CN111269212A - Antimicrobial metal complex, application method and product prepared by using antimicrobial metal complex - Google Patents

Antimicrobial metal complex, application method and product prepared by using antimicrobial metal complex Download PDF

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Publication number
CN111269212A
CN111269212A CN202010248222.0A CN202010248222A CN111269212A CN 111269212 A CN111269212 A CN 111269212A CN 202010248222 A CN202010248222 A CN 202010248222A CN 111269212 A CN111269212 A CN 111269212A
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metal complex
antimicrobial metal
product
antimicrobial
metal
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商蔚
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Shenzhen Kangyi Health Care Products Co Ltd
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Shenzhen Kangyi Health Care Products Co Ltd
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Priority to CN202010248222.0A priority Critical patent/CN111269212A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/30—Nitrogen atoms not forming part of a nitro radical
    • C07D235/32—Benzimidazole-2-carbamic acids, unsubstituted or substituted; Esters thereof; Thio-analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/418—Cyclic amides, e.g. lactams; Amides of oxalic acid
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    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
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Abstract

Disclosed is an antimicrobial metal complex composed of a metal-containing substance and a heterocycle-containing organic compound; the metal-containing substance is a simple metal and/or a metal compound. The metal complex improves the stability of metal and obviously reduces the occurrence of metal discoloration phenomenon by matching the metal-containing substance with the heterocyclic compound, delays the time of the drug resistance of microorganisms to the heterocyclic compound due to the synergistic effect of the metal-containing substance and the heterocyclic compound, further improves the antimicrobial effect and has wide application prospect.

Description

Antimicrobial metal complex, application method and product prepared by using antimicrobial metal complex
Technical Field
The invention relates to the technical field of antimicrobial, in particular to an antimicrobial metal complex, an application method and a product prepared by the antimicrobial metal complex.
Background
With the improvement of living standards, higher requirements are put on living environment, including the cleanness and safety of the environment, so that various sterilizing and disinfecting products are on the market, however, most of the products may cause damage to the ecological environment in the nature and threat to human health, such as triclosan, hydrocortisone, chlorhexidine, chloroxylenol, and the like, and the products are not suitable for products which are in close contact with human, such as textiles.
Many metals have antimicrobial effects, such as metallic silver, which is widely used as a bactericide with excellent performance and high safety, but the metals have active properties and are easily oxidized and discolored, and the products added with the metallic elements change their colors to be dull after long-term use, which affects the beauty, thereby limiting the application range of the antimicrobial agents.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides an antimicrobial metal complex composed of a metal-containing substance and a heterocycle-containing organic compound; the metal-containing substance is a simple metal and/or a metal compound.
As a preferred technical solution, the metal is selected from one or more of lanthanum, cerium, praseodymium, gadolinium, terbium, samarium, europium, dysprosium, holmium, erbium, yttrium, ytterbium, platinum, palladium, gold, tin, silver, zinc, copper, molybdenum and titanium; further preferably, the metal is selected from one or more of cerium, neodymium, lanthanum, samarium, silver, zinc and copper.
As a preferable technical scheme, the heterocyclic ring is selected from one or more of pyrimidine, pyridine, pyrrole, imidazole, imidazoline, imidazolone, bisimidazole, tetrazole, isothiazolinone, benzisothiazolinone, benzoxazole, benzothiazole, benzimidazole, thiadiazole, thiophene, quinoline, pyrrolidone, phenanthroline, hydantoin and derivatives thereof.
In a preferred embodiment, the organic compound containing a heterocycle is a polymer containing a monomer having a heterocycle structure.
As a preferred embodiment, the complex further comprises water and/or an organic solvent.
In a second aspect of the invention there is provided a product comprising an antimicrobial metal complex as described above, the product being selected from one of a coating, paint, plastic, rubber, sponge, latex, leather, paper, apparel, fibre, textile, hygiene, medical material, filtration material, vehicle, decorative material, domestic appliance, communications means.
A third aspect of the invention provides a process for the preparation of a product as described above, comprising the steps of: the antimicrobial metal complex is added to the interior of the product or to the outer layer of the product.
As a preferred embodiment, the product is a fiber containing an antimicrobial metal complex;
the preparation method of the fiber comprises the following steps: adding an antimicrobial metal complex to the interior of the fiber;
the adding method comprises the following steps: adding the antimicrobial metal complex into spinning solution for wet spinning, or adding the antimicrobial metal complex into fiber master batch for melt spinning.
As a preferred embodiment, the product is a fabric containing an antimicrobial metal complex;
the preparation method of the fabric comprises the following steps: adding an antimicrobial metal complex to the outer layer of the fabric;
the adding method comprises the following steps: the metal complex is added to the adhesive and applied to the fabric by spraying, padding, printing or coating.
A fourth aspect of the invention provides the use of an antimicrobial metal complex as described above for deodorisation.
Has the advantages that: the invention provides an antimicrobial metal complex, which improves the stability of metal and remarkably reduces the occurrence of metal discoloration by matching a metal-containing substance with a heterocyclic compound, delays the time of the drug resistance of microorganisms to the heterocyclic compound due to the synergistic effect of the metal-containing substance and the heterocyclic compound, further improves the antimicrobial effect, and has wide application prospect.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above problems, a first aspect of the present invention provides an antimicrobial metal complex composed of a metal-containing substance and a heterocycle-containing organic compound; the metal-containing substance is a simple metal and/or a metal compound.
In some preferred embodiments, the metal is selected from the group consisting of lanthanum, cerium, praseodymium, gadolinium, terbium, samarium, europium, dysprosium, holmium, erbium, yttrium, ytterbium, platinum, palladium, gold, tin, silver, zinc, copper, molybdenum, titanium, and mixtures thereof; further preferably, the metal is selected from one or more of cerium, neodymium, lanthanum, samarium, silver, zinc and copper.
In some preferred embodiments, the metal compound is selected from a mixture of one or more of metal oxides, metal chlorides, metal nitrates, metal sulfates, metal carbonates, metal phosphates, metal silicates, metal hydroxides, metal acetates, metal carboxylates.
The principle of killing microorganisms by a part of metal ions is that the metal ions can penetrate through cell membranes of the microorganisms to enter cells, so that cell components escape, cell metabolism is interfered, the cells lose due biological functions, and finally the cells die; part of the metal can generate free radicals under the photocatalysis effect, and has the effect of inhibiting or killing microorganisms. However, when the metal-containing substance is directly made into an antimicrobial product, the metal property is active, and the discoloration phenomenon occurs due to chemical reaction, particularly when the metal-containing substance is used in products such as fibers and textiles, the discoloration can cause the products to have poor appearance, and the quality of the products is reduced after long-term use.
In some preferred embodiments, the heterocycle is selected from the group consisting of a mixture of one or more of pyrimidine, pyridine, pyrrole, imidazole, imidazoline, imidazolidinone, bisimidazole, tetrazole, isothiazolinone, benzisothiazolinone, benzoxazole, benzothiazole, benzimidazole, thiadiazole, thiophene, quinoline, pyrrolidone, phenanthroline, hydantoin, and derivatives thereof.
The term "heterocyclic ring" as used herein means that the atoms constituting the ring contain at least one atom other than carbon, i.e., a heteroatom, which may be a nitrogen atom, a sulfur atom, an oxygen atom, etc., as is common.
The term "derivative" as used herein refers to a product derived from a simple compound in which a hydrogen atom or an atomic group is substituted with another atom or an atomic group, and examples of derivatives of imidazole include imidazolidinyl urea, N-substituted imidazole, N-hydrocarbyl imidazole, N- (trisubstituted silyl) imidazole, imazethapyr, methylimidazopyr; derivatives of bisimidazole such as bisimidazolidinyl urea; derivatives of imidazolidinones can be illustrated by hydrocarbyl imidazolinones.
The heterocyclic compound can be used as a drug intermediate to identify each target point in cells to generate bactericidal action, but microorganisms can generate drug resistance after long-term use. The inventor unexpectedly finds that the combination of the metal and the heterocyclic compound can prolong the antimicrobial effect and reduce the occurrence of metal discoloration phenomena, and the reason is that the metal atom loses electrons to form an empty orbit and can be just combined with a lone electron pair of a heteroatom in the heterocyclic ring through a coordination bond, so that the metal compound is stabilized and the discoloration is reduced; the indiscriminate sterilization effect of the metal-containing substances can effectively delay the generation of microbial drug resistance and ensure the antimicrobial effect of the complex.
In some preferred embodiments, the organic compound containing heterocyclic ring may also be a polymer containing monomers with heterocyclic structure, and the polymerization may be addition polymerization between monomers containing double bond or condensation between monomers to release simple molecules through chemical combination reaction.
In some preferred embodiments, the weight ratio of the metal-containing substance to the heterocycle-containing organic compound is (1-3): 10.
in some preferred embodiments, the complex further comprises water and/or an organic solvent. The complexing conditions are adjusted by adding a solvent, thereby improving the antimicrobial properties of the complex.
Organic solvents in this application include, but are not limited to, alcohols, esters, alkanes, aromatics, ethylene oxide adducts; examples of the alcohols include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, hexylene glycol, and pentylene glycol; examples of the esters include ethyl acetate and butyl acetate; examples of the ethylene oxide adduct include polyethylene glycol and fatty alcohol-polyoxyethylene ether.
In some preferred embodiments, the concentration of the heterocyclic ring-containing organic compound is 0.001 to 0.1 wt% when the complex is mixed with water/organic solvent.
The method of preparation of the antimicrobial metal complexes described herein may be any of those well known to those skilled in the art, such as physical mixing.
In a second aspect of the invention there is provided a product comprising an antimicrobial metal complex as described above, the product being selected from one of a coating, paint, plastic, rubber, sponge, latex, leather, paper, apparel, fibre, textile, hygiene, medical material, filtration material, vehicle, decorative material, domestic appliance, communications means.
A third aspect of the invention provides a process for the preparation of a product as described above, comprising the steps of: the antimicrobial metal complex is added to the interior of the product or to the outer layer of the product.
In some preferred embodiments, the product is a fiber containing an antimicrobial metal complex;
the preparation method of the fiber comprises the following steps: adding an antimicrobial metal complex to the interior of the fiber;
the adding method comprises the following steps: adding the antimicrobial metal complex into spinning solution for wet spinning, or adding the antimicrobial metal complex into fiber master batch for melt spinning.
The wet spinning and melt spinning processes described herein can be performed according to procedures well known to those skilled in the art.
In some preferred embodiments, the product is a fabric containing an antimicrobial metal complex;
the preparation method of the fabric comprises the following steps: adding an antimicrobial metal complex to the outer layer of the fabric;
the adding method comprises the following steps: the metal complex is added to the adhesive and applied to the fabric by spraying, padding, printing or coating.
The spraying, padding, printing, coating, etc. processes described herein can be performed according to procedures well known to those skilled in the art. The adhesive in the present application is not particularly limited, and examples thereof include acrylic adhesives, polyurethane adhesives, polyolefin adhesives, and the like.
A fourth aspect of the invention provides the use of an antimicrobial metal complex as described above for deodorisation.
Examples
The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples. The starting materials used in this application are commercially available unless otherwise specified.
Example 1
Example 1 provides an antimicrobial metal complex consisting of, by weight, 3: 10 silver powder and imazapyr (CAS number: 81334-34-1), and the two are physically blended to obtain the silver powder.
Example 2
Example 2 provides an antimicrobial metal complex consisting of, by weight, 2: 10 zinc chloride and 2, 4-pyridinedicarboxylic acid (CAS number: 499-80-9), and the two are physically blended.
Example 3
Example 3 provides an antimicrobial metal complex consisting of, by weight, 1: 10 silver nitrate and 2-methyl-4-isothiazolin-3-one (CAS number: 2682-20-4), and the two are physically blended to obtain the product.
Example 4
Example 4 provides an antimicrobial metal complex consisting of, by weight, 1: 10 lanthanum oxide and benzimidazole-2-yl methyl carbamate (CAS number: 10605-21-7), and the two are physically blended to obtain the product.
Example 5
Example 5 provides an antimicrobial metal complex in a weight ratio of 3: 10 silver powder and imazapyr (CAS number: 81334-34-1) were dispersed in an aqueous ethanol solution (70% by volume), wherein the concentration of imazapyr in the solution was 0.01% by weight.
Comparative example 1
Comparative example 1 is silver powder.
Comparative example 2
Comparative example 2 was silver nitrate.
Comparative example 3
Comparative example 3 is imazapic.
Comparative example 4
Comparative example 4 is 2-methyl-4-isothiazolin-3-one.
Evaluation of Performance
The adhesive (Zhenlong ZL 149D) prepared by mixing the adhesive (Zhenlong) in the ratio of 1: 50 parts by weight of the mixture was padded on white cotton cloth, and tests were performed using the white cotton cloth after drying, the test contents including persistent antibacterial property and color stability.
1. And (3) persistent antibacterial property: according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: the method described in agar plate diffusion method "comprises testing a sample and a control sample, cutting the sample into a round sample with a diameter of 25mm, placing the test bacteria such as Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli on a culture medium, culturing at 37 + -2 deg.C for 7d, observing the antibacterial band, and evaluating the antibacterial effect, wherein the evaluation standard and the test result are shown in Table 1 and Table 2, respectively.
2. Color stability: the dried cotton cloth was dried in the sun for 7d, and the whiteness before and after drying was measured with a whiteness meter to calculate the degree of change in whiteness, which is [ (whiteness before drying-whiteness after drying)/whiteness before drying ] × 100%, and the results are shown in table 2.
TABLE 1 evaluation of antibacterial Effect
Figure BDA0002434538290000061
Figure BDA0002434538290000071
TABLE 2
Figure BDA0002434538290000072
The antimicrobial metal complex provided by the invention has excellent persistent antibacterial property and color stability, can realize a long-acting antibacterial effect when being used in fibers or fabrics, does not gradually dim in color after being used for a long time, and has a wide application prospect as can be known from examples 1-5 and comparative examples 1-4.
Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An antimicrobial metal complex, characterized in that it consists of a metal-containing substance and a heterocycle-containing organic compound; the metal-containing substance is a simple metal and/or a metal compound.
2. The antimicrobial metal complex of claim 1, wherein the metal is selected from the group consisting of lanthanum, cerium, praseodymium, gadolinium, terbium, samarium, europium, dysprosium, holmium, erbium, yttrium, ytterbium, platinum, palladium, gold, tin, silver, zinc, copper, molybdenum, titanium, and mixtures thereof; preferably, the metal is selected from one or more of cerium, neodymium, lanthanum, samarium, silver, zinc and copper.
3. An antimicrobial metal complex according to claim 1, wherein the heterocyclic ring is selected from one or more of pyrimidine, pyridine, pyrrole, imidazole, imidazoline, imidazolidinone, bisimidazole, tetrazole, isothiazolinone, benzisothiazolinone, benzoxazole, benzothiazole, benzimidazole, thiadiazole, thiophene, quinoline, pyrrolidone, phenanthroline, hydantoin and derivatives thereof.
4. An antimicrobial metal complex according to claim 1 or 3, wherein the organic compound containing a heterocycle is a polymer containing a monomer with a heterocyclic structure.
5. An antimicrobial metal complex according to claim 1, wherein the complex further comprises water and/or an organic solvent.
6. A product containing the antimicrobial metal complex according to any one of claims 1 to 5, wherein the product is selected from one of a coating, a paint, a plastic, a rubber, a sponge, a latex, a leather, a paper, a dress, a fiber, a fabric, a textile, a hygiene product, a medical material, a filter material, a vehicle, a decorative material, a household appliance, and a communication tool.
7. A method of preparing the product of claim 6, comprising the steps of: the antimicrobial metal complex is added to the interior of the product or to the outer layer of the product.
8. The product of claim 6, wherein the product is a fiber comprising an antimicrobial metal complex;
the preparation method of the fiber comprises the following steps: adding an antimicrobial metal complex to the interior of the fiber;
the adding method comprises the following steps: adding the antimicrobial metal complex into spinning solution for wet spinning, or adding the antimicrobial metal complex into fiber master batch for melt spinning.
9. The product of claim 6, wherein the product is a fabric comprising an antimicrobial metal complex;
the preparation method of the fabric comprises the following steps: adding an antimicrobial metal complex to the outer layer of the fabric;
the adding method comprises the following steps: the metal complex is added to the adhesive and applied to the fabric by spraying, padding, printing or coating.
10. Use of an antimicrobial metal complex according to any one of claims 1 to 5 for deodorizing.
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