TPU (Thermoplastic Polyurethane) master batch, TPU film as well as preparation method and application of TPU film

Abstract

The invention discloses a TPU (thermoplastic polyurethane) master batch, a TPU film as well as a preparation method and application of the TPU film. The TPU master batch comprises a main raw material, and the main raw material is composed of the following components in percentage by mass based on the main raw material: 83%-95% of a TPU base material, 3%-8% of polyvinylidene fluoride, 1%-8% of polyolefin wax and 0.4%-1% of hydrophobic white carbon black; the particle size of the hydrophobic white carbon black is 5-30nm. The TPU film prepared from the TPU master batch disclosed by the invention has relatively good hydrophobic, carbon dioxide permeable and air permeable effects. The preparation process of the TPU master batch and the TPU film is simple.

Description

TECHNICAL FIELD

[0001] The application relates to a TPU master batch, a TPU film and a preparation method and application thereof. BACKGROUND

[0002] Waterproof and moisture-permeable materials are widely used in various fields. Waterproof and moisture-permeability (also known as waterproof and air-permeability) refers to that the material does not allow water droplets and other liquids to penetrate, but allows small molecule gases to freely permeate.

[0003] Thermoplastic polyurethane material (TPU) has excellent high tension, high pulling force, toughness and aging resistance, and is a mature environment-friendly material. TPU is an environment-friendly polymer, and its Chinese name is thermoplastic polyurethane. It is a major breakthrough for the application of new environment-friendly materials to waterproof and air-permeable fabrics. It overcomes many defects of PVC and PU leather. It not only has most of the properties of rubber and ordinary plastics, but also has excellent comprehensive physical and chemical properties, so it is also known as future material. In recent decades, TPU has become one of the fastest growing polymer materials. TPU film is an important application form of TPU material, and in recent years, with the development and progress of high technology, it has also been more and more widely used.

[0004] However, the existing TPU film cannot well balance waterproof and air permeability, and further improvement is needed. SUMMARY

[0005] The technical problem to be solved by the application is to overcome the defects that the TPU film in the prior art is difficult to have better hydrophobic and air permeability, and to provide a TPU master batch, a TPU film and a preparation method and application thereof. The TPU film prepared by using the TPU master batch of the application can have better hydrophobic, carbon dioxide permeability and air permeability. The preparation process of the TPU master batch and the TPU film of the application is simple.

[0006] The application solves the above technical problems through the following technical scheme:

[0007] The application provides a TPU master batch, which comprises a main raw material, and based on the main raw material, the main raw material is composed of the following components in terms of mass percentage: 83%-95% TPU base material, 3%-8% polyvinylidene fluoride, 1%-8% polyolefin wax and 0.4%-1% hydrophobic white carbon black; wherein the particle size of the hydrophobic white carbon black is 5-30 nm.

[0008] In the application, the TPU base material can be a conventional thermoplastic polyurethane material in the art, and is preferably a polyether type TPU or a polyester type TPU, for example, a polyester type TPU.

[0009] In the application, the melt flow rate of the TPU base material can be 10-30 g / 10 min, for example, 20 g / 10 min.

[0010] In the present application, the tensile strength of the TPU base material can be 30-70 MPa, for example 50 MPa.

[0011] In the present application, the elongation at break of the TPU base material can be 500%-700%, for example 600% or 650%.

[0012] In the present application, the tear strength of the TPU base material can be 100-140 KN / m, for example 120 KN / m.

[0013] In the present application, the Shore hardness of the TPU base material can be 55A-95A, for example 87A.

[0014] In the present application, the model of the TPU base material is preferably HF-3385 produced by Huafeng.

[0015] In the present application, the mass percentage of the TPU base material is preferably 85%-94%, for example 87%, 90%, 90.2% or 93.2%.

[0016] In the present application, the present inventors have found that during the blending and processing of the polyvinylidene fluoride (PVDF) with the thermoplastic polyurethane material (TPU base material), the fluorine-containing groups rich in the molecular chain of the polyvinylidene fluoride migrate to the surface layer of the material, forming a hydrophobic layer with low surface energy, and giving the matrix good hydrophobic properties.

[0017] In the present application, the melt flow rate of the polyvinylidene fluoride can be 5-10 g / 10 min, for example 6 g / 10 min.

[0018] In the present application, the density of the polyvinylidene fluoride is preferably 1.75-1.78 g / cm 3 , for example 1.78 g / cm 3 .

[0019] In the present application, the melting point of the polyvinylidene fluoride is preferably 171-180℃, for example 173℃.

[0020] In the present application, the mass percentage of the polyvinylidene fluoride is preferably 3.5%-7%, for example 5% or 6.5%.

[0021] In the present application, the polyolefin wax preferably includes polyethylene wax and / or polypropylene wax.

[0022] The number average molecular weight of the polyethylene wax can be 3000-5000, for example 3500.

[0023] The softening point of the polyethylene wax can be 40-60℃, for example 50, 52 or 58℃.

[0024] The polyethylene wax has a melt flow rate of 50-150 g / 10 min, for example 100 g / 10 min.

[0025] The polypropylene wax has a number average molecular weight of 4500-5500, for example 5000.

[0026] The polypropylene wax has a softening point of 133-135℃, for example 135℃.

[0027] The polypropylene wax has a melt flow rate of 55-140 g / 10 min, for example 100 g / 10 min.

[0028] In the present application, the mass percentage of the polyolefin wax is preferably 3%-8%, for example 4%, 5% or 6%.

[0029] In the present application, the hydrophobic white carbon black refers to white carbon black that is surface-modified by a silane coupling agent or silicone oil. The silane coupling agent preferably includes methyltrichlorosilane and / or hexamethyldisilazane, for example hexamethyldisilazane.

[0030] In the present application, the hydrophobic white carbon black is preferably fumed hydrophobic white carbon black, for example Silica SK 200s.

[0031] In the present application, the particle size of the hydrophobic white carbon black is preferably 5-20 nm, for example 5, 10 or 15 nm.

[0032] In the present application, the pH value of the hydrophobic white carbon black can be 3.6-4.4.

[0033] In the present application, the mass percentage of the hydrophobic white carbon black is preferably 0.42%-0.5%, for example 0.45%.

[0034] In the present application, the difference between the melt flow rate of the polyolefin wax and the melt flow rate of the TPU base material can be 20-140 g / 10 min, for example 50-100 g / 10 min, for example 80 g / 10 min.

[0035] In the present application, the TPU master batch preferably further includes auxiliary raw materials. The auxiliary raw materials preferably include an antioxidant and / or a crosslinking agent.

[0036] The type of the antioxidant can be conventional in the art, and is preferably a hindered phenol compound and / or a phosphite compound, for example tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and / or tris[2.4-di-tert-butylphenyl]phosphite.

[0037] When the antioxidant is a hindered phenolic compound and a phosphite compound, the mass ratio of the hindered phenolic compound to the phosphite compound is preferably (0.5-1.5): 1, for example 1:1.

[0038] The mass percentage of the antioxidant is preferably 0.2%-0.3% of the total mass of the main raw material, for example 0.3%.

[0039] The type of the crosslinking agent can be conventional in the art, and preferably includes dicumyl peroxide.

[0040] The mass of the crosslinking agent is preferably 0.05%-0.5% of the total mass of the main raw material, for example 0.5%.

[0041] In a preferred embodiment, the TPU masterbatch includes a main raw material composed of 90% TPU base material, 3.5% polyvinylidene fluoride, 6% polyethylene wax, and 0.5% hydrophobic white carbon black. Preferably, the TPU masterbatch further includes 0.5% crosslinking agent and 0.3% antioxidant. The mass percentage indicates the mass percentage of each component in the total mass of the main raw material. The particle size of the hydrophobic white carbon black is preferably 5-20 nm, for example 10 nm.

[0042] In a preferred embodiment, the TPU masterbatch includes a main raw material composed of 93.2% TPU base material, 3.5% polyvinylidene fluoride, 3% polyethylene wax, and 0.3% hydrophobic white carbon black. Preferably, the TPU masterbatch further includes 0.5% crosslinking agent and 0.3% antioxidant. The mass percentage indicates the mass percentage of each component in the total mass of the main raw material.

[0043] In a preferred embodiment, the TPU masterbatch includes a main raw material composed of 87% TPU base material, 6.5% polyvinylidene fluoride, 6% polyethylene wax, and 0.5% hydrophobic white carbon black. Preferably, the TPU masterbatch further includes 0.5% crosslinking agent and 0.3% antioxidant. The mass percentage indicates the mass percentage of each component in the total mass of the main raw material.

[0044] In a preferred embodiment, the TPU masterbatch includes a main raw material composed of 90% base material, 3.5% polyvinylidene fluoride, 6% polyethylene wax, and 0.5% hydrophobic white carbon black. Preferably, the TPU masterbatch further includes 0.5% crosslinking agent and 0.3% antioxidant. The mass percentage indicates the mass percentage of each component in the total mass of the main raw material.

[0045] In a preferred embodiment, the TPU masterbatch comprises a main raw material consisting of 90% base material, 3.5% polyvinylidene fluoride, 6% polypropylene wax, and 0.5% hydrophobic silica. Preferably, the TPU masterbatch further comprises 0.5% crosslinking agent and 0.3% antioxidant. The mass percentages represent the percentage of each component's mass relative to the total mass of the main raw material.

[0046] The present invention also provides a method for preparing TPU masterbatch as described above, which includes the following steps: mixing and granulating the components of the TPU masterbatch to obtain the TPU masterbatch.

[0047] In this invention, the granulation operation can be conventional in the art, for example, carried out in a single-screw granulator or a twin-screw granulator.

[0048] In this invention, the granulation process preferably includes the steps of melt blending, cooling, drying, and pelletizing. The temperature of the melt blending can be 70-180°C. The cooling method can be water cooling. The drying method can be air drying.

[0049] The melt blending is carried out in a twin-screw granulator, and the preferred process conditions for the melt blending are as follows:

[0050] The temperature in Zone 1 is 70-90℃;

[0051] The temperature in Zone 2 is 150-160℃;

[0052] The temperature in Zone 3 is 160-170℃;

[0053] The temperature in Zone 4 is 160-180℃;

[0054] The temperature in Zone 5 is 160-180℃;

[0055] The temperature in Zone 6 is 160-180℃;

[0056] The temperature in Zone 7 is 150-170℃.

[0057] More preferably:

[0058] The temperature in Zone 1 is 85℃;

[0059] The temperature in Zone 2 is 155℃;

[0060] The temperature in Zone 3 is 165℃;

[0061] The temperature in Zone 4 is 170℃;

[0062] The temperature in Zone 5 is 175℃;

[0063] The temperature in Zone 6 is 170℃;

[0064] The temperature in Zone 7 is 160℃.

[0065] The present invention provides a method for preparing a TPU film, which includes the following steps: forming a film from the raw material of the TPU masterbatch.

[0066] In this invention, the film formation method can be film casting.

[0067] The film casting process preferably employs a single-screw casting machine.

[0068] In this invention, the film-forming temperature can be 160-200℃.

[0069] In some embodiments, the film formation is performed using a single-screw casting machine, and the preferred process conditions for the single-screw casting machine are:

[0070] The temperature in zone one of the barrel is 160-170℃;

[0071] The temperature in zone two of the barrel is 160-180℃;

[0072] The temperature in the three zones of the barrel is 170-180℃;

[0073] The temperature in zone four of the barrel is 170-180℃;

[0074] The temperature in zone one of the mold is 160-180℃;

[0075] The temperature in zone two of the mold is 160-180℃;

[0076] The temperature in the three zones of the mold is 160-180℃;

[0077] The temperature of the middle roller is 20-40℃;

[0078] The front roller temperature is 20-40℃.

[0079] More preferably:

[0080] The temperature in zone one of the barrel is 160℃;

[0081] The temperature in zone two of the barrel is 170℃;

[0082] The barrel temperature in three zones is 180℃;

[0083] The temperature in the fourth zone of the barrel is 180℃;

[0084] The temperature in zone one of the molds is 170℃;

[0085] The temperature in zone two of the mold is 170℃;

[0086] The temperature in zone three of the mold is 170℃;

[0087] The temperature of the middle roller is 30℃;

[0088] The front roll temperature is 30℃.

[0089] In the above embodiments, the temperatures of the zones of the cylinder and the zones of the die are film forming temperatures, and the temperatures of the middle roll and the front roll are cooling temperatures.

[0090] The present application provides a TPU film prepared by the method for preparing a TPU film as described above.

[0091] The present application forms a TPU film with a specific structure by selecting a TPU master batch with a specific composition. In the film forming process, the TPU base in the TPU master batch forms a TPU base film, the polyvinylidene fluoride migrates to the surface layer of the TPU base film in the film forming process due to the enrichment of fluorine-containing groups to form a polyvinylidene fluoride inner layer on the surface of the TPU base film; the polyolefin wax and the TPU base undergo dynamic phase separation in the film forming process to form a polyolefin wax outer layer on the outer layer of the TPU base film to block the transmission of water molecules; in addition, the hydrophobic silica forms micro-nano gas channels in the film forming process to achieve gas transmission. Further, by adjusting the particle size of the silica, the selective control of the transmission and flux of different gas molecules can be achieved.

[0092] The present application provides a TPU film, which comprises a main film, the main film comprising a TPU base film, both sides of the TPU base film being respectively provided with a polyvinylidene fluoride inner layer and a polyolefin wax outer layer distributed in a direction away from the TPU base film; the TPU film is further provided with a through channel, and the channel is distributed with hydrophobic silica.

[0093] Based on the main film, the main film comprises 83%-95% TPU base film, 3%-8% polyvinylidene fluoride inner layer, 1%-8% polyolefin wax outer layer, and 0.4%-1% hydrophobic silica, in terms of mass percentage.

[0094] In the present application, the content of each component does not change after the TPU master batch is formed into a TPU film.

[0095] In the present application, the mass percentage of the TPU base film in the main film can be 85%-94%, for example, 87%, 90%, 90.2%, or 93.2%.

[0096] In the present application, the mass percentage of the polyvinylidene fluoride inner layer in the main film can be 3.5%-7%, for example, 5% or 6.5%.

[0097] In the present application, the mass percentage of the polyolefin wax outer layer in the main film can be 3%-8%, for example, 4%, 5%, or 6%.

[0098] In the present application, the mass percentage of the hydrophobic white carbon black in the main film can be 0.42%-0.5%, for example, 0.45%.

[0099] In the present application, the TPU film preferably further comprises an auxiliary material.

[0100] Preferably, the auxiliary material comprises an antioxidant and / or a crosslinking agent.

[0101] The mass percentage of the antioxidant is preferably 0.2%-0.3% of the total mass of the main film, for example, 0.3%.

[0102] The mass of the crosslinking agent is preferably 0.05%-0.5% of the total mass of the main film, for example, 0.5%.

[0103] In the present application, the thickness of the TPU film can be 0.03-2mm.

[0104] In the present application, the water permeability of the TPU film can be 0.4-0.8g / (m 2 ·24h),for example, 0.63, 0.77, 0.42, 0.66, 0.69 or 0.64 g / (m 2 ·24h)。

[0105] In the present application, the carbon dioxide permeability of the TPU film can be 13500-25000 cm 3 / (m 2 ·24h·0.1MPa),for example, 18741, 15312, 17648, 18993, 19032 or 18637 cm 3 / (m 2 ·24h·0.1MPa)。

[0106] In the present application, the air permeability of the TPU film can be 13000-30000 cm 3 / (m 2 ·24h·0.1MPa),for example, 24174, 23337, 24316, 24193, 25731 or 24268 cm 3 / (m 2 ·24h·0.1MPa)。

[0107] The present application also provides an application of the TPU master batch or TPU film as described above in the field of waterproof and breathable.

[0108] In the present application, the field of waterproof and breathable preferably includes the field of electronic components or clothing.

[0109] On the basis of common sense in the art, the above-mentioned preferred conditions can be combined arbitrarily, i.e., to obtain each preferred example of the present application.

[0110] The reagents and raw materials used in the present application are commercially available.

[0111] The positive progress effect of the present application is that:

[0112] (1) By selecting a TPU masterbatch with a specific composition, a TPU film with a specific structure can be formed after film formation, which can have better hydrophobic and breathable effects.

[0113] (2) The preparation process of the TPU masterbatch and TPU film of the present application is simple. BRIEF DESCRIPTION OF DRAWINGS

[0114] Figure 1 The figure is a schematic diagram of the structure of the TPU film of the present application.

[0115] BRIEF DESCRIPTION OF DRAWINGS

[0116] 1-TPU base film; 2-1-polyvinylidene fluoride inner layer; 2-2-polyolefin wax outer layer; 3-penetrating channel; 4-hydrophobic silica. DETAILED DESCRIPTION

[0117] The present application will be further illustrated by the following examples, but the present application is not limited to the scope of the examples.

[0118] The types and manufacturers of the raw materials used in the following examples and comparative examples are shown in the following table:

[0119]

[0120] The preparation method of the TPU film of Examples 1-5 and Comparative Examples 1-5 is as follows:

[0121] 1) A weighed amount of thermoplastic polyurethane elastomer (TPU base material), polyvinylidene fluoride (PVDF), polyolefin wax, hydrophobic silica (SiO2), crosslinking agent and antioxidant (1010 and 168 in a mass ratio of 1:1) were mixed in the proportions shown in Table 1 and added to a twin-screw granulator, and melt blended at a first zone temperature of 80°C, a second zone temperature of 155°C, a third zone temperature of 165°C, a fourth zone temperature of 170°C, a fifth zone temperature of 175°C, a sixth zone temperature of 170°C, and a seventh zone temperature of 160°C, then water-cooled, air-dried, and cut into granules to obtain a TPU masterbatch.

[0122] 2) The above TPU masterbatch was added to a single-screw casting machine for casting and film formation, with a barrel first zone temperature of 160°C, a barrel second zone temperature of 170°C, a barrel third zone temperature of 180°C, a barrel fourth zone temperature of 180°C, a die first zone temperature of 170°C, a die second zone temperature of 170°C, a die third zone temperature of 170°C, a front roller temperature of 30°C, and a middle roller temperature of 30°C.

[0123] Table 1

[0124]

[0125] Note: The mass percentage of each component in Table 1 is represented, taking the total mass of the thermoplastic polyurethane elastomer, the polyvinylidene fluoride, the polyolefin wax, and the hydrophobic silica as 100%, and the mass percentage of each component.

[0126] Effect implementation examples

[0127] The structural schematic diagram of the TPU film prepared in Examples 1-6 is shown in Figure 1 It can be seen from Figure 1 that the TPU film comprises a TPU base film 1, a polyvinylidene fluoride inner layer 2-1 and a polyolefin wax outer layer 2-2 distributed in a direction away from the TPU base film 1; the TPU film is also provided with a through channel 3, and the through channel 3 is distributed with hydrophobic silica 4.

[0128] The TPU films prepared in the above Examples 1-6 and Comparative Examples 1-5 were respectively detected for water permeability, carbon dioxide permeation amount, and air permeation amount, and the detection methods were respectively:

[0129] Water permeability: GB / T 1037-2021;

[0130] Carbon dioxide permeation amount and air permeation amount: GB / T 1038.2-2022 Test methods for gas transmission of plastic products, films and sheets.

[0131] The detection results are shown in Table 2 below.

[0132] Table 2

[0133]

[0134] As can be seen from Table 2, compared with Comparative Example 1-5, the TPU film prepared in Example 1-6 can have better hydrophobic effect, carbon dioxide permeation effect and air permeation effect, and can simultaneously satisfy the requirements of water permeability less than 0.81 g / (m 2 ·24h), carbon dioxide permeation amount greater than 13165 cm 3 / (m 2 ·24h·0.1MPa), and air permeation amount greater than 12137 cm 3 / (m 2 ·24h·0.1MPa).

[0135] Compared with Example 1, no polyvinylidene fluoride was added when preparing the TPU film in Comparative Example 1, and the prepared TPU film had high water permeability, with water permeability as high as 0.81 g / (m 2 ·24h), and poor hydrophobic effect.

[0136] Compared with Example 1, no polyolefin wax was added in the preparation of the TPU film in Comparative Example 2, and the prepared TPU film had a higher water permeability, with a water permeability of 2.3 g / (m 2 ·24h), and a poor hydrophobic effect.

[0137] Compared with Example 1, no hydrophobic silica was added in the preparation of the TPU film in Comparative Example 3, and the prepared TPU film had a lower carbon dioxide permeability, with a carbon dioxide permeability of only 8275 cm 3 / (m 2 ·24h·0.1MPa), a lower air permeability, with an air permeability of only 12137 cm 3 / (m 2 ·24h·0.1MPa), and a poor air permeability effect.

[0138] Compared with Example 1, the mass percentage of the hydrophobic silica was less in Comparative Example 4, and the prepared TPU film had a lower carbon dioxide permeability, with a carbon dioxide permeability of only 13165 cm 3 / (m 2 ·24h·0.1MPa), and a poor air permeability effect.

[0139] Compared with Example 1, when the particle size of the hydrophobic silica was larger in Comparative Example 5, the prepared TPU film had a higher water permeability, with a water permeability of 0.89 g / (m 2 ·24h), and a poor hydrophobic effect.

[0140] Although the specific embodiments of the present application are described above, those skilled in the art should understand that this is only an example, and the protection scope of the present application is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present application, and such changes and modifications fall within the protection scope of the present application.

Claims

1. A TPU masterbatch, characterized in that, It includes main raw materials, which, by mass percentage, consist of the following components: 83%-95% TPU base material, 3%-8% polyvinylidene fluoride, 1%-8% polyolefin wax and 0.4%-1% hydrophobic silica; wherein the particle size of the hydrophobic silica is 5-30 nm.

2. The TPU masterbatch as described in claim 1, characterized in that, The TPU masterbatch meets one or more of the following conditions: (1) The TPU base material is polyether-type TPU or polyester-type TPU; (2) The melt flow rate of the TPU base material is 10-30 g / 10 min; (3) The tensile strength of the TPU base material is 30-70 MPa; (4) The elongation at break of the TPU base material is 500%-700%; (5) The tear strength of the TPU base material is 100-140 KN / m; (6) The Shore hardness of the TPU base material is 55A-95A; (7) The TPU base material has a mass percentage of 85%-94%; (9) The melt flow rate of the polyvinylidene fluoride is 5-10 g / 10 min; (10) The density of the polyvinylidene fluoride is 1.75-1.78 g / cm³. 3 ; (11) The melting point of the polyvinylidene fluoride is 171-180℃; (12) The polyvinylidene fluoride has a mass percentage of 3.5%-7%; (13) The polyolefin wax includes polyethylene wax and / or polypropylene wax; (14) The polyolefin wax has a mass percentage of 3%-8%; (15) The particle size of the hydrophobic silica is 5-20 nm; (16) The pH value of the hydrophobic silica is 3.6-4.4; (17) The hydrophobic silica has a mass percentage of 0.42%-0.5%; (18) The difference between the melt flow rate of the polyolefin wax and the melt flow rate of the TPU base material is 20-140 g / 10min.

3. The TPU masterbatch as described in claim 1, characterized in that, The TPU masterbatch also includes antioxidants and / or crosslinking agents.

4. The TPU masterbatch as described in claim 3, characterized in that, The TPU masterbatch meets one or more of the following conditions: (1) The antioxidants are hindered phenolic compounds and / or phosphite compounds; (2) The antioxidant is 0.2%-0.3% of the total mass of the main raw materials; (3) The crosslinking agent includes dicumyl peroxide; (4) The mass of the crosslinking agent is 0.05%-0.5% of the total mass of the main raw materials.

5. A method for preparing TPU masterbatch as described in any one of claims 1-4, characterized in that, It includes the following steps: mixing and granulating the components of the TPU masterbatch to obtain the TPU masterbatch.

6. A method for preparing a TPU film, characterized in that, It includes the following steps: forming a film from a raw material comprising the TPU masterbatch as described in any one of claims 1-4.

7. A TPU film, characterized in that, It is prepared using the TPU film preparation method as described in claim 6.

8. A TPU film, characterized in that, It includes a main film, which includes a TPU base film. On both sides of the TPU base film, there are polyvinylidene fluoride inner layers and polyolefin wax outer layers distributed in a direction away from the TPU base film. The TPU film also has through channels in which hydrophobic silica is distributed. Based on the main membrane, by mass percentage, the main membrane consists of 83%-95% TPU base membrane, 3%-8% polyvinylidene fluoride inner layer, 1%-8% polyolefin wax outer layer and 0.4%-1% hydrophobic silica.

9. The TPU film as described in claim 8, characterized in that, The TPU film satisfies one or more of the following conditions: (1) In the main film, the TPU base film accounts for 85%-94% by mass; (2) In the main membrane, the mass percentage of the polyvinylidene fluoride inner layer is 3.5%-7%; (3) In the main film, the mass percentage of the polyolefin wax outer layer is 3%-8%; (4) In the main membrane, the mass percentage of the hydrophobic silica is 0.42%-0.5%; (5) The TPU film further includes antioxidants and / or crosslinking agents; (6) The water permeability of the TPU membrane is 0.4-0.8 g / (m³). 2 ·24h); (7) The carbon dioxide permeability of the TPU membrane is 13,500-25,000 cm³. 3 / (m 2 ·24h·0.1MPa); (8) The air permeability of the TPU film is 13000-30000 cm³. 3 / (m 2 ·24h·0.1MPa).

10. The application of a TPU masterbatch as described in any one of claims 1-4 or a TPU film as described in any one of claims 7-9 in the field of waterproof and breathable technology.

Images