding liquid, wherein the raw materials of the antibacterial bonding liquid comprise the composite metal colloid inorganic antibacterial agent, the antibacterial bonding liquid is used for bonding the solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
The antibacterial bonding liquid is used for bonding solid raw materials of the inorganic artificial stone and is uniformly distributed in the inorganic artificial stone. Include in the inorganic antibiotic agent of composite metal colloid even distribution in antibiotic bonding liquid in the inorganic rostone, and be bonded in the inorganic rostone, can make the antibiotic effect of inorganic rostone more stable and even.
The solid raw materials of the inorganic artificial stone comprise quartz stone, marble, granite, feldspar, super quartz stone and colorant.
Further, the composite metal colloid inorganic antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
Has the advantages that: the inorganic artificial stone containing 1-3% of the composite metal colloid inorganic antibacterial agent can meet the requirements of JC/T897-2014 antibacterial ceramic product antibacterial performance standard through detection on antibacterial performance and antibacterial durability. The content of the composite metal colloid inorganic antibacterial agent contained in the inorganic artificial stone is lower than 1%, and the antibacterial performance index does not reach the standard; the content of the composite metal colloid inorganic antibacterial agent contained in the inorganic artificial stone is higher than 3%, the antibacterial performance is excessive, and resources are wasted.
Because the main raw materials of prior art's inorganic rostone are mostly cement system material, and basicity is higher, contains water with the raw materials antibiotic bonding liquid disposes, adds the prefabricated material of inorganic rostone again, can avoid the basicity of the cement system material in the inorganic rostone to destroy silver ion that antibiotic bonding liquid contains avoids silver ion to become silver hydroxide, leads to the conversion rate reduction of copper atom conversion copper ion, and influences the antibacterial property of the inorganic rostone that composite metal colloid inorganic antibacterial agent made.
Examples and comparative examples
The inorganic artificial stone of each example and comparative example was prepared as follows, and commercially available sodium zirconium phosphate hydroxide fine powder having a particle size D50 ≦ 10 μm and a specific surface area ≧ 50m was used as the sodium zirconium phosphate hydroxide fine powder2And/g, the purity is not less than 95%, and the silver nitrate, the nano titanium dioxide, the copper nitrate and the zinc oxide are commercially available chemically pure powder.
The method comprises the following specific steps:
1. a composite metal colloid inorganic antibacterial agent comprises zirconium hydroxy phosphate micro powder, silver atoms, copper atoms, nano titanium dioxide and zinc oxide, wherein the silver atoms, the copper atoms and the nano titanium dioxide are all colloids adsorbed on the zirconium hydroxy phosphate micro powder; the ultraviolet sterilization body is nano titanium dioxide, and the silver atoms and the copper atoms are adsorbed on the surface micropores of the ultraviolet sterilization body;
the molar contents of copper atoms, zinc oxide and silver atoms adsorbed on the zirconium hydroxy phosphate micro powder and the nano titanium dioxide are sequentially reduced.
The molar content ratio of the copper atoms to the nano titanium dioxide to the zinc oxide to the silver atoms is 4:2:2: 1.
2. The preparation method of the composite metal colloid inorganic antibacterial agent comprises the following specific steps:
s1) preparing an aqueous solution containing silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide to obtain a silver-copper-zinc nitric acid solution;
s2) adding zirconium sodium hydroxy phosphate micro powder into silver-copper-zinc-nitric acid solution, adjusting the pH value by using dilute nitric acid and dilute sodium hydroxide solution, carrying out water bath at constant temperature, and rapidly and uniformly stirring to obtain zirconium hydroxy phosphate micro powder adsorption solution;
s3) putting the zirconium hydroxy phosphate micro powder adsorption solution into an oven for drying to prepare zirconium hydroxy phosphate micro powder adsorption dry powder;
s4) conveying the zirconium hydroxy phosphate micro powder adsorption dry powder into a reduction sintering furnace for heating and roasting;
s5) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain zirconium hydroxy phosphate micro powder adsorption baking powder;
s6) sieving the zirconium hydroxy phosphate micro powder adsorption baking powder to obtain the composite metal colloid inorganic antibacterial agent.
In the step S1, the silver-copper-zinc-nitric acid solution contains copper nitrate, nano titanium dioxide, zinc oxide, silver nitrate and water at a mixing molar ratio of 2.5:1:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the water bath temperature is 50 ℃, and the pH value is 3-4; in the step 3, the drying temperature is 100-120 ℃; in the step S4, the roasting temperature is 500-600 ℃, and the roasting time is 3-4 hours. In the step S5, the pressure of adding the carbon monoxide is 0.1-0.15MPa, and the time of the reduction reaction is 0.8-1 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.
3. The preparation inorganic rostone, the raw materials of inorganic rostone include antibiotic bonding liquid, antibiotic bonding liquid contains more than compound metal colloid inorganic antibacterial agent, the raw materials composition of antibiotic bonding liquid still includes water, antibiotic bonding liquid is prefabricated mixed liquid, compound metal colloid inorganic antibacterial agent accounts for the percentage of the total quality of inorganic rostone and is 1-3%.
4. The contents and ratios of the specific raw material components and the parameters in each example are shown in Table 1, and the contents and ratios of the specific raw material components and the parameters in each ratio are shown in Table 2.
5. The inorganic artificial stone prepared in each example and comparative example was sampled with reference to JC/T897-2014 "antibacterial property of antibacterial ceramic article" standard, and the antibacterial properties and antibacterial durability of escherichia coli, staphylococcus aureus and candida albicans were tested, and the test results of examples and base materials are shown in table 1, and the test results of comparative example are shown in table 1.
TABLE 1 data and test results for the examples and substrates
TABLE 2 comparative data and test results
The following is an analysis explanation based on the above cases and test results of the respective 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, and the detection results of the antibacterial rates of the antibacterial performance and the antibacterial rate of the antibacterial durability of escherichia coli, staphylococcus aureus and candida albicans of the base material are unqualified.
2. Analysis of the test results of examples 1 to 6:
(1) the antibacterial performance and antibacterial durability of the escherichia coli, staphylococcus aureus and candida albicans of examples 1-3 were all the percent (%) pass, and the numerical values of the antibacterial rates were increased in order, which shows that the antibacterial effect is enhanced with the increase of the active copper ions.
(2) Examples 1 and 2 differ from example 3 in that: the molar ratio of copper nitrate is less than 2.5, the molar ratio is respectively 2.0 and 2.3, and the detection results of the antibacterial rate (%) of the antibacterial performance and the antibacterial rate (%) of the antibacterial durability performance of the enterobacteria, the staphylococcus aureus and the candida albicans in the examples 1 and 2 are both qualified and meet the qualified standard; the comparison with the detection results of the examples 1 and 2 shows that the antibacterial and bactericidal effect of the example 3 is best, and the silver-copper-zinc-nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and water in a molar mixing ratio of 2.5:1:0.5: 20; therefore, the ratio of the silver-copper-zinc-nitric acid solution to the zirconium hydroxy phosphate micro powder is 1:4, the contained composite metal colloid inorganic antibacterial agent accounts for 1% of the total mass of the inorganic artificial stone, the molar mixing ratio of copper nitrate, zinc oxide, silver nitrate and water in the silver-copper-zinc-nitric acid solution is 2:1:0.5:20, the inorganic artificial stone prepared from the composite metal colloid inorganic antibacterial agent can have a good antibacterial effect, and the inorganic artificial stone is suitable for being used in places with high standard requirements; the molar content ratio of copper atoms, nano titanium dioxide, zinc oxide and silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is 4:2:2:1, so that the cost performance is high, and the requirements of conventional antibacterial and bactericidal standards can be met.
(3) Example 4 differs from example 3 in that: the zinc oxide is not added in the embodiment 4, and the detection results of the antibacterial performance and antibacterial durability antibacterial rate of escherichia coli and staphylococcus aureus in the embodiment 4 are both very excellent and higher than 95%; but the detection results of the antibacterial performance and antibacterial durability of the candida albicans in the example 4 are not qualified; the zinc oxide has a relatively outstanding antibacterial effect on candida albicans, and the copper ions have a general antibacterial effect on candida albicans;
(4) example 5 differs from example 4 in that: in example 5, the silver nitrate with the content increased by 0.5 mol ratio is not added, and the detection results of the antibacterial performance and antibacterial durability of the candida albicans of example 5 are qualified, which indicates that the increased content of 0.5 mol of the silver nitrate has a prominent antibacterial effect on the candida albicans; comparing with the examples 1-5, the zinc oxide with the concentration ratio of 1 mol ratio can replace silver ions to have more outstanding antibacterial effect on candida albicans;
(5) example 6 differs from example 1 in that: the illumination conditions are different, the daily indoor light in daytime is adopted in the example 1, the ultraviolet irradiation for 8 hours is adopted in the example 8, the antibacterial performance and antibacterial rate detection results of the example 8 are all qualified, and the food processing field can obtain good sterilizing and antibacterial effects only by adopting the ultraviolet irradiation for 8 hours at night; the mode of ultraviolet irradiation is not suitable for durability test, so that relevant detection is not implemented;
(6) the components and the detection results of examples 1 to 6 were comprehensively analyzed to find that: the raw material components of the antibacterial binding liquid also comprise water, and the antibacterial binding liquid is a pre-prepared mixed liquid; the composite metal colloid inorganic antibacterial agent is effective, and the antibacterial binding liquid and the prepared inorganic artificial stone have good antibacterial effect and good durability. The ratio of the silver-copper-zinc-nitric acid solution to the zirconium hydroxy phosphate micro powder is 1:4, the contained composite metal colloid inorganic antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone, and the molar mixing ratio of copper nitrate, zinc oxide, silver nitrate and water in the silver-copper-zinc-nitric acid solution is 2.5:1:0.5: 20; the inorganic artificial stones prepared from the composite metal colloid inorganic antibacterial agent can be guaranteed to have optimal antibacterial effect; the molar content ratio of copper atoms, zinc oxide atoms and silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is 4:2:2:1, so that the cost performance is high.
3. Comparative example 1 was analyzed, comparing to example 1, the difference of comparative example 1 is: the time of the reduction reaction of comparative example 1 is 0.5 hour, and the lower limit of less than 0.8 hour decreases the reduction rate of silver oxide, thus decreasing the conversion rate of copper ions of the antibacterial function, resulting in that the results of the tests of antibacterial performance antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus of comparative example 1 are not good.
4. Comparative example 2 was analyzed, and compared to example 1, the difference of comparative example 2 was: the molar ratio of the copper nitrate added in the comparative example 2 is 1.5, and the molar content ratio of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms which are less than the molar content ratio of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed by the zirconium hydroxyphosphate micropowder is set to be 4:2:2:1, so that the content of copper ions with an antibacterial function is reduced, and the detection results of the antibacterial performance antibacterial rate and the antibacterial durability antibacterial rate (%) of escherichia coli and staphylococcus aureus in the comparative example 2 are unqualified.
5. Comparative example 3 was analyzed, and compared to example 1, the difference of comparative example 3 was: the molar ratio of the silver nitrate added in the comparative example 3 is 1, the molar content ratio of copper atoms, nano titanium dioxide, zinc oxide and silver atoms which are adsorbed by the zirconium hydroxy phosphate micro powder is set to be 4:2:2:1, and the detection results of the antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus and candida albicans in the comparative example 3 reach the highest limit, so that resources are wasted due to excessive quality.
6. Comparative example 4 was analyzed, comparing to example 1, the difference of comparative example 4 is: the molar ratio of the silver nitrate added in the comparative example 4 is 0.3, and the molar content ratio of copper atoms, nano titanium dioxide, zinc oxide and silver atoms which are lower than that of the zirconium hydroxy phosphate micro powder is set to be 4:2:2:1, so that copper ions are not completely converted, and the detection results of the antibacterial performance and antibacterial rate (%) of the antibacterial durability performance of escherichia coli and staphylococcus aureus in the comparative example 4 are not qualified; therefore, the molar content ratio of copper atoms, nano titanium dioxide, zinc oxide and silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is set to be 4:2:2:1, which is more suitable.
7. Comparative example 5 was analyzed, and compared to example 1, the difference of comparative example 5 was: the antibacterial bonding solution of comparative example 5 is not a pre-prepared mixed solution, and the zinc oxide is not added, silver atoms adsorbed by the zirconium hydroxy phosphate micro powder are alkalized in an alkaline environment, the effect of copper oxide atoms as copper ions is lost, and the detection results of antibacterial performance antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus and candida albicans of the prepared inorganic artificial stone are not qualified.
8. Comparative example 6 was analyzed, comparing with example 1 and comparative example 5, the difference of comparative example 6 is: although the antibacterial binding fluid of comparative example 5 is not a prefabricated mixed fluid, the detection results of the antibacterial performance and antibacterial durability (%) of escherichia coli, staphylococcus aureus and candida albicans of the prepared inorganic artificial stone are all not qualified by adding the zinc oxide, but the antibacterial performance and antibacterial durability (%) of the escherichia coli, staphylococcus aureus and candida albicans of the detection results are better improved than those of comparative example 5, which shows that the zinc oxide has a specific and obvious delaying effect on basification of silver atoms in an alkaline environment and has a good stability effect on the composite metal colloid inorganic antibacterial agent.
9. Comparative examples 7 and 8 were analyzed, and in contrast to example 1, comparative examples 7 and 8 differ by: the content ratios of the added antibacterial active carbon antibacterial agents are different, wherein 0.7 percent of the comparative example 7 is less than 1 percent, and 3.5 percent of the comparative example 8 is more than 3 percent; the results of the tests of the antibacterial performance and antibacterial durability (%) of comparative example 7 were all unqualified; the results of the tests of antibacterial property antibacterial rate and antibacterial durability antibacterial rate (%) of comparative example 8 were all acceptable, but the improvement in comparison with example 3 was limited, and the results of the tests of antibacterial property antibacterial rate and antibacterial durability antibacterial rate (%) of example 3 were all excellent, so that it was appropriate to set the composite metal colloid inorganic antibacterial agent to 1-3% by mass of the total mass of the inorganic artificial stone.
10. Comparative example 9 was analyzed, and compared to example 1, comparative example 9 differs in that: the detection result of the comparative example 9 shows that the nano titanium dioxide is unqualified, but the nano titanium dioxide still has obvious effect and reaches 80 percent of sterilization rate, which shows that the photosensitive sterilization performance of the nano titanium dioxide has good effect.
In conclusion, the inorganic artificial stone prepared by using the composite metal colloid inorganic antibacterial agent has excellent antibacterial effects on escherichia coli, staphylococcus aureus and candida albicans.
The inorganic artificial stone containing 1-3% of the inorganic antibacterial agent of the composite metal colloid has antibacterial performance and antibacterial durability which can meet the standard requirements of JC/T897-2014 antibacterial ceramic product antibacterial performance.
The nano titanium dioxide has good bactericidal effect under the irradiation of ultraviolet rays, has catalytic effect on the oxidative decomposition of organic pollutants, and also has better adsorption performance. The ultraviolet sterilization and decontamination agent is very suitable for the daily working environment requiring ultraviolet sterilization, can provide sterilization and decontamination effects, and can assist the adsorbed antibacterial substances to improve the broad-spectrum sterilization efficiency.
The composite metal colloid inorganic antibacterial agent contains double adsorption carriers and various antibacterial substances, has good broad-spectrum sterilization effect, is not easy to run off, is suitable for places with high antibacterial sterilization requirements, and is particularly suitable for the medical and food processing industries.
The invention provides a preparation method of the composite metal colloid inorganic antibacterial agent, and the prepared inorganic antibacterial agent containing a double-carrier structure and multiple antibacterial substances is convenient to store and use.
The inorganic artificial stone using the composite metal colloid inorganic antibacterial agent has excellent antibacterial performance and antibacterial durability.
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 (10)
1. The inorganic antibacterial agent of a composite metal colloid is characterized by comprising zirconium phosphate hydroxyl micro powder, silver atoms, copper atoms and nano titanium dioxide; wherein the silver atom and copper atom colloid are adsorbed on the surface micropores of the nano titanium dioxide, and the silver atom, copper atom and nano titanium dioxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder; the silver atoms are used as an activating agent, the copper atoms are used as an antibacterial agent to be activated, and the nano titanium dioxide is used as an ultraviolet sterilizing body.
2. The inorganic antibacterial agent of composite metal colloid according to claim 1, further comprising zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is colloid adsorbed on zirconium hydroxy phosphate micropowder, and the zinc oxide is used for delaying silver oxide from being alkalized in an alkaline environment and avoiding silver oxide from being converted into silver hydroxide first and being separated out, so that copper atoms cannot be converted into copper ions.
3. The composite metal colloid inorganic antibacterial agent according to claim 2, characterized in that the molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the zirconium hydroxy phosphate fine powder and nano titanium dioxide are all decreased in this order.
4. The composite metal colloid inorganic antibacterial agent according to claim 2, wherein the molar content ratio of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed by the zirconium hydroxyphosphate micropowder is 4:2:2: 1.
5. The method for preparing the composite metal colloid inorganic antibacterial agent according to any one of claims 1 to 4, characterized by comprising the following specific steps:
s1) adding silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide into water, and stirring and mixing uniformly to obtain a silver-copper-zinc nitric acid solution;
s2) adding zirconium sodium hydroxy phosphate micro powder into silver-copper-zinc-nitric acid solution, adjusting the pH value by using dilute nitric acid and dilute sodium hydroxide solution, carrying out water bath at constant temperature, and rapidly and uniformly stirring to obtain zirconium hydroxy phosphate micro powder adsorption solution;
s3) putting the zirconium hydroxy phosphate micro powder adsorption solution into an oven for drying to prepare zirconium hydroxy phosphate micro powder adsorption dry powder;
s4) conveying the zirconium hydroxy phosphate micro powder adsorption dry powder into a reduction sintering furnace for heating and roasting;
s5) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain zirconium hydroxy phosphate micro powder adsorption baking powder;
s6) sieving the zirconium hydroxy phosphate micro powder adsorption baking powder to obtain the composite metal colloid inorganic antibacterial agent.
6. The method of claim 5, wherein in step S1, the silver-copper-zinc nitrate solution contains copper nitrate, nano titanium dioxide, zinc oxide, silver nitrate and water at a mixing molar ratio of 2.5:1:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the water bath temperature is 50 ℃, and the pH value is 3-4.
7. The method for preparing the composite metal colloid inorganic antibacterial agent according to claim 5, wherein in the step 3, the drying temperature is 100-120 ℃; in the step S4, the roasting temperature is 500-600 ℃, and the roasting time is 3-4 hours.
8. The method for producing a composite metal colloid inorganic antibacterial agent according to claim 5, wherein in the step S5, the pressure of adding the carbon monoxide is 0.1 to 0.15MPa, and the time of the reduction reaction is 0.8 to 1 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.
9. An inorganic artificial stone, characterized in that raw materials comprise an antibacterial bonding liquid, the raw material composition of the antibacterial bonding liquid comprises the composite metal colloid inorganic antibacterial agent of any one of claims 1 to 4, the antibacterial bonding liquid is used for bonding solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
10. The inorganic artificial stone according to claim 9, wherein the composite metal colloid inorganic antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
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