A warm, waterproof, moisture-permeable membrane, its method of manufacture and use in clothing

Abstract

The application provides a warm waterproof and moisture-permeable film, a preparation method thereof and application in clothes, wherein the preparation method of the waterproof and moisture-permeable film comprises the following steps: applying polyimide slurry on a release substrate to form a polyimide film layer; the polyimide slurry is obtained by converting a polyamide acid solution, the solid content of the polyamide acid solution is 20%-30%, and the room temperature viscosity of the polyimide slurry is 5000-20000 cps; combining a microporous polyurethane film with the polyimide film layer through extrusion and drying, and peeling off the release substrate to obtain the warm waterproof and moisture-permeable film. The waterproof and moisture-permeable film provided by the application has good waterproof and moisture-permeable and warm properties, and the clothes applied can maintain the body comfort in a cold environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of clothing materials, in particular to a warm waterproof and moisture-permeable film, a preparation method thereof and application in clothing. BACKGROUND

[0002] In recent years, with the popularity of outdoor sports, the demand for outdoor clothing is increasing. Outdoor clothing has a multi-layer structure, and the market pays more attention to waterproof and moisture-permeable properties; the clothing worn can resist rain weather, and the moisture-permeable property can remove internal sweat, and the R&D personnel upgrade the waterproof and moisture-permeable properties more often. The film commonly used for outdoor jackets on the market is mainly polytetrafluoroethylene (PTFE) film and polyurethane (PU) film, which are good waterproof and moisture-permeable materials for clothing.

[0003] However, few people pay attention to the problem of warmth during outdoor activities in autumn and winter. A large amount of sweat vapor is generated from the human body during outdoor activities, and the evaporation of these sweat vapors from the human body will take away a large amount of heat, and the cold wind will easily make people catch a cold. Therefore, the human body needs to maintain body temperature after outdoor activities to achieve thermal comfort. The above-mentioned waterproof and moisture-permeable film for clothing usually does not have warmth, and the existing technology reports a warmth film material used in the industrial field of greenhouse warmth. For example, a kind of expanded polytetrafluoroethylene composite film is prepared in Chinese patent document with publication number CN 117162638 A, wherein the expanded polytetrafluoroethylene film has warmth performance, and the preparation process comprises: mixing polytetrafluoroethylene dispersion resin, modified fly ash floating beads prepared, a mixture of boron fibers and nano cerium dioxide, and kerosene, vacuum pressing into a columnar blank after curing, the columnar blank is extruded into a rod-shaped object by a pusher, the rod-shaped object is fed into a calender, and a sheet is pressed out; the sheet is sintered and shaped after being stretched in the longitudinal and transverse directions, and the expanded polytetrafluoroethylene film is obtained.

[0004] The expanded polytetrafluoroethylene film involved in the document can be called an expanded polytetrafluoroethylene warmth film, which can insulate and keep warm, but the maximum hydrostatic pressure is only 20 KPa, while the minimum requirement of the national standard for waterproof performance of the jacket category is 50 KPa. The waterproof performance of this warmth film cannot be applied to the jacket category. SUMMARY

[0005] Therefore, the present application provides a warm waterproof and moisture-permeable film, a preparation method thereof and application in clothing. The waterproof and moisture-permeable film provided by the present application has good waterproof, moisture-permeable and warm properties, and the clothing applied can maintain thermal comfort in a cold environment.

[0006] The present application provides a preparation method of a warm waterproof and moisture-permeable film, comprising:

[0007] A polyimide slurry is applied on a release substrate to form a polyimide film layer; the polyimide slurry is converted from a polyamic acid solution, the solid content of the polyamic acid solution is 20-30%, and the room temperature viscosity of the polyimide slurry is 5000-20000 cps;

[0008] A microporous polyurethane film is combined with the polyimide film layer by extrusion and drying, and the release substrate is peeled off to obtain a warm waterproof and moisture-permeable film.

[0009] In some embodiments, the conversion of the polyimide slurry comprises: in the presence of a catalyst and under gas protection, condensation polymerization of diamine monomers and dianhydride monomers in an organic solvent to obtain a polyamic acid solution, and after dilution, imidization is performed to obtain the polyimide slurry.

[0010] In some embodiments, the diamine monomers are selected from one or more of 2,2'-bis(trifluoromethyl) biphenyl diamine, p-phenylenediamine, m-phenylenediamine, and 4,4'-diamino diphenyl ether; and the dianhydride monomers are selected from one or more of aromatic 4,4'-oxybisphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene diacid anhydride, tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, and 3,3',4,4'-biphenyl tetracarboxylic dianhydride.

[0011] In some embodiments, the catalyst is selected from one or more of pyridine, isoquinoline, triethylenediamine, and triethylamine; and the organic solvent is selected from one or more of N-methylpyrrolidone, m-cresol, N,N-dimethylacetamide, dimethyl sulfoxide, and gamma-butyrolactone.

[0012] In some embodiments, the organic solvent is preheated to dissolve the diamine monomers and the dianhydride monomers; the condensation polymerization is performed at a temperature of 100-300°C for 1.5-8h.

[0013] In some embodiments, the drying is performed at a temperature of 100-130°C, and the extrusion is performed at a pressure of 1-2MPa.

[0014] In some embodiments, after the release substrate is peeled off, the waterproof and moisture-permeable film is further dried at a temperature of 100-160°C for 3-5h.

[0015] The present application provides a warm waterproof and moisture-permeable film prepared by the above-mentioned method, and the gram weight of the warm waterproof and moisture-permeable film is 10-15g / m 2 .

[0016] The present application provides a garment comprising the above-mentioned warm waterproof and moisture-permeable film.

[0017] Compared with the prior art, the polyimide slurry with the room temperature viscosity of 5000-20000 cps is mainly used, and the polyimide film formed by the polyimide slurry is transferred from the release substrate to the microporous PU film, and the warm waterproof and moisture-permeable film is obtained after extrusion and drying. The polyimide is a material with a thermal conductivity close to air, and has excellent warm-keeping performance, and the microporous PU film has good waterproof and moisture-permeable performance, and the combination of the two will make the clothing film have the performance of waterproof and moisture-permeable and warm-keeping, and the human body is well protected in a cold environment. Compared with the ordinary polyurethane film, the polyimide transfer coating layer is formed on the surface of the clothing film, so that the waterproof performance of the clothing film is better, the waterproof performance of the clothing film meets the requirements of the outdoor clothing, and the polyimide has a thermal conductivity close to air, so that the clothing film has excellent warm-keeping performance, and the thermal comfort of the clothing is met. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 A structure schematic diagram of the warm waterproof and moisture-permeable film provided by the embodiment of the present application is shown. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application is further described in detail below in combination with embodiments. Unless otherwise defined, all professional terms used in the following have the same meaning as understood by those skilled in the art. The professional terms used in the present application are only for the purpose of describing the specific embodiments, and are not intended to limit the protection scope of the present application.

[0020] The present application provides a preparation method of a warm waterproof and moisture-permeable film, comprising:

[0021] The polyimide slurry is applied on the release substrate to form a polyimide film layer; the polyimide slurry is obtained by converting a polyamide acid solution, the solid content of the polyamide acid solution is 20%-30%, and the room temperature viscosity of the polyimide slurry is 5000-20000 cps;

[0022] The microporous polyurethane film and the polyimide film layer are combined together through extrusion and drying, and the release substrate is peeled off to obtain the warm waterproof and moisture-permeable film.

[0023] The waterproof and moisture-permeable film prepared by the embodiment of the present application has good waterproof and moisture-permeable and warm-keeping performance, and the clothing applied can maintain the comfortable feeling in a cold environment.

[0024] The polyimide slurry is prepared by a two-step method, and has a room temperature viscosity of 5000-20000 cps, and further 8000-18000 cps. The preparation process comprises: under the conditions of gas protection and catalyst, polycondensation reaction of diamine monomers and dianhydride monomers in an organic solvent to obtain a polyamide acid solution, and after dilution, imidization to obtain the polyimide slurry. The viscosity unit cps is the fluid viscosity measured by a Brookfield viscometer, and the slurry viscosity is mainly measured at 25 DEG C.

[0025] The polyimide is a polymer containing imine structure in the main chain, and the polyimide in the embodiment is mainly a polycondensation type polyimide obtained by polycondensation reaction of aromatic tetracarboxylic acid dianhydride and diamine as monomer raw materials. The polyimide belongs to high heat-resistant plastic material. Specifically, the diamine monomer is selected from one or more of 2,2'-bis(trifluoromethyl) biphenyl diamine, p-phenylenediamine, m-phenylenediamine and 4,4'-diamino diphenyl ether; and the dianhydride monomer is selected from one or more of aromatic 4,4'-oxybisphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride, tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride and 3,3',4,4'-biphenyl tetracarboxylic dianhydride.

[0026] In the embodiment, the organic solvent is preheated under the conditions of gas protection and catalyst, the heating temperature is 40-100 DEG C, the diamine monomer is mixed and dissolved with the preheated organic solvent, the dianhydride monomer is added after sufficient dissolution, the temperature is continuously increased, the heating temperature is 100-230 DEG C, the molar ratio of amino group and anhydride group can be kept at 1:(1-1.1), and the mass percentage of the sum of diamine and dianhydride to the organic solvent is 40%-60%. In the polycondensation reaction process, the final polymerization reaction temperature is kept at 230 DEG C-300 DEG C, and the polymerization reaction time is preferably 1.5 h-8 h, and more preferably 2-6 h. After the polymerization is completed, a polyamide acid solution is obtained.

[0027] The gas protection is preferably at least one of argon and nitrogen. The catalyst is preferably one or more of pyridine, isoquinoline, triethylenediamine and triethylamine, and the catalyst dosage is 0.6 g-2 g. The organic solvent is preferably one or more of N-methyl pyrrolidone, m-methyl phenol, N,N-dimethylacetamide, dimethyl sulfoxide and gamma-butyrolactone, and further N-methyl pyrrolidone and N,N-dimethylacetamide, and can be preheated at 80-100 DEG C.

[0028] The polyimide slurry is obtained by adding the same organic solvent as described above to dilute the polyamic acid solution to a solid content of 20% to 30% in the polymerization reaction system, and then heating for imidization. The imidization is generally a process of multi-stage heating in the range of 70 to 320°C, and the diamine and diacid form a polymer containing an imide ring (—CO—NH—CO—). Specifically, under hydrochloric acid conditions, the temperature is first increased from room temperature to 70 to 80°C, and the temperature is maintained for 1 to 2 hours; then the temperature is increased to 120 to 130°C, and the temperature is maintained for 1 to 2 hours; then the temperature is increased to 180 to 200°C, and the temperature is maintained for 1 to 2 hours; then the temperature is increased to 260 to 280°C, and the temperature is maintained for 0.5 to 1 hour; and finally the temperature is increased to 300 to 320°C, and the temperature is maintained for 0.5 to 1 hour.

[0029] In some embodiments of the present application, the release paper is bonded together with the obtained polyimide slurry to form a polyimide film layer, and then the microporous polyurethane film is combined with the polyimide film layer by a bonding roller, the temperature can be 100 to 130°C, and the pressure is 1 to 2 MPa. Finally, the release paper is removed, preferably dried at 100 to 160°C for 3 to 5 hours, to obtain a warm waterproof and moisture permeable film.

[0030] The release paper is mainly polypropylene material with a thickness of 2 to 3 mm and a peeling force in the range of 1 to 5 N. In the embodiments of the present application, the polyimide slurry can be coated on the release paper to form a continuous, uniform and porous polyimide film layer by drying the coating agent. The microporous polyurethane film has micrometer-sized pores, and the average pore size of the example microporous PU film is less than 0.2 μm, and the porosity is more than 80 to 85%. Commercially available microporous PU film can be used.

[0031] In the embodiments of the present application, the transfer combination method is used, and the interlayer structure between the polyimide film layer and the microporous PU film does not block the pores of the film itself, prevents the pores of the microporous PU film from being blocked by glue during the bonding process, and ensures that the polyimide is uniformly distributed on the film, so that the microporous PU film can maintain uniform thickness and good moisture permeability and air permeability. In addition, the transfer method combined with polyimide in the embodiments of the present application can make the microporous PU film have better film hand feeling and softness.

[0032] The embodiments of the present application provide a warm waterproof and moisture permeable film prepared by the preparation method described above, which can be referred to as a warm waterproof and moisture permeable polyurethane clothing film. Referring to Figure 1 , the warm waterproof and moisture permeable film has a two-layer structure, which is a microporous polyurethane film 1 as a bottom layer and a polyimide film layer 2 as a surface layer. In some embodiments, the warm waterproof and moisture permeable film has a grammage of 10 g / m 2 -15 g / m 2 .

[0033] The embodiment of the present application provides a garment which comprises the warm waterproof and moisture-permeable film described above, and has good waterproof and moisture-permeability and warmth.

[0034] Unless otherwise specified, all reagents and raw materials used in the present application are commercially available or can be prepared by known methods.

[0035] Example 1

[0036] 1. Preparation of polyimide slurry

[0037] In the presence of nitrogen atmosphere and catalyst (1g), the reaction raw materials and catalyst are fed into a tubular flow reactor; the organic solvent is preheated at 100℃, the diamine monomer is mixed and dissolved with the organic solvent, after sufficient dissolution, the dianhydride monomer is added, and the heating temperature is increased to 210℃, the molar ratio of amino group to anhydride group is kept at 1:1.1, and the mass ratio of the total of diamine and dianhydride to the organic solvent is 50%; in the polycondensation reaction, the final polymerization temperature is kept at 260℃, and the polymerization reaction time is 5h; after the polymerization is completed, the polyamic acid solution is obtained, the organic solvent is added to dilute the solution to a solid content of 30%, and then imidization is carried out by heating to obtain the polyimide slurry; the imidization is as follows: first, the temperature is increased from room temperature to 70-80℃ under hydrochloric acid condition, and kept for 1-2h; then the temperature is increased to 120-130℃, and kept for 1-2h; then the temperature is increased to 180-200℃, and kept for 1-2h; then the temperature is increased to 260-280℃, and kept for 0.5-1h; finally, the temperature is increased to 300-320℃, and kept for 0.5-1h; the viscosity of the polyimide slurry is 12000cps.

[0038] The catalyst comprises isoquinoline, triethylenediamine and triethylamine; and the organic solvent comprises N-methylpyrrolidone and N,N-dimethylacetamide.

[0039] The diamine monomer is 2,2'-bis(trifluoromethyl) biphenyl diamine; and the dianhydride monomer is aromatic 4,4'-oxydiphthalic anhydride.

[0040] 2. Preparation of warm waterproof and moisture-permeable polyurethane garment film

[0041] The release paper is installed on the coating machine, the release paper is kept straight by tension adjustment, the thickness of the release paper is 2mm, the distance between the scraper and the roller shaft is adjusted to 3.5mm, the polyimide slurry is poured into the coating machine, the stirring speed of the coating machine is started at 5000r / min, the coating machine is wound up, the winding speed is 3m / min, the release paper is bonded with the polyimide slurry to form a polyimide film layer; then the microporous polyurethane film (the thickness of the film is 15μm, the porosity is 85%, and the micropore size is 15nm) is bonded with the polyimide film layer through a bonding roller, the hot melt adhesive used is a single-component moisture reaction type polyurethane hot melt adhesive (the density is 1.1g / cm 3 , the viscosity is 13600cps at 80℃, 8500cps at 90℃, and 5800cps at 100℃), the temperature is 100℃, the pressure is 1MPa, finally the release paper is removed, and the obtained product is dried at 160℃ for 4h, and finally a warm-keeping, waterproof and moisture-permeable polyurethane clothing film is prepared, and the grammage is 10g / m 2 .

[0042] Example Two

[0043] 1. Preparation of polyimide slurry

[0044] In the presence of nitrogen atmosphere and catalyst (1g), the raw materials and catalyst are put into a tubular flow reactor; the organic solvent is preheated at 100℃, the diamine monomer is mixed and dissolved with the organic solvent, the dianhydride monomer is added after sufficient dissolution, the temperature is continuously increased to 210℃, the molar ratio of amino group to anhydride group is kept at 1:1.1, and the total mass ratio of diamine and dianhydride to organic solvent is 60%; in the polycondensation reaction, the final polymerization temperature is kept at 260℃, and the polymerization time is 5h. After the polymerization is completed, the polyamide acid solution is obtained, the organic solvent is added for dilution to a solid content of 40%, and then imidization is carried out (the same as in Example 1) to obtain the polyimide slurry. The viscosity of the polyimide slurry is 15000cps.

[0045] The catalyst includes isoquinoline, triethylenediamine and triethylamine; and the organic solvent includes N-methylpyrrolidone and N,N-dimethylacetamide.

[0046] The diamine monomer is 2,2'-bis(trifluoromethyl) biphenyl diamine; and the dianhydride monomer is aromatic 4,4'-oxydiphthalic anhydride.

[0047] 2. Preparation of warm-keeping, waterproof and moisture-permeable polyurethane clothing film

[0048] The release paper was attached to the polyimide slurry according to the operation in Example 1 to form a polyimide film layer, and then the microporous polyurethane film was hot-melt attached to the polyimide film layer by a laminating roller (same as in Example 1) at a temperature of 100°C and a pressure of 1 MPa, and finally the release paper was removed and dried at 160°C for 4 h, to finally prepare a warm and waterproof and moisture-permeable polyurethane clothing film with a grammage of 13 g / m 2 .

[0049] Comparative Example 1

[0050] The untreated polyurethane film with a PU coating layer (directly purchased from the British Porelle Membrane Company) had a film thickness of 15 μm, a total grammage of 8 g / m 2 , a porosity of 50%, and a micropore size of 10 nm.

[0051] Comparative Example 2

[0052] Polyimide slurry-coated microporous polyurethane film

[0053] The prepared polyimide slurry was dissolved in N,N-dimethylacetamide (DMF) at a ratio of 2:1 to form a syrup, which was then directly coated on the microporous polyurethane film by means of a doctor blade (the distance between the doctor blade and the film was 3.5 mm, the film thickness was 15 μm, the porosity was 85%, and the micropore size was 15 nm), to form a coating layer on the surface of the film, and the solvent was volatilized by drying at 160°C for 4 h, to finally prepare a warm and waterproof and moisture-permeable polyurethane clothing film with a grammage of 10 g / m 2 .

[0054] The obtained Example 1 and Example 2 and Comparative Examples were tested, and the test methods and results are as follows.

[0055] Moisture permeability test: according to GB / T 12704.2-2009 Method B (inverted cup method) and GB / T 12704.1-2009;

[0056] Hydrostatic pressure test: GB / T 8629-2017;

[0057] CLO value and warmth rate test: according to GB / T 35762-2017 Textiles-Test Methods for Thermal Transmittance-Flat-Plate Method.

[0058] Table 1 Performance test results of the waterproof and moisture-permeable film obtained in the inventive examples

[0059]

[0060]

[0061] From the above examples, the present application mainly uses polyimide slurry with a room temperature viscosity of 5000-20000 cps, and transfers the polyimide film formed therefrom from a release substrate to a microporous PU film, and obtains a warm waterproof and moisture permeable film after extrusion and drying. Polyimide has excellent warm-keeping performance, and the microporous PU film has good waterproof and moisture permeable performance, and the combination of the two will make the clothing film have waterproof and moisture permeable and warm-keeping performance, and make the human body well protected in a cold environment. The present application has better waterproof performance due to the polyimide transfer coating treatment on the surface, which meets the requirements of the combat clothes, and the polyimide close to the thermal conductivity of air endows the film with excellent warm-keeping performance, which meets the thermal comfort requirements of the clothes.

[0062] The above merely describes the preferred embodiments of the present application, and is not used to limit the present application, and any modification, equivalent replacement or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for producing a warm, waterproof, moisture-permeable film, characterized by, The application relates to a warm and waterproof moisture-permeable film. The polyimide slurry is converted from a polyamide acid solution, the solid content of the polyamide acid solution is 20-30%, and the room-temperature viscosity of the polyimide slurry is 5000-20000 cps. The microporous polyurethane film is combined with the polyimide film layer through extrusion and drying, and the release substrate is peeled off to obtain the warm and waterproof moisture-permeable film. The conversion of the polyimide slurry comprises the following steps: under the conditions of gas protection and catalyst, diamine monomers and dianhydride monomers are subjected to a polycondensation reaction in an organic solvent to obtain a polyamide acid solution, and after dilution, the polyamide acid solution is subjected to imidization to obtain the polyimide slurry; the diamine monomers are selected from one or more of 2,2'-bis(trifluoromethyl) biphenyl diamine, p-phenylenediamine, m-phenylenediamine and 4,4'-diamino diphenyl ether; the dianhydride monomers are selected from one or more of aromatic 4,4'-oxydiphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene diacid anhydride, tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride and 3,3',4,4'-biphenyl tetracarboxylic dianhydride; the catalyst is selected from one or more of pyridine, isoquinoline, triethylenediamine and triethylamine; and the organic solvent is selected from one or more of N-methyl pyrrolidone, m-methyl phenol, N,N-dimethylacetamide, dimethyl sulfoxide and gamma-butyrolactone. The diamine monomers and the dianhydride monomers are dissolved after the organic solvent is preheated; the temperature of the polycondensation reaction is 100-300 DEG C, and the time is 1.5-8 h.

2. The method for producing a waterproof and moisture-permeable film according to claim 1, characterized by, The temperature of the drying is 100-130 DEG C, and the pressure of the extrusion is 1-2 MPa.

3. The method of producing a waterproof and moisture-permeable film according to any one of claims 1 to 2, characterized by, After the release substrate is peeled off, the waterproof moisture-permeable film is also dried, the drying is baking at 100-160 DEG C for 3-5 h.

4. The method of producing a waterproof and moisture-permeable film according to claim 3, characterized by, The application further relates to a warm and waterproof moisture-permeable film comprising the warm and waterproof moisture-permeable film according to claim 5.

5. A warm, waterproof, moisture-permeable film, characterized by The warm, waterproof, moisture-permeable membrane has a grammage of 10-15 g / m 2 .

6. A garment characterized in that, ​

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