A rigid-flexible particle blended modified TPU anti-puncture composite film and a preparation method and application thereof

Abstract

The present application relates to a kind of rigid-flexible particle blend modified TPU anti-stab composite film and its preparation method and application.The preparation method is as follows: rigid particle SiO2 is modified with silane coupling agent KH550, and modified SiO2 is obtained, dispersed in organic solvent, and the pre-dispersion of modified SiO2 is obtained;Flexible particle SBR is modified with silane coupling agent Si69, and modified SBR is obtained, dissolved in organic solvent, and the pre-dispersion of modified SBR is obtained;TPU particles are dissolved in organic solvent, and the pre-dispersion of modified SiO2 and the pre-dispersion of modified SBR are added, and mixed and dispersed uniformly;The obtained mixed solution is transferred to polytetrafluoroethylene mold, and TPU composite film is obtained by drying;The TPU composite film is compounded with at least one side of polyester non-woven fabric by hot-pressing, and the anti-stab composite film is obtained.The present application modifies the composite film and designs components, so that it can meet excellent anti-stab performance, maintain softness and improve applicability.

Description

Technical Field

[0001] This invention relates to the technical field of stab-resistant composite films, and in particular to a stab-resistant composite film of rigid-flexible particle blend modified TPU, its preparation method and application. Background Technology

[0002] Based on their flexibility, stab-resistant materials can be categorized into rigid, semi-rigid, and flexible types. Rigid stab-resistant materials possess excellent stab-resistant performance, but as demands for comfort and ease of movement in stab-resistant materials increase, flexible stab-resistant clothing has gradually become a research hotspot. Traditional flexible stab-resistant clothing is composed of multiple layers of high-performance fiber fabrics, sacrificing flexibility to enhance its stab-resistant performance. Flexible protective membranes, on the other hand, are a complete, integrated structure. They are not only thinner and lighter but also possess good flexibility, elasticity, and modulus. This allows them to instantly deform and disperse the impact force as much as possible when faced with a sharp needle / knife piercing, thus meeting the requirements for stab protection. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention provides a puncture-resistant composite film of rigid-flexible particle blended modified TPU, its preparation method, and its application.

[0004] The first objective of this invention is to provide a method for preparing a puncture-resistant composite film of rigid-flexible particle blend modified TPU, comprising the following steps:

[0005] S1: Rigid particles SiO2 are modified with silane coupling agent KH550 to obtain modified SiO2, which is then dispersed in an organic solvent to obtain a pre-dispersion of modified SiO2; Flexible particles SBR are modified with silane coupling agent Si69 to obtain modified SBR, which is then dissolved in an organic solvent to obtain a pre-dispersion of modified SBR.

[0006] S2: Dissolve TPU particles in an organic solvent, and add the modified SiO2 predispersant and modified SBR predispersant obtained in step S1. Mix and disperse evenly to obtain a mixture.

[0007] S3: Transfer the mixed solution obtained in step S2 into a polytetrafluoroethylene mold and dry it to obtain a TPU composite film;

[0008] S4: The TPU composite film is laminated with at least one side of the polyester nonwoven fabric by hot pressing to obtain the puncture-resistant composite film.

[0009] In one embodiment of the present invention, in step S1, the mass ratio of the silane coupling agent KH550 to the rigid particles SiO2 is 0.5:1-1.2:1; the mass ratio of the silane coupling agent Si-69 to the flexible particles SBR is 0.5:1-1.2:1.

[0010] In one embodiment of the present invention, in step S1, the concentration of the pre-dispersion of modified SiO2 is 0.1wt%-0.5wt%.

[0011] In one embodiment of the present invention, in step S1, the concentration of the modified SBR predispersant is 1wt%-2wt%.

[0012] In one embodiment of the present invention, in step S1, the dispersion preparation of the pre-dispersion liquid is carried out by ultrasonic dispersion, and the ultrasonic time is preferably controlled to be more than 0.5 h.

[0013] In one embodiment of the present invention, in steps S1 and S2, the organic solvent is DMF.

[0014] In one embodiment of the present invention, in step S2, the volume ratio of the modified SiO2 predispersant to the modified SBR predispersant is 1:1-1.2:1.

[0015] In one embodiment of the present invention, in step S2, the mixing and dispersion method is magnetic stirring.

[0016] In one embodiment of the present invention, step S2 further includes transferring the uniformly dispersed mixture into a cell disruptor for further dispersion. The power of the cell disruptor is controlled at 90W-110W, and the dispersion time is 20min-30min.

[0017] In one embodiment of the present invention, in step S3, the drying conditions are: drying temperature of 50℃-70℃ and drying time of 4h-6h.

[0018] In one embodiment of the present invention, in step S3, the thickness of the TPU composite film is 0.2-0.4 mm.

[0019] In one embodiment of the present invention, in step S4, the conditions for hot-pressing composite are: hot-pressing temperature of 180℃-200℃, pressure of 10MPa-20MPa, and hot-pressing time of 25min-35min.

[0020] The second objective of this invention is to provide a puncture-resistant composite film of rigid-flexible particle blended modified TPU prepared by the above-described preparation method.

[0021] A third objective of this invention is to provide the application of the stab-resistant composite film of the rigid-flexible particle blend modified TPU in personal stab-resistant clothing.

[0022] The technical solution of the present invention has the following advantages compared with the prior art:

[0023] The preparation method described in this invention is low-cost and highly operable. While using rigid particles alone as fillers can significantly toughen TPU, it also results in high TPU stiffness. Therefore, it can be blended with a certain amount of flexible particles before being filled into TPU to obtain a composite film with high flexibility and high puncture resistance. Furthermore, to meet the growing demand for various static puncture protection products, the TPU flexible puncture-resistant composite film can not only be used alone but also combined with a fabric layer through methods such as hot pressing to achieve a dual puncture-resistant effect, making it highly practical. Attached Figure Description

[0024] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings, wherein...

[0025] Figure 1 This is a flowchart illustrating the manufacturing process of the rigid-flexible particle blend modified TPU anti-stab composite film of the present invention.

[0026] Figure 2 These are scanning electron microscope images of the TPU composite film and its bilayer composite material with nonwoven fabric after being punctured in Embodiment 1 of the present invention. The left image shows the cross-sectional morphology of the TPU composite film after being punctured, and the right image shows the damage morphology of the bilayer composite material after being punctured. Detailed Implementation

[0027] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0028] The following will further elaborate on the more effective and simple method for improving the static puncture resistance of fabrics provided by the present invention, using several specific embodiments.

[0029] Example 1

[0030] This embodiment provides a method for preparing a stab-resistant composite film using rigid-flexible particle blended modified TPU, as detailed below:

[0031] Step 1: Modify rigid SiO2 particles with KH550 (mass ratio KH550:SiO2 = 0.85:1), and prepare a 0.3wt% rigid particle dispersion with DMF as solvent.

[0032] Step 2: Modify the flexible particle SBR with Si69 (Si69: SBR=0.85:1) and prepare a 1wt% flexible particle dispersion with DMF as solvent.

[0033] Step 3: Dissolve 10 wt% TPU particles in DMF solution, and pour in 0.3 wt% SiO2 dispersion and 1 wt% SBR dispersion and mix thoroughly to disperse them.

[0034] Step 4: Transfer the mixed solution into polytetrafluoroethylene molds, 12g per portion, and place them in an oven to dry. Set the oven temperature to 60℃ and the drying time to 5 hours.

[0035] Step 5: Set the hot-pressing temperature to 190 ℃, the pressure to 15 MPa, and the hot-pressing time to 30 min. Through hot pressing, a layer of TPU composite film is laminated to each side of the polyester nonwoven fabric, resulting in a double-sided single-layer composite material. The obtained material is characterized, and the results are shown below. Figure 2 .

[0036] Example 2

[0037] This embodiment provides a method for preparing a stab-resistant composite film using rigid-flexible particle blended modified TPU, as detailed below:

[0038] Step 1: Modify rigid SiO2 particles with KH550 (mass ratio KH550:SiO2 = 0.85:1), and prepare a 0.3wt% rigid particle dispersion with DMF as solvent.

[0039] Step 2: Modify the flexible particle SBR with Si-69 (Si-69: SBR=0.85:1) and prepare a 1wt% flexible particle dispersion with DMF as solvent.

[0040] Step 3: Dissolve 10 wt% TPU particles in DMF solution, and pour in 0.3 wt% SiO2 dispersion and 1 wt% SBR dispersion and mix thoroughly to disperse them.

[0041] Step 4: Transfer the mixed solution into polytetrafluoroethylene molds, 12g per portion, and place them in an oven to dry. Set the oven temperature to 60℃ and the drying time to 5 hours.

[0042] Step 5: Set the hot pressing temperature to 190 ℃, the pressure to 15 MPa, and the hot pressing time to 30 min. By hot pressing, two identical TPU composite films are laminated on one side of the polyester nonwoven fabric to obtain a single-sided double-layer composite material.

[0043] Example 3

[0044] This embodiment provides a method for preparing a stab-resistant composite film using rigid-flexible particle blended modified TPU, as detailed below:

[0045] Step 1: Modify rigid SiO2 particles with KH550 (mass ratio KH550:SiO2 = 0.85:1), and prepare a 0.5wt% rigid particle dispersion with DMF as solvent.

[0046] Step 2: Modify the flexible particle SBR with Si69 (Si69: SBR=0.85:1) and prepare a 1wt% flexible particle dispersion with DMF as solvent.

[0047] Step 3: Dissolve 10 wt% TPU particles in DMF solution, and pour in 0.5 wt% SiO2 dispersion and 1 wt% SBR dispersion and mix thoroughly to disperse them.

[0048] Step 4: Transfer the mixed solution into polytetrafluoroethylene molds, 12g per portion, and place them in an oven to dry. Set the oven temperature to 60℃ and the drying time to 5 hours.

[0049] Step 5: Set the hot pressing temperature to 190 ℃, the pressure to 15 MPa, and the hot pressing time to 30 min. By hot pressing, a TPU composite film is coated onto one side of the polyester nonwoven fabric to obtain a single-layer composite material.

[0050] Example 4

[0051] This embodiment provides a method for preparing a stab-resistant composite film using rigid-flexible particle blended modified TPU, as detailed below:

[0052] Step 1: Modify rigid SiO2 particles with KH550 (mass ratio KH550:SiO2 = 0.85:1), and prepare a 0.5wt% rigid particle dispersion with DMF as solvent.

[0053] Step 2: Modify the flexible particle SBR with Si69 (Si69: SBR=0.85:1) and prepare a 1wt% flexible particle dispersion with DMF as solvent.

[0054] Step 3: Dissolve 10 wt% TPU particles in DMF solution, and pour in 0.1 wt% SiO2 dispersion and 3 wt% SBR dispersion and mix thoroughly to disperse them.

[0055] Step 4: Transfer the mixed solution into polytetrafluoroethylene molds, 12g per portion, and place them in an oven to dry. Set the oven temperature to 60℃ and the drying time to 5 hours.

[0056] Step 5: Set the hot pressing temperature to 190 ℃, the pressure to 15 MPa, and the hot pressing time to 30 min. By hot pressing, a layer of TPU composite film is laminated to each side of the polyester nonwoven fabric to obtain a double-sided single-layer composite material.

[0057] Comparative Example

[0058] The preparation method is similar to that in Example 1. A series of comparative materials were prepared, specifically: a TPU film doped with 0.3 wt% rigid SiO2 particles alone (B2-TPU, comparative group 1), a TPU film doped with 3 wt% flexible SBR particles alone (C2-TPU, comparative group 2), a TPU film co-doped with 0.1 wt% SiO2 and 3 wt% SBR (B1C2-TPU, comparative group 3), a TPU film co-doped with 0.5 wt% SiO2 and 3 wt% SBR (B3C2-TPU, comparative group 4), a TPU film co-doped with 0.3 wt% SiO2 and 5 wt% SBR (B2C3-TPU, comparative group 5), and a TPU film co-doped with 0.3 wt% SiO2 and 1 wt% SBR (B2C1-TPU, experimental group 1).

[0059] Test case

[0060] The tensile properties, stiffness, and puncture resistance of the materials obtained in the examples and comparative examples were tested, and the test results are shown in Table 1. As can be seen from Table 1, the puncture strength of the rigid-flexible hybrid TPU composite film with a suitable mixing ratio is significantly improved (as in experimental group 1). This is because the filling amount of rigid / flexible particles in the blend system is within a reasonable range. The rigid particles provide frictional resistance and good interfacial strength to disperse the puncture force, while the flexible particles resist puncture by enhancing flexibility and crosslinking density. The two work synergistically, have strong compatibility with TPU and an interfacial layer, and can effectively disperse and dissipate puncture energy, jointly hindering the advance of the needle. Table 1 also shows that the positive synergistic effect can only be exhibited when the mixing ratio of rigid and flexible particles is within a suitable range. It is not that mixing in any ratio can improve performance.

[0061] The maximum stress of TPU composite films filled with blended particles is lower than that of composite films filled with rigid particles, but higher than that of composite films filled with flexible particles. This is because the flexible particles in the rigid-flexible blend cause a decrease in the modulus of the composite film, and when the content of flexible particles is high, stress concentration points are easily formed at the interface, resulting in uneven stress distribution and premature failure of the composite film.

[0062] Table 1. Puncture and tensile properties of TPU composite films filled with blended particles of different concentrations.

[0063]

[0064] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method of making a stab-resistant composite film of rigid-flex particle blend modified TPU, characterized in that, The preparation method comprises the following steps: S1: modifying rigid particles SiO2 with silane coupling agent KH550 to obtain modified SiO2, dispersing the modified SiO2 in an organic solvent to obtain a pre-dispersion of the modified SiO2; the concentration of the pre-dispersion of the modified SiO2 is 0.1wt%-0.5wt%; modifying flexible particles SBR with silane coupling agent Si-69 to obtain modified SBR, dissolving the modified SBR in an organic solvent to obtain a pre-dispersion of the modified SBR; the concentration of the pre-dispersion of the modified SBR is 1wt%-2wt%; S2: dissolving TPU particles in an organic solvent, and adding the pre-dispersion of the modified SiO2 and the pre-dispersion of the modified SBR obtained in step S1, mixing and uniformly dispersing to obtain a mixed solution; the volume ratio of the pre-dispersion of the modified SiO2 and the pre-dispersion of the modified SBR is 1:1-1.2:1; S3: transferring the mixed solution obtained in step S2 to a polytetrafluoroethylene mold, and drying to obtain a TPU composite film; S4: compounding the TPU composite film with at least one side of a polyester non-woven fabric by a hot-pressing method to obtain the anti-stabbing composite film.

2. The production method according to claim 1, characterized by, In step S1, the mass ratio of the silane coupling agent KH550 to the rigid particles SiO2 is controlled in the range of 0.5:1-1.2:1; and the mass ratio of the silane coupling agent Si-69 to the flexible particles SBR is controlled in the range of 0.5:1-1.2:

1.

3. The preparation method according to claim 1, characterized in that, In step S3, the drying conditions are as follows: the drying temperature is 50 ℃-70 ℃, and the drying time is 4 h-6 h.

4. The method of claim 1, wherein, In step S3, the thickness of the TPU composite film is 0.2-0.4 mm.

5. The preparation method according to claim 1, characterized in that, In step S4, the hot-pressing conditions are as follows: the hot-pressing temperature is 180 ℃-200 ℃, the pressure is 10 MPa-20 MPa, and the hot-pressing time is 25 min-35 min.

6. The anti-stabbing composite film of rigid-flexible particle blended modified TPU prepared by the preparation method in any one of claims 1-5.

7. The anti-stabbing composite film of rigid-flexible particle blended modified TPU in claim 6 is applied in individual protective equipment.

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