A TPU composite melt-blown film and a composite fabric using the TPU composite melt-blown film

Abstract

The present application relates to the technical field of composite fabrics, and more particularly to a TPU composite meltblown film and a composite fabric using the TPU composite meltblown film. The TPU composite meltblown film is modified by using a quaternary ammonium salt cationic surfactant to improve the moisture permeability, air permeability, antibacterial properties, and electrical conductivity of the TPU composite meltblown film. Furthermore, the TPU composite meltblown film is used to composite a nylon-spandex four-way stretch fabric with good moisture permeability and air permeability with a woven / knitted composite base fabric into a whole, and a film layer with conductive and antibacterial properties is formed between the nylon-spandex four-way stretch fabric and the woven / knitted composite base fabric, resulting in the composite fabric using the TPU composite meltblown film having good moisture permeability, air permeability, antibacterial properties, antibacterial washability, and electrical conductivity.

Description

Technical Field

[0001] The present application relates to the technical field of composite fabrics, and in particular to a TPU composite meltblown film and a composite fabric using the TPU composite meltblown film. Background Art

[0002] Composite fabric refers to a composite fabric prepared by bonding one or more layers of fabric together with adhesive strength. It is often used to make professional outdoor sportswear such as sports jackets and sportswear.

[0003] Professional outdoor sportswear produces a lot of sweat during exercise, which easily breeds bacteria. Therefore, composite fabrics are not only required to have protective and warming functions, but also to achieve good breathability and moisture permeability, and have certain antibacterial functions. However, existing outdoor sportswear generally has poor antibacterial and washability. Summary of the Invention

[0004] The present application solves the problem that existing composite fabrics are difficult to have good air permeability, moisture permeability and antibacterial and washable properties at the same time. The present application provides a TPU composite melt-blown film and a composite fabric using the TPU composite melt-blown film.

[0005] A first aspect provides a TPU composite meltblown film.

[0006] A TPU composite melt-blown film is prepared by mixing, extruding, blowing, and hot pressing a mixture into a web;

[0007] The mixture includes 20-30 parts by mass of functional masterbatch and 30-70 parts by mass of TPU particles;

[0008] The functional masterbatch is prepared by mixing, melt-extruding and granulating TPU particles and functional raw materials; the functional raw materials include 10-20 parts by mass of TPU particles and 3-10 parts by mass of modified bamboo charcoal;

[0009] The modified bamboo charcoal is prepared by modifying the surface of the bamboo charcoal with a quaternary ammonium salt cationic surfactant.

[0010] By adopting the above technical solution, the surface of bamboo charcoal is modified with quaternary ammonium salt cationic surfactants, which not only improves the antibacterial and conductive properties of bamboo charcoal, but also promotes the dispersion of bamboo charcoal with good air permeability, moisture permeability, antibacterial and conductive properties in TPU raw materials, further improving the air permeability, moisture permeability, antibacterial properties, antibacterial washability and conductivity of the TPU composite melt-blown film.

[0011] Preferably, the modified bamboo charcoal is prepared by mixing a quaternary ammonium salt cationic surfactant, bamboo charcoal and water in a mass ratio of (8-10):10:100, stirring for 15-20 minutes at a speed of 300-500 rpm and a temperature of 50-70°C, and then filtering, washing with water and drying.

[0012] By adopting the above technical scheme, the surface of bamboo charcoal is modified by quaternary ammonium salt cationic surfactants, thereby improving the antibacterial properties, conductive properties and dispersion properties of bamboo charcoal in TPU raw materials, thereby improving the air permeability, moisture permeability, antibacterial properties and conductivity of the TPU composite melt-blown film, so that the prepared composite fabric using the TPU composite melt-blown film has good moisture permeability, air permeability, antibacterial properties and conductivity.

[0013] Preferably, the functional raw materials further include 5-8 parts by mass of modified zinc oxide, wherein the modified zinc oxide is prepared by modifying the surface of zinc oxide with a quaternary ammonium salt cationic surfactant; the particle size of the zinc oxide is 0.01-3 μm; and the TPU composite melt-blown film is treated with an acidic solution with a pH of 3-4 for 3-4 hours after melt-blown film formation.

[0014] By adopting the above technical scheme, the quaternary ammonium salt cationic surfactant used in the modified zinc oxide is combined with zinc oxide to enhance the conductivity and antibacterial properties of the TPU composite melt-blown film; after being treated with hydrochloric acid, the acid reacts with the zinc oxide in the TPU composite melt-blown film, thereby increasing the porosity of the TPU composite melt-blown film, thereby improving the air permeability and moisture permeability, and the zinc ions generated by the reaction of hydrochloric acid and zinc oxide are adsorbed by the modified graphene and modified bamboo charcoal, thereby improving the antibacterial properties and conductivity of the TPU composite melt-blown film, and further improving the moisture permeability, air permeability, antibacterial properties and conductivity of the composite fabric using the TPU composite melt-blown film.

[0015] Preferably, the functional raw material further includes 5-8 parts by mass of modified graphene, which is prepared by mixing an aluminum zirconium ester coupling agent, graphene oxide and water in a mass ratio of (9-12):10:100, stirring at 300-500 rpm for 15-20 minutes, and then filtering, washing with water and drying.

[0016] By adopting the above technical solution, the aluminum zirconium ester coupling agent is used to modify the surface of graphene oxide, thereby improving the antibacterial properties, conductive properties and dispersion properties of graphene oxide in TPU raw materials, thereby improving the air permeability, moisture permeability, antibacterial properties and conductivity of the TPU composite melt-blown film, so that the prepared composite fabric using the TPU composite melt-blown film has good moisture permeability, air permeability, antibacterial properties and conductivity.

[0017] Preferably, a magnetic field with a magnetic induction intensity of 2.0-2.5T is applied to the TPU composite melt-blown film during the extrusion process.

[0018] By adopting the above technical solution, the modified graphene prepared by treating graphene oxide with an aluminum zirconium ester coupling agent has metallic properties. The modified graphene moves in a magnetic field at a certain angle to the direction of the magnetic field. The magnetic field will give the modified graphene a force, so that there is a certain movement difference between the modified graphene and the TPU raw material, which is conducive to the modified graphene entering between the hard segments with stronger molecular chain forces of TPU, thereby making the modified graphene more evenly dispersed in the TPU composite melt-blown film, thereby improving the moisture permeability, air permeability, antibacterial properties and conductive properties of the composite fabric using the TPU composite melt-blown film.

[0019] Preferably, the hot pressing temperature of the TPU composite melt-blown film is 170° C.-230° C., and the hot pressing time of the TPU composite melt-blown film is 15-20 seconds.

[0020] By adopting the above technical solution and setting the hot pressing temperature and time, the TPU composite melt-blown film is better composited together and has better air permeability and moisture permeability.

[0021] Preferably, the quaternary ammonium salt cationic surfactant is dodecyldimethylbenzyl ammonium chloride or polyquaternium salt.

[0022] By adopting the above technical scheme, dodecyldimethylbenzyl ammonium chloride or polyquaternium salt has a good compatibility effect with bamboo charcoal, which improves the dispersion performance of modified bamboo charcoal, while enhancing the antibacterial and conductive properties of bamboo charcoal, and improving the moisture permeability, air permeability, antibacterial and conductive properties of the TPU composite melt-blown film, so that the composite fabric using the TPU composite melt-blown film has good moisture permeability, air permeability, antibacterial and conductive properties.

[0023] Preferably, the mixture further comprises 1-5 parts by mass of masterbatch.

[0024] By adopting the above technical solution and using masterbatch to adjust the color, the sensory experience of the composite fabric using TPU composite melt-blown film can be improved, and it can also serve as a logo.

[0025] Preferably, the TPU composite melt-blown film has a gram weight of 30-60 g / m2, and a thickness of 0.1-0.2 mm.

[0026] By adopting the above technical solution, the gram weight and thickness of the TPU composite melt-blown film are adjusted, so that the TPU composite melt-blown film can better combine the nylon spandex four-way stretch fabric with good moisture permeability and air permeability and the woven / knitted composite base fabric into a whole, and at the same time, the composite fabric using the TPU composite melt-blown film has good moisture permeability and air permeability.

[0027] On the other hand, the present application provides a composite fabric using a TPU composite meltblown film.

[0028] A composite fabric using a TPU composite melt-blown film, the preparation process of which is as follows:

[0029] First, the TPU composite melt-blown film and the nylon spandex four-way stretch fabric are compounded by hot melt adhesive to prepare a first composite film; then the woven / knitted composite base is placed on the TPU composite melt-blown film of the first composite film and compounded again at a compounding temperature of 170-200°C and a compounding time of 10-18s to prepare a composite fabric; the amount of the hot melt adhesive is 15-25g / m 2 ; The fibers of the woven / knitted composite base fabric are a blend of at least two of polyester, cotton, linen, bamboo fiber, and Tencel. By adopting the above-mentioned technical scheme, the TPU composite melt-blown membrane with good moisture permeability, air permeability, antibacterial properties and electrical conductivity not only combines the nylon spandex four-way stretch fabric with good moisture permeability and air permeability and the woven / knitted composite base fabric into a whole; but also maintains the moisture permeability and air permeability of the nylon spandex four-way stretch fabric and the woven / knitted composite base fabric; and forms a membrane layer with conductive and antibacterial properties between the nylon spandex four-way stretch fabric and the woven / knitted composite base fabric, so that the prepared composite fabric using the TPU composite melt-blown membrane has good moisture permeability, air permeability, antibacterial properties and electrical conductivity.

[0030] In summary, this application has the following beneficial effects:

[0031] 1. This application uses quaternary ammonium salt cationic surfactants to modify the surface of bamboo charcoal to improve the moisture permeability, air permeability, antibacterial properties and electrical conductivity of the TPU composite melt-blown membrane; and uses the TPU composite melt-blown membrane to composite the nylon spandex four-way stretch fabric with good moisture permeability and air permeability and the woven / knitted composite base fabric into a whole, and forms a layer of conductive and antibacterial membrane between the nylon spandex four-way stretch fabric and the woven / knitted composite base fabric, so that the composite fabric using the TPU composite melt-blown membrane has good moisture permeability, air permeability, antibacterial properties, antibacterial washability and electrical conductivity.

[0032] 2. The use of modified graphene, modified zinc oxide and modified bamboo charcoal in the TPU composite melt-blown film improves the moisture permeability, air permeability, antibacterial properties and electrical conductivity of the TPU composite melt-blown film, so that the composite fabric using the TPU composite melt-blown film has better moisture permeability, air permeability, antibacterial properties and electrical conductivity.

[0033] 3. Modified zinc oxide is used in the TPU composite melt-blown film, and the TPU composite melt-blown film is treated with an acidic solution. After the acid reacts with the zinc oxide in the TPU composite melt-blown film, the air permeability, moisture permeability, antibacterial properties and electrical conductivity of the TPU composite melt-blown film are further improved, thereby improving the composite fabric using the TPU composite melt-blown film to have better moisture permeability, air permeability, antibacterial properties and electrical conductivity. DETAILED DESCRIPTION

[0034] raw material

[0035] Nylon spandex four-way stretch fabric (87% nylon 13% spandex, 155g / ㎡), hot melt adhesive (polyamide hot melt adhesive, melting point 120-135℃), woven / knitted composite base fabric (weight: 300±50g / ㎡), graphene oxide (oxygen content 36-53%, diameter 0.8-2um), TPU particles (processing level: drawing grade, marked material).

[0036] Preparation examples of intermediates

[0037] Preparation Example 1-1, a method for preparing modified bamboo charcoal, wherein a quaternary ammonium salt cationic surfactant (using dodecyl dimethyl benzyl ammonium chloride), bamboo charcoal (particle size: 1200 mesh) and water are mixed in a mass ratio of 8:10:100, and stirred at 300 rpm and 70°C for 15 minutes to obtain modified bamboo charcoal, which is then washed with water, filtered and dried to obtain a solid powder.

[0038] Preparation Example 1-2, a method for preparing modified bamboo charcoal, wherein a quaternary ammonium salt cationic surfactant (using polyquaternium-11), bamboo charcoal (particle size: 1500 mesh) and water are mixed in a mass ratio of 9:10:100, and stirred at 400 rpm and 60°C for 18 minutes to obtain modified bamboo charcoal, which is then washed with water, filtered and dried to obtain a solid powder.

[0039] Preparation Example 1-3, a method for preparing modified bamboo charcoal, wherein a quaternary ammonium salt cationic surfactant (using polyquaternium-22), bamboo charcoal (particle size: 1000 mesh) and water are mixed in a mass ratio of 10:10:100, and stirred at 500 rpm and 50°C for 20 minutes to prepare modified bamboo charcoal, which is then washed with water, filtered and dried to obtain a solid powder.

[0040] Preparation Example 1-4, a method for preparing modified bamboo charcoal, differs from Preparation Example 1-1 in that the mass ratio of dodecyldimethylbenzyl ammonium chloride, bamboo charcoal and water is 10:10:100.

[0041] Preparation Example 1-5, a preparation method for modified bamboo charcoal, differs from Preparation Example 1-1 in that the mass ratio of dodecyldimethylbenzyl ammonium chloride, bamboo charcoal and water is 5:10:10.

[0042] Preparation Example 2-1, a method for preparing modified zinc oxide, wherein a quaternary ammonium salt cationic surfactant (using dodecyldimethylbenzyl ammonium chloride), zinc oxide (particle size: 0.2 μm) and water are mixed in a mass ratio of 8:10:100, and stirred at 100 rpm and 70°C for 20 minutes to prepare modified zinc oxide, which is then washed with water, filtered, and dried to obtain a solid powder.

[0043] Preparation Example 2-2, a method for preparing modified zinc oxide, wherein a quaternary ammonium salt cationic surfactant (using polyquaternium-11), zinc oxide (particle size: 3 μm) and water are mixed in a mass ratio of 10:10:100 to prepare modified zinc oxide, and the mixture is stirred at 150 rpm and 60°C for 15 minutes to obtain a solid powder.

[0044] Preparation Example 2-3, a method for preparing modified zinc oxide, wherein a quaternary ammonium salt cationic surfactant (using polyquaternium-22), zinc oxide (particle size: 0.01 μm) and water are mixed in a mass ratio of 12:10:100 to prepare modified zinc oxide, and the mixture is stirred at 200 rpm and 50°C for 15 minutes, washed with water, filtered, and dried to obtain a solid powder.

[0045] Preparation Example 2-4 is a method for preparing modified zinc oxide. The difference from Preparation Example 2-1 is that sodium dodecylbenzenesulfonate is used in equal amounts to replace dodecyldimethylbenzylammonium chloride.

[0046] Preparation Example 3-1, a method for preparing modified graphene, comprising mixing an aluminum zirconium ester coupling agent (using aluminum zirconium coupling agent LD-139, metal content 4.8±0.2%; solid content ≥45%), graphene oxide, and water in a mass ratio of 9:10:100, stirring at 300 rpm for 15 minutes to prepare modified graphene, which is then washed with water, filtered, and dried.

[0047] Preparation Example 3-2, a method for preparing modified graphene, comprising mixing an aluminum zirconium ester coupling agent (using aluminum zirconium coupling agent 550, metal content 4.8±0.2%; solid content ≥45%), graphene oxide and water in a mass ratio of 10:10:100, stirring at 400 rpm for 18 minutes to prepare modified graphene, and then washing with water, filtering and drying.

[0048] Preparation Example 3-3, a method for preparing modified graphene, comprising mixing an aluminum zirconium ester coupling agent (using aluminum zirconium coupling agent LD-139, metal content 4.8±0.2%; solid content ≥45%), graphene oxide and water in a mass ratio of 12:10:100, stirring at 500 rpm for 20 minutes to prepare modified graphene, and then washing, filtering and drying.

[0049] Preparation Example 3-4, a preparation method for modified graphene, differs from Preparation Example 1-1 in that an equal amount of silane coupling agent KH560 is used to replace the aluminum zirconium ester coupling agent.

[0050] Preparation Example 3-5, a method for preparing modified graphene, differs from Preparation Example 1-1 in that the mass ratio of aluminum zirconium ester coupling agent, graphene oxide and water is set to 15:10:100.

[0051] Preparation Example 3-6, a method for preparing modified graphene, differs from Preparation Example 1-1 in that the mass ratio of aluminum zirconium ester coupling agent, graphene oxide and water is set to 5:10:100.

[0052] Preparation Example 4-1, a functional masterbatch, using raw materials as shown in Table 1, the functional raw materials and TPU particles are mixed, melt-extruded, and granulated to obtain the functional masterbatch.

[0053] The temperature of zone one of the screw extruder for preparing functional masterbatch is 165±5°C, the temperature of zone two is 185±5°C, the temperature of zone three is 190±5°C, the temperature of zone four is 190±10°C, the temperature of zone five is 185±5°C, the temperature of zone six is ​​180±5°C, the temperature of zone seven is 180±5°C, and the die temperature of the die head is 195±5°C.

[0054] Preparation Example 4-2 to Preparation Example 4-3 are functional masterbatches, which differ from Preparation Example 4-1 in that the types and weight settings of raw materials used are different, as shown in Table 1.

[0055] Table 1. List of raw material types and weights used in the functional masterbatches of Preparation Examples 4-1 to 4-3

[0056]

[0057]

[0058] Preparation Examples 4-4 to 4-5 are functional masterbatches, which differ from Preparation Example 4-1 in that the modified bamboo charcoal uses the modified bamboo charcoal of Preparation Examples 1-4 and 1-5, respectively.

[0059] Preparation Example 4-6 is a functional masterbatch, which differs from Preparation Example 4-1 in that the modified zinc oxide uses the modified zinc oxide of Preparation Example 2-4.

[0060] Preparation Examples 4-7 to 4-9 are functional masterbatches, which differ from Preparation Example 4-1 in that the modified graphenes are the modified graphenes of Preparation Examples 3-4 to 3-6, respectively.

[0061] Preparation Example 4-10, a functional masterbatch, differs from Preparation Example 4-1 in that modified graphene is not used.

[0062] Preparation Example 4-11 is a functional masterbatch, which differs from Preparation Example 4-1 in that modified zinc oxide is not used.

[0063] Preparation Example 4-12, a functional masterbatch, differs from Preparation Example 4-1 in that modified graphene and modified zinc oxide are not used.

[0064] Preparation Example 4-13, a functional masterbatch, differs from Preparation Example 4-1 in that a constant magnetic field is applied outside the extruder, the magnetic induction intensity is 2.0T, and the angle between the direction of the magnetic induction intensity and the extrusion direction of the raw material in the screw extruder is less than or equal to 90° (90° is used in this preparation example).

[0065] Preparation Example 4-14, a functional masterbatch, differs from Preparation Example 4-2 in that a constant magnetic field is applied outside the extruder, the magnetic induction intensity is 2.3T, and the angle between the direction of the magnetic induction intensity and the extrusion direction of the raw material in the screw extruder is 45°.

[0066] Preparation Example 4-15, a functional masterbatch, differs from Preparation Example 4-7 in that a constant magnetic field is applied outside the extruder, the magnetic induction intensity is 2.5T, and the angle between the direction of the magnetic induction intensity and the extrusion direction of the raw material in the screw extruder is 90°.

[0067] Example

[0068] Example 1-1, a TPU composite melt-blown film, is prepared by mixing, extruding, blowing, and hot pressing a mixture into a web; the raw materials used in the mixture are shown in Table 2.

[0069] The temperature of zone 1 of the screw extruder for preparing functional masterbatch is 165°C, the temperature of zone 2 is 185°C, the temperature of zone 3 is 190°C, the temperature of zone 4 is 200°C, the temperature of zone 5 is 200°C, the temperature of zone 6 is 185°C, the temperature of zone 7 is 180°C, and the die temperature of the die head is 195°C.

[0070] The hot air temperature of the high-speed high-temperature air flow sprayed is 220°C, and the hot air pressure is 0.2MPa; during hot pressing, the hot pressing temperature is 170°C, the hot pressing pressure is 0.05MPa, and the hot pressing time is 15s, and a TPU composite melt-blown film with a gram weight of 30g / ㎡ and a thickness of 0.1mm is prepared.

[0071] Example 1-2, a TPU composite melt-blown film, differs from Example 1-1 in that different raw materials and preparation processes are used. The raw materials used are shown in Table 2, and the preparation process is as follows:

[0072] The temperature of zone 1 of the screw extruder for preparing functional masterbatch is 170°C, the temperature of zone 2 is 190°C, the temperature of zone 3 is 195°C, the temperature of zone 4 is 200°C, the temperature of zone 5 is 205°C, the temperature of zone 6 is 190°C, the temperature of zone 7 is 185°C, and the die temperature of the die head is 200°C.

[0073] The hot air temperature of the high-speed high-temperature air flow sprayed was 215°C and the hot air pressure was 0.3 MPa; during hot pressing, the hot pressing temperature was 200°C and the hot pressing time was 18s, and a TPU composite melt-blown film with a gram weight of 45g / ㎡ and a thickness of 0.15mm was prepared.

[0074] Example 1-3, a TPU composite melt-blown film, differs from Example 1-1 in that different raw materials and preparation processes are used. The raw materials are shown in Table 2, and the preparation process is as follows:

[0075] The temperature of zone 1 of the screw extruder for preparing functional masterbatch is 160°C, the temperature of zone 2 is 180°C, the temperature of zone 3 is 185°C, the temperature of zone 4 is 195°C, the temperature of zone 5 is 195°C, the temperature of zone 6 is 180°C, the temperature of zone 7 is 175°C, and the die temperature of the die head is 190°C.

[0076] The hot air temperature of the high-speed high-temperature air flow sprayed was 220°C and the hot air pressure was 0.1 MPa; during hot pressing, the hot pressing temperature was 230°C and the hot pressing time was 20s, and a TPU composite melt-blown film with a gram weight of 60g / ㎡ and a thickness of 0.2mm was prepared.

[0077] Table 2. List of raw material types and weights used in the mixtures of the TPU composite melt-blown films of Examples 1-1 to 1-3

[0078]

[0079] Examples 1-4 to 1-15 are TPU composite melt-blown films, which differ from Example 1-1 in that the functional masterbatches used are the functional masterbatches of Preparation Examples 4-4 to 4-15, respectively.

[0080] Example 1-16 is a TPU composite melt-blown film, which differs from Example 1-1 in that the TPU composite melt-blown film is treated with an acidic solution with a pH of 3 for 4 hours after melt-blown film formation, and the bath ratio is 1:6.

[0081] Example 1-17 is a TPU composite melt-blown film, which differs from Example 1-2 in that the TPU composite melt-blown film is treated with an acidic solution with a pH of 4 for 3 hours after melt-blown film formation, and the bath ratio is 1:8.

[0082] Example 1-18 is a TPU composite melt-blown film, which differs from Example 1-4 in that the TPU composite melt-blown film is treated with an acidic solution with a pH of 3 for 4 hours after melt-blown film formation, and the bath ratio is 1:6.

[0083] Example 1-19 is a TPU composite melt-blown film, which differs from Example 1-5 in that the TPU composite melt-blown film is treated with an acidic solution with a pH of 3 for 4 hours after melt-blown film formation, and the bath ratio is 1:6.

[0084] Example 1-20 is a TPU composite melt-blown film, which differs from Example 1-8 in that the TPU composite melt-blown film is treated with an acidic solution with a pH of 3 for 4 hours after melt-blown film formation, and the bath ratio is 1:6.

[0085] Example 1-21 is a TPU composite melt-blown film, which differs from Example 1-9 in that the TPU composite melt-blown film is treated with an acidic solution with a pH of 3 for 4 hours after melt-blown film formation, and the bath ratio is 1:6.

[0086] Example 1-22 is a TPU composite melt-blown film, which differs from Example 1-1 in that no masterbatch is used in the mixture.

[0087] The stretching ratio of a TPU composite melt-blown film of Example 1-1 to Example 1-22 is greater than 100%.

[0088] Example 2-1, a composite fabric using a TPU composite melt-blown film, the preparation process is as follows:

[0089] Using a hot melt adhesive dispensing machine, the TPU composite melt-blown film and the nylon spandex four-way stretch fabric were composited with hot melt adhesive, so that the positions of the TPU composite melt-blown film (using Example 1-1) and the nylon spandex four-way stretch fabric were relatively fixed to prepare a first composite film, wherein the amount of hot melt adhesive was 25g / m 2 ; Then the woven / knitted composite bottom is arranged on the TPU composite melt-blown film of the first composite film and composited again at a composite temperature of 170°C and a composite time of 10s to prepare a composite fabric.

[0090] The fibers of the woven / knitted composite base fabric are prepared by blending at least two of polyester, cotton, linen, bamboo fiber, and Tencel. In this embodiment, a blend of 70% cotton and 30% polyester is used.

[0091] Examples 2-2 to 2-3 are composite fabrics using a TPU composite meltblown film. The difference from Example 2-1 is that different raw materials and preparation processes are used. The raw materials used are shown in Table 3, and the preparation process is as follows:

[0092] Table 3. List of raw materials and preparation processes used in composite fabrics using TPU composite meltblown films from Examples 2-1 to 3-3

[0093] distinguish Example 2-1 Example 2-2 Example 2-3 TPU composite meltblown film Example 1-1 Example 1-2 Examples 1-3 Woven / knitted composite base fabric 70% cotton + 30% polyester 70% linen + 30% polyester 50% polyester + 50% bamboo fiber Composite temperature / ℃ 170 180 200 Composite time / s 10 12 18 Hot melt adhesive dosage / (g / m2) 25 20 15

[0094] Examples 2-4 to 2-22 are composite fabrics using a TPU composite meltblown film. The difference from Example 2-1 is that the TPU composite meltblown film uses the TPU composite meltblown film of Examples 1-2 to 1-22 in sequence.

[0095] Comparative Example

[0096] Comparative Example 1-1 is a TPU composite melt-blown film, which differs from Example 1-12 in that no functional masterbatch is used.

[0097] Comparative Example 1-2 is a TPU composite melt-blown film, which differs from Example 1-12 in that sodium dodecylbenzenesulfonate is used in an equal amount to replace dodecyldimethylbenzylammonium chloride during the preparation of the modified bamboo charcoal.

[0098] Comparative Example 1-3 is a TPU composite melt-blown film, which differs from Example 1-12 in that an equal amount of bamboo charcoal is used to replace the modified bamboo charcoal.

[0099] Comparative Examples 2-1 to 2-3 are composite fabrics using a TPU composite meltblown film. The difference from Example 2-1 is that the TPU composite meltblown film uses the TPU composite meltblown films of Comparative Examples 1-1 to 1-3 in sequence.

[0100] Performance testing

[0101] Test 1: Moisture Permeability

[0102] The moisture permeability of the test samples was tested in accordance with GB / T12704.2-2009-B, and the test temperature was set at 38°C.

[0103] The water vapor transmission rate (WVP) is calculated using the following formula:

[0104] WVP=(M1-M2)×24 / (T*S)

[0105] Where: WVP is the moisture permeability, unit is g / (m 2 d);

[0106] M1-M2 is the mass change in the moisture permeable cup (unit: g), and T is the test time (unit: d);

[0107] S is the area of ​​the mouth of the moisture permeable cup (unit: m 2 ).

[0108] Test 2: Breathability

[0109] Refer to GB / T5453-1997 "Determination of Air Permeability of Textile Fabrics" and conduct the test at a temperature of 20°C and a relative humidity of 65%. Each test sample is measured 10 times, and the average value is taken as the air permeability of the sample.

[0110] Test 3: Antibacterial properties

[0111] According to GBT20944.3-2008 “Evaluation of antibacterial properties of textiles”, the antibacterial properties of the test samples against Staphylococcus aureus and the antibacterial properties after 50 standard washes were tested.

[0112] Test 4: Resistivity

[0113] The resistivity of the test samples was tested in accordance with GB / T12703.4-2010 “Evaluation of electrostatic properties of textiles”.

[0114] Test samples: The composite fabrics using the TPU composite melt-blown film of Examples 2-1 to 2-16 were used as example samples; the composite fabrics using the TPU composite melt-blown film of Comparative Examples 2-1 to 2-3 were used as comparative example samples.

[0115] Test results: The moisture permeability, air permeability, antibacterial properties and resistivity of the composite fabrics using the TPU composite melt-blown film of Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-3 are shown in Table 4.

[0116] The corresponding relationship between the embodiments and the preparation examples is shown in Table 5.

[0117] Table 4. Evaluation results of moisture permeability, air permeability, antibacterial properties and resistivity of composite fabrics using TPU composite melt-blown films in Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-3

[0118]

[0119]

[0120] Table 5. List of correspondence between Examples and Preparation Examples

[0121]

[0122] Combining Examples 2-1 to 2-22 and Comparative Examples 2-1 to 2-3 and combining Tables 4 and 5, it can be seen that the moisture permeability, air permeability, antibacterial properties and conductivity of the composite fabrics using the TPU composite melt-blown film of Examples 2-1 to 2-22 are better than those of Comparative Examples 2-1 to 2-3, indicating that the use of modified bamboo charcoal in the TPU composite melt-blown film improves the air permeability, moisture permeability, antibacterial properties and conductivity of the fibers of the TPU composite melt-blown film; thereby improving the air permeability, moisture permeability, antibacterial properties and conductivity of the composite fabric using the TPU composite melt-blown film.

[0123] The reason may be that the modification of the bamboo charcoal surface with quaternary ammonium salt cationic surfactants not only improves the antibacterial and conductive properties of bamboo charcoal, but also promotes the dispersion of bamboo charcoal with good air permeability, moisture permeability, antibacterial and conductive properties in TPU raw materials, thereby improving the air permeability, moisture permeability, antibacterial properties, antibacterial washability and conductivity of the TPU composite melt-blown film.

[0124] The TPU composite melt-blown membrane with good moisture permeability, air permeability, antibacterial properties and electrical conductivity not only combines the nylon spandex four-way stretch fabric with good moisture permeability and air permeability and the woven / knitted composite base fabric into a whole; it also better maintains the moisture permeability and air permeability of the nylon spandex four-way stretch fabric and the woven / knitted composite base fabric; and forms a membrane layer with good electrical conductivity and antibacterial properties between the nylon spandex four-way stretch fabric and the woven / knitted composite base fabric, so that the composite fabric using the TPU composite melt-blown membrane has good moisture permeability, air permeability, antibacterial properties and electrical conductivity.

[0125] The moisture permeability, air permeability, antibacterial property and electrical conductivity of the composite fabrics using the TPU composite melt-blown film in Examples 2-1 to 2-3 are better than those in Examples 2-4 and 2-5, indicating that the modified bamboo charcoal used in Examples 2-4 and 2-5 (corresponding to Preparation Examples 1-4 and 1-5, respectively) is too much or too little quaternary ammonium salt cationic surfactant used in the preparation of the modified bamboo charcoal. The composite fabrics using the TPU composite melt-blown film have decreased moisture permeability, air permeability, antibacterial property and electrical conductivity.

[0126] The reason may be that: in the preparation of TPU composite melt-blown film, when the content of quaternary ammonium salt cationic surfactant is low, the dispersion performance of bamboo charcoal decreases, resulting in a decrease in the moisture permeability, air permeability, antibacterial properties and conductivity of the composite fabric of TPU composite melt-blown film; when the content of quaternary ammonium salt cationic surfactant is high, the relative content of bamboo charcoal decreases, and the synergistic effect between bamboo charcoal and quaternary ammonium salt cationic surfactant deteriorates, resulting in a decrease in the moisture permeability, air permeability, antibacterial properties and conductivity of the TPU composite melt-blown film, and then a decrease in the moisture permeability, air permeability, antibacterial properties and conductivity of the composite fabric using TPU composite melt-blown film.

[0127] The antibacterial properties and resistivity of the composite fabrics using the TPU composite melt-blown film in Examples 2-1 to 2-3 are better than those in Example 2-6, indicating that compared with quaternary ammonium salt cationic surfactants, the surface of zinc oxide is modified using the anionic surfactant sodium dodecylbenzenesulfonate, resulting in a decrease in the antibacterial properties and conductivity of the composite fabric using the TPU composite melt-blown film.

[0128] The reason may be that the modified zinc oxide of Preparation Example 2-4 is used in the functional masterbatch, and the compatibility between sodium dodecylbenzenesulfonate and zinc oxide is poor compared with dodecyldimethylbenzyl ammonium chloride, resulting in poor dispersion of the modified zinc oxide in the TPU composite melt-blown film, which reduces the antibacterial and electrical conductivity of the composite fabric using the TPU composite melt-blown film.

[0129] The moisture permeability, air permeability, antibacterial properties and conductivity of the composite fabric using the TPU composite melt-blown film in Example 2-1 are better than those of Examples 2-10 to 2-12, indicating that the combination of modified graphene, modified zinc oxide and modified bamboo charcoal improves the moisture permeability, air permeability, antibacterial properties and conductive properties of the composite fabric using the TPU composite melt-blown film.

[0130] The reason may be that: modified bamboo charcoal is added to the TPU composite melt-blown film, which improves the air permeability and moisture permeability of the fibers of the TPU composite melt-blown film; the quaternary ammonium salt cationic surfactant, zinc oxide and bamboo charcoal used in the modified graphene, modified zinc oxide and modified bamboo charcoal are combined to enhance the conductivity and antibacterial properties of the TPU composite melt-blown film; the TPU composite melt-blown film with good moisture permeability, air permeability, antibacterial property and electrical conductivity not only combines the nylon spandex four-way stretch fabric and the woven / knitted composite base fabric with good moisture permeability and air permeability into a whole; but also maintains the moisture permeability and air permeability of the nylon spandex four-way stretch fabric and the woven / knitted composite base fabric; and forms a membrane layer with conductive and antibacterial properties between the nylon spandex four-way stretch fabric and the woven / knitted composite base fabric, so that the composite fabric using the TPU composite melt-blown film has good moisture permeability, air permeability, antibacterial property, antibacterial washability and electrical conductivity.

[0131] Compared with the test results of Example 2-1, Example 2-13 and Example 2-2, Example 2-14 showed that the modified graphene prepared by treating graphene oxide with an aluminum zirconium ester coupling agent and applying a constant magnetic field outside the extruder improved the moisture permeability, air permeability, antibacterial properties and conductive properties of the composite fabric using the TPU composite melt-blown film; while the modified graphene prepared by using the silane coupling agent KH560 (Example 2-7 / Preparation Example 3-4), even if a constant magnetic field was applied outside the extruder, did not significantly improve the moisture permeability, air permeability, antibacterial properties, antibacterial washability and conductive properties of the composite fabric using the TPU composite melt-blown film.

[0132] The reason may be that the modified graphene prepared by treating graphene oxide with aluminum zirconium ester coupling agent has metallic properties. The modified graphene moves in the magnetic field at a certain angle to the direction of the magnetic field. The magnetic field will give the modified graphene a force, so that there is a certain movement difference between the modified graphene and the TPU raw material, which is conducive to the modified graphene entering between the hard segments with stronger molecular chain forces of TPU, thereby making the modified graphene more evenly dispersed in the TPU composite melt-blown film, thereby improving the moisture permeability, air permeability, antibacterial properties and conductive properties of the composite fabric using the TPU composite melt-blown film.

[0133] Compared with Example 2-1, Example 2-17 with Example 2-2, Example 2-18 with Example 2-4, Example 2-19 with Example 2-5, Example 2-20 with Example 2-8, and Example 2-21 with Example 2-9, the moisture permeability, air permeability, antibacterial properties, antibacterial properties after washing 50 times, and resistivity of the composite fabric of the TPU composite melt-blown film treated with an acidic solution are improved, and the increase is shown in Table 6.

[0134] Table 6. Changes in moisture permeability, air permeability, antibacterial properties and resistivity of TPU composite melt-blown films after hydrochloric acid treatment

[0135]

[0136]

[0137] Comparing the test results of Example 2-16 with Example 2-1, Example 2-17 with Example 2-2, Example 2-18 with Example 2-4, Example 2-19 with Example 2-5, Example 2-20 with Example 2-8, and Example 2-21 with Example 2-9, and combining them with Table 5, it can be seen that after treatment with hydrochloric acid, the moisture permeability, air permeability, antibacterial properties, and electrical conductivity of the TPU composite melt-blown film are improved. This may be because after treatment with hydrochloric acid, the hydrochloric acid reacts with the zinc oxide in the TPU composite melt-blown film, decomposing the zinc oxide into zinc ions, thereby increasing the porosity of the TPU composite melt-blown film and thereby improving the air permeability and moisture permeability. The zinc ions generated by the reaction of hydrochloric acid with zinc oxide are adsorbed by the modified graphene and modified bamboo charcoal, thereby improving the antibacterial properties, antibacterial washability, and electrical conductivity of the TPU composite melt-blown film.

[0138] Compared with the increase in moisture permeability, air permeability, antibacterial property and antibacterial wash resistance of the composite fabrics using TPU composite melt-blown film in Examples 2-16 and 2-17 before treatment with hydrochloric acid, the reduction in resistivity is better than that in Examples 2-18 and 2-19; ​​indicating that the modified bamboo charcoal prepared by mixing a quaternary ammonium salt cationic surfactant, bamboo charcoal and water in a mass ratio of (7-10): 10:100 and then modified has good adsorption and compatibility effects with zinc ions.

[0139] This may be because when the content of quaternary ammonium salt cationic surfactants increases relatively, the content of bamboo charcoal is relatively low, and the adsorption amount of zinc ions decreases; when the content of quaternary ammonium salt cationic surfactants decreases relatively, the dispersibility of the modified bamboo charcoal deteriorates and the dispersion becomes uneven, resulting in a worse compatibility effect between the modified bamboo charcoal and zinc ions, resulting in a decrease in the moisture permeability, air permeability, and antibacterial properties of the TPU composite melt-blown membranes used in Examples 2-18 and 2-19, and a decrease in the decrease in resistivity.

[0140] Compared with the increase in moisture permeability, air permeability, antibacterial property, and antibacterial washability of the composite fabrics using TPU composite melt-blown films in Examples 2-16 and 2-17 before treatment with hydrochloric acid, the decrease in resistivity is better than that in Examples 2-20 and 2-21; this indicates that the modified graphene prepared by mixing an aluminum zirconium ester coupling agent, graphene oxide, and water in a mass ratio of (8-10):10:100 and then modifying the modified graphene has a better compatibility effect and better adsorption effect on zinc ions.

[0141] This may be because when the content of aluminum zirconium ester coupling agent increases relatively, the content of graphene oxide is relatively low, and the adsorption amount of zinc ions decreases; when the content of aluminum zirconium ester coupling agent decreases relatively, the dispersibility of modified graphene deteriorates and the dispersion is uneven, resulting in a worse compatibility effect of modified graphene and zinc ions, resulting in a decrease in the moisture permeability, air permeability, and antibacterial properties of the TPU composite melt-blown membranes of Examples 2-20 and 2-21, and a decrease in the decrease in resistivity.

[0142] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A TPU composite melt-blown film, characterized in that: It is prepared by mixing, extruding, blowing and hot pressing the mixed materials into a net; The mixture includes 20-30 parts by mass of functional masterbatch and 30-70 parts by mass of TPU particles; The functional masterbatch is prepared by mixing, melt-extruding and granulating TPU particles and functional raw materials; the functional raw materials include 10-20 parts by mass of TPU particles and 3-10 parts by mass of modified bamboo charcoal; The functional raw materials further include 5-8 parts by mass of modified zinc oxide and 5-8 parts by mass of modified graphene; The modified zinc oxide is prepared by modifying the surface of zinc oxide with a quaternary ammonium salt cationic surfactant, wherein the quaternary ammonium salt cationic surfactant is dodecyldimethylbenzyl ammonium chloride or polyquaternium salt; the particle size of the zinc oxide is 0.01-3 μm; the TPU composite melt-blown film is treated with an acidic solution with a pH of 3-4 for 3-4 hours after melt-blown film formation; and a magnetic field with a magnetic induction intensity of 2.0-2.5 T is applied to the TPU composite melt-blown film during the extrusion process; The modified graphene is prepared from an aluminum zirconium ester coupling agent, graphene oxide and water in a mass ratio of (9-12):10:100; The modified bamboo charcoal is prepared by modifying the surface of bamboo charcoal with a quaternary ammonium salt cationic surfactant; the modified bamboo charcoal is composed of a quaternary ammonium salt cationic surfactant, bamboo charcoal and water in a mass ratio of (8-10):10:

100.

2. A TPU composite melt-blown film according to claim 1, characterized in that: The quaternary ammonium salt cationic surfactant, bamboo charcoal and water are mixed and stirred at a rotation speed of 300-500 rpm and a temperature of 50-70° C. for 15-20 minutes to prepare modified bamboo charcoal, which is then filtered, washed with water and dried.

3. A TPU composite melt-blown film according to claim 1, characterized in that: The aluminum zirconium ester coupling agent, graphene oxide and water are mixed and stirred at 300-500 rpm for 15-20 minutes to prepare modified graphene, which is then filtered, washed with water and dried.

4. A TPU composite melt-blown film according to claim 1, characterized in that: The hot pressing temperature of the TPU composite melt-blown film is 170° C.-230° C., and the hot pressing time of the TPU composite melt-blown film is 15-20 seconds.

5. A TPU composite melt-blown film according to claim 1, characterized in that: The mixture also includes 1-5 parts by mass of masterbatch.

6. A TPU composite melt-blown film according to claim 1, characterized in that: The gram weight of the TPU composite melt-blown film is 30-60 g / m2, and the thickness of the TPU composite melt-blown film is 0.1-0.2 mm.

7. A composite fabric using the TPU composite melt-blown film according to any one of claims 1 to 6, characterized in that: Its preparation process is as follows: First, the TPU composite melt-blown film and nylon spandex four-way stretch fabric are compounded by hot melt adhesive to prepare a first composite film; then a woven / knitted composite substrate is placed on the TPU composite melt-blown film of the first composite film and compounded again at a compounding temperature of 170-200°C and a compounding time of 10-18 seconds to prepare a composite fabric; the amount of the hot melt adhesive used is 15-25 g / m2; The fibers of the woven / knitted composite base fabric are prepared by blending at least two of polyester, cotton, linen, bamboo fiber and tencel.

Images