WO2022062244A1 - 家具用环保型彩色tpu薄膜及其制备方法 - Google Patents

家具用环保型彩色tpu薄膜及其制备方法 Download PDF

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Publication number
WO2022062244A1
WO2022062244A1 PCT/CN2020/140448 CN2020140448W WO2022062244A1 WO 2022062244 A1 WO2022062244 A1 WO 2022062244A1 CN 2020140448 W CN2020140448 W CN 2020140448W WO 2022062244 A1 WO2022062244 A1 WO 2022062244A1
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parts
furniture
tpu film
preparation
mixing
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PCT/CN2020/140448
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English (en)
French (fr)
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何建雄
杨博
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何建雄
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the invention belongs to the technical field of polymer materials, in particular to a TPU film and a preparation method thereof, in particular to an environment-friendly colored TPU film for furniture and a preparation method thereof.
  • TPU thermoplastic polyyrethane
  • thermoplastic polyurethane is a new type of organic polymer synthetic material with excellent properties; for example, wear resistance and resilience are better than ordinary polyurethane and PVC, and its aging resistance is better than rubber. It is an alternative to PVC and PU.
  • the ideal material is an internationally recognized new polymer material.
  • the main use is to add pigment products or dye products directly into the polyurethane resin for synthetic leather, and after stirring, fully mix the pigment products or dye products with the polyurethane resin to achieve the purpose of coloring the polyurethane resin.
  • Most of the pigments are inorganic metal pigments, which are dispersed in the resin in the form of pigment particles.
  • the pigment is not easy to migrate, the brightness and transparency of the color are poor, and it is not environmentally friendly enough, and it will cause greater harm to the human body. .
  • its elasticity, toughness, wear resistance, cold resistance and other properties are still not enough to manufacture some high-demand products. When used for the protection of furniture, it is easy to crack and rupture after long-term use.
  • CN106084733A discloses a TPU film with high color fastness and a preparation method thereof.
  • the TPU film is mainly prepared from the following components in parts by weight: 50-60 parts of polybutylene glycol, isophorone diisocyanate 35-40 parts, 25-30 parts of 1,4-butanediol, 10-20 parts of colored masterbatch, 10-20 parts of aromatic polycarbonate, 5-10 parts of N-phenylmaleamide and isopropanol 5 to 10 servings.
  • the invention uses aromatic polycarbonate to modify the polyurethane elastomer to increase its color fastness, but its color is not bright enough, and also has a certain dependence on the external temperature, with the extension of the use time, the material is easy to turn yellow , the color is difficult to keep bright, affecting the appearance.
  • CN110256834A discloses a TPU ultra-thin color waterproof and moisture-permeable film.
  • the components of the film and the weight parts of each component are: 50-100 parts of TPU particles, 10-20 parts of color masterbatch and 5-10 parts of dispersant light calcium ;
  • the components of the color masterbatch and the weight fraction of each component are: 10-40 parts of pigment, 60-80 parts of TPU carrier, 0.1-1 part of diffusing agent NNO, when TPU color masterbatch is used to color TPU, due to The fluidity of the color masterbatch is poor, and the molding processing type is easy to cause the dispersion uniformity of the color masterbatch in the TPU to be poor, and it is prone to the phenomenon that the color is unstable, the color is easy to fade, and the color difference is not easy to control.
  • the purpose of the present invention is to provide an environment-friendly colored TPU film for furniture and a preparation method thereof.
  • the environment-friendly color TPU film for furniture has uniform color dispersion, no color stripes and no local color difference, and also has excellent waterproof performance and various mechanical properties, and is suitable for the protection field of furniture.
  • the present invention provides an environment-friendly colored TPU film for furniture, and the preparation raw materials of the environment-friendly colored TPU film for furniture include the following components in parts by weight:
  • TPU film is prepared by using polyether polyol and diisocyanate as raw materials, and polytetrafluoroethylene and basalt fiber are introduced to improve the waterproof performance and various mechanical properties of the TPU film.
  • the modification enhances the compatibility of inorganic components and organic components, and cooperates with each other, thereby further improving the waterproof performance and barrier performance of the film.
  • the present invention adds the combination of vegetable pigment and epoxy-containing silane coupling agent, so that the color of the pigment is uniformly dispersed, which increases the color fastness of the film, ensures that the material will not turn yellow under the extension of time, and selects Plant pigments can further ensure the environmental protection and color vividness of the film.
  • the parts by weight of the TPU particles are 55-75 parts, such as 55 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 71 parts, 73 parts servings, 75 servings, etc.
  • the weight part of the diisocyanate is 25-35 parts, for example, it can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts servings, 35 servings, etc.
  • the weight part of the chain extender is 1-10 parts, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 servings etc.
  • the weight parts of the modified polytetrafluoroethylene is 10-20 parts, for example, it can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18, 19, 20, etc.
  • the weight parts of the modified basalt fiber is 1-10 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts , 10 copies, etc.
  • the weight part of the nano-photocatalyst is 1-5 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.
  • the weight part of the plant pigment is 1-5 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.
  • the weight part of the epoxy group-containing silane coupling agent is 0.5-3 parts, such as 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.
  • the weight part of the catalyst is 0.05-0.1 part, for example, 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, 0.1 part and the like.
  • the polyether polyol is selected from any one or a combination of at least two selected from polyethylene oxide diol, polyoxypropylene polyether triol or polytetrahydrofuran diol, preferably polytetrahydrofuran diol.
  • the weight average molecular weight of the polyether polyol is 1000-3000, for example, it can be 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000 and the like.
  • the diisocyanate is selected from any one or a combination of at least two of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate, preferably isophor Ketone diisocyanate.
  • the raw materials for preparing the modified polytetrafluoroethylene include: sodium naphthalene solution and polytetrafluoroethylene.
  • the polytetrafluoroethylene is modified by sodium naphthalene solution, so that some fluorine atoms on the surface of polytetrafluoroethylene are attached with polar groups such as hydroxyl, carbonyl, unsaturated bonds, etc., these groups can simultaneously combine and prepare raw materials Inorganic components and organic components in the material, further improve the compatibility of each component, reduce the friction coefficient of the inorganic components, and because the modified polytetrafluoroethylene plays the role of deformation buffer stress, and forms on the surface of the inorganic components
  • the local mobile phase can fill or repair cracks in time, thereby further increasing the wear resistance of the TPU film.
  • the mass ratio of the sodium naphthalene solution to the polytetrafluoroethylene is (2-3):1, for example, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3: 1 and so on.
  • the number average molecular weight of the polytetrafluoroethylene is 300,000-500,000, for example, it can be 300,000, 350,000, 400,000, 450,000, 500,000, and the like.
  • the sodium naphthalene solution comprises: sodium 3-4% and naphthalene 10-15%, and the balance is tetrahydrofuran.
  • the sodium content is 3-4%, such as 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, etc.
  • the naphthalene content is 10-15%, such as 10%, 11%, 12%, 13%, 14%, 15%, etc.
  • the modified polytetrafluoroethylene is prepared by the following preparation method: the sodium naphthalene solution and the polytetrafluoroethylene are mixed and stirred, filtered and dried to obtain the modified polytetrafluoroethylene.
  • the mixing and stirring time is 5-10min, such as 5min, 6min, 7min, 8min, 9min, 10min, etc.
  • the mixing and stirring temperature is 10-30°C, such as 10°C, 15°C , 20°C, 25°C, 30°C, etc.
  • the drying time is 1-2h, such as 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, etc.
  • the drying temperature is 20-40°C, such as 20°C, 25°C, 30°C, 35°C, 40°C, etc.
  • the raw materials for preparing the modified basalt fiber include, in parts by weight: 100 parts of basalt fiber, 40-50 parts of acid solution, 10-20 parts of surfactant, 10-20 parts of silane coupling agent and alcohol solution 40-50 servings.
  • the weight part of the acid solution is 40-50 parts, for example, it can be 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts , 48 copies, 49 copies, 50 copies, etc.
  • the acid solution includes any one or a combination of at least two of an aqueous hydrochloric acid solution, an aqueous acetic acid solution or an aqueous citric acid solution.
  • the concentration of the acid solution is 2-3 mol/L, such as 2 mol/L, 2.2 mol/L, 2.4 mol/L, 2.6 mol/L, 2.8 mol/L, 3 mol/L, etc.
  • the surfactant is selected from any one of dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide or diddecyldimethylammonium bromide or at least A combination of the two, preferably diddecyldimethylammonium bromide.
  • the silane coupling agent is an amino group-containing silane coupling agent, preferably ⁇ -aminopropyltrimethoxysilane and/or ⁇ -aminopropyltriethoxysilane.
  • the alcohol solution is selected from methanol aqueous solution and/or ethanol aqueous solution.
  • the modified basalt fiber is prepared by the following preparation method: the basalt fiber is dipped in an acid solution, then dried, mixed with a surfactant and a silane coupling agent in an alcohol solution, subjected to heat treatment, washed and dried, The modified basalt fiber is obtained.
  • the temperature of the immersion is 20-30°C, such as 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, etc.
  • the immersion time is 1-2h, such as 1h , 1.2h, 1.4h, 1.6h, 1.8h, 2h, etc.
  • the temperature of the heat treatment is 80-100°C, such as 80°C, 85°C, 90°C, 95°C, 100°C, etc.
  • the heat treatment time is 3-4h, such as 3h, 3.2h , 3.4h, 3.6h, 3.8h, 4h, etc.
  • the nano-photocatalyst is rutile titanium dioxide.
  • the particle size of the rutile-type titanium dioxide is 10-30 nm, such as 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, 20 nm, 22 nm, 24 nm, 26 nm, 28 nm, 30 nm.
  • the plant pigment is selected from any one or a combination of at least two of indigo, madder red, locust yellow, turmeric, comfrey, diospyros brown or hematoxylin.
  • the epoxy-containing silane coupling agent is selected from ⁇ -glycidoxypropyltrimethoxysilane and/or ⁇ -glycidoxypropyltriethoxysilane.
  • the catalyst is selected from any one or a combination of at least two in stannous octoate, dibutyltin dioctoate or dibutyltin dilaurate.
  • the present invention provides a preparation method of the environment-friendly colored TPU film for furniture as described in the first aspect, and the preparation method of the environment-friendly colored TPU film for furniture comprises the following steps:
  • step (1) mixing part of the polyurethane elastomer, modified basalt fiber, nano-photocatalyst, vegetable pigment and epoxy-containing silane coupling agent obtained in step (1), and kneading to obtain a premix;
  • step (3) mixing the premix obtained in step (2) and the remaining polyurethane elastomer obtained in step (1), and extruding to obtain the environment-friendly colored TPU film for furniture.
  • the temperature of the reaction is 80-120°C, such as 80°C, 90°C, 100°C, 110°C, 120°C, etc.
  • the reaction time is 2-4h, for example Can be 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, etc.
  • the mass of the part of the polyurethane elastomer accounts for 10-20% of the total mass of the polyurethane elastomer obtained by the reaction in step (1), such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.
  • the mixing temperature in step (2) is 80-100°C, such as 80°C, 85°C, 90°C, 95°C, 100°C, and the mixing time is 1-2h, For example, it can be 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h and so on.
  • the mixing temperature is 60-80°C, such as 60°C, 65°C, 70°C, 75°C, 80°C, etc.
  • the mixing time is 1-2h, such as Can be 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, etc.
  • the extrusion molding is performed by a twin-screw extruder
  • the temperature of the mixing section of the twin-screw extruder is 100-120°C (for example, it can be 100°C, 105°C, 110°C) , 115°C, 120°C, etc.)
  • the temperature of the extrusion section of the twin-screw extruder is 120-140°C (for example, it can be 120°C, 125°C, 130°C, 135°C, 140°C, etc.)
  • the head temperature of the screw extruder is 100-120°C (for example, it can be 100°C, 105°C, 110°C, 115°C, 120°C, etc.).
  • the preparation method of the environment-friendly colored TPU film for furniture comprises the following steps:
  • step (3) The premix obtained in step (2) and the remaining polyurethane elastomer obtained in step (1) are mixed and stirred at 60-80° C. for 1-2 hours, and extruded by a twin-screw extruder.
  • the temperature of the mixing section of the extruder is 100-120 °C
  • the temperature of the extrusion section of the twin-screw extruder is 120-140 °C
  • the temperature of the head of the twin-screw extruder is 100-120 °C.
  • the present invention has the following beneficial effects:
  • the TPU film of the present invention uses TPU particles, PETG particles, modified polytetrafluoroethylene, modified basalt fibers, nano-photocatalysts, vegetable pigments, epoxy-containing silane coupling agents and lubricants as raw materials.
  • the components cooperate with each other to increase the color fastness of the film, ensuring that the material will not turn yellow under the extension of time, and the color brightness can still be maintained; at the same time, the excellent water resistance and mechanical properties of the film make it suitable for application in Protection of furniture.
  • the tensile strength of the environmentally friendly colored TPU film for furniture according to the present invention is 45-55MPa, the elongation at break is 700-800%, the tear strength is 75-82MPa, and the hydrostatic pressure resistance range is 11000-12500mm Between the water columns, the aging yellowing index is below 1.2.
  • This preparation example provides a modified polytetrafluoroethylene I
  • the modified polytetrafluoroethylene I is prepared by the following preparation method: 100 g of sodium naphthalene solution (calculated based on the mass of the sodium naphthalene solution as 100%, sodium 3%, 12% naphthalene, the balance is tetrahydrofuran) and 40g polytetrafluoroethylene (number average molecular weight is 400,000) after mixing and stirring at 15°C for 6min, filtered, and dried at 30°C for 2h to obtain modified polytetrafluoroethylene Ethylene I.
  • This preparation example provides a modified polytetrafluoroethylene II
  • the modified polytetrafluoroethylene II is prepared by the following preparation method: 100 g of sodium naphthalene solution (calculated based on the mass of the sodium naphthalene solution as 100%, sodium 4%, 15% naphthalene, the balance is tetrahydrofuran) and 50 g of polytetrafluoroethylene (number average molecular weight of 500,000) were mixed and stirred at 20 ° C for 10 min, filtered, and dried at 35 ° C for 1.5 h to obtain modified polytetrafluoroethylene vinyl fluoride II.
  • This preparation example provides a modified polytetrafluoroethylene III
  • the modified polytetrafluoroethylene III is prepared by the following preparation method: 100 g of sodium naphthalene solution (calculated based on the mass of the sodium naphthalene solution as 100%, sodium 3%, 10% naphthalene, the balance is tetrahydrofuran) and 30 g of polytetrafluoroethylene (number average molecular weight is 300,000) after mixing and stirring at 10 ° C for 10 min, filtered, and dried at 20 ° C for 2 h to obtain modified polytetrafluoroethylene Ethylene III.
  • This preparation example provides a modified polytetrafluoroethylene IV
  • the modified polytetrafluoroethylene IV is prepared by the following preparation method: 100 g of sodium naphthalene solution (calculated based on the mass of the sodium naphthalene solution as 100%, sodium 3%, 12% naphthalene, the balance is tetrahydrofuran) and 100 g of polytetrafluoroethylene (number average molecular weight of 400,000) were mixed and stirred at 15 ° C for 6 min, filtered, and dried at 30 ° C for 2 h to obtain modified polytetrafluoroethylene Ethylene IV.
  • This preparation example provides a modified polytetrafluoroethylene V
  • the modified polytetrafluoroethylene V is prepared by the following preparation method: 100 g of sodium naphthalene solution (calculated based on the mass of the sodium naphthalene solution as 100%, sodium 3%, 12% naphthalene, the balance is tetrahydrofuran) and 25g polytetrafluoroethylene (number average molecular weight is 400,000) after mixing and stirring at 15°C for 6min, filtered, and dried at 30°C for 2h to obtain modified polytetrafluoroethylene Ethylene V.
  • This preparation example provides a modified basalt fiber I.
  • the modified basalt fiber I is prepared by the following preparation method: 100 g of basalt fiber is immersed in 50 g of a 2moL/L citric acid aqueous solution at 30°C for 1 hour, and then dried. Then mix with 15g of dodecyldimethylammonium bromide and 15g of ⁇ -aminopropyltrimethoxysilane in an aqueous ethanol solution, heat treatment at 90°C for 3.5h, wash and dry to obtain the modified Basalt Fiber I.
  • This preparation example provides a modified basalt fiber II.
  • the modified basalt fiber II is prepared by the following preparation method: 100 g of basalt fiber is immersed in 40 g of a 3moL/L citric acid aqueous solution at 20°C for 2 hours, and then dried. It is then mixed with 12 g of dodecyldimethylammonium bromide and 18 g of ⁇ -aminopropyltriethoxysilane in an aqueous ethanol solution, heat treated at 100° C. for 3 hours, washed and dried to obtain the modified Basalt Fiber II.
  • This preparation example provides a modified basalt fiber III.
  • the modified basalt fiber III is prepared by the following preparation method: 100 g of basalt fiber is immersed in 40 g of a 3moL/L citric acid aqueous solution at 25°C for 1.5 hours and then dried. , and then mixed with 18g of dodecyldimethylammonium bromide and 12g of ⁇ -aminopropyltriethoxysilane in an aqueous ethanol solution, heat-treated at 80°C for 4h, washed and dried to obtain the modified Sexual Basalt Fiber III.
  • This preparation example provides a modified basalt fiber IV.
  • the modified basalt fiber IV is prepared by the following preparation method: 100 g of basalt fiber is immersed in 50 g of a 2moL/L citric acid aqueous solution at 30 ° C for 1 hour, and then dried. It is then mixed with 15 g of dodecyltrimethylammonium bromide and 15 g of ⁇ -aminopropyltrimethoxysilane in an aqueous ethanol solution, heat-treated at 90° C. for 3.5 hours, washed and dried to obtain the modified Basalt Fiber IV.
  • This preparation example provides a modified basalt fiber V.
  • the modified basalt fiber V is prepared by the following preparation method: 100 g of basalt fiber is immersed in 50 g of a 2moL/L citric acid aqueous solution at 30°C for 1 hour, and then dried. It is then mixed with 15 g of dodecyldimethylammonium bromide and 15 g of ⁇ -glycidyloxypropyltrimethoxysilane in an aqueous ethanol solution, heat-treated at 90° C. for 3.5 hours, washed and dried to obtain the obtained product. Described modified basalt fiber V.
  • the present embodiment provides an environmentally friendly colored TPU film for furniture, which is prepared by the following preparation method:
  • step (3) The premix obtained in step (2) and the remaining polyurethane elastomer obtained in step (1) were mixed and stirred at 70° C. for 1.5 hours, and extruded by a twin-screw extruder.
  • the mixing of the twin-screw extruder The temperature of the section is 110 °C, the temperature of the extrusion section of the twin-screw extruder is 130 °C, and the temperature of the head of the twin-screw extruder is 110 °C, and then the single-screw extrusion is used to cast a film to obtain the obtained
  • the environment-friendly color TPU film for furniture is described.
  • the present embodiment provides an environmentally friendly colored TPU film for furniture, which is prepared by the following preparation method:
  • step (3) The premix obtained in step (2) and the remaining polyurethane elastomer obtained in step (1) were mixed and stirred at 80° C. for 1 hour, and extruded by a twin-screw extruder.
  • the mixing section of the twin-screw extruder was The temperature is 100°C, the temperature of the extrusion section of the twin-screw extruder is 120°C, and the temperature of the head of the twin-screw extruder is 100°C, and then the single-screw extrusion blow molding is used to form a film to obtain the described Eco-friendly color TPU film for furniture.
  • the present embodiment provides an environmentally friendly colored TPU film for furniture, which is prepared by the following preparation method:
  • step (3) The premix obtained in step (2) and the remaining polyurethane elastomer obtained in step (1) were mixed and stirred at 65° C. for 2 hours, and extruded by a twin-screw extruder.
  • the mixing section of the twin-screw extruder The temperature is 100°C, the temperature of the extrusion section of the twin-screw extruder is 120°C, and the temperature of the head of the twin-screw extruder is 100°C, and then the single-screw extrusion blow molding is used to form a film to obtain the described Eco-friendly color TPU film for furniture.
  • This embodiment provides an environment-friendly colored TPU film for furniture, the difference from Example 1 is that the modified polytetrafluoroethylene I is replaced with the same quality of modified polytetrafluoroethylene IV, the contents of other components and the preparation
  • the method is the same as in Example 1.
  • the present embodiment provides an environmentally friendly colored TPU film for furniture, the difference from Example 1 is only that the modified polytetrafluoroethylene I is replaced with the same quality modified polytetrafluoroethylene V, the contents of other components and the preparation The method is the same as in Example 1.
  • the present embodiment provides a kind of environment-friendly colored TPU film for furniture, the only difference from Example 1 is that the modified basalt fiber I is replaced by the modified basalt fiber IV of equal quality, and the contents of other components and the preparation method are the same as those in the embodiment. 1.
  • the present embodiment provides a kind of environment-friendly colored TPU film for furniture, the only difference from Example 1 is that the modified basalt fiber I is replaced by the modified basalt fiber V of equal quality, and the contents of other components and the preparation method are the same as those in the embodiment. 1.
  • the present embodiment provides an environmentally friendly colored TPU film for furniture, which is prepared by the following preparation method:
  • step (1) 15% of polyurethane elastomer, 15 parts of modified polytetrafluoroethylene 1, 5 parts of modified basalt fiber 1, 2 parts of rutile titanium are obtained by reacting in step (1)
  • White powder particle size is 20nm
  • step (3) The premix obtained in step (2) and the remaining polyurethane elastomer obtained in step (1) were mixed and stirred at 70° C. for 1.5 hours, and extruded by a twin-screw extruder.
  • the mixing of the twin-screw extruder The temperature of the section is 110 °C, the temperature of the extrusion section of the twin-screw extruder is 130 °C, and the temperature of the head of the twin-screw extruder is 110 °C, and then the single-screw extrusion is used to cast a film to obtain the obtained
  • the environment-friendly color TPU film for furniture is described.
  • the present embodiment provides an environmentally friendly colored TPU film for furniture, which is prepared by the following preparation method:
  • step (1) is obtained to obtain polyurethane elastomer, 5 parts of modified basalt fiber 1, 2 parts of rutile type titanium dioxide (particle size is 20nm), 2 parts of madder red and 2 parts of ⁇ -glycidyl oxygen propylpropyltrimethoxysilane was mixed, kneaded at 90°C for 3 hours, and extruded with a twin-screw extruder.
  • the temperature of the mixing section of the twin-screw extruder was 110°C.
  • the temperature of the exit section is 130° C.
  • the temperature of the head of the twin-screw extruder is 110° C.
  • the single-screw extruder is then used to extrude and cast into a film to obtain the environment-friendly colored TPU film for furniture.
  • This embodiment provides an environment-friendly colored TPU film for furniture, the difference from Embodiment 1 is that polytetrahydrofuran diol (weight-average molecular weight is 2000) is replaced with polyethylene oxide diol (weight-average molecular weight is 2000) of equal quality 2000), other component content and preparation method are the same as Example 1.
  • Embodiment 1 provides an environment-friendly colored TPU film for furniture, the difference from Embodiment 1 is only that isophorone diisocyanate is replaced with hexamethylene diisocyanate of the same quality, and the contents and preparation methods of other components are the same Example 1.
  • Embodiment 1 provides an environment-friendly colored TPU film for furniture.
  • the only difference from Embodiment 1 is that the rutile type titanium dioxide is replaced with an anatase titanium dioxide of equal quality (particle size is 20 nm), the contents of other components and the preparation
  • the method is the same as in Example 1.
  • This comparative example provides an environment-friendly colored TPU film for furniture, which differs from Example 1 only in that polytetrahydrofuran diol (weight average molecular weight is 2000) is replaced with polybutylene succinate (weight average molecular weight) of equal quality. The average molecular weight is 2000).
  • This comparative example provides an environment-friendly colored TPU film for furniture.
  • the difference from Example 1 is that no modified polytetrafluoroethylene I is added, the content of modified basalt fiber I is increased to 20 parts, and the contents of other components and preparations
  • the method is the same as in Example 1.
  • This comparative example provides an environment-friendly color TPU film for furniture, the difference from Example 1 is that the modified polytetrafluoroethylene is replaced with unmodified polytetrafluoroethylene of the same quality, the contents of other components and the preparation The method is the same as in Example 1.
  • This comparative example provides an environment-friendly colored TPU film for furniture.
  • the difference from Example 1 is that no modified basalt fiber I is added, the content of modified polytetrafluoroethylene I is increased to 20 parts, and the contents of other components and preparations
  • the method is the same as in Example 1.
  • This comparative example provides an environment-friendly colored TPU film for furniture.
  • the only difference from Example 1 is that the modified basalt fibers are replaced with unmodified basalt fibers of the same quality, and the contents and preparation methods of other components are the same as those in the embodiment. 1.
  • This comparative example provides an environment-friendly colored TPU film for furniture, which differs from Example 1 only in that no rutile titanium dioxide is added, and the contents and preparation methods of other components are the same as those of Example 1.
  • This comparative example provides a kind of environment-friendly colored TPU film for furniture, and the difference from Example 1 is only that madder red is replaced with iron oxide red of equal quality, and the content of other components and the preparation method are the same as those of Example 1.
  • This comparative example provides an environmentally friendly colored TPU film for furniture, the difference from Example 1 is that ⁇ -glycidoxypropyltrimethoxysilane is replaced with ⁇ -aminopropyltrimethoxysilane of the same quality , the content of other components and the preparation method are the same as those in Example 1.
  • the tensile strength of the environmentally friendly colored TPU film for furniture according to the present invention is 45-55MPa
  • the elongation at break is 700-800%
  • the tear strength is 75-82MPa
  • the hydrostatic pressure resistance range is Between 11000-12500mm water column
  • the color fastness grade is above 7, and the aging yellowing index is below 1.2.
  • the TPU film of the present invention uses TPU particles, PETG particles, modified polytetrafluoroethylene, modified basalt fibers, nano-photocatalysts, vegetable pigments, epoxy-containing silane coupling agents and lubricants as raw materials.
  • the color fastness of the film is increased, ensuring that the material will not turn yellow and the color brightness can be maintained under the extension of time; at the same time, the excellent water resistance and mechanical properties of the film make it suitable for use in furniture. protection.
  • the present invention illustrates the environment-friendly colored TPU film for furniture and its preparation method through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented .
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

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Abstract

一种家具用环保型彩色TPU薄膜及其制备方法。所述家具用环保型彩色TPU薄膜的制备原料按重量份数计包括如下组分：聚醚多元醇55-75份、二异氰酸酯25-35份、扩链剂1-10份、改性聚四氟乙烯10-20份、改性玄武岩纤维1-10份、纳米光触媒1-5份、植物颜料1-5份、含环氧基的硅烷偶联剂0.5-3份和催化剂0.05-0.1份。所述家具用环保型彩色TPU薄膜各组分颜色分散的均匀，无色条和无局部色差，同时还具有优异的防水性能和各项力学性能，且各组分原料绿色环保，适用于家具的防护领域。

Description

[根据细则37.2由ISA制定的发明名称]　家具用环保型彩色TPU薄膜及其制备方法
本公开基于申请号为202011004724.5，申请日为2020年09月22日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本发明属于高分子材料技术领域，具体涉及一种TPU薄膜及其制备方法，尤其涉及一种家具用环保型彩色TPU薄膜及其制备方法。
背景技术
TPU(Thermoplasticpolyyrethane，热塑性聚氨酯)是一种新型的有机高分子合成材料，具有优异的性能；例如耐磨性和回弹力都优于普通聚氨酯和PVC，耐老化性优于橡胶，是替代PVC和PU的理想的材料，是国际公认的新型聚合物材料。在TPU材料着色方面，现在主要使用是将颜料制品或染料制品直接加入合成革用聚氨酯树脂中，经过搅拌，将颜料制品或染料制品与聚氨酯树脂充分混合，以达到聚氨酯树脂着色的目的。颜料多为无机金属颜料，其以颜料微粒的形式分散于树脂中，因此虽然颜料着色不容易迁移，但是颜色的鲜艳度和透明性较差，且不够环保，还会对人体造成较大的伤害。另外，其弹性、韧性、耐磨性、耐寒性等性能仍不能满足于制造一些高要求的产品，用于家具的防护时，长期使用容易龟裂、破裂的现象。
CN106084733A公开了一种高色牢度的TPU薄膜及其制备方法，所述TPU薄膜按重量份计主要由以下组分制备得到：聚丁烯乙二醇50～60份、异佛尔酮二异氰酸酯35～40份、1，4-丁二醇25～30份、有色母粒10～20份、芳香族聚碳酸酯10～20份、N-苯基马来酰胺5～10份和异丙醇5～10份。该发明通过采用芳香族聚碳酸酯对聚氨酯弹性体进行改性，增加其色牢度，但是其颜色鲜艳度不够， 对于外界温度也存在一定依赖性，随着使用时间的延长，材料容易变黄，彩色难以保持鲜亮，影响美观。
CN110256834A公开了一种TPU超薄彩色防水透湿薄膜，该薄膜的组份及各组份的重量份为：TPU颗粒50-100份、色母10-20份及分散剂轻钙5-10份；其中色母的组分及各组分的重量分数为：颜料10-40份、TPU载体60-80份、扩散剂NNO 0.1-1份，其采用TPU色母粒对TPU进行着色时，由于色母粒的流动性较差，成型加工型容易造成色母粒在TPU中的分散均匀性欠佳，容易出现颜色不稳定，容易掉色且色差不易控制的现象。
因此，开发一种环保型彩色TPU薄膜是家具防护领域研究的重点。
发明内容
针对现有技术的不足，本发明的目的在于提供一种家具用环保型彩色TPU薄膜及其制备方法。所述家具用环保型彩色TPU薄膜颜色分散的均匀，无色条和无局部色差，同时还具有优异的防水性能和各项力学性能，适用于家具的防护领域。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种家具用环保型彩色TPU薄膜，所述家具用环保型彩色TPU薄膜的制备原料按重量份数计包括如下组分：
Figure PCTCN2020140448-appb-000001
Figure PCTCN2020140448-appb-000002
在本发明中，以聚醚多元醇和二异氰酸酯为原料制备TPU薄膜，并引入聚四氟乙烯和玄武岩纤维提高TPU薄膜的防水性能和各项力学性能，通过对聚四氟乙烯和对玄武岩纤维的改性，增强了无机组分和有机组分的相容性，协同配合，从而进一步提高薄膜的防水性能以及阻隔性能。同时，本发明添加植物颜料和含环氧基的硅烷偶联剂的配合，使得颜料颜色分散的均匀，增加了薄膜的色牢度，保证在时间的延长下，材料不会变黄，且选择植物颜料能够进一步保证薄膜的环保性和颜色鲜艳度。
在本发明中，所述TPU颗粒的重量份数为55-75份，例如可以是55份、56份、58份、60份、62份、64份、66份、68份、71份、73份、75份等。
在本发明中，所述二异氰酸酯的重量份数为25-35份，例如可以是25份、26份、27份、28份、29份、30份、31份、32份、33份、34份、35份等。
在本发明中，所述扩链剂的重量份数为1-10份，例如可以是1份、2份、3份、4份、5份、6份、7份、8份、9份、10份等。
在本发明中，所述改性聚四氟乙烯的重量份数为10-20份，例如可以是10份、11份、12份、13份、14份、15份、16份、17份、18份、19份、20份等。
在本发明中，所述改性玄武岩纤维的重量份数为1-10份，例如可以是1份、2份、3份、4份、5份、6份、7份、8份、9份、10份等。
在本发明中，所述纳米光触媒的重量份数为1-5份，例如可以是1份、2份、3份、4份、5份等。
在本发明中，所述植物颜料的重量份数为1-5份，例如可以是1份、2份、 3份、4份、5份等。
在本发明中，所述含环氧基的硅烷偶联剂的重量份数为0.5-3份，例如可以是0.5份、1份、1.5份、2份、2.5份、3份等。
在本发明中，所述催化剂的重量份数为0.05-0.1份，例如可以是0.05份、0.06份、0.07份、0.08份、0.09份、0.1份等。
优选地，所述聚醚多元醇选自聚氧化乙烯二醇、聚氧化丙烯聚醚三醇或聚四氢呋喃二醇中的任意一种或至少两种的组合，优选为聚四氢呋喃二醇。
优选地，所述聚醚多元醇的重均分子量为1000-3000，例如可以是1000、1200、1500、1800、2000、2200、2500、2800、3000等。
优选地，所述二异氰酸酯选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯中的任意一种或至少两种的组合，优选为异佛尔酮二异氰酸酯。
优选地，所述改性聚四氟乙烯的制备原料包括：钠萘溶液和聚四氟乙烯。通过钠萘溶液对聚四氟乙烯进行改性，使得聚四氟乙烯表面的部分氟原子被附上了羟基、羰基、不饱和键等极性基团，这些基团能够使能够同时结合制备原料中的无机组分和有机组分，进一步提高各组分的相容性，降低无机组分的摩擦系数，且由于改性聚四氟乙烯起变形缓冲应力的作用，并在无机组分表面形成局部流动相，及时填充或修复裂纹，从而进一步日高起到TPU薄膜的耐磨性。
优选地，所述钠萘溶液和聚四氟乙烯的质量比为(2-3)∶1，例如可以是2∶1、2.2∶1、2.4∶1、2.6∶1、2.8∶1、3∶1等。
优选地，所述聚四氟乙烯的数均分子量为30-50万，例如可以是30万、35万、40万、45万、50万等。
优选地，以所述钠萘溶液的质量为100％计，所述钠萘溶液包括：钠3-4％ 和萘10-15％，余量为四氢呋喃。
以所述钠萘溶液的质量为100％计，钠含量为3-4％，例如可以是3％、3.2％、3.4％、3.6％、3.8％、4％等。
以所述钠萘溶液的质量为100％计，萘含量为10-15％，例如可以是10％、11％、12％、13％、14％、15％等。
优选地，所述改性聚四氟乙烯由以下制备方法制备得到：将钠萘溶液和聚四氟乙烯混合搅拌，过滤、干燥，得到所述改性聚四氟乙烯。
优选地，所述混合搅拌的时间为5-10min，例如可以是5min、6min、7min、8min、9min、10min等，所述混合搅拌的温度为10-30℃，例如可以是10℃、15℃、20℃、25℃、30℃等。
优选地，所述干燥的时间为1-2h，例如可以是1h、1.2h、1.4h、1.6h、1.8h、2h等，所述干燥的温度为20-40℃，例如可以是20℃、25℃、30℃、35℃、40℃等。
优选地，所述改性玄武岩纤维的制备原料按重量份数计包括：玄武岩纤维100份、酸液40-50份、表面活性剂10-20份、硅烷偶联剂10-20份和醇液40-50份。
在所述改性玄武岩纤维的制备原料中，酸液的重量份数为40-50份，例如可以是40份、41份、42份、43份、44份、45份、46份、47份、48份、49份、50份等。
优选地，所述酸液包括盐酸水溶液、醋酸水溶液或柠檬酸水溶液中的任意一种或至少两种的组合。
优选地，所述酸液的浓度为2-3mol/L，例如可以是2mol/L、2.2mol/L、2.4mol/L、2.6mol/L、2.8mol/L、3mol/L等。
优选地，所述表面活性剂选自十二烷基三甲基溴化铵、十六烷基三甲基溴化铵或双十二烷基二甲基溴化铵中的任意一种或至少两种的组合，优选为双十二烷基二甲基溴化铵。
优选地，所述硅烷偶联剂为含氨基的硅烷偶联剂，优选为γ-氨丙基三甲氧基硅烷和/或γ-氨丙基三乙氧基硅烷。
优选地，所述醇液选自甲醇水溶液和/或乙醇水溶液。
优选地，所述改性玄武岩纤维由以下制备方法制备得到：将玄武岩纤维浸渍在酸液后干燥，再与表面活性剂和硅烷偶联剂在醇液中混合，进行热处理后，洗涤、干燥，得到所述改性玄武岩纤维。
优选地，所述浸渍的温度为20-30℃，例如可以是20℃、22℃、24℃、26℃、28℃、30℃等，所述浸渍的时间为1-2h，例如可以是1h、1.2h、1.4h、1.6h、1.8h、2h等。
优选地，所述热处理的温度为80-100℃，例如可以是80℃、85℃、90℃、95℃、100℃等，所述热处理的时间为3-4h，例如可以是3h、3.2h、3.4h、3.6h、3.8h、4h等。
优选地，所述纳米光触媒为金红石型钛白粉。
优选地，所述金红石型钛白粉的粒径为10-30nm，例如可以是10nm、12nm、14nm、16nm、18nm、20nm、22nm、24nm、26nm、28nm、30nm德国。
优选地，所述植物颜料选自靛蓝、茜草红、槐花黄、姜黄、紫草、薯莨棕或苏木黑中的任意一种或至少两种的组合。
优选地，所述含环氧基的硅烷偶联剂选自γ-缩水甘油氧基丙基三甲氧基硅烷和/或γ-缩水甘油醚氧丙基三乙氧基硅烷。
优选地，所述催化剂选自辛酸亚锡、二辛酸二丁锡或二月桂酸二丁锡中的 任意一种或至少两种的组合。
第二方面，本发明提供一种如第一方面所述的家具用环保型彩色TPU薄膜的制备方法，所述家具用环保型彩色TPU薄膜的制备方法包括以下步骤：
(1)将聚醚多元醇、二异氰酸酯、改性聚四氟乙烯、扩链剂和催化剂混合，反应得到聚氨酯弹性体；
(2)将步骤(1)得到的部分聚氨酯弹性体、改性玄武岩纤维、纳米光触媒、植物颜料和含环氧基的硅烷偶联剂混合，进行混炼，得到预混料；
(3)将步骤(2)得到的预混料和步骤(1)得到的剩余聚氨酯弹性体混合，挤出成型，得到所述家具用环保型彩色TPU薄膜。
优选地，步骤(1)中，所述反应的温度为80-120℃，例如可以是80℃、90℃、100℃、110℃、120℃等，所述反应的时间为2-4h，例如可以是2h、2.2h、2.4h、2.6h、2.8h、3h、3.2h、3.4h、3.6h、3.8h、4h等。
优选地，步骤(2)中，所述部分聚氨酯弹性体的质量占步骤(1)反应得到聚氨酯弹性体总质量的10-20％，例如可以是10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％等。
优选地，步骤(2)中所述混炼的温度为80-100℃，例如可以是80℃、85℃、90℃、95℃、100℃、，所述混炼的时间为1-2h，例如可以是1h、1.2h、1.4h、1.6h、1.8h、2h等。
优选地，步骤(3)中，所述混合的温度为60-80℃，例如可以是60℃、65℃、70℃、75℃、80℃等，所述混合的时间为1-2h，例如可以是1h、1.2h、1.4h、1.6h、1.8h、2h等。
优选地，步骤(3)中，所述挤出成型采用双螺杆挤出机进行，所述双螺杆挤出机的混合段温度为100-120℃(例如可以是100℃、105℃、110℃、115℃、 120℃等)，所述双螺杆挤出机的挤出段温度为120-140℃(例如可以是120℃、125℃、130℃、135℃、140℃等)，所述双螺杆挤出机的机头温度为100-120℃(例如可以是100℃、105℃、110℃、115℃、120℃等)。
优选地，所述家具用环保型彩色TPU薄膜的制备方法包括以下步骤：
(1)将聚醚多元醇、二异氰酸酯、改性聚四氟乙烯、扩链剂和催化剂，在80-120℃反应2-4h，反应得到聚氨酯弹性体；
(2)将占步骤(1)反应得到聚氨酯弹性体总质量的10-20％的聚氨酯弹性体、改性玄武岩纤维、纳米光触媒、植物颜料和含环氧基的硅烷偶联剂混合，在80-100℃进行混炼1-2h，得到预混料；
(3)将步骤(2)得到的预混料和步骤(1)得到的剩余聚氨酯弹性体在60-80℃混合搅拌1-2h，采用双螺杆挤出机挤出，所述双螺杆挤出机的混合段温度为100-120℃，所述双螺杆挤出机的挤出段温度为120-140℃，所述双螺杆挤出机的机头温度为100-120℃，再利用单螺杆挤出流延成膜或吹塑成膜，得到所述家具用环保型彩色TPU薄膜。
相对于现有技术，本发明具有以下有益效果：
(1)本发明所述TPU薄膜以TPU颗粒、PETG颗粒、改性聚四氟乙烯、改性玄武岩纤维、纳米光触媒、植物颜料、含环氧基的硅烷偶联剂和润滑剂为原料，各组分相互配合，增加了薄膜的色牢度，保证在时间的延长下，材料仍不会变黄，颜色鲜艳度仍能够维持；同时还薄膜优异的耐水性和力学性能，使其能够应用于家具的防护。
(2)本发明所述家具用环保型彩色TPU薄膜的拉伸强度为45-55MPa，断裂伸长率为700-800％，撕裂强度为75-82MPa，耐静水压范围在11000-12500mm水柱之间，老化黄变指数在1.2以下。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
制备例1
本制备例提供一种改性聚四氟乙烯I，所述改性聚四氟乙烯I由以下制备方法制备得到：将100g钠萘溶液(以所述钠萘溶液的质量为100％计，钠3％、萘12％，余量为四氢呋喃)和40g聚四氟乙烯(数均分子量为40万)在15℃下混合搅拌6min后，过滤，在30℃下干燥2h，得到改性聚四氟乙烯I。
制备例2
本制备例提供一种改性聚四氟乙烯II，所述改性聚四氟乙烯II由以下制备方法制备得到：将100g钠萘溶液(以所述钠萘溶液的质量为100％计，钠4％、萘15％，余量为四氢呋喃)和50g聚四氟乙烯(数均分子量为50万)在20℃下混合搅拌10min后，过滤，在35℃下干燥1.5h，得到改性聚四氟乙烯II。
制备例3
本制备例提供一种改性聚四氟乙烯III，所述改性聚四氟乙烯III由以下制备方法制备得到：将100g钠萘溶液(以所述钠萘溶液的质量为100％计，钠3％、萘10％，余量为四氢呋喃)和30g聚四氟乙烯(数均分子量为30万)在10℃下混合搅拌10min后，过滤，在20℃下干燥2h，得到改性聚四氟乙烯III。
制备例4
本制备例提供一种改性聚四氟乙烯IV，所述改性聚四氟乙烯IV由以下制备方法制备得到：将100g钠萘溶液(以所述钠萘溶液的质量为100％计，钠 3％、萘12％，余量为四氢呋喃)和100g聚四氟乙烯(数均分子量为40万)在15℃下混合搅拌6min后，过滤，在30℃下干燥2h，得到改性聚四氟乙烯IV。
制备例5
本制备例提供一种改性聚四氟乙烯V，所述改性聚四氟乙烯V由以下制备方法制备得到：将100g钠萘溶液(以所述钠萘溶液的质量为100％计，钠3％、萘12％，余量为四氢呋喃)和25g聚四氟乙烯(数均分子量为40万)在15℃下混合搅拌6min后，过滤，在30℃下干燥2h，得到改性聚四氟乙烯V。
制备例6
本制备例提供一种改性玄武岩纤维I，所述改性玄武岩纤维I由以下制备方法制备得到：在30℃下将100g玄武岩纤维在50g的2moL/L的柠檬酸水溶液中浸渍1h后干燥，再与15g的十二烷基二甲基溴化铵和15g的γ-氨丙基三甲氧基硅烷在乙醇水溶液中混合，在90℃下热处理3.5h后，洗涤、干燥，得到所述改性玄武岩纤维I。
制备例7
本制备例提供一种改性玄武岩纤维II，所述改性玄武岩纤维II由以下制备方法制备得到：在20℃下将100g玄武岩纤维在40g的3moL/L的柠檬酸水溶液中浸渍2h后干燥，再与12g的十二烷基二甲基溴化铵和18g的γ-氨丙基三乙氧基硅烷在乙醇水溶液中混合，在100℃下热处理3h后，洗涤、干燥，得到所述改性玄武岩纤维II。
制备例8
本制备例提供一种改性玄武岩纤维III，所述改性玄武岩纤维III由以下制备方法制备得到：在25℃下将100g玄武岩纤维在40g的3moL/L的柠檬酸水 溶液中浸渍1.5h后干燥，再与18g的十二烷基二甲基溴化铵和12g的γ-氨丙基三乙氧基硅烷在乙醇水溶液中混合，在80℃下热处理4h后，洗涤、干燥，得到所述改性玄武岩纤维III。
制备例9
本制备例提供一种改性玄武岩纤维IV，所述改性玄武岩纤维IV由以下制备方法制备得到：在30℃下将100g玄武岩纤维在50g的2moL/L的柠檬酸水溶液中浸渍1h后干燥，再与15g的十二烷基三甲基溴化铵和15g的γ-氨丙基三甲氧基硅烷在乙醇水溶液中混合，在90℃下热处理3.5h后，洗涤、干燥，得到所述改性玄武岩纤维IV。
制备例10
本制备例提供一种改性玄武岩纤维V，所述改性玄武岩纤维V由以下制备方法制备得到：在30℃下将100g玄武岩纤维在50g的2moL/L的柠檬酸水溶液中浸渍1h后干燥，再与15g的十二烷基二甲基溴化铵和15g的γ-缩水甘油氧基丙基三甲氧基硅烷在乙醇水溶液中混合，在90℃下热处理3.5h后，洗涤、干燥，得到所述改性玄武岩纤维V。
实施例1
本实施例提供一种家具用环保型彩色TPU薄膜，所述家具用环保型彩色TPU薄膜由以下制备方法制备得到：
(1)将60份聚四氢呋喃二醇(重均分子量为2000)、30份的异佛尔酮二异氰酸酯、15份的改性聚四氟乙烯I、5份的乙二醇和0.06份的二月桂酸二丁锡，在100℃反应3h，反应得到聚氨酯弹性体；
(2)将占步骤(1)反应得到聚氨酯弹性体总质量的15％的聚氨酯弹性体、5份的改性玄武岩纤维I、2份的金红石型钛白粉(粒径为20nm)、2份的茜草 红和2份的γ-缩水甘油氧基丙基三甲氧基硅烷混合，在90℃进行混炼1.5h，得到预混料；
(3)将步骤(2)得到的预混料和步骤(1)得到的剩余聚氨酯弹性体在70℃混合搅拌1.5h，采用双螺杆挤出机挤出，所述双螺杆挤出机的混合段温度为110℃，所述双螺杆挤出机的挤出段温度为130℃，所述双螺杆挤出机的机头温度为110℃，再利用单螺杆挤出流延成膜，得到所述家具用环保型彩色TPU薄膜。
实施例2
本实施例提供一种家具用环保型彩色TPU薄膜，所述家具用环保型彩色TPU薄膜由以下制备方法制备得到：
(1)将65份聚四氢呋喃二醇(重均分子量为2200)、32份的异佛尔酮二异氰酸酯、18份的改性聚四氟乙烯II、6份的1，3-丙二醇和0.08份的二月桂酸二丁锡，在110℃反应2h，反应得到聚氨酯弹性体；
(2)将占步骤(1)反应得到聚氨酯弹性体总质量的20％的聚氨酯弹性体、4份的改性玄武岩纤维II、3份的金红石型钛白粉(粒径为20nm)、2份的槐花黄和3份的γ-缩水甘油氧基丙基三甲氧基硅烷混合，在80℃进行混炼2h，得到预混料；
(3)将步骤(2)得到的预混料和步骤(1)得到的剩余聚氨酯弹性体在80℃混合搅拌1h，采用双螺杆挤出机挤出，所述双螺杆挤出机的混合段温度为100℃，所述双螺杆挤出机的挤出段温度为120℃，所述双螺杆挤出机的机头温度为100℃，再利用单螺杆挤出吹塑成膜，得到所述家具用环保型彩色TPU薄膜。
实施例3
本实施例提供一种家具用环保型彩色TPU薄膜，所述家具用环保型彩色TPU薄膜由以下制备方法制备得到：
(1)将70份聚四氢呋喃二醇(重均分子量为1500)、26份的异佛尔酮二异氰酸酯、13份的改性聚四氟乙烯III、3份的1，4-丁二醇和0.05份的二月桂酸二丁锡，在90℃反应3h，反应得到聚氨酯弹性体；
(2)将占步骤(1)反应得到聚氨酯弹性体总质量的10％的聚氨酯弹性体、6份的改性玄武岩纤维III、2份的金红石型钛白粉(粒径为20nm)、2份的姜黄和4份的γ-缩水甘油醚氧丙基三乙氧基硅烷，在80℃进行混炼2h，得到预混料；
(3)将步骤(2)得到的预混料和步骤(1)得到的剩余聚氨酯弹性体在65℃混合搅拌2h，采用双螺杆挤出机挤出，所述双螺杆挤出机的混合段温度为100℃，所述双螺杆挤出机的挤出段温度为120℃，所述双螺杆挤出机的机头温度为100℃，再利用单螺杆挤出吹塑成膜，得到所述家具用环保型彩色TPU薄膜。
实施例4
本实施例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将改性聚四氟乙烯I替换为等质量的改性聚四氟乙烯IV，其他组分含量及制备方法同实施例1。
实施例5
本实施例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将改性聚四氟乙烯I替换为等质量的改性聚四氟乙烯V，其他组分含量及制备方法同实施例1。
实施例6
本实施例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将改性玄武岩纤维I替换为等质量的改性玄武岩纤维IV，其他组分含量及制备方法同实施例1。
实施例7
本实施例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将改性玄武岩纤维I替换为等质量的改性玄武岩纤维V，其他组分含量及制备方法同实施例1。
实施例8
本实施例提供一种家具用环保型彩色TPU薄膜，所述家具用环保型彩色TPU薄膜由以下制备方法制备得到：
(1)将60份聚四氢呋喃二醇(重均分子量为2000)、30份的异佛尔酮二异氰酸酯、5份的乙二醇和0.06份的二月桂酸二丁锡，在100℃反应3h，反应得到聚氨酯弹性体；
(2)将占步骤(1)反应得到聚氨酯弹性体总质量的15％的聚氨酯弹性体、15份的改性聚四氟乙烯I、5份的改性玄武岩纤维I、2份的金红石型钛白粉(粒径为20nm)、2份的茜草红和2份的γ-缩水甘油氧基丙基三甲氧基硅烷混合，在90℃进行混炼1.5h，得到预混料；
(3)将步骤(2)得到的预混料和步骤(1)得到的剩余聚氨酯弹性体在70℃混合搅拌1.5h，采用双螺杆挤出机挤出，所述双螺杆挤出机的混合段温度为110℃，所述双螺杆挤出机的挤出段温度为130℃，所述双螺杆挤出机的机头温度为110℃，再利用单螺杆挤出流延成膜，得到所述家具用环保型彩色TPU薄膜。
实施例9
本实施例提供一种家具用环保型彩色TPU薄膜，所述家具用环保型彩色TPU薄膜由以下制备方法制备得到：
(1)将60份聚四氢呋喃二醇(重均分子量为2000)、30份的异佛尔酮二异氰酸酯、15份的改性聚四氟乙烯I、5份的乙二醇和0.06份的二月桂酸二丁锡，在100℃反应3h，反应得到聚氨酯弹性体；
(2)将步骤(1)得到聚氨酯弹性体、5份的改性玄武岩纤维I、2份的金红石型钛白粉(粒径为20nm)、2份的茜草红和2份的γ-缩水甘油氧基丙基三甲氧基硅烷混合，在90℃进行混炼3h，采用双螺杆挤出机挤出，所述双螺杆挤出机的混合段温度为110℃，所述双螺杆挤出机的挤出段温度为130℃，所述双螺杆挤出机的机头温度为110℃，再利用单螺杆挤出流延成膜，得到所述家具用环保型彩色TPU薄膜。
实施例10
本实施例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将聚四氢呋喃二醇(重均分子量为2000)替换为等质量的聚氧化乙烯二醇(重均分子量为2000)，其他组分含量及制备方法同实施例1。
实施例11
本实施例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将异佛尔酮二异氰酸酯替换为等质量的六亚甲基二异氰酸酯，其他组分含量及制备方法同实施例1。
实施例12
本实施例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将金红石型钛白粉替换为等质量的锐型钛白粉(粒径为20nm)，其他组分含量及制备方法同实施例1。
对比例1
本对比例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将聚四氢呋喃二醇(重均分子量为2000)替换为等质量的聚丁二酸丁二醇酯(重均分子量为2000)。
对比例2
本对比例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，不添加改性聚四氟乙烯I，改性玄武岩纤维I含量增至20份，其他组分含量及制备方法同实施例1。
对比例3
本对比例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将改性聚四氟乙烯替换为等质量的未经改性聚四氟乙烯，其他组分含量及制备方法同实施例1。
对比例4
本对比例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，不添加改性玄武岩纤维I，改性聚四氟乙烯I含量增至20份，其他组分含量及制备方法同实施例1。
对比例5
本对比例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将改性玄武岩纤维换为等质量的未经改性玄武岩纤维，其他组分含量及制备方法同实施例1。
对比例6
本对比例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，不添加金红石型钛白粉，其他组分含量及制备方法同实施例1。
对比例7
本对比例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将茜草红替换为等质量的氧化铁红，其他组分含量及制备方法同实施例1。
对比例8
本对比例提供一种家具用环保型彩色TPU薄膜，与实施例1的区别仅在于，将γ-缩水甘油氧基丙基三甲氧基硅烷替换为等质量的γ-氨丙基三甲氧基硅烷，其他组分含量及制备方法同实施例1。
性能测试
对上述实施例1-12制备得到的家具用环保型彩色TPU薄膜和对比例1-8制备得到的家具用环保型彩色TPU薄膜进行各项性能测试。其中，根据GB/T 1040.1-2006测试各薄膜材料的断裂伸长率，根据GB/T16578.1-2008测试各薄膜材料的撕裂强度，根据GB/74744-1997测试各薄膜材料的耐静水压；根据ISO105-A01：1994测试色牢度；老化黄变指数ΔYi(测试方法为GB2409-88)(其中，无变色ΔYi≤1.5，很轻微变色1.6＜ΔYi≤3.0，轻微变色3.1＜ΔYi≤6.0，明显变色6.1＜ΔYi≤9.0，较大变色9.1＜ΔYi≤12.0，严重变色12.0＜ΔYi)；
具体测试结果如表1所示：
表1
Figure PCTCN2020140448-appb-000003
Figure PCTCN2020140448-appb-000004
由表1测试数据可知，本发明所述家具用环保型彩色TPU薄膜的拉伸强度为45-55MPa，断裂伸长率为700-800％，撕裂强度为75-82MPa，耐静水压范围在11000-12500mm水柱之间，色牢度等级在7级以上，老化黄变指数在1.2以下。说明本发明所述TPU薄膜以TPU颗粒、PETG颗粒、改性聚四氟乙烯、改性玄武岩纤维、纳米光触媒、植物颜料、含环氧基的硅烷偶联剂和润滑剂为原料，各组分相互配合，增加了薄膜的色牢度，保证在时间的延长下，材料仍 不会变黄，颜色鲜艳度仍能够维持；同时还薄膜优异的耐水性和力学性能，使其能够应用于家具的防护。
申请人声明，本发明通过上述实施例来说明所述家具用环保型彩色TPU薄膜及其制备方法，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种家具用环保型彩色TPU薄膜，其特征在于，所述家具用环保型彩色TPU薄膜的制备原料按重量份数计包括如下组分：
    Figure PCTCN2020140448-appb-100001
  2. 根据权利要求1所述的家具用环保型彩色TPU薄膜，其特征在于，所述聚醚多元醇选自聚氧化乙烯二醇、聚氧化丙烯聚醚三醇或聚四氢呋喃二醇中的任意一种或至少两种的组合，优选为聚四氢呋喃二醇；
    优选地，所述聚醚多元醇的重均分子量为1000-3000；
    优选地，所述二异氰酸酯选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯中的任意一种或至少两种的组合，优选为异佛尔酮二异氰酸酯；
    优选地，所述扩链剂选自乙二醇、1，3-丙二醇、1，4-丁二醇或1，5-戊二醇中的任意一种或至少两种的组合。
  3. 根据权利要求1或2所述的家具用环保型彩色TPU薄膜，其特征在于，所述改性聚四氟乙烯的制备原料包括：钠萘溶液和聚四氟乙烯；
    优选地，所述钠萘溶液和聚四氟乙烯的质量比为(2-3)∶1；
    优选地，所述聚四氟乙烯的数均分子量为30-50万；
    优选地，以所述钠萘溶液的质量为100％计，所述钠萘溶液包括：钠3-4％和萘10-15％，余量为四氢呋喃；
    优选地，所述改性聚四氟乙烯由以下制备方法制备得到：将钠萘溶液和聚四氟乙烯混合搅拌，过滤、干燥，得到所述改性聚四氟乙烯；
    优选地，所述混合搅拌的时间为5-10min，所述混合搅拌的温度为10-30℃；
    优选地，所述干燥的时间为1-2h，所述干燥的温度为20-40℃。
  4. 根据权利要求1-3中任一项所述的家具用环保型彩色TPU薄膜，其特征在于，所述改性玄武岩纤维的制备原料按重量份数计包括：玄武岩纤维100份、酸液40-50份、表面活性剂10-20份、硅烷偶联剂10-20份和醇液40-50份；
    优选地，所述酸液包括盐酸水溶液、醋酸水溶液或柠檬酸水溶液中的任意一种或至少两种的组合；
    优选地，所述酸液的浓度为2-3mol/L；
    优选地，所述表面活性剂选自十二烷基三甲基溴化铵、十六烷基三甲基溴化铵或双十二烷基二甲基溴化铵中的任意一种或至少两种的组合，优选为双十二烷基二甲基溴化铵；
    优选地，所述硅烷偶联剂为含氨基的硅烷偶联剂，优选为γ-氨丙基三甲氧基硅烷和/或γ-氨丙基三乙氧基硅烷；
    优选地，所述醇液选自甲醇水溶液和/或乙醇水溶液；
    优选地，所述改性玄武岩纤维由以下制备方法制备得到：将玄武岩纤维浸渍在酸液后干燥，再与表面活性剂和硅烷偶联剂在醇液中混合，进行热处理后，洗涤、干燥，得到所述改性玄武岩纤维；
    优选地，所述浸渍的温度为20-30℃，所述浸渍的时间为1-2h；
    优选地，所述热处理的温度为80-100℃，所述热处理的时间为3-4h。
  5. 根据权利要求1-4中任一项所述的家具用环保型彩色TPU薄膜，其特征在于，所述纳米光触媒为金红石型钛白粉；
    优选地，所述金红石型钛白粉的粒径为10-30nm。
  6. 根据权利要求1-5中任一项所述的家具用环保型彩色TPU薄膜，其特征在于，所述植物颜料选自靛蓝、茜草红、槐花黄、姜黄、紫草、薯莨棕或苏木黑中的任意一种或至少两种的组合；
    优选地，所述含环氧基的硅烷偶联剂选自γ-缩水甘油氧基丙基三甲氧基硅烷和/或γ-缩水甘油醚氧丙基三乙氧基硅烷；
    优选地，所述催化剂选自辛酸亚锡、二辛酸二丁锡或二月桂酸二丁锡中的任意一种或至少两种的组合。
  7. 根据权利要求1-6中任一项所述的家具用环保型彩色TPU薄膜的制备方法，其特征在于，所述家具用环保型彩色TPU薄膜的制备方法包括以下步骤：
    (1)将聚醚多元醇、二异氰酸酯、改性聚四氟乙烯、扩链剂和催化剂混合，反应得到聚氨酯弹性体；
    (2)将步骤(1)得到的部分聚氨酯弹性体、改性玄武岩纤维、纳米光触媒、植物颜料和含环氧基的硅烷偶联剂混合，进行混炼，得到预混料；
    (3)将步骤(2)得到的预混料和步骤(1)得到的剩余聚氨酯弹性体混合，挤出成型，得到所述家具用环保型彩色TPU薄膜。
  8. 根据权利要求7所述的制备方法，其特征在于，步骤(1)中，所述反应的温度为80-120℃，所述反应的时间为2-4h；
    优选地，步骤(2)中，所述部分聚氨酯弹性体的质量占步骤(1)反应得到聚氨酯弹性体总质量的10-20％；
    优选地，步骤(2)中所述混炼的温度为80-100℃，所述混炼的时间为1-2h。
  9. 根据权利要求7或8所述的制备方法，其特征在于，步骤(3)中，所述混合的温度为60-80℃，所述混合的时间为1-2h；
    优选地，步骤(3)中，所述挤出成型采用双螺杆挤出机进行，所述双螺杆挤出机的混合段温度为100-120℃，所述双螺杆挤出机的挤出段温度为120-140℃，所述双螺杆挤出机的机头温度为100-120℃。
  10. 根据权利要求7-9中任一项所述的制备方法，其特征在于，所述家具用环保型彩色TPU薄膜的制备方法包括以下步骤：
    (1)将聚醚多元醇、二异氰酸酯、改性聚四氟乙烯、扩链剂和催化剂，在80-120℃反应2-4h，反应得到聚氨酯弹性体；
    (2)将占步骤(1)反应得到聚氨酯弹性体总质量的10-20％的聚氨酯弹性体、改性玄武岩纤维、纳米光触媒、植物颜料和含环氧基的硅烷偶联剂混合，在80-100℃进行混炼1-2h，得到预混料；
    (3)将步骤(2)得到的预混料和步骤(1)得到的剩余聚氨酯弹性体在60-80℃混合搅拌1-2h，采用双螺杆挤出机挤出，所述双螺杆挤出机的混合段温度为100-120℃，所述双螺杆挤出机的挤出段温度为120-140℃，所述双螺杆挤出机的机头温度为100-120℃，再利用单螺杆挤出流延成膜或吹塑成膜，得到所述家具用环保型彩色TPU薄膜。
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