A multi-layer composite clothing fabric with high elastic recovery and its preparation method

Abstract

The present invention discloses a multi-layer composite clothing fabric with high elastic recovery and a preparation method thereof, belonging to the technical field of fabric processing, and is used to solve the technical problems that the elastic recovery performance and water washing resistance of the existing clothing fabrics are poor, and the puncture strength of the clothing fabrics needs to be further improved; the present invention includes a plurality of sub-fabric layers, and the plurality of sub-fabric layers are bonded and fixed by an adhesive. After mixing composite polyurethane and polyethylene terephthalate to prepare composite polyurethane fibers, the sub-fabric layers are prepared through blending and weaving. Then, based on the sub-fabric layers, layer-by-layer lamination is carried out with polyurethane glue to prepare a multi-layer composite clothing fabric, which not only effectively improves the elastic recovery performance of the clothing fabric, but also improves the water washing resistance and puncture strength of the clothing fabric.

Description

Technical Field

[0001] The present invention relates to the technical field of fabric processing, and particularly relates to a multi-layer composite clothing fabric with high elastic recovery and a preparation method thereof. Background Art

[0002] In the fields of textile and clothing, with the improvement of people's living standards and the enhancement of health awareness, the requirements for clothing are no longer limited to warmth and modesty, but more pursue wearing comfort, functionality and aesthetics. Fabrics with high elastic recovery have become a new trend in the development of clothing fabrics due to their good elasticity, recovery, durability and comfort. Especially in the fields of sports, fitness, outdoor, etc., fabrics with high elastic recovery are more favored.

[0003] Traditional elastic fabrics, such as spandex, Lycra, etc., while providing a certain degree of elasticity, often face the problem of insufficient elastic recovery performance, that is, after being stretched by an external force, the fabric is difficult to quickly and completely return to its original shape, resulting in fabric deformation and relaxation, and thus affecting the wearing effect and comfort of the clothing.

[0004] In the prior art, in order to improve the elastic recovery performance of the fabric, a multi-layer composite technology is usually used to composite materials with excellent elasticity (such as TPU, polyurethane, etc.) with the base fabric to form a multi-layer structure. This structure not only retains the excellent characteristics of the high-elasticity material, but also enhances the overall elastic recovery ability of the fabric through the interaction between layers; however, the multi-layer composite clothing fabric has poor washability, is prone to deformation or loss of its original performance during the washing process, and in daily use, the clothing fabric is inevitably in contact with sharp objects, and the traditional elastic fabric has poor puncture resistance and is easily punctured and damaged when in contact with sharp objects.

[0005] In view of the technical deficiencies in this regard, a solution is now proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a multi-layer composite clothing fabric with high elastic recovery and a preparation method thereof, which are used to solve the technical problems of poor elastic recovery performance and washability of the clothing fabric in the prior art, and the puncture strength of the clothing fabric needs to be further improved.

[0007] The purpose of the present invention can be achieved by the following technical solutions: A multi-layer composite clothing fabric with high elastic recovery, including a plurality of sub-fabric layers, and the plurality of sub-fabric layers are bonded and fixed through an adhesive;

[0008] The sub-fabric layer is obtained by weaving a blended yarn on a circular knitting machine;

[0009] The blended yarn is composed of composite polyurethane fiber and spandex fiber blended in a weight ratio of 10:2-3.

[0010] Furthermore, the preparation method of the composite polyurethane fiber is as follows: After mixing composite polyurethane, polyethylene terephthalate, and additives, add them to a melt spinning machine for melt spinning to obtain composite polyurethane fiber.

[0011] Furthermore, the weight ratio of the composite polyurethane, polyethylene terephthalate, and additives is 70-80:20-25:4-6. The additives are composed of a dispersant, a lubricant, an antioxidant, and a plasticizer in a weight ratio of 2:1:1:5. The dispersant is ethylene bisstearamide, the lubricant is sodium stearate, the antioxidant is one or more of antioxidant DPPD, antioxidant PPD, and antioxidant H, the plasticizer is phthalate, the spinning temperature of the melt spinning machine is 280-290 °C, the aperture of the spinneret hole is 0.25-0.35 mm, and the winding speed is 3000-3400 m / min.

[0012] Furthermore, the composite polyurethane is obtained by the following steps:

[0013] A1. Add succinic acid, neopentyl glycol, a catalyst, and an antioxidant to a reaction kettle and stir. Raise the temperature of the reaction kettle to 170-180 °C and lower the pressure to 80-90 Pa. React until the acid value of the system drops to 2-3 mg NaOH / g, and then perform post-treatment to obtain a prepolymer.

[0014] The synthesis reaction formula of the prepolymer is:

[0015]

[0016] The synthesis principle of the prepolymer is:

[0017] During the reaction process, the carboxyl group on succinic acid and the hydroxyl group on neopentyl glycol form an ester bond by dehydrating water molecules in the presence of a catalyst. An esterification polycondensation reaction occurs between succinic acid and neopentyl glycol to prepare a polyester with a methyl-modified long alkane straight chain and a molecular weight of about 1000. During the feeding process, keep neopentyl glycol in excess to form a hydroxyl-terminated polyester molecular chain and obtain a prepolymer.

[0018] A2. Add the prepolymer, hydroxyl silicone oil, a catalyst, and N,N-dimethylformamide to a reaction kettle protected by nitrogen and stir. Raise the temperature of the reaction kettle to 65-75 °C, add 4,4'-diphenylmethane diisocyanate to the reaction kettle, keep the temperature for reaction for 2-3 h, add a crosslinking chain extender solution to the reaction kettle, keep the temperature for reaction for 4-6 h, add octylamine, and then perform post-treatment to obtain composite polyurethane.

[0019] The synthesis reaction formula of the composite polyurethane is:

[0020]

[0021]

[0022] In the formula:

[0023] R1:

[0024] R2:

[0025] R3:

[0026] The synthesis reaction principle of the composite polyurethane is as follows:

[0027] Under the protection of nitrogen and the action of a catalyst, the hydroxyl groups in the prepolymer and the hydroxyl silicone oil molecules undergo a nucleophilic addition reaction with the isocyanate groups in the 4,4'-diphenylmethane diisocyanate molecules to form a polyurethane prepolymer in which the prepolymer and the hydroxyl silicone oil molecular chains are co-embedded. Then, taking the hydroxyl group in the crosslinking chain extender as the active group, it further condenses with the isocyanate group on the polyurethane prepolymer to increase the crosslinking degree between the polyurethane prepolymer molecules and increase the molecular weight of the polyurethane. Octylamine is used as a capping agent to react with the isocyanate group on the chain-extended polyurethane prepolymer to form a capping agent, and the composite polyurethane is prepared.

[0028] Further, in step A1, the dosage ratio of succinic acid to 1,5-pentanediol is 1 mol: 1.1 mol, the weight ratio of 1,5-pentanediol, the catalyst and the antioxidant is 100: 0.5: 0.2, the catalyst is stannous chloride, the antioxidant is sodium pyrophosphate, and the post-treatment includes: after the reaction is completed, the pressure in the reaction kettle returns to normal pressure, the temperature is reduced to 70-80 °C, toluene is added to the reaction kettle, and stirred until the system is dissolved. The temperature of the reaction kettle is reduced to room temperature, purified water is added to the reaction kettle, the organic phase is washed twice with purified water and then transferred to a rotary evaporator with a water bath temperature of 70-80 °C, and distilled under reduced pressure until no liquid is collected to obtain the prepolymer; in step A2, the dosage ratio of the prepolymer, the hydroxyl silicone oil, the catalyst, N,N-dimethylformamide, 4,4'-diphenylmethane diisocyanate, the crosslinking chain extender solution, and octylamine is 38-42 g: 20-24 g: 0.5 g: 300 mL: 12-14 g: 50 g: 5 g, the catalyst is dibutyltin dilaurate, the crosslinking chain extender solution is composed of a crosslinking chain extender and N,N-dimethylformamide according to a weight ratio of 1: 3, and the post-treatment includes: after the reaction is completed, the temperature of the reaction kettle is raised to 90-100 °C, and distilled under reduced pressure until no liquid is collected to obtain the composite polyurethane.

[0029] Further, the crosslinking chain extender is prepared by the following steps:

[0030] B1. Add pimelic acid, 1,4-butanediol, toluene and a catalyst into a reaction kettle under nitrogen protection and stir. Raise the temperature of the reaction kettle to the reflux temperature of the system, keep the temperature for reaction for 6 - 8 h, and perform post-treatment to obtain intermediate I.

[0031] The synthesis reaction formula of intermediate I is:

[0032]

[0033] The synthesis reaction principle of intermediate I is:

[0034] Under the action of a catalyst, the carboxyl group of pimelic acid and the hydroxyl group of 1,4-butanediol remove one molecule of water to form an ester bond. Pimelic acid and 1,4-butanediol crosslink through dehydration esterification to form a polyester containing a long alkane straight-chain structure. By controlling the amount of 1,4-butanediol to be higher than that of pimelic acid, hydroxyl groups are formed at both ends of the polyester to prepare intermediate I.

[0035] B2. Add intermediate I, epoxidized soybean oil, toluene and a catalyst into a reaction kettle and stir. Raise the temperature of the reaction kettle to 70 - 80 °C, keep the temperature for reaction for 6 - 8 h, and perform post-treatment to obtain a crosslinking chain extender.

[0036] The synthesis reaction formula of the crosslinking chain extender is:

[0037]

[0038] R4:

[0039] In the formula

[0040] The synthesis reaction principle of the crosslinking chain extender is:

[0041] Under the action of tetrabutyl titanate as a catalyst, the hydroxyl group on the molecule of intermediate I and the epoxy group in epoxidized soybean oil undergo a ring-opening polymerization reaction to form crosslinks and form new hydroxyl groups, thus preparing a crosslinking chain extender with a longer molecular chain and a crosslinking network using hydroxyl groups as active groups.

[0042] Further, in step B1, the dosage ratio of pimelic acid to 1,4-butanediol is 1 mol: 1.1 mol, the dosage ratio of pimelic acid, toluene and the catalyst is 1 g: 7 mL: 0.1 g, the catalyst is 90-98 wt% sulfuric acid, and the post-treatment includes: after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, purified water is added to the reaction kettle, stirred for 20-30 min, allowed to stand for liquid separation, the organic phase is washed with purified water until neutral and then transferred to a rotary evaporator with a water bath temperature of 70-80 °C, and distilled under reduced pressure until no liquid is collected to obtain intermediate I; in step B2, the dosage ratio of intermediate I, epoxidized soybean oil, toluene and the catalyst is 5 g: 2 g: 30 mL: 0.05 g, the catalyst is tetrabutyl titanate, and the post-treatment includes: after the reaction is completed, the reaction kettle is kept at 70-80 °C, and the solvent is distilled off under reduced pressure to obtain the crosslinking chain extender.

[0043] Further, the adhesive is polyurethane glue; the weaving method of the sub-fabric layer is one-up-one-down warp and weft weaving, using blended yarn as the warp and weft yarns, the warp density is 198-206 threads / 10 cm, and the weft density is 186-194 threads / 10 cm.

[0044] The present invention also provides a preparation method of a multi-layer composite clothing fabric with high elastic recovery, including the following steps:

[0045] S1. Blending composite polyurethane fibers and spandex fibers to obtain a blended yarn with a fineness of 40-50 D;

[0046] S2. Feeding the blended yarn into a circular knitting machine for knitting, and then cutting it into uniform specifications to obtain the sub-fabric layer;

[0047] S3. Laying the sub-fabric layer flat on a flat tabletop, coating an adhesive on the upper surface layer of the sub-fabric layer to form an adhesive layer on the surface layer of the sub-fabric layer, laying another sub-fabric layer on the adhesive layer, and hot pressing for 40-60 s;

[0048] S4. Repeating the operation of step S3 to obtain a multi-layer composite clothing fabric composed of several sub-fabric layers.

[0049] Further, in step S3, the coating amount of the adhesive is 20-25 g / m 2 , the temperature of the hot pressing is 75-85 °C, and the pressure is 3-4 MPa.

[0050] The present invention has the following beneficial effects:

[0051] 1. The multi-layer composite clothing fabric with high elastic recovery of the present invention uses a polyester with a methyl-modified long alkane straight chain and a polyorganosiloxane copolymer block and a cross-linking chain extender containing an epoxy group as a chain extender to prepare a composite polyurethane with a high cross-linking density, which improves the cohesion and tear resistance of the material. Then, the composite polyurethane is compounded with polyethylene terephthalate. Polyethylene terephthalate itself is a semi-crystalline polymer with multiple crystal forms. The composite polyurethane fiber is prepared by melt spinning, which promotes the crystallization of the composite polyurethane and improves the elastic recovery performance and puncture strength of the composite polyurethane fiber. When preparing the composite polyurethane, the water resistance is improved by optimizing the chain segment composition of the composite polyurethane, so that the fiber fabric has good washability. The multi-layer composite clothing fabric with high elastic recovery of the present application uses polyurethane glue as an adhesive to compound and form several sub-fabric layers woven from mixed spun yarns composed of composite polyurethane fibers and spandex fibers. The high elasticity of spandex enhances the composite polyurethane fiber, further improving the overall performance of the clothing fabric.

[0052] 2. The multi-layer composite clothing fabric with high elastic recovery of the present invention uses a prepolymer of methyl-modified long alkane straight-chain polyester and hydroxy silicone oil as soft segments, and 4,4'-diphenylmethane diisocyanate as hard segments. After preparing the polyurethane prepolymer by condensation, it is cross-linked and extended with a cross-linking chain extender, and octylamine is used as a capping agent to prepare the composite polyurethane; when preparing the prepolymer, neopentyl glycol is selected as the reaction monomer, and a large amount of methyl groups are introduced into the prepolymer. The two methyl groups in the neopentyl glycol molecule are located on the central carbon atom. This structure results in a large steric hindrance between the methyl groups. The steric hindrance effect of the methyl groups will slow down the close packing of the chain segments, increase the free volume between the chain segments, and moreover, the neopentyl glycol unit can rotate and twist around its central carbon atom to form various conformations, increasing the conformational flexibility of the neopentyl glycol molecular chain and improving the elastic recovery performance of the polyurethane. Hydroxy silicone oil is an organosilicon polyol with a unique silicon-oxygen bond structure, which endows it with excellent softness, wear resistance and water resistance. In the composite polyurethane, the prepolymer and hydroxy silicone oil are used as soft segments, and 4,4'-diphenylmethane diisocyanate is used as the hard segment, forming the interaction of the soft and hard segments cooperating with each other, so that the polyurethane has better elastic recovery performance while maintaining sufficient strength.

[0053] 3. The multi-layer composite clothing fabric with high elastic recovery of the present invention prepares a crosslinking chain extender by modifying epoxy soybean oil with intermediate I. The long-chain alkane groups of epoxy soybean oil in the crosslinking chain extender endow the polyurethane segment with higher flexibility. The long-chain alkane polyester linear structure of intermediate I usually has good flexibility. After intermediate I modifies epoxy soybean oil, a large number of hydroxyl groups are introduced onto the crosslinking chain extender, improving the reaction activity of the crosslinking chain extender, thereby increasing the intermolecular crosslinking degree of the composite polyurethane, and further improving the puncture resistance of the composite polyurethane. The introduction of the long-chain structures of epoxy soybean oil and intermediate I, combined with the prepolymer, hydroxyl silicone oil, and hard segments, further improves the elastic recovery performance of the composite polyurethane material; the composite polyurethane is prepared by polymerization of various monomers, and its molecular chain contains various functional groups such as hydroxyl groups, epoxy groups, and imino groups. These functional groups can interact with the ester groups in the molecular chain of polyethylene terephthalate, improving the compatibility between the two. The ester groups in the molecular chain of polyethylene terephthalate can serve as nucleation points, promoting the crystallization of the soft or hard segments in the composite polyurethane, shortening the crystallization induction period, and increasing the crystallization rate. Moreover, the epoxy groups on the molecular chain of the composite polyurethane can form bonds with the active groups on polyethylene terephthalate under high-temperature action, increasing the intermolecular crosslinking degree between the composite polyurethane and polyethylene terephthalate. The higher crosslinking density enhances the stability of the polyurethane network, reduces the penetration and swelling of water molecules, thereby improving the wash resistance, and improving the resilience performance and mechanical properties of the mixture. Detailed Embodiments

[0054] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0055] The polyethylene terephthalate used in the present invention is selected from Dongguan Kaiwan Engineering Plastic Raw Material Co., Ltd., with the grade Z6018;

[0056] The hydroxyl silicone oil is selected from Hubei Longsheng Sihai New Materials Co., Ltd., with the product code SH-30CS, a hydroxyl content of 8.5 - 9.0, and a molecular weight of 500 - 600;

[0057] The polyurethane glue is selected from Wenzhou Guoshibang High Polymer Materials Co., Ltd., with the model GSB-58B; the spandex fiber is a commercially available material with a fineness of 15D;

[0058] The epoxy soybean oil is selected from Jinan Runbenxiang Chemical Co., Ltd., with a molecular weight of about 1000 and a density of 0.988 - 0.999 g / cm 3 。

[0059] Example 1

[0060] A preparation method of composite polyurethane fiber for a multi-layer composite clothing fabric with high elastic recovery in this example includes the following steps:

[0061] S1. Prepare a crosslinking chain extender

[0062] Weigh: 160.2 g of pimelic acid, 99.1 g of 1,4-butanediol, 1121.4 mL of toluene and 16 g of 90 wt% sulfuric acid, add them to a reaction kettle protected by nitrogen and stir. The temperature of the reaction kettle is raised to the reflux of the system, and the reaction is kept for 6 h. After the reaction is completed, the temperature of the reaction kettle is lowered to room temperature. Add 500 mL of purified water to the reaction kettle, stir for 20 min, let it stand for liquid separation, wash the organic phase with purified water until neutral, and then transfer it to a rotary evaporator with a water bath temperature of 70 °C. Distill under reduced pressure until no liquid is collected to obtain intermediate I;

[0063] Weigh: 200 g of intermediate I, 80 g of epoxidized soybean oil, 1200 mL of toluene and 2 g of tetrabutyl titanate, add them to the reaction kettle and stir. The temperature of the reaction kettle is raised to 70 °C, and the reaction is kept for 6 h. After the reaction is completed, keep the temperature of the reaction kettle at 70 °C and distill off the solvent under reduced pressure to obtain the crosslinking chain extender.

[0064] S2. Prepare composite polyurethane

[0065] Weigh: 118.1 g of succinic acid, 114.6 g of neopentyl glycol, 0.52 g of stannous chloride and 0.23 g of sodium pyrophosphate, add them to the reaction kettle and stir. The temperature of the reaction kettle is raised to 170 °C, the pressure is reduced to 80 Pa, and the reaction is carried out until the acid value of the system drops to 2 mg NaOH / g. After the reaction is completed, the pressure of the reaction kettle returns to normal pressure, and the temperature is lowered to 70 °C. Add 800 mL of toluene to the reaction kettle and stir until the system dissolves. The temperature of the reaction kettle is lowered to room temperature. Add 300 mL of purified water to the reaction kettle. Wash the organic phase with purified water twice and then transfer it to a rotary evaporator with a water bath temperature of 70 °C. Distill under reduced pressure until no liquid is collected to obtain the prepolymer;

[0066] Mix the crosslinking chain extender and N,N-dimethylformamide evenly according to the weight ratio of 1:3 to obtain a crosslinking chain extender solution;

[0067] Weigh: 380 g of prepolymer, 200 g of hydroxyl silicone oil, 5 g of dibutyltin dilaurate, and 3000 mL of N,N-dimethylformamide are added to a reaction kettle protected by nitrogen and stirred. The temperature of the reaction kettle is raised to 65 °C, 120 g of 4,4′-diphenylmethane diisocyanate is added to the reaction kettle, and the reaction is carried out under insulation for 2 h. 500 g of crosslinking chain extender solution is added to the reaction kettle, and the reaction is carried out under insulation for 4 h. 50 g of octylamine is added to the reaction kettle. After the reaction is completed, the temperature of the reaction kettle is raised to 90 °C, and vacuum distillation is carried out until no liquid is drawn out to obtain composite polyurethane.

[0068] S3. Prepare composite polyurethane fiber

[0069] Ethylene bisstearamide, sodium stearate, antioxidant DPPD and dimethyl phthalate are mixed evenly according to the weight ratio of 2:1:1:5 to obtain an additive;

[0070] Weigh by weight: 70 parts of composite polyurethane, 20 parts of polyethylene terephthalate, and 4 parts of additive are mixed, and then added to a melt spinning machine with a spinning temperature of 280 °C, a spinneret hole diameter of 0.25 mm, and a winding speed of 3000 m / min for melt spinning to obtain composite polyurethane fiber.

[0071] Example 2

[0072] A preparation method of composite polyurethane fiber for a multi-layer composite clothing fabric with high elastic recovery in this example includes the following steps:

[0073] S1. Prepare crosslinking chain extender

[0074] Weigh: 160.2 g of pimelic acid, 99.1 g of 1,4-butanediol, 1121.4 mL of toluene, and 16 g of 94 wt% sulfuric acid are added to a reaction kettle protected by nitrogen and stirred. The temperature of the reaction kettle is raised to the system reflux temperature, and the reaction is carried out under insulation for 7 h. After the reaction is completed, the temperature of the reaction kettle is lowered to room temperature. 500 mL of purified water is added to the reaction kettle, stirred for 25 min, and then left to stand for liquid separation. The organic phase is washed with purified water until neutral and then transferred to a rotary evaporator with a water bath temperature of 75 °C for vacuum distillation until no liquid is drawn out to obtain intermediate I;

[0075] Weigh: 200 g of intermediate I, 80 g of epoxy soybean oil, 1200 mL of toluene, and 2 g of tetrabutyl titanate are added to the reaction kettle and stirred. The temperature of the reaction kettle is raised to 75 °C, and the reaction is carried out under insulation for 7 h. After the reaction is completed, the reaction kettle is kept at 75 °C, and the solvent is removed by vacuum distillation to obtain the crosslinking chain extender.

[0076] S2. Prepare composite polyurethane

[0077] Weigh: 118.1 g of succinic acid, 114.6 g of neopentyl glycol, 0.52 g of stannous chloride and 0.23 g of sodium pyrophosphate, add them to a reaction kettle and stir. Heat the temperature of the reaction kettle to 175 °C and reduce the pressure to 85 Pa. React until the acid value of the system drops to 2.5 mg NaOH / g. After the reaction is completed, restore the pressure in the reaction kettle to normal pressure and reduce the temperature to 75 °C. Add 800 mL of toluene to the reaction kettle and stir until the system dissolves. Then reduce the temperature of the reaction kettle to room temperature. Add 300 mL of purified water to the reaction kettle. Wash the organic phase with purified water twice and then transfer it to a rotary evaporator with a water bath temperature of 75 °C. Distill under reduced pressure until no liquid is collected to obtain a prepolymer;

[0078] Mix the crosslinking chain extender and N,N-dimethylformamide evenly according to a weight ratio of 1:3 to obtain a crosslinking chain extender solution;

[0079] Weigh: 400 g of prepolymer, 220 g of hydroxy silicone oil, 5 g of dibutyltin dilaurate and 3000 mL of N,N-dimethylformamide, add them to a reaction kettle protected by nitrogen and stir. Heat the temperature of the reaction kettle to 70 °C. Add 130 g of 4,4′-diphenylmethane diisocyanate to the reaction kettle and keep the temperature for reaction for 2.5 h. Add 500 g of the crosslinking chain extender solution to the reaction kettle and keep the temperature for reaction for 5 h. Add 50 g of octylamine to the reaction kettle. After the reaction is completed, raise the temperature of the reaction kettle to 95 °C and distill under reduced pressure until no liquid is collected to obtain a composite polyurethane.

[0080] S3. Prepare composite polyurethane fibers

[0081] Mix ethylene bisstearamide, sodium stearate, antioxidant PPD and diethyl phthalate evenly according to a weight ratio of 2:1:1:5 to obtain an additive;

[0082] Weigh by weight parts: 75 parts of composite polyurethane, 23 parts of polyethylene terephthalate, and 5 parts of additive. After mixing, add them to a melt spinning machine with a spinning temperature of 285 °C, a spinneret hole diameter of 0.30 mm, and a winding speed of 3200 m / min for melt spinning to obtain composite polyurethane fibers.

[0083] Example 3

[0084] A preparation method of composite polyurethane fibers for a high-elasticity recovery multi-layer composite clothing fabric in this example includes the following steps:

[0085] S1. Prepare a crosslinking chain extender

[0086] Weigh: 160.2 g of pimelic acid, 99.1 g of 1,4-butanediol, 1121.4 mL of toluene and 16 g of 98 wt% sulfuric acid, add them to a reaction kettle protected by nitrogen and stir. Raise the temperature of the reaction kettle to the reflux temperature of the system, keep the temperature for 8 h. After the reaction is completed, lower the temperature of the reaction kettle to room temperature. Add 500 mL of purified water to the reaction kettle, stir for 30 min, let it stand for liquid separation. Wash the organic phase with purified water until neutral, then transfer it to a rotary evaporator with a water bath temperature of 80 °C, and distill under reduced pressure until no liquid is collected to obtain Intermediate I;

[0087] Weigh: 200 g of Intermediate I, 80 g of epoxidized soybean oil, 1200 mL of toluene and 2 g of tetrabutyl titanate, add them to a reaction kettle and stir. Raise the temperature of the reaction kettle to 80 °C, keep the temperature for 8 h. After the reaction is completed, keep the temperature of the reaction kettle at 80 °C, distill off the solvent under reduced pressure to obtain the crosslinking chain extender.

[0088] S2. Preparation of composite polyurethane

[0089] Weigh: 118.1 g of succinic acid, 114.6 g of neopentyl glycol, 0.52 g of stannous chloride and 0.23 g of sodium pyrophosphate, add them to a reaction kettle and stir. Raise the temperature of the reaction kettle to 180 °C, lower the pressure to 90 Pa, react until the acid value of the system drops to 3 mg NaOH / g. After the reaction is completed, restore the pressure of the reaction kettle to normal pressure, lower the temperature to 80 °C. Add 800 mL of toluene to the reaction kettle, stir until the system is dissolved. Lower the temperature of the reaction kettle to room temperature. Add 300 mL of purified water to the reaction kettle. Wash the organic phase with purified water twice, then transfer it to a rotary evaporator with a water bath temperature of 80 °C, and distill under reduced pressure until no liquid is collected to obtain the prepolymer;

[0090] Mix the crosslinking chain extender and N,N-dimethylformamide evenly according to the weight ratio of 1:3 to obtain the crosslinking chain extender solution;

[0091] Weigh: 420 g of prepolymer, 240 g of hydroxy silicone oil, 5 g of dibutyltin dilaurate and 3000 mL of N,N-dimethylformamide, add them to a reaction kettle protected by nitrogen and stir. Raise the temperature of the reaction kettle to 75 °C. Add 140 g of 4,4′-diphenylmethane diisocyanate to the reaction kettle, keep the temperature for 3 h. Add 500 g of the crosslinking chain extender solution to the reaction kettle, keep the temperature for 6 h. Add 50 g of octylamine to the reaction kettle. After the reaction is completed, raise the temperature of the reaction kettle to 100 °C, and distill under reduced pressure until no liquid is collected to obtain the composite polyurethane.

[0092] S3. Preparation of composite polyurethane fibers

[0093] Mix ethylene bis-stearamide, sodium stearate, antioxidant H and dioctyl phthalate evenly according to the weight ratio of 2:1:1:5 to obtain the additive;

[0094] Weigh by parts by weight: 80 parts of composite polyurethane, 25 parts of polyethylene terephthalate, and 6 parts of additives. After mixing, add them to a melt spinning machine with a spinning temperature of 290 °C, a spinneret hole diameter of 0.35 mm, and a winding speed of 3400 m / min for melt spinning to obtain composite polyurethane fibers.

[0095] Example 4

[0096] A method for preparing a multi-layer composite clothing fabric with high elastic recovery in this example includes the following steps:

[0097] Step 1: Blend the composite polyurethane fibers prepared in Example 1 and spandex fibers in a weight ratio of 10:2 to obtain a blended yarn with a fineness of 40 D.

[0098] Step 2: Feed the blended yarn into a circular loom for weaving. According to the warp and weft knitting method of one up and one down, use the blended yarn as the warp and weft yarns to weave a fabric with a warp density of 198 threads / 10 cm and a weft density of 186 threads / 10 cm. Cut the fabric into uniform sizes to obtain a sub-fabric layer.

[0099] Step 3: Lay the sub-fabric layer flat on a flat tabletop. Apply polyurethane glue on the upper surface layer of the sub-fabric layer at a coating amount of 20 g / m 2 to form an adhesive layer on the surface layer of the sub-fabric layer. Lay another sub-fabric layer flat on the adhesive layer and hot press for 40 s in a hot pressing environment at a temperature of 75 °C and a pressure of 3 MPa to obtain a rough fabric.

[0100] Step 4: Lay the rough fabric flat on a flat tabletop. Apply polyurethane glue on the upper surface layer of the sub-fabric layer at a coating amount of 20 g / m 2 to form an adhesive layer on the surface layer of the rough fabric. Lay another sub-fabric layer flat on the adhesive layer and hot press for 40 s in a hot pressing environment at a temperature of 75 °C and a pressure of 3 MPa to obtain a multi-layer composite clothing fabric composed of 3 sub-fabric layers.

[0101] Example 5

[0102] A method for preparing a multi-layer composite clothing fabric with high elastic recovery in this example includes the following steps:

[0103] Step 1: Blend the composite polyurethane fibers prepared in Example 2 and spandex fibers in a weight ratio of 4:1 to obtain a blended yarn with a fineness of 45 D.

[0104] Step 2: Feed the blended yarn into a large circular loom for weaving. Using the blended yarn as the warp and weft yarns, and following the warp and weft knitting method of one up and one down, weave a fabric with a warp density of 202 threads / 10 cm and a weft density of 190 threads / 10 cm. Cut the fabric into uniformly sized specifications to obtain sub-fabric layers;

[0105] Step 3: Lay the sub-fabric layer flat on a flat tabletop. Apply polyurethane glue to the upper surface of the sub-fabric layer at a coating amount of 23 g / m 2 to form an adhesive layer on the surface of the sub-fabric layer. Lay another sub-fabric layer on the adhesive layer and hot-press for 50 s in a hot-pressing environment at a temperature of 80 °C and a pressure of 3.5 MPa to obtain a rough fabric;

[0106] Step 4: Lay the rough fabric flat on a flat tabletop. Apply polyurethane glue to the upper surface of the sub-fabric layer at a coating amount of 23 g / m 2 to form an adhesive layer on the surface of the rough fabric. Lay another sub-fabric layer on the adhesive layer and hot-press for 50 s in a hot-pressing environment at a temperature of 80 °C and a pressure of 3.5 MPa to obtain a multi-layer composite clothing fabric composed of 3 sub-fabric layers.

[0107] Example 6

[0108] A preparation method of a multi-layer composite clothing fabric with high elastic recovery in this example includes the following steps:

[0109] Step 1: Blend the composite polyurethane fiber and spandex fiber prepared in Example 3 in a weight ratio of 10:3 to obtain a blended yarn with a fineness of 50 D;

[0110] Step 2: Feed the blended yarn into a large circular loom for weaving. Using the blended yarn as the warp and weft yarns, and following the warp and weft knitting method of one up and one down, weave a fabric with a warp density of 206 threads / 10 cm and a weft density of 194 threads / 10 cm. Cut the fabric into uniformly sized specifications to obtain sub-fabric layers;

[0111] Step 3: Lay the sub-fabric layer flat on a flat tabletop. Apply polyurethane glue to the upper surface of the sub-fabric layer at a coating amount of 25 g / m 2 to form an adhesive layer on the surface of the sub-fabric layer. Lay another sub-fabric layer on the adhesive layer and hot-press for 60 s in a hot-pressing environment at a temperature of 85 °C and a pressure of 4 MPa to obtain a rough fabric;

[0112] Step 4: Lay the rough fabric flat on a flat tabletop. Apply polyurethane glue to the upper surface of the sub-fabric layer at a coating amount of 25 g / m 2For the coating amount, apply polyurethane glue on the upper surface layer of the sub-fabric layer to form an adhesive layer on the surface of the rough fabric. Lay another sub-fabric layer flat on the adhesive layer. Under a hot pressing environment with a temperature of 85°C and a pressure of 4 MPa, hot press for 60 s to obtain a multi-layer composite clothing fabric composed of 3 sub-fabric layers.

[0113] Comparative Example 1

[0114] The difference between this comparative example and Example 6 is that during the preparation of the composite polyurethane fiber in Example 3, the intermediate I in step S1 was used to replace the crosslinking chain extender in step S2.

[0115] Comparative Example 2

[0116] The difference between this comparative example and Example 6 is that in step S2 of the preparation of the composite polyurethane fiber in Example 3, 1,5-pentanediol was used to replace neopentyl glycol.

[0117] Comparative Example 3

[0118] The difference between this comparative example and Example 6 is that in step S2 of the preparation of the composite polyurethane fiber in Example 3, polyethylene glycol 1000 was used to replace hydroxy silicone oil.

[0119] Comparative Example 4

[0120] The difference between this comparative example and Example 6 is that in step S3 of the preparation of the composite polyurethane fiber in Example 3, polyethylene terephthalate was not added.

[0121] Performance test:

[0122] Test the elastic properties, puncture resistance and wash resistance of the multi-layer composite clothing fabrics prepared in Examples 4 - 6 and Comparative Examples 1 - 4. Among them, for the elastic properties, refer to the industry standard FZ / T 01034-2008 "Test Method for Tensile Elasticity of Textile Woven Fabrics" to measure the elastic recovery rate of the specimen at a specified elongation of 15% and 30%, and the elastic recovery rate of the specimen after 20 cycles at a specified elongation of 15% and 30%. For the puncture resistance, refer to the standard GB / T 23318-2009 "Determination of Puncture Strength of Textiles" to measure the puncture strength of the specimen. For the wash resistance, after washing the specimen 100 times, measure the elastic properties of the specimen. The specific test results are shown in Table 1:

[0123] Table 1 - Data Sheet of Performance Detection of Specimens

[0124]

[0125] Data analysis:

[0126] Comparing and analyzing the data in Table 1 above, for the multi-layer composite clothing fabric prepared by the present invention, the elastic recovery rate at 15% fixed elongation reaches 98.7% before washing, the elastic recovery rate at 30% fixed elongation reaches 97.9% before washing, the elastic recovery rate at 15% fixed elongation reaches 97.8% after washing, the elastic recovery rate at 30% fixed elongation reaches 96.2% after washing, the elastic recovery rate reaches 95.4% after 20 cycles at 15% fixed elongation, the elastic recovery rate at 30% fixed elongation reaches 91.6%, and the puncture strength reaches 2,657.0 N. All the performance test data are better than those of the comparative example. It shows that after preparing a composite polyurethane with a high crosslinking density by using a polyester and polysiloxane co-block modified with methyl on the long alkane straight chain and a crosslinking chain extender containing an epoxy group as the chain extender, mixing it with polyethylene terephthalate, preparing composite polyurethane fibers, and then through blending and weaving to prepare a sub-fabric layer, and based on the sub-fabric layer, layer-by-layer compounding with polyurethane glue to prepare a multi-layer composite clothing fabric, not only effectively improves the elastic recovery performance of the clothing fabric, but also improves the water-washing resistance and puncture resistance of the clothing fabric.

[0127] The above content is only an example and explanation of the structure of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined by this claim book, they should belong to the protection scope of the present invention.

[0128] In the description of this specification, the description with reference to terms such as "an embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0129] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not elaborate all the details, nor do they limit the present invention to only the specific implementation manners. Obviously, many modifications and changes can be made according to the content of this specification. The present specification selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the art of this technology can understand and utilize the present invention well. The present invention is only limited by the claim book and its full scope and equivalents.

Claims

1. A multi-layer composite clothing fabric with high elastic recovery, characterized in that: It comprises a plurality of sub-fabric layers, wherein the plurality of sub-fabric layers are bonded and fixed by adhesive; The sub-fabric layer is obtained by weaving the blended yarn through a large circular weaving machine; The blended yarn is composed of composite polyurethane fiber and spandex fiber blended in a weight ratio of 10:2-3; The preparation method of the composite polyurethane fiber is as follows: after mixing composite polyurethane, polyethylene terephthalate and additives, adding the mixture into a melt spinning machine, and melt spinning to obtain composite polyurethane fiber; Composite polyurethane is processed by the following steps: A1. Add succinic acid, neopentyl glycol, a catalyst and an antioxidant into a reactor and stir. Raise the temperature of the reactor to 170-180° C., reduce the pressure to 80-90 Pa, and react until the acid value of the system drops to 2-3 mg NaOH / g. Post-treat to obtain a prepolymer. A2, adding prepolymer, hydroxy silicone oil, catalyst and N,N-dimethylformamide into a nitrogen-protected reactor and stirring, raising the temperature of the reactor to 65-75°C, adding 4,4'-diphenylmethane diisocyanate into the reactor, keeping the temperature for reaction for 2-3h, adding crosslinking chain extender solution into the reactor, keeping the temperature for reaction for 4-6h, adding octylamine into the reactor, and post-treating to obtain composite polyurethane; The cross-linking chain extender is processed by the following steps: B1, adding pimelic acid, 1,4-butanediol, toluene and a catalyst into a nitrogen-protected reactor and stirring, raising the temperature of the reactor to reflux the system, keeping the temperature for 6-8 hours, and post-treating to obtain intermediate I; B2. Add intermediate I, epoxidized soybean oil, toluene and catalyst into a reactor and stir. Raise the temperature of the reactor to 70-80° C. and keep the temperature for 6-8 hours. Post-treat to obtain a cross-linking chain extender.

2. The multi-layer composite clothing fabric with high elastic recovery according to claim 1, characterized in that: The weight ratio of the composite polyurethane, polyethylene terephthalate and additives is 70-80:20-25:4-6, the additives are composed of a dispersant, a lubricant, an antioxidant and a plasticizer in a weight ratio of 2:1:1:5, the dispersant is ethylene bisstearamide, the lubricant is sodium stearate, the antioxidant is one or more of antioxidant DPPD, antioxidant PPD, and antioxidant H, the plasticizer is phthalate, the spinning temperature of the melt spinning machine is 280-290°C, the spinneret hole diameter is 0.25-0.35mm, and the winding speed is 3000-3400m / min.

3. The multi-layer composite clothing fabric with high elastic recovery according to claim 1, characterized in that: In step A1, the catalyst is stannous chloride, the antioxidant is sodium pyrophosphate, and the post-treatment comprises: after the reaction is completed, the pressure of the reactor is restored to normal pressure, the temperature is reduced to 70-80°C, toluene is added to the reactor, stirred until the system is dissolved, the temperature of the reactor is reduced to room temperature, purified water is added to the reactor, the organic phase is washed twice with purified water and then transferred to a rotary evaporator with a water bath temperature of 70-80°C, and distilled under reduced pressure until no liquid is extracted to obtain a prepolymer; in step A2, the prepolymer, hydroxy silicone oil, catalyst, N,N -dimethylformamide, 4,4´-diphenylmethane diisocyanate, crosslinking extender solution, octylamine are used in a ratio of 38-42g:20-24g:0.5g:300mL:12-14g:50g:5g, the catalyst is dibutyltin dilaurate, the crosslinking extender solution is composed of a crosslinking extender and N,N-dimethylformamide in a weight ratio of 1:3, and the post-treatment comprises: after the reaction is completed, the temperature of the reactor is increased to 90-100°C, and the reduced pressure distillation is performed until no liquid is produced to obtain a composite polyurethane.

4. The multi-layer composite clothing fabric with high elastic recovery according to claim 1, characterized in that: In step B1, the amount ratio of the pimelic acid and 1,4-butanediol is 1 mol:1.1 mol, the amount ratio of the pimelic acid, toluene and the catalyst is 1 g:7 mL:0.1 g, the catalyst is 90-98 wt% sulfuric acid, and the post-treatment comprises: after the reaction is completed, the temperature of the reactor is lowered to room temperature, purified water is added to the reactor, stirred for 20-30 min, allowed to stand for liquid separation, the organic phase is washed with purified water until neutral, and then transferred to a rotary evaporator with a water bath temperature of 70-80° C., and distilled under reduced pressure until no liquid is produced to obtain intermediate I; in step B2, the amount ratio of the intermediate I, epoxidized soybean oil, toluene and the catalyst is 5 g:2 g:30 mL:0.05 g, the catalyst is tetrabutyl titanate, and the post-treatment comprises: after the reaction is completed, the reactor is kept at 70-80° C., and the solvent is distilled under reduced pressure to obtain a cross-linking chain extender.

5. The multi-layer composite clothing fabric with high elastic recovery according to claim 1, characterized in that: The adhesive is polyurethane glue; the weaving method of the sub-fabric layer is one-up-one-down warp and weft weaving, with blended yarns as warp and weft, the warp density is 198-206 yarns / 10cm, and the weft density is 186-194 yarns / 10cm.

6. The method for preparing a multi-layer composite clothing fabric with high elastic recovery according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, blending the composite polyurethane fiber and the spandex fiber to obtain a blended yarn with a fineness of 40-50D; S2, feeding the blended yarn into a large circular spinning machine for spinning, and then cutting it into uniform size specifications to obtain a sub-fabric layer; S3, laying the sub-fabric layer flat on a flat table, applying adhesive on the upper surface of the sub-fabric layer to form an adhesive layer on the surface of the sub-fabric layer, laying another sub-fabric layer flat on the adhesive layer, and hot pressing for 40-60 seconds; S4, repeating the operation of step S3 to obtain a multi-layer composite clothing fabric composed of a plurality of sub-fabric layers.

7. The method for preparing a multi-layer composite clothing fabric with high elastic recovery according to claim 6, characterized in that: In step S3, the coating amount of the adhesive is 20-25 g / m 2 The temperature of hot pressing is 75-85℃ and the pressure is 3-4MPa.

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