Fluorine-free, glue-free and solvent-free film, double-layer composite fabric and preparation method of double-layer composite fabric

Abstract

The invention belongs to the technical field of windproof and moisture permeable composite fabrics, and particularly discloses a fluoride-free, glue-free and solvent-free film, a double-layer composite fabric and a preparation method thereof, the film comprises the following components by mass: 58-74% of a polyurethane elastomer TPU, 7-11% of a polyester elastomer TPEE, 12-22% of vulcanized silicone rubber micro powder, 2-8% of silica aerogel powder, and 1-5% of an ultraviolet light absorber. The double-layer composite fabric comprises a fabric body and the thin film, and the thin film and the fabric body are compounded through an infiltration method. According to the fluorine-free, glue-free and solvent-free film, the double-layer composite fabric and the preparation method of the double-layer composite fabric, a novel fluorine-free and glue-free fabric and film infiltration type composite technology is achieved, the fabric waterproof treatment procedure is omitted, and the fluorine-free, glue-free and solvent-free film and the preparation method of the double-layer composite fabric are lower in carbon, environmentally friendly and resistant to wind and water and high in breathability and moisture permeability.

Description

Technical Field

[0001] The invention relates to the technical field of windproof and moisture-permeable composite fabrics, and in particular to a fluorine-free, glue-free and solvent-free film, a double-layer composite fabric and a preparation method thereof. Background Art

[0002] In recent years, the comfort, appearance, and special properties of fabrics have received increasing attention. Functional fabrics refer to fabrics with special properties and uses, such as waterproof, windproof, breathable, moisture-permeable, UV-resistant, anti-static, radiation-proof, flame-retardant, high-temperature resistant, and acid and alkali-resistant.

[0003] In existing technology, functional fabrics are often laminated composites, combining fabric + glue + film + glue + fabric, with the film typically being a PTFE (polytetrafluoroethylene) membrane. Because PTFE (polytetrafluoroethylene) membranes lack the ability to melt, they must be laminated with glue, resulting in a thick, stiff composite fabric with poor breathability and low durability. Furthermore, to meet surface moisture resistance requirements, the fabrics require specialized waterproofing treatment, which carries the risk of PFAS contamination from both the waterproofing treatment and the PTFE (polytetrafluoroethylene) membrane. Summary of the Invention

[0004] The purpose of the present invention is to provide a fluorine-free, glue-free and solvent-free film, a double-layer composite fabric and a preparation method thereof, to realize a new fluorine-free and glue-free fabric + film melt-infiltration composite process, eliminating the fabric waterproofing process, being more low-carbon and environmentally friendly, and embodying windproof, waterproof and high breathable and moisture permeability.

[0005] To achieve the above object, the present invention provides a fluorine-free, glue-free, and solvent-free film comprising the following mass-array components: Polyurethane elastomer TPU 58-74%, polyester elastomer TPEE 7-11%, vulcanized silicone rubber powder 12-22%, silica aerogel powder 2-8%, UV absorber 1-5%.

[0006] The present invention also provides a method for preparing a fluorine-free, glue-free and solvent-free film, comprising the following steps: S1. Add polyurethane elastomer TPU, polyester elastomer TPEE, vulcanized silicone rubber powder, silica aerogel powder and ultraviolet absorber in a constant speed mixer in proportion and mix well to obtain a mixture; S2, transferring the mixture obtained in S1 to a twin-screw granulator for extrusion granulation; S3. Transfer the granules obtained in S2 to a casting machine or a blow molding machine for processing to obtain a film.

[0007] Preferably, in S1, the speed of the uniform speed stirrer is 0-30 rpm and the temperature is 0-40°C.

[0008] Preferably, in S2, the temperature of the twin-screw granulator is 190-230°C.

[0009] Preferably, in S3, the casting machine melts the granules and extrude the melted granules, and casts the melted granules onto a cooling roller to form a film, wherein the temperature of the cooling roller is 20-50° C.; The blow molding machine melts the granules and blows them up to obtain a film. The blowing pressure is 1-1.5 MPa and the blowing ratio is 2-4 times.

[0010] The present invention also provides a fluorine-free, glue-free and solvent-free double-layer composite fabric, comprising a fabric and the film, wherein the film and the fabric are composited by a melt infiltration method.

[0011] Preferably, the fabric is woven from one or more of polyester, nylon, spandex, and cotton.

[0012] The present invention also provides a method for preparing a fluorine-free, glue-free and solvent-free double-layer composite fabric, comprising the following steps: T1. Lay the film flat on the surface of the fabric to obtain a double-layer fabric; T2. Use two rollers to perform synchronous heat pressing treatment on the lower surface and the upper surface, and obtain a double-layer composite fabric after cooling.

[0013] Preferably, in T2, the heat pressing treatment is performed by first increasing the pressure and then decreasing the pressure, and at the same time, first increasing the temperature and then decreasing the temperature. The pressure range of the heat pressing treatment is 0.1-0.5 MPa, and the treatment time is 1-30 min.

[0014] Preferably, in T2, the temperature range of the roller is 120-180°C.

[0015] Therefore, the present invention adopts the above-mentioned fluorine-free, glue-free and solvent-free film, double-layer composite fabric and preparation method thereof, and the beneficial effects are as follows: (1) The film of the present invention introduces a silica aerogel material with a porosity greater than 90%, which forms an island structure with the elastomer material. Before the film with the island structure is compounded with the fabric, the elastomer material is wrapped around the outer surface of the silica aerogel, sealing the aerogel's micropores. At this time, the air and moisture permeability is still poor. When compounded with the fabric, the elastomer melts at high temperature, penetrates and disperses into the fibers, and firmly bonds with the fabric. At this time, the silica aerogel does not change its shape, and the micropores become visible, just like the reefs exposed when the sea ebbs, reflecting high air and moisture permeability.

[0016] (2) The film of the present invention utilizes TPU and TPEE, both of which are lipophilic and non-hydrophilic, with a contact angle with water greater than 120°, high hydrophobicity, and non-hydrolyzed. The molecular structure is not easily degraded in water. Furthermore, TPU and TPEE have complementary properties, possessing both plasticity and high elasticity, while combining the dual properties of plastic and rubber, optimizing the strength and toughness of the film while also taking into account compatibility and lamination performance with a variety of fabrics.

[0017] (3) The double-layer composite fabric of the present invention pioneers the use of melt-infiltration composite technology, which uses heat to melt the film of the new windproof and moisture-permeable material Quadra-Tex membrane. It is simple and efficient, fluorine-free and glue-free, and has no dielectric composite, is environmentally friendly and low-carbon. It also does not contain fluorine-based thermoplastic elastomer Quadra-Tex membrane, is low-priced, and has great cost advantages.

[0018] (4) During the hot pressing process of the present invention, the high-temperature molten polyurethane TPU and polyester TPEE elastomer in the Quadra-Tex membrane penetrate into the fibers of the fabric. The fabric gradually absorbs the molten TPU and TPEE elastomer, and the microporous structure of the Quadra-Tex membrane becomes apparent. As the elastomer melts and seeps out more, the microporous structure of the windproof and breathable membrane becomes more prominent, making the composite fabric more breathable and breathable. The membrane penetrates into the pores of the fabric fibers under pressure, and then cools and solidifies to form a composite. The entire process is fluorine-free and glue-free. In addition, the membrane can be directly used as the outer layer of clothing, and the fabric as the inner layer of clothing. Because the membrane already has surface moisture resistance and hydrophobicity, the waterproofing process of the fabric is omitted, which is more low-carbon and environmentally friendly, and can fully realize the functions of clothing such as windproof, waterproof, breathable and breathable.

[0019] (5) In the double-layer composite fabric of the present invention, when the molten TPU and TPEE are cooled, a physical cross-linking reaction occurs again, and a cross-linked elastomer is formed inside and outside the fiber structure of the fabric, so that both sides of the composite layer of the fabric are made of elastomer materials, which are firmly bonded, soft and elastic, resistant to rubbing without creases, resistant to water washing, and difficult to delaminate and bubble and peel. Therefore, the functions of the clothing such as windproof and waterproof, breathable and moisture permeable, composite and washable, light and skin-friendly can be fully realized.

[0020] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a diagram showing the air permeability results of an embodiment of a fluorine-free, glue-free, and solvent-free film, a double-layer composite fabric, and a preparation method thereof according to the present invention; Figure 2 This is a diagram showing the moisture permeability results of an embodiment of a fluorine-free, glue-free, and solvent-free film, a double-layer composite fabric, and a preparation method thereof according to the present invention; Figure 3 This is a contact angle result diagram of a fluorine-free, glue-free, and solvent-free film, a double-layer composite fabric, and an embodiment of a preparation method thereof of the present invention; Figure 4 This is an infrared spectrum result diagram of a fluorine-free, glue-free and solvent-free film, a double-layer composite fabric and a preparation method thereof according to an embodiment of the present invention; Figure 5 These are test result diagrams of Example 6 of a fluorine-free, glue-free, and solvent-free film, a double-layer composite fabric, and a preparation method thereof of the present invention, wherein (a) is an air permeability result diagram, (b) is a moisture permeability result diagram, (c) is a contact angle result diagram, and (d) is an infrared spectrum result diagram. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments.

[0023] Unless otherwise defined, technical or scientific terms used in the present invention shall have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

[0024] Example 1 A fluorine-free, glue-free and solvent-free double-layer composite fabric, comprising a TPER membrane and a nylon-spandex plain knitted fabric. The raw materials of the TPER membrane include the following mass-group components: Polyurethane elastomer TPU 58%, polyester elastomer TPEE 9%, vulcanized silicone rubber powder 20%, silica aerogel powder 8%, UV absorber 5%.

[0025] Quadra-Tex membrane elastic material is made primarily of polyurethane elastomer TPU and supplemented by polyester elastomer TPEE. Quadra-Tex membrane elastic material has the properties of melting at high temperatures and forming an elastomer through physical crosslinking upon cooling. It possesses both plasticity and high elasticity, combining the properties of both plastic and rubber: lipophilic but not hydrophilic, with a contact angle with water greater than 120°. It is highly hydrophobic and resists hydrolysis, and its molecular structure is not easily degraded in water. Furthermore, because TPU is relatively soft, with a Shore hardness of 80A, high toughness, and a tensile strength of 30 MPa, it withstands repeated flexing and exhibits excellent resilience. TPEE, with a Shore hardness greater than 90A, is relatively hard and strong, with a tensile strength of 50 MPa and relatively low resilience. Therefore, in terms of physical properties, TPU and TPEE are complementary, achieving a balance of strength, toughness, and durability. In terms of application scenarios, TPU and TPEE also complement each other. For example, polyester fabric is made from polyester fiber, and TPEE is highly compatible with polyester fabric; nylon fabric is made from polyamide fiber, has strong polarity, and has strong adhesion to TPU; Lycra fabric processed from spandex is polyurethane fiber, which has better compatibility with TPU; among blended fabrics, the more common ones are polyester-spandex blends, nylon-spandex blends, polyester-nylon blends, and nylon-spandex-cotton blends, all of which are compatible with Quadra-Tex membrane materials.

[0026] Vulcanized silicone rubber powder can enhance the smooth feel of the film surface, giving it a leather-like texture and enhancing its stain resistance. As the outer layer of clothing, it provides a better wearing experience. The use of vulcanized silicone rubber powder takes advantage of its good compatibility with TPU and TPEE, as well as its high affinity with silica aerogel powder, making it easily dispersed in the system, eliminating the need for an external compatibilizer.

[0027] The bulk density of silica aerogel powder is 0.1, the particle size is 10nm, the porosity is greater than 90%, and it has many micropores. The use of nano-scale silica aerogel powder, in addition to improving the strength of the film, can also help the film form microporous channels that are breathable and moisture-permeable. Below 800°C, the morphological structure of silica aerogel powder will not be destroyed and the high porosity will always be maintained. The porous properties can be maintained during the extrusion granulation, cast film and later fabric composite processes, reflecting the permeability. Since TPU and TPEE are inherently highly hydrophobic and lack breathable and moisture-permeable capabilities, the microporous characteristics of silica aerogel powder are used to meet the breathable and moisture-permeable functions and also meet the technical requirements of the melt-infiltration lamination process.

[0028] The preparation method is as follows: The above materials were added sequentially to a constant-speed mixer and mixed uniformly at room temperature. In this example, a drum mixer was used at a speed of 20 rpm. The mixture was then fed into a twin-screw granulator for extrusion and granulation at 200°C. The mixture was then processed using a casting machine to obtain a TPER film. In this example, the cooling roll temperature was 35°C.

[0029] The TPER film was spread flat on the surface of the fabric, and two rollers were used to perform synchronous hot pressing on the lower and upper surfaces. First, the pressure was set to 0.35 MPa and the roller temperature was set to 150°C. The rolling pressing was performed for 10 minutes. Then the pressure was reduced to 0.1 MPa, the roller temperature was lowered to 120°C at a cooling rate of 5°C / min, and the rolling pressing was performed for 8 minutes. The fabric was naturally cooled to room temperature to obtain a double-layer composite fabric, which was marked as sample 1.

[0030] Example 2 The difference from Example 1 is that the raw materials of the TPER film include the following mass-group components: Polyurethane elastomer TPU 62%, polyester elastomer TPEE 9%, vulcanized silicone rubber powder 18%, silica aerogel powder 7%, UV absorber 4%.

[0031] A double-layer composite fabric was obtained, which was marked as sample 2.

[0032] Example 3 The difference from Example 1 is that the raw materials of the TPER film include the following mass-group components: Polyurethane elastomer TPU 65%, polyester elastomer TPEE 9%, vulcanized silicone rubber powder 16%, silica aerogel powder 6%, UV absorber 4%.

[0033] A double-layer composite fabric was obtained, which was marked as sample 3.

[0034] Example 4 The difference from Example 1 is that the raw materials of the TPER film include the following mass-group components: Polyurethane elastomer TPU 70%, polyester elastomer TPEE 9%, vulcanized silicone rubber powder 12%, silica aerogel powder 5%, UV absorber 4%.

[0035] A double-layer composite fabric was obtained, which was marked as sample 4.

[0036] Example 5 The difference from Example 1 is that the raw materials of the TPER film include the following mass-group components: Polyurethane elastomer TPU 74%, polyester elastomer TPEE 8%, vulcanized silicone rubber powder 14%, silica aerogel powder 3%, UV absorber 1%.

[0037] A double-layer composite fabric was obtained, which was marked as sample 5.

[0038] Example 6

[0039] The difference from Example 1 is that the casting machine is replaced by a blow molding machine, and the preparation method is as follows: The materials were added sequentially to a constant-speed mixer and mixed uniformly at room temperature. In this example, a drum mixer was used at a speed of 20 rpm. The materials were then fed into a twin-screw granulator for extrusion and granulation at 200°C. The materials were then processed using a blow molding machine to produce a SEBS film. In this example, the inflation pressure was 1.2 MPa, and the blow-up ratio was 2.3.

[0040] The SEBS membrane was spread flat on the surface of the fabric, and two rollers were used to perform synchronous hot pressing on the lower and upper surfaces. First, the pressure was set to 0.35 MPa and the roller temperature was set to 150°C. The rolling pressing was performed for 10 minutes. Then the pressure was reduced to 0.1 MPa, the roller temperature was lowered to 120°C at a cooling rate of 5°C / min, and the rolling pressing was performed for 8 minutes. The fabric was naturally cooled to room temperature to obtain a double-layer composite fabric, which was marked as sample 6.

[0041] Experimental testing The double-layer composite fabrics prepared in Examples 1 to 5 and the TPER film prepared in Example 1 were tested for air permeability, moisture permeability and contact angle. The test results are shown in the figure. Figure 1-Figure 3 shown.

[0042] The air permeability test method is as follows: According to GB / T5453-1997, the test pressure difference is 100Pa and the test area is 20cm 2 The air permeability of the membrane and the composite fabric was tested under the following conditions.

[0043] The moisture permeability test method is as follows: According to GB / T 12704.1-2009, the temperature is set at 38°C, the humidity is 50%, and the wind speed is 0.3-0.5m / s. The evaporation method is used to measure the moisture permeability. The moisture permeability is calculated using the following formula.

[0044] ; Where, Indicates moisture permeability, unit is g / (m 2 24h), Refers to the difference between two weighings of the same experimental combination. It is the difference between two weighings of the same test combination of blank samples, usually 0. The sample area is 0.00283m 2 , For the experimental time.

[0045] The contact angle test method is as follows: According to GB / T 30693-2014, the sample to be tested was attached to a glass slide and the contact angle was measured.

[0046] Depend on Figure 1 It can be seen that the air permeability of TPER membrane itself is low, and its air permeability remains low even after being laminated with breathable fabrics. However, when a TPER membrane made from 65% polyurethane elastomer TPU, 9% polyester elastomer TPEE, 16% vulcanized silicone rubber powder, 6% silica aerogel powder, and 4% UV absorber is laminated with breathable fabrics, a higher air permeability is achieved.

[0047] Depend on Figure 2 It can be seen that the moisture permeability of the TPER film itself is low, and after being laminated with a moisture permeable fabric, its moisture permeability is still low. When the TPER films prepared in Examples 3 and 4 are laminated with a moisture permeable fabric, the moisture permeability can be significantly improved.

[0048] Depend on Figure 3 The contact angle of the TPER film is 124.7°, while the contact angles of the two-layer composite fabric are 118.0°, 118.6°, 110.0°, 121.3°, and 131.3°, respectively. Before lamination with the TPER film, water dripped onto the fabric quickly penetrated. However, after lamination with the TPER film, the water droplets on the two-layer composite fabric formed spherical shapes, making it difficult for the fabric surface to absorb water. This suggests that the penetration of TPEE, TPU, and other materials into the fabric increases its overall hydrophobicity.

[0049] Fourier infrared tests were performed on the nylon-spandex plain knitted fabric, the TPER film obtained in Example 4, and the double-layer composite fabric obtained in Example 4. Figure 4 The characteristic peak of TPER film is mainly concentrated at 1450cm -1 and 2900cm -1 , representing the stretching vibration of styrene and vinyl groups. In the infrared spectrum of nylon-spandex plain knitted fabric, obvious polyamide and spandex characteristic peaks are shown, especially in the range of 500-1500cm -1 Range and 2800-3000cm -1 The C-H stretching vibration peaks in the upper and lower layers of the double-layer composite fabric are not only characterized by polyamide and spandex, but also by the TPER film, with peaks more prominent in the lower layer. This suggests that the TPER film has been dispersed throughout the upper and lower layers of the double-layer composite fabric during the lamination process.

[0050] The double-layer composite fabrics prepared in Examples 2 to 4 and 6 and the cast film prepared in Example 6 were tested for air permeability, moisture permeability, contact angle and Fourier infrared. The test results are as follows: Figure 5 shown.

[0051] Depend on Figure 5 It can be seen that by replacing the cast film machine with a blow molding machine, the SEBS film obtained by this equipment can be dispersed into the upper and lower layers of the double-layer composite fabric through compounding, and its performance is basically consistent with that of the TPER film.

[0052] Therefore, the present invention adopts the above-mentioned fluorine-free, glue-free and solvent-free film, double-layer composite fabric and its preparation method to realize a new fluorine-free and glue-free fabric + film melting and infiltration composite process, which eliminates the fabric waterproofing treatment process, is more low-carbon and environmentally friendly, and embodies windproof, waterproof and high breathable and moisture permeability.

[0053] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A fluorine-free, glue-free and solvent-free film, characterized in that: The following quality group components are included: Polyurethane elastomer TPU 58-74%, polyester elastomer TPEE 7-11%, vulcanized silicone rubber powder 12-22%, silica aerogel powder 2-8%, UV absorber 1-5%.

2. A method for preparing a fluorine-free, glue-free and solvent-free film, characterized in that: The following steps are involved: S1. Add polyurethane elastomer TPU, polyester elastomer TPEE, vulcanized silicone rubber powder, silica aerogel powder and ultraviolet absorber in a constant speed mixer in proportion and mix well to obtain a mixture; S2, transferring the mixture obtained in S1 to a twin-screw granulator for extrusion granulation; S3. Transfer the granules obtained in S2 to a casting machine or a blow molding machine for processing to obtain a film.

3. The method for preparing a fluorine-free, glue-free and solvent-free film according to claim 2, characterized in that: In S1, the speed of the uniform speed mixer is 0-30 rpm, and the temperature is 0-40°C.

4. The method for preparing a fluorine-free, glue-free and solvent-free film according to claim 2, characterized in that: In S2, the temperature of the twin-screw granulator is 190-230°C.

5. The method for preparing a fluorine-free, glue-free and solvent-free film according to claim 2, characterized in that: In S3, the casting machine melts the granules and extrude them, casting them onto a cooling roller to form a film, wherein the temperature of the cooling roller is 20-50°C; The blow molding machine melts the granules and blows them up to obtain a film. The blowing pressure is 1-1.5 MPa and the blowing ratio is 2-4 times.

6. A fluorine-free, glue-free and solvent-free double-layer composite fabric, characterized in that: The invention comprises a fabric and the film according to claim 1 or a film prepared by the preparation method according to any one of claims 2 to 5, wherein the film and the fabric are compounded by a melt infiltration method.

7. The fluorine-free, glue-free and solvent-free double-layer composite fabric according to claim 6, characterized in that: The fabric is woven from one or more of polyester, nylon, spandex and cotton.

8. A method for preparing a fluorine-free, glue-free and solvent-free double-layer composite fabric, characterized in that: The following steps are involved: T1. Lay the film flat on the surface of the fabric to obtain a double-layer fabric; T2. Use two rollers to perform synchronous heat pressing treatment on the lower surface and the upper surface, and obtain a double-layer composite fabric after cooling.

9. The method for preparing a fluorine-free, glue-free and solvent-free double-layer composite fabric according to claim 8, characterized in that: In T2, the heat pressing treatment is to increase the pressure first and then decrease the pressure, and at the same time, increase the temperature first and then decrease the temperature. The pressure range of the heat pressing treatment is 0.1-0.5 MPa, and the treatment time is 1-30 min.

10. The method for preparing a fluorine-free, glue-free and solvent-free double-layer composite fabric according to claim 8, characterized in that: In T2, the temperature range of the roller is 120-180°C.

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