Puncture-resistant and washing-resistant flexible breathable composite material and preparation method thereof

Abstract

The invention discloses a needling-resistant and washing-resistant flexible breathable composite material and a preparation method thereof. The flexible breathable composite material comprises a stab-resistant composite material and a waterproof material coating the surface of the stab-resistant composite material, the stab-resistant composite material is at least compounded by weft-knitted fabric and shear thickening fluid prepared from inorganic nanoparticles and a solvent. When the inorganic nanoparticles, the solvent and the waterproof material are compounded on the weft-knitted fabric, due to the fact that the weft-knitted fabric is of a three-dimensional structure, the waterproof material cannot completely fill and block pores of the weft-knitted fabric, the air permeability of the weft-knitted fabric can be reserved, and due to the compounding of the waterproof material, the fabric is resistant to washing, high in stability and long in service life. And it can be ensured that the anti-needling performance is not reduced.

Description

Technical Field

[0001] The invention relates to a flexible breathable composite material which is resistant to needle puncture and washing, and also relates to a preparation method of the flexible breathable composite material. Background Art

[0002] With the enhancement of personal safety awareness and the increase in safety protection needs, the development and application of puncture-proof materials have received widespread attention. Anti-puncture by injection needles is a global problem. The diameter of the needle tube of an injection needle is very small, generally 300-700 microns, and there is a blade at the tip of the needle. When the needle punctures an object, it both punctures and cuts, which places extremely high requirements on materials and structures.

[0003] Patent application WO2012024532A1 discloses a needle puncture-resistant material named Superfabric. The material is based on nylon fabric, and dense, millimeter-sized hard protective blocks are pasted on the surface of the fabric. When the injection needle pierces the material, the needle will pierce the hard protective block, thereby generating needle puncture resistance. However, the needle puncture resistance of a single layer of the material is very limited, so it is usually used in a multi-layer stacking method to resist needle puncture, and the material has poor air permeability.

[0004] Patent application CN201620983735.5 discloses a method of implanting rigid particles into the surface of a base glue layer through a sand planting process, and then forming a protective layer through a curing treatment to prepare a composite material with anti-cutting and water-washing resistance. However, this method requires repeated gluing, the process is complicated, and the air permeability and anti-puncture performance are uncertain.

[0005] Patent application CN116590911B discloses a method for compounding a shear thickening fluid with a fabric to prepare a new composite material with both protective properties and flexibility. However, this material generally faces a common problem: once the material is exposed to a humid environment, moisture will penetrate into the material, thereby affecting the mechanical strength and durability of the material, and further accelerating the degradation of the material. Summary of the invention

[0006] The first object of the present invention is to provide a flexible breathable composite material which is resistant to needle puncture and washing and has excellent anti-puncture performance and durability in use and simple process.

[0007] The first object of the present invention is achieved through the following technical measures: a needle-puncture-resistant and washing-resistant flexible breathable composite material, characterized in that it includes a puncture-proof composite material and a waterproof material coated on the surface of the puncture-proof composite material, and the puncture-proof composite material is at least composed of a weft-knitted fabric and a shear thickening fluid made of inorganic nanoparticles and a solvent.

[0008] When the present invention uses inorganic nanoparticles, solvents and waterproof materials to be compounded on a weft knitted fabric, since the weft knitted fabric has a three-dimensional structure, the waterproof material will not completely fill or block the pores of the weft knitted fabric, and the air permeability of the weft knitted fabric can be retained. In addition, the compounding of the waterproof material makes the present invention resistant to water washing and has high stability, and can ensure that the anti-needle puncture performance is not reduced.

[0009] In order to further improve the water-washing resistance and air permeability of the present invention, the present invention is not prone to precipitate when boiled in boiling water, repeatedly scrubbed, or machine washed.

[0010] The waterproof material of the present invention is acrylic resin emulsion or water-based polyurethane emulsion.

[0011] The mass fraction of the waterproof material of the present invention on the unit area of ​​the flexible breathable composite material is 3.5%-21.0%.

[0012] In order to further improve the needle puncture resistance of the present invention, only a single layer of the present invention can have a needle puncture resistance of more than 3.0N.

[0013] The inorganic nanoparticles described in the present invention are nano silicon dioxide spheres or calcium carbonate.

[0014] The volume fraction of the inorganic nanoparticles in the shear thickening fluid is 45%-55%.

[0015] The mass fraction of the inorganic nanoparticles on the unit area of ​​the flexible breathable composite material is 1.0%-18.0%.

[0016] The solvent of the present invention is a polyol solvent.

[0017] The polyol solvent of the present invention is polyethylene glycol, polypropylene glycol or polyester polyol.

[0018] The mass fraction of the polyol solvent per unit area of ​​the flexible breathable composite material is 0.5%-7.0%.

[0019] To further improve the filling effect of the inorganic nanoparticles, solvent and waterproof material in the weft knitted fabric of the present invention.

[0020] The weft knitted fabric of the present invention is a weft knitted fabric with a double-sided cotton wool structure; the tightness of the weft knitted fabric is 14-49.5, and preferably, the tightness of the weft knitted fabric is 14-23.

[0021] The yarn material of the weft knitted fabric of the present invention is ultra-high molecular weight polyethylene, aramid or a mixed material of ultra-high molecular weight polyethylene and aramid.

[0022] The yarn count of the weft knitted fabric of the present invention is 200D-600D, the transverse density of the weft knitted fabric is 18-30 wales / inch, and the longitudinal density is 30-43 rows / inch.

[0023] The yarn count of the weft knitted fabric of the present invention is 300D-590D, the transverse density of the weft knitted fabric is 23-30 wales / inch, and the longitudinal density is 30-40 horizontal lines / inch.

[0024] The second object of the present invention is to provide a method for preparing the above-mentioned needle-puncture-resistant, washable, flexible, breathable composite material.

[0025] The second object of the present invention is achieved by the following technical measures: A method for preparing the above-mentioned needle-puncture-resistant, washable, flexible, breathable composite material, characterized by comprising the following steps:

[0026] S1. dispersing and suspending inorganic nanoparticles in a solvent to prepare a shear thickening fluid;

[0027] S2, uniformly mixing the shear thickening fluid and the diluent to obtain an immersion treatment liquid;

[0028] S3, fully immersing the weft knitted fabric in an immersion treatment solution and then drying it to obtain a stab-proof composite material;

[0029] S4. Immerse the stab-proof composite material in a liquid waterproof material, and then dry and solidify the waterproof material to form a waterproof film on the surface of the stab-proof composite material, thereby obtaining a needle-puncture-resistant, washable, flexible and breathable composite material.

[0030] In the step S4 of the present invention, the drying temperature is 105-135°C.

[0031] Compared with the prior art, the present invention has the following significant effects:

[0032] (1) When the inorganic nanoparticles, polyol solvent and waterproof material are compounded on the weft knitted fabric, the pores of the weft knitted fabric will not be filled or blocked, and the air permeability of the weft knitted fabric can be retained to the greatest extent. Therefore, the present invention has good air permeability.

[0033] (2) The present invention can have a needle puncture resistance of more than 3.0N with only a single layer, so that the practical value of the protective performance of the present invention when used as a single layer is already very high, while traditional puncture-proof materials need to be used in multiple layers to meet the high practical value of puncture-proof capabilities.

[0034] ⑶ The flexible breathable composite material of the present invention has extremely high stability. No precipitate will be produced when boiled in boiling water, repeatedly scrubbed, or machine washed, and the needle puncture resistance performance can be ensured not to be reduced. Therefore, the present invention has excellent needle puncture resistance performance and durability in use, and has high practical value.

[0035] (4) The preparation method of the present invention is simple, easy to implement, low in cost, has high economic benefits, and is suitable for wide promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0037] Figure 1 are scanning electron microscope images of the fabric substrate (Comparative Example 9) and its composites with the components (Comparative Example 7, Comparative Example 8, Example 2 and Comparative Example 5);

[0038] Figure 2 It is a comparison picture of the turbidity of the fabric substrate (Comparative Example 8) and the materials after being composited with various components (Comparative Example 7, Comparative Example 8 and Example 2) after being boiled in boiling water;

[0039] Figure 3 It is a comparison picture of the turbidity of the fabric substrate (Comparative Example 8) and the materials after it is composited with various components (Comparative Example 7, Comparative Example 8 and Example 2) after the scrubbing resistance test. DETAILED DESCRIPTION

[0040] The invention discloses a needle-puncture-resistant and washing-resistant flexible breathable composite material, which consists of a puncture-resistant composite material and a waterproof material coated on the surface of the puncture-resistant composite material. The puncture-resistant composite material is composited by a weft-knitted fabric with a double-sided cotton wool structure and a shear thickening fluid made of inorganic nanoparticles and a polyol solvent. The tightness of the weft-knitted fabric is 14-49.5, preferably 14-23. The tightness of the weft-knitted fabric, that is, the underfill coefficient, is expressed by the ratio of the coil length of the weft-knitted fabric to the yarn diameter.

[0041] The yarn material of the weft knitted fabric can be ultra-high molecular weight polyethylene, aramid, or a mixed material of ultra-high molecular weight polyethylene and aramid. The thickness of the yarn count is 200D-600D, the transverse density of the weft knitted fabric is 18-30 wales / inch, and the longitudinal density is 30-43 rows / inch. Preferably, the thickness of the yarn count is 300D-590D, the transverse density of the weft knitted fabric is 23-30 wales / inch, and the longitudinal density is 30-40 rows / inch.

[0042] Inorganic nanoparticles have a highly regular, single morphology and can be monodisperse nano-silica spheres or calcium carbonate.

[0043] The polyol solvent is preferably polyethylene glycol with a relative molecular mass of 100, 200, 300, 400, polypropylene glycol or polyester polyol.

[0044] Waterproof material is a substance that can form a film after drying and prevent liquid from penetrating into the interior, such as acrylic resin emulsion or water-based polyurethane emulsion.

[0045] Polyol solvents and waterproof materials can be properly cross-linked at high temperatures of 105-135°C.

[0046] Inorganic nanoparticles exist in the form of single particle dispersion suspension in the polyol solvent. Under the SEM electron microscope, there is no direct contact between inorganic nanoparticles, and the gaps between particles are filled with the polyol solvent.

[0047] In the high concentration shear thickening fluid prepared from inorganic nanoparticles and polyol solvent, the volume fraction of the inorganic nanoparticles in the shear thickening fluid is 45%-55% (the volume fraction is defined as "total volume of inorganic nanoparticles / total volume of high concentration shear thickening fluid*100%"), and the volume fraction of the inorganic nanoparticles is preferably 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, and 55%.

[0048] For the flexible breathable composite material per unit area of ​​the present invention, the mass fraction of inorganic nanoparticles (defined as "total mass of inorganic nanoparticles / total mass of flexible breathable composite material*100%) is 1.0%-18.0%.

[0049] For the flexible breathable composite material per unit area of ​​the present invention, the mass fraction of the polyol solvent (defined as "total mass of the polyol solvent / total mass of the flexible breathable composite material*100%) is 0.5%-7.0%.

[0050] For the flexible breathable composite material per unit area of ​​the present invention, the mass fraction of the waterproof material (defined as "total mass of the waterproof material / total mass of the flexible breathable composite material*100%) is 3.5%-21.0%.

[0051] A method for preparing the above-mentioned needle-puncture-resistant and washing-resistant flexible breathable composite material specifically comprises the following steps:

[0052] S1, dispersing and suspending inorganic nanoparticles in a polyol solvent to prepare a shear thickening fluid;

[0053] S2, uniformly mixing the shear thickening fluid and the diluent to obtain an immersion treatment liquid;

[0054] S3, fully immersing the weft knitted fabric in the immersion treatment solution, and then roller-drying to obtain the stab-proof composite material;

[0055] S4, immersing the stab-proof composite material in a liquid waterproof material, and then roller-drying it, so that the waterproof material is cured to form a waterproof film on the surface of the stab-proof composite material, thereby obtaining a needle-resistant, washable, flexible and breathable composite material.

[0056] Specific examples:

[0057] Example 1

[0058] The inorganic nanoparticles of this embodiment are calcium carbonate particles, and the polyol solvent is polyethylene glycol with a relative molecular mass of 200. 51 vol% of nano calcium carbonate particles are dispersed and suspended in the polyethylene glycol to prepare a shear thickening fluid. The density of the calcium carbonate particles used in this embodiment is 2.71 g / cm 3 The moisture content of the particle powder (defined as: the mass of water in the particle powder / the mass of the particle powder*100%) is 0.57wt%, and the density of polyethylene glycol with a relative molecular mass of 200 is 1.12g / cm 3 The density of calcium carbonate particles is the actual particle density obtained by dividing the mass of a single particle by the volume of a single particle. The mass fraction of calcium carbonate particles is calculated to be 71.60 wt % based on the density of calcium carbonate particles, polyethylene glycol 200, the volume fraction of calcium carbonate particles and the moisture content of calcium carbonate particles.

[0059] The shear thickening fluid is mixed with an appropriate amount of diluent (e.g., industrial alcohol) to obtain an impregnation treatment liquid. The double-sided cotton wool structure weft knitted fabric made of ultra-high molecular weight polyethylene is fully impregnated in the impregnation treatment liquid, and after roller drying, a surface density of 493.47 g / m 2 The stab-proof composite material was then immersed in an acrylic resin emulsion (waterproof material) with a solid content of 10% (Note: "solid content" here is defined as the mass of water-based acrylic resin / mass of emulsion in the emulsion * 100%), and roller-dried (drying temperature 105-135°C) to obtain a surface density of 537.73g / m 2 Waterproof and puncture-proof composite material.

[0060] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 12.45wt%, the content of polyethylene glycol is 4.94wt%, and the content of acrylic resin emulsion is 8.23wt%.

[0061] Example 2

[0062] The difference between this embodiment and embodiment 1 is that the ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the waterproof and stab-proof composite material is prepared according to the process in embodiment 1. The surface density of the stab-proof composite material is 472.67 g / m 2The surface density of the waterproof and stab-proof composite material is 542.4g / m 2 .

[0063] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.59wt%, the content of polyethylene glycol is 3.80wt%, and the content of acrylic resin emulsion is 12.86wt%.

[0064] Example 3

[0065] The difference between this embodiment and embodiment 1 is that the ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the process in embodiment 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 427.47 g / m 2 The surface density of the waterproof and stab-proof composite material is 527.87g / m 2 .

[0066] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 3.73wt%, the content of polyethylene glycol is 1.48wt%, and the content of acrylic resin emulsion is 19.02wt%.

[0067] Example 4

[0068] The difference between this embodiment and embodiment 1 is that the ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the process in embodiment 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 420.53 g / m 2 The surface density of the waterproof and stab-proof composite material is 493.87g / m 2 .

[0069] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 2.98wt%, the content of polyethylene glycol is 1.18wt%, and the content of acrylic resin emulsion is 14.85wt%.

[0070] Example 5

[0071] The difference between this embodiment and embodiment 1 is that the ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the process in embodiment 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 415.47 g / m 2 The surface density of the waterproof and stab-proof composite material is 489.6g / m 2 .

[0072] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 2.27wt%, the content of polyethylene glycol is 0.89wt%, and the content of acrylic resin emulsion is 15.14wt%.

[0073] Example 6

[0074] The difference between this embodiment and embodiment 1 is that the solid content of the aqueous acrylic resin emulsion (Note: the "solid content" here is defined as the mass of aqueous acrylic resin in the emulsion / the mass of emulsion*100%) is 5wt%.

[0075] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 493.47 g / m 2 The surface density of the waterproof and stab-proof composite material is 515.60g / m 2 .

[0076] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 12.98 wt %, the content of polyethylene glycol is 5.15 wt %, and the content of acrylic resin emulsion is 4.29 wt %.

[0077] Example 7

[0078] The difference between this embodiment and embodiment 1 is that the solid content of the aqueous acrylic resin emulsion (Note: the "solid content" here is defined as the mass of aqueous acrylic resin in the emulsion / the mass of the emulsion*100%) is 2 wt %.

[0079] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 493.47 g / m 2 The surface density of the waterproof and stab-proof composite material is 502.32g / m 2 .

[0080] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 13.32wt%, the content of polyethylene glycol is 5.28wt%, and the content of acrylic resin emulsion is 1.76wt%.

[0081] Example 8

[0082] The difference between this embodiment and embodiment 1 is that the volume fraction of the calcium carbonate particles is 45 vol%.

[0083] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 409.47 g / m 2 The surface density of the waterproof and stab-proof composite material is 489.6g / m 2 .

[0084] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 1.29wt%, the content of polyethylene glycol is 0.65wt%, and the content of acrylic resin emulsion is 16.37wt%.

[0085] Example 9

[0086] The difference between this embodiment and embodiment 1 is that the volume fraction of the calcium carbonate particles is 46 vol%.

[0087] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 466.67 g / m 2 The surface density of the waterproof and stab-proof composite material is 542.4g / m 2 .

[0088] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 8.80wt%, the content of polyethylene glycol is 4.38wt%, and the content of acrylic resin emulsion is 12.86wt%.

[0089] Example 10

[0090] The difference between this embodiment and embodiment 1 is that the volume fraction of the calcium carbonate particles is 47 vol%.

[0091] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 469.1 g / m 2 The surface density of the waterproof and stab-proof composite material is 548.7g / m 2 .

[0092] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.02wt%, the content of polyethylene glycol is 3.58wt%, and the content of acrylic resin emulsion is 14.51wt%.

[0093] Embodiment 11

[0094] The difference between this embodiment and embodiment 1 is that the volume fraction of the calcium carbonate particles is 48 vol%.

[0095] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 425.8 g / m 2 The surface density of the waterproof and stab-proof composite material is 530.07g / m 2 .

[0096] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 3.48wt%, the content of polyethylene glycol is 1.38wt%, and the content of acrylic resin emulsion is 19.67wt%.

[0097] Example 12

[0098] The difference between this embodiment and embodiment 1 is that the volume fraction of the calcium carbonate particles is 49 vol%.

[0099] The ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the process in Example 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 471 g / m 2 The surface density of the waterproof and stab-proof composite material is 545g / m 2 .

[0100] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.33wt%, the content of polyethylene glycol is 3.70wt%, and the content of acrylic resin emulsion is 13.58wt%.

[0101] Embodiment 13

[0102] The difference between this embodiment and embodiment 1 is that the volume fraction of the calcium carbonate particles is 50 vol%.

[0103] The ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the process in Example 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 471 g / m 2 The surface density of the waterproof and stab-proof composite material is 540g / m 2 .

[0104] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.30wt%, the content of polyethylene glycol is 3.84wt%, and the content of acrylic resin emulsion is 12.78wt%.

[0105] Embodiment 14

[0106] The difference between this embodiment and embodiment 1 is that the volume fraction of the calcium carbonate particles is 52 vol%.

[0107] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 429.31 g / m 2 The surface density of the waterproof and stab-proof composite material is 537.17g / m 2 .

[0108] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 3.91wt%, the content of polyethylene glycol is 1.55wt%, and the content of acrylic resin emulsion is 20.08wt%.

[0109] Embodiment 15

[0110] The difference between this embodiment and embodiment 1 is that the volume fraction of the calcium carbonate particles is 53 vol%.

[0111] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 475.28 g / m2 The surface density of the waterproof and stab-proof composite material is 539.18g / m 2 .

[0112] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.88wt%, the content of polyethylene glycol is 4.08wt%, and the content of acrylic resin emulsion is 11.85wt%.

[0113] Example 16

[0114] The difference between this embodiment and embodiment 1 is that the inorganic nanoparticles are nano-silica spheres, and the volume fraction of the particles in the nano-silica spheres is 54 vol%.

[0115] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 473.72 g / m 2 The surface density of the waterproof and stab-proof composite material is 541.26g / m 2 .

[0116] In the waterproof and stab-proof composite material, the content of nano-silicon dioxide balls is 9.17wt%, the content of polyethylene glycol is 4.45wt%, and the content of acrylic resin emulsion is 12.48wt%.

[0117] Embodiment 17

[0118] The difference between this embodiment and embodiment 1 is that the inorganic nanoparticles are nano-silica spheres, and the volume fraction of the particles in the nano-silica spheres is 55 vol%.

[0119] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 429.31 g / m 2 The surface density of the waterproof and stab-proof composite material is 519.68g / m 2 .

[0120] In the waterproof and stab-proof composite material, the content of nano silicon dioxide balls is 3.85wt%, the content of polyethylene glycol is 1.79wt%, and the content of acrylic resin emulsion is 17.39wt%.

[0121] Embodiment 18

[0122] The difference between this embodiment and embodiment 1 is that the polyol solvent is polyethylene glycol 100, and the volume fraction of the particles in the calcium carbonate particles is 54 vol%.

[0123] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 473.72 g / m2 The surface density of the waterproof and stab-proof composite material is 542.14g / m 2 .

[0124] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 10.32wt%, the content of polyethylene glycol 100 is 3.28wt%, and the content of acrylic resin emulsion is 12.62wt%.

[0125] Embodiment 19

[0126] The difference between this embodiment and embodiment 1 is that the polyol solvent is polyethylene glycol 300, and the volume fraction of the particles in the calcium carbonate particles is 53 vol%.

[0127] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 475.21 g / m 2 The surface density of the waterproof and stab-proof composite material is 544.72g / m 2 .

[0128] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 10.08wt%, the content of polyethylene glycol 300 is 3.73wt%, and the content of acrylic resin emulsion is 12.76wt%.

[0129] Embodiment 20

[0130] The difference between this embodiment and embodiment 1 is that the polyol solvent is polyethylene glycol 400, and the volume fraction of the particles in the calcium carbonate particles is 52 vol%.

[0131] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 468.92 g / m 2 The surface density of the waterproof and stab-proof composite material is 546.78g / m 2 .

[0132] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 8.80wt%, the content of polyethylene glycol 400 is 3.81wt%, and the content of acrylic resin emulsion is 14.24wt%.

[0133] Embodiment 21

[0134] The difference between this embodiment and embodiment 1 is that the polyol solvent uses polypropylene glycol 400, and the volume fraction of the calcium carbonate particles is 51 vol%.

[0135] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 468.92 g / m2 The surface density of the waterproof and stab-proof composite material is 546.78g / m 2 .

[0136] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.03wt%, the content of polypropylene glycol 400 is 3.48wt%, and the content of acrylic resin emulsion is 14.24wt%.

[0137] Embodiment 22

[0138] The difference between this embodiment and embodiment 1 is that the polyol solvent adopts polyester polyol (propylene terephthalate), and the volume fraction of the particles in the calcium carbonate particles is 51 vol%.

[0139] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 468.92 g / m 2 The surface density of the waterproof and stab-proof composite material is 546.78g / m 2 .

[0140] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.78wt%, the content of polyester polyol is 3.62wt%, and the content of acrylic resin emulsion is 14.24wt%.

[0141] Embodiment 23

[0142] The difference between this embodiment and embodiment 1 is that the fabric base material is a weft-knitted fabric with a double-sided cotton-wool structure woven with aramid yarn.

[0143] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 476.83 g / m 2 The surface density of the waterproof and stab-proof composite material is 536.79g / m 2 .

[0144] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.99wt%, the content of polyethylene glycol is 4.32wt%, and the content of acrylic resin emulsion is 11.17wt%.

[0145] Embodiment 24

[0146] The difference between this embodiment and embodiment 1 is that the fabric base material is a weft-knitted fabric with a double-sided cotton wool structure woven with aramid yarn, and the volume fraction of the calcium carbonate particles is 54 vol%.

[0147] The ratio of the shear thickening fluid to the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material was 471.09 g / m2 The surface density of the waterproof and stab-proof composite material is 533.21g / m 2 .

[0148] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.86wt%, the content of polyethylene glycol is 3.47wt%, and the content of acrylic resin emulsion is 11.65wt%.

[0149] Embodiment 25

[0150] The difference between this embodiment and embodiment 1 is that the waterproof material adopts water-based polyurethane emulsion, and the solid content of the water-based polyurethane (Note: "solid content" here is defined as the mass of water-based polyurethane in the emulsion / the mass of the emulsion*100%) is 7.5%, and the volume fraction of calcium carbonate in the shear thickening fluid made of calcium carbonate particles and polyethylene glycol is 51 vol%.

[0151] The ratio of the shear thickening fluid and the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the waterproof and stab-proof composite material finally obtained was 517.6 g / m 2 .

[0152] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 10.07%, the content of polyethylene glycol is 3.97%, and the content of water-based polyurethane is 8.68%, and all contents are mass fractions.

[0153] Embodiment 26

[0154] The difference between this embodiment and embodiment 1 is that: the inorganic nanoparticles are nano-silica ball powder with a particle size of 100 nm, the polyol solvent is polyethylene glycol with a relative molecular mass of 400, the waterproof material is an aqueous polyurethane emulsion, and the solid content of the aqueous polyurethane dispersion (Note: the "solid content" here is defined as the mass of aqueous polyurethane in the emulsion / the mass of the emulsion*100%) is 10%; in the shear thickening fluid made of nano-silica balls and polyethylene glycol, the volume fraction of the nano-silica balls is 45.8 vol%.

[0155] The ratio of the shear thickening fluid and the diluent was appropriately adjusted, and the process in Example 1 was used to prepare a waterproof and stab-proof composite material. The surface density of the waterproof and stab-proof composite material finally obtained was 555.67 g / m 2 .

[0156] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 17.59wt%, the content of polyethylene glycol is 6.94wt%, and the content of waterborne polyurethane is 3.62wt%.

[0157] Comparative Example 1

[0158] The difference between this comparative example and Example 1 is that the ratio of the shear thickening fluid and the diluent is appropriately adjusted, and the process in Example 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 613.33 g / m 2 The surface density of the waterproof and stab-proof composite material is 617.33g / m 2 .

[0159] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 24.78 wt %, the content of polyethylene glycol is 9.78 wt %, and the content of acrylic resin emulsion is 0.65 wt %.

[0160] Comparative Example 2

[0161] The difference between this comparative example and Example 1 is that the ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the process in Example 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 584.27 g / m 2 The surface density of the waterproof and stab-proof composite material is 613.47g / m 2 .

[0162] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 21.54 wt %, the content of polyethylene glycol is 8.5 wt %, and the content of acrylic resin emulsion is 4.76 wt %.

[0163] Comparative Example 3

[0164] The difference between this comparative example and Example 1 is that the ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the process in Example 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 563.87 g / m 2 The surface density of the waterproof and stab-proof composite material is 600.40g / m 2 .

[0165] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 19.57 wt %, the content of polyethylene glycol is 7.72 wt %, and the content of acrylic resin emulsion is 6.08 wt %.

[0166] Comparative Example 4

[0167] The difference between this comparative example and Example 1 is that the ratio of the shear thickening fluid and the diluent is appropriately adjusted, and the process in Example 1 is adopted to prepare a waterproof and stab-proof composite material. The surface density of the stab-proof composite material is 536.53 g / m 2 The surface density of the waterproof and stab-proof composite material is 600.40g / m 2 .

[0168] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 17.81 wt %, the content of polyethylene glycol is 7.03 wt %, and the content of acrylic resin emulsion is 2.37 wt %.

[0169] Comparative Example 5

[0170] The difference between this comparative example and Example 1 is that the solid content of the aqueous polyurethane emulsion is appropriately adjusted to 30% (Note: the "solid content" here is defined as the mass of aqueous polyurethane in the emulsion / the mass of the emulsion*100%), and the waterproof and stab-proof composite material is prepared by the process in Example 1. The surface density of the stab-proof composite material is 493.47g / m 2 The surface density of the waterproof and stab-proof composite material is 690g / m 2 .

[0171] In the waterproof and stab-proof composite material, the content of calcium carbonate particles is 9.71wt%, the content of polyethylene glycol is 3.83wt%, and the content of waterborne polyurethane is 28.48wt%.

[0172] Comparative Example 6

[0173] The difference between this comparative example and Example 1 is that the inorganic nanoparticles are nano-silica spheres, and no waterproof material is used.

[0174] The ratio of the shear thickening fluid to the diluent is appropriately adjusted, and the process in Example 1 is used to prepare a stab-proof composite material. The surface density of the stab-proof composite material is 660 g / m 2 .

[0175] Comparative Example 7

[0176] The difference between this comparative example and Example 1 is that no waterproof material is used.

[0177] The stab-proof composite material was prepared by the process in Example 1. The surface density of the stab-proof composite material was 668 g / m 2 .

[0178] Comparative Example 8

[0179] The difference between this comparative example and Example 1 is that no inorganic nanoparticles and polyol solvent are used.

[0180] The acrylic resin emulsion is directly coated on the fabric substrate and then fully dried to obtain the "composite material".

[0181] Comparative Example 9

[0182] This comparative example uses a pure fabric substrate, and the selected fabric substrate is completely consistent with the fabric substrate in Example 1.

[0183] The following table summarizes the details of all embodiments and comparative examples:

[0184]

[0185]

[0186]

[0187]

[0188] (Table 1)

[0189] The method for determining the performance of stab-resistant composite materials is as follows:

[0190] 1. Needle puncture resistance test: The needle puncture resistance mentioned in the present invention refers to the maximum force required to resist the injection needle from piercing the material to be tested at a uniform and low speed. We define this kind of needle puncture resistance as "quasi-static needle puncture force" in order to distinguish it from the concept of "impact puncture". Impact puncture refers to a knife or cone piercing the material to be tested quickly (at a speed of several meters per second). This puncture and the "quasi-static needle puncture" discussed in the present invention (the speed generally does not exceed 1000mm / min) are completely different puncture mechanisms and should not be confused. The needle puncture mentioned in the present invention only refers to the case of "quasi-static needle puncture". The needle puncture resistance test of stab-proof composites is carried out in accordance with the standard ASTM F2878-10. The test method is briefly summarized as follows: fix the material to be tested horizontally on the tester, load the injection needle (needle number is 25G) and make it perpendicular to the plane of the material to be tested, and then let the needle pierce the material to be tested at a uniform speed of 500mm / min. The tester is equipped with a sensor on one side of the injection needle, which can detect the force applied to the needle during the insertion of the material in real time, and display a curve of "needle puncture force-penetration depth" on the computer. The highest point of the curve is the force required for the needle to pierce the material, that is, the material's puncture resistance. Each material needs to measure 12 sets of data, and the average value of these 12 sets of data is calculated to obtain the puncture resistance of the material. According to Section 5.1.3 of ANSI / ISEA 105-2016 for puncture performance rating, the puncture performance is generally required to reach at least level 1, that is, the puncture resistance is not less than 2.0N, and the material is of practical value; if the puncture performance is level 0, that is, the puncture resistance is less than 2.0N, it is considered that the material is too easy to be penetrated by the needle and the material has little practical value.

[0191] 2. Stability test: The composite material has a high degree of environmental stability. No matter it is repeatedly scrubbed or machine washed, or even boiled in boiling water for a long time, no obvious precipitate will be produced.

[0192] The material's resistance to scrubbing and washing is tested as follows: cut the material into 5cm*5cm squares, immerse them in 1L of water, rub the material 10 times as you would wash clothes, then take out the material and test the water after scrubbing with a turbidity meter to determine the degree of particle precipitation. The turbidity is then compared with the turbidity of the water after scrubbing the composite material that has not been waterproofed to determine the degree of resistance to scrubbing and washing.

[0193] The method for testing the material's resistance to boiling water is as follows: place the material in 500mL of boiling water and boil for 15 minutes, take out the material, dilute the water used to boil the material to 1L, and test its turbidity value.

[0194] The samples prepared in Examples 1-24 and Comparative Examples 1-8 were all subjected to needle puncture resistance test, water boiling resistance test and scrubbing resistance test. These test methods are briefly described as follows.

[0195] Needle puncture resistance test: Test the material's resistance to injection needle puncture according to standard ASTM F2878-10. Cut the material to be tested into regular small pieces and fix them horizontally on the test instrument. Install the injection needle (needle number 25G) vertically on the test instrument and pierce the material to be tested at a uniform speed of 500mm / min until the needle completely penetrates the material. Record the maximum force generated by the needle completely penetrating the entire material to be tested. This maximum force is the needle puncture resistance of the material to be tested. Test 12 sets of data for each material to be tested, and calculate the average value of these 12 sets of data, and use the average value to represent the needle puncture resistance of the material to be tested. The grading of needle puncture resistance is based on the measured needle puncture resistance and refers to Section 5.1.3 of ANSI / ISEA 105-2016. If the needle puncture resistance is less than 2N, it is rated as level 0, which does not have much practical performance. If the needle puncture resistance is 2N-4N, it is rated as level 1, which has basic practical performance. If the puncture resistance is 4N-6N, it is rated as Level 2, which has good practical performance. If the puncture resistance is 6N-8N, it is rated as Level 3, which has very good practical performance. If the puncture resistance is 8N-10N, it is rated as Level 4, which has very high practical performance. If the puncture resistance is greater than 10N, it is rated as Level 5, which is top-level puncture resistance. Based on a large number of experiments and usage experience, we found that the puncture resistance of a single layer of material is generally greater than 3.0N, which is a higher safety factor. Therefore, the present invention defines that the puncture resistance of a single layer must be no less than 3.0N.

[0196] Boiling resistance test: Test a standard small piece of the material to be tested with a size of 5cm*5cm, place the material in 500mL boiling water and boil for 15 minutes, take out the material, dilute the water after boiling the material to 1L, observe whether there is precipitation of the material to be tested in the water, and take a sample to test the turbidity of the water with a turbidity meter. Based on a large number of experiments and observations of experimental phenomena, we found that the precipitation amount of the boiling-resistant particles of the material is proportional to the turbidity of the water. The present invention defines that the turbidity of the water after boiling is ≤20NTU, which means that there is basically no particle precipitation phenomenon.

[0197] Washing resistance test: Cut the material into 5cm*5cm squares, immerse them in 1L of water, and rub the material vigorously for 10 times as you would rub clothes. Observe whether there is any precipitate of the material to be tested in the water. Then take out the material and test the water after washing with a turbidity meter to determine the degree of particle precipitation. Compare the turbidity with the turbidity of the water after washing the composite material that has not been waterproofed to determine the degree of washing resistance. The amount of particles precipitated during the washing process is proportional to the turbidity of the water. Taking into account that scrubbing will cause more intense friction, this patent defines that if the turbidity of the water after scrubbing is ≤30NTU, there is basically no particle precipitation. If it exceeds 30NTU, the water will be visually very turbid.

[0198] The prepared composite material must simultaneously meet the requirements of needle puncture resistance ≥ 3.0N, turbidity after boiling ≤ 20NTU, and turbidity after scrubbing ≤ 30NTU to be considered a qualified waterproof and puncture-resistant composite material.

[0199] Scanning electron microscope micromorphology test: Scanning electron microscope was used to observe the microscopic surface of the fabric substrate and its composite with each component at an accelerating voltage of 10.0 kV. Before SEM observation, the sample was fixed on an aluminum short column using conductive double-sided tape and then sputtered with gold under high vacuum conditions.

[0200] Figure 1 The following are scanning electron microscope images of the fabric substrate (Comparative Example 9) and its composites with various components (Comparative Example 7, Comparative Example 8, Example 2 and Comparative Example 5). Figure 1 (a) shows the structure of the fabric substrate, by observing Figure 1 (a) It was found that the surface of the fabric substrate was flat and smooth, without obvious bumps or holes, and presented a uniform texture. Figure 1 As shown in (b), a large amount of nanoparticles are filled on the surface of the stab-proof composite and between the fibers. These nanoparticles effectively enhance the composite material's ability to resist needle puncture. Figure 1 (c) shows a waterproof composite material formed by a waterproof material and a textile substrate. It can be observed that the surface of the composite material is smooth and glossy. This is because the waterproof material can form a uniform and stable coating on the substrate. Figure 1(d) shows the puncture-proof waterproof composite material composed of a fabric substrate, a shear thickening fluid and a waterproof material. After the puncture-proof composite material composed of the fabric substrate and the shear thickening fluid is immersed in the waterproof material and cured, a continuous and dense coating is indeed formed on its surface, which encapsulates the shear thickening fluid. Under the premise of not destroying the structural integrity and functionality of the puncture-proof composite material, a layer of waterproof material is coated on the surface to form a protective layer, which can effectively prevent the shear thickening fluid from seeping out when it encounters water. At the same time, the waterproof material will increase the resistance of the fabric fibers to move against each other, and has a certain enhancement effect on needle puncture protection. Figure 1 (e) and (f) are the surface morphologies of waterproof materials with a solid content of 30% (Note: the content in the system is 28.48%), where: Figure 1 (f) shows Figure 1 The microstructure at G in (e) shows that when it accounts for a large proportion in the system, the fibers and the surface of the composite are completely covered, which not only reduces the softness of the composite, but also affects its air permeability. Figure 1 In (e), the same phenomenon can be observed by taking electron microscope images at different positions to observe the microstructure. The results show that the proportion of waterproof material in the system is an important factor affecting the waterproofness and air permeability of the composite.

[0201] Figure 2 and Figure 3 The turbidity comparison of the fabric substrate (Comparative Example 8) and the materials after it is composited with various components (Comparative Example 7, Comparative Example 8 and Example 2) after boiling water resistance and scrubbing resistance tests is shown. Figure 2 (a) is a picture of a fabric substrate that is resistant to boiling water. Figure 2 (b) is a picture of the boiling water resistance of the stab-resistant composite material after the fabric substrate and the shear thickening fluid are combined. Figure 2 (c) is a picture of the waterproof composite material after the fabric substrate and acrylic resin emulsion are compounded to resist boiling water. Figure 2 (d) is a picture of the boiling water resistance of the puncture-proof and waterproof composite material after the composite of the fabric substrate, shear thickening fluid and acrylic resin emulsion. Figure 2 (f) is a picture of the turbidity limit of 20 NTU after boiling water; Figure 3 (a) is a picture of the fabric substrate being resistant to scrubbing. Figure 3 (b) is a picture of the washability of the stab-resistant composite material after the fabric substrate and the shear thickening fluid are combined. Figure 3 (c) is a picture of the washability of the waterproof composite material after the fabric substrate and acrylic resin emulsion are combined. Figure 3 (d) is a picture of the washability of the puncture-proof and waterproof composite material after the composite of the fabric substrate, shear thickening fluid and acrylic resin emulsion. Figure 3 (f) is a picture of the turbidity limit of water after scrubbing, 30 NTU.

[0202] from Figure 2(b) and Figure 3 It can be clearly observed in (b) that the stab-resistant composite material that has not been treated with acrylic resin has particle precipitation, and its performance and service life are significantly affected when used in humid or wet conditions. Figure 2 (d) and Figure 3 As shown in (d), the waterproof and puncture-resistant composite material treated with acrylic resin can maintain good performance regardless of whether it is in an extreme boiling water environment or after strong scrubbing. In addition, according to the data in Table 2-2, the sample after washing and drying still maintains its original anti-puncture properties and is almost unaffected. This result shows that acrylic resin treatment can effectively improve the stability and durability of the material under harsh conditions.

[0203] The following table summarizes the boiling water resistance and turbidity values ​​of all embodiments and comparative examples:

[0204]

[0205]

[0206]

[0207] (Table 2)

[0208] In the description of the test method, we have stipulated that the composite material must simultaneously meet the requirements of needle resistance ≥ 3.0N, turbidity after boiling ≤ 20NTU, and turbidity after scrubbing ≤ 30NTU to be considered a qualified waterproof and puncture-resistant composite material. According to this standard, by comparing the experimental data in Table 2, we found that only when the content of inorganic nanoparticles is 1.0%-18.0%, the content of polyol solvent is 0.5%-7.0%, and the content of waterproof material is 3.5%-21.0%, the waterproof and puncture-resistant material can meet the practical requirements. If the content of the component exceeds the range, a large amount of precipitates will be generated by scrubbing; if the content of the component is lower than the range, the needle resistance performance will be less than expected, and the practicality of the material will be greatly reduced.

Claims

1. A flexible breathable composite material that is resistant to needle puncture and washing, characterized in that: The stab-proof composite material comprises a waterproof material coated on the surface of the stab-proof composite material. The stab-proof composite material is at least composed of a weft knitted fabric and a shear thickening fluid made of inorganic nanoparticles and a solvent.

2. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 1, characterized in that: The waterproof material is acrylic resin emulsion or water-based polyurethane emulsion.

3. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 1, characterized in that: The mass fraction of the waterproof material per unit area of ​​the flexible breathable composite material is 3.5%-21.0%.

4. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 1, characterized in that: The inorganic nanoparticles are nano silicon dioxide spheres or calcium carbonate.

5. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 1, characterized in that: The volume fraction of the inorganic nanoparticles in the shear thickening fluid is 45%-55%.

6. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 1, characterized in that: The mass fraction of the inorganic nanoparticles per unit area of ​​the flexible breathable composite material is 1.0%-18.0%.

7. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 1, characterized in that: The solvent is a polyol solvent.

8. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 7, characterized in that: The polyol solvent is polyethylene glycol, polypropylene glycol or polyester polyol.

9. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 7, characterized in that: The mass fraction of the polyol solvent per unit area of ​​the flexible breathable composite material is 0.5%-7.0%.

10. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 1, characterized in that: The weft knitted fabric is a weft knitted fabric with a double-sided cotton wool structure.

11. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 10, characterized in that: The tightness of the weft knitted fabric is 14-49.

5.

12. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 11, characterized in that: The tightness of the weft knitted fabric is 14-23.

13. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 12, characterized in that: The yarn material of the weft knitted fabric is ultra-high molecular weight polyethylene, aramid or a mixed material of ultra-high molecular weight polyethylene and aramid, the yarn count is 200D-600D, the transverse density of the weft knitted fabric is 18-30 wales / inch, and the longitudinal density is 30-43 horizontal lines / inch.

14. The needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 13, characterized in that: The yarn count of the weft knitted fabric is 300D-590D, the transverse density of the weft knitted fabric is 23-30 wales / inch, and the longitudinal density is 30-40 horizontal lines / inch.

15. A method for preparing the needle-puncture-resistant and washing-resistant flexible breathable composite material according to claim 1, characterized in that The following steps are involved: S1. dispersing and suspending inorganic nanoparticles in a solvent to prepare a shear thickening fluid; S2, uniformly mixing the shear thickening fluid and the diluent to obtain an immersion treatment liquid; S3, fully immersing the weft knitted fabric in an immersion treatment solution and then drying it to obtain a stab-proof composite material; S4. Immerse the stab-proof composite material into a liquid waterproof material, and then dry and solidify the waterproof material to form a waterproof film on the surface of the stab-proof composite material, thereby obtaining a needle-resistant, washable, flexible and breathable composite material.

16. The preparation method according to claim 15, characterized in that: In the step S4, the drying temperature is 105-135°C.

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