CN113237386B - Composite multilayer bulletproof stab-resistant fabric and preparation method thereof - Google Patents

Composite multilayer bulletproof stab-resistant fabric and preparation method thereof Download PDF

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Publication number
CN113237386B
CN113237386B CN202110433958.XA CN202110433958A CN113237386B CN 113237386 B CN113237386 B CN 113237386B CN 202110433958 A CN202110433958 A CN 202110433958A CN 113237386 B CN113237386 B CN 113237386B
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fabric
plain weave
polyethylene
stab
drying
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CN113237386A (en
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韩国方
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Zhejiang Tianyuan Fabric Co ltd
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Zhejiang Tianyuan Fabric Co ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H1/00—Personal protection gear
    • F41H1/02—Armoured or projectile- or missile-resistant garments; Composite protection fabrics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2571/00—Protective equipment
    • B32B2571/02—Protective equipment defensive, e.g. armour plates, anti-ballistic 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

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Woven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention provides a composite multilayer bulletproof stab-resistant fabric and a preparation method thereof, wherein the composite multilayer bulletproof stab-resistant fabric is obtained by overlapping and stitching sheets, and the sheets are prepared by the following steps: firstly, preparing polyethylene with the viscosity average molecular weight of 200-300 ten thousand into polyethylene fibers; then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber; twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics; uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, introducing methane-hydrogen mixed gas, and carrying out microwave treatment to obtain a surface-modified fabric; and finally, putting the surface-modified fabric into impregnating solution, impregnating, drying and hot-pressing to obtain the finished product. The fabric has good bulletproof and stab-proof effects and good softness.

Description

Composite multilayer bulletproof stab-resistant fabric and preparation method thereof
Technical Field
The invention relates to the technical field of protective articles, in particular to a composite multilayer bulletproof stab-resistant fabric and a preparation method thereof.
Background
The existing individual soldier protective component (or antiriot suit) mainly depends on the combination of an external injection molding piece (made of high-quality high-strength engineering plastics) and a buffer lining (made of soft energy absorbing materials) to resist external impact energy in the design thought, and has a certain limitation on the protection degree of important organs of a human body. The protective clothing is protected by cloth with a certain thickness (such as common nylon fiber fabric), and the life safety of national staff and people is difficult to ensure.
The bulletproof material and the stab-resistant material have obvious differences in protection mechanisms, the main energy absorption modes of the bulletproof material are fiber elastic deformation and tensile fracture, the main energy absorption modes of the stab-resistant material are knife tip bursting and fiber shearing fracture, and the two different energy absorption modes determine obvious differences in the design of the bulletproof material and the stab-resistant material. The bulletproof material is mostly high-strength fiber unidirectional cloth or fabric lamination with low resin content, soft in texture and easy to deform, and the stab-resistant material is mostly high-strength fiber fabric composite material with high resin content or metal net. Therefore, the preparation of the bulletproof and stab-resistant material needs to have the advantages of both materials.
The stab-resistant clothing can be divided into three types of hardness, semi-hardness and flexibility according to the softness of the stab-resistant clothing protective material. The protective material of the hard stab-resistant clothing is generally formed by overlapping metal materials or metal sheets, but the stab-resistant clothing of the hard alloy plate protective layer has poor elastic resistance, and the weight of the hard alloy plate protective layer exceeds the standard requirement of 3.5 kg unless the hard alloy plate protective layer reaches a certain thickness. The semi-hard is generally laminated and compounded by adopting fiber materials such as high-strength polyethylene, aramid fiber, carbon fiber and the like and high polymer resin, and the softness of the stab-resistant layer is greatly reduced after the layers are overlapped. The soft bulletproof clothes are characterized in that a protective layer is arranged between the fabric and the inside of the clothes, the protective layer is generally formed by overlapping and sewing tens of layers of special fiber plain woven fabrics or non-woven fabrics formed by unidirectionally arranging and bonding tens of layers of special fibers into a whole, or sewing the layers into parts in groups, sewing the protective layer into the inside by using outer striking surface cloth and inner lining cloth, and finally assembling the bulletproof clothes. Compared with hard material such as metal, the body armor is comfortable, portable and has better bulletproof effect. However, such body armor made of plain woven fabrics woven from warp and weft or laid fabrics bonded by an adhesive in an orthogonal unidirectional arrangement is likely to be penetrated by a cone-shaped murder or a sharp knife, and therefore, these low-level body armor are excellent in ballistic performance but cannot be stab-resistant.
Patent application CN101762210a discloses a method for manufacturing bulletproof stab-resistant clothing and protective layer thereof, the bulletproof stab-resistant clothing comprises a front piece and a rear piece of protective vest composed of a fabric, a clothing lining, a plurality of mutually connected hard special alloy plates and a plurality of layers of special fiber cloth protective layers which are sequentially arranged between the fabric and the clothing lining, wherein the special fiber cloth protective layers comprise hard fiber cloth protective plates which are respectively cured on the hard special alloy plates in a hot pressing way and flexible special fiber cloth protective layers which are positioned at the connecting positions of the hard special alloy plates. The technology relies on a hard special alloy plate, has poor softness and poor wearing experience.
Disclosure of Invention
The invention aims to provide a composite multilayer bulletproof stab-resistant fabric and a preparation method thereof, which have good bulletproof stab-resistant effect and good softness.
In order to achieve the above purpose, the invention is realized by the following scheme:
the preparation method of the composite multilayer bulletproof stab-resistant fabric is characterized in that the fabric is formed by superposing and sewing 5-7 layers of sheets, and the sheets are prepared by the following steps:
(1) Firstly, preparing polyethylene with the viscosity average molecular weight of 200-300 ten thousand into polyethylene fibers;
(2) Then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber;
(3) Twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics;
(4) Uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, and introducing the carbon nanotubes into the vacuum-pumping closed space according to the volume ratio of 4:1, carrying out 400-500W microwave treatment on the methane-hydrogen mixed gas for 2-3 minutes to obtain a surface modified fabric;
(5) Finally, putting the surface-modified fabric into impregnating solution, impregnating, drying and hot-pressing to obtain the sheet;
the impregnating solution is prepared by uniformly oscillating the following components in parts by weight by ultrasonic wave: 1 part of nano glass fiber powder, 3-5 parts of polyethylene glycol 4003-10 parts of ethanol.
Preferably, the polyethylene fiber is prepared as follows: adding polyethylene fiber into decalin to prepare a solution with the mass concentration of 10-12%, extruding the solution through a circular spinneret plate to form spinning trickle, and sequentially carrying out flash evaporation, cooling and solidification to form spinning fine yarn, and carrying out post-treatment to obtain the polyethylene fiber.
Further preferably, the specific method of flash evaporation is as follows: entering a cylinder filled with nitrogen, wherein the temperature in the cylinder is 120-140 ℃, so that the steamed decalin is extracted from the cylinder along with the nitrogen; the concrete method for cooling and solidifying comprises the following steps: and the mixture enters a cooling box containing purified water at the temperature of 8-10 ℃ for 2000-2300 mm.
More preferably, the spinneret plate has an area of 50 to 55cm 2 The hole number is 1000-1200, the area ratio of the spinneret plate to the bottom surface of the cylinder is 1:1.5 to 2, the length of the cylinder is 0.2 to 0.3 times of the diameter of the bottom surface of the cylinder.
Further preferably, the specific method of post-treatment is as follows: extruding by a compression roller with the pressure of 0.5-0.6 MPa, extruding by a scraper with the pressure of 0.2-0.3 MPa, and drying for 3-4 hours at the temperature of 100-110 ℃.
Preferably, in the step (2), the preparation method of the mixed solution is as follows: adding polyvinyl butyral resin into aqueous polyurethane resin with 5-7 times of solid content and 5-7% of weight, stirring and emulsifying for 2-3 hours at 10000-12000 r/min to obtain the final product.
Preferably, in step (2), the process conditions for the impregnation are: ultrasonic oscillation of 300-500W for 5-8 min.
Preferably, in the step (2), the drying process conditions are as follows: and drying at 100-110 deg.c for 4-6 hr.
Preferably, in the step (3), the plain weave fabric has a wale count of 78 to 80 wales/10 cm and a wale count of 95 to 98 courses/10 cm.
Preferably, in the step (4), the carbon nanotube spraying amount of each surface is 0.1 to 0.2% by weight of the plain weave fabric.
Preferably, in the step (4), the initial vacuum degree in the closed space is 1×10 -3 Pa, the vacuum degree is 1 multiplied by 10 after the mixed gas is introduced -1 Pa。
Preferably, in step (5), the process conditions for the impregnation are: ultrasonic oscillation of 300-400W for 20-30 min.
Preferably, in the step (5), the drying process conditions are as follows: drying at 80-90 deg.c for 5-7 hr.
Preferably, in the step (5), the hot pressing process conditions are as follows: the treatment is carried out for 20 to 30 minutes at 160 to 170 ℃ and 3 to 5 MPa.
The composite multilayer bulletproof stab-resistant fabric is obtained by the preparation method.
The beneficial effects of the invention are as follows:
the invention discloses a composite multilayer bulletproof stab-resistant fabric which is obtained by using sheet material superposition stitching, wherein the sheet material is prepared by the following steps: firstly, preparing polyethylene with the viscosity average molecular weight of 200-300 ten thousand into polyethylene fibers; then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber; twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics; uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, introducing methane-hydrogen mixed gas, and carrying out microwave treatment to obtain a surface-modified fabric; and finally, putting the surface-modified fabric into impregnating solution, impregnating, drying and hot-pressing to obtain the finished product. The fabric has good bulletproof and stab-proof effects and good softness.
The main raw material of the invention is polyethylene fiber, has high molecular weight and has certain bulletproof and stab-proof effects. The polyvinyl fibers are soaked by the mixed liquid of the polyvinyl butyral resin and the aqueous polyurethane resin and then interwoven into the fabric, so that the polyvinyl butyral resin and the aqueous polyurethane resin are wrapped on the surfaces of the polyvinyl fibers, and the bulletproof and stab-proof effects of the polyvinyl fibers are improved.
And spraying carbon nano tubes on two surfaces of the plain weave fabric, and depositing a carbon nano tube layer on the surfaces of the plain weave fabric to form a buffer space between sheets, so that the bulletproof and stab-proof effects are further improved. The surface-modified fabric is finally immersed by the immersion liquid, so that the surface and the inside of the sheet are filled with the nano glass fiber powder, the filling and buffering effects are achieved, and the bulletproof and stab-proof effects of the sheet are further improved.
The sheet material single sheet has good bulletproof and stab-proof effects, and the better bulletproof and stab-proof effects can be realized only by overlapping 5-7 sheet materials.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but 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.
Example 1
The preparation method of the composite multilayer bulletproof stab-resistant fabric is characterized in that the fabric is formed by superposing and sewing 5 layers of sheets, and the sheets are prepared by the following steps:
(1) Firstly, preparing polyethylene with the viscosity average molecular weight of 300 ten thousand into polyethylene fibers;
(2) Then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber;
(3) Twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics;
(4) Uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, and introducing the carbon nanotubes into the vacuum-pumping closed space according to the volume ratio of 4:1, carrying out 400W microwave treatment on the methane-hydrogen mixed gas for 3 minutes to obtain a surface modified fabric;
(5) Finally, putting the surface-modified fabric into impregnating solution, impregnating, drying and hot-pressing to obtain the sheet;
the impregnating solution is prepared by uniformly oscillating the following components in parts by weight by ultrasonic wave: 1kg of nano glass fiber powder, 4003kg of polyethylene glycol and 10kg of ethanol.
The preparation method of the polyethylene fiber comprises the following steps: adding polyethylene fiber into decalin to prepare a solution with the mass concentration of 10%, extruding the solution through a circular spinneret plate to form spinning thin flow, and sequentially carrying out flash evaporation, cooling and solidification to form spinning thin yarn, and carrying out post-treatment to obtain the polyethylene fiber.
The specific method for flash evaporation comprises the following steps: entering a cylinder filled with nitrogen, wherein the temperature in the cylinder is 120 ℃, so that the steamed decalin is extracted from the cylinder along with the nitrogen; the concrete method for cooling and solidifying comprises the following steps: and the mixture enters a cooling box containing purified water at the temperature of 10 ℃ for 2000mm in stroke.
The area of the spinneret plate is 55cm 2 The number of holes is 1000, and the spinning is performedThe area ratio of the plate to the bottom surface of the cylinder is 1:2, the length of the cylinder is 0.2 times of the diameter of the bottom surface.
The specific method for post-treatment comprises the following steps: extruding by a 0.6MPa press roller, extruding by a 0.2MPa scraper, and drying for 3 hours at 110 ℃.
In the step (2), the preparation method of the mixed solution comprises the following steps: adding polyvinyl butyral resin into aqueous polyurethane resin with solid content of 5% and weight of 7 times of the polyvinyl butyral resin, stirring and emulsifying for 2 hours at 12000r/min to obtain the polyvinyl butyral resin.
In the step (2), the dipping process conditions are as follows: 500W ultrasonic wave was oscillated for 5 minutes.
In the step (2), the drying process conditions are as follows: oven dried at 110deg.C for 4 hr.
In the step (3), the plain weave fabric has a wale density of 80 wales/10 cm and a wale density of 95 courses/10 cm.
In the step (4), the sprayed amount of the carbon nanotubes on each surface was 0.2% of the weight of the plain weave fabric.
In the step (4), the initial vacuum degree in the closed space is 1×10 -3 Pa, the vacuum degree is 1 multiplied by 10 after the mixed gas is introduced -1 Pa。
In the step (5), the dipping process conditions are as follows: ultrasonic oscillation was performed at 300W for 30 minutes.
In the step (5), the drying process conditions are as follows: oven dried at 80deg.C for 7 hr.
In the step (5), the hot pressing process conditions are as follows: the treatment is carried out for 20 minutes at 160℃and 5 MPa.
Example 2
The preparation method of the composite multilayer bulletproof stab-resistant fabric is characterized in that the fabric is formed by superposing and sewing 6 layers of sheets, and the sheets are prepared by the following steps:
(1) Firstly, preparing polyethylene with the viscosity average molecular weight of 200 ten thousand into polyethylene fibers;
(2) Then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber;
(3) Twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics;
(4) Uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, and introducing the carbon nanotubes into the vacuum-pumping closed space according to the volume ratio of 4:1, carrying out 500W microwave treatment on the methane-hydrogen mixed gas for 2 minutes to obtain a surface modified fabric;
(5) Finally, putting the surface-modified fabric into impregnating solution, impregnating, drying and hot-pressing to obtain the sheet;
the impregnating solution is prepared by uniformly oscillating the following components in parts by weight by ultrasonic wave: 1kg of nano glass fiber powder, 4005kg of polyethylene glycol and 8kg of ethanol.
The preparation method of the polyethylene fiber comprises the following steps: adding polyethylene fiber into decalin to prepare a solution with the mass concentration of 12%, extruding the solution through a circular spinneret plate to form spinning thin flow, and sequentially carrying out flash evaporation, cooling and solidification to form spinning thin yarn, and carrying out post-treatment to obtain the polyethylene fiber.
The specific method for flash evaporation comprises the following steps: entering a cylinder filled with nitrogen, wherein the temperature in the cylinder is 140 ℃, so that the flashed decalin is extracted from the cylinder along with the nitrogen; the concrete method for cooling and solidifying comprises the following steps: putting into a cooling box containing purified water at 8 ℃ for 2300mm of travel.
The area of the spinneret plate is 50cm 2 The hole number is 1200, and the area ratio of the spinneret plate to the bottom surface of the cylinder is 1:1.5, the length of the cylinder is 0.3 times the diameter of the bottom surface.
The specific method for post-treatment comprises the following steps: extruding by a 0.5MPa press roller, extruding by a 0.3MPa scraper, and drying for 4 hours at 100 ℃.
In the step (2), the preparation method of the mixed solution comprises the following steps: adding polyvinyl butyral resin into aqueous polyurethane resin with solid content of 7% which is 5 times of the polyvinyl butyral resin, stirring and emulsifying for 3 hours at 10000r/min to obtain the polyvinyl butyral resin.
In the step (2), the dipping process conditions are as follows: ultrasonic oscillation was performed at 300W for 8 minutes.
In the step (2), the drying process conditions are as follows: oven-dried at 100deg.C for 6 hr.
In the step (3), the plain weave fabric has a wale/10 cm of 78 and a wale/10 cm of 98.
In the step (4), the sprayed amount of the carbon nanotubes on each surface was 0.1% by weight of the plain weave fabric.
In the step (4), the initial vacuum degree in the closed space is 1×10 -3 Pa, the vacuum degree is 1 multiplied by 10 after the mixed gas is introduced -1 Pa。
In the step (5), the dipping process conditions are as follows: ultrasonic oscillation was performed at 400W for 20 minutes.
In the step (5), the drying process conditions are as follows: drying at 90 ℃ for 5 hours.
In the step (5), the hot pressing process conditions are as follows: the treatment was carried out at 170℃and 3MPa for 30 minutes.
Example 3
The preparation method of the composite multilayer bulletproof stab-resistant fabric is characterized in that the fabric is formed by overlapping and sewing 7 layers of sheets, and the sheets are prepared by the following steps:
(1) Firstly, preparing polyethylene with the viscosity average molecular weight of 250 ten thousand into polyethylene fibers;
(2) Then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber;
(3) Twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics;
(4) Uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, and introducing the carbon nanotubes into the vacuum-pumping closed space according to the volume ratio of 4:1, carrying out 450W microwave treatment on the methane-hydrogen mixed gas for 2.5 minutes to obtain a surface modified fabric;
(5) Finally, putting the surface-modified fabric into impregnating solution, impregnating, drying and hot-pressing to obtain the sheet;
the impregnating solution is prepared by uniformly oscillating the following components in parts by weight by ultrasonic wave: 1kg of nano glass fiber powder, 4004kg of polyethylene glycol and 9kg of ethanol.
The preparation method of the polyethylene fiber comprises the following steps: adding polyethylene fiber into decalin to prepare a solution with the mass concentration of 11%, extruding the solution through a circular spinneret plate to form spinning thin flow, and sequentially carrying out flash evaporation, cooling and solidification to form spinning thin yarn, and carrying out post-treatment to obtain the polyethylene fiber.
The specific method for flash evaporation comprises the following steps: entering a cylinder filled with nitrogen, wherein the temperature in the cylinder is 130 ℃, so that the flashed decalin is extracted from the cylinder along with the nitrogen; the concrete method for cooling and solidifying comprises the following steps: enters a cooling box containing purified water at 9 ℃ and has a stroke of 2200mm.
The area of the spinneret plate is 53cm 2 The hole number is 1100, the area ratio of the spinneret plate to the bottom surface of the cylinder is 1: 1.8, the length of the cylinder is 0.25 times the diameter of the bottom surface thereof.
The specific method for post-treatment comprises the following steps: extruding by a 0.55MPa press roller, extruding by a 0.25MPa scraper, and drying for 3.5 hours at 105 ℃.
In the step (2), the preparation method of the mixed solution comprises the following steps: adding polyvinyl butyral resin into aqueous polyurethane resin with 6% of solid content and 6% of 6 times of the weight of the polyvinyl butyral resin, stirring and emulsifying for 2.5 hours at 11000r/min to obtain the polyvinyl butyral resin.
In the step (2), the dipping process conditions are as follows: ultrasonic oscillation was performed at 400W for 6 minutes.
In the step (2), the drying process conditions are as follows: drying at 105 ℃ for 5 hours.
In the step (3), the plain weave fabric has a wale density of 79 wales/10 cm and a wale density of 97 courses/10 cm.
In the step (4), the sprayed amount of the carbon nanotubes on each surface was 0.15% by weight of the plain weave fabric.
In the step (4), the initial vacuum degree in the closed space is 1×10 -3 Pa, the vacuum degree is 1 multiplied by 10 after the mixed gas is introduced -1 Pa。
In the step (5), the dipping process conditions are as follows: ultrasonic oscillation at 400W for 25 minutes.
In the step (5), the drying process conditions are as follows: oven-dried at 85deg.C for 6 hr.
In the step (5), the hot pressing process conditions are as follows: the treatment is carried out for 25 minutes at 165℃and 4 MPa.
Comparative example 1
The preparation method of the composite multilayer bulletproof stab-resistant fabric is characterized in that the fabric is formed by superposing and sewing 5 layers of sheets, and the sheets are prepared by the following steps:
(1) Firstly, preparing polyethylene with the viscosity average molecular weight of 300 ten thousand into polyethylene fibers;
(2) Twisting polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics;
(3) Uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, and introducing the carbon nanotubes into the vacuum-pumping closed space according to the volume ratio of 4:1, carrying out 400W microwave treatment on the methane-hydrogen mixed gas for 3 minutes to obtain a surface modified fabric;
(4) Finally, putting the surface-modified fabric into impregnating solution, impregnating, drying and hot-pressing to obtain the sheet;
the impregnating solution is prepared by uniformly oscillating the following components in parts by weight by ultrasonic wave: 1kg of nano glass fiber powder, 4003kg of polyethylene glycol and 10kg of ethanol.
The preparation method of the polyethylene fiber comprises the following steps: adding polyethylene fiber into decalin to prepare a solution with the mass concentration of 10%, extruding the solution through a circular spinneret plate to form spinning thin flow, and sequentially carrying out flash evaporation, cooling and solidification to form spinning thin yarn, and carrying out post-treatment to obtain the polyethylene fiber.
The specific method for flash evaporation comprises the following steps: entering a cylinder filled with nitrogen, wherein the temperature in the cylinder is 120 ℃, so that the steamed decalin is extracted from the cylinder along with the nitrogen; the concrete method for cooling and solidifying comprises the following steps: and the mixture enters a cooling box containing purified water at the temperature of 10 ℃ for 2000mm in stroke.
The area of the spinneret plate is 55cm 2 The hole number is 1000, and the area ratio of the spinneret plate to the bottom surface of the cylinder is 1:2, the length of the cylinder is 0.2 times of the diameter of the bottom surface.
The specific method for post-treatment comprises the following steps: extruding by a 0.6MPa press roller, extruding by a 0.2MPa scraper, and drying for 3 hours at 110 ℃.
In the step (2), the plain weave fabric has a wale density of 80 wales/10 cm and a wale density of 95 courses/10 cm.
In the step (3), the sprayed amount of the carbon nanotubes on each surface was 0.2% by weight of the plain weave fabric.
In the step (3), the initial vacuum degree in the closed space is 1×10 -3 Pa, the vacuum degree is 1 multiplied by 10 after the mixed gas is introduced -1 Pa。
In the step (4), the dipping process conditions are as follows: ultrasonic oscillation was performed at 300W for 30 minutes.
In the step (4), the drying process conditions are as follows: oven dried at 80deg.C for 7 hr.
In the step (4), the hot pressing process conditions are as follows: the treatment is carried out for 20 minutes at 160℃and 5 MPa.
Comparative example 2
The preparation method of the composite multilayer bulletproof stab-resistant fabric is characterized in that the fabric is formed by superposing and sewing 5 layers of sheets, and the sheets are prepared by the following steps:
(1) Firstly, preparing polyethylene with the viscosity average molecular weight of 300 ten thousand into polyethylene fibers;
(2) Then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber;
(3) Twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics;
(4) Finally, the plain weave fabric is put into impregnating solution, impregnated, dried and hot pressed, and the sheet is obtained;
the impregnating solution is prepared by uniformly oscillating the following components in parts by weight by ultrasonic wave: 1kg of nano glass fiber powder, 4003kg of polyethylene glycol and 10kg of ethanol.
The preparation method of the polyethylene fiber comprises the following steps: adding polyethylene fiber into decalin to prepare a solution with the mass concentration of 10%, extruding the solution through a circular spinneret plate to form spinning thin flow, and sequentially carrying out flash evaporation, cooling and solidification to form spinning thin yarn, and carrying out post-treatment to obtain the polyethylene fiber.
The specific method for flash evaporation comprises the following steps: entering a cylinder filled with nitrogen, wherein the temperature in the cylinder is 120 ℃, so that the steamed decalin is extracted from the cylinder along with the nitrogen; the concrete method for cooling and solidifying comprises the following steps: and the mixture enters a cooling box containing purified water at the temperature of 10 ℃ for 2000mm in stroke.
The area of the spinneret plate is 55cm 2 The hole number is 1000, and the area ratio of the spinneret plate to the bottom surface of the cylinder is 1:2, the length of the cylinder is 0.2 times of the diameter of the bottom surface.
The specific method for post-treatment comprises the following steps: extruding by a 0.6MPa press roller, extruding by a 0.2MPa scraper, and drying for 3 hours at 110 ℃.
In the step (2), the preparation method of the mixed solution comprises the following steps: adding polyvinyl butyral resin into aqueous polyurethane resin with solid content of 5% and weight of 7 times of the polyvinyl butyral resin, stirring and emulsifying for 2 hours at 12000r/min to obtain the polyvinyl butyral resin.
In the step (2), the dipping process conditions are as follows: 500W ultrasonic wave was oscillated for 5 minutes.
In the step (2), the drying process conditions are as follows: oven dried at 110deg.C for 4 hr.
In the step (3), the plain weave fabric has a wale density of 80 wales/10 cm and a wale density of 95 courses/10 cm.
In the step (4), the dipping process conditions are as follows: ultrasonic oscillation was performed at 300W for 30 minutes.
In the step (4), the drying process conditions are as follows: oven dried at 80deg.C for 7 hr.
In the step (4), the hot pressing process conditions are as follows: the treatment is carried out for 20 minutes at 160℃and 5 MPa.
Comparative example 3
The preparation method of the composite multilayer bulletproof stab-resistant fabric is characterized in that the fabric is formed by superposing and sewing 5 layers of sheets, and the sheets are prepared by the following steps:
(1) Firstly, preparing polyethylene with the viscosity average molecular weight of 300 ten thousand into polyethylene fibers;
(2) Then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber;
(3) Twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics;
(4) Uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, and introducing the carbon nanotubes into the vacuum-pumping closed space according to the volume ratio of 4:1, and carrying out 400W microwave treatment on the mixed gas of methane and hydrogen for 3 minutes to obtain the sheet.
The preparation method of the polyethylene fiber comprises the following steps: adding polyethylene fiber into decalin to prepare a solution with the mass concentration of 10%, extruding the solution through a circular spinneret plate to form spinning thin flow, and sequentially carrying out flash evaporation, cooling and solidification to form spinning thin yarn, and carrying out post-treatment to obtain the polyethylene fiber.
The specific method for flash evaporation comprises the following steps: entering a cylinder filled with nitrogen, wherein the temperature in the cylinder is 120 ℃, so that the steamed decalin is extracted from the cylinder along with the nitrogen; the concrete method for cooling and solidifying comprises the following steps: and the mixture enters a cooling box containing purified water at the temperature of 10 ℃ for 2000mm in stroke.
The area of the spinneret plate is 55cm 2 The hole number is 1000, and the area ratio of the spinneret plate to the bottom surface of the cylinder is 1:2, the length of the cylinder is 0.2 times of the diameter of the bottom surface.
The specific method for post-treatment comprises the following steps: extruding by a 0.6MPa press roller, extruding by a 0.2MPa scraper, and drying for 3 hours at 110 ℃.
In the step (2), the preparation method of the mixed solution comprises the following steps: adding polyvinyl butyral resin into aqueous polyurethane resin with solid content of 5% and weight of 7 times of the polyvinyl butyral resin, stirring and emulsifying for 2 hours at 12000r/min to obtain the polyvinyl butyral resin.
In the step (2), the dipping process conditions are as follows: 500W ultrasonic wave was oscillated for 5 minutes.
In the step (2), the drying process conditions are as follows: oven dried at 110deg.C for 4 hr.
In the step (3), the plain weave fabric has a wale density of 80 wales/10 cm and a wale density of 95 courses/10 cm.
In the step (4), the sprayed amount of the carbon nanotubes on each surface was 0.2% of the weight of the plain weave fabric.
In the step (4), the initial vacuum degree in the closed space is 1×10 -3 Pa, the vacuum degree is 1 multiplied by 10 after the mixed gas is introduced -1 Pa。
Test examples
The softness of the fabrics obtained in examples 1 to 3 was examined, and the results are shown in Table 1. And (3) testing by adopting a three-point bending method, taking a 34cm multiplied by 5cm fabric sample, placing two ends of the fabric sample on a bending clamp, enabling the distance between two clamp points to be 30cm, naturally hanging the fabric, and measuring the hanging height H of the central point of the fabric.
TABLE 1 examination of softness
Height H (cm)
Example 1 5.9
Example 2 5.8
Example 3 6.1
The ballistic and stab resistant effects of the fabrics obtained in examples 1 to 3 and comparative examples 1 to 3 were examined and the results are shown in table 2. The ballistic test used 1.1g fsp, the content of the test was V50, i.e. the rate of penetration was 50%. The puncture protection test is referenced NIJ 0115.00.
TABLE 2 investigation of ballistic and stab protection effects
Bulletproof (m/s) Puncture-proof device
Example 1 881 Grade 3
Example 2 883 Grade 3
Example 3 889 Grade 3
Comparative example 1 767 Class 2
Comparative example 2 704 Grade 1
Comparative example 3 722 Class 2
As is clear from tables 1 and 2, the fabrics obtained in examples 1 to 3 were excellent in flexibility and had excellent ballistic and stab resistance.
Step (2) is omitted in comparative example 1, step (4) is omitted in comparative example 2, step (5) is omitted in comparative example 3, and the bulletproof and stab-resistant effects of the obtained fabric are obviously deteriorated, which means that the resin treatment of the fiber and the surface modification of the carbon nano tube and the impregnation of the impregnating solution synergistically improve the bulletproof and stab-resistant effects of the product.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.

Claims (10)

1. The preparation method of the composite multilayer bulletproof stab-resistant fabric is characterized by comprising 5-7 layers of sheets in a superposition and stitching mode, and the sheets are prepared by the following steps:
(1) Firstly, preparing polyethylene with the viscosity average molecular weight of 200-300 ten thousand into polyethylene fibers;
(2) Then, putting the polyethylene fiber into the mixed liquid of polyvinyl butyral resin and aqueous polyurethane resin, dipping and drying to obtain pretreated polyethylene fiber;
(3) Twisting the pretreated polyethylene fibers into warp yarns and weft yarns, and interweaving the warp yarns and the weft yarns into plain weave fabrics;
(4) Uniformly spraying carbon nanotubes on two surfaces of the plain weave fabric, transferring the plain weave fabric into a vacuum-pumping closed space, and introducing the carbon nanotubes into the vacuum-pumping closed space according to the volume ratio of 4:1, carrying out 400-500W microwave treatment on the methane-hydrogen mixed gas for 2-3 minutes to obtain a surface modified fabric;
(5) Finally, putting the surface-modified fabric into impregnating solution, impregnating, drying and hot-pressing to obtain the sheet;
the impregnating solution is prepared by uniformly oscillating the following components in parts by weight by ultrasonic wave: 1 part of nano glass fiber powder, 3-5 parts of polyethylene glycol 4003-10 parts of ethanol.
2. The method of producing polyethylene fiber according to claim 1, wherein the method of producing polyethylene fiber comprises: adding polyethylene fiber into decalin to prepare a solution with the mass concentration of 10-12%, extruding the solution through a circular spinneret plate to form spinning trickle, and sequentially carrying out flash evaporation, cooling and solidification to form spinning fine yarn, and carrying out post-treatment to obtain the polyethylene fiber.
3. The method according to claim 1, wherein in the step (2), the method for preparing the mixed liquid comprises the steps of: adding polyvinyl butyral resin into aqueous polyurethane resin with 5-7 times of solid content and 5-7% of weight, stirring and emulsifying for 2-3 hours at 10000-12000 r/min to obtain the final product.
4. The method according to claim 1, wherein in the step (2), the process conditions for impregnation are: ultrasonic oscillation of 300-500W for 5-8 min.
5. The method according to claim 1, wherein in the step (2), the process conditions of drying are: and drying at 100-110 deg.c for 4-6 hr.
6. The method according to claim 1, wherein in the step (3), the plain weave fabric has a wale-tightness of 78 to 80 wales/10 cm and a wale-tightness of 95 to 98 courses/10 cm.
7. The method of claim 1, wherein the carbon nanotubes are sprayed on each surface in the step (4) in an amount of 0.1 to 0.2% by weight of the plain weave fabric.
8. The method according to claim 1, wherein in step (5), the process conditions for impregnation are: ultrasonic oscillation of 300-400W for 20-30 min.
9. The method according to claim 1, wherein in the step (5), the hot pressing process conditions are: the treatment is carried out for 20 to 30 minutes at 160 to 170 ℃ and 3 to 5 MPa.
10. A composite multilayer ballistic and stab resistant fabric obtainable by the method of any one of claims 1 to 9.
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CN201428044Y (en) * 2009-06-25 2010-03-24 浙江天源网业有限公司 Screen cloth
CN102490416A (en) * 2011-11-25 2012-06-13 中国纺织科学研究院 High strength and high modulus polyethylene fiber resin composite sheet and bulletproof and stab-resistant armor containing same
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US20100124862A1 (en) * 2008-06-06 2010-05-20 Bls Textiles Woven bullet resistant fabric
US20150300782A1 (en) * 2013-03-14 2015-10-22 Richard Gene Craig Carbon nanotube-reinforced fabric, assembly and related methods of manufacture
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CN201428044Y (en) * 2009-06-25 2010-03-24 浙江天源网业有限公司 Screen cloth
CN102490416A (en) * 2011-11-25 2012-06-13 中国纺织科学研究院 High strength and high modulus polyethylene fiber resin composite sheet and bulletproof and stab-resistant armor containing same
CN104197786A (en) * 2014-09-16 2014-12-10 山东大学 Bulletproof plate made of carbon fiber composites and method for manufacturing bulletproof plate

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