CN110835845A - Antibacterial finishing agent, antibacterial fabric and preparation method thereof - Google Patents
Antibacterial finishing agent, antibacterial fabric and preparation method thereof Download PDFInfo
- Publication number
- CN110835845A CN110835845A CN201810942825.3A CN201810942825A CN110835845A CN 110835845 A CN110835845 A CN 110835845A CN 201810942825 A CN201810942825 A CN 201810942825A CN 110835845 A CN110835845 A CN 110835845A
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- fabric
- antimicrobial
- finishing agent
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
-
- 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
- D06M11/83—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
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
The invention relates to an antibacterial finishing agent, which comprises an antibacterial substance and an aqueous medium, wherein the antibacterial substance is selected from metals and/or metal oxides of molybdenum and/or tungsten. In addition, the fabric formed by the antibacterial finishing agent and a preparation method of the antibacterial fabric are also provided. The antibacterial fabric is prepared by the preparation method, and can effectively resist common pathogenic microorganisms and super bacteria; the product is safe and harmless, does not change the cell genetic characteristics, does not cause cancer, and does not generate drug resistance; high efficiency and durability, long effective time of one-time manufacture, and the antibacterial validity period is the same as the service life of the base material.
Description
Technical Field
The invention belongs to the technical field of textiles, relates to a textile finishing agent, and particularly relates to an antibacterial finishing agent. The invention also relates to a fabric formed by the antibacterial finishing agent and a preparation method of the antibacterial fabric.
Background
Scientific research has found that non-living surfaces can accumulate a large number of pathogenic bacteria and viruses, which are particularly dangerous for multiple drug resistant bacteria and viruses. These pathogenic bacteria and viruses can survive or survive on the surface of an object for several months, and if preventive sterilization measures are not taken, pathogens attached to the surface of the object become a persistent source of infection transmission.
In the case of fabrics, bacteriostatic and/or antibacterial functions are often imparted to the fabric by dyeing and finishing techniques in order to prevent the spread of diseases and to improve the healthy living standard. The core component of the textile finishing agent is the bacteriostatic agent. Common bacteriostatic agents are classified into three categories, namely organic bacteriostatic agents, natural bacteriostatic agents and inorganic bacteriostatic agents according to different sources.
As the organic antibacterial agent, quaternary ammonium salt compounds, quaternary phosphonium salt compounds, azole compounds, guanidine compounds and the like are most commonly used. The antibacterial agent has good antibacterial effect, is environment-friendly and safe, and has no irritation to skin. However, organic antibacterial agents are easily lost under environmental conditions and have short antibacterial aging.
Chitosan, chitin, mugwort, aloe, etc. are most commonly used as natural antibacterial agents. The antibacterial agent has the same antibacterial effect and is environment-friendly and safe. However, natural antibacterial agents are difficult to process, have poor heat resistance, and have short antibacterial aging.
The inorganic bacteriostatic agent is most commonly metal or metal oxide, and can make different fabrics generate antibacterial property and remove pathogens attached to the surfaces of objects. It is known that a large number of metal ions have effective antibacterial properties, such as Ag+，Cd2+，Hg2+And Cu2+. In addition to copper, silver is often used. The inorganic bacteriostatic agent has long antibacterial time and wide antibacterial spectrum. However, the conventional inorganic bacteriostatic agents have slightly insufficient antibacterial activity.
To further combat these pathogenic bacteria and viruses, it has been found that transition metal oxides form weak metal acids upon contact with water, aided by H at the fabric surface3O+The ions form an effective antimicrobial agent. Such metal compounds provide better results than the above metals or metal ions under different conditions, thereby having safe and long-lasting antibacterial effects.
The inventor finds that the weak acid microenvironment on the surface of the antibacterial fabric can rapidly kill and durably inhibit pathogenic microorganisms (bacteria, viruses and molds) and multiple drug-resistant bacteria under the action of multiple antibacterial mechanisms. The sterile state can be kept for a long time only by once manufacturing, frequent disinfection and cleaning are not needed, and repeated consumption and secondary environmental pollution are avoided.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide an antimicrobial finish.
In particular, the invention relates to the following:
1. an antibacterial finishing agent comprising an antibacterial substance and an aqueous medium, characterised in that the antibacterial substance is selected from metals and/or metal oxides of molybdenum and/or tungsten.
2. The antibacterial finish according to item 1, wherein the aqueous medium may be water, an aqueous solution or a suspension.
3. The antibacterial finishing agent according to item 1, wherein the weight ratio of the antibacterial substance is 0.01 to 50%, preferably 0.05 to 20%, and more preferably 0.5 to 5%, based on the total weight of the antibacterial finishing agent.
4. The antimicrobial finish of item 1, further comprising a silica sol.
5. The antimicrobial finish of claim 1, further comprising an amino silicone oil.
6. The antimicrobial finish of item 1, further comprising a binder.
7. An antibacterial fabric, which is characterized by being prepared by the following method: applying the antimicrobial finish of any of claims 1-6 to a fabric, and then dry forming at a suitable temperature.
8. The antimicrobial fabric of claim 7, wherein the application method comprises spraying, brushing, dipping, padding.
9. The antimicrobial fabric of claim 7, wherein the fabric comprises a natural fiber fabric, a synthetic fiber fabric, and a blend fiber fabric and/or a union fiber fabric thereof.
10. A method for preparing an antibacterial fabric, characterized in that the antibacterial finishing agent according to any one of items 1 to 6 is applied to the fabric, and then dried and formed at a suitable temperature; preferably, the process is carried out after a conventional dyeing and finishing process.
11. An antimicrobial fabric, characterized in that it is obtained by the process of item 10.
12. An antimicrobial fabric, wherein the fabric comprises molybdenum and/or tungsten as detected by X-ray fluorescence spectroscopy (XRF).
13. The antibacterial fabric according to item 12, wherein the content of molybdenum and/or tungsten element in the main element detected by X-ray fluorescence spectroscopy analysis is 5% or more, preferably 6% or more, further preferably 8% or more, further preferably 10% or more, further preferably 15% or more as detected by X-ray fluorescence spectroscopy (XRF).
In order to solve the technical problems, the invention provides the following technical scheme: an antibacterial finishing agent comprising an antibacterial substance and an aqueous medium, characterised in that the antibacterial substance is selected from metals and/or metal oxides of molybdenum and/or tungsten.
The antibacterial substance can be a simple metal substance of molybdenum and/or tungsten, and can also be a metal oxide of molybdenum and/or tungsten.
The antibacterial finishing agent according to the present invention, wherein the aqueous medium may be water, an aqueous solution or a suspension. The aqueous medium is exposed at the surface of the fabric substrate and penetrates into the interior of the fabric substrate over time. Advantageously, the fabric substrate surface is dried. Upon re-exposure to air, the fabric substrate is capable of absorbing moisture at or near the surface area, thereby resulting in improved wettability with water or aqueous media at the surface of the fabric. Further, the antibacterial substance is released with the aid of water.
Preferably, the aqueous medium is selected from aqueous solutions. In a specific embodiment, the aqueous medium comprises water and a polar solvent. The polar solvent includes, but is not limited to, organic solvents such as alcohols, ethers, esters, ketones, and the like; further preferred are alcohol and ether solvents.
As examples of the alcohol and ether solvents, methanol, ethanol, propanol, isopropanol, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol, and dipropylene glycol, and the like can be cited. Preferably, the alcoholic and etheric solvents are selected from the group consisting of ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol and dipropylene glycol; more preferably, the alcohol and ether solvents are selected from the group consisting of ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol and dipropylene glycol; and, most preferably, the alcoholic solvent is selected from diethylene glycol and dipropylene glycol; the ether solvent is selected from ethylene glycol monomethyl ether.
In a particular embodiment, the alcoholic solvent is selected from diethylene glycol.
The antibacterial finishing agent according to the foregoing invention, wherein the antibacterial substance is selected from molybdenum or an oxide of molybdenum; alternatively, tungsten or an oxide of tungsten; alternatively, the oxides of molybdenum and tungsten are mixed in a certain ratio.
Wherein, as the mixture, the weight proportion of the molybdenum oxide in the mixture can be, for example, 0.1-99.9%, 0.5-99.5%, 1-99%, 2-98%, 3-97%, 4-96%, 5-95%, 8-92%, 10-90%, 12-88%, 15-85%, 18-82%, 20-80%, 22-78%, 25-75%, 28-72%, 30-70%, 32-68%, 35-65%, 38-62%, 40-60%, 42-58%, 45-55%, 48-52%.
In a particular embodiment, the proportion by weight of the molybdenum oxide in the mixture is 50%.
According to the aforementioned antibacterial finish of the present invention, the metal and/or metal oxide of molybdenum and/or tungsten may be used in combination with at least another oxide. Another oxide includes, but is not limited to, alumina, silica, zirconia, tungsten oxide, titanium oxide, and the like.
Taking molybdenum oxide as an example, the combination form of the molybdenum oxide and another oxide can be as follows: molybdenum oxide/aluminum oxide composites, molybdenum oxide/silicon dioxide composites, molybdenum oxide/zirconium oxide composites, molybdenum oxide/tungsten oxide composites, molybdenum oxide/titanium oxide composites, and the like. Wherein the weight ratio of the molybdenum oxide in the molybdenum oxide compound is 0.1-90%, 0.5-89.5%, 1-89%, 2-88%, 3-87%, 4-86%, 5-85%, 8-82%, 10-80%, 12-78%, 15-75%, 18-72%, 20-70%, 22-68%, 25-65%, 28-62%, 30-60%, 32-58%, 35-55%, 38-52%, 40-50% and 42-48%. The compounding mode can be mixing, coprecipitation, sintering, dipping, loading, modification, gel mixing and the like, and molybdenum oxide is preferably on the surface.
In one specific embodiment, the weight proportion of molybdenum oxide in the molybdenum oxide composite is 45%, and the composite mode is a coprecipitation method.
Without wishing to be bound by any theory, in the present invention molybdic and/or tungstic acids, which utilize the reaction of molybdenum and/or tungsten with water molecules, cause the pH of the medium in contact with the substance to decrease, thereby effectively sterilizing. For example, molybdenum oxide reacts with water to form molybdic acid (H)2MoO4) Which in turn is reacted with H2Reaction of O to form H3O+And MoO4 -Or MoO4 2-. Tungsten oxide is also H2Formation of tungstic acid (H) from O2WO4) Of which is in contact with H2Reaction of O to form H3O+And WO4 -Or WO4 2-。
The inventors have found that molybdic and/or tungstic acids, due to their low solubility, are capable of producing a long lasting antimicrobial effectiveness when in contact with aqueous media.
The antibacterial finishing agent according to the present invention, wherein the weight ratio of the antibacterial substance is 0.01-50% based on the total weight of the antibacterial finishing agent. The weight ratio may further be, for example, 0.02 to 49.9%, 0.05 to 49.5%, 0.1 to 49%, 0.2 to 48%, 0.3 to 47%, 0.4 to 46%, 0.5 to 45%, 0.8 to 42%, 1.0 to 40%, 1.2 to 38%, 1.5 to 35%, 1.8 to 32%, 2.0 to 30%, 2.2 to 28%, 2.5 to 25%, 2.8 to 22%, 3.0 to 20%, 3.2 to 18%, 3.5 to 15%, 3.8 to 12%, 4.0 to 10%, 4.2 to 8%, 4.5 to 6%, 4.8 to 5.2%.
Preferably, the weight proportion of the antibacterial substance is 0.05-40%; more preferably, the weight ratio of the antibacterial substance is 0.1-30%; and, most preferably, the weight proportion of the antibiotic substance is 0.5-20%.
In a specific embodiment, the weight proportion of the antimicrobial substance is 5%, based on the total weight of the antimicrobial finish.
The antibacterial finishing agent according to the present invention, wherein the antibacterial substance is present in a solid powder form.
Advantageously, the solid powder has an average particle size of 10nm to 100 μm. Preferably, the solid powder has an average particle size of 50nm to 50 μm; more preferably, the solid powder has a particle size of 100nm to 10 μm; and, most preferably, the solid powder has an average particle size of 500nm to 5 μm.
In a specific embodiment, the solid powder has an average particle size of 2 μm.
The antimicrobial finish according to the invention as described above, wherein the metal and/or metal oxide of molybdenum and/or tungsten may be used in combination with at least one second antimicrobial substance.
The second antibacterial substance is preferably an organic antibacterial agent and a natural antibacterial agent. As examples of the organic antibacterial agent, quaternary ammonium salt compounds, quaternary phosphonium salt compounds, azole compounds, guanidine compounds, and the like can be given. As examples of natural antibacterial agents, chitosan, chitin, mugwort, aloe, and the like can be cited.
In a specific embodiment, the second antimicrobial substance is selected from quaternary ammonium salt compounds.
As examples of the quaternary ammonium salt compounds, dodecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl phenoxyethyl ammonium bromide, tetradecyl-2-methylpyridine ammonium bromide, hexadecyl pyridine ammonium chloride, hexadecyl pyridine ammonium bromide, dimethyl dioctylammonium chloride, dimethyl dioctadecyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, diisobutylphenoxyethyl dimethyl benzyl ammonium chloride, and 3- (trimethoxysilyl) propyl octadecyl dimethyl ammonium chloride, and the like can be cited.
The antibacterial finishing agent according to the present invention, wherein the weight ratio of the second antibacterial substance is 0 to 50% based on the total weight of the antibacterial substance.
Preferably, the weight ratio of the second antibiotic substance is 0-40%; more preferably, the weight proportion of the second antibiotic substance is 0-30%; and, most preferably, the weight proportion of the second antibiotic substance is 0 to 20%.
In a specific embodiment, the weight proportion of the second antibiotic substance is 10% based on the total weight of the antibiotic substances.
The antibacterial finishing agent according to the invention further comprises silica sol.
Advantageously, the silica sol has an average particle size of from 1nm to 1 μm. Preferably, the silica sol has an average particle size of 2nm to 200 nm; more preferably, the silica sol has a particle size of 5nm to 100 nm; and, most preferably, the silica sol has an average particle size of 10nm to 50 nm.
In a specific embodiment, the silica sol has an average particle size of 20 nm.
According to the antibacterial finishing agent, the weight proportion of the silica sol is 0.1-10% based on the total weight of the antibacterial finishing agent. Preferably, the weight proportion of the silica sol is 0.2-8%; more preferably, the weight proportion of the silica sol is 0.5-5%; and, most preferably, the silica sol is present in a proportion of 1 to 3% by weight.
In a specific embodiment, the weight proportion of the silica sol is 2%, based on the total weight of the antimicrobial finish.
The antibacterial finishing agent according to the invention further comprises amino silicone oil.
According to the antibacterial finishing agent, the weight proportion of the amino silicone oil is 0.01-10% based on the total weight of the antibacterial finishing agent. Preferably, the weight proportion of the amino silicone oil is 0.1-8%; more preferably, the weight proportion of the amino silicone oil is 0.2-5%; and, most preferably, the weight proportion of the amino silicone oil is 0.5-3%.
In a particular embodiment, the weight proportion of the amino silicone oil is 1%, based on the total weight of the antimicrobial finish.
Advantageously, the amino silicone oil has an ammonia value of 0.3 to 0.6.
The antibacterial finishing agent according to the invention further comprises a binder.
As examples of the binder, acrylic emulsion, urethane emulsion, polyvinyl alcohol emulsion, and the like, or a mixture of two or more thereof may be cited.
In a particular embodiment, the binder is selected from acrylate emulsions.
The antibacterial finishing agent according to the invention is characterized in that the weight proportion of the binder is 0.05-5% based on the total weight of the antibacterial finishing agent. Preferably, the weight proportion of the binder is 0.1-4%; more preferably, the weight proportion of the binder is 0.2-2.5%; and, most preferably, the weight proportion of the binder is 0.5-1.5%.
In a specific embodiment, the weight proportion of the binder is 1% based on the total weight of the antimicrobial finish.
The antibacterial finishing agent according to the invention further comprises a nonionic surfactant.
As examples of the nonionic surfactant, there may be mentioned polyhydric alcohol fatty acid ester type nonionic surfactants and fatty alcohol polyoxyethylene ether nonionic surfactants, or a mixture of two or more thereof. Examples of the polyol fatty acid ester nonionic surfactant include span-60, span-80, span-83, tween-20, tween-40, tween-60, tween-80, tween-81, tween-85 and the like. As the fatty alcohol-polyoxyethylene ether nonionic surfactant, for example, peregal O-10, peregal O-25, peregal O-35, peregal A-20, SG-10, LAE-9, AEO8, AEO9 and the like can be cited.
In a specific embodiment, the nonionic surfactant is selected from tween-80.
The antibacterial finishing agent according to the present invention, wherein the weight ratio of the nonionic surfactant is 0.5-5% based on the total weight of the antibacterial finishing agent. Preferably, the weight proportion of the nonionic surfactant is 1-4%; more preferably, the weight proportion of the nonionic surfactant is 2-4%; and, most preferably, the weight proportion of the nonionic surfactant is 2-3%.
In a specific embodiment, the weight proportion of the nonionic surfactant is 2.5% based on the total weight of the antimicrobial finish.
In addition to the above, the antibacterial finish according to the present invention optionally includes various adjuvants or auxiliary ingredients well known in the art. Such adjuvants or auxiliary ingredients include, but are not limited to, dyes, pigments, dispersants, softeners, thickeners, softeners, crosslinking agents, leveling agents, brighteners, dye fixatives, fuzzing agents, refiners, stabilizers, complexing agents, defoamers, levelers, brighteners, soaping agents, resists, penetrants, deodorants, uv inhibitors, antistatic agents, and the like.
The amounts of these auxiliaries or auxiliary components are well known to those skilled in the art.
The invention also aims to provide an antibacterial fabric, which is characterized by being prepared by the following method: the antibacterial finishing agent is applied to the fabric, and then dried and formed at a proper temperature.
The antibacterial fabric according to the present invention, wherein the application method includes, but is not limited to, spraying, brushing, dipping, padding, and the like. These application methods are well known to those skilled in the art.
Examples of the spray coating include: the antibacterial finishing agent is diluted by water by a certain multiple, is uniformly sprayed on the surface of the fabric by a spray gun, and is shaped and dried. Advantageously, the dilution factor is 1 to 200, preferably 2 to 100, more preferably 5 to 50 and most preferably 10 to 20.
Examples of brushing include: the antimicrobial finish of the present invention is adjusted to a suitable viscosity, uniformly brushed onto the fabric surface using a brush, and then set and dried.
Examples of impregnation include: diluting the antibacterial finishing agent by water by a certain multiple, soaking the fabric in the diluted antibacterial finishing agent by a certain multiple at a bath temperature of 40-95 ℃ at a bath ratio of 1:10-40 to fully soak the fabric to fully contact the antibacterial finishing agent with the fabric, and then cooling to room temperature for spin-drying.
Examples of padding include: the fabric is made to pass through the said diluent, bath ratio is controlled at 1:10-40, bath temperature is controlled at 40-95 deg.c, and the mangle ratio is 110-40%, and the fabric is finally shaped and dried. If necessary, the composite material can be padded for two or more times to achieve the required combination amount and antibacterial performance of the antibacterial agent.
According to the antibacterial fabric, the drying temperature is 20-80 ℃. Preferably, the drying temperature is 25-70 ℃; more preferably, the drying temperature is 30-60 ℃; and, most preferably, the drying temperature is 35-50 ℃.
In a specific embodiment, the drying temperature is 40 ℃.
The antibacterial fabric according to the present invention, wherein the dry weight of the antibacterial finishing agent is 0.1-20% based on the dry weight of the antibacterial fabric.
Preferably, the dry weight of the antibacterial finishing agent is 0.2-15%; more preferably, the dry weight of the antimicrobial finish is 0.5-10%; and, most preferably, the antimicrobial finish is 1-5% dry weight.
In a specific embodiment, the antimicrobial finish has a dry weight of 3% based on the dry weight of the antimicrobial fabric.
The antibacterial fabric according to the present invention, wherein the fabric includes, but is not limited to, natural fiber fabric, synthetic fiber fabric, and blended fiber fabric and/or blended fiber fabric thereof.
Examples of natural fibers include: cotton, wool, silk, hemp, etc.
Examples of synthetic fibers include: silk, acrylic, nylon, polyester, polypropylene, vinylon, polyethylene fibers, carbon fibers, and the like.
From a morphological point of view, the types of fabrics of the present invention include, but are not limited to, yarns, wool tops, woven fabrics, knitted fabrics, nonwoven fabrics, apertured films, and the like.
The antibacterial fabric according to the present invention may be used as underwear and pants, sportswear, socks, insoles, gloves, neckerchief, hat, carpet, curtain, tablecloth, shower curtain, bedding, seat cushion, automotive upholstery fabric, mask, medical gauze, medical cloth, surgical gown, medical coveralls, hospital gowns, air filter nets, diapers, sanitary napkins, and the like.
The invention also aims to provide a preparation method of the antibacterial fabric, which is characterized in that the antibacterial finishing agent is applied to the fabric, and then the fabric is dried and formed at a proper temperature.
The preparation method according to the invention is carried out after the conventional dyeing and finishing process.
Further, the invention also provides an antibacterial fabric, wherein the fabric is obtained by the preparation method.
In yet another aspect, the present invention provides an antimicrobial fabric, wherein the fabric comprises molybdenum and/or tungsten as detected by X-ray fluorescence spectroscopy (e.g., shimadzu XRF-1800X-ray fluorescence spectroscopy).
In the present invention, any instrument capable of X-ray fluorescence spectroscopy can be used, and the detection can be carried out according to the manual of the specific instrument, the method described in the manual and/or the specification, and in the specific example, Shimadzu XRF-1800X-ray fluorescence spectrometer is used.
In analyzing the antibacterial fabric using the X-ray fluorescence spectroscopy, since all elements except C, H and O contained in the antibacterial fabric can be analyzed using this method, for convenience, the elements analyzed and detected by the X-ray fluorescence spectroscopy are collectively referred to as main elements in the antibacterial fabric.
Thus, in a particular embodiment of the invention, the main elements contained in the antimicrobial fabric may be, for example: si, Mo, Ca, K, P, Fe and Al. In another specific embodiment, the main elements contained in the antibacterial fabric may be, for example: si, W, Ca, K, P, Fe and Al. Of course, it is fully understood by those skilled in the art that in other embodiments, the primary elements contained in the antimicrobial fabric may be, for example: si, W, Mo, Ca, K, P, Fe and Al.
The antibacterial fabric according to the present invention, wherein the ratio of molybdenum and/or tungsten elements to the main elements detected by X-ray fluorescence spectroscopy analysis is 5% or more, preferably 6% or more, preferably 8% or more, and more preferably 15% or more, as detected by X-ray fluorescence spectroscopy (XRF).
In a specific embodiment, the weight proportion of molybdenum in the Si, Mo, Ca, K, P, Fe and Al elements contained in the fabric (the elements detected by X-ray fluorescence spectroscopy analysis are collectively referred to herein as the main elements in the antimicrobial fabric) is 18%.
In another specific embodiment, the fabric contains elements Si, W, Ca, K, P, Fe and Al (the elements detected by X-ray fluorescence spectroscopy analysis are collectively referred to herein as the main elements in the antimicrobial fabric), the proportion by weight of the tungsten element is 16%.
In another specific embodiment, the weight proportion of the molybdenum element in the Si, Mo, Ca, K, P, Fe and Al elements contained in the fabric (the elements detected by X-ray fluorescence spectroscopy analysis are collectively referred to herein as the main elements in the antimicrobial fabric) is 15%.
The antibacterial fabric is prepared by a post-finishing method, has no toxic or side effect, and effectively resists common pathogenic microorganisms and super bacteria; the product is safe and harmless, does not change the cell genetic characteristics, does not cause cancer, and does not generate drug resistance; the efficiency is long, the one-time manufacture is long-term effective, and the antibacterial validity period is the same as the service life of the base material; the application is wide, and the medical, civil, military and industrial fields are covered.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the contents of the present invention, and those equivalents may fall within the scope of the present invention defined by the appended claims.
Examples
The present invention is described in further detail below with reference to specific examples.
Wherein, the antibacterial performance of the antibacterial fabric is evaluated according to the second part of the national standard GB/T20944.2-2007' antibacterial performance of textiles: absorption method "and the test bacterium is Escherichia coli.
Example 1
Soaking the pure-spun cotton fabric in the antibacterial finishing agent for 30 minutes in a cotton gauze base material 1 of the pure-spun fabric at the temperature of 50 ℃, then soaking twice and rolling twice, and drying and forming according to the manufacturing process of the fabric base material, wherein the drying temperature is 80 ℃ to obtain the antibacterial cotton fabric. Wherein, the antibacterial finishing agent comprises the following components: 10 parts of molybdenum trioxide, 4 parts of silica sol, 2 parts of amino silicone oil, 805 parts of tween, 2 parts of acrylate emulsion adhesive, 7 parts of diethylene glycol and 170 parts of deionized water.
The antibacterial performance test is carried out according to the national standard, and the antibacterial performance is more than 99.0 percent.
The antibacterial gauze is detected by an X-ray fluorescence spectrometry (Shimadzu XRF-1800X-ray fluorescence spectrometer) according to the operation steps of the specification, and the detection result shows that the antibacterial gauze contains Si, Mo, Ca, K, P, Fe and Al (the elements detected by the X-ray fluorescence spectrometry are collectively referred to as main elements in the antibacterial fabric), wherein the weight proportion of the molybdenum element in the main elements is 18%.
Example 2
The surface of a non-woven fabric base material 2 of 80-20 cotton-real silk blended fabric is soaked in the antibacterial finishing liquid for 30 minutes. And after the liquid permeates into the fabric base material, drying at the temperature of 90 ℃, and performing a color fixing process to obtain the antibacterial fabric. Wherein, the antibacterial finishing agent comprises the following components: 3 parts of tungsten trioxide, 1 part of silica sol, 0.5 part of amino silicone oil, 1 part of tween-802, 17.5 parts of diethylene glycol and 175 parts of deionized water.
The antibacterial performance experiment completed according to the enterprise standard shows that the antibacterial performance can completely kill 10 percent within 6 hours8CFU/ml bacteria can be killed within 12 hours after 20 times of washing6CFU/ml of bacteria.
The antibacterial gauze is detected by an X-ray fluorescence spectrometry (Shimadzu XRF-1800X-ray fluorescence spectrometer) according to the operation steps of the specification, the experimental method is the same as that of the example 1, and the detected result shows that the antibacterial gauze contains Si, W, Ca, K, P, Fe and Al (the elements detected by the X-ray fluorescence spectrometry are collectively referred to as main elements in the antibacterial fabric), wherein the weight proportion of the tungsten element in the main elements is 16%.
Example 3
Soaking the polyester-cotton fabric base material 3 in the antibacterial finishing liquid for 30 minutes. And after the liquid permeates into the fabric base material, drying the fabric base material at the temperature of 60 ℃, and performing a color fixing process to obtain the washing-resistant antibacterial fabric. Wherein, the antibacterial finishing agent comprises the following components: 5 parts of molybdenum trioxide, 8 parts of silica sol, 8 parts of amino silicone oil, 804 parts of tween-804, 5 parts of acrylate emulsion adhesive, 10 parts of diethylene glycol and 160 parts of deionized water.
The antibacterial performance experiment completed according to the enterprise standard shows that the antibacterial performance can completely kill 10 percent within 6 hours8CFU/ml bacteria can be killed within 12 hours after 30 times of washing6CFU/ml of bacteria.
The antibacterial gauze is detected by an X-ray fluorescence spectrometry (Shimadzu XRF-1800X-ray fluorescence spectrometer) according to the operation steps of the specification, the experimental method is the same as that of the example 1, and the detected result shows that the antibacterial gauze contains Si, Mo, Ca, K, P, Fe and Al (the elements detected by the X-ray fluorescence spectrometry are collectively referred to as main elements in the antibacterial fabric), wherein the weight proportion of the molybdenum element in the main elements is 15%.
It can be seen that the antimicrobial fabric of the present invention is effective against common pathogenic microorganisms and superbacteria; the product is safe and harmless, does not change the cell genetic characteristics, does not cause cancer, and does not generate drug resistance; high efficiency and durability, long effective time of one-time manufacture, and the antibacterial validity period is the same as the service life of the base material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 antibacterial finishing agent comprising an antibacterial substance and an aqueous medium, characterised in that the antibacterial substance is selected from metals and/or metal oxides of molybdenum and/or tungsten.
2. Antimicrobial finish according to claim 1, characterized in that the aqueous medium can be water, an aqueous solution or a suspension.
3. Antimicrobial finish according to claim 1, characterized in that the weight proportion of the antimicrobial substance is 0.01-50%, preferably 0.05-20%, more preferably 0.5-5%, based on the total weight of the antimicrobial finish.
4. The antimicrobial finish of claim 1, further comprising a silica sol.
5. The antimicrobial finish of claim 1, further comprising an amino silicone oil.
6. The antimicrobial finish of claim 1, further comprising a binder.
7. An antibacterial fabric, which is characterized by being prepared by the following method: applying the antimicrobial finish according to any one of claims 1-6 to a fabric and then dry forming at a suitable temperature.
8. The antimicrobial fabric of claim 7, wherein said application method comprises spraying, brushing, dipping, padding.
9. The antimicrobial fabric of claim 7, wherein the fabric comprises a natural fiber fabric, a synthetic fiber fabric, and a blend fiber fabric and/or a union fiber fabric thereof.
10. A method for preparing an antibacterial fabric, characterized in that the antibacterial finishing agent according to any one of claims 1 to 6 is applied to the fabric, and then dried and formed at a suitable temperature; preferably, the process is carried out after a conventional dyeing and finishing process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810942825.3A CN110835845A (en) | 2018-08-17 | 2018-08-17 | Antibacterial finishing agent, antibacterial fabric and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810942825.3A CN110835845A (en) | 2018-08-17 | 2018-08-17 | Antibacterial finishing agent, antibacterial fabric and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110835845A true CN110835845A (en) | 2020-02-25 |
Family
ID=69573734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810942825.3A Pending CN110835845A (en) | 2018-08-17 | 2018-08-17 | Antibacterial finishing agent, antibacterial fabric and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110835845A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111802405A (en) * | 2020-08-20 | 2020-10-23 | 三河市安霸生物技术有限公司 | Aqueous solution antibacterial disinfectant and preparation method and application thereof |
| CN112007426A (en) * | 2020-07-08 | 2020-12-01 | 山东联科科技股份有限公司 | Preparation method of high-performance mesoporous silica-chitosan composite antibacterial filter sheet |
| CN112726219A (en) * | 2020-12-28 | 2021-04-30 | 广东广油华丰科技研究有限公司 | Emulsion containing nano cuprous oxide/copper oxide/silver oxide for non-woven fabric and application thereof |
| CN113718519A (en) * | 2021-09-14 | 2021-11-30 | 三河市安霸生物技术有限公司 | Antiviral finishing agent, antiviral fabric and preparation method thereof |
| CN114158798A (en) * | 2020-08-20 | 2022-03-11 | 三河市安霸生物技术有限公司 | Antibacterial mask |
| CN114481488A (en) * | 2021-12-31 | 2022-05-13 | 吴江市新三养纺织有限公司 | Preparation method of antibacterial yarn and antibacterial yarn production device |
| CN115216958A (en) * | 2022-07-27 | 2022-10-21 | 杭州迪亚特纺织有限公司 | Antibacterial breathable polyester fabric and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101610679A (en) * | 2006-11-13 | 2009-12-23 | 约瑟夫·彼得·古根比齐勒 | Material with antibacterial action |
| CN101960070A (en) * | 2007-06-11 | 2011-01-26 | 纳诺柏立有限公司 | Manufacture method of wet-tissue with antimicrobial and anti-fungus function |
| CN103797181A (en) * | 2011-08-25 | 2014-05-14 | 鞠承沅 | Novel metal polyoxide, and functional fiber or textile prepared using metal polyoxide |
| CN104411167A (en) * | 2012-04-10 | 2015-03-11 | 埃米斯泰克有限公司 | Composite material with a supporting material and an antimicrobial agent |
| CN105256532A (en) * | 2015-11-24 | 2016-01-20 | 王晓伟 | Photocatalyst finishing agent for silk stockings and silk stockings production technology |
| CN106544870A (en) * | 2015-09-23 | 2017-03-29 | 上海沪正纳米科技有限公司 | A kind of functional textile auxiliary agent and preparation method thereof |
| CN107556852A (en) * | 2017-10-17 | 2018-01-09 | 三河市安霸生物技术有限公司 | A kind of one-component antibiotic paint |
| CN108166251A (en) * | 2017-12-27 | 2018-06-15 | 爹地宝贝股份有限公司 | The application of the preparation method of anti-bacterial deodorization shell fabric, the fabric in paper diaper |
-
2018
- 2018-08-17 CN CN201810942825.3A patent/CN110835845A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101610679A (en) * | 2006-11-13 | 2009-12-23 | 约瑟夫·彼得·古根比齐勒 | Material with antibacterial action |
| CN101960070A (en) * | 2007-06-11 | 2011-01-26 | 纳诺柏立有限公司 | Manufacture method of wet-tissue with antimicrobial and anti-fungus function |
| CN103797181A (en) * | 2011-08-25 | 2014-05-14 | 鞠承沅 | Novel metal polyoxide, and functional fiber or textile prepared using metal polyoxide |
| CN104411167A (en) * | 2012-04-10 | 2015-03-11 | 埃米斯泰克有限公司 | Composite material with a supporting material and an antimicrobial agent |
| CN106544870A (en) * | 2015-09-23 | 2017-03-29 | 上海沪正纳米科技有限公司 | A kind of functional textile auxiliary agent and preparation method thereof |
| CN105256532A (en) * | 2015-11-24 | 2016-01-20 | 王晓伟 | Photocatalyst finishing agent for silk stockings and silk stockings production technology |
| CN107556852A (en) * | 2017-10-17 | 2018-01-09 | 三河市安霸生物技术有限公司 | A kind of one-component antibiotic paint |
| CN108166251A (en) * | 2017-12-27 | 2018-06-15 | 爹地宝贝股份有限公司 | The application of the preparation method of anti-bacterial deodorization shell fabric, the fabric in paper diaper |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112007426A (en) * | 2020-07-08 | 2020-12-01 | 山东联科科技股份有限公司 | Preparation method of high-performance mesoporous silica-chitosan composite antibacterial filter sheet |
| CN111802405A (en) * | 2020-08-20 | 2020-10-23 | 三河市安霸生物技术有限公司 | Aqueous solution antibacterial disinfectant and preparation method and application thereof |
| CN114158798A (en) * | 2020-08-20 | 2022-03-11 | 三河市安霸生物技术有限公司 | Antibacterial mask |
| CN114158798B (en) * | 2020-08-20 | 2024-03-01 | 三河市安霸生物技术有限公司 | Antibacterial mask |
| CN112726219A (en) * | 2020-12-28 | 2021-04-30 | 广东广油华丰科技研究有限公司 | Emulsion containing nano cuprous oxide/copper oxide/silver oxide for non-woven fabric and application thereof |
| CN113718519A (en) * | 2021-09-14 | 2021-11-30 | 三河市安霸生物技术有限公司 | Antiviral finishing agent, antiviral fabric and preparation method thereof |
| CN113718519B (en) * | 2021-09-14 | 2023-09-26 | 三河市安霸生物技术有限公司 | Antiviral finishing agent, antiviral fabric and preparation method thereof |
| CN114481488A (en) * | 2021-12-31 | 2022-05-13 | 吴江市新三养纺织有限公司 | Preparation method of antibacterial yarn and antibacterial yarn production device |
| CN114481488B (en) * | 2021-12-31 | 2024-02-13 | 吴江市新三养纺织有限公司 | Preparation method of antibacterial yarn and antibacterial yarn production device |
| CN115216958A (en) * | 2022-07-27 | 2022-10-21 | 杭州迪亚特纺织有限公司 | Antibacterial breathable polyester fabric and preparation method thereof |
| CN115216958B (en) * | 2022-07-27 | 2024-01-30 | 杭州迪亚特纺织有限公司 | Antibacterial breathable polyester fabric and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110835845A (en) | Antibacterial finishing agent, antibacterial fabric and preparation method thereof | |
| EP3187654B1 (en) | Wash-durable antimicrobial textile material having stain-release capabilities, in particular for reusable sanitary napkin | |
| EP3804550A1 (en) | Wash-durable face mask with antimicrobial properties and/or improved washability | |
| KR102477967B1 (en) | Method for producing a fiber material with antibacterial properties | |
| El-Shafei et al. | Herbal extract as an ecofriendly antibacterial finishing of cotton fabric | |
| EP2094903A2 (en) | Method for providing textiles with desensitised silver components | |
| US20130095240A1 (en) | Antimicrobial finish on fabrics | |
| KR20110108389A (en) | Method and treatment composition for imparting durable antimicrobial properties to carpet | |
| JP5506265B2 (en) | Textile treatment agent, antibacterial and antifungal fiber product manufacturing method | |
| KR20220123529A (en) | Reduces odors and controls bacteria in textile materials | |
| JP2009155732A (en) | Anti-microbial fiber product and method for producing the same | |
| KR101187276B1 (en) | Antibacterial Finish Of Polypropylene fabrics Using Cardanol Antibacterial-agents | |
| JP6092510B2 (en) | Antibacterial fiber structure | |
| CN113718519B (en) | Antiviral finishing agent, antiviral fabric and preparation method thereof | |
| JP5254756B2 (en) | Cloth | |
| DE60027951T2 (en) | Cellulose fibers containing fabric | |
| WO2021210025A1 (en) | Compositions and methods for coatings, antimicrobial textiles, sanitization and disinfection | |
| US20240060229A1 (en) | Textile formulation and product with odor control | |
| JP2006225780A (en) | Antimicrobial fiber | |
| JP2020007661A (en) | Deodorant fabric and clothing | |
| JP7259150B2 (en) | Antibacterial and antiviral processing agents and products processed therefrom | |
| JP7321062B2 (en) | Antibacterial deodorant for textiles, treatment liquid for textiles and antibacterial deodorant textiles | |
| Subashini et al. | Sustainable Finishes for Healthcare Apparels | |
| JPH01266277A (en) | Antimicrobial treatment of yarn | |
| WO2023225395A1 (en) | Odor control polymer coatings on textiles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200225 |