CN113293512A - Antibacterial skin-friendly non-woven fabric and preparation method thereof - Google Patents
Antibacterial skin-friendly non-woven fabric and preparation method thereof Download PDFInfo
- Publication number
- CN113293512A CN113293512A CN202110561132.1A CN202110561132A CN113293512A CN 113293512 A CN113293512 A CN 113293512A CN 202110561132 A CN202110561132 A CN 202110561132A CN 113293512 A CN113293512 A CN 113293512A
- Authority
- CN
- China
- Prior art keywords
- parts
- antibacterial
- woven fabric
- polyethylene glycol
- skin
- 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
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/492—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres by fluid jet
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
- D04H3/11—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by fluid jet
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
- D04H5/02—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by mechanical methods, e.g. needling
- D04H5/03—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by mechanical methods, e.g. needling by fluid jet
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/02—Moisture-responsive characteristics
- D10B2401/022—Moisture-responsive characteristics hydrophylic
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/12—Physical properties biodegradable
Abstract
The invention discloses an antibacterial skin-friendly non-woven fabric and a preparation method thereof, wherein the antibacterial skin-friendly non-woven fabric is prepared from the following raw materials in parts by weight: 70-80 parts of ethylene terephthalate, 12-15 parts of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, 4-6 parts of bio-based polyethylene glycol succinate, 4-6 parts of glycidyl methacrylate grafted ethylene-octene copolymer, 2-2.5 parts of porous nano hydroxyapatite, 2-2.5 parts of porous nano silica micropowder, 1.4-1.7 parts of zinc sulfadiazine, 1-1.2 parts of flusilazole, 2.4-2.8 parts of nano silver ion antibacterial powder, 3-3.5 parts of epoxy soybean octyl oleate and 2.5-3 parts of epoxy soybean oil. The antibacterial skin-friendly non-woven fabric has high bacteriostasis rate, excellent antibacterial performance and good antibacterial effect; the water contact angle is large, and the hydrophilic skin-friendly performance is good; high breaking strength, high elongation at break and good comprehensive mechanical properties.
Description
Technical Field
The invention relates to the technical field of non-woven fabrics, in particular to an antibacterial skin-friendly non-woven fabric and a preparation method thereof.
Background
The fiber for producing the non-woven fabric is mainly polypropylene (PP) and Polyester (PET). In addition, there are Polyamide (PA), viscose, acrylic, polyethylene (HDPE), polyvinyl chloride (PVC). The non-woven fabric is classified into a disposable type and a durable type according to application requirements.
The Polyester (PET) non-woven fabric has the advantages of low investment, light weight, corrosion resistance, good mechanical property and chemical stability and the like, is developed quickly in recent years, has high yield, and is a fiber commonly used in the field of synthetic fibers.
However, the currently used antibacterial skin-friendly nonwoven fabric has the following problems:
1. the antibacterial effect is poor;
2. the polyester non-woven fabric has poor hydrophilic and skin-friendly performance;
3. the polyester non-woven fabric modified by antibacterial filler and the like has poor mechanical properties such as breaking strength, breaking elongation and the like and is limited in use.
Disclosure of Invention
Based on the above situation, the present invention aims to provide an antibacterial skin-friendly non-woven fabric and a preparation method thereof, which can effectively solve the above problems. The antibacterial skin-friendly non-woven fabric is prepared from composite fibers through a spunlace non-woven fabric production process, the composite fibers consist of raw materials, the content of each raw material is optimized, and proper proportions of ethylene glycol terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, bio-based polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micropowder, zinc sulfadiazine, flusilazole, nano-silver ion antibacterial powder, epoxy soybean octyl oleate and epoxy soybean oil are selected, so that the advantages of the composite fibers are fully exerted, the composite fibers are mutually supplemented and mutually promoted, and the prepared antibacterial skin-friendly non-woven fabric is high in bacteriostasis rate, excellent in antibacterial performance and good in antibacterial effect; the water contact angle is large, and the hydrophilic skin-friendly performance is good; high breaking strength, high elongation at break and good comprehensive mechanical properties.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an antibacterial skin-friendly non-woven fabric is prepared from the following raw materials in parts by weight:
70-80 parts of ethylene terephthalate,
12-15 parts of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
4-6 parts of bio-based polyethylene glycol succinate,
4-6 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
2-2.5 parts of porous nano-hydroxyapatite,
2-2.5 parts of porous nano-silica micro powder,
1.4 to 1.7 parts of sulfadiazine zinc,
1-1.2 parts of flusilazole,
2.4 to 2.8 portions of nano silver ion antibacterial powder,
3-3.5 parts of epoxy soybean octyl oleate,
2.5-3 parts of epoxidized soybean oil.
The antibacterial skin-friendly non-woven fabric is prepared from composite fibers through a spunlace non-woven fabric production process, the composite fibers consist of raw materials, the content of each raw material is optimized, and proper proportions of ethylene glycol terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, bio-based polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micropowder, zinc sulfadiazine, flusilazole, nano-silver ion antibacterial powder, epoxy soybean octyl oleate and epoxy soybean oil are selected, so that the advantages of the composite fibers are fully exerted, the composite fibers are mutually supplemented and mutually promoted, and the prepared antibacterial skin-friendly non-woven fabric is high in bacteriostasis rate, excellent in antibacterial performance and good in antibacterial effect; the water contact angle is large, and the hydrophilic skin-friendly performance is good; high breaking strength, high elongation at break and good comprehensive mechanical properties.
Preferably, the antibacterial skin-friendly non-woven fabric is prepared from the following raw materials in parts by weight:
75 parts of ethylene terephthalate,
13.5 parts of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
5 parts of bio-based polyethylene glycol succinate,
5 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
22.5 parts of porous nano-hydroxyapatite,
22.5 parts of porous nano silicon dioxide micro powder,
1.6 parts of sulfadiazine zinc,
1.1 parts of flusilazole,
2.6 portions of nano silver ion antibacterial powder,
3.25 parts of epoxy soybean octyl oleate,
2.7 parts of epoxidized soybean oil.
Preferably, the bio-based polyethylene glycol succinate is prepared by polymerization reaction of petroleum-based succinic acid and bio-based ethylene glycol.
Preferably, the flusilazole is flusilazole EC.
Preferably, the particle diameter of the porous nano-silica micro powder is 105-115 nm, and the pore diameter is 13-17 nm.
Preferably, the feed also comprises the following raw materials in parts by weight: thermal stabilizer: 3-4 parts.
Preferably, the heat stabilizer is zinc stearate.
Meanwhile, the invention also provides a preparation method of the antibacterial skin-friendly non-woven fabric, which comprises the following steps:
A. weighing the following components in parts by weight: ethylene terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, biobased polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micro powder, sulfadiazine zinc, flusilazole, nano-silver ion antibacterial powder, epoxy soybean oil and epoxy soybean oil;
B. uniformly ball-milling and mixing the porous nano-hydroxyapatite, the porous nano-silica micro powder, the sulfadiazine zinc, the flusilazole and the nano-silver ion antibacterial powder by using an ultrafine ball mill to obtain the antibacterial agent;
C. feeding the ethylene terephthalate, the polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, the bio-based polyethylene glycol succinate, the glycidyl methacrylate grafted ethylene-octene copolymer, the epoxy soybean octyl oleate, the epoxy soybean oil and the antibacterial agent prepared in the step B into a double-screw extruder for melting and extruding into a mixed melt;
the mixed melt is metered through a gear pump, the metered mixed melt enters a die head of a spinning machine, and spinning is carried out through a spinneret plate of the spinning machine, so as to obtain composite fibers; the fineness of the composite fiber is 1-3 dtex;
E. and drafting the composite fibers through air flow, uniformly paving the drafted composite fibers on a net curtain in sequence, and reinforcing to obtain the antibacterial skin-friendly non-woven fabric.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the antibacterial skin-friendly non-woven fabric is prepared from composite fibers through a spunlace non-woven fabric production process, the composite fibers consist of raw materials, the content of each raw material is optimized, and proper proportions of ethylene glycol terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, bio-based polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micropowder, zinc sulfadiazine, flusilazole, nano-silver ion antibacterial powder, epoxy soybean octyl oleate and epoxy soybean oil are selected, so that the advantages of the composite fibers are fully exerted, the composite fibers are mutually supplemented and mutually promoted, and the prepared antibacterial skin-friendly non-woven fabric is high in bacteriostasis rate, excellent in antibacterial performance and good in antibacterial effect; the water contact angle is large, and the hydrophilic skin-friendly performance is good; high breaking strength, high elongation at break and good comprehensive mechanical properties.
The bio-based polyethylene glycol succinate with a proper proportion is added into the antibacterial skin-friendly non-woven fabric, so that the effect of improving the hydrophilic skin-friendly performance of the antibacterial skin-friendly non-woven fabric is mainly achieved, and the antibacterial skin-friendly non-woven fabric is degradable; the bio-based polyethylene glycol succinate is prepared by polymerization reaction of petroleum-based succinic acid and bio-based glycol.
The glycidyl methacrylate grafted ethylene-octene copolymer added in a proper proportion in the antibacterial skin-friendly non-woven fabric mainly plays a role in improving the hydrophilic skin-friendly performance of the antibacterial skin-friendly non-woven fabric, and the elasticity can be greatly improved; the polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin with a proper proportion is added into the antibacterial skin-friendly non-woven fabric, so that the hydrophilic skin-friendly performance of the antibacterial skin-friendly non-woven fabric is improved; the polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, the bio-based polyethylene glycol succinate and the glycidyl methacrylate grafted ethylene-octene copolymer are matched with each other to play a good synergistic effect, so that the antibacterial skin-friendly non-woven fabric disclosed by the invention is large in breaking strength, high in breaking elongation and good in comprehensive mechanical property.
The antibacterial skin-friendly non-woven fabric is added with the porous nano-hydroxyapatite (hydrophilic skin-friendly, enhanced and used as a carrier) and the porous nano-silica micro powder (enhanced and used as a carrier) in proper proportion, the zinc sulfadiazine and the flusilazole are added in proper proportion, the flusilazole is flusilazole EC and nano-silver ion antibacterial powder, and the components are matched with each other to play a good synergistic effect, so that the antibacterial performance of the antibacterial skin-friendly non-woven fabric is greatly improved, and the durability of the antibacterial performance of the antibacterial skin-friendly non-woven fabric is greatly improved by matching the porous nano-hydroxyapatite and the porous nano-silica micro powder, and the mechanical performance, the hydrophilic skin-friendly performance and the like of the antibacterial skin-friendly non-woven fabric are not influenced.
The antibacterial skin-friendly non-woven fabric is added with epoxy soybean octyl oleate and epoxy soybean oil in proper proportion as plasticizers, wherein epoxy groups can be slightly crosslinked with active groups (hydroxyl or carboxyl) in ethylene terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, bio-based polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer and the like at high temperature in the spinning process, so that the antibacterial skin-friendly non-woven fabric is high in breaking strength, high in breaking elongation and good in comprehensive mechanical property.
The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
an antibacterial skin-friendly non-woven fabric is prepared from the following raw materials in parts by weight:
70-80 parts of ethylene terephthalate,
12-15 parts of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
4-6 parts of bio-based polyethylene glycol succinate,
4-6 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
2-2.5 parts of porous nano-hydroxyapatite,
2-2.5 parts of porous nano-silica micro powder,
1.4 to 1.7 parts of sulfadiazine zinc,
1-1.2 parts of flusilazole,
2.4 to 2.8 portions of nano silver ion antibacterial powder,
3-3.5 parts of epoxy soybean octyl oleate,
2.5-3 parts of epoxidized soybean oil.
In this embodiment, the antibacterial skin-friendly non-woven fabric is preferably prepared from the following raw materials in parts by weight:
75 parts of ethylene terephthalate,
13.5 parts of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
5 parts of bio-based polyethylene glycol succinate,
5 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
22.5 parts of porous nano-hydroxyapatite,
22.5 parts of porous nano silicon dioxide micro powder,
1.6 parts of sulfadiazine zinc,
1.1 parts of flusilazole,
2.6 portions of nano silver ion antibacterial powder,
3.25 parts of epoxy soybean octyl oleate,
2.7 parts of epoxidized soybean oil.
In this embodiment, the bio-based polyethylene glycol succinate is preferably prepared by polymerizing petroleum-based succinic acid and bio-based ethylene glycol.
In the present embodiment, the flusilazole is preferably flusilazole EC.
In the present embodiment, the porous nano-silica fine powder preferably has a particle size of 105 to 115nm and a pore diameter of 13 to 17 nm.
In this embodiment, the antibacterial skin-friendly non-woven fabric preferably further comprises the following raw materials in parts by weight: thermal stabilizer: 3-4 parts.
In this embodiment, the heat stabilizer is preferably zinc stearate.
The embodiment also provides a preparation method of the antibacterial skin-friendly non-woven fabric, which comprises the following steps:
A. weighing the following components in parts by weight: ethylene terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, biobased polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micro powder, sulfadiazine zinc, flusilazole, nano-silver ion antibacterial powder, epoxy soybean oil and epoxy soybean oil;
B. uniformly ball-milling and mixing the porous nano-hydroxyapatite, the porous nano-silica micro powder, the sulfadiazine zinc, the flusilazole and the nano-silver ion antibacterial powder by using an ultrafine ball mill to obtain the antibacterial agent;
C. feeding the ethylene terephthalate, the polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, the bio-based polyethylene glycol succinate, the glycidyl methacrylate grafted ethylene-octene copolymer, the epoxy soybean octyl oleate, the epoxy soybean oil and the antibacterial agent prepared in the step B into a double-screw extruder for melting and extruding into a mixed melt;
the mixed melt is metered through a gear pump, the metered mixed melt enters a die head of a spinning machine, and spinning is carried out through a spinneret plate of the spinning machine, so as to obtain composite fibers; the fineness of the composite fiber is 1-3 dtex;
E. and (3) drafting the composite fibers through air flow, uniformly paving the drafted composite fibers on a net curtain in sequence, and reinforcing (such as fixing the net through a rolling mill) to obtain the antibacterial skin-friendly non-woven fabric.
Example 2:
an antibacterial skin-friendly non-woven fabric is prepared from the following raw materials in parts by weight:
70 portions of ethylene terephthalate,
12 portions of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
4 portions of bio-based polyethylene glycol succinate,
4 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
2 portions of porous nano-hydroxyapatite,
2 portions of porous nano silicon dioxide micro powder,
1.4 parts of sulfadiazine zinc,
1 part of flusilazole,
2.4 parts of nano silver ion antibacterial powder,
3 parts of epoxy soybean octyl oleate,
2.5 parts of epoxidized soybean oil.
In this example, the bio-based polyethylene glycol succinate is prepared by polymerizing petroleum-based succinic acid and bio-based ethylene glycol.
In this embodiment, the flusilazole is flusilazole EC.
In this embodiment, the porous nano-silica fine powder has a particle size of 105 to 115nm and a pore diameter of 13 to 17 nm.
In this embodiment, the composition further comprises the following raw materials in parts by weight: thermal stabilizer: and 3 parts.
In this example, the thermal stabilizer is zinc stearate.
In this embodiment, the preparation method of the antibacterial skin-friendly non-woven fabric includes the following steps:
A. weighing the following components in parts by weight: ethylene terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, biobased polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micro powder, sulfadiazine zinc, flusilazole, nano-silver ion antibacterial powder, epoxy soybean oil and epoxy soybean oil;
B. uniformly ball-milling and mixing the porous nano-hydroxyapatite, the porous nano-silica micro powder, the sulfadiazine zinc, the flusilazole and the nano-silver ion antibacterial powder by using an ultrafine ball mill to obtain the antibacterial agent;
C. feeding the ethylene terephthalate, the polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, the bio-based polyethylene glycol succinate, the glycidyl methacrylate grafted ethylene-octene copolymer, the epoxy soybean octyl oleate, the epoxy soybean oil and the antibacterial agent prepared in the step B into a double-screw extruder for melting and extruding into a mixed melt;
the mixed melt is metered through a gear pump, the metered mixed melt enters a die head of a spinning machine, and spinning is carried out through a spinneret plate of the spinning machine, so as to obtain composite fibers; the fineness of the composite fiber is 2 dtex;
E. and drafting the composite fibers through air flow, uniformly paving the drafted composite fibers on a net curtain in sequence, and reinforcing to obtain the antibacterial skin-friendly non-woven fabric.
Example 3:
an antibacterial skin-friendly non-woven fabric is prepared from the following raw materials in parts by weight:
80 portions of ethylene terephthalate,
15 portions of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
6 portions of bio-based polyethylene glycol succinate,
6 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
2.5 parts of porous nano-hydroxyapatite,
2.5 parts of porous nano silicon dioxide micro powder,
1.7 parts of sulfadiazine zinc,
1.2 parts of flusilazole,
2.8 portions of nano silver ion antibacterial powder,
3.5 parts of epoxy soybean octyl oleate,
3 parts of epoxidized soybean oil.
In this example, the bio-based polyethylene glycol succinate is prepared by polymerizing petroleum-based succinic acid and bio-based ethylene glycol.
In this embodiment, the flusilazole is flusilazole EC.
In this embodiment, the porous nano-silica fine powder has a particle size of 105 to 115nm and a pore diameter of 13 to 17 nm.
In this embodiment, the composition further comprises the following raw materials in parts by weight: thermal stabilizer: 4 parts.
In this example, the thermal stabilizer is zinc stearate.
In this embodiment, the preparation method of the antibacterial skin-friendly non-woven fabric includes the following steps:
A. weighing the following components in parts by weight: ethylene terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, biobased polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micro powder, sulfadiazine zinc, flusilazole, nano-silver ion antibacterial powder, epoxy soybean oil and epoxy soybean oil;
B. uniformly ball-milling and mixing the porous nano-hydroxyapatite, the porous nano-silica micro powder, the sulfadiazine zinc, the flusilazole and the nano-silver ion antibacterial powder by using an ultrafine ball mill to obtain the antibacterial agent;
C. feeding the ethylene terephthalate, the polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, the bio-based polyethylene glycol succinate, the glycidyl methacrylate grafted ethylene-octene copolymer, the epoxy soybean octyl oleate, the epoxy soybean oil and the antibacterial agent prepared in the step B into a double-screw extruder for melting and extruding into a mixed melt;
the mixed melt is metered through a gear pump, the metered mixed melt enters a die head of a spinning machine, and spinning is carried out through a spinneret plate of the spinning machine, so as to obtain composite fibers; the fineness of the composite fiber is 2 dtex;
E. and drafting the composite fibers through air flow, uniformly paving the drafted composite fibers on a net curtain in sequence, and reinforcing to obtain the antibacterial skin-friendly non-woven fabric.
Example 4:
an antibacterial skin-friendly non-woven fabric is prepared from the following raw materials in parts by weight:
75 parts of ethylene terephthalate,
13.5 parts of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
5 parts of bio-based polyethylene glycol succinate,
5 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
2.25 parts of porous nano-hydroxyapatite,
2.25 parts of porous nano silicon dioxide micro powder,
1.6 parts of sulfadiazine zinc,
1.1 parts of flusilazole,
2.6 portions of nano silver ion antibacterial powder,
3.25 parts of epoxy soybean octyl oleate,
2.7 parts of epoxidized soybean oil.
In this example, the bio-based polyethylene glycol succinate is prepared by polymerizing petroleum-based succinic acid and bio-based ethylene glycol.
In this embodiment, the flusilazole is flusilazole EC.
In this embodiment, the porous nano-silica fine powder has a particle size of 105 to 115nm and a pore diameter of 13 to 17 nm.
In this embodiment, the antibacterial skin-friendly non-woven fabric further comprises the following raw materials in parts by weight: thermal stabilizer: 3.5 parts.
In this example, the thermal stabilizer is zinc stearate.
In this embodiment, the preparation method of the antibacterial skin-friendly non-woven fabric includes the following steps:
A. weighing the following components in parts by weight: ethylene terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, biobased polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micro powder, sulfadiazine zinc, flusilazole, nano-silver ion antibacterial powder, epoxy soybean oil and epoxy soybean oil;
B. uniformly ball-milling and mixing the porous nano-hydroxyapatite, the porous nano-silica micro powder, the sulfadiazine zinc, the flusilazole and the nano-silver ion antibacterial powder by using an ultrafine ball mill to obtain the antibacterial agent;
C. feeding the ethylene terephthalate, the polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, the bio-based polyethylene glycol succinate, the glycidyl methacrylate grafted ethylene-octene copolymer, the epoxy soybean octyl oleate, the epoxy soybean oil and the antibacterial agent prepared in the step B into a double-screw extruder for melting and extruding into a mixed melt;
the mixed melt is metered through a gear pump, the metered mixed melt enters a die head of a spinning machine, and spinning is carried out through a spinneret plate of the spinning machine, so as to obtain composite fibers; the fineness of the composite fiber is 2 dtex;
E. and drafting the composite fibers through air flow, uniformly paving the drafted composite fibers on a net curtain in sequence, and reinforcing to obtain the antibacterial skin-friendly non-woven fabric.
Comparative example 1:
the difference from example 4 is that no polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin was used, and the other is the same as example 4.
Comparative example 2:
the difference from example 4 is that there is no bio-based polyethylene succinate, and the other is the same as example 4.
Comparative example 3:
the difference from example 4 is that no glycidyl methacrylate grafted ethylene-octene copolymer was used, and the rest was the same as example 4.
Comparative example 4:
the difference from the example 4 is that the porous nano hydroxyapatite is not present, and the rest is the same as the example 4.
Comparative example 5:
the difference from example 4 is that no porous fine nano-silica powder is present, and the other steps are the same as example 4.
Comparative example 6:
the difference from example 4 is that there is no zinc sulfadiazine, otherwise the same as example 4.
Comparative example 7:
the difference from example 4 is that flusilazole EC is absent, and the rest is the same as example 4.
Comparative example 8:
the difference from example 4 is that there is no nano silver ion antibacterial powder, and the other is the same as example 4.
Comparative example 9:
the difference from example 4 is that there are no epoxidized octyl soyate and epoxidized soybean oil, and the rest is the same as example 4.
The antibacterial skin-friendly nonwoven fabrics obtained in examples 2 to 4 of the present invention and the nonwoven fabrics obtained in comparative examples 1 to 9 (grammage 500 g/m) were treated as follows2) The performance test was performed, and the test results are shown in table 1.
TABLE 1
As can be seen from the above table, the antibacterial skin-friendly non-woven fabric of the present invention has the following advantages: the antibacterial rate is high, the antibacterial performance is excellent, and the antibacterial effect is good; the water contact angle is large, and the hydrophilic skin-friendly performance is good; high breaking strength, high elongation at break and good comprehensive mechanical properties.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (8)
1. The antibacterial skin-friendly non-woven fabric is characterized by being prepared from the following raw materials in parts by weight:
70-80 parts of ethylene terephthalate,
12-15 parts of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
4-6 parts of bio-based polyethylene glycol succinate,
4-6 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
2-2.5 parts of porous nano-hydroxyapatite,
2-2.5 parts of porous nano-silica micro powder,
1.4 to 1.7 parts of sulfadiazine zinc,
1-1.2 parts of flusilazole,
2.4 to 2.8 portions of nano silver ion antibacterial powder,
3-3.5 parts of epoxy soybean octyl oleate,
2.5-3 parts of epoxidized soybean oil.
2. The antibacterial skin-friendly non-woven fabric according to claim 1, which is prepared from the following raw materials in parts by weight:
75 parts of ethylene terephthalate,
13.5 parts of polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin,
5 parts of bio-based polyethylene glycol succinate,
5 parts of glycidyl methacrylate grafted ethylene-octene copolymer,
22.5 parts of porous nano-hydroxyapatite,
22.5 parts of porous nano silicon dioxide micro powder,
1.6 parts of sulfadiazine zinc,
1.1 parts of flusilazole,
2.6 portions of nano silver ion antibacterial powder,
3.25 parts of epoxy soybean octyl oleate,
2.7 parts of epoxidized soybean oil.
3. The antibacterial skin-friendly non-woven fabric according to claim 1, wherein the bio-based polyethylene glycol succinate is prepared by polymerization of petroleum-based succinic acid and bio-based ethylene glycol.
4. The antibacterial skin-friendly non-woven fabric according to claim 1, wherein the flusilazole is flusilazole EC.
5. The antibacterial skin-friendly non-woven fabric according to claim 1, wherein the porous nano-silica micro powder has a particle size of 105 to 115nm and a pore diameter of 13 to 17 nm.
6. The antibacterial skin-friendly non-woven fabric according to claim 1, which is characterized by further comprising the following raw materials in parts by weight: thermal stabilizer: 3-4 parts.
7. The antibacterial skin-friendly nonwoven fabric according to claim 6, wherein the heat stabilizer is zinc stearate.
8. A method for preparing the antibacterial skin-friendly non-woven fabric according to any one of claims 1 to 7, which comprises the following steps:
A. weighing the following components in parts by weight: ethylene terephthalate, polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, biobased polyethylene glycol succinate, glycidyl methacrylate grafted ethylene-octene copolymer, porous nano-hydroxyapatite, porous nano-silica micro powder, sulfadiazine zinc, flusilazole, nano-silver ion antibacterial powder, epoxy soybean oil and epoxy soybean oil;
B. uniformly ball-milling and mixing the porous nano-hydroxyapatite, the porous nano-silica micro powder, the sulfadiazine zinc, the flusilazole and the nano-silver ion antibacterial powder by using an ultrafine ball mill to obtain the antibacterial agent;
C. feeding the ethylene terephthalate, the polyethylene glycol etherified dimethylol dihydroxy ethylene urea resin, the bio-based polyethylene glycol succinate, the glycidyl methacrylate grafted ethylene-octene copolymer, the epoxy soybean octyl oleate, the epoxy soybean oil and the antibacterial agent prepared in the step B into a double-screw extruder for melting and extruding into a mixed melt;
D. the mixed melt enters a spinning machine, is sprayed out from a spinneret plate to form a strand silk, and then is subjected to air blowing cooling, stretching and winding to obtain composite fibers; the fineness of the composite fiber is 1-3 dtex;
E. and drafting the composite fibers through air flow, uniformly paving the drafted composite fibers on a net curtain in sequence, and reinforcing to obtain the antibacterial skin-friendly non-woven fabric.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110561132.1A CN113293512A (en) | 2021-05-22 | 2021-05-22 | Antibacterial skin-friendly non-woven fabric and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110561132.1A CN113293512A (en) | 2021-05-22 | 2021-05-22 | Antibacterial skin-friendly non-woven fabric and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113293512A true CN113293512A (en) | 2021-08-24 |
Family
ID=77323906
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110561132.1A Pending CN113293512A (en) | 2021-05-22 | 2021-05-22 | Antibacterial skin-friendly non-woven fabric and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113293512A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115142197A (en) * | 2022-07-05 | 2022-10-04 | 福建冠泓工业有限公司 | Mosquito-repelling skin-friendly non-woven fabric and preparation method thereof |
CN115161886A (en) * | 2022-07-05 | 2022-10-11 | 福建冠泓工业有限公司 | High-strength high-elasticity skin-friendly non-woven fabric and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101015300A (en) * | 2006-02-07 | 2007-08-15 | 张志稳 | Silver-containing antibacterial agent |
CN110670242A (en) * | 2019-10-25 | 2020-01-10 | 福建冠泓工业有限公司 | Antibacterial non-woven fabric and manufacturing process thereof |
CN111979645A (en) * | 2020-08-25 | 2020-11-24 | 福建尚龙新材料科技有限公司 | Bio-based polyester non-woven fabric and preparation method thereof |
CN112111854A (en) * | 2020-08-15 | 2020-12-22 | 福建冠泓工业有限公司 | Antibacterial and deodorizing hot-air non-woven fabric and preparation method thereof |
-
2021
- 2021-05-22 CN CN202110561132.1A patent/CN113293512A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101015300A (en) * | 2006-02-07 | 2007-08-15 | 张志稳 | Silver-containing antibacterial agent |
CN110670242A (en) * | 2019-10-25 | 2020-01-10 | 福建冠泓工业有限公司 | Antibacterial non-woven fabric and manufacturing process thereof |
CN112342691A (en) * | 2019-10-25 | 2021-02-09 | 福建冠泓工业有限公司 | Elastic antibacterial non-woven fabric and manufacturing process thereof |
CN112111854A (en) * | 2020-08-15 | 2020-12-22 | 福建冠泓工业有限公司 | Antibacterial and deodorizing hot-air non-woven fabric and preparation method thereof |
CN111979645A (en) * | 2020-08-25 | 2020-11-24 | 福建尚龙新材料科技有限公司 | Bio-based polyester non-woven fabric and preparation method thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115142197A (en) * | 2022-07-05 | 2022-10-04 | 福建冠泓工业有限公司 | Mosquito-repelling skin-friendly non-woven fabric and preparation method thereof |
CN115161886A (en) * | 2022-07-05 | 2022-10-11 | 福建冠泓工业有限公司 | High-strength high-elasticity skin-friendly non-woven fabric and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102071542B (en) | Method for preparing polymeric nano-micro fiber non-woven fabric | |
CN111560663B (en) | Preparation method of cross-shaped skin-core moisture absorption and moisture removal fiber | |
CN113279144A (en) | Environment-friendly degradable non-woven fabric and preparation method thereof | |
CN113293512A (en) | Antibacterial skin-friendly non-woven fabric and preparation method thereof | |
CN110699857B (en) | Water-absorbing melt-blown nonwoven fabric and preparation method thereof | |
CN101747624B (en) | Hygroscopic fine denier/superfine denier nylon masterbatch, nylon and preparation method thereof | |
CN1212031A (en) | Heat-fusible composite fiber and non-woven fabric produced from same | |
CN113068882B (en) | Fully degradable mask and manufacturing method thereof | |
CN111349325B (en) | Modified bio-based polymer fiber composition, modified bio-based polymer fiber and preparation method thereof | |
CN113308803B (en) | Preparation method of fully-degradable non-woven fabric produced by spun-bonding method | |
CN101407627A (en) | Nano silicon oxide modified high polymer composite material and preparation technique thereof | |
JP4128580B2 (en) | Polyvinyl alcohol composite fiber | |
CN106637441B (en) | A kind of 6 preoriented yarn of anti-bacterial wear-resisting polyamide fibre | |
CN114717685B (en) | Preparation method of PBAT short fiber | |
JP2011208293A (en) | Polyvinyl alcohol-based composite fiber and method for producing the same | |
CN113136636B (en) | Super-absorbent ES composite fiber and preparation method thereof | |
CN104451936B (en) | Optical obscurations hydrophilic fibers and preparation method thereof | |
JP2004285538A (en) | Method for producing polymer alloy filament and method for producing nano fiber | |
CN114351286B (en) | High-strength polylactic acid melt-blown fiber and preparation method and application thereof | |
CN110359126A (en) | A kind of preparation method of moisture absorption cool feeling face liber | |
JP5565971B2 (en) | Polymer alloy comprising polylactic acid resin and polyethylene terephthalate resin and method for producing the same | |
CN107586373A (en) | A kind of crystal property adjustable spinning polyoxymethylene resin and its spinning process | |
CN111455494A (en) | Antibacterial nanofiber and preparation method and application thereof | |
CN104060345B (en) | High wet conductivity bright polyester dacron fiber and production method thereof | |
CN113584636B (en) | Production process of PP (polypropylene) composite non-woven fabric |
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: 20210824 |