CN115300657A - Antibacterial deodorant as well as preparation method and application thereof - Google Patents
Antibacterial deodorant as well as preparation method and application thereof Download PDFInfo
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- CN115300657A CN115300657A CN202211139979.1A CN202211139979A CN115300657A CN 115300657 A CN115300657 A CN 115300657A CN 202211139979 A CN202211139979 A CN 202211139979A CN 115300657 A CN115300657 A CN 115300657A
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
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- 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
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- 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
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
- A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
- A61L2101/26—Inorganic materials containing copper
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
- A61L2101/30—Inorganic materials containing zinc
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses an antibacterial deodorant and a preparation method and application thereof. The antibacterial deodorant comprises porous glass and metal ions; porous glassIs one or more of silicate porous glass, borate porous glass and borosilicate porous glass; porous glass containing 20-70mol% 2 O 3 And 20-56mol% of SiO 2 (ii) a The aperture of the porous glass is 20-130nm; the metal ion being Ag + 、Zn 2+ Or Cu 2+ . The antibacterial deodorant has quick time effect of exerting deodorization and antibacterial performance, and has lasting antibacterial deodorization performance; the preparation method is simple, is suitable for large-scale production, can be widely applied to antibacterial deodorizing materials as a raw material, and particularly has wide development prospect in fibers and plastic products.
Description
Technical Field
The invention particularly relates to an antibacterial deodorant and a preparation method and application thereof.
Background
In recent years, with the improvement of the living standard of human beings, the demand of human beings for deodorants is increasing. In our daily life, common odors are mainly classified into three categories: 1) Nitrogen-containing compounds such as ammonia, methylamine, nicotine; 2) Sulfur-containing compounds, such as hydrogen sulfide, mercaptans, sulfides; 3) Oxygen-containing compounds, such as acetic acid, butyric acid, small molecular acid, aldehyde, ketone, etc. The long-term odor environment can harm the health of human beings and affect the respiratory, digestive and endocrine systems of the human beings, so that researchers are always seeking for the development of deodorizing products.
With the development of deodorization technology, common deodorization products are classified into physical deodorants, chemical deodorants, biological deodorants, and the like. Physical deodorants usually achieve the effect of deodorization by means of adsorption, absorption or covering, and the main products are activated carbon, zeolite and diatomite; microbial deodorants generally utilize enzymes or bacteria to decompose odor to achieve a deodorizing effect; chemical deodorants generally achieve a deodorising effect by a chemical reaction. Chemical deodorants are classified into inorganic and organic types, and the common deodorizing mechanism is oxidation, neutralization, complexation or salt formation. The prior chemical deodorant is the deodorant which is most applied because of quick effect, high stability and lasting deodorization performance.
As a technique related to chemical deodorization, patent literature (JP 1992067868 a) discloses the following: by applying at P 2 O 5 The soluble glass as main component is introduced with any one of silver, copper and iron and adjusted with PO 4 2- Ions, ag + Ions, cu 2+ Ions, fe 2+ The dissolution rate of the ions is in a specific range, thereby deodorizing the sulfur-based malodors. Since its deodorizing mechanism is by Ag produced by dissolution + Ion, cu 2+ Ions, fe 2+ The ion and sulfur component vulcanization reaction, so when reaching the equilibrium state, no longer continues the deodorization reaction, deodorization effect is reduced, in addition, because P 2 O 5 Dissolution of the main componentThe chemical stability of the glass is poor, so that the application of the product in the fields of later buildings, clothes, home decoration and the like is limited.
While the patent document (JP 2009213992 a) discloses another deodorization solution: deodorant obtained by dispersing copper oxide in activated carbon is used to remove odor such as methyl mercaptan. However, in the technique of this patent, the effect of copper oxide dispersed in activated carbon is reduced by the reaction with malodorous gases, and there is a problem that the deodorizing effect is poor in durability.
Therefore, there is still a need in the art to provide a chemical deodorant with good deodorizing effect, long deodorizing duration and good sterilizing function.
Disclosure of Invention
The invention provides an antibacterial deodorant and a preparation method and application thereof, aiming at solving the defects of poor deodorization effect and poor deodorization durability of a chemical deodorant in the prior art. The antibacterial deodorant has the advantages of quick time effect of exerting the deodorization and antibacterial performance and lasting antibacterial deodorization performance. The preparation method is simple, is suitable for large-scale production, can be widely applied to antibacterial deodorizing materials as a raw material, and particularly has wide development prospect in fibers and plastic products.
The invention solves the technical problems through the following technical scheme.
The invention provides an antibacterial deodorant, which comprises porous glass and metal ions;
the porous glass is one or more of silicate porous glass, borate porous glass and borosilicate porous glass;
the porous glass comprises B 2 O 3 And SiO 2 (ii) a B is 2 O 3 The molar content of (a) is 20-70moL%; the SiO 2 The molar content of (A) is 20-56moL%;
the pore diameter of the porous glass is 20-130nm;
the metal ion is Ag + 、Zn 2+ Or Cu 2+ ；
When the metal ion is Ag + When the Ag is + And the porous glassThe mass ratio of the glass is (0.003-0.4) to 1;
when the metal ion is Zn 2+ When said Zn is present 2+ The mass ratio of the porous glass to the porous glass is (0.15-0.37): 1;
when the metal ion is Cu 2+ When being in contact with Cu 2+ The mass ratio of the porous glass to the porous glass is (0.15-0.4): 1.
In the present invention, the porous glass may further include an alkali metal oxide and/or an alkaline earth metal oxide. Wherein the type and molar content of the alkali metal oxide may be conventional in the art. The type and molar content of the alkaline earth metal oxide may be conventional in the art.
In the present invention, the porous glass is preferably borosilicate porous glass.
Wherein the borosilicate porous glass generally refers to a porous glass obtained by subjecting the borosilicate glass to phase separation heat treatment and acid treatment, and for example, contains B 2 O 3 、SiO 2 Alkali metal oxides and alkaline earth metal oxides.
Preferably, the borosilicate porous glass comprises the following components in molar content:
20-70moL％B 2 O 3 ；
20-56moL％SiO 2 ；
5-18moL% of alkali metal oxide;
1-15moL% of alkaline earth metal oxide;
the percentage is the mole percentage of each component in the borosilicate porous glass.
Wherein, B is 2 O 3 Preferably 25-60moL%, more preferably 25-50moL%, such as 28moL%, 30moL%, 35moL%, 38moL%, 40moL% or 45moL%, the percentage being said B 2 O 3 In terms of mole percent of the borosilicate porous glass.
Wherein the SiO 2 Preferably in a molar amount of from 25 to 55moL%, more preferably from 30 to 55moL%, for example 32moL%, 35moL%, 38moL%, 40moL%, 45moL%, 48moL% or 50moL%, percentIn a ratio of said SiO 2 In terms of mole percent of the borosilicate porous glass.
Wherein the molar content of the alkali metal oxide is preferably 8-17moL%, such as 9moL%, 10moL%, 12moL%, 13moL%, 14moL%, 15moL% or 16moL%, the percentage being the molar percentage of the alkali metal oxide in the borosilicate porous glass.
Wherein the alkali metal oxide may be an alkali metal oxide conventional in the art, such as Li 2 O、Na 2 O and K 2 One or more of O, preferably Na 2 O and/or K 2 O。
Wherein the molar content of the alkaline earth metal oxide is preferably 2 to 10moL%, such as 3moL%, 5moL%, 7moL%, 8moL% or 9moL%, as a percentage of the molar percentage of the alkaline earth metal oxide to the borosilicate porous glass.
The alkaline earth metal oxide may be, among others, an alkaline earth metal oxide conventional in the art, such as MgO and/or CaO.
When the alkaline earth metal oxide is MgO, the MgO is preferably present in a molar amount of 2 to 8moL%, for example 3moL%, 4moL%, 5moL%, 6moL% or 7moL%.
When the alkaline earth metal oxide is CaO, the CaO is preferably present in a molar amount of 3 to 8moL%, for example 4moL%, 5moL%, 6moL% or 7moL%.
When the alkaline earth metal oxide is MgO and CaO, it is preferably 2-5MoL% MgO and 3-8MoL% CaO, for example 2MoL% MgO and 5MoL% CaO, 2MoL% MgO and 8MoL% CaO, 5MoL% MgO and 5MoL% CaO, or 2MoL% MgO and 3MoL% CaO.
In the present invention, the pore size of the porous glass may be conventional in the art, and generally refers to the diameter of the pores. The pore size of the porous glass is preferably 30-70nm, such as 36nm, 40nm, 45nm, 55nm, 60nm or 65nm.
In the present invention, the particle diameter D of the porous glass 99 It may be 1 to 50 μm, for example 2 to 30 μm.
When the metal ion is Ag + When the Ag is + And the porous glassThe mass ratio of (1), (0.004-0.4), for example, (0.005): 1, (0.015): 1, (0.02): 1, (0.025): 1, (0.1): 1, (0.2): 1, (0.3): 1 or (0.35): 1.
When the metal ion is Zn 2+ When said Zn is present 2+ The mass ratio to the porous glass is preferably (0.17 to 0.37): 1, for example, (0.2): 1, (0.3): 1, (0.32): 1 or (0.35): 1.
When the metal ion is Cu 2+ When being in contact with Cu 2+ The mass ratio to the porous glass is preferably (0.17 to 0.4): 1, for example, (0.18): 1, (0.2): 1, (0.25): 1, (0.3): 1, (0.35): 1, (0.37): 1 or (0.39): 1.
In the present invention, in the antibacterial deodorant, the porous glass may be used as a carrier. Preferably, the metal ions are supported on the porous glass.
The invention also provides a preparation method of the antibacterial deodorant, which comprises the following steps:
mixing the solution containing metal ions with the slurry containing the porous glass, and reacting;
wherein the porous glass is one or more of silicate porous glass, borate porous glass and borosilicate porous glass;
the porous glass comprises B 2 O 3 And SiO 2 (ii) a B is 2 O 3 The molar content of (A) is 20-70moL%; the SiO 2 The molar content of (A) is 20-56moL%;
the pore diameter of the porous glass is 20-130nm;
the metal ion is Ag + 、Zn 2+ Or Cu 2+ ；
When the metal ion is Ag + When the ratio of the metal ion-containing solution to the porous glass-containing slurry is (0.003-0.4): 1;
when the metal ion is Zn 2+ When the ratio of the mixing ratio of the solution containing metal ions to the slurry containing porous glass is (0.15-0.37): 1;
when the metal ion is Cu 2+ When the solution containing the metal ions is mixed with the slurry containing the porous glassThe liquid mixing ratio is (0.15-0.4) to 1.
In the present invention, when the metal ion is Ag + In the case of the above method, the mixing ratio of the metal ion-containing solution to the porous glass-containing slurry is preferably (0.004 to 0.4): 1, for example, (0.005): 1, (0.015): 1, (0.02): 1, (0.025): 1, (0.1): 1, (0.2): 1, (0.3): 1 or (0.35): 1.
In the present invention, when the metal ion is Zn 2+ In the case of the above, the mixing ratio of the metal ion-containing solution to the porous glass-containing slurry is preferably (0.17 to 0.37): 1, for example, (0.2): 1, (0.3): 1, (0.32): 1 or (0.35): 1.
In the present invention, when the metal ion is Cu 2+ In the case of the above method, the mixing ratio of the metal ion-containing solution to the porous glass-containing slurry is preferably (0.17 to 0.4): 1, for example, (0.18): 1, (0.2): 1, (0.25): 1, (0.3): 1, (0.35): 1, (0.37): 1 or (0.39): 1.
In the present invention, the solution containing metal ions is generally obtained by dissolving a metal salt in a solvent. The solvent may be conventional in the art, such as deionized water.
In the present invention, the solid content of the porous glass-containing slurry may be 10 to 40wt.%, preferably 20 to 30wt.%, for example 20wt.% or 25wt.%.
In the present invention, the porous glass is preferably borosilicate porous glass.
Wherein the borosilicate porous glass is as described above.
In the present invention, the pore diameter of the porous glass is preferably 30 to 70nm, for example, 36nm, 40nm, 45nm, 55nm, 60nm or 65nm.
In the present invention, the particle diameter D of the porous glass 99 May be 10-50 μm, for example 20-30 μm.
In the present invention, the method for producing the porous glass preferably includes: and (3) carrying out hot phase separation and acid leaching on the porous glass matrix.
In the method for preparing the porous glass, the porous glass matrix can be prepared by a conventional method in the field, and preferably comprises the following steps: melting, quenching, crushing and balling the porous glass raw material.
In the preparation method of the porous glass matrix, the porous glass raw material can be one or more of silicate, borate and borosilicate, and is preferably borosilicate.
Preferably, the borosilicate contains the same components as those contained in the aforementioned borosilicate porous glass.
In the method for preparing the porous glass substrate, the operation and conditions of the melting may be conventional in the art. Generally, the temperature of the melting may be 1100 to 1300 ℃, preferably 1200 ℃. The melting time may be 30-120min, preferably 60-90min, e.g. 70min or 80min.
As is known to those skilled in the art, the quenching operation is generally performed by directly water-cooling a molten glass obtained by melting a mixture containing a porous glass raw material, or by quenching the molten glass by means of a pair of rolls having cooling water attached thereto.
In the method for preparing the porous glass matrix, the quenching mode can be a quenching mode conventional in the field, such as water quenching.
In the preparation method of the porous glass matrix, the pulverization mode can be a conventional pulverization mode in the field, and is generally ball milling, and dry ball milling is preferred.
As known to those skilled in the art, beading mainly refers to the self-sphericization of the glass frit due to surface tension at a certain temperature.
In the method for preparing the porous glass substrate, the beading operation and conditions may be conventional in the art. Generally, the beading temperature may be 600 to 1200 ℃, preferably 800 to 1000 ℃, for example 850 ℃, 880 ℃ or 900 ℃. The beading time may be 20-80min, preferably 30-60min, for example 35min, 45min or 55min.
As known to those skilled in the art, thermal phase separation generally refers to the formation of aggregates of polyanionic groups in a glass matrix at a certain temperature.
In the method for producing the porous glass, the temperature of the thermal phase separation may be 500 to 650 ℃, preferably 550 to 650 ℃, for example 650 ℃.
In the preparation method of the porous glass, the time for thermal phase separation can be 8-45h, preferably 10-36h, such as 12h, 14h, 16h, 18h, 20h, 22h, 24h, 28h, 30h, 32h or 34h.
As known to those skilled in the art, acid leaching generally refers to the step of forming a pore structure in the glass matrix upon immersion in an acid solution.
In the method for preparing the porous glass, the acid solution used in the acid leaching can be obtained by acid which is conventional in the field, such as one or more of sulfuric acid solution, nitric acid solution and hydrochloric acid solution, and is preferably hydrochloric acid solution.
In the method for preparing the porous glass, the concentration of the acid solution used for acid leaching can be 1-5mol/L, such as 1.5mol/L, 2.5mol/L, 3mol/L, 4mol/L or 4.5mol/L.
In the method for producing the porous glass, the temperature of the acid leaching may be 60 to 90 ℃, preferably 70 to 80 ℃, for example 75 ℃.
In the preparation method of the porous glass, the acid leaching time can be 8-50h, preferably 12-48h, such as 12h, 14h, 16h, 18h, 20h, 22h, 24h, 28h, 30h, 32h, 34h or 36h.
In the present invention, the manner and conditions of the mixing may be conventional in the art, for example, the metal ion-containing solution may be mixed with the porous glass-containing slurry at room temperature.
In the present invention, the reaction is generally a supported reaction which is conventional in the art. Among them, the mode of the supporting reaction is preferably a solution impregnation method.
The temperature of the solution impregnation method may be, among others, 40 to 90 ℃, preferably 60 to 80 ℃, such as 70 ℃ or 75 ℃.
Wherein the time of the solution impregnation method may be 2 to 12h, preferably 4 to 8h, such as 5h, 6h or 7h.
In the present invention, the reaction preferably further includes washing, solid-liquid separation and drying operations.
Wherein the washing manner and conditions may be conventional in the art. The degree of washing is generallyThe detection reagent is used for detecting no precipitate. For example, if Ag is supported in the antibacterial deodorant + The degree of washing is generally determined by the absence of white precipitate detected with HCl.
The manner and conditions of the solid-liquid separation may be conventional in the art.
Wherein the drying means and conditions may be conventional in the art.
The invention also provides an antibacterial deodorant prepared by the preparation method.
The invention also provides the application of the antibacterial deodorant as the raw material in the fiber and/or plastic products, wherein the antibacterial deodorant is as described above.
In the present invention, the fiber and/or plastic article can be applied to any field, such as various fields of construction, clothing, home decoration, and the like.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) According to the antibacterial deodorant prepared by the invention, metal ions can be loaded in the pores of the porous glass, and the antibacterial deodorant can play a role in sterilizing odor entering the pores of the porous glass while performing physical deodorization and chemical deodorization. Compared with a silver ion mode in which a glass component is dissolved and released, the antibacterial deodorant has the advantages of more obvious sterilization effect, higher glass stability, quick deodorization and antibacterial performance (the deodorization effect on odorous gas can reach more than 80% in about 5 min), and excellent and durable antibacterial deodorization performance (the antibacterial deodorant is mainly used for the antibacterial deodorization of materials such as synthetic fibers, plastics, rubber and the like in the polymer field, and particularly has the service life of one year in plastics).
(2) The preparation method is simple and suitable for large-scale production.
(3) The antibacterial deodorant prepared by the invention has wide application field, and can be widely applied to plastic products or fiber products.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The reagents in the following examples and comparative examples are commercially available.
Example 1
1) Preparation of porous glass carrier:
subjecting 25mol to 2 O 3 、55moL％SiO 2 、8moL％Li 2 O、4moL％Na 2 O and 8mol, placing in a corundum crucible, melting at 1200 ℃ for 90min (i.e. the melting temperature is 1200 ℃ and the melting time is 90 min), water-quenching glass, drying and ball-milling until the particle size is about 30 mu m. Placing the glass powder in a corundum crucible, and keeping the temperature at 900 ℃ for 45min (the bead forming temperature is 900 ℃ and the bead forming time is 45 min) to form glass spheres under the action of surface tension. And then the glass spheres are placed at 650 ℃ for heat preservation for 12 hours to separate phases (namely the phase separation temperature is 650 ℃ and the phase separation time is 12 hours). Then soaking the porous borosilicate glass carrier in 1mol/L HCl solution at 70 ℃ (namely the leaching temperature is 70 ℃) for 12h (namely the leaching time is 12 h) to form a porous microstructure in the porous borosilicate glass carrier, and finally washing and drying the porous borosilicate glass carrier by deionized water to obtain the porous borosilicate glass carrier.
2) Preparation of porous glass antibacterial deodorant
Dispersing the porous borosilicate glass carrier prepared in the step 1) in deionized water to prepare slurry with the concentration of 20wt.% of solid content, and then adding silver nitrate solution with certain concentration into the slurry to enable Ag to be in + Mass was 0.5wt.% (i.e., ag) relative to the mass of the porous borosilicate glass support + The mass ratio of the porous glass to the solution is 0.005) and then the solution is stirred for 4 hours at 60 ℃ (namely the loading temperature is 60 ℃ and the loading time is 4 hours), and the solution after reaction is washed until no white AgCl precipitate is detected by HCl. And finally, separating and drying the prepared slurry to obtain the porous borosilicate glass antibacterial deodorant.
Examples 2 to 8
Examples 2-8 were prepared in the same manner as example 1, except for the conditions listed in Table 1 below.
TABLE 1
Remarking: in Table 1, "/" indicates that the substance was not added.
Comparative examples 1 to 8
Comparative examples 1-8 were prepared in the same manner as example 1 except for the conditions listed in Table 2 below.
TABLE 2
Remarking: in Table 2, "/" indicates that the substance was not added.
Effect example 1 measurement of particle diameter and pore diameter of borosilicate porous glass support
Test objects: examples 1 to 8 and comparative examples 1 to 8 the borosilicate porous glass support obtained in step 1).
The test method comprises the following steps: light scattering method and BET specific surface area test method.
And (3) testing results: the particle diameter D of the borosilicate porous glass supports prepared in the steps 1) of examples 1 to 8 and comparative examples 1 to 8 was measured 99 Pore diameter of 20-30 μmSee tables 1-2 above for data.
Effect example 2 evaluation of antibacterial Effect and deodorizing Effect
Test objects: examples 1 to 8 and comparative examples 1 to 8.
The test method comprises the following steps:
the antibacterial effect is as follows: GB/T21510 'method for detecting antibacterial property of nano inorganic material' is adopted to test the antibacterial property of the powder. The strain in this test was E.coli.
The deodorization effect is as follows: the deodorization effect is evaluated by testing the reduction amount of the odor concentration in the closed container before and after spraying the deodorant, the deodorization effect of the ammonia gas is mainly evaluated by the deodorant of the invention, and the specific test method is as follows:
firstly, preparing a deodorant into a concentration of 1wt.%, and filling the deodorant into an atomizer for later use; then adding 1mL of ammonia water into a 250mL flask, stirring for 20min, sucking air to be tested by using an injector, and testing the initial odor concentration; and then quickly spraying a deodorant into the bottle for three times, stirring for 5min, sucking air to be tested by the same method, and testing the concentration of the odor after deodorization. Deodorization rate = (initial odor concentration-odor concentration after deodorization)/initial odor concentration 100%. See tables 3-4 below for specific data.
Effect example 3 evaluation of stability and discoloration effect of antibacterial deodorant
Test objects: examples 1 to 8 and comparative examples 1 to 8.
The test method comprises the following steps:
the stability effect is as follows: dispersing an antibacterial deodorant in deionized water to prepare slurry with solid content of 2wt%, placing the slurry at 37 ℃ and stirring for 24 hours, and then evaluating the dissolution loss amount of the deodorant, wherein if the dissolution loss amount of the antibacterial deodorant in 24 hours is lower than 0.1%, the stability of the deodorant is good, and if the dissolution loss amount of the antibacterial deodorant in 24 hours is higher than 1%, the stability of the deodorant is poor.
Color change effect: placing antibacterial deodorant in ultraviolet aging box, and adjusting illumination intensity to 20w/m 2 Irradiating at 50-60 deg.C and humidity of 25-35% for 7 days, and observingIf the color of the antibacterial deodorant does not change obviously, the discoloration resistance of the deodorant is better, and if the discoloration occurs, the discoloration resistance of the deodorant is poorer.
And (3) testing the effect: as shown in tables 3-4 below.
TABLE 3
TABLE 4
As can be seen from the data in tables 3 and 4:
(1) The antibacterial effect (antibacterial property > 99%) and the deodorizing effect (deodorizing rate 82-88%) of the antibacterial deodorant in examples 1-8 are significantly superior to those of comparative examples 1-8, specifically:
in comparison with example 1, siO in comparative example 1 2 High content (60 moL%), B 2 O 3 The content (15 moL%) is low, and the deodorizing performance of the antibacterial deodorant is reduced.
Ag in comparative example 2, in comparison with example 1 + Compared with the mass ratio of the porous glass carrier (0.002.
In comparison with example 1, zn in comparative example 3 2+ The mass ratio of the antibacterial deodorant to the porous glass carrier is lower (0.1; zn in comparative example 4 2+ The deodorizing adsorption property of the antibacterial deodorant is lowered as compared with the mass ratio of the porous glass carrier (0.4.
Comparative example 5 Cu compared to example 1 2+ The mass ratio of the antibacterial deodorant to the porous glass carrier is lower (0.4; cu in comparative example 6 2+ The deodorizing adsorption property of the antibacterial deodorant is lowered as compared with the mass ratio of the porous glass carrier (0.45.
The pore size of the porous glass support in comparative example 7 is excessively large (150 nm) compared to example 1, resulting in a decrease in the deodorizing effect of the final antibacterial and deodorant agent; in comparative example 8, the pore diameter of the porous glass carrier was too small (15 nm), and the loading effect of the ions was deteriorated, thereby resulting in a decrease in both the antibacterial and deodorant effects of the final antibacterial deodorant.
(2) The antibacterial deodorant in examples 1 to 6 also has excellent stability effect and discoloration-resistant effect compared to the antibacterial deodorant in examples 7 to 8, specifically: in example 7, B is compared with example 1 2 O 3 The content is high (50 moL%), and the stability of the antibacterial deodorant is poor; in example 8, ag compares with example 1 + Compared with the mass ratio of the porous glass carrier (0.025: 1), the antibacterial deodorant has poor discoloration resistance.
(3) In addition, the inventor has determined through a large number of repeated tests that the antibacterial deodorant of examples 1 to 8 is added to a plastic base material and has a service life of one year in an environment of about 35 ℃ and about 50% humidity.
In summary, the antibacterial deodorant in examples 1 to 8 has excellent antibacterial and deodorizing effects, and has a quick aging time for exerting the deodorizing and antibacterial effects, and excellent and durable antibacterial and deodorizing effects, and the antibacterial deodorant in examples 1 to 6 has excellent antibacterial and deodorizing effects, and has an excellent stability effect and discoloration resistance effect while exerting the deodorizing and antibacterial effects quickly, and excellent and durable antibacterial and deodorizing effects.
Claims (10)
1. An antibacterial deodorant, characterized in that it comprises porous glass and metal ions;
the porous glass is one or more of silicate porous glass, borate porous glass and borosilicate porous glass;
the porous glass comprises B 2 O 3 And SiO 2 (ii) a B is 2 O 3 The molar content of (A) is 20-70moL%; the SiO 2 The molar content of (A) is 20-56moL%;
the pore diameter of the porous glass is 20-130nm;
the metal ion is Ag + 、Zn 2+ Or Cu 2+ ；
When the metal ion is Ag + When the Ag is + The mass ratio of the porous glass to the porous glass is (0.003-0.4) 1;
when the metal ion is Zn 2+ When said Zn is 2+ The mass ratio of the porous glass to the porous glass is (0.15-0.37): 1;
when the metal ion is Cu 2+ When being in contact with Cu 2+ The mass ratio of the porous glass to the porous glass is (0.15-0.4): 1.
2. The antibacterial deodorant according to claim 1, wherein the antibacterial deodorant satisfies one or more of the following conditions a to f:
a. the porous glass further comprises an alkali metal oxide and/or an alkaline earth metal oxide;
b. the porous glass is borosilicate porous glass;
preferably, the borosilicate porous glass comprises the following components in molar content:
20-70moL％B 2 O 3 ；
20-56moL％SiO 2 ；
5-18moL% of alkali metal oxide;
1-15moL% of alkaline earth metal oxide;
the percentage is the mole percentage of each component in the borosilicate porous glass;
c. the pore size of the porous glass is 30-70nm, such as 36nm, 40nm, 45nm, 55nm, 60nm or 65nm;
d. particle diameter D of the porous glass 99 From 1 to 50 μm, for example from 2 to 30 μm;
e. when the metal ion is Ag + When the Ag is + The mass ratio of the porous glass to the porous glass is (0.004-0.4): 1, for example, (0.005): 1, (0.015): 1, (0.02): 1, (0.025): 1, (0.1): 1, (0.2): 1, (0.3): 1 or (0.35): 1;
when the metal ion is Zn 2+ When said Zn is 2+ The mass ratio of the porous glass to the porous glass is (0.17-0.37): 1, for example, (0.2): 1, (0.3): 1, (0.32)1 or (0.35) is 1;
when the metal ion is Cu 2+ When being in contact with Cu 2+ The mass ratio to the porous glass is (0.17-0.4): 1, for example, (0.18): 1, (0.2): 1, (0.25): 1, (0.3): 1, (0.35): 1, (0.37): 1 or (0.39): 1;
f. in the antibacterial deodorant, the porous glass is used as a carrier; preferably, the metal ions are supported on the porous glass;
preferably, the antibacterial deodorant simultaneously satisfies the conditions a to f.
3. The antibacterial deodorant according to claim 2, wherein the antibacterial deodorant satisfies one or more of the following conditions (1) to (7):
(1) in the borosilicate porous glass, B 2 O 3 In a molar amount of from 25 to 60moL%, preferably from 25 to 50moL%, for example 28moL%, 30moL%, 35moL%, 38moL%, 40moL% or 45moL%, the percentage being said B 2 O 3 (ii) a mole percent of the borosilicate porous glass;
(2) in the borosilicate porous glass, the SiO 2 In a molar amount of from 25 to 55moL%, preferably from 30 to 55moL%, for example 32moL%, 35moL%, 38moL%, 40moL%, 45moL%, 48moL% or 50moL%, based on the SiO 2 (ii) a mole percent of the borosilicate porous glass;
(3) the borosilicate porous glass has a molar content of the alkali metal oxide of 8 to 17moL%, for example 9moL%, 10moL%, 12moL%, 13moL%, 14moL%, 15moL% or 16moL%, the percentage being the molar percentage of the alkali metal oxide in the borosilicate porous glass;
(4) in the borosilicate porous glass, the alkali metal oxide is Li 2 O、Na 2 O and K 2 One or more of O, preferably Na 2 O and/or K 2 O；
(5) The borosilicate porous glass has a molar content of the alkaline earth metal oxide of 2 to 10moL%, for example 3moL%, 5moL%, 7moL%, 8moL% or 9moL%, the percentage being the molar percentage of the alkaline earth metal oxide in the borosilicate porous glass;
(6) in the borosilicate porous glass, the alkaline earth metal oxide is MgO and/or CaO;
(7) when the alkaline earth metal oxide is MgO, the MgO has a molar content of 2 to 8moL%, for example 3moL%, 4moL%, 5moL%, 6moL% or 7moL%;
when the alkaline earth metal oxide is CaO, the CaO is present in a molar amount of 3 to 8moL%, for example 4moL%, 5moL%, 6moL% or 7moL%;
2-5mol% MgO and 3-8mol% CaO when the alkaline earth metal oxide is MgO and CaO, e.g., 2mol% MgO and 5mol% CaO, 2mol% MgO and 8mol% CaO, 5mol% MgO and 5mol% CaO, or 2mol% MgO and 3mol% CaO;
preferably, the antibacterial deodorant simultaneously satisfies the conditions (1) to (7).
4. The preparation method of the antibacterial deodorant is characterized by comprising the following steps: mixing the solution containing metal ions with the slurry containing porous glass, and reacting;
wherein the porous glass is one or more of silicate porous glass, borate porous glass and borosilicate porous glass;
the porous glass comprises B 2 O 3 And SiO 2 (ii) a B is 2 O 3 The molar content of (A) is 20-70moL%; the SiO 2 The molar content of (a) is 20-56moL%;
the pore diameter of the porous glass is 20-130nm;
the metal ion is Ag + 、Zn 2+ Or Cu 2+ ；
When the metal ion is Ag + When the ratio of the metal ion-containing solution to the porous glass-containing slurry is (0.003-0.4): 1;
when the metal ion is Zn 2+ When the mixing ratio of the metal ion-containing solution to the porous glass-containing slurry is (0).15-0.37):1；
When the metal ion is Cu 2+ When the ratio of the mixing ratio of the solution containing metal ions to the slurry containing porous glass is 0.15-0.4: 1.
5. The method for preparing an antibacterial deodorant according to claim 4, wherein when the metal ion is Ag + When the ratio of the metal ion-containing solution to the porous glass-containing slurry is (0.004-0.4): 1, for example, (0.005): 1, (0.015): 1, (0.02): 1, (0.025): 1, (0.1): 1, (0.2): 1, (0.3): 1 or (0.35): 1;
when the metal ion is Zn 2+ When the ratio of the metal ion-containing solution to the porous glass-containing slurry is (0.17-0.37) 1, for example (0.2) 1, (0.3) 1, (0.32) 1 or (0.35) 1;
when the metal ion is Cu 2+ In the case where the ratio of the mixture of the metal ion-containing solution and the porous glass-containing slurry is (0.17 to 0.4): 1, for example, (0.18): 1, (0.2): 1, (0.25): 1, (0.3): 1, (0.35): 1, (0.37): 1 or (0.39): 1.
6. The method for producing an antibacterial deodorant according to claim 4 or 5, wherein the method for producing an antibacterial deodorant satisfies one or more of the following conditions I to IV:
I. the solid content of the slurry containing porous glass is 10-40wt.%, preferably 20-30wt.%, e.g. 20wt.% or 25wt.%;
II. The porous glass is borosilicate porous glass;
III, the pore diameter of the porous glass is 30-70nm, such as 36nm, 40nm, 45nm, 55nm, 60nm or 65nm;
IV, particle diameter D of the porous glass 99 10-50 μm, for example 20-30 μm;
preferably, the preparation method of the antibacterial deodorant simultaneously meets the conditions I to IV.
7. The method for preparing an antibacterial deodorant according to claim 4 or 5, characterized in that the method for preparing the porous glass comprises: carrying out hot phase separation and acid leaching on the porous glass substrate;
wherein, the preparation method of the porous glass matrix preferably comprises: melting, quenching, crushing and balling the porous glass raw material;
preferably, the porous glass raw material is one or more of silicate, borate and borosilicate, preferably borosilicate;
preferably, the temperature of the melting is 1100-1300 ℃, preferably 1200 ℃;
preferably, the time of melting is 30-120min, preferably 60-90min, such as 70min or 80min;
preferably, the quenching mode is water quenching;
preferably, the crushing mode is ball milling, preferably dry ball milling;
preferably, the beading temperature is 600-1200 ℃, preferably 800-1000 ℃, e.g. 850 ℃, 880 ℃ or 900 ℃;
preferably, the beading time is 20-80min, preferably 30-60min, such as 35min, 45min or 55min;
wherein the temperature of the hot phase separation is preferably 500-650 ℃, more preferably 550-650 ℃, for example 650 ℃;
the time for the thermal phase separation is preferably 8 to 45h, more preferably 10 to 36h, such as 12h, 14h, 16h, 18h, 20h, 22h, 24h, 28h, 30h, 32h or 34h;
wherein the acid solution used for acid leaching is preferably one or more of a sulfuric acid solution, a nitric acid solution and a hydrochloric acid solution, and is preferably a hydrochloric acid solution;
the concentration of the acid solution used for the acid leaching is preferably 1 to 5mol/L, such as 1.5mol/L, 2.5mol/L, 3mol/L, 4mol/L or 4.5mol/L;
the temperature of the acid leaching is preferably 60-90 ℃, more preferably 70-80 ℃, e.g. 75 ℃;
the time for the acid leaching is preferably 8 to 50h, more preferably 12 to 48h, e.g. 12h, 14h, 16h, 18h, 20h, 22h, 24h, 28h, 30h, 32h, 34h or 36h.
8. The method for producing an antibacterial deodorant according to claim 4 or 5, characterized in that the reaction is a loading reaction;
wherein, the mode of the load reaction is preferably a solution impregnation method;
the temperature of the solution impregnation process is preferably in the range 40 to 90 ℃, more preferably 60 to 80 ℃, for example 70 ℃ or 75 ℃;
the time of the solution impregnation process is preferably 2 to 12h, more preferably 4 to 8h, e.g. 5h, 6h or 7h.
9. An antibacterial deodorant characterized by being produced by the production method according to any one of claims 4 to 8.
10. Use of an antibacterial deodorant as a raw material for fibers and/or plastic products, characterized in that the antibacterial deodorant is as defined in any one of claims 1, 2, 3 and 9;
preferably, the fibers and/or plastic articles are used in the building, apparel and home furnishing fields.
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| JPH09301802A (en) * | 1996-05-09 | 1997-11-25 | Nitto Boseki Co Ltd | Antibacterial porous glass fiber |
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