CN1459476A - Silver phosphate antibacterial modified titanium dioxide composite particle and preparation method and application thereof - Google Patents
Silver phosphate antibacterial modified titanium dioxide composite particle and preparation method and application thereof Download PDFInfo
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- CN1459476A CN1459476A CN 02117493 CN02117493A CN1459476A CN 1459476 A CN1459476 A CN 1459476A CN 02117493 CN02117493 CN 02117493 CN 02117493 A CN02117493 A CN 02117493A CN 1459476 A CN1459476 A CN 1459476A
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- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 68
- 239000011246 composite particle Substances 0.000 title claims abstract description 63
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 23
- 229910000161 silver phosphate Inorganic materials 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 246
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 122
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 53
- 239000010410 layer Substances 0.000 claims abstract description 40
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000011247 coating layer Substances 0.000 claims abstract description 13
- -1 silver phosphate modified titanium dioxide Chemical class 0.000 claims abstract description 8
- 239000004033 plastic Substances 0.000 claims abstract description 6
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 60
- 239000011259 mixed solution Substances 0.000 claims description 56
- 239000008187 granular material Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 42
- 230000003115 biocidal effect Effects 0.000 claims description 38
- 238000003483 aging Methods 0.000 claims description 32
- 230000032683 aging Effects 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 32
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 28
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 27
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 27
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 26
- 235000019800 disodium phosphate Nutrition 0.000 claims description 26
- 239000004332 silver Substances 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229960001866 silicon dioxide Drugs 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004115 Sodium Silicate Substances 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 14
- 235000019353 potassium silicate Nutrition 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000001488 sodium phosphate Substances 0.000 claims description 12
- 239000003242 anti bacterial agent Substances 0.000 claims description 9
- 229940088710 antibiotic agent Drugs 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical group N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- NDYNABNWLRVCDO-UHFFFAOYSA-N phosphoric acid silver Chemical compound [Ag].P(O)(O)(O)=O NDYNABNWLRVCDO-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical compound S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000013536 elastomeric material Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- 238000000926 separation method Methods 0.000 description 17
- 238000004062 sedimentation Methods 0.000 description 16
- 230000000845 anti-microbial effect Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- 235000011008 sodium phosphates Nutrition 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the field of inorganic nano modified functional materials and application thereof, and particularly relates to silver phosphate antibacterial modified titanium dioxide composite particles and a preparation method and application thereof. The antibacterial silver phosphate modified titanium dioxide composite particle with the antibacterial function is prepared by taking nano or submicron titanium dioxide particles as an inner core, coating the surfaces of the titanium dioxide particles with silicon dioxide and an aluminum oxide layer, or a silicon dioxide layer or an aluminum oxide layer to obtain porous titanium dioxide composite particles, and coating the surfaces of the titanium dioxide composite particles with a silver phosphate layer; the size of the obtained silver phosphate antibacterial modified titanium dioxide composite particles is 52-2150 nm, and the thicknesses of the silicon dioxide coating layer, the aluminum oxide coating layer and the silver phosphate coating layer are 1-50 nm respectively. (ii) a The composite particles are doped in paint, ceramic, plastic or rubber materials to be used as antibacterial materials. The composite particle has high purity, good dispersibility and antibacterial property.
Description
Technical field
The invention belongs to inorganic nanometer modified functional materials and Application Areas thereof, particularly relate to silver phosphate antibacterial modified titanium dioxide composite particle and its production and use.
Background technology
Along with the high speed development of industry and the raising of people's living standard, the requirement that improves environment for human survival is urgent day by day, and anti-biotic material is the important component part of environment-friendly materials.Since the eighties in 20th century, developed countries such as U.S., day begin to use in a large number anti-biotic material at aspects such as hospital, dwelling house, public place, daily necessitiess.
Titanium dioxide is a kind of important Inorganic Chemicals, is widely used in numerous areas such as coating, printing ink, plastics, rubber, papermaking, chemical fibre, pottery, enamel, with people's lives and national economy close getting in touch is arranged.A.Fujishima is at Pure ﹠amp; Appl.Chem., Vol.70, NO.11, P.2177-2187Interfacial photochemistry:Fundamentals andapplication middle finger goes out nano-TiO
2Be a kind of photocatalyst, have good anti-microbial effect.Point out general TiO among " but Chinese first anti-biotic material industry development conference collection of thesis " P49-55 " the antibacterial and mouldproof application performance research of nano titanium oxide "
2Thick product powder is assembled serious, and the coacervate granularity reaches submicron and micron order, is difficult for producing active group, can not bring into play due anti-microbial property.While TiO
2Anatase titanium dioxide TiO particularly
2Be subjected to uviolizing, oxygen can break away from the following TiO of reduction, particularly 100nm
2Particle, because surface-area is big, the photocatalytic activity height, the easier degraded that causes other organic supplementary component, and cause the variation of self tone causes the efflorescence of filming, fades, variable color, becomes fragile, and sticking power, corrosion resistance nature descend.Therefore in the practical application, how not only suppress but also utilize TiO
2Photocatalytic activity, develop a kind of TiO with antibacterial
2Very extensive fields be can be applied to, huge social benefit and economic benefit created.
The anti-bacterial powder, the antibacterial matrices that have had some excellent performances on the current market.Common antimicrobial prod adds these anti-biotic materials in the antimicrobial prod to exactly according to a certain percentage.The consistency of anti-bacterial powder or master batch and antimicrobial prod main component just affects the dispersiveness of anti-biotic material like this.If both consistencies are poor, will cause anti-biotic material skewness in goods, even occur reuniting, make it be difficult to bring into play anti-microbial effect, and can influence the apparent state and the mechanical property of goods.Therefore to being entrained in the inorganic composition TiO in the materials such as coating, plastics, pottery, enamel
2Carry out antibacterial modified preparation antimicrobial prod, not only avoided adding the possible defective that antiseptic-germicide brings but also can reduce adjustment original production process.
Summary of the invention
One of purpose of the present invention provides a kind of silver phosphate antibacterial modified titanium dioxide composite particle, this composite particles purity height, and good dispersity, and have micropore; This particle is a characteristic of utilizing Trisilver phosphate, coats the Trisilver phosphate of desired thickness on the titanium dioxide granule surface, makes particle have antibacterial properties.
Two of purpose of the present invention provides a kind of preparation method of silver phosphate antibacterial modified titanium dioxide composite particle.
Three of purpose of the present invention provides a kind of purposes of silver phosphate antibacterial modified titanium dioxide composite particle.
Four of purpose of the present invention provides a kind of preparation method of antibacterial powder paint.
Purpose of the present invention will further be set forth by following detailed description.
Silver phosphate antibacterial modified titanium dioxide composite particle with antibacterial of the present invention is as kernel with nanometer or submicron titanium dioxide granule, be coated with silicon oxide and alumina layer, silicon dioxide layer or alumina layer on the titanium dioxide granule surface, obtain having the titanium dioxide composite particle of porous character, be coated with the phosphoric acid silver layer on the titanium dioxide composite particle surface;
Or the layer that is coated with silicon oxide on the titanium dioxide granule surface, the titanium dioxide composite particle that obtains having porous character is coated with the phosphoric acid silver layer on the titanium dioxide composite particle surface, is coated with alumina layer at the phosphoric acid silver layer then;
Or be coated with alumina layer on the titanium dioxide granule surface, and obtain having the titanium dioxide composite particle of porous character, coat the phosphoric acid silver layer on the titanium dioxide composite particle surface, be coated with silicon dioxide layer at the phosphoric acid silver layer then;
The size that obtains silver phosphate antibacterial modified titanium dioxide composite particle is between 52nm-2150nm;
The particle diameter of titanium dioxide granule is between 50nm-2000nm, and described silicon-dioxide, aluminum oxide, Trisilver phosphate coating thickness are respectively 1~50nm.
Preparation method with silver phosphate antibacterial modified titanium dioxide composite particle of antibacterial of the present invention is:
A. be A1 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, aluminum oxide, Trisilver phosphate successively;
B. be A2 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, Trisilver phosphate, aluminum oxide successively;
C. be A3 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, Trisilver phosphate successively;
D. be A4 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, Trisilver phosphate successively;
E. be A5 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, Trisilver phosphate, silicon-dioxide successively;
F. be A6 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, silicon-dioxide, Trisilver phosphate successively;
This method steps is:
(1). in water, the weight percent concentration of gained titanium dioxide in water is 5~40%, is preferably 5~25% with the titanium dioxide granule dispersed with stirring.
(2). the aqueous solution of preparation water glass, its volumetric molar concentration is 0.01~1mol/L, is preferably 0.01~0.3mol/L; The thickness of the silicon-dioxide of the required coating of foundation is determined the volumetric molar concentration and the consumption thereof of water glass.
(3). the aqueous solution of preparation Tai-Ace S 150, its volumetric molar concentration is 0.01~1mol/L, is preferably 0.01~0.3mol/L; The thickness of the aluminum oxide of the required coating of foundation is determined the volumetric molar concentration and the consumption thereof of Tai-Ace S 150.
(4). the aqueous solution of preparation Sodium phosphate dibasic, its volumetric molar concentration is 0.01~1mol/L, is preferably 0.01~0.3mol/L.
(5). preparation silver complex solution, its volumetric molar concentration is 0.01~1mol/L, is preferably 0.01~0.3mol/L.
(6). the sodium silicate aqueous solution of step (2) preparation is slowly joined in the aqueous solution of titanium dioxide of step (1) preparation, preparation is used to prepare A1, A2 or A3 particulate solution;
Wherein, the consumption of sodium silicate aqueous solution is determined titanium dioxide in the mixed solution according to the thickness requirement of required coated with silica layer: the mol ratio of water glass is 1: 0.01~1: 0.4;
Or the aqueous solution of the Tai-Ace S 150 of step (3) preparation slowly joined in the titanium dioxide granule aqueous solution of step (1) preparation, preparation is used to prepare A4, A5 or A6 particulate solution;
Wherein, the consumption of aluminum sulfate aqueous solution is determined titanium dioxide in the mixed solution according to the size of titanium dioxide composite particle, the thickness requirement of required aluminum oxide coating layer: the mol ratio of Tai-Ace S 150 is 1: 0.01~1: 0.4.
(7). the water glass of continuous whipping step (6) preparation, the mixed solution of titanium dioxide, with acid the pH value of solution is adjusted to 9~10, in temperature is ageing 0.5~5 hour under 60~100 ℃, agitation as appropriate speed, separate mixed solution, to throw out washing, drying, prepare A1, A2 or A3 particulate coated with silica layer;
Or the Tai-Ace S 150 of constantly whipping step (6) preparation, the aqueous solution liquid of titanium dioxide, with alkali the pH value of solution is adjusted to 5~8, in temperature is 60~100 ℃, ageing is 2~8 hours under the agitation as appropriate speed, separate mixed solution, to throw out washing, drying, prepare A4, A5 or A6 particulate alumina-coated layer.
(8). with A1, A2, A3, A4, A5 or the A6 particle of step (7), dispersed with stirring is in water, and weight percent concentration is 5~40%, is preferably 5~25%.
(9). for the A1 particle in the step (8), the aqueous solution with the Tai-Ace S 150 of step (3) preparation, slowly join in step (8) aqueous solution, wherein, the consumption of alum liquor is determined titanium dioxide in the mixed solution according to the size of titanium dioxide composite particle, the thickness requirement of required aluminum oxide coating layer: the mol ratio of Tai-Ace S 150 is 1: 0.01~1: 0.4; Constantly mixing liquid, with alkali the pH value of solution is adjusted to 5~8, is 60~100 ℃ in temperature, and ageing is 2~8 hours under the agitation as appropriate speed, separates mixed solution, and to the throw out washing, drying is prepared A1 particulate alumina-coated layer.
Or for A2, A3 in the step (8), A4 or A5 particle, disodium phosphate soln with step (4) preparation, slowly join in step (8) aqueous solution, wherein, the consumption of disodium phosphate soln is determined titanium dioxide in the mixed solution according to the thickness of required Trisilver phosphate coating layer: the mol ratio of Sodium phosphate dibasic is 1: 0.02~1: 0.5; And then slowly adding the silver complex solution that step (5) is prepared, the consumption of silver complex solution is determined according to the consumption of Sodium phosphate dibasic, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver complex is 1: 1~1: 4; Stir ageing, separate mixed solution, to the throw out washing, drying is prepared A2, A3, A4 or A5 particulate Trisilver phosphate coating layer; Promptly obtain successively titanium dioxide antibiotic particle A3, or obtain successively titanium dioxide antibiotic particle A4 titanium dioxide granule coated aluminum oxide, Trisilver phosphate to titanium dioxide granule coated silica, Trisilver phosphate;
Or for the A6 particle in the step (8), sodium silicate aqueous solution with step (2) preparation, slowly join in step (8) aqueous solution, the consumption of sodium silicate solution is determined titanium dioxide in the mixed solution according to the thickness requirement of required coated with silica layer: the mol ratio of water glass is 1: 0.01~1: 0.4.Constantly stirring, with acid the pH value of solution is adjusted to 9~10, is ageing 0.5~5 hour under 60~100 ℃, agitation as appropriate speed in temperature, and the separation mixed solution washs throw out, and drying is prepared A6 particulate coated with silica layer.
(10). in water, weight percent concentration is 5~40%, is preferably 5~25% with the A1 of step (9) or A6 particles dispersed.The disodium phosphate soln of step (4) preparation is slowly joined in the mixed solution.Wherein, the consumption of disodium phosphate soln is determined titanium dioxide in the mixed solution according to the thickness of required Trisilver phosphate coating layer: the mol ratio of Sodium phosphate dibasic is 1: 0.02~1: 0.5.Silver complex solution with step (5) preparation slowly joins in the mixed solution, and the consumption of silver complex solution is determined according to the consumption of Sodium phosphate dibasic, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver complex is 1: 1~1: 4.Stir ageing, separate mixed solution, to the throw out washing, drying is prepared A1 or A6 particulate Trisilver phosphate coating layer, promptly obtains successively the titanium dioxide antibiotic particle A1 to titanium dioxide granule coated silica, aluminum oxide, Trisilver phosphate; Or obtain successively titanium dioxide antibiotic particle A6 to titanium dioxide granule coated aluminum oxide, silicon-dioxide, Trisilver phosphate.
(11). in water, weight percent concentration is 5~40%, is preferably 5~25% with the A2 particles dispersed of step (9) preparation.The aqueous solution of the Tai-Ace S 150 of step (3) preparation is slowly joined in the mixed solution.Wherein, the consumption of alum liquor is determined titanium dioxide in the mixed solution according to the size of titanium dioxide composite particle, the thickness requirement of required aluminum oxide coating layer: the mol ratio of Tai-Ace S 150 is 1: 0.01~1: 0.40.Constantly mix liquid, with alkali the pH value of solution is adjusted to 5~8, in temperature is 60~100 ℃, ageing is 2~8 hours under the agitation as appropriate speed, separate mixed solution, to throw out washing, drying, prepare A2 particulate alumina-coated layer, promptly obtain successively titanium dioxide antibiotic particle A2 titanium dioxide granule coated silica, Trisilver phosphate, aluminum oxide;
(12). in water, weight percent concentration is 5~40%, is preferably 5~25% with the A5 particles dispersed of step (9) preparation.The sodium silicate solution of step (2) preparation is slowly joined in the mixed solution.The consumption of sodium silicate solution is determined titanium dioxide in the mixed solution according to the thickness requirement of required coated with silica layer: the mol ratio of water glass is 1: 0.01~1: 0.4.Constantly stir, with acid the pH value of solution is adjusted to 9~10, in temperature is ageing 0.5~5 hour under 60~100 ℃, agitation as appropriate speed, separate mixed solution, throw out is washed, drying is prepared A5 particulate coated with silica layer, promptly obtains successively the titanium dioxide antibiotic particle A5 to titanium dioxide granule coated aluminum oxide, Trisilver phosphate, silicon-dioxide.
(13). A3 and A4 antibacterial granule that step (9) is obtained, A1 that step (10) obtains and A6 antibacterial granule, the A2 antibacterial granule that step (11) obtains, the A5 antibacterial granule that step (12) obtains, be 300 ℃ of-900 ℃ of roastings in temperature respectively, pulverize, finally obtain silver phosphate antibacterial modified titanium dioxide composite particle respectively.
Described silver complex can be silver-ammonia complex or silver thiosulfate complex etc., is preferably silver-ammonia complex.
The acid of described adjustment pH value is nitric acid, hydrochloric acid or sulfuric acid etc.; The alkali of described adjustment pH value is sodium hydroxide or ammoniacal liquor etc.
Described titanium dioxide is sharp attitude type titanium dioxide.
The titanium dioxide composite particle that this is antibacterial modified is entrained in coating, pottery, plastics or the elastomeric material and uses as anti-biotic material.
Silver phosphate antibacterial modified titanium dioxide composite particle of the present invention can also have multiple coating, as directly titanium dioxide granule being coated Trisilver phosphate etc.
Silver phosphate antibacterial modified titanium dioxide composite particle of the present invention is a kind of novel high functional inorganic materials, and the content of its antimicrobial component Trisilver phosphate can be entrained in the materials such as coating, pottery, plastics or rubber and use as anti-biotic material at 0.5-30%.
Antibacterial modified titanium dioxide composite particle is replaced titanium dioxide in the powder coating, mix, push, pulverize, sieve, spray, step such as baking just can prepare antibacterial powder paint.The anti-microbial property of the antibacterial powder coating of heat curing-type is tested with reference to GB15981-1995, Q/HDHKH002-2000 detection method and standard.Behind the testing sample sterilization and drying, 0.2ml bacterium bacterium to be measured liquid is evenly dripped on sample respectively, cover with film, put in the sterilising vessel, after placing 24 hours under 36 ℃ of temperature, the humidity 90%RH, add the 20ml elutriant respectively, wash-out fully vibrates, switching NA substratum carries out live bacterial count, with antibacterial powder paint sample and ordinary powder coating in the same old way recovery bacterium number is calculated its bacteriostasis rate.Test result shows that antibiotic paint all reaches more than 96% the antibiotic rate of intestinal bacteria and streptococcus aureus, has good antimicrobial property.
Silver phosphate antibacterial modified titanium dioxide composite particle of the present invention has:
1. prepare simplely, be easy to apply.
2. the white pigment TiO that is widely used of apparatus
2As antibiotic base material, the preparation anti-bacterial powder is not only utilized TiO
2Covering power, and be easy to the toning.
3. because TiO
2Be non-stripping property antiseptic-germicide, thereby be a kind of semi-permanent mould antiseptic-germicide, can effect descend gradually along with the stripping of antiseptic-germicide unlike other antiseptic-germicide.
4. with comparatively inexpensive anatase titanium dioxide TiO
2Make carrier compound phosphoric acid silver, can improve the dispersiveness of titanium dioxide, well keep the optically catalytic TiO 2 activity.
5. the TiO that is widely used of apparatus
2As antibiotic substrate preparation anti-bacterial powder, not only avoided the preparation antimicrobial prod to add the possible defective that antiseptic-germicide brings but also can reduce adjustment original production process.This method is a very economical and superior.
6. the TiO that is equipped with of porous silica of Bao Fuing and aluminum oxide and compound silvery
2Antibacterial granule just has very strong anti-microbial effect under more weak visible light effect.
7. coat TiO by adjusting
2Silicon-dioxide, alumina-coated layer, and coating thickness, be easy to make can with the compatible antimicrobial product of other composition of different sorts antimicrobial prod.
Embodiment
Embodiment 1
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 10%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 85 ℃, make TiO
2The initial molar ratio of-water glass is 5: 1, and its dropping time is 20 minutes.Use sulfuric acid adjusts to 9.5 with the pH of mixed solution, stirs ageing down 2 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the TiO that obtains having coated with silica
2Composite particles.Again with the TiO of this coated with silica
2The composite particles dispersed with stirring slowly adds the Sodium phosphate dibasic aqueous solution in the aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is: 1: 0.05.Slowly be added dropwise to silver-ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 2.Stir ageing and obtain faint yellow turbid solution, sedimentation, washing, separation, drying, 500 ℃ of roastings obtain the titanium dioxide composite particle of coated silica, Trisilver phosphate successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 2
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 20%.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃, make TiO
2The initial molar ratio of-Tai-Ace S 150 is 5: 1.Use sodium hydroxide adjusts to 7.0 with the pH of mixed solution, stirs ageing down 4 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the TiO that obtains having alumina-coated
2Composite particles.Again with the TiO of this alumina-coated
2The composite particles dispersed with stirring is in the aqueous solution, and weight percent concentration is 20%.Slowly add the Sodium phosphate dibasic aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is 1: 0.06.Slowly be added dropwise to silver-ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 2.Stir ageing 1 hour, obtain faint yellow turbid solution, sedimentation, washing, separation, drying.550 ℃ of following roastings obtain the titanium dioxide composite particle of coated aluminum oxide, Trisilver phosphate successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 3
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 15%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 85 ℃, make TiO
2The initial molar ratio of-water glass is 6: 1, and its dropping time is 25 minutes.Use hydrochloric acid adjusts to 9.5 with the pH of mixed solution, stirs ageing down 2.5 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the TiO that obtains having coated with silica
2Composite particles.In the aqueous solution, weight percent concentration is 25% with its dispersed with stirring.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃, make TiO
2The initial molar ratio of-Tai-Ace S 150 is 1: 0.04.Use sodium hydroxide that the pH of mixed solution is adjusted to 7, stir ageing down 4 hours, obtain white opacity solution, sedimentation, washing, separation, drying obtain having aluminum oxide, the TiO of coated with silica
2Composite particles.Again with this TiO
2The composite particles dispersed with stirring is in the aqueous solution, and weight percent concentration is 20%.Slowly add the Sodium phosphate dibasic aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is 1: 0.08.Slowly be added dropwise to silver ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 1.Stir ageing and obtain faint yellow turbid solution, sedimentation, washing, separation, drying, 500 ℃ of following roastings obtain the titanium dioxide composite particle of coated silica, aluminum oxide and Trisilver phosphate successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 4
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 15%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 85 ℃, make TiO
2The initial molar ratio of-water glass is 4: 1, and its dropping time is 30 minutes.Use sulfuric acid adjusts to 9.5 with the pH of mixed solution, stirs ageing down 2.5 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the TiO that obtains having coated with silica
2Composite particles.Again with this TiO
2The composite particles dispersed with stirring is in the aqueous solution, and weight percent concentration is 30%.Slowly add the Sodium phosphate dibasic aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is 1: 0.1.Slowly be added dropwise to silver-ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 3.Stir ageing and obtain faint yellow turbid solution, sedimentation, washing, separation, drying obtain the titanium dioxide composite particle that silicon-dioxide and Trisilver phosphate coat.It is distributed in the water once more, and weight percent concentration is 18%.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃, make TiO
2The initial molar ratio of-Tai-Ace S 150 is 7: 1.Use sodium hydroxide adjusts to 7 with the pH of mixed solution, stir ageing down 4 hours, obtain turbid solution, sedimentation, washing, separation, drying, 650 ℃ of following roastings obtain the titanium dioxide composite particle of coated silica, Trisilver phosphate and aluminum oxide successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 5
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 30%.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃, make TiO
2The initial molar ratio of-Tai-Ace S 150 is 6: 1.Use sodium hydroxide adjusts to 7 with the pH of mixed solution, stirs ageing down 4 hours, obtains white opacity solution, and sedimentation, washing, separation, drying obtain having alumina-coated TiO
2Composite particles.Again with this TiO
2The composite particles dispersed with stirring is in water, and weight percent concentration is 35%.Slowly add the Sodium phosphate dibasic aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is 1: 0.12.Slowly be added dropwise to silver ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 1.Stir ageing and obtain faint yellow turbid solution, sedimentation, washing, separation, drying obtain having the titanium dioxide composite particle of Tai-Ace S 150 and Trisilver phosphate coating layer.It is distributed in the water once more, and weight percent concentration is 15%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 85 ℃, make TiO
2The initial molar ratio of-water glass is 7: 1, and its dropping time is 25 minutes.Use sulfuric acid adjusts to 9.5 with the pH of mixed solution, stir ageing down 2 hours, obtain turbid solution, sedimentation, washing, separation, drying, 550 ℃ of following roastings obtain the titanium dioxide composite particle of coated aluminum oxide, Trisilver phosphate and silicon-dioxide successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 6
In the aqueous solution, weight percent concentration is 20% with the titanium dioxide granule dispersed with stirring.Slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃ in this mixing solutions, the initial molar ratio that makes titanium dioxide and Tai-Ace S 150 is 5: 1.Use sodium hydroxide adjusts to 7 with the pH of mixed solution, stirs ageing down 3.5 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the titanium dioxide composite particle that obtains having alumina-coated.In the aqueous solution, weight percent concentration is 25% with its dispersed with stirring.Slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 80 ℃ in this mixing solutions, the initial molar ratio that makes titanium dioxide and water glass is 6: 1, and its dropping time is 25 minutes.Use sulfuric acid that the pH of mixed solution is adjusted to 9.5, stir ageing down 4 hours, obtain white opacity solution, sedimentation, washing, separation, drying obtain having aluminum oxide, the titanium dioxide composite particle of coated with silica.Again with this titanium dioxide composite particle dispersed with stirring in the aqueous solution, slowly add the Sodium phosphate dibasic aqueous solution, the initial molar ratio that makes titanium dioxide and Sodium phosphate dibasic is 1: 0.04.Slowly be added dropwise to silver complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver complex is 1: 3.Stir ageing 1 hour, obtain faint yellow turbid solution, sedimentation, washing, separation, drying, 650 ℃ of following roastings obtain having the antibacterial modified titanium dioxide composite particle that coats Tai-Ace S 150, silicon-dioxide and Trisilver phosphate successively.
Embodiment 7
Modification TiO with embodiment 1-6 preparation
2Composite particles replaces the TiO in the powder coating respectively
2, mix, push, pulverize, sieve, step such as spraying, roasting just can prepare antibacterial powder paint.To the antibiotic rate of intestinal bacteria, streptococcus aureus all more than 96%.
Claims (11)
1. silver phosphate antibacterial modified titanium dioxide composite particle, it is characterized in that: this composite particles is as kernel with nanometer or submicron titanium dioxide granule, be coated with silicon oxide and alumina layer, silicon dioxide layer or alumina layer on the titanium dioxide granule surface, obtain having the titanium dioxide composite particle of porous character, be coated with the phosphoric acid silver layer on the titanium dioxide composite particle surface;
The size that obtains silver phosphate antibacterial modified titanium dioxide composite particle is between 52nm-2150nm;
The particle diameter of titanium dioxide granule is between 50nm-2000nm, and described silicon-dioxide, aluminum oxide, Trisilver phosphate coating thickness are respectively 1~50nm.
2. particle as claimed in claim 1 is characterized in that: the described outer Trisilver phosphate laminar surface of silicon dioxide layer that is coated on further is coated with alumina layer.
3. particle as claimed in claim 1 is characterized in that: the described outer Trisilver phosphate laminar surface of the alumina layer layer that further is coated with silicon oxide that is coated on.
4. preparation method as any described silver phosphate antibacterial modified titanium dioxide composite particle of claim 1-3 is characterized in that:
A. be A1 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, aluminum oxide, Trisilver phosphate successively;
B. be A2 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, Trisilver phosphate, aluminum oxide successively;
C. be A3 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, Trisilver phosphate successively;
D. be A4 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, Trisilver phosphate successively;
E. be A5 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, Trisilver phosphate, silicon-dioxide successively;
F. be A6 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, silicon-dioxide, Trisilver phosphate successively;
Steps of the method are:
(1). in water, the weight percent concentration of gained titanium dioxide in water is 5~40% with the titanium dioxide granule dispersed with stirring;
(2). the aqueous solution of preparation water glass;
(3). the aqueous solution of preparation Tai-Ace S 150;
(4). the aqueous solution of preparation Sodium phosphate dibasic;
(5). preparation silver complex solution;
(6). the sodium silicate aqueous solution of step (2) preparation is slowly joined in the aqueous solution of titanium dioxide of step (1) preparation, preparation is used to prepare A1, A2 or A3 particulate solution;
Wherein, titanium dioxide in the mixed solution: the mol ratio of water glass is 1: 0.01~1: 0.4;
Or the aqueous solution of the Tai-Ace S 150 of step (3) preparation slowly joined in the titanium dioxide granule aqueous solution of step (1) preparation, preparation is used to prepare A4, A5 or A6 particulate solution;
Wherein, titanium dioxide in the mixed solution: the mol ratio of Tai-Ace S 150 is 1: 0.01~1: 0.4;
(7). the water glass of whipping step (6) preparation, the mixed solution of titanium dioxide, with acid the pH value of solution being adjusted to 9~10, is 60~100 ℃ of following ageings in temperature, separates mixed solution, to throw out washing, drying, prepare A1, A2 or A3 particulate coated with silica layer;
Or the Tai-Ace S 150 of constantly whipping step (6) preparation, the aqueous solution liquid of titanium dioxide, with alkali the pH value of solution being adjusted to 5~8, is 60~100 ℃ of following ageings in temperature, separates mixed solution, to throw out washing, drying, prepare A4, A5 or A6 particulate alumina-coated layer;
(8). with A1, A2, A3, A4, A5 or the A6 particle of step (7), dispersed with stirring is in water, and weight percent concentration is 5~40%;
(9). for the A1 particle in the step (8), the aqueous solution with the Tai-Ace S 150 of step (3) preparation slowly joins in step (8) aqueous solution, and wherein, titanium dioxide in the mixed solution: the mol ratio of Tai-Ace S 150 is 1: 0.01~1: 0.4; Mixing liquid, with alkali the pH value of solution is adjusted to 5~8, is 60~100 ℃ of following ageings in temperature, separates mixed solution, and to the throw out washing, drying is prepared A1 particulate alumina-coated layer;
Or for A2, A3 in the step (8), A4 or A5 particle, the disodium phosphate soln with step (4) preparation slowly joins in step (8) aqueous solution, and wherein, titanium dioxide in the mixed solution: the mol ratio of Sodium phosphate dibasic is 1: 0.02~1: 0.5; And then slowly adding the silver complex solution that step (5) is prepared, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver complex is 1: 1~1: 4; Stir ageing, separate mixed solution, to the throw out washing, drying is prepared A2, A3, A4 or A5 particulate Trisilver phosphate coating layer; Promptly obtain successively titanium dioxide antibiotic particle A3, or obtain successively titanium dioxide antibiotic particle A4 titanium dioxide granule coated aluminum oxide, Trisilver phosphate to titanium dioxide granule coated silica, Trisilver phosphate;
Or for the A6 particle in the step (8), the sodium silicate aqueous solution with step (2) preparation slowly joins in step (8) aqueous solution, and titanium dioxide in the mixed solution: the mol ratio of water glass is 1: 0.01~1: 0.4; Stirring, with acid the pH value of solution is adjusted to 9~10, is 60~100 ℃ of following ageings in temperature, separates mixed solution, and to the throw out washing, drying is prepared A6 particulate coated with silica layer;
(10). the A1 of step (9) or A6 particles dispersed in water, are slowly joined the disodium phosphate soln of step (4) preparation in the mixed solution, and wherein, titanium dioxide in the mixed solution: the mol ratio of Sodium phosphate dibasic is 1: 0.02~1: 0.5; Silver complex solution with step (5) preparation, slowly join in the mixed solution, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver complex is 1: 1~1: 4, stir ageing, separate mixed solution, to throw out washing, drying, prepare A1 or A6 particulate Trisilver phosphate coating layer, promptly obtain successively titanium dioxide antibiotic particle A1 titanium dioxide granule coated silica, aluminum oxide, Trisilver phosphate; Or obtain successively titanium dioxide antibiotic particle A6 to titanium dioxide granule coated aluminum oxide, silicon-dioxide, Trisilver phosphate;
(11). with the A2 particles dispersed of step (9) in water, slowly join the aqueous solution of the Tai-Ace S 150 of step (3) preparation in the mixed solution, wherein, titanium dioxide in the mixed solution: the mol ratio of Tai-Ace S 150 is 1: 0.01~1: 0.40, mix liquid, with alkali the pH value of solution is adjusted to 5~8, in temperature is 60~100 ℃ of following ageings, separate mixed solution, throw out is washed, drying is prepared A2 particulate alumina-coated layer, promptly obtains successively the titanium dioxide antibiotic particle A2 to titanium dioxide granule coated silica, Trisilver phosphate, aluminum oxide;
(12). with the A5 particles dispersed of step (9) in water, slowly join the sodium silicate solution of step (2) preparation in the mixed solution, titanium dioxide in the mixed solution: the mol ratio of water glass is 1: 0.01~1: 0.4, stir, with acid the pH value of solution is adjusted to 9~10, in temperature is 60~100 ℃ of following ageings, separate mixed solution, throw out is washed, dry, prepare A5 particulate coated with silica layer, promptly obtain successively titanium dioxide antibiotic particle A5 titanium dioxide granule coated aluminum oxide, Trisilver phosphate, silicon-dioxide;
(13). A3 and A4 antibacterial granule that step (9) is obtained, A1 that step (1) obtains or A6 antibacterial granule, the A2 antibacterial granule that step (11) obtains, the A5 antibacterial granule that step (12) obtains, be 300 ℃ of-900 ℃ of roastings in temperature respectively, pulverize, finally obtain silver phosphate antibacterial modified titanium dioxide composite particle respectively.
5. method as claimed in claim 4 is characterized in that: described silver complex is silver-ammonia complex or silver thiosulfate complex.
6. method as claimed in claim 4 is characterized in that: the volumetric molar concentration of the aqueous solution of described step (2) water glass is 0.01~1mol/L.
7. method as claimed in claim 4 is characterized in that: the aqueous solution volumetric molar concentration of described step (3) Tai-Ace S 150 is 0.01~1mol/L.
8. method as claimed in claim 4 is characterized in that: the volumetric molar concentration of the aqueous solution of described step (4) Sodium phosphate dibasic is 0.01~1mol/L.
9. method as claimed in claim 4 is characterized in that: the volumetric molar concentration of described step (5) the silver complex aqueous solution is 0.01~1mol/L.
10. method as claimed in claim 4 is characterized in that: described acid is nitric acid, hydrochloric acid or sulfuric acid; Described alkali is sodium hydroxide or ammoniacal liquor.
11. the purposes as the described silver phosphate antibacterial modified titanium dioxide composite particle of claim 1-3 is characterized in that: described particle dopedly in coating, pottery, plastics or elastomeric material, use as anti-biotic material.
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