Polyurethane resin as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of polyurethane resin, and particularly discloses polyurethane resin which comprises a component A and a component B. In the polyurethane resin, the mass ratio of the component A to the component B is 100: (5-15). According to the polyurethane resin and the preparation method and application thereof, the polyurethane resin is applied to shoe leather, the prepared shoe leather has better wear resistance, higher bending resistance and better tensile strength, in the production process of the polyurethane resin, less harmful substances are discharged, and the increasingly-improved environmental protection requirement of the shoe leather industry can be met.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane resins, and in particular relates to a polyurethane resin and a preparation method and application thereof. Background Art

[0002] In the past shoemaking industry, traditional shoe leather materials (such as synthetic leather materials) often have some limitations. For example, some materials have insufficient wear resistance, which causes shoes to be easily worn and damaged after a period of use; poor breathability makes the feet prone to sweating and odor, affecting the comfort of wearing; poor aging resistance makes the service life of shoes short.

[0003] With the continuous advancement of science and technology and the improvement of people's quality of life, higher requirements are also placed on the performance of shoe leather materials. Traditional synthetic leather materials also have certain problems in environmental protection. A large amount of pollution and waste may be generated during the production process, which does not meet the pursuit of sustainable development in modern society. Summary of the invention

[0004] The purpose of the present invention is to overcome the above problems existing in the prior art, to provide a polyurethane resin and a preparation method and application thereof, and to apply the polyurethane resin to shoe leather. The prepared shoe leather has better wear resistance, stronger bending resistance, and better tensile strength. In addition, during its production process, less harmful substances are emitted, which helps the shoe leather industry meet the increasingly stringent environmental protection requirements.

[0005] In order to achieve the above technical objectives and the above technical effects, the present invention is implemented through the following technical solutions:

[0006] In a first aspect, the present invention provides a polyurethane resin, comprising component A and component B, wherein the mass ratio of component A to component B in the polyurethane resin is 100:(5-15);

[0007] Component A includes the following raw materials in parts by weight: 5-40 parts of polytetramethylene glycol, 15-40 parts of polypropylene glycol, 15-50 parts of polyester glycol, 5-20 parts of diisocyanate monomer, 10-40 parts of specific chain extender, and 2-5 parts of fluorine-containing functional monomer;

[0008] Calculated by weight, component B includes the following raw materials in parts by weight: 0.3-0.5 parts of defoaming agent, 2-4 parts of wetting agent, 0.5-1 parts of hand feeling agent, 0.4-0.6 parts of cross-linking agent, 1-5 parts of thickener, and 0.6-2 parts of curing agent.

[0009] Further, the molecular weight of the polytetramethylene ether glycol is 500-4000;

[0010] The molecular weight of the polypropylene ether glycol is 1000-4000;

[0011] The molecular weight of the polyester diol is 500-4000.

[0012] Furthermore, the diisocyanate monomer is a prepolymer synthesized at 60-80° C. and having an isocyanate functional group at the terminal.

[0013] Furthermore, the specific chain extender is any one or more of ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol mixed in any proportion.

[0014] Furthermore, the crosslinking agent is any one or more of a blocked isocyanate crosslinking agent, a crosslinking agent TAIC8, and TTMAP mixed in any proportion;

[0015] The wetting agent is any one or more of sulfate, sulfonate and quaternary ammonium salt mixed in any proportion;

[0016] The curing agent is any one or more of aliphatic amine, alicyclic amine, aromatic amine, phthalic anhydride, and maleic anhydride mixed in any proportion;

[0017] The defoaming agent is any one or more of DREWPLUS T-4201, Dehydran1208, BYK-016, BYK-1730, BYK-093 mixed in any proportion;

[0018] The thickener is any one or more of attapulgite, ACRYSOL TT-935, B-30K, and B-100K mixed in any proportion.

[0019] In a second aspect, the present invention provides a method for preparing a polyurethane resin, the preparation method comprising the following steps:

[0020] S1: Weigh the raw materials of component A and component B respectively according to their weight proportions;

[0021] S2: respectively mixing the raw materials of component A and the raw materials of component B to prepare component A and component B;

[0022] S3: After weighing component A and component B according to the raw materials of the polyurethane resin and the weight ratio of the raw materials, mix them evenly at room temperature, and mix and react for 4-6 hours to prepare a mixed solution;

[0023] S4: The mixed liquid is allowed to stand until no bubbles are generated in the mixed liquid, thereby obtaining the polyurethane resin.

[0024] In a third aspect, the present invention provides an application of a polyurethane resin in shoe leather.

[0025] Furthermore, the preparation method of the shoe leather comprises the following steps:

[0026] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0027] Step (2): immersing the pretreated non-woven fabric in a polyurethane resin to prepare a prepreg;

[0028] Step (3): drying the prepreg to obtain a composite material layer;

[0029] Step (4): The composite material layer is cut, embossed and dyed to prepare shoe leather.

[0030] Furthermore, an antibacterial fiber layer is provided on the surface of the main body of the non-woven fabric, and the antibacterial fiber layer is woven by warp and weft;

[0031] The warp comprises the following raw materials in parts by weight: 10-20 parts of camphor wood fiber, 10-20 parts of bamboo fiber, and 10-20 parts of hemp fiber;

[0032] The weft includes the following raw materials in parts by weight: 10-20 parts of camphor wood fiber, 10-20 parts of bamboo fiber, 10-20 parts of hemp fiber, and 10-20 parts of composite fiber.

[0033] Furthermore, the preparation method of the modified fiber is as follows:

[0034] Step a, dissolving chitosan in 1-2% glacial acetic acid solution to prepare a chitosan solution;

[0035] Step b, dissolving calcium chloride in water to prepare a 2-5% calcium chloride solution;

[0036] Step c, mixing the chitosan solution and the calcium chloride solution in a mass ratio of 1:(1-3) to prepare a mixed solution;

[0037] Step d, after the camphor wood fiber, bamboo fiber and hemp fiber are mixed evenly, mixed fibers are prepared, the mixed fibers are put into a dissolving kettle, N-methylpyrrolidone is used as a solvent, the mixture is stirred evenly and then allowed to stand to prepare a spinning solution, the spinning solution and the mixed solution are mixed in a mass ratio of (1-5): 1, and the wet spinning process is used for spinning to prepare a composite fiber.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1. The present invention provides a polyurethane resin, comprising component A and component B. By controlling the ratio of raw material component A and component B, and controlling the raw material composition of component A and component B, a polyurethane resin with high elongation and low crystallinity is prepared.

[0040] 2. The polyurethane resin with high elongation and low crystallinity provided by the present invention can effectively improve the tear strength of the non-woven fabric after impregnation, thereby overcoming the limitations of traditional polyurethane materials in this regard; at the same time, the polyurethane resin provided by the present invention is applied to the production of new shoe leather, and the prepared new shoe leather not only retains the appearance and feel advantages of the polyurethane material, but also significantly improves its physical properties.

[0041] 3. The method for preparing a polyurethane resin provided by the present invention has mild reaction conditions; the polyurethane resin is applied to the production of new shoe leather, and less harmful substances are discharged during the production process, which is more energy-saving and environmentally friendly.

[0042] 4. The polyurethane resin provided by the present invention is applied to shoe leather materials. The prepared shoe leather has better wear resistance, that is, in daily use, the shoe leather is more resistant to wear, thereby extending the service life of the shoes; the prepared shoe leather also has stronger resistance to bending, that is, it can better adapt to the movement and bending of the foot and is not prone to cracks or damage; the prepared shoe leather also has excellent tensile strength, that is, the shoe leather has higher strength and is not easily deformed by pulling.

[0043] 5. In the preparation method of a polyurethane resin and a preparation method of shoe leather provided by the present invention, the reaction conditions are carried out under relatively mild conditions, and there are fewer harmful substances in the reaction process. While meeting the environmental protection requirements of energy conservation and emission reduction, the release of substances harmful to the environment and human health can be reduced.

[0044] 6. In the present invention, the production process is simple and easy to operate, which makes it easier to produce shoe leather, reduce the scrap rate, improve production efficiency, and save production costs.

[0045] 7. In the present invention, an antibacterial fiber layer is woven on the surface of the non-woven fabric. The antibacterial fiber layer is made of natural plant fibers and has good antibacterial properties. DETAILED DESCRIPTION

[0046] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0047] In a first aspect, the present invention provides a polyurethane resin, comprising component A and component B, wherein the mass ratio of component A to component B in the polyurethane resin is 100:(5-15);

[0048] Component A includes the following raw materials in parts by weight: 5-40 parts of polytetramethylene glycol, 15-40 parts of polypropylene glycol, 15-50 parts of polyester glycol, 5-20 parts of diisocyanate monomer, 10-40 parts of specific chain extender, and 2-5 parts of fluorine-containing functional monomer;

[0049] In component A, the molecular weight of polytetramethylene ether diol is 500-4000, the molecular weight of polypropylene ether diol is 1000-4000, and the molecular weight of polyester diol is 500-4000;

[0050] The diisocyanate monomer is a prepolymer with an isocyanate functional group at the terminal end synthesized at 60-80°C;

[0051] The specific chain extender is any one or more of ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol mixed in any proportion;

[0052] Component B includes the following raw materials in parts by weight: 0.3-0.5 parts of defoamer, 2-4 parts of wetting agent, 0.5-1 parts of hand feeling agent, 0.4-0.6 parts of crosslinking agent, 1-5 parts of thickener, and 0.6-2 parts of curing agent;

[0053] In component B, the crosslinking agent is any one or more of a blocked isocyanate crosslinking agent, a crosslinking agent TAIC8, and a TTMAP (aziridine crosslinking agent) mixed in any proportion;

[0054] In addition, the defoaming agent is specifically any one or more of DREWPLUS T-4201, Dehydran1208, BYK-016, BYK-1730, BYK-093 mixed in any proportion;

[0055] The thickener is specifically any one or more of attapulgite, ACRYSOLTT-935, B-30K, and B-100K mixed in any proportion;

[0056] The wetting agent is any one or more of sulfate, sulfonate, and quaternary ammonium salt mixed in any proportion;

[0057] The curing agent is any one or more of aliphatic amine, alicyclic amine, aromatic amine, phthalic anhydride and maleic anhydride mixed in any proportion.

[0058] In a second aspect, the present invention provides a method for preparing a polyurethane resin, which is used to prepare the polyurethane resin provided by an embodiment of the first aspect of the present invention. Specifically, the method for preparing the polyurethane resin comprises the following steps:

[0059] S1: Weigh the raw materials of component A and component B respectively according to their weight proportions;

[0060] S2: respectively mixing the raw materials of component A and the raw materials of component B to prepare component A and component B;

[0061] S3: After weighing component A and component B according to the raw materials of the polyurethane resin and the weight ratio of the raw materials, mix them evenly at room temperature, and mix and react for 4-6 hours to prepare a mixed solution;

[0062] S4: The mixed liquid is allowed to stand until no bubbles are generated in the mixed liquid, thereby obtaining the polyurethane resin.

[0063] In a third aspect, the present invention provides an application of a polyurethane resin, specifically, applying the polyurethane resin provided by the embodiment of the first aspect of the present invention to shoe leather;

[0064] In addition, the preparation method of the shoe leather is as follows:

[0065] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0066] Step (2): immersing the pretreated non-woven fabric in a polyurethane resin to prepare a prepreg;

[0067] Step (3): drying the prepreg to obtain a composite material layer;

[0068] Step (4): The composite material layer is cut, embossed and dyed to prepare shoe leather.

[0069] The following are specific preparation examples, embodiments and comparative examples. Unless otherwise specified, all raw materials can be obtained from commercial sources.

[0070] In the following preparation examples, embodiments and comparative examples, the molecular weight of polytetrahydrofuran ether diol is about 3000; the molecular weight of polypropylene ether diol is about 2000; the molecular weight of polyester diol is about 2000;

[0071] The diisocyanate monomers are all prepolymers with isocyanate functional groups at the terminal end synthesized at about 70°C;

[0072] The defoamers are all DREWPLUS T-4201; the wetting agents are all sulfates; the cross-linking agents are all blocked isocyanate cross-linking agents; the thickeners are all attapulgite; and the curing agents are all phthalic anhydride.

[0073] Preparation Example 1

[0074] This preparation example provides a method for preparing a polyurethane resin, which comprises the following steps:

[0075] S1: Weigh the raw materials of component A and component B respectively according to their weight proportions;

[0076] S2: respectively mixing the raw materials of component A and the raw materials of component B to prepare component A and component B;

[0077] S3: After weighing component A and component B according to the raw materials of the polyurethane resin and the weight ratio of the raw materials, the components are mixed evenly at room temperature, and the mixture is reacted for 4 hours to prepare a mixed solution;

[0078] S4: The mixed liquid is allowed to stand until no bubbles are generated in the mixed liquid, thereby obtaining the polyurethane resin.

[0079] Preparation Example 2

[0080] This preparation example provides a method for preparing a polyurethane resin, which comprises the following steps:

[0081] S1: Weigh the raw materials of component A and component B respectively according to their weight proportions;

[0082] S2: respectively mixing the raw materials of component A and the raw materials of component B to prepare component A and component B;

[0083] S3: After weighing component A and component B according to the raw materials of the polyurethane resin and the weight ratio of the raw materials, the components are mixed evenly at room temperature, and the mixture is reacted for 5 hours to prepare a mixed solution;

[0084] S4: The mixed liquid is allowed to stand until no bubbles are generated in the mixed liquid, thereby obtaining the polyurethane resin.

[0085] Preparation Example 3

[0086] This preparation example provides a method for preparing a polyurethane resin, which comprises the following steps:

[0087] S1: Weigh the raw materials of component A and component B respectively according to their weight proportions;

[0088] S2: respectively mixing the raw materials of component A and the raw materials of component B to prepare component A and component B;

[0089] S3: After weighing component A and component B according to the raw materials of the polyurethane resin and the weight ratio of the raw materials, mixing them evenly at room temperature, and mixing and reacting for 6 hours to prepare a mixed solution;

[0090] S4: The mixed liquid is allowed to stand until no bubbles are generated in the mixed liquid, thereby obtaining the polyurethane resin.

[0091] Preparation Example 4

[0092] This preparation example provides a polyurethane resin, including component A and component B, wherein the mass ratio of component A to component B in the polyurethane resin is 100:10;

[0093] Component A includes the following raw materials in parts by weight: 30 parts of polytetramethylene glycol, 30 parts of polypropylene glycol, 35 parts of polyester glycol, 10 parts of diisocyanate monomer, 25 parts of specific chain extender, and 3 parts of fluorine-containing functional monomer;

[0094] The specific chain extender is prepared by mixing 1,4-butanediol and 1,6-hexanediol in a mass ratio of 3.5:6.5;

[0095] In terms of weight parts, component B includes the following raw materials: 0.4 parts of defoaming agent, 3 parts of wetting agent, 0.8 parts of hand feeling agent, 0.5 parts of cross-linking agent, 3 parts of thickener, and 1.3 parts of curing agent.

[0096] This preparation example also provides a preparation method of a polyurethane resin, and the preparation method is carried out with reference to the preparation method provided in Preparation Example 1.

[0097] Preparation Example 5

[0098] This preparation example provides a polyurethane resin, including component A and component B, wherein the mass ratio of component A to component B in the polyurethane resin is 100:5;

[0099] Component A includes the following raw materials in parts by weight: 40 parts of polytetramethylene glycol, 15 parts of polypropylene glycol, 15 parts of polyester glycol, 5 parts of diisocyanate monomer, 10 parts of specific chain extender, and 2 parts of fluorine-containing functional monomer;

[0100] The specific chain extender is prepared by mixing 1,4-butanediol and 1,6-hexanediol in a mass ratio of 3:7;

[0101] In terms of weight, component B includes the following raw materials: 0.5 parts of defoaming agent, 4 parts of wetting agent, 0.5 parts of hand feeling agent, 0.6 parts of cross-linking agent, 1 part of thickener, and 2 parts of curing agent.

[0102] This preparation example also provides a preparation method of a polyurethane resin, and the preparation method is carried out with reference to the preparation method provided in Preparation Example 2.

[0103] Preparation Example 6

[0104] This preparation example provides a polyurethane resin, including component A and component B, wherein the mass ratio of component A to component B in the polyurethane resin is 100:15;

[0105] Component A includes the following raw materials in parts by weight: 5 parts of polytetramethylene glycol, 40 parts of polypropylene glycol, 50 parts of polyester glycol, 20 parts of diisocyanate monomer, 40 parts of specific chain extender, and 5 parts of fluorine-containing functional monomer;

[0106] The specific chain extender is prepared by mixing 1,4-butanediol and 1,6-hexanediol in a mass ratio of 4:6;

[0107] In terms of weight parts, component B includes the following raw materials: 0.3 parts of defoaming agent, 2 parts of wetting agent, 1 part of hand feeling agent, 0.4 parts of cross-linking agent, 5 parts of thickener, and 0.6 parts of curing agent.

[0108] This preparation example also provides a preparation method of a polyurethane resin, and the preparation method is carried out with reference to the preparation method provided in Preparation Example 3.

[0109] Preparation Example 7

[0110] This preparation example provides a polyurethane resin, including component A and component B. In the polyurethane resin, the mass ratio of component A to component B is 100:10; the difference from Preparation Example 4 is that in this preparation example, 30 parts of polypropylene ether diol are removed from the raw material composition of component A, and the remaining raw material compositions are the same as those in Preparation Example 4.

[0111] This preparation example also provides a preparation method of a polyurethane resin, and the preparation method is carried out with reference to the preparation method provided in Preparation Example 1.

[0112] Preparation Example 8

[0113] This preparation example provides a polyurethane resin, including component A and component B. In the polyurethane resin, the mass ratio of component A to component B is 100:10; the difference from Preparation Example 4 is that in this preparation example, 30 parts of polypropylene ether diol are removed from the raw material composition of component B, and the remaining raw material compositions are the same as those in Preparation Example 4.

[0114] This preparation example also provides a preparation method of a polyurethane resin, and the preparation method is carried out with reference to the preparation method provided in Preparation Example 1.

[0115] Preparation Example 9

[0116] This preparation example provides a polyurethane resin, including component A and component B. In the polyurethane resin, the mass ratio of component A to component B is 100:10; the difference from Preparation Example 4 is that in this preparation example, the curing agent is removed from the raw material composition of component B, and the remaining raw material compositions are the same as those in Preparation Example 4.

[0117] This preparation example also provides a preparation method of a polyurethane resin, and the preparation method is carried out with reference to the preparation method provided in Preparation Example 1.

[0118] Example 1

[0119] This embodiment provides a shoe leather, and the preparation method of the shoe leather is as follows:

[0120] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0121] Step (2): immersing the pretreated non-woven fabric into a polyurethane resin (prepared in Preparation Example 4) to prepare a prepreg;

[0122] Step (3): drying the prepreg to obtain a composite material layer;

[0123] Step (4): the composite material layer is cut, embossed and dyed to prepare shoe leather;

[0124] The surface of the main body of the non-woven fabric is provided with an antibacterial fiber layer, which is woven from warp and weft; specifically, the warp includes the following raw materials by weight: 10 parts of camphor wood fiber, 20 parts of bamboo fiber, and 20 parts of hemp fiber;

[0125] The weft yarn includes the following raw materials by weight: 10 parts of camphor wood fiber, 20 parts of bamboo fiber, 20 parts of hemp fiber, and 20 parts of composite fiber;

[0126] The preparation method of the modified fiber is as follows:

[0127] Step a, dissolving chitosan in 1% glacial acetic acid solution to prepare a chitosan solution;

[0128] Step b, dissolving calcium chloride in water to prepare a 2% calcium chloride solution;

[0129] Step c, mixing the chitosan solution and the calcium chloride solution in a mass ratio of 1:3 to prepare a mixed solution;

[0130] Step d, after the camphor wood fiber, bamboo fiber and hemp fiber are mixed evenly, mixed fiber is prepared, the mixed fiber is put into a dissolving kettle, N-methylpyrrolidone is used as a solvent, the spinning solution is prepared after being stirred evenly, the spinning solution and the mixed solution are mixed in a mass ratio of 1:1, and the spinning is carried out by a wet spinning process to prepare a composite fiber.

[0131] Example 2

[0132] This embodiment provides a shoe leather, and the preparation method of the shoe leather is as follows:

[0133] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0134] Step (2): immersing the pretreated non-woven fabric into a polyurethane resin (prepared in Preparation Example 5) to prepare a prepreg;

[0135] Step (3): drying the prepreg to obtain a composite material layer;

[0136] Step (4): the composite material layer is cut, embossed and dyed to prepare shoe leather;

[0137] The surface of the main body of the non-woven fabric is provided with an antibacterial fiber layer, which is woven from warp and weft; specifically, the warp includes the following raw materials by weight: 15 parts of camphor wood fiber, 15 parts of bamboo fiber, and 15 parts of hemp fiber;

[0138] The weft yarn includes the following raw materials in parts by weight: 15 parts of camphor wood fiber, 15 parts of bamboo fiber, 15 parts of hemp fiber, and 15 parts of composite fiber;

[0139] The preparation method of the modified fiber is as follows:

[0140] Step a, dissolving chitosan in 1.5% glacial acetic acid solution to prepare a chitosan solution;

[0141] Step b, dissolving calcium chloride in water to prepare a 3.5% calcium chloride solution;

[0142] Step c, mixing the chitosan solution and the calcium chloride solution in a mass ratio of 1:2 to prepare a mixed solution;

[0143] Step d, after the camphor wood fiber, bamboo fiber and hemp fiber are mixed evenly, mixed fiber is prepared, the mixed fiber is put into a dissolving kettle, N-methylpyrrolidone is used as a solvent, the spinning solution is prepared after being stirred evenly, the spinning solution and the mixed solution are mixed in a mass ratio of 3:1, and the wet spinning process is used for spinning to prepare a composite fiber.

[0144] Example 3

[0145] This embodiment provides a shoe leather, and the preparation method of the shoe leather is as follows:

[0146] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0147] Step (2): immersing the pretreated non-woven fabric into a polyurethane resin (prepared in Preparation Example 6) to prepare a prepreg;

[0148] Step (3): drying the prepreg to obtain a composite material layer;

[0149] Step (4): the composite material layer is cut, embossed and dyed to prepare shoe leather;

[0150] The surface of the main body of the non-woven fabric is provided with an antibacterial fiber layer, which is woven from warp and weft; specifically, the warp includes the following raw materials by weight: 20 parts of camphor wood fiber, 10 parts of bamboo fiber, and 10 parts of hemp fiber;

[0151] The weft yarn includes the following raw materials in terms of weight: 20 parts of camphor wood fiber, 10 parts of bamboo fiber, 10 parts of hemp fiber, and 10 parts of composite fiber;

[0152] The preparation method of the modified fiber is as follows:

[0153] Step a, dissolving chitosan in 2% glacial acetic acid solution to prepare a chitosan solution;

[0154] Step b, dissolving calcium chloride in water to prepare a 5% calcium chloride solution;

[0155] Step c, mixing the chitosan solution and the calcium chloride solution in a mass ratio of 1:1 to prepare a mixed solution;

[0156] Step d, after the camphor wood fiber, bamboo fiber and hemp fiber are mixed evenly, mixed fiber is prepared, the mixed fiber is put into a dissolving kettle, N-methylpyrrolidone is used as a solvent, the spinning solution is prepared after being stirred evenly, the spinning solution and the mixed solution are mixed in a mass ratio of 5:1, and the spinning is carried out by a wet spinning process to prepare a composite fiber.

[0157] Comparative Example 1

[0158] This comparative example provides a shoe leather, and the preparation method of the shoe leather is as follows:

[0159] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0160] Step (2): immersing the pretreated non-woven fabric into a polyurethane resin (prepared in Preparation Example 7) to prepare a prepreg;

[0161] Step (3): drying the prepreg to obtain a composite material layer;

[0162] Step (4): the composite material layer is cut, embossed and dyed to prepare shoe leather;

[0163] The surface of the main body of the non-woven fabric is provided with an antibacterial fiber layer, which is woven from warp and weft; specifically, the warp includes the following raw materials by weight: 10 parts of camphor wood fiber, 20 parts of bamboo fiber, and 20 parts of hemp fiber;

[0164] The weft yarn includes the following raw materials by weight: 10 parts of camphor wood fiber, 20 parts of bamboo fiber, 20 parts of hemp fiber, and 20 parts of composite fiber;

[0165] The preparation method of the modified fiber is carried out by referring to the preparation method of the modified fiber provided in Example 1.

[0166] Comparative Example 2

[0167] This comparative example provides a shoe leather, and the preparation method of the shoe leather is as follows:

[0168] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0169] Step (2): immersing the pretreated non-woven fabric into a polyurethane resin (prepared in Preparation Example 8) to prepare a prepreg;

[0170] Step (3): drying the prepreg to obtain a composite material layer;

[0171] Step (4): the composite material layer is cut, embossed and dyed to prepare shoe leather;

[0172] The surface of the main body of the non-woven fabric is provided with an antibacterial fiber layer, which is woven from warp and weft; specifically, the warp includes the following raw materials by weight: 10 parts of camphor wood fiber, 20 parts of bamboo fiber, and 20 parts of hemp fiber;

[0173] The weft yarn includes the following raw materials by weight: 10 parts of camphor wood fiber, 20 parts of bamboo fiber, 20 parts of hemp fiber, and 20 parts of composite fiber;

[0174] The preparation method of the modified fiber is carried out by referring to the preparation method of the modified fiber provided in Example 1.

[0175] Comparative Example 3

[0176] This comparative example provides a shoe leather, and the preparation method of the shoe leather is as follows:

[0177] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0178] Step (2): immersing the pretreated non-woven fabric in a polyurethane resin (prepared in Preparation Example 9) to prepare a prepreg;

[0179] Step (3): drying the prepreg to obtain a composite material layer;

[0180] Step (4): the composite material layer is cut, embossed and dyed to prepare shoe leather;

[0181] The surface of the main body of the non-woven fabric is provided with an antibacterial fiber layer, which is woven from warp and weft; specifically, the warp includes the following raw materials by weight: 10 parts of camphor wood fiber, 20 parts of bamboo fiber, and 20 parts of hemp fiber;

[0182] The weft yarn includes the following raw materials by weight: 10 parts of camphor wood fiber, 20 parts of bamboo fiber, 20 parts of hemp fiber, and 20 parts of composite fiber;

[0183] The preparation method of the modified fiber is carried out by referring to the preparation method of the modified fiber provided in Example 1.

[0184] Comparative Example 4

[0185] This comparative example provides a shoe leather, and the preparation method of the shoe leather is as follows:

[0186] Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric;

[0187] Step (2): immersing the pretreated non-woven fabric into a polyurethane resin (prepared in Preparation Example 4) to prepare a prepreg;

[0188] Step (3): drying the prepreg to obtain a composite material layer;

[0189] Step (4): the composite material layer is cut, embossed and dyed to prepare shoe leather;

[0190] Compared with Example 1, in this comparative example, the surface of the main body of the non-woven fabric is not provided with an antibacterial fiber layer.

[0191] Experimental example

[0192] The performance of the prepared shoe leather is tested, and the relevant test items are as follows:

[0193] 1. Test the performance of explosion-proof needles. If the outer edge of the pinhole does not crack, it is qualified. If the outer edge of the pinhole cracks, it is unqualified.

[0194] 2. Adhesion performance test: The synthetic leather and the PVC sole are injection molded at one time, and the peeling strength between the synthetic leather and the PVC sole is tested using a tensile testing machine. The peeling strength is measured again after being placed at room temperature for 1 month;

[0195] 3. Folding resistance: The test method adopts ISO 5402-1;

[0196] 4. Wear resistance: The test method adopts SATRATM31A;

[0197] The test results are shown in Table 1;

[0198] Table 1

[0199]

[0200] It can be seen from the data in Table 1 that the performance test results of the shoe leathers prepared in Examples 1-3 are better than those of Comparative Examples 1-3, and the performance test results of the shoe leather prepared in Example 1 are better than those of the shoe leather prepared in Comparative Example 4 in terms of peel strength and wear rate tests, which further indicates that the formula of the polyurethane resin provided by the present invention, combined with the application method thereof in shoe leather provided by the present invention, has better comprehensive performance;

[0201] In addition, the antibacterial performance of the shoe leather prepared by Examples 1-3 and Comparative Examples 1-3 was tested (testing the antibacterial rate of Escherichia coli and Staphylococcus aureus), and the antibacterial rates were all above 99.5%; while in Comparative Example 4, an antibacterial fiber layer was provided, and its antibacterial rate was less than 50%, indicating that the non-woven fabric provided by the present invention has an antibacterial fiber layer on its surface, which can improve the antibacterial performance of the base fabric (non-woven fabric), thereby further extending the service life of the prepared shoe leather and improving the use effect of the shoe leather.

[0202] Therefore, the present invention provides a polyurethane resin, including component A and component B, and the polyurethane resin with high elongation and low crystallinity is prepared by controlling the ratio of raw material component A and component B, and controlling the raw material composition of component A and component B; in addition, in the present invention, during the preparation of shoe leather, an antibacterial fiber layer is woven on the surface of the non-woven fabric, and the antibacterial fiber layer is made of natural plant fiber and has good antibacterial properties.

[0203] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0204] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A polyurethane resin, characterized in that The polyurethane resin comprises component A and component B, wherein the mass ratio of component A to component B is 100:(5-15); Component A includes the following raw materials in parts by weight: 5-40 parts of polytetramethylene glycol, 15-40 parts of polypropylene glycol, 15-50 parts of polyester glycol, 5-20 parts of diisocyanate monomer, 10-40 parts of specific chain extender, and 2-5 parts of fluorine-containing functional monomer; Calculated by weight, component B includes the following raw materials in parts by weight: 0.3-0.5 parts of defoaming agent, 2-4 parts of wetting agent, 0.5-1 parts of hand feeling agent, 0.4-0.6 parts of cross-linking agent, 1-5 parts of thickener, and 0.6-2 parts of curing agent.

2. A polyurethane resin according to claim 1, characterized in that: The molecular weight of the polytetrahydrofuran ether glycol is 500-4000; The molecular weight of the polypropylene ether glycol is 1000-4000; The molecular weight of the polyester diol is 500-4000.

3. A polyurethane resin according to claim 1, characterized in that: The diisocyanate monomer is a prepolymer synthesized at 60-80° C. and having an isocyanate functional group at the terminal.

4. The polyurethane resin according to claim 1, characterized in that: The specific chain extender is any one or more of ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol mixed in any proportion.

5. The polyurethane resin according to claim 1, characterized in that: The cross-linking agent is any one or more of a blocked isocyanate cross-linking agent, a cross-linking agent TAIC8, and TTMAP mixed in any proportion; The wetting agent is any one or more of sulfate, sulfonate and quaternary ammonium salt mixed in any proportion; The curing agent is any one or more of aliphatic amine, alicyclic amine, aromatic amine, phthalic anhydride and maleic anhydride mixed in any proportion.

6. A method for preparing the polyurethane resin according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: S1: Weigh the raw materials of component A and component B respectively according to their weight proportions; S2: respectively mixing the raw materials of component A and the raw materials of component B to prepare component A and component B; S3: After weighing component A and component B according to the raw materials of the polyurethane resin and the weight ratio of the raw materials, mix them evenly at room temperature, and mix and react for 4-6 hours to prepare a mixed solution; S4: The mixed liquid is allowed to stand until no bubbles are generated in the mixed liquid, thereby obtaining the polyurethane resin.

7. Use of the polyurethane resin according to any one of claims 1 to 6 in shoe leather.

8. The use of a polyurethane resin in shoe leather according to claim 7, characterized in that: The preparation method of the shoe leather comprises the following steps: Step (1): selecting a non-woven fabric as a base fabric, and washing and drying the non-woven fabric to obtain a pre-treated non-woven fabric; Step (2): immersing the pretreated non-woven fabric in a polyurethane resin to prepare a prepreg; Step (3): drying the prepreg to obtain a composite material layer; Step (4): The composite material layer is cut, embossed and dyed to prepare shoe leather.

9. The use of a polyurethane resin in shoe leather according to claim 8, characterized in that: The surface of the main body of the non-woven fabric is provided with an antibacterial fiber layer, and the antibacterial fiber layer is woven by warp and weft; The warp comprises the following raw materials in parts by weight: 10-20 parts of camphor wood fiber, 10-20 parts of bamboo fiber, and 10-20 parts of hemp fiber; The weft includes the following raw materials in parts by weight: 10-20 parts of camphor wood fiber, 10-20 parts of bamboo fiber, 10-20 parts of hemp fiber, and 10-20 parts of composite fiber.

10. The use of a polyurethane resin in shoe leather according to claim 9, characterized in that: The preparation method of the modified fiber is as follows: Step a, dissolving chitosan in 1-2% glacial acetic acid solution to prepare a chitosan solution; Step b, dissolving calcium chloride in water to prepare a 2-5% calcium chloride solution; Step c, mixing the chitosan solution and the calcium chloride solution in a mass ratio of 1:(1-3) to prepare a mixed solution; Step d, after the camphor wood fiber, bamboo fiber and hemp fiber are mixed evenly, mixed fibers are prepared, the mixed fibers are put into a dissolving kettle, N-methylpyrrolidone is used as a solvent, the mixture is stirred evenly and then allowed to stand to prepare a spinning solution, the spinning solution and the mixed solution are mixed in a mass ratio of (1-5): 1, and the wet spinning process is used for spinning to prepare a composite fiber.

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