A TPU composite meltblown film, a preparation method thereof, and a laminated composite TPU fabric

Abstract

The present application discloses a TPU composite meltblown film, a preparation method thereof, and a laminated composite TPU fabric. The TPU composite meltblown film is obtained by meltblowing a TPU composite masterbatch, and the TPU composite masterbatch includes a compatibilizer, which is a modified SEBS-g-MAH, and the modified SEBS-g-MAH contains a phenol group. The laminated composite TPU fabric includes a TPU composite meltblown film, a four-way stretch woven fabric, and a woven / knit composite bottom cloth, and the TPU composite meltblown film is located between the four-way stretch woven fabric and the woven / knit composite bottom cloth. After blending TPU and PA6, crystallization is improved, which can increase the regularity between molecular chains in the system, change the gap density between molecular chains in the original TPU material, and form exhaust channels in the TPU composite. The modified SEBS-g-MAH enables good compatibility between TPU and PA6, thereby improving the breathability of the TPU composite.

Description

Technical Field

[0001] The present application relates to the field of TPU composite fabrics, and particularly to a TPU composite meltblown film, a preparation method thereof, and a laminated composite TPU fabric. Background Art

[0002] The TPU composite fabric is a bonded composite multi-layer material, mainly a single-structured fabric with various excellent properties prepared by laminating and compounding a TPU film and a fabric.

[0003] Now, as people gradually pay more attention to health, more and more people join the ranks of outdoor sports. Therefore, the demand for professional outdoor sports clothing is gradually increasing. Due to its good elasticity, toughness, wear resistance, and cold resistance, the TPU composite fabric can be applied to the preparation of sports coats and sportswear. In the application of sportswear, although the TPU composite fabric has good moisture permeability, its air permeability is not good. The sweat and heat generated by people during exercise cannot be discharged in time, significantly reducing people's wearing experience. Summary of the Invention

[0004] To solve the problem that the air permeability of the TPU composite fabric is not good when preparing sportswear, resulting in a decline in the dressing experience, the present application provides a TPU composite meltblown film, a preparation method thereof, and a laminated composite TPU fabric. The laminated composite TPU fabric of the present application has good air permeability and moisture permeability, and maintains the good elasticity of the fabric, improving the wearing experience.

[0005] In the first aspect, the present application provides a TPU composite meltblown film obtained by meltblowing from a TPU composite masterbatch, characterized in that the TPU composite masterbatch comprises the following raw materials in parts by mass:

[0006] 70 - 80 parts of a polyether-based thermoplastic polyurethane compound;

[0007] 20 - 30 parts of polycaprolactam;

[0008] 4 - 8 parts of hyperbranched polyester;

[0009] 3 - 5 parts of a compatibilizer;

[0010] The compatibilizer is modified SEBS-g-MAH, and the modified SEBS-g-MAH contains a phenol group.

[0011] By adopting the above technical solution, the TPU composite melt-blown film is prepared from a TPU composite masterbatch, and the TPU composite masterbatch is an alloy material of TPU and PA6. The raw material used is a polyether-based thermoplastic polyurethane compound. Compared with polyester-based TPU, polyether-based TPU contains more polar groups, which can form hydrogen bonds with the polar groups in polycaprolactam and bind to each other. In addition, there is generally only physical cross-linking mainly based on hydrogen bonds between the molecular chains in the TPU material, and there is no chemical cross-linking. Hydrogen bonds are not stable chemical connection structures, and the molecular chains are prone to slippage due to external forces, and the arrangement of the molecular chains is irregular. Although the tensile properties are excellent, the strength is not high. PA6, as a crystalline polymer, has a regular molecular chain arrangement. After the two are blended, the crystallization is perfect, which can increase the regularity between the molecular chains in the system, change the gap density between the molecular chains in the original TPU material, and make there be exhaust channels in the TPU composite material, thereby improving the air permeability of the TPU composite material. And the regular molecular chain arrangement can also increase the strength of the composite material.

[0012] However, when PA6 and TPU are blended, since TPU is an amorphous polymer and PA6 is a crystalline polymer, their compatibility is poor, and there will be a small amount of voids between their molecular chains, which will affect the toughness and strength of the composite material, and the processing performance of the material will also decline. Therefore, a compatibilizer is added to the TPU composite material to improve the interfacial compatibility between the two. The compatibilizer used is SEBS-g-MAH. The maleic anhydride contained in it can undergo a condensation reaction with the terminal amino group of PA6 to form a graft copolymer. In this way, the graft copolymer located at the phase interface can strengthen the adhesion force of the phase interface through covalent bonds, enabling the two to be well compatible. And SEBS-g-MAH has been modified, and it contains phenol groups. The steric hindrance of phenol can increase the gap between the molecular chains of the TPU composite material, thereby improving the air permeability of the TPU composite melt-blown film.

[0013] Preferably, the raw materials of the modified SEBS-g-MAH include tannic acid and SEBS-g-MAH with a mass ratio of (1.2 - 1.5):1.

[0014] By adopting the above technical solution, the addition of the compatibilizer can enhance the binding between PA6 and TPU, making their binding tight, which is helpful for further improving the mechanical properties and processing performance of the TPU composite material. Tannic acid contains a large number of phenol groups, which can increase the gap between the molecular chains of the TPU composite material, thereby effectively improving the air permeability of the TPU composite melt-blown film, making the gas easy to discharge without affecting the compatibility between TPU and PA. At the same time, tannic acid also contains a large number of hydroxyl groups, which is beneficial to increasing the hydrophilicity of the TPU composite material, and thus is beneficial to improving the moisture permeability of the TPU composite material.

[0015] Preferably, the preparation method of the modified SEBS-g-MAH is as follows:

[0016] The SEBS-g-MAH is left standing in hydrochloric acid solution for 4 - 6 h, then washed and added to sodium hydroxide solution; tannic acid is added to deionized water, stirred and dissolved, and then added to SEBS-g-MAH. The temperature is raised to 60 - 80 °C and stirred for reaction for 2 - 3 h. After the reaction is completed, the mixed solution is added to hydrochloric acid solution for acidification, and then filtered, washed and dried to obtain the modified SEBS-g-MAH.

[0017] By adopting the above technical scheme, the phenolic hydroxyl groups contained in tannic acid can directly esterify with the anhydride groups in SEBS-g-MAH, enabling tannic acid to be connected to SEBS-g-MAH.

[0018] Preferably, the hyperbranched polyester comprises end-hydroxyl hyperbranched polyester and end-phenyl hyperbranched polyester with a mass ratio of (2 - 3):1.

[0019] Preferably, the raw materials of the end-phenyl hyperbranched polyester include the end-hydroxyl hyperbranched polyester and toluoyl chloride with a mass ratio of 1:(0.3 - 0.5).

[0020] Preferably, the end-phenyl hyperbranched polyester is prepared by the following method:

[0021] The end-hydroxyl hyperbranched polyester is added to a solvent, stirred and dissolved, then a catalyst and toluoyl chloride are added. The temperature is raised to 60 - 70 °C and stirred for reaction for 6 - 8 h, and then filtered, washed and dried to obtain the end-phenyl hyperbranched polyester.

[0022] Preferably, the solvent includes one or a combination of N,N-dimethylformamide and tetrahydrofuran; the catalyst is triethylamine.

[0023] By adopting the above technical scheme, in the TPU / PA alloy system, adding a certain compatibilizer improves the compatibility of the system, and adding hyperbranched polyester can increase the toughness of the TPU composite. A large number of end-hydroxyl groups contained therein can also form connections with the surrounding matrix, becoming the connection bridge of the molecular chains of the TPU composite. While there are certain pores between the molecular chains of the obtained TPU composite melt-blown film, the tensile strength of the material is improved. At the same time, the hyperbranched polyester has a unique esterification molecular structure, there is no entanglement between molecules, and there are cavities inside itself, which can increase the air permeability of the TPU composite. At the same time, the cavity structure can buffer the external force situation, increasing the toughness and elasticity of the material.

[0024] In this application, a composition of hydroxyl-terminated hyperbranched polyester and phenyl-terminated hyperbranched polyester is used. A large number of hydroxyl groups can increase the hydrophilicity of the TPU composite material. When a person sweats and there is a difference in the internal and external vapor pressures, the hydrophilic groups can absorb the internal water molecules and conduct transmission, thereby increasing the moisture permeability of the composite material. In addition, due to the small addition amount of the PA component, the crystallization rate is slow, resulting in an extended processing cycle and affecting the processing performance of the TPU composite material. Adding phenyl-terminated hyperbranched polyester can be used for adjustment. On the one hand, the phenyl groups can undergo a conjugation effect with the PA molecular chain to enhance the bonding force at the two-phase interface. On the other hand, a large number of branching points in the phenyl-terminated hyperbranched polyester can act as heterogeneous nucleating agents, thereby improving the processing property of the TPU composite material.

[0025] Second, this application also provides a method for preparing a melt-blown film of a TPU composite material, which is prepared by the following method:

[0026] S1. Dry the polyether-based thermoplastic polyurethane compound and polycaprolactam at 100-110°C for 5-6 hours, then weigh the polyether-based thermoplastic polyurethane compound, polycaprolactam, hyperbranched polyester, and compatibilizer according to mass parts, mix them evenly, carry out melt blending and extrusion granulation, and then obtain the TPU composite masterbatch after drying.

[0027] S2. Put the TPU composite masterbatch obtained in S1 into a melt-blown machine and melt-blown at a temperature of 190-230°C to obtain a melt-blown film of the TPU composite material.

[0028] Preferably, the thickness of the melt-blown film of the TPU composite material is 0.1-0.2 mm.

[0029] Preferably, the temperature of the melt blending is 220-230°C.

[0030] Third, this application also provides a laminated composite TPU fabric, which includes the melt-blown film of the TPU composite material according to any one of claims 1-6, a four-way stretch woven fabric, and a woven / knit composite bottom cloth, and the melt-blown film of the TPU composite material is located in the middle of the four-way stretch woven fabric and the woven / knit composite bottom cloth.

[0031] More preferably, the content of the melt-blown film of the TPU composite material in the laminated composite TPU fabric is 30-60 g / m 2 .

[0032] Preferably, the melt-blown film of the TPU composite material and the four-way stretch woven fabric are composite through a hot-melt adhesive; the hot-melt adhesive is a polyurethane hot-melt adhesive.

[0033] Preferably, the composite time of the melt-blown film of the TPU composite material and the four-way stretch woven fabric is 15-20 s.

[0034] Preferably, after the TPU composite melt-blown film is laminated with the four-way stretch woven fabric, the laminated fabric is laminated with the woven / knitted composite base fabric through a pressure roller.

[0035] Preferably, the woven / knitted composite base fabric is a combination of one or more of polyester, nylon, spandex, and cotton; the four-way stretch woven fabric is a composition of nylon and spandex.

[0036] More preferably, the mass ratio of nylon to spandex in the four-way stretch woven fabric is (80-90):(10-20).

[0037] By adopting the above technical solution, the TPU composite melt-blown film is used as an intermediate layer to achieve the effect of high air permeability and moisture permeability of the laminated composite TPU fabric, so that the obtained laminated composite TPU fabric can be used in the preparation of professional sportswear. After the TPU composite melt-blown film and the four-way stretch woven fabric are laminated with hot-melt adhesive, they are laminated with the woven / knitted composite base fabric through a pressure roller, so that the three-layer fabrics can be tightly combined. At the same time, since the SEBS-g-MAH used in the TPU composite melt-blown film is modified, the modified SEBS-g-MAH also contains catechol groups, which can provide hydrogen atoms for the hydroxyl groups on the surface of the woven / knitted composite base fabric to form strong hydrogen bonds and form chemical crosslinks, thereby increasing the adhesion between the TPU composite melt-blown film and the woven / knitted composite base fabric, so that while the laminated composite TPU fabric maintains good air permeability and moisture permeability, the connection between layers is tight and not easy to peel off.

[0038] In summary, the present application has the following beneficial effects:

[0039] 1. The TPU composite masterbatch used in the TPU composite melt-blown film in the present application is an alloy material of TPU and PA6. As a crystalline polymer, the molecular chains of PA6 are arranged regularly. After blending the two, the crystallization is perfect, which can increase the regularity between the molecular chains in the system, change the interstitial density between the molecular chains in the original TPU material, and form exhaust channels in the TPU composite, thereby improving the air permeability of the TPU composite. In addition, the regular arrangement of molecular chains can also increase the strength of the composite material.

[0040] 2. The present application also adds modified SEBS-g-MAH to the TPU composite masterbatch. The maleic anhydride contained can undergo a condensation reaction with the terminal amino groups of PA6, and the formed graft copolymer can strengthen the adhesion force of the phase interface through covalent bonds, enabling good compatibility between TPU and PA6; the steric hindrance of phenol can increase the gap between the molecular chains of the TPU composite material, thereby improving the air permeability of the melt-blown film of the TPU composite material. At the same time, the modified SEBS-g-MAH also contains catechol groups, which can increase the adhesion to other surface layers during the preparation of the laminated composite TPU fabric and is not prone to peeling.

[0041] 3. The present application also adds hyperbranched polyester to the TPU composite masterbatch. There are cavities inside itself, which can increase the air permeability of the TPU composite material. At the same time, the cavity structure can buffer the external force and increase the toughness and elasticity of the material; a large number of terminal hydroxyl groups contained can increase the hydrophilicity of the TPU composite material, thereby increasing the moisture permeability of the composite material; a large number of branching points contained inside the hyperbranched polyester can act as heterogeneous nucleating agents, thereby improving the processability of the TPU composite material. Brief Description of the Drawings

[0042] Figure 1 It is a scanning electron microscope image of the melt-blown film of the TPU composite material prepared in Example 1-1 under a magnification of 140 times.

[0043] Figure 2 It is a scanning electron microscope image of the melt-blown film of the TPU composite material prepared in Example 1-1 under a magnification of 500 times.

[0044] Figure 3 It is a scanning electron microscope image of the melt-blown film of the TPU composite material prepared in Example 1-8 under a magnification of 500 times.

[0045] Figure 4 It is a scanning electron microscope image of the melt-blown film of the TPU composite material prepared in Example 1-1 under a magnification of 1000 times. Detailed Description of the Embodiments

[0046] Preparation Example of Terminal Phenyl Hyperbranched Polyester

[0047] Preparation Example 1-1, a kind of terminal phenyl hyperbranched polyester, is prepared according to the following method:

[0048] Take 10 g of terminal hydroxyl hyperbranched polyester (model: HyPer C100) and add it to 100 ml of N,N-dimethylformamide. After stirring and dissolving, add 0.4 g of triethylamine and 4 g of toluyl chloride. Raise the temperature to 60 °C, stir and react for 8 h, and then obtain the terminal phenyl hyperbranched polyester through suction filtration, washing, and drying.

[0049] Preparation Example of Modified SEBS-g-MAH

[0050] Preparation Example 2-1, a modified SEBS-g-MAH, was prepared by the following method:

[0051] Take 10 g of SEBS-g-MAH (maleic anhydride grafting rate is 1.7%) and let it stand in 250 ml of hydrochloric acid solution (mass fraction of hydrochloric acid is 15%) for 6 h, then wash it and add it to 100 ml of sodium hydroxide solution (mass fraction of sodium hydroxide is 20%); take 13 g of tannic acid and add it to 100 ml of deionized water, stir to dissolve and then add it to the sodium hydroxide solution of SEBS-g-MAH, raise the temperature to 70 °C, stir and react for 3 h. After the reaction is completed, add the mixed solution to the hydrochloric acid solution for acidification, and then filter, wash and dry to obtain the modified SEBS-g-MAH.

[0052] Preparation Example 2-2, a modified SEBS-g-MAH, is different from Preparation Example 2-1 only in that the addition amount of tannic acid is 12 g.

[0053] Preparation Example 2-3, a modified SEBS-g-MAH, is different from Preparation Example 2-1 only in that the addition amount of tannic acid is 15 g.

[0054] Preparation Example 2-4, a modified SEBS-g-MAH, is different from Preparation Example 2-1 only in that the addition amount of tannic acid is 10 g.

[0055] Preparation Example 2-5, a modified SEBS-g-MAH, is different from Preparation Example 2-1 only in that the addition amount of tannic acid is 18 g.

[0056] Examples of TPU composite melt-blown membranes

[0057] Example 1-1, a TPU composite melt-blown membrane, was prepared by the following method:

[0058] The polyether-based thermoplastic polyurethane compound (model ER-95A) and polycaprolactam (density 1.13 g / cm 3 ) were dried at 100 °C for 6 h, and then 750 g of polyether-based thermoplastic polyurethane compound, 250 g of polycaprolactam, 60 g of hyperbranched polyester and 40 g of the modified SEBS-g-MAH prepared in Preparation Example 1-1 were weighed according to mass parts, mixed evenly, then melt-blended and extruded into pellets, and then dried to obtain TPU composite masterbatch;

[0059] The obtained TPU composite masterbatch was melt-blown by a melt-blown machine at a temperature of 220 °C to obtain a TPU composite melt-blown membrane, and the thickness of the TPU composite melt-blown membrane was 0.1 mm.

[0060] The hyperbranched polyester consists of a hydroxyl-terminated hyperbranched polyester (model: HyPer C100) and a phenyl-terminated hyperbranched polyester prepared in Preparation Example 1-1 with a mass ratio of 2.5:1.

[0061] The raw materials of the TPU composite masterbatch are melt-blended and pelletized through a twin-screw extruder. The temperatures of each section of the extruder are as follows: section 1 at 200 °C, section 2 at 220 °C, section 3 at 230 °C, section 4 at 220 °C, and the die head at 200 °C. The rotational speed of the extruder is 150 r / min.

[0062] Example 1-2, a melt-blown film of a TPU composite material. The difference from Example 1-1 is only that the addition amount of the polyether-based thermoplastic polyurethane compound is 700 g, and the addition amount of polycaprolactam is 300 g; the modified SEBS-g-MAH prepared in Preparation Example 2-2 is used to replace the modified SEBS-g-MAH prepared in Preparation Example 2-1 in an equal amount.

[0063] Example 1-3, a melt-blown film of a TPU composite material. The difference from Example 1-1 is only that the addition amount of the polyether-based thermoplastic polyurethane compound is 800 g, and the addition amount of polycaprolactam is 200 g; the modified SEBS-g-MAH prepared in Preparation Example 2-3 is used to replace the modified SEBS-g-MAH prepared in Preparation Example 2-1 in an equal amount.

[0064] Example 1-4, a melt-blown film of a TPU composite material. The difference from Example 1-1 is only that the addition amount of the hyperbranched polyester is 40 g.

[0065] Example 1-5, a melt-blown film of a TPU composite material. The difference from Example 1-1 is only that the addition amount of the hyperbranched polyester is 80 g.

[0066] Example 1-6, a melt-blown film of a TPU composite material. The difference from Example 1-1 is only that the addition amount of the modified SEBS-g-MAH prepared in Preparation Example 2-1 is 30 g.

[0067] Example 1-7, a melt-blown film of a TPU composite material. The difference from Example 1-1 is only that the addition amount of the modified SEBS-g-MAH prepared in Preparation Example 2-1 is 50 g.

[0068] Example 1-8, a melt-blown film of a TPU composite material. The difference from Example 1-1 is only that the hyperbranched polyester composed of a hydroxyl-terminated hyperbranched polyester and a phenyl-terminated hyperbranched polyester prepared in Preparation Example 1-1 with a mass ratio of 2:1 is used to replace the hyperbranched polyester composed of a hydroxyl-terminated hyperbranched polyester and a phenyl-terminated hyperbranched polyester prepared in Preparation Example 1-1 with a mass ratio of 2.5:1 in an equal amount.

[0069] Examples 1-9, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the hyperbranched polyester composed of hydroxyl-terminated hyperbranched polyester and phenyl-terminated hyperbranched polyester prepared in Preparation Example 1-1 with an equal mass ratio of 3:1 is used to replace the hyperbranched polyester composed of hydroxyl-terminated hyperbranched polyester and phenyl-terminated hyperbranched polyester prepared in Preparation Example 1-1 with a mass ratio of 2.5:1.

[0070] Examples 1-10, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the modified SEBS-g-MAH prepared in Preparation Example 2-4 with an equal amount is used to replace the modified SEBS-g-MAH prepared in Preparation Example 2-1.

[0071] Examples 1-11, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the modified SEBS-g-MAH prepared in Preparation Example 2-5 with an equal amount is used to replace the modified SEBS-g-MAH prepared in Preparation Example 2-1.

[0072] Examples 1-12, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the hydroxyl-terminated hyperbranched polyester with an equal amount is used to replace the hyperbranched polyester composed of hydroxyl-terminated hyperbranched polyester and phenyl-terminated hyperbranched polyester prepared in Preparation Example 1-1 with a mass ratio of 2.5:1.

[0073] Examples 1-13, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the phenyl-terminated hyperbranched polyester with an equal amount is used to replace the hyperbranched polyester composed of hydroxyl-terminated hyperbranched polyester and phenyl-terminated hyperbranched polyester prepared in Preparation Example 1-1 with a mass ratio of 2.5:1.

[0074] Comparative Examples of the Melt-Blown Film of the TPU Composite Material

[0075] Comparative Example 1-1, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the addition amount of the modified SEBS-g-MAH prepared in Preparation Example 2-1 is 20 g.

[0076] Comparative Example 1-2, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the addition amount of the modified SEBS-g-MAH prepared in Preparation Example 2-1 is 60 g.

[0077] Comparative Example 1-3, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the addition amount of the hyperbranched polyester is 30 g.

[0078] Comparative Example 1-4, a melt-blown film of a TPU composite material, which is different from Example 1-1 only in that the addition amount of the hyperbranched polyester is 90 g.

[0079] Comparative Examples 1-5, a melt-blown film of a TPU composite material, the difference from Example 1-1 is only that an equal amount of SEBS-g-MAH is used to replace the modified SEBS-g-MAH prepared in Preparation Example 2-1.

[0080] Comparative Example 1-6, a melt-blown film of a TPU composite material, the difference from Example 1-1 is only that the addition amount of the polyether-based thermoplastic polyurethane compound is 100 g and polycaprolactam is not added.

[0081] Comparative Example 1-7, a melt-blown film of a TPU composite material, the difference from Example 1-1 is only that hyperbranched polyester is not added.

[0082] Performance detection test

[0083] Air permeability and moisture permeability test: According to the test method in GB / T 1037-2021 "Plastics - Films and Sheets - Determination of Water Vapor Transmission Rate - Cup Method, Gravimetric and Manometric", the air permeability and moisture permeability of the melt-blown films of the TPU composite materials obtained in the examples and comparative examples were tested, and the test results are shown in Table 1:

[0084] Table 1 Test results of air permeability and moisture permeability of melt-blown films of TPU composite materials

[0085]

[0086] Examples of laminated composite TPU fabrics

[0087] Example 2-1, a laminated composite TPU fabric, was prepared by the following method:

[0088] The melt-blown film of the TPU composite material prepared in Example 1-1 was compounded with a nylon-spandex four-way stretch woven fabric (the mass ratio of nylon to spandex is 9:1) through a polyurethane hot melt adhesive (model 5377A) at a compounding temperature of 180 °C for 10 s. Then the obtained composite fabric was compounded with a cotton knitted composite bottom cloth through a pressure roller to obtain a laminated composite TPU fabric.

[0089] Among them, the content of the melt-blown film of the TPU composite material is 40 g / m 2 .

[0090] Example 2-2, a laminated composite TPU fabric, the difference from Example 2-1 is only that the melt-blown film of the TPU composite material prepared in Example 1-12 is used to replace the melt-blown film of the TPU composite material prepared in Example 1-1 in an equal amount.

[0091] Example 2-3. A laminated composite TPU fabric, which is different from Example 2-1 only in that the TPU composite meltblown film prepared in Example 1-13 is replaced with an equal amount of the TPU composite meltblown film prepared in Example 1-1.

[0092] Example 2-4. A laminated composite TPU fabric, which is different from Example 2-1 only in that the TPU composite meltblown film prepared in Comparative Example 1-1 is replaced with an equal amount of the TPU composite meltblown film prepared in Example 1-1.

[0093] Example 2-5. A laminated composite TPU fabric, which is different from Example 2-1 only in that the TPU composite meltblown film prepared in Comparative Example 1-2 is replaced with an equal amount of the TPU composite meltblown film prepared in Example 1-1.

[0094] Example 2-6. A laminated composite TPU fabric, which is different from Example 2-1 only in that the TPU composite meltblown film prepared in Comparative Example 1-3 is replaced with an equal amount of the TPU composite meltblown film prepared in Example 1-1.

[0095] Example 2-7. A laminated composite TPU fabric, which is different from Example 2-1 only in that the TPU composite meltblown film prepared in Comparative Example 1-4 is replaced with an equal amount of the TPU composite meltblown film prepared in Example 1-1.

[0096] Example 2-8. A laminated composite TPU fabric, which is different from Example 2-1 only in that the TPU composite meltblown film prepared in Comparative Example 1-5 is replaced with an equal amount of the TPU composite meltblown film prepared in Example 1-1.

[0097] Example 2-9. A laminated composite TPU fabric, which is different from Example 2-1 only in that the TPU composite meltblown film prepared in Comparative Example 1-6 is replaced with an equal amount of the TPU composite meltblown film prepared in Example 1-1.

[0098] Example 2-10. A laminated composite TPU fabric, which is different from Example 2-1 only in that the TPU composite meltblown film prepared in Comparative Example 1-7 is replaced with an equal amount of the TPU composite meltblown film prepared in Example 1-1.

[0099] Performance detection test

[0100] 1. Air permeability test: The air permeability of the laminated composite TPU fabrics obtained in Examples 2-1 to 2-7 was tested according to GB / T 5453-1997 "Determination of fabric air permeability".

[0101] 2. Moisture permeability test: The air permeability of the laminated composite TPU fabrics obtained in Examples 2-1 to 2-7 was tested according to GB / T 12704.1-2009 "Textiles - Test methods for fabric moisture permeability - Part 1: Moisture absorption method".

[0102] 3. Peel strength performance test: The peel strength in the warp and weft directions of the laminated composite TPU fabrics obtained in Examples 2-1 to 2-10 was tested according to the industry standard FZ / T 80007.1-2006 "Test method for peel strength of garments using adhesive interlinings".

[0103] The above test results are shown in Table 2:

[0104] Table 2 Test results of laminated composite TPU fabrics

[0105]

[0106]

[0107] According to Table 1, in combination with Examples 1-1 to 1-9, it can be seen that there is no significant difference in the water vapor transmission rate between Examples 1-2 to 1-9, indicating that there is no significant difference in the air permeability and moisture permeability of the TPU composite melt-blown membranes in Examples 1-2 to 1-9 compared with Example 1-1. The reason may be that in Examples 1-2 to 1-7, only the raw materials and the ratios in the raw material preparation process are changed, and in Examples 1-8 to 1-9, only the mass ratio of the hyperbranched polyester with terminal hydroxyl groups to the hyperbranched polyester with terminal phenyl groups in the hyperbranched polyester is changed, and the above changes are all within the required range, indicating that changing the relevant ratios and mass ratios within the required range has no significant impact on the air permeability and moisture permeability of the TPU composite melt-blown membranes.

[0108] According to Table 1, in combination with Example 1-1, Example 1-10, and Example 1-11, it can be seen that the water vapor transmission rate of Example 1-10 and Example 1-11 is lower than that of Example 1-1, indicating that the air permeability and moisture permeability of Example 1-10 and Example 1-11 are lower than those of Example 1-1. The reason may be that the addition amount of tannic acid in the preparation of modified SEBS-g-MAH in Example 1-10 is reduced, resulting in a decrease in the content of phenol groups in the obtained modified SEBS-g-MAH, a decrease in the effect on the pores between molecular chains, and thus a decrease in the air permeability and moisture permeability of the TPU composite melt-blown film; in Example 1-11, the addition amount of tannic acid in the preparation of modified SEBS-g-MAH is increased. Since tannic acid contains a large number of hydroxyl groups, when added in excess, it is easy to cause a too tight cross-linked structure to form between molecular chains, a decrease in the interstitial rate between molecular chains, and also a decrease in the air permeability and moisture permeability of the TPU composite melt-blown film.

[0109] According to Table 1 and Table 2, in combination with Example 1-1, Example 1-12, and Example 1-13, and at the same time in combination with Example 2-1, Example 2-2, and Example 2-3, it can be seen that the water vapor transmission rate of Example 1-12 and Example 1-13 is lower than that of Example 1-1, indicating that the air permeability and moisture permeability of Example 1-12 and Example 1-13 are lower than those of Example 1-1; the air permeability, moisture permeability, and peel strength of Example 2-2 and Example 2-3 are lower than those of Example 2-1, and the peel strength of Example 2-3 decreases more significantly, indicating that the air permeability and moisture permeability of Example 2-2 and Example 2-3 and the adhesion between layers are lower than those of Example 2-1. The reason may be that the hyperbranched polyester used in Example 1-12 is only hydroxyl-terminated hyperbranched polyester. Without the effect of phenyl-terminated hyperbranched polyester, on the one hand, the binding force with PA6 decreases, the gap between molecular chains without the phenyl effect shrinks, and the processing performance also decreases. As shown in Example 2-2, the air permeability and moisture permeability of the laminated composite TPU fabric are affected and the performance decreases; the hyperbranched polyester used in Example 1-13 is only phenyl-terminated hyperbranched polyester. Without the effect of hydroxyl-terminated hyperbranched polyester, on the one hand, the hydroxyl content decreases and the hydrophilicity decreases, and on the other hand, the binding force with PA6 and TPU decreases, and the phenyl effect also makes the intermolecular gap too large. As shown in Example 2-3, the air permeability and moisture permeability of the laminated composite TPU fabric are affected, and the too large gap also leads to a decrease in the adhesion performance with other surface layers.

[0110] According to Table 1 and Table 2, in combination with Examples 1-1, Comparative Examples 1-1, Comparative Example 1-2 and Comparative Example 1-5, and also in combination with Examples 2-1, Example 2-4, Example 2-5 and Example 2-8, it can be seen that the water vapor transmission rate of Comparative Example 1-1 and Comparative Example 1-2 decreased compared with that of Example 1-1, and the water vapor transmission rate of Comparative Example 1-5 decreased significantly compared with that of Example 1-1, indicating that the air permeability and moisture permeability of Comparative Example 1-1 and Comparative Example 1-2 decreased, and the air permeability and moisture permeability of Comparative Example 1-5 decreased significantly; the air permeability, moisture permeability and peel strength of Example 2-4 and Example 2-5 decreased compared with those of Example 2-1, and the performance of Example 2-8 decreased significantly compared with that of Example 2-1. The reason may be that in Comparative Example 1-1, the addition amount of modified SEBS-g-MAH decreased, the role of modified SEBS-g-MAH between PA6 and TPU was lacking, the compatibility decreased, and the performance decreased. Moreover, the role of phenol in modified SEBS-g-MAH was lacking, the intermolecular gap could not be reasonably controlled, and the air permeability and moisture permeability decreased. As shown in Example 2-4 for the laminated composite TPU fabric, its air permeability and moisture permeability decreased. And due to the decrease in compatibility and the decrease in the addition amount of modified SEBS-g-MAH, the content of catechol groups decreased, and the adhesion performance of the TPU composite melt-blown film to other surface layers also decreased. In Comparative Example 1-5, no modified SEBS-g-MAH was added, the compatibility between the PA and TPU materials decreased significantly, and the processing performance decreased significantly. As shown in Example 2-8 for the laminated composite TPU fabric, the air permeability and moisture permeability decreased significantly. And due to the poor compatibility between TPU and PA6, the bonding force with the surface layer decreased significantly. In Comparative Example 1-2, the addition amount of modified SEBS-g-MAH increased, the combination of the two was too tight, and the air permeability and moisture permeability decreased. As shown in Example 2-5 for the laminated composite TPU fabric, its air permeability and moisture permeability decreased.

[0111] According to Table 1 and Table 2, in combination with Examples 1-1, Comparative Examples 1-3, Comparative Examples 1-4, and Comparative Example 1-7, and also in combination with Examples 2-1, Example 2-6, Example 2-7, and Example 2-10, it can be seen that the water vapor transmission rate of Comparative Examples 1-3 and Comparative Example 1-4 decreased compared to Example 1-1, and the water vapor transmission rate of Comparative Example 1-7 decreased significantly compared to Example 1-1, indicating that the air permeability and moisture permeability of Comparative Examples 1-1 and Comparative Example 1-2 decreased, and Comparative Example 1-7 decreased significantly; the air permeability, moisture permeability, and peel strength of Examples 2-6 and Example 2-7 decreased compared to Example 2-1, and Example 2-10 decreased significantly. The reason may be that in Comparative Example 1-3, the addition amount of hyperbranched polyester decreased, the toughness of the TPU composite material decreased, at the same time the content of phenyl decreased, the interaction between molecular chains decreased, and the hydrophilic hydroxyl groups also decreased accordingly, resulting in a decrease in air permeability and moisture permeability. As shown in Example 2-6, on the laminated composite TPU fabric, its air permeability and moisture permeability decreased, and due to the decrease in the polar hydroxyl groups, the adhesion performance between the melt-blown film of the TPU composite material and other surface layers also decreased. In Comparative Example 1-7, no hyperbranched polyester was added, the improvement of PA6 crystallization decreased, and the hydroxyl groups and phenyl groups decreased, resulting in a decrease in air permeability and moisture permeability. As shown in Example 2-10, on the laminated composite TPU fabric, the air permeability and moisture permeability of the composite fabric decreased. In Comparative Example 1-4, the addition amount of hyperbranched polyester increased, the content of hydroxyl increased, and the connection in the system was too tight, resulting in a decrease in air permeability and moisture permeability. As shown in Example 2-5, on the laminated composite TPU fabric, its air permeability and moisture permeability decreased, and with the increase of hyperbranched polyester, the interaction force between molecular chains decreased more significantly, and the adhesion performance between the melt-blown film of the TPU composite material and other surface layers also decreased.

[0112] According to Table 1 and Table 2, in combination with Example 1-1 and Comparative Example 1-6, and also in combination with Example 2-1 and Example 2-9, it can be seen that the water vapor transmission rate of Comparative Example 1-6 decreased significantly compared to Example 1-1, indicating that the air permeability and moisture permeability of Comparative Example 1-6 decreased significantly compared to Example 1-1; the air permeability, moisture permeability, and peel strength of Example 2-9 decreased significantly compared to Example 2-1. The reason may be that in Comparative Example 1-6, no PA6 was added, resulting in a further reduction in the performance of the TPU composite material. At the same time, due to the lack of the role of the crystalline polymer PA6, the molecular chains in the TPU composite material were arranged irregularly, and the gaps between the molecular chains were small, resulting in a significant decrease in the air permeability of the melt-blown film of the obtained TPU composite material. As shown in Example 2-9, on the laminated composite TPU fabric, the performance of the composite fabric decreased significantly.

[0113] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A TPU composite melt-blown film, obtained by melt-blowing a TPU composite masterbatch, characterized in that: The TPU composite masterbatch comprises the following raw materials in parts by mass: 70-80 parts of polyether thermoplastic polyurethane compound; 20-30 parts of polycaprolactam; 4-8 parts of hyperbranched polyester; 3-5 parts of compatibilizer; The compatibilizer is modified SEBS-g-MAH, which contains a phenol group. The raw materials of the modified SEBS-g-MAH include tannic acid and SEBS-g-MAH in a mass ratio of (1.2-1.5):

1. The preparation method of the modified SEBS-g-MAH is as follows: SEBS-g-MAH is allowed to stand in a hydrochloric acid solution for 4-6 hours, washed, and added to a sodium hydroxide solution; tannic acid is added to deionized water, stirred to dissolve, and then added to the SEBS-g-MAH. The temperature is raised to 60-80°C, and the reaction is stirred for 2-3 hours. After the reaction is completed, the mixed solution is added to a hydrochloric acid solution for acidification, and then filtered, washed, and dried to obtain the modified SEBS-g-MAH.

2. The TPU composite melt-blown film according to claim 1, characterized in that The hyperbranched polyester comprises a hydroxyl-terminated hyperbranched polyester and a phenyl-terminated hyperbranched polyester in a mass ratio of (2-3):

1.

3. The TPU composite melt-blown film according to claim 2, characterized in that The raw materials of the phenyl-terminated hyperbranched polyester include the hydroxy-terminated hyperbranched polyester and toluoyl chloride in a mass ratio of 1:(0.3-0.5).

4. The method for preparing a TPU composite meltblown film according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: S1. The polyether thermoplastic polyurethane compound and polycaprolactam are dried at 100-110° C. for 5-6 h, and then the polyether thermoplastic polyurethane compound, polycaprolactam, hyperbranched polyester and compatibilizer are weighed in parts by mass, mixed evenly, melt blended, extruded and granulated, and then dried to obtain a TPU composite masterbatch; S2. The TPU composite masterbatch obtained in S1 is passed through a melt-blown machine and melt-blown at a temperature of 190-230° C. to obtain a TPU composite melt-blown film.

5. The method for preparing the TPU composite melt-blown film according to claim 4, wherein: The thickness of the TPU composite melt-blown film is 0.1 to 0.2 mm.

6. A laminated composite TPU fabric, characterized in that: The laminated composite TPU fabric comprises a TPU composite meltblown film according to any one of claims 1 to 3, a four-way stretch woven fabric and a woven / knitted composite base fabric, wherein the TPU composite meltblown film is located between the four-way stretch woven fabric and the woven / knitted composite base fabric.

7. The laminated composite TPU fabric according to claim 6, characterized in that: The TPU composite melt-blown film and the four-way stretch woven fabric are compounded by hot-melt adhesive; the hot-melt adhesive is polyurethane hot-melt adhesive.

8. The laminated composite TPU fabric according to claim 7, characterized in that: The woven / knitted composite base fabric is one or a combination of polyester, nylon, spandex, and cotton; and the four-way stretch woven fabric is a combination of nylon and spandex.

Images