CN116254706A - Puncture-resistant fabric for fencing clothes and preparation method thereof - Google Patents

Puncture-resistant fabric for fencing clothes and preparation method thereof Download PDF

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Publication number
CN116254706A
CN116254706A CN202310193414.XA CN202310193414A CN116254706A CN 116254706 A CN116254706 A CN 116254706A CN 202310193414 A CN202310193414 A CN 202310193414A CN 116254706 A CN116254706 A CN 116254706A
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fiber
fibers
parts
drying
fencing
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CN202310193414.XA
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CN116254706B (en
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李哲明
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Wuxi Weihao Sport Equipment Co ltd
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Wuxi Weihao Sport Equipment Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0013—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using multilayer webs
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
    • D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/18—Other fabrics or articles characterised primarily by the use of particular thread materials elastic threads
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/142—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer
    • D06N3/144—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer with polyurethane and polymerisation products, e.g. acrylics, PVC
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • 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
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
    • D10B2321/0211—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene high-strength or high-molecular-weight polyethylene, e.g. ultra-high molecular weight polyethylene [UHMWPE]
    • 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
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/022—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
    • 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
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
    • 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
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/06—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyethers
    • D10B2331/061—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyethers polyetherketones, polyetheretherketones, e.g. PEEK
    • 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
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/062—Load-responsive characteristics stiff, shape retention
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    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
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    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • 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
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a puncture-resistant fabric for fencing and a preparation method thereof, wherein the fabric comprises a base cloth layer, a puncture-resistant layer and a coating layer, and the puncture-resistant layer is formed by blending ultra-high molecular weight polyethylene fibers, polyether-ether-ketone fibers and aramid fibers; the coating layer is prepared from the following raw materials in parts by weight: 60-80 parts of epoxy resin, 20-30 parts of thermoplastic polyurethane, 10-20 parts of diethylaminopropylamine, 5-10 parts of modified inorganic fiber, 80-100 parts of N, N-dimethylformamide and 5-10 parts of sodium dodecyl benzene sulfonate. The fabric solves the problems of poor light effect of the fabric of the fencing suit and poor protective effect of the fencing suit prepared in the prior art, and has good wearing comfort, excellent puncture performance and lower fabric gram weight through improvement of the formula and the process manufacturing of the fabric.

Description

Puncture-resistant fabric for fencing clothes and preparation method thereof
Technical Field
The invention belongs to the technical field of fabrics, and particularly relates to a puncture-resistant fabric for fencing and a preparation method thereof.
Background
The fencing suit is used for preventing potential threat in fencing, protecting human body and greatly reducing the risk of the sports. The fabric of the fencing suit has high requirements on piercing strength, and the average stress of the second-level fencing suit in the standard of puncture resistance is more than or equal to 800N. The fabric for fencing in the current market is mainly woven by metal wires, high-strength acrylic fibers and cotton, and the anti-cutting textile fabric is woven by using ultra-high-strength high-modulus polyethylene fibers as a base material through a special high-density knitting machine.
The existing puncture-resistant fabric is mainly prepared by the following three methods: the first method comprises the following steps: coating thermoplastic resin with a certain pattern on the surface of the base cloth to obtain a cutting-resistant and stab-resistant fabric; the method is mainly realized by a coating process on the surface of the non-woven fabric, has high requirement on the surface evenness of the base fabric, and limits the selection of the base fabric of the anti-cutting and anti-stab fabric. The second method comprises the following steps: the three materials of the surface fabric, the middle metal net layer and the inner fabric are simply compounded to obtain the composite anti-cutting and anti-puncturing fabric, the method is mainly used for connecting and stitching the fabric in a manual mode, and the produced product is poor in comfort, low in efficiency and high in production cost; the third method comprises the following steps: attaching a resin condensate on the surface of the fabric to obtain the anti-cutting and anti-stabbing fabric; the method involves manually arranging resin cured products on a fabric, and cannot ensure uniformity of distribution of the resin cured products in the composite fabric; but also has the defects of low production efficiency and high production cost.
The Chinese patent application number 201510684194.6 discloses an anti-stab protective fabric containing a cooling material, which is characterized in that the protective material takes any one of ultra-high molecular weight polyethylene fiber, aromatic polyamide fiber, poly-p-phenylene benzobisoxazole fiber, carbon fiber, high-strength polyester fiber and imitation spider silk fiber as a base layer, and the base layer is arranged in a plurality of layers; the fibers on the base layer are blended with Coolking fibers or Coolplus fibers which can absorb moisture and release sweat; the shear thickening fluid is uniformly adhered to the base layer, and is compounded with the base layer by using a static impregnation method. The fabric achieves the purpose of quick-drying and cooling by introducing the hair fiber with the functions of moisture absorption and sweat release, and solves the damp-heat problem caused by the air permeability problem of the fabric. However, the anti-piercing protective fabric adopting the moisture-absorbing and sweat-releasing functional fibers usually adopts a weaving process, the moisture-absorbing and sweat-releasing functional fibers are mixed in the weaving process, and the piercing place of the fabric is usually at the moisture-absorbing and sweat-releasing functional fibers with low strength, so that the puncture resistance of the fabric is not up to the standard.
Fencing apparel should provide satisfactory light weight and high strength while providing good softness and comfort. Based on these requirements, some products have been commercially promoted and applied. However, with the development of athletic sports, performance requirements of fencing protective clothing are also higher and higher, and higher requirements are put on the protection and comfort of the clothing. In the prior art, the fencing suit still has the defects of light weight, protective strength, flexibility and comfort.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the puncture-resistant fabric for fencing clothes and the preparation method thereof, which solve the problems of poor light effect of the fabric for fencing clothes and poor protective effect of the prepared fencing clothes in the prior art, and the fabric has good wearing comfort, excellent puncture property and lower fabric gram weight through the improvement of the formula and the process of the fabric.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the penetration-resistant fabric for fencing comprises a base cloth layer, a penetration-resistant layer and a coating layer, wherein the penetration-resistant layer is formed by blending ultra-high molecular weight polyethylene fibers, polyether-ether-ketone fibers and aramid fibers;
The coating layer is prepared from the following raw materials in parts by weight: 60-80 parts of epoxy resin, 20-30 parts of thermoplastic polyurethane, 10-20 parts of diethylaminopropylamine, 5-10 parts of modified inorganic fiber, 80-100 parts of N, N-dimethylformamide and 5-10 parts of sodium dodecyl benzene sulfonate.
Preferably, the base cloth layer is formed by blending polyester fiber and polypropylene fiber; the mass ratio of the polyester fiber to the polypropylene fiber is 1:1; the fineness of the polyester fiber is 350D-450D, the strength is 7-9 g/denier, and the fineness of the polypropylene fiber is 400-450D, and the strength is 5-7 g/denier.
Preferably, the ultra-high molecular weight polyethylene fibers are 360D-400D, and have a strength of 36-45 g/denier; the fineness of the aramid fiber is 420D-450D.
Preferably, the preparation method of the polyether-ether-ketone fiber comprises the following steps:
(a) Adding diatomite into ammonia water solution, stirring at 50-60deg.C for 1-3 hr, and adding AlCl 3 Stirring at 80-90 ℃ for 2-4h, filtering, washing, drying and calcining after the reaction is completed to obtain pretreated diatomite;
(b) Adding the pretreated diatomite in the step (a) into toluene, then adding gamma-aminopropyl triethoxysilane and sodium dodecyl sulfonate, then stirring for reaction, and filtering and drying after the reaction is finished to obtain modified diatomite;
(c) Drying the polyether-ether-ketone powder at 100-120 ℃ for 3-5 hours, then uniformly mixing the powder with the modified diatomite in the step (b), adding the mixture into a double-screw extruder for granulating to obtain polyether-ether-ketone master batch, drying the master batch at 120 ℃ for 4 hours, and carrying out melt spinning to obtain the polyether-ether-ketone fiber.
Preferably, the mass concentration of the ammonia water solution in the step (a) is 10-15%, and the diatomite, the ammonia water solution and the AlCl are 3 The mass ratio of (2) is 10:150-200:5-10, the calcining temperature is 400-500 ℃, and the calcining time is 1-2h; the mass ratio of the pretreated diatomite, the gamma-aminopropyl triethoxysilane and the sodium dodecyl sulfonate in the step (b) is 100:5-8:1-3, the temperature of the stirring reaction is 90-100 ℃, and the reaction time is 4-5h; the mass ratio of the polyether-ether-ketone powder to the modified diatomite in the step (c) is 100:10-15; the titer of the polyether-ether-ketone fiber is 380-420D.
Preferably, the preparation method of the modified inorganic fiber comprises the following steps:
s1, uniformly mixing glass fibers, carbon fibers and silicon carbide whiskers, then adding the mixture into a potassium permanganate solution, soaking the mixture for 4 to 6 hours at room temperature, and filtering and drying the mixture after the soaking is finished to obtain pretreated mixed fibers;
S2, adding the pretreated fiber in the step S1 into toluene, then adding gamma-mercaptopropyl trimethoxy silane, stirring for reaction, and filtering and drying after the reaction is finished to obtain a mercapto compound fiber;
and S3, adding the sulfhydrylation mixed fiber obtained in the step S2 into absolute ethyl alcohol, then adding succinic anhydride and tertiary glycidyl ester, carrying out constant-temperature reaction, and filtering, washing, drying and ball-milling after the reaction is finished to obtain the modified inorganic fiber.
Preferably, the mass concentration of the potassium permanganate in the step S1 is 3-6%; the mass ratio of the glass fiber to the carbon fiber to the silicon carbide whisker is 10:2-4:5-8; the mass ratio of the pretreated fibers to the gamma-mercaptopropyl trimethoxy silane in the step S2 is 100:4-8, the temperature of the stirring reaction is 80-90 ℃, and the reaction time is 3-5h; in the step S3, the mass ratio of the sulfhydrylation mixed fiber to the succinic anhydride to the tertiary glycidyl ester is 100:5-10:5-10, the constant temperature reaction temperature is 60-80 ℃, the reaction time is 2-4h, the ball milling rotating speed is 1500-2500r/min, and the ball milling time is 1-2h.
The invention also provides a preparation method of the puncture-resistant fabric for fencing, which comprises the following steps:
(1) Preparation of a base cloth layer: twisting polyester fiber and polypropylene fiber, controlling the twist to be 80-90 twist/cm, warping the twisted polyester fiber and polypropylene fiber, weaving by a double-sided knitting circular knitting machine after warping, wherein the yarn feeding number of the polyester fiber is the same as the yarn feeding number of the polypropylene fiber, and weaving to obtain a base cloth layer;
(2) Preparation of puncture-preventing layer: the warp yarn is formed by twisting ultra-high molecular weight polyethylene fibers and polyether-ether-ketone fibers according to the proportion of 1:1, 6-12 fibers are twisted into yarn, and the twist is 50-150 twists/cm; the weft yarn is formed by twisting ultra-high molecular weight polyethylene fibers and aramid fibers according to the proportion of 1:1, 6-18 fibers are twisted into yarn, and the twist is 50-150 twists/cm; weaving the warp yarns and the weft yarns, wherein the density of the warp yarns and the weft yarns is 200-250 pieces/10 cm, and the density of the weft yarns is 160-200 pieces/10 cm, so that a puncture-preventing layer is obtained;
(3) Preparation of the coating liquid: weighing raw materials according to weight, adding thermoplastic polyurethane into N, N-dimethylformamide, stirring and dissolving at 90 ℃, cooling to room temperature, then adding epoxy resin, modified inorganic fibers and sodium dodecyl benzene sulfonate, stirring for 15-30min, finally adding diethylaminopropylamine, and uniformly mixing to obtain the coating liquid;
(4) Preparation of puncture-resistant fabric: and (3) putting the base cloth layer in the step (1) and the stab-resistant layer in the step (2) into a finishing agent for dipping, drying and shaping after the dipping is finished, then using an adhesive to bond the stab-resistant layer on the surface of the base cloth layer, drying, coating a coating liquid on the surface of the stab-resistant layer after the drying is finished, and heating and curing after the coating is finished to obtain the stab-resistant fabric for fencing.
Preferably, the preparation method of the finishing agent in the step (4) is as follows: uniformly mixing 55-70 parts of perfluorohexyl ethyl methyl acrylate, 6-9 parts of dodecyl trimethyl ammonium sulfate, 5-10 parts of methyltrimethoxysilane, 4-7 parts of polyvinylpyrrolidone and 3-6 parts of p-tert-butylbenzoic acid, stirring for 30-50min at 50-60 ℃, then adding 3-5 parts of fatty alcohol polyoxyethylene ether AEO-9, 10-15 parts of zinc stearate, 1-4 parts of tween 80 and 2-5 parts of lauryldiacid, finally adding 200-250 parts of deionized water, and continuously stirring and mixing for 20-30min at 65-75 ℃ to obtain the finishing agent.
Preferably, the temperature of the impregnation in the step (4) is 40-60 ℃ and the impregnation time is 4-7h; the temperature of the drying and shaping is 60-80 ℃ and the drying time is 5-8h; the drying temperature is 70-90 ℃ and the drying time is 3-5h; the coating weight is 150-200g/m 2 The curing condition is that the curing is carried out for 1-2 hours at 60-80 ℃.
Preferably, the sizing amount of the adhesive is 30-60g/m 2 。
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the penetration-resistant fabric for fencing, the polyester fiber and the polypropylene fiber are blended to be used as the base fabric layer, and the polyester fiber and the polypropylene fiber have excellent wrinkle resistance and shape retention, have certain mechanical strength, elastic recovery capability, thermoplasticity and stability, can improve the performances of the fabric in all aspects, are soft in matrix, and improve the wearing comfort of the fabric; the ultra-high molecular weight polyethylene fiber, the polyether-ether-ketone fiber and the aramid fiber are blended to prepare the puncture-preventing layer, and the ultra-high molecular weight polyethylene fiber and the polyether-ether-ketone fiber are used as warp yarns, so that the breaking strength of the fabric can be enhanced, and the fabric has a better protection effect; the ultra-high molecular weight polyethylene fiber and the aramid fiber are adopted as weft yarns, so that the breaking strength of the fabric can be improved to a certain extent, and the ultra-high molecular weight polyethylene fiber and the aramid fiber have ultra-high strength and modulus, so that the beneficial effects of the fibers can be effectively combined and the structural performance of the prepared fabric can be improved by compounding the ultra-high molecular weight polyethylene fiber, the aramid fiber and the polyether-ether-ketone, so that the stab resistance of the fabric can be improved; finally, coating liquid is coated on the surface of the puncture-proof layer, and the coating liquid can be filled in gaps among fabric yarns, so that the puncture resistance and strength of the fabric are greatly improved, the interfacial adhesion between the coating layer and the puncture-proof layer is good, the coating layer is not easy to fall off under long-time and high-strength use conditions, and the fabric has good air permeability, so that the prepared fabric is more comfortable.
(2) According to the puncture-resistant fabric for fencing, the diatomite is modified, alkali treatment is firstly carried out to enable the diatomite surface to be partially dissolved, aluminum chloride is then added to form an aluminum silicate compound to be deposited on the diatomite large mesoporous surface, the aluminum silicate compound is enabled to form a porous structure in the diatomite surface after calcination, the specific surface area of the diatomite is greatly improved, a great amount of subsequent polyether-ether-ketone enters into the pore channels of the diatomite, defects existing in polyether-ether-ketone fibers are reduced, the strength and toughness of the polyether-ether-ketone fibers are improved, gamma-aminopropyl triethoxysilane and sodium dodecyl sulfonate are then used for carrying out grafting modification on the diatomite, the diatomite surface is aminated, the interface interaction between the diatomite and a polyether-ether-ketone body is improved, and the addition of sodium dodecyl sulfonate is beneficial to improving the dispersibility of the diatomite in a resin matrix, so that the polyether-ether-ketone fibers with better performance are prepared.
(3) According to the penetration-resistant fabric for fencing, thermoplastic polyurethane and epoxy resin are compounded in the coating layer, flexible molecular chains are contained in the polyurethane, so that the fabric has excellent bending resistance and impact resistance, breaking absorption capacity is high, the epoxy resin can reduce slippage of yarns, so that the yarns can be prevented from penetrating through a cutter more effectively in a damaged area, further better penetration resistance is provided, meanwhile, the added modified inorganic fibers are subjected to oxidation activation treatment through potassium permanganate to generate more active sites on the surface, gamma-mercaptopropyl trimethoxysilane is used for carrying out sulfhydrylation on the mixed fibers, then the sulfhydrylation mixed fibers are reacted with succinic anhydride and tertiary glycidyl carbonate, tertiary carbonic acid ester is connected to the surfaces of the fibers, compatibility of the fibers with the epoxy resin and the polyurethane is improved, further the coating layer has better mechanical properties, and as reactive groups are introduced to the surfaces of glass fibers, carbon fibers and silicon carbide whiskers, fiber networks can be formed through crosslinking in the subsequent curing process of a coating liquid, and the penetration resistance of the fabric is further improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The polyether-ether-ketone powder is purchased from Fusen plasticizing Co Ltd in the city of Yuyao, and has the brand of VICTREX Weigas L150 and the mesh number of 300 meshes; the diatomite is purchased from Shijiu Tianxu environmental protection technology Co., ltd, and the mesh number is 325 mesh; the glass fiber is purchased from the Innovative materials science and technology Co., ltd, and has the diameter of 9-13 μm and the length of 100-200 μm; the carbon fiber is purchased from Shanghai composite material technology Co., ltd, and has the length of 1-3mm and the diameter of 5-10 mu m; the silicon carbide whisker is purchased from Beijing De island gold technology Co., ltd, and has an average particle size of 50-100nm; the epoxy resin is purchased from Jinan Zesheng chemical industry Co., ltd, is bisphenol A type epoxy resin, and has the model of E51; the thermoplastic polyurethane is purchased from Shanghai, underwort, inc. under the brand name Wanhua TPU1195; the adhesive is purchased from Beijing Guangdong decorative Co., ltd and is an aqueous neoprene latex adhesive.
Example 1
A preparation method of a puncture-resistant fabric for fencing comprises the following steps:
(1) Preparation of a base cloth layer: respectively twisting polyester fiber and polypropylene fiber, controlling the twist to be 90 twist/cm, warping the twisted polyester fiber and polypropylene fiber, weaving by a double-sided circular knitting machine after warping, wherein the yarn feeding number of the polyester fiber is the same as the yarn feeding number of the polypropylene fiber, and weaving to obtain a base cloth layer;
the mass ratio of the polyester fiber to the polypropylene fiber is 1:1; the titer of the polyester fiber is 400D, the strength is 8 g/denier, and the titer of the polypropylene fiber is 430D, the strength is 6 g/denier;
(2) Preparation of puncture-preventing layer: the warp yarn is formed by twisting ultra-high molecular weight polyethylene fibers and polyether-ether-ketone fibers according to the proportion of 1:1, 10 fibers are twisted into yarn, and the twist is 100 twists/cm; the weft yarn is formed by twisting ultra-high molecular weight polyethylene fibers and aramid fibers according to the proportion of 1:1, and 14 fibers are twisted into yarn with the twist of 100 twists/cm; weaving warp yarns and weft yarns, wherein the density of the warp yarns and the weft yarns is 250 pieces/10 cm, and the density of the weft yarns is 200 pieces/10 cm, so that a puncture-preventing layer is obtained;
the ultra-high molecular weight polyethylene fiber 380D has a strength of 40 grams per denier; the titer of the aramid fiber is 450D;
(3) Preparation of the coating liquid: weighing raw materials according to weight, adding 250g of thermoplastic polyurethane into 900g of N, N-dimethylformamide, stirring and dissolving at 90 ℃, cooling to room temperature, then adding 700g of epoxy resin, 80g of modified inorganic fiber and 80g of sodium dodecyl benzene sulfonate, stirring for 20min, finally adding 150g of diethylaminopropylamine, and uniformly mixing to obtain the coating liquid;
(4) Preparation of puncture-resistant fabric: putting the base cloth layer in the step (1) and the stab-resistant layer in the step (2) into a finishing agent, soaking for 6 hours at 50 ℃, drying and shaping for 7 hours at 70 ℃ after soaking, and then bonding the surfaces of the base cloth layers by using an adhesivePuncture-proof layer, the sizing amount of the adhesive is 50g/m 2 Drying at 80deg.C for 4 hr, and coating the surface of the puncture-preventing layer with coating solution with coating weight of 200g/m 2 And (5) curing at 70 ℃ for 1.5 hours after coating is finished, so as to obtain the penetration-resistant fabric for fencing.
The preparation method of the finishing agent in the step (4) comprises the following steps: uniformly mixing 60g of perfluorohexyl ethyl methyl acrylate, 8g of dodecyl trimethyl ammonium sulfate, 8g of methyltrimethoxysilane, 6g of polyvinylpyrrolidone and 5g of p-tert-butylbenzoic acid, stirring at 55 ℃ for 40min, then adding 4g of fatty alcohol polyoxyethylene ether AEO-9, 12g of zinc stearate, 3g of tween 80 and 4g of lauryldiacid, finally adding 230g of deionized water, and continuously stirring and mixing at 70 ℃ for 25min to obtain the finishing agent;
The preparation method of the polyether-ether-ketone fiber comprises the following steps:
(a) 10g of kieselguhr is added into 180g of 15% ammonia water solution, stirred for 2h at 55 ℃, and then 8g of AlCl is added 3 Stirring at 85 ℃ for reaction for 3 hours, filtering, washing and drying after the reaction is finished, and calcining at 450 ℃ for 1.5 hours to obtain pretreated diatomite;
(b) Adding the pretreated diatomite (100 g) obtained in the step (a) into 600mL of toluene, then adding 7g of gamma-aminopropyl triethoxysilane and 2g of sodium dodecyl sulfonate, then stirring at 95 ℃ for reaction for 4.5 hours, and filtering and drying after the reaction is completed to obtain modified diatomite;
(c) Drying 1000g of polyether-ether-ketone powder at 110 ℃ for 4 hours, then uniformly mixing the powder with the modified diatomite (130 g) in the step (b), adding the mixture into a double-screw extruder for granulation, extruding and granulating, wherein the reaction temperatures (DEG C) of all the sections are 110, 360, 380, 400, 410, 405 and 400 in sequence to obtain polyether-ether-ketone master batches, drying the master batches at 120 ℃ for 4 hours, and carrying out melt spinning, wherein the reaction temperatures (DEG C) of all the sections are 110, 370, 410, 420, 425, 415 and 410 in sequence, and the spinning speed is 0.8km/min to obtain the polyether-ether-ketone fiber, and the fineness of the polyether-ether-ketone fiber is 400D.
The preparation method of the modified inorganic fiber comprises the following steps:
s1, uniformly mixing 100g of glass fiber, carbon fiber and silicon carbide whisker with the mass ratio of 10:3:7, then adding into 500mL of potassium permanganate solution with the mass concentration of 5%, soaking for 5 hours at room temperature, filtering and drying after the soaking is completed, and obtaining pretreated mixed fiber;
s2, adding the pretreated fiber (100 g) in the step S1 into 600mL of toluene, then adding 6g of gamma-mercaptopropyl trimethoxy silane, stirring at 85 ℃ for reaction for 4 hours, and filtering and drying after the reaction is finished to obtain a mercapto compound fiber;
s3, adding the sulfhydrylation mixed fiber (100 g) obtained in the step S2 into 600mL of absolute ethyl alcohol, then adding 8g of succinic anhydride and 8g of tertiary glycidyl ester, reacting for 3 hours at a constant temperature of 70 ℃, filtering, washing and drying after the reaction is finished, and ball-milling for 1.5 hours at 2000r/min to obtain the modified inorganic fiber.
Example 2
A preparation method of a puncture-resistant fabric for fencing comprises the following steps:
(1) Preparation of a base cloth layer: respectively twisting polyester fiber and polypropylene fiber, controlling the twist to be 90 twist/cm, warping the twisted polyester fiber and polypropylene fiber, weaving by a double-sided circular knitting machine after warping, wherein the yarn feeding number of the polyester fiber is the same as the yarn feeding number of the polypropylene fiber, and weaving to obtain a base cloth layer;
The mass ratio of the polyester fiber to the polypropylene fiber is 1:1; the titer of the polyester fiber is 400D, the strength is 8 g/denier, and the titer of the polypropylene fiber is 430D, the strength is 6 g/denier;
(2) Preparation of puncture-preventing layer: the warp yarn is formed by twisting ultra-high molecular weight polyethylene fibers and polyether-ether-ketone fibers according to the proportion of 1:1, 10 fibers are twisted into yarn, and the twist is 100 twists/cm; the weft yarn is formed by twisting ultra-high molecular weight polyethylene fibers and aramid fibers according to the proportion of 1:1, and 14 fibers are twisted into yarn with the twist of 100 twists/cm; weaving warp yarns and weft yarns, wherein the density of the warp yarns and the weft yarns is 250 pieces/10 cm, and the density of the weft yarns is 200 pieces/10 cm, so that a puncture-preventing layer is obtained;
the ultra-high molecular weight polyethylene fiber 380D has a strength of 40 grams per denier; the titer of the aramid fiber is 450D;
(3) Preparation of the coating liquid: weighing raw materials according to weight, adding 200g of thermoplastic polyurethane into 800g of N, N-dimethylformamide, stirring and dissolving at 90 ℃, cooling to room temperature, then adding 600g of epoxy resin, 50g of modified inorganic fiber and 50g of sodium dodecyl benzene sulfonate, stirring for 15min, finally adding 100g of diethylaminopropylamine, and uniformly mixing to obtain the coating liquid;
(4) Preparation of puncture-resistant fabric: putting the base cloth layer in the step (1) and the stab-resistant layer in the step (2) into a finishing agent, soaking for 7 hours at 40 ℃, drying and shaping for 8 hours at 60 ℃ after soaking, and then bonding the stab-resistant layer on the surface of the base cloth layer by using an adhesive, wherein the sizing amount of the adhesive is 50g/m 2 Drying at 70deg.C for 5 hr, and coating the surface of the puncture-preventing layer with a coating solution of 200g/m 2 And (5) curing for 2 hours at 60 ℃ after coating is finished, so as to obtain the penetration-resistant fabric for fencing.
The preparation method of the finishing agent in the step (4) comprises the following steps: uniformly mixing 55g of perfluorohexyl ethyl methyl acrylate, 6g of dodecyl trimethyl ammonium sulfate, 5g of methyltrimethoxysilane, 4g of polyvinylpyrrolidone and 3g of p-tert-butylbenzoic acid, stirring at 50 ℃ for 50min, then adding 3g of fatty alcohol polyoxyethylene ether AEO-9, 10g of zinc stearate, 1g of tween 80 and 2g of lauryldiacid, finally adding 200g of deionized water, and continuously stirring and mixing at 65 ℃ for 30min to obtain the finishing agent;
the preparation method of the polyether-ether-ketone fiber comprises the following steps:
(a) 10g of kieselguhr is added into 150g of 10% strength by mass aqueous ammonia solution, stirred for 3h at 50℃and then 5g of AlCl are added 3 Stirring at 80 ℃ for reaction for 4 hours, filtering, washing and drying after the reaction is finished, and calcining at 400 ℃ for 2 hours to obtain pretreated diatomite;
(b) Adding the pretreated diatomite (100 g) obtained in the step (a) into 600mL of toluene, then adding 5g of gamma-aminopropyl triethoxysilane and 1g of sodium dodecyl sulfonate, stirring at 90 ℃ for reaction for 5 hours, and filtering and drying after the reaction is completed to obtain modified diatomite;
(c) Drying 1000g of polyether-ether-ketone powder at 110 ℃ for 4 hours, then uniformly mixing the powder with the modified diatomite (130 g) in the step (b), adding the mixture into a double-screw extruder for granulation, extruding and granulating, wherein the reaction temperatures (DEG C) of all the sections are 110, 360, 380, 400, 410, 405 and 400 in sequence to obtain polyether-ether-ketone master batches, drying the master batches at 120 ℃ for 4 hours, and carrying out melt spinning, wherein the reaction temperatures (DEG C) of all the sections are 110, 370, 410, 420, 425, 415 and 410 in sequence, and the spinning speed is 0.8km/min to obtain the polyether-ether-ketone fiber, and the fineness of the polyether-ether-ketone fiber is 400D.
The preparation method of the modified inorganic fiber comprises the following steps:
s1, uniformly mixing 100g of glass fiber, carbon fiber and silicon carbide whisker with the mass ratio of 10:2:8, then adding into 500mL of potassium permanganate solution with the mass concentration of 3%, soaking for 6 hours at room temperature, filtering and drying after the soaking is completed, and obtaining pretreated mixed fiber;
S2, adding the pretreated fiber (100 g) in the step S1 into 600mL of toluene, then adding 4g of gamma-mercaptopropyl trimethoxy silane, stirring at 80 ℃ for reaction for 5 hours, and filtering and drying after the reaction is finished to obtain a mercapto compound fiber;
s3, adding the sulfhydrylation mixed fiber (100 g) obtained in the step S2 into 600mL of absolute ethyl alcohol, then adding 5g of succinic anhydride and 5g of tertiary glycidyl ester, reacting for 4 hours at a constant temperature of 60 ℃, filtering, washing, drying after the reaction is finished, and ball-milling for 2 hours at 1500r/min to obtain the modified inorganic fiber.
Example 3
A preparation method of a puncture-resistant fabric for fencing comprises the following steps:
(1) Preparation of a base cloth layer: respectively twisting polyester fiber and polypropylene fiber, controlling the twist to be 90 twist/cm, warping the twisted polyester fiber and polypropylene fiber, weaving by a double-sided circular knitting machine after warping, wherein the yarn feeding number of the polyester fiber is the same as the yarn feeding number of the polypropylene fiber, and weaving to obtain a base cloth layer;
the mass ratio of the polyester fiber to the polypropylene fiber is 1:1; the titer of the polyester fiber is 400D, the strength is 8 g/denier, and the titer of the polypropylene fiber is 430D, the strength is 6 g/denier;
(2) Preparation of puncture-preventing layer: the warp yarn is formed by twisting ultra-high molecular weight polyethylene fibers and polyether-ether-ketone fibers according to the proportion of 1:1, 10 fibers are twisted into yarn, and the twist is 100 twists/cm; the weft yarn is formed by twisting ultra-high molecular weight polyethylene fibers and aramid fibers according to the proportion of 1:1, and 14 fibers are twisted into yarn with the twist of 100 twists/cm; weaving warp yarns and weft yarns, wherein the density of the warp yarns and the weft yarns is 250 pieces/10 cm, and the density of the weft yarns is 200 pieces/10 cm, so that a puncture-preventing layer is obtained;
the ultra-high molecular weight polyethylene fiber 380D has a strength of 40 grams per denier; the titer of the aramid fiber is 450D;
(3) Preparation of the coating liquid: weighing raw materials according to the weight, adding 300g of thermoplastic polyurethane into 1000g of N, N-dimethylformamide, stirring and dissolving at 90 ℃, cooling to room temperature, then adding 800g of epoxy resin, 100g of modified inorganic fiber and 100g of sodium dodecyl benzene sulfonate, stirring for 15min, finally adding 200g of diethylaminopropylamine, and uniformly mixing to obtain the coating liquid;
(4) Preparation of puncture-resistant fabric: putting the base cloth layer in the step (1) and the stab-resistant layer in the step (2) into a finishing agent, soaking for 4 hours at 60 ℃, drying and shaping for 5 hours at 80 ℃ after soaking, and then bonding the stab-resistant layer on the surface of the base cloth layer by using an adhesive, wherein the sizing amount of the adhesive is 50g/m 2 Then drying at 90deg.C for 3 hr, and coating the surface of the puncture-preventing layer with a coating solution with a coating weight of 200g/m 2 And (3) curing for 1h at 80 ℃ after coating is finished, so as to obtain the penetration-resistant fabric for fencing.
The preparation method of the finishing agent in the step (4) comprises the following steps: uniformly mixing 70g of perfluorohexyl ethyl methyl acrylate, 9g of dodecyl trimethyl ammonium sulfate, 10g of methyltrimethoxysilane, 7g of polyvinylpyrrolidone and 6g of p-tert-butylbenzoic acid, stirring at 60 ℃ for 30min, then adding 5g of fatty alcohol polyoxyethylene ether AEO-9, 15g of zinc stearate, 4g of tween 80 and 5g of lauryldiacid, finally adding 250g of deionized water, and continuously stirring and mixing at 75 ℃ for 20min to obtain the finishing agent;
the preparation method of the polyether-ether-ketone fiber comprises the following steps:
(a) 10g of kieselguhr is added into 200g of 15% strength by mass aqueous ammonia solution, stirred at 60℃for 1h, and then 10g of AlCl are added 3 Stirring at 90 ℃ for reaction for 2 hours, filtering, washing, drying after the reaction is completed, and calcining at 500 ℃ for 1 hour to obtain pretreated diatomite;
(b) Adding the pretreated diatomite (100 g) obtained in the step (a) into 600mL of toluene, then adding 8g of gamma-aminopropyl triethoxysilane and 3g of sodium dodecyl sulfonate, stirring at 100 ℃ for reaction for 4 hours, and filtering and drying after the reaction is completed to obtain modified diatomite;
(c) Drying 1000g of polyether-ether-ketone powder at 110 ℃ for 4 hours, then uniformly mixing the powder with the modified diatomite (130 g) in the step (b), adding the mixture into a double-screw extruder for granulation, extruding and granulating, wherein the reaction temperatures (DEG C) of all the sections are 110, 360, 380, 400, 410, 405 and 400 in sequence to obtain polyether-ether-ketone master batches, drying the master batches at 120 ℃ for 4 hours, and carrying out melt spinning, wherein the reaction temperatures (DEG C) of all the sections are 110, 370, 410, 420, 425, 415 and 410 in sequence, and the spinning speed is 0.8km/min to obtain the polyether-ether-ketone fiber, and the fineness of the polyether-ether-ketone fiber is 400D.
The preparation method of the modified inorganic fiber comprises the following steps:
s1, uniformly mixing 100g of glass fiber, carbon fiber and silicon carbide whisker with the mass ratio of 10:4:6, then adding into 500mL of potassium permanganate solution with the mass concentration of 6%, soaking for 4 hours at room temperature, filtering and drying after the soaking is completed, and obtaining pretreated mixed fiber;
s2, adding the pretreated fiber (100 g) in the step S1 into 600mL of toluene, then adding 8g of gamma-mercaptopropyl trimethoxy silane, stirring at 90 ℃ for reaction for 3 hours, and filtering and drying after the reaction is completed to obtain a mercapto compound fiber;
S3, adding the sulfhydrylation mixed fiber (100 g) obtained in the step S2 into 600mL of absolute ethyl alcohol, then adding 10g of succinic anhydride and 10g of tertiary glycidyl ester, reacting at the constant temperature of 80 ℃ for 2 hours, filtering, washing, drying after the reaction is finished, and ball-milling for 1 hour at 2500r/min to obtain the modified inorganic fiber.
Comparative example 1
A preparation method of a puncture-resistant fabric for fencing comprises the following steps:
(1) Preparation of a base cloth layer: respectively twisting polyester fiber and polypropylene fiber, controlling the twist to be 90 twist/cm, warping the twisted polyester fiber and polypropylene fiber, weaving by a double-sided circular knitting machine after warping, wherein the yarn feeding number of the polyester fiber is the same as the yarn feeding number of the polypropylene fiber, and weaving to obtain a base cloth layer;
the mass ratio of the polyester fiber to the polypropylene fiber is 1:1; the titer of the polyester fiber is 400D, the strength is 8 g/denier, and the titer of the polypropylene fiber is 430D, the strength is 6 g/denier;
(2) Preparation of puncture-preventing layer: the warp yarn is formed by twisting ultra-high molecular weight polyethylene fibers and polyether-ether-ketone fibers according to the proportion of 1:1, 10 fibers are twisted into yarn, and the twist is 100 twists/cm; the weft yarn is formed by twisting ultra-high molecular weight polyethylene fibers and aramid fibers according to the proportion of 1:1, and 14 fibers are twisted into yarn with the twist of 100 twists/cm; weaving warp yarns and weft yarns, wherein the density of the warp yarns and the weft yarns is 250 pieces/10 cm, and the density of the weft yarns is 200 pieces/10 cm, so that a puncture-preventing layer is obtained;
The ultra-high molecular weight polyethylene fiber 380D has a strength of 40 grams per denier; the titer of the aramid fiber is 450D;
(3) Preparation of the coating liquid: weighing raw materials according to weight, adding 250g of thermoplastic polyurethane into 900g of N, N-dimethylformamide, stirring and dissolving at 90 ℃, cooling to room temperature, then adding 700g of epoxy resin, 80g of modified inorganic fiber and 80g of sodium dodecyl benzene sulfonate, stirring for 20min, finally adding 150g of diethylaminopropylamine, and uniformly mixing to obtain the coating liquid;
(4) Preparation of puncture-resistant fabric: putting the base fabric layer in the step (1) and the stab-resistant layer in the step (2) into a finishing agent, soaking for 6 hours at 50 ℃, drying and shaping for 7 hours at 70 ℃ after the soaking is finished, and then putting the base fabric layer on the surface of the base fabric layerThe surface is adhered with the puncture-proof layer by using an adhesive, and the adhesive coating amount of the adhesive is 50g/m 2 Drying at 80deg.C for 4 hr, and coating the surface of the puncture-preventing layer with coating solution with coating weight of 200g/m 2 And (5) curing at 70 ℃ for 1.5 hours after coating is finished, so as to obtain the penetration-resistant fabric for fencing.
The preparation method of the finishing agent in the step (4) comprises the following steps: uniformly mixing 60g of perfluorohexyl ethyl methyl acrylate, 8g of dodecyl trimethyl ammonium sulfate, 8g of methyltrimethoxysilane, 6g of polyvinylpyrrolidone and 5g of p-tert-butylbenzoic acid, stirring at 55 ℃ for 40min, then adding 4g of fatty alcohol polyoxyethylene ether AEO-9, 12g of zinc stearate, 3g of tween 80 and 4g of lauryldiacid, finally adding 230g of deionized water, and continuously stirring and mixing at 70 ℃ for 25min to obtain the finishing agent;
The preparation method of the polyether-ether-ketone fiber comprises the following steps:
drying 1000g of polyether-ether-ketone powder for 4 hours at 110 ℃, then uniformly mixing the powder with 130g of diatomite, adding the mixture into a double-screw extruder for granulating, extruding and granulating, wherein the reaction temperatures (DEG C) of all sections are 110, 360, 380, 400, 410, 405 and 400 in sequence to obtain polyether-ether-ketone master batches, drying the master batches at 120 ℃ for 4 hours, and carrying out melt spinning, wherein the reaction temperatures (DEG C) of all sections of the melt spinning are 110, 370, 410, 420, 425, 415 and 410 in sequence, and the spinning speed is 0.8km/min, so that the polyether-ether-ketone fiber is obtained, and the fineness of the polyether-ether-ketone fiber is 400D.
The preparation method of the modified inorganic fiber comprises the following steps:
s1, uniformly mixing 100g of glass fiber, carbon fiber and silicon carbide whisker with the mass ratio of 10:3:7, then adding into 500mL of potassium permanganate solution with the mass concentration of 5%, soaking for 5 hours at room temperature, filtering and drying after the soaking is completed, and obtaining pretreated mixed fiber;
s2, adding the pretreated fiber (100 g) in the step S1 into 600mL of toluene, then adding 6g of gamma-mercaptopropyl trimethoxy silane, stirring at 85 ℃ for reaction for 4 hours, and filtering and drying after the reaction is finished to obtain a mercapto compound fiber;
S3, adding the sulfhydrylation mixed fiber (100 g) obtained in the step S2 into 600mL of absolute ethyl alcohol, then adding 8g of succinic anhydride and 8g of tertiary glycidyl ester, reacting for 3 hours at a constant temperature of 70 ℃, filtering, washing and drying after the reaction is finished, and ball-milling for 1.5 hours at 2000r/min to obtain the modified inorganic fiber.
Comparative example 2
A preparation method of a puncture-resistant fabric for fencing comprises the following steps:
(1) Preparation of a base cloth layer: respectively twisting polyester fiber and polypropylene fiber, controlling the twist to be 90 twist/cm, warping the twisted polyester fiber and polypropylene fiber, weaving by a double-sided circular knitting machine after warping, wherein the yarn feeding number of the polyester fiber is the same as the yarn feeding number of the polypropylene fiber, and weaving to obtain a base cloth layer;
the mass ratio of the polyester fiber to the polypropylene fiber is 1:1; the titer of the polyester fiber is 400D, the strength is 8 g/denier, and the titer of the polypropylene fiber is 430D, the strength is 6 g/denier;
(2) Preparation of puncture-preventing layer: the warp yarn is formed by twisting ultra-high molecular weight polyethylene fibers and polyether-ether-ketone fibers according to the proportion of 1:1, 10 fibers are twisted into yarn, and the twist is 100 twists/cm; the weft yarn is formed by twisting ultra-high molecular weight polyethylene fibers and aramid fibers according to the proportion of 1:1, and 14 fibers are twisted into yarn with the twist of 100 twists/cm; weaving warp yarns and weft yarns, wherein the density of the warp yarns and the weft yarns is 250 pieces/10 cm, and the density of the weft yarns is 200 pieces/10 cm, so that a puncture-preventing layer is obtained;
The ultra-high molecular weight polyethylene fiber 380D has a strength of 40 grams per denier; the titer of the aramid fiber is 450D;
(3) Preparation of the coating liquid: weighing raw materials according to weight, adding 250g of thermoplastic polyurethane into 900g of N, N-dimethylformamide, stirring and dissolving at 90 ℃, cooling to room temperature, then adding 700g of epoxy resin, 80g of glass fiber and 80g of sodium dodecyl benzene sulfonate, stirring for 20min, finally adding 150g of diethylaminopropylamine, and uniformly mixing to obtain the coating liquid;
(4) Preparation of puncture-resistant fabric: the base cloth layer in the step (1) and the stab prevention layer in the step (2) are combinedThe layers are put into a finishing agent, soaked for 6 hours at 50 ℃, dried and shaped for 7 hours at 70 ℃ after the soaking is finished, then the puncture-proof layer is bonded on the surface of the base cloth layer by using an adhesive, and the sizing amount of the adhesive is 50g/m 2 Drying at 80deg.C for 4 hr, and coating the surface of the puncture-preventing layer with coating solution with coating weight of 200g/m 2 And (5) curing at 70 ℃ for 1.5 hours after coating is finished, so as to obtain the penetration-resistant fabric for fencing.
The preparation method of the finishing agent in the step (4) comprises the following steps: uniformly mixing 60g of perfluorohexyl ethyl methyl acrylate, 8g of dodecyl trimethyl ammonium sulfate, 8g of methyltrimethoxysilane, 6g of polyvinylpyrrolidone and 5g of p-tert-butylbenzoic acid, stirring at 55 ℃ for 40min, then adding 4g of fatty alcohol polyoxyethylene ether AEO-9, 12g of zinc stearate, 3g of tween 80 and 4g of lauryldiacid, finally adding 230g of deionized water, and continuously stirring and mixing at 70 ℃ for 25min to obtain the finishing agent;
The preparation method of the polyether-ether-ketone fiber comprises the following steps:
(a) 10g of kieselguhr is added into 180g of 15% ammonia water solution, stirred for 2h at 55 ℃, and then 8g of AlCl is added 3 Stirring at 85 ℃ for reaction for 3 hours, filtering, washing and drying after the reaction is finished, and calcining at 450 ℃ for 1.5 hours to obtain pretreated diatomite;
(b) Adding the pretreated diatomite (100 g) obtained in the step (a) into 600mL of toluene, then adding 7g of gamma-aminopropyl triethoxysilane and 2g of sodium dodecyl sulfonate, then stirring at 95 ℃ for reaction for 4.5 hours, and filtering and drying after the reaction is completed to obtain modified diatomite;
(c) Drying 100g of polyether-ether-ketone powder at 110 ℃ for 4 hours, then uniformly mixing the powder with the modified diatomite (13 g) in the step (b), adding the mixture into a double-screw extruder for granulating, extruding and granulating, wherein the reaction temperatures (DEG C) of all the sections are 110, 360, 380, 400, 410, 405 and 400 in sequence to obtain polyether-ether-ketone master batches, drying the master batches at 120 ℃ for 4 hours, and carrying out melt spinning, wherein the reaction temperatures (DEG C) of all the sections are 110, 370, 410, 420, 425, 415 and 410 in sequence, and the spinning speed is 0.8km/min to obtain the polyether-ether-ketone fiber, and the fineness of the polyether-ether-ketone fiber is 400D.
Performing performance test on the fabrics prepared in the examples 1-3 and the comparative examples 1-2, wherein the puncture strength is measured by an INSTRON3369 type universal strength machine according to ASTM F1342-2005, the puncture strength of a sample is measured, the sample is clamped by a self-designed cylindrical clamp, a bolt is selected to clamp the sample to avoid sliding, the sample is placed on an instrument, the direction of a cutter edge is consistent with the direction of a fabric warp, a test head is a single-edge cutter, the size of the sample to be tested is 10cm multiplied by 10cm, the relative humidity of a test environment is 65%, the test temperature is 20 ℃, and the test speed is 508mm/min; the moisture permeability adopts YG (B) 216-II type fabric moisture permeability measuring instrument, refer to GB/T12704.2-2009 textile fabric moisture permeability test method part 2: the evaporation method tests the moisture permeability of the fabric. The temperature of the experimental box is 38 ℃, the relative humidity is 50%, 3 round samples with the diameter of 70mm are taken from each sample, and the average value is obtained; the air permeability of the fabrics was tested by using YG (B) 461D-I type digital fabric air permeability meter, referring to GB/T5453-1997 determination of air permeability of fabrics of textiles. The area of the sample was 20cm 2 The pressure drop was 100Pa, and each sample was tested 10 times, and the average value was obtained; the test results are shown in Table 1 below.
TABLE 1
Gram weight (g/m) 2 ) Puncture strength/N Moisture permeability (g/m) 2 ·h) Air permeability (mm/s)
Example 1 621 1037 97.8 27.9
Example 2 614 958 89.4 25.6
Example 3 627 972 92.5 26.1
Comparative example 1 618 768 85.9 24.8
Comparative example 2 624 783 90.7 25.9
As can be seen from Table 1, the puncture-resistant fabric for fencing prepared by the invention has larger puncture strength, lighter gram weight, better moisture permeability and air permeability and good application prospect. The diatomite of the polyether-ether-ketone fiber in the comparative example 1 is not modified, and the inorganic fiber in the coating liquid in the comparative example 2 is not modified, so that the puncture resistance of the fabric is greatly affected.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The penetration-resistant fabric for fencing is characterized by comprising a base cloth layer, a penetration-resistant layer and a coating layer, wherein the penetration-resistant layer is formed by blending ultra-high molecular weight polyethylene fibers, polyether-ether-ketone fibers and aramid fibers;
the coating layer is prepared from the following raw materials in parts by weight: 60-80 parts of epoxy resin, 20-30 parts of thermoplastic polyurethane, 10-20 parts of diethylaminopropylamine, 5-10 parts of modified inorganic fiber, 80-100 parts of N, N-dimethylformamide and 5-10 parts of sodium dodecyl benzene sulfonate.
2. The penetration-resistant fabric for fencing of claim 1, wherein the base cloth layer is formed by blending polyester fibers and polypropylene fibers; the mass ratio of the polyester fiber to the polypropylene fiber is 1:1; the fineness of the polyester fiber is 350D-450D, the strength is 7-9 g/denier, and the fineness of the polypropylene fiber is 400-450D, and the strength is 5-7 g/denier.
3. The fencing stab resistant fabric of claim 1, wherein said ultra high molecular weight polyethylene fibers are 360D-400D with a strength of 36-45 g/denier; the fineness of the aramid fiber is 420D-450D.
4. The penetration-resistant fabric for fencing as in claim 1, wherein said method for preparing polyetheretherketone fibers comprises the steps of:
(a) Adding diatomite into ammonia water solution, stirring at 50-60deg.C for 1-3 hr, and adding AlCl 3 Stirring at 80-90 deg.c for 2-4 hr, filtering, washing, drying and calcining to obtain pretreated siliconAlgae soil;
(b) Adding the pretreated diatomite in the step (a) into toluene, then adding gamma-aminopropyl triethoxysilane and sodium dodecyl sulfonate, then stirring for reaction, and filtering and drying after the reaction is finished to obtain modified diatomite;
(c) Drying the polyether-ether-ketone powder at 100-120 ℃ for 3-5 hours, then uniformly mixing the powder with the modified diatomite in the step (b), adding the mixture into a double-screw extruder for granulating to obtain polyether-ether-ketone master batch, drying the master batch at 120 ℃ for 4 hours, and carrying out melt spinning to obtain the polyether-ether-ketone fiber.
5. The penetration-resistant fabric for fencing as in claim 4, wherein in step (a) the mass concentration of said ammonia solution is 10-15%, said diatomite, ammonia solution, alCl 3 The mass ratio of (2) is 10:150-200:5-10, the calcining temperature is 400-500 ℃, and the calcining time is 1-2h; the mass ratio of the pretreated diatomite, the gamma-aminopropyl triethoxysilane and the sodium dodecyl sulfonate in the step (b) is 100:5-8:1-3, the temperature of the stirring reaction is 90-100 ℃, and the reaction time is 4-5h; the mass ratio of the polyether-ether-ketone powder to the modified diatomite in the step (c) is 100:10-15; the titer of the polyether-ether-ketone fiber is 380-420D.
6. The penetration-resistant fabric for fencing as in claim 1, wherein said modified inorganic fiber is prepared by a process comprising the steps of:
s1, uniformly mixing glass fibers, carbon fibers and silicon carbide whiskers, then adding the mixture into a potassium permanganate solution, soaking the mixture for 4 to 6 hours at room temperature, and filtering and drying the mixture after the soaking is finished to obtain pretreated mixed fibers;
S2, adding the pretreated fiber in the step S1 into toluene, then adding gamma-mercaptopropyl trimethoxy silane, stirring for reaction, and filtering and drying after the reaction is finished to obtain a mercapto compound fiber;
and S3, adding the sulfhydrylation mixed fiber obtained in the step S2 into absolute ethyl alcohol, then adding succinic anhydride and tertiary glycidyl ester, carrying out constant-temperature reaction, and filtering, washing, drying and ball-milling after the reaction is finished to obtain the modified inorganic fiber.
7. The penetration-resistant fabric for fencing according to claim 6, wherein the mass concentration of the potassium permanganate in the step S1 is 3-6%; the mass ratio of the glass fiber to the carbon fiber to the silicon carbide whisker is 10:2-4:5-8; the mass ratio of the pretreated fibers to the gamma-mercaptopropyl trimethoxy silane in the step S2 is 100:4-8, the temperature of the stirring reaction is 80-90 ℃, and the reaction time is 3-5h; in the step S3, the mass ratio of the sulfhydrylation mixed fiber to the succinic anhydride to the tertiary glycidyl ester is 100:5-10:5-10, the constant temperature reaction temperature is 60-80 ℃, the reaction time is 2-4h, the ball milling rotating speed is 1500-2500r/min, and the ball milling time is 1-2h.
8. A method of making a penetration resistant fabric for fencing as claimed in any one of claims 1 to 7, comprising the steps of:
(1) Preparation of a base cloth layer: twisting polyester fiber and polypropylene fiber, controlling the twist to be 80-90 twist/cm, warping the twisted polyester fiber and polypropylene fiber, weaving by a double-sided knitting circular knitting machine after warping, wherein the yarn feeding number of the polyester fiber is the same as the yarn feeding number of the polypropylene fiber, and weaving to obtain a base cloth layer;
(2) Preparation of puncture-preventing layer: the warp yarn is formed by twisting ultra-high molecular weight polyethylene fibers and polyether-ether-ketone fibers according to the proportion of 1:1, 6-12 fibers are twisted into yarn, and the twist is 50-150 twists/cm; the weft yarn is formed by twisting ultra-high molecular weight polyethylene fibers and aramid fibers according to the proportion of 1:1, 6-18 fibers are twisted into yarn, and the twist is 50-150 twists/cm; weaving the warp yarns and the weft yarns, wherein the density of the warp yarns and the weft yarns is 200-250 pieces/10 cm, and the density of the weft yarns is 160-200 pieces/10 cm, so that a puncture-preventing layer is obtained;
(3) Preparation of the coating liquid: weighing raw materials according to weight, adding thermoplastic polyurethane into N, N-dimethylformamide, stirring and dissolving at 90 ℃, cooling to room temperature, then adding epoxy resin, modified inorganic fibers and sodium dodecyl benzene sulfonate, stirring for 15-30min, finally adding diethylaminopropylamine, and uniformly mixing to obtain the coating liquid;
(4) Preparation of puncture-resistant fabric: and (3) putting the base cloth layer in the step (1) and the stab-resistant layer in the step (2) into a finishing agent for dipping, drying and shaping after the dipping is finished, then using an adhesive to bond the stab-resistant layer on the surface of the base cloth layer, drying, coating a coating liquid on the surface of the stab-resistant layer after the drying is finished, and heating and curing after the coating is finished to obtain the stab-resistant fabric for fencing.
9. The method for producing a penetration-resistant fabric for fencing according to claim 8, wherein the method for producing the finishing agent in the step (4) is as follows: uniformly mixing 55-70 parts of perfluorohexyl ethyl methyl acrylate, 6-9 parts of dodecyl trimethyl ammonium sulfate, 5-10 parts of methyltrimethoxysilane, 4-7 parts of polyvinylpyrrolidone and 3-6 parts of p-tert-butylbenzoic acid, stirring for 30-50min at 50-60 ℃, then adding 3-5 parts of fatty alcohol polyoxyethylene ether AEO-9, 10-15 parts of zinc stearate, 1-4 parts of tween 80 and 2-5 parts of lauryldiacid, finally adding 200-250 parts of deionized water, and continuously stirring and mixing for 20-30min at 65-75 ℃ to obtain the finishing agent.
10. The method for producing a penetration-resistant fabric for fencing according to claim 8, wherein the temperature of the impregnation in the step (4) is 40-60 ℃ and the impregnation time is 4-7 hours; the temperature of the drying and shaping is 60-80 ℃ and the drying time is 5-8h; the drying temperature is 70-90 ℃ and the drying time is 3-5h; the coating weight is 150-200g/m 2 The curing condition is that the curing is carried out for 1-2 hours at 60-80 ℃.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105167268A (en) * 2015-05-25 2015-12-23 袁明富 Lightweight high-strength fabric for fencing protective clothing and preparation process thereof
CN105231565A (en) * 2015-10-20 2016-01-13 杭州华水布艺有限公司 Stab-resistant protective fabric comprising ice-cold material
CN111455540A (en) * 2020-05-17 2020-07-28 宜春希宇生物制品有限公司 Skin-friendly light high-strength fabric and preparation process thereof
CN113529428A (en) * 2021-08-03 2021-10-22 东台市东驰服装有限公司 Wear-resistant and puncture-resistant fabric and processing technology thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105167268A (en) * 2015-05-25 2015-12-23 袁明富 Lightweight high-strength fabric for fencing protective clothing and preparation process thereof
CN105231565A (en) * 2015-10-20 2016-01-13 杭州华水布艺有限公司 Stab-resistant protective fabric comprising ice-cold material
CN111455540A (en) * 2020-05-17 2020-07-28 宜春希宇生物制品有限公司 Skin-friendly light high-strength fabric and preparation process thereof
CN113529428A (en) * 2021-08-03 2021-10-22 东台市东驰服装有限公司 Wear-resistant and puncture-resistant fabric and processing technology thereof

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