WO2022036496A1 - 一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法 - Google Patents

一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法 Download PDF

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WO2022036496A1
WO2022036496A1 PCT/CN2020/109488 CN2020109488W WO2022036496A1 WO 2022036496 A1 WO2022036496 A1 WO 2022036496A1 CN 2020109488 W CN2020109488 W CN 2020109488W WO 2022036496 A1 WO2022036496 A1 WO 2022036496A1
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recycled fiber
cloth
waste
recycled
preparation
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PCT/CN2020/109488
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English (en)
French (fr)
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游训
方华玉
姜兴盛
沃尔特施密特托马斯
李天源
林鹏
刘猛
陈珂
吴剑晗
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福建华峰运动用品科技有限公司
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Priority to DE112020003283.3T priority Critical patent/DE112020003283T5/de
Priority to CN202080005037.7A priority patent/CN112703233B/zh
Priority to PCT/CN2020/109488 priority patent/WO2022036496A1/zh
Priority to US17/601,108 priority patent/US20220325132A1/en
Publication of WO2022036496A1 publication Critical patent/WO2022036496A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/445—Use of auxiliary substances before, during or after dyeing or printing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the invention belongs to the technical field of recycling and reuse of waste cloth, and more particularly relates to a recycled fiber coating slurry containing waste cloth, a coating and a preparation method thereof.
  • the recycling methods of waste fabrics mainly include chemical methods and physical methods.
  • the physical recovery method is relatively simple and economical. It is mainly to sort, clean and dry the collected waste fabrics, and then directly conduct melt spinning or bottle making or other products after crushing.
  • the performance of the recycled products is poor, and the recycling The product is relatively low-end.
  • Chemical method refers to the process of depolymerizing waste fabrics into polymerized monomers or polymerized intermediates by chemical reaction, and then performing regeneration polymerization and melt spinning after purification and separation.
  • the chemical recovery methods on the market mainly include: hydrolysis, alcoholysis, ammonolysis, aminolysis, thermal cracking and other degradation methods.
  • chemical recycling of waste fabrics requires more equipment, complicated production processes, and high technical level requirements.
  • Chinese invention patent application CN101838471A discloses textile fiber-reinforced resin-based composite material and its production process. It involves composite materials, including resin-based composite materials. Fibers for enhancing the properties of resin matrix composites, including textile fibers.
  • the production process of textile fiber reinforced resin-based composite material includes a fiber production process and a resin-based composite material production process, and the fiber production process includes the following steps: 1) selecting fabrics containing textile fibers; 2) forming small pieces in a rag machine; 3 ) to break small pieces into textile fibers.
  • the particle size of the crushed textile fibers is large, and the prepared reinforced resin-based composite material has a rough surface and poor flatness. Although the strength is enhanced, the performance enhancement effect and application range of anti-bending and anti-breaking are very good. limited. Converting waste fabrics into microfiber powder and then reusing them is a new path for the physical recycling of waste fabrics. However, due to the electrostatic properties of waste fabrics, it greatly increases the difficulty of making waste fabrics into microfiber powder.
  • the recycled fiber coating slurry containing waste cloth should contain a certain proportion of waste
  • the recycled fiber of the cloth, and the fiber coating containing the waste cloth needs to have excellent bending resistance and mechanical properties, and the source of the waste cloth raw materials that can be used in the preparation method should be relatively wide, which can truly reduce the environmental impact of the waste cloth.
  • the inventor provides a recycled fiber coating slurry containing waste cloth, which, in parts by weight, contains: 0.5 to 8 parts of recycled fiber of waste cloth, 95 to 110 parts of water-based polyurethane and 4 to 6 parts of curing agent.
  • the recycled fiber coating slurry containing waste cloth is prepared into recycled fiber coating slurry by using recycled fiber of waste cloth, water-based polyurethane and curing agent, and the field of physical method recycling of waste cloth is expanded to the coating field.
  • the recycled fibers of waste fabrics have fine particle size, and the recycled fiber coating slurry obtained by mixing with water-based polyurethane and curing agent in an appropriate ratio has excellent dispersibility and stability.
  • the inventor provides a method for preparing a recycled fiber coating containing waste cloth, comprising the following steps:
  • Preparation of recycled fibers crushing and sieving waste fabrics to obtain recycled fibers, and the waste fabrics are one or more of chemical fiber, cotton, hemp, silk, woolen and blended fabrics;
  • Preparation of recycled fiber coating slurry mixing 0.5-8 parts by weight of the recycled fiber, 95-110 parts by weight of water-based polyurethane and 4-6 parts by weight of curing agent to obtain recycled fiber coating slurry;
  • Printing printing the recycled fiber coating slurry on a base cloth or a substrate, and drying to obtain a recycled fiber coating containing waste cloth.
  • the inventor provides a recycled fiber coating containing waste cloth, which is prepared according to the preparation method described in the second aspect of the present invention, and the thickness of the recycled fiber coating is 0.1-1.0 mm .
  • the recycled fiber made of waste cloth, water-based polyurethane and curing agent are mixed in a certain proportion to obtain a recycled fiber coating slurry, and the recycled fiber coating slurry is printed on the base cloth and dried to obtain a recycled fiber coating containing waste cloth.
  • the process technology is simple and easy to operate.
  • the bending resistance, wear resistance and mechanical properties of the recycled fiber coating containing waste fabrics are greatly enhanced, which enriches the recycling methods of waste fabrics and improves the added value of waste fabrics. , reducing the negative impact of waste fabrics on the environment.
  • Fig. 1 is the sample picture of the recycled fiber coating containing waste cloth (40 mesh) according to the specific embodiment
  • FIG. 2 is a sample picture of the recycled fiber coating containing waste cloth (20 mesh) according to the specific embodiment.
  • a recycled fiber coating slurry containing waste and old cloth, in parts by weight, contains: 0.5-8 parts of recycled fiber of waste and old cloth, 95-110 parts of water-based polyurethane and 4-6 parts of curing agent.
  • the waste cloth is one or more of chemical fiber, cotton, linen, silk, woolen and blended.
  • the curing agent is an isocyanate.
  • the recycled fiber coating slurry containing waste cloth according to the present invention can be used to prepare various coatings, but it does not limit other applications of the recycled fiber coating slurry containing waste cloth in the non-coating field .
  • a preparation method of recycled fiber coating containing waste cloth comprising the following steps:
  • waste and old fabrics are crushed and screened to obtain recycled fibers, and the waste and old fabrics are one or more of chemical fiber, cotton, hemp, silk, woolen and blended fabrics;
  • Preparation of recycled fiber coating slurry mixing 0.5 to 8 parts by weight of the recycled fiber, 95 to 110 parts by weight of aqueous polyurethane and 4 to 6 parts by weight of a curing agent to obtain a recycled fiber coating slurry, the curing agent is Isocyanates;
  • Printing printing the recycled fiber coating slurry on a base cloth or a substrate, and drying to obtain a recycled fiber coating containing waste cloth.
  • lignocellulose high-consistency, medium-consistency or low-consistency refiners are used for the crushing of waste cloth, and the process control of hot grinding with pressure avoids the flying of fiber powder and fibers caused by static electricity during the cutting process of traditional waste cloth fibers.
  • the problem of uneven particle size After the crushing step, the waste cloth fiber powder is passed through a sieve with a specific mesh to ensure that the recovered fiber powder with fine and uniform size is obtained.
  • the raw material source of waste fabrics is not particularly limited, and can be selected from any one of chemical fiber, cotton, linen, silk, woolen and blended fabrics, or any mixture thereof.
  • the chemical fiber raw materials can be, for example, but not limited to, polyester, acrylic, nylon, polypropylene, vinylon, and special fibers.
  • the curing agent isocyanate used in the present invention can realize slow curing, prolong the active time of paste printing, and use the isocyanate curing agent to coat with less bubbles, high transparency and better mechanical properties.
  • the substrate of the recycled fiber coating can be cloth, and in other embodiments, the recycled fiber slurry can also be coated on substrates including, but not limited to, plastic plates, metal plates, glass plates, and the like.
  • a fiber refiner is used for crushing the waste cloth, the feeding speed of the waste cloth is 60-300 kg/h, and the steam pressure is 4-16 bar.
  • a 20-40 mesh sieve is used for the sieving. In order to ensure that the fabric recovery rate reaches more than 50% and does not affect the performance and appearance of printed products, this interval sieve is selected.
  • the particle size of the waterborne polyurethane is 0.001-0.1 ⁇ m.
  • Waterborne polyurethane in this range is more suitable for thickening the coating to ensure the mechanical properties of the coating.
  • the printing is one of screen printing, plate printing, roll coating, thin coating and blade coating, and the thickness of the printing coating slurry is 0.1-1 mm, and the drying temperature is 60-80°C.
  • the step further includes vacuuming and defoaming, and the vacuum degree is -0.095-0.1 mPa.
  • a recycled fiber coating containing waste cloth is prepared according to the preparation method described in the second aspect of the present invention, and the thickness of the recycled fiber coating is 0.1-1.0 mm.
  • Embodiment 1 a kind of recycled fiber coating slurry containing waste and old cloth, coating and preparation method thereof
  • Preparation of recycled fiber The waste mixed-color polyester fabric is crushed with an Andritz mill.
  • the feeding speed of the waste fabric is 60-300kg/h, and the steam pressure of the Andritz mill is 4-16 bar, and it is passed through a 40-mesh sieve to obtain an average
  • the particle size is less than or equal to 40 mesh recycled fiber;
  • FIG. 1 shows a sample of recycled fiber coatings containing waste cloth (40 mesh).
  • Embodiment 2 a kind of recycled fiber coating slurry, coating and preparation method thereof containing waste and old cloth
  • Preparation of recycled fiber The waste blue acrylic fabric is crushed with an Andritz mill, the feed rate of the waste fabric is 60-300kg/h, and the steam pressure of the Andritz mill is 4-16 bar, and it is passed through a 20-mesh sieve to obtain The average particle size is less than or equal to 20 mesh recycled fibers;
  • Screen printing prepare a 20-mesh screen or pre-prepared screen, screen-print the prepared recycled fiber slurry on the fabric base within 2 hours, control the printing thickness at 0.1mm, and set the screen-printed coating at 60 Dry at ⁇ 80°C to obtain a recycled fiber coating with a thickness of 0.1 mm.
  • Figure 2 shows a sample of recycled fiber coatings containing waste cloth (20 mesh).
  • Embodiment 3 a kind of recycled fiber coating slurry, coating and preparation method thereof containing waste cloth
  • Preparation of recycled fiber The waste white cotton cloth is crushed with an Andritz mill, the feeding speed of the waste cloth is 60-300 kg/h, the steam pressure of the Andritz mill is 4-16 bar, and the sieve is passed through a 30-mesh sieve to obtain an average particle size. Recycled fibers with a diameter less than or equal to 30 mesh;
  • Preparation of recycled fiber coating slurry After mixing 30 mesh recycled fiber and water-based polyurethane with a particle size of 0.001 to 0.1 ⁇ m uniformly, add isocyanate curing agent and stir evenly to obtain a slurry containing recycled fiber, wherein recycled fiber, water-based polyurethane ,
  • the mass ratio of isocyanate curing agent is 5:110:4;
  • Screen printing prepare a 30-mesh screen or pre-prepared screen, screen-print the prepared recycled fiber slurry on the fabric base within 2 hours, control the printing thickness at 1.0mm, and set the screen-printed coating at 60 After drying at ⁇ 80°C, a recycled fiber coating with a thickness of 1.0 mm was obtained.
  • Embodiment 4 a kind of recycled fiber coating slurry, coating and preparation method thereof containing waste cloth
  • Preparation of recycled fiber The waste gray linen is crushed with a lignin fiber low-consistency mill.
  • the feed rate of the waste fabric is 60-300kg/h during crushing, and the steam pressure of the lignin-fiber low-consistency mill is 4-16 bar, and Pass through a 40-mesh sieve to obtain recycled fibers with an average particle size less than or equal to 40-mesh;
  • Vacuuming and defoaming the recycled fiber coating slurry the vacuum degree is -0.095 ⁇ 0.1mPa;
  • Squeegee printing Scratch the prepared recycled fiber slurry on a plastic substrate within 2 hours, control the thickness of the squeegee to be 0.5mm, and dry the squeegee coating at 60-80°C to obtain a thickness of 0.5mm Recycled fiber coating.
  • Embodiment 5 a kind of recycled fiber coating slurry, coating and preparation method thereof containing waste cloth
  • Preparation of recycled fiber The waste blended fabric is crushed with a lignin fiber medium-concentration mill.
  • the feeding speed of the waste fabric is 60-300kg/h, and the steam pressure of the lignin-fiber medium-concentration mill is 4-16 bar.
  • 30-mesh sieve to obtain recycled fibers with an average particle size of less than or equal to 30-mesh;
  • Vacuuming and defoaming the recycled fiber coating slurry the vacuum degree is -0.095 ⁇ 0.1mPa;
  • the prepared recycled fiber coating slurry was thinly coated with 0.5 mm on a metal substrate within 2 hours, and dried at 60-80° C. to obtain a recycled fiber coating with a thickness of 0.5 mm.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that no recycled fibers are added to the coating slurry, and all of them are made of water-based polyurethane and isocyanate curing agent mixed uniformly in a mass ratio of 115:5.
  • the tearing strength test method is as follows: according to GB/T3917.3-2009 "Tearing properties of textile fabrics - Part 3 Determination of tearing strength of trapezoidal specimens", YG0268 electronic fabric strength tester is used to measure the tearing strength of coated fabrics.
  • test method of abrasion resistance is: according to GB/T 21196.3-2007 "Determination of Abrasion Resistance of Textiles by Martindale Method Part 3 Determination of Mass Loss", using GT-7012-M Abrasion Tester to test.
  • Table 1 shows the test results of tear strength and abrasion resistance of the coated fabrics of Examples 1-5 and Comparative Example 1 and the fabrics without coating.
  • Example 1 Example 2
  • Example 3 Example 4

Abstract

一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法。将0.5～8重量份废旧布料的回收纤维、95～110重量份水性聚氨酯和4～6重量份固化剂制备成回收纤维涂层浆料，并将回收纤维涂层浆料印刷在基布或基板上，烘干，得到回收纤维涂层，所述回收纤维涂层的厚度为0.1～1.0mm，该方法将废旧布料的物理法回收利用领域拓展到了涂层领域，由于废旧布料的回收纤维粒径微细，与水性聚氨酯和固化剂在适当配比下混合得到的回收纤维涂层具有优良的耐磨性能和力学性能。

Description

一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法 技术领域
本发明属于废旧布料回收再利用技术领域，更具体地涉及一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法。
背景技术
随着人民生活水平的提高，城市生活垃圾中的废旧布料数量在逐年增长。截止2019年底，我国的废旧布料总产量大约为2亿吨，此外，我国每年将至少新增3000万吨的废旧布料，但回收利用率不足10％，废旧布料处理面临着重大挑战。基于环境保护意识、资源节约及可持续性需求的增强，废旧布料的回收再利用日益受到重视。
现阶段，废旧布料的回收再利用方法主要有化学法和物理法两大类。物理回收方法较为简单、经济，主要是将收集的废旧布料进行分拣清洗干燥之后，再经过破碎之后直接进行熔融纺丝或制瓶或制备其他产品的过程，但其再生产品的性能差，再生产品比较低端。化学法是指利用化学反应将废旧布料解聚为聚合单体或聚合中间体，经过提纯分离等步骤后进行再生聚合和熔融纺丝的过程。目前市场上的化学回收方法主要有：水解法、醇解法、氨解法、胺解法、热裂解法和其他降解法。但化学法回收利用废旧布料需要投入的仪器设备较多，生产工艺复杂，且对于技术水平要求高。
废旧衣服或布料的传统物理法回收都少不了破碎步骤，但现有废旧布料的粉碎机或破碎机裁切出来的废旧布料碎片尺寸都比较大，粗细不一，应用领域和场景都很有限。以下专利文献中公开了废旧布料的物理法回收利用处理技术。中国发明专利申请CN201811240099.7“一种含有废旧布料碎条的塑料包装物的制造方法”公开了一种含有废旧布料碎条的塑料包装物的制造方 法，将废旧布料绞成碎布条，与塑料包装袋配合增强塑料包装物的强度，提高其重复利用率，有效减少塑料包装物垃圾的产生。但该技术方案只是简单将废旧布料裁剪之后与塑料袋通过胶水黏合在一起，并未真正增强塑料袋的强度，大量胶水的应用很可能使塑料袋具有刺鼻的异味，同时也可能会降低塑料袋安全性。
在废旧布料纤维复合材料的应用方面，同样由于废旧布料被裁切的尺寸不够细微，影响了废旧布料回收利用的效果。中国发明专利申请CN101838471A“纺织纤维增强树脂基复合材料及其生产工艺”公开了纺织纤维增强树脂基复合材料及其生产工艺涉及复合材料，包括树脂基复合材料，所述树脂基复合材料内混有用于增强树脂基复合材料性能的纤维，所述纤维包括纺织纤维。纺织纤维增强树脂基复合材料生产工艺，包括纤维制作流程、树脂基复合材料生产流程，纤维制作流程包括如下步骤：1)选取含有纺织纤维的布料；2)在碎布机制成小碎块；3)将小碎块打成纺织纤维。该技术中破碎后的纺织纤维粒径较大，制备出的增强树脂基复合材料表面粗糙，平整度差，虽然强度有所增强，但抗弯折和防破裂的性能增强效果和适用范围都很有限。将废旧布料变成微细纤维粉然后加以利用是废旧布料物理法回收利用的一条全新路径，然而由于废旧布料成分的静电特性，大大增加了废旧布料制成微细纤维粉的难度。
发明内容
鉴于背景技术存在的上述技术问题，需要提供一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法，所述含废旧布料的回收纤维涂层浆料中应含有一定比例的废旧布料的回收纤维，且所述含废旧布料的纤维涂层需具备优良的抗弯折性能和力学性能，所述制备方法能够采用的废旧布料原料来源应当较为广泛，能够真正实现减轻废旧布料对环境造成的压力以及发挥废旧布料资源的积极作用的目的。
为实现上述目的，在本发明的第一方面，发明人提供了一种含废旧布料的回收纤维涂层浆料，以重量份数计，含有：0.5～8份废旧布料的回收纤维、95～110份水性聚氨酯和4～6份固化剂。
区别于现有技术，上述技术方案至少具有以下有益效果：
本发明中含废旧布料的回收纤维涂层浆料采用废旧布料的回收纤维、水性聚氨酯和固化剂制备成回收纤维涂层浆料，将废旧布料的物理法回收利用领域拓展到涂层领域，由于废旧布料的回收纤维粒径微细，与水性聚氨酯和固化剂在适当配比下混合得到的回收纤维涂层浆料具有优良的分散性和稳定性。
在本发明的第二方面，发明人提供了一种含废旧布料的回收纤维涂层的制备方法，包括以下步骤：
制备回收纤维：将废旧布料破碎，过筛，得到回收纤维，所述废旧布料为化纤、棉、麻、丝绸、呢绒和混纺布料中的一种或多种；
制备回收纤维涂层浆料：将0.5～8重量份所述回收纤维、95～110重量份水性聚氨酯和4～6重量份固化剂混合均匀，得到回收纤维涂层浆料；
印刷：将所述回收纤维涂层浆料印刷在基布或基板上，烘干，得到含废旧布料的回收纤维涂层。
在本发明的第三方面，发明人提供了一种含废旧布料的回收纤维涂层，根据本发明第二方面所述的制备方法制备得到，所述回收纤维涂层的厚度为0.1～1.0mm。
区别于现有技术，上述技术方案至少具有以下有益效果：
将废旧布料制成的回收纤维、水性聚氨酯和固化剂按一定比例混合得到回收纤维涂层浆料，将该回收纤维涂层浆料印刷在基布上烘干后得到含废旧布料的回收纤维涂层，工艺技术简单、易于操作，所述含废旧布料的回收纤维涂层抗弯折性能、耐磨性能和力学性能得到大大增强，丰富了废旧布料的回收利用途径，提高了废旧布料的附加值，减轻了废旧布料对环境的负面影 响。
附图说明
图1为具体实施方式所述含废旧布料(40目)的回收纤维涂层的样品图片；
图2为具体实施方式所述含废旧布料(20目)的回收纤维涂层的样品图片。
具体实施方式
下面详细说明本发明第一方面所述的含废旧布料的回收纤维涂层浆料、本发明第二方面所述的含废旧布料的回收纤维涂层的制备方法和本发明第三方面所述的含废旧布料的回收纤维涂层。
首先说明本发明第一方面所述的含废旧布料的回收纤维涂层浆料。
一种含废旧布料的回收纤维涂层浆料，以重量份数计，含有：0.5～8份废旧布料的回收纤维、95～110份水性聚氨酯和4～6份固化剂。
优选地，所述废旧布料为化纤、棉、麻、丝绸、呢绒和混纺中的一种或多种。
优选地，所述固化剂为异氰酸酯。
本发明所述的含废旧布料的回收纤维涂层浆料，可以用来制备各种涂层，但并不因此限制所述含废旧布料的回收纤维涂层浆料在非涂层领域的其他应用。
其次说明本发明第二方面所述的含废旧布料的回收纤维涂层的制备方法。
一种含废旧布料的回收纤维涂层的制备方法，包括以下步骤：
制备回收纤维：将废旧布料破碎，过筛，得到回收纤维，所述废旧布料 为化纤、棉、麻、丝绸、呢绒和混纺布料中的一种或多种；
制备回收纤维涂层浆料：将0.5～8重量份所述回收纤维、95～110重量份水性聚氨酯和4～6重量份固化剂混合均匀，得到回收纤维涂层浆料,所述固化剂为异氰酸酯；
印刷：将所述回收纤维涂层浆料印刷在基布或基板上，烘干，得到含废旧布料的回收纤维涂层。
本发明中废旧布料的破碎采用了木质纤维素高浓、中浓或低浓磨浆机，带压热磨的工艺控制避免了传统废旧布料纤维在切割过程中因静电产生的纤维粉末飞扬以及纤维颗粒粗细不均的问题。在破碎步骤之后使废旧布料纤维粉末通过特定目数的筛子，保证得到的是尺寸微细均匀的回收纤维粉。废旧布料的原料来源并无很具体的限制，可以选自化纤、棉、麻、丝绸、呢绒和混纺布料中任一种，或是其中的任意几种混合物。化纤原料例如可以是但不限于涤纶、腈纶、锦纶、丙纶、维纶以及特种纤维等。本发明中应用的固化剂异氰酸酯可实现缓慢固化，延长浆料印刷活性时间，且使用异氰酸酯固化剂涂层中产生的气泡少，透明度高，力学性能更好。
具体实施方式中，回收纤维涂层的基材可以为布料，在其他实施例中，回收纤维浆料还可以在包括但不限于塑料板、金属板、玻璃板等基板上进行涂层的印刷。
并且，为了保持所述回收纤维涂层浆料的最佳应用性能，应尽快进行使用，优选地是在其制备出之后的2h之内进行印刷。
优选地，所述将废旧布料破碎采用纤维磨浆机，废旧布料的进料速度为60～300kg/h，蒸汽压力为4～16bar。
优选地，所述过筛采用20～40目筛子。为了保证布料回收率达到50％以上同时不影响印刷产品性能和外观，选此区间筛子。
优选地，所述水性聚氨酯的粒径为0.001～0.1μm。该区间水性聚氨酯更适用于涂层起厚，确保涂层力学性能。
优选地，所述印刷为丝网印刷、制版印刷、辊涂、薄涂和刮涂中的一种，且印刷涂层浆料的厚度为0.1～1mm，烘干温度为60～80℃。
优选地，所述制备回收纤维涂层浆料步骤之后还包括抽真空除泡，真空度为-0.095～0.1mPa。
最后说明本发明第三方面所述的含废旧布料的回收纤维涂层。一种含废旧布料的回收纤维涂层，根据本发明第二方面所述的制备方法制备得到，所述回收纤维涂层的厚度为0.1～1.0mm。
为详细说明技术方案的技术内容、构造特征、所实现目的及效果，以下结合具体实施例并配合附图详予说明。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
实施例1：一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法
制备回收纤维：用Andritz磨机将废旧混色涤纶布料进行破碎，破碎时废旧布料的进料速度为60～300kg/h，Andritz磨机的蒸汽压力为4～16bar，并过40目筛子，得到平均粒径为小于或等于40目的回收纤维；
制备回收纤维涂层浆料：将40目回收纤维与粒径为0.001～0.1μm的水性聚氨酯混合均匀后，加入异氰酸酯固化剂并搅拌均匀，得到回收纤维涂层浆料，其中回收纤维、水性聚氨酯、异氰酸酯固化剂的质量比为0.5:100:4；
丝网印刷：制备40目的网版或预先准备已制备好的网版，将制备的回收纤维涂层浆料在2h内丝印在布料基面上，将丝印的涂层在60～80℃烘干，得到厚度为0.5mm回收纤维涂层。图1显示了含废旧布料(40目)的回收纤维涂层的样品。
实施例2：一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法
制备回收纤维：用Andritz磨机将废旧蓝色腈纶布料进行破碎，破碎时废旧布料的进料速度为60～300kg/h，Andritz磨机的蒸汽压力为4～16bar，并过 20目筛子，得到平均粒径为小于或等于20目的回收纤维；
制备回收纤维涂层浆料：将20目回收纤维与粒径为0.001～0.1μm的水性聚氨酯混合均匀后，加入异氰酸酯固化剂并搅拌均匀，得到回收纤维涂层浆料，其中回收纤维、水性聚氨酯、异氰酸酯固化剂的质量比为1.5:95:6；
丝网印刷：制备20目的网版或预先准备已制备好的网版，将制备的回收纤维浆料在2h内丝印在布料基面上，控制印刷厚度在0.1mm，将丝印的涂层在60～80℃烘干，得到厚度为0.1mm回收纤维涂层。图2显示了含废旧布料(20目)的回收纤维涂层的样品。
实施例3：一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法
制备回收纤维：用Andritz磨机将废旧白色棉布进行破碎，破碎时废旧布料的进料速度为60～300kg/h，Andritz磨机的蒸汽压力为4～16bar，并过30目筛子，得到平均粒径为小于或等于30目的回收纤维；
制备回收纤维涂层浆料：将30目回收纤维与粒径为0.001～0.1μm的水性聚氨酯混合均匀后，加入异氰酸酯固化剂并搅拌均匀，得到含有回收纤维的浆料，其中回收纤维、水性聚氨酯、异氰酸酯固化剂的质量比为5:110:4；
丝网印刷：制备30目的网版或预先准备已制备好的网版，将制备的回收纤维浆料在2h内丝印在布料基面上，控制印刷厚度在1.0mm，将丝印的涂层在60～80℃烘干，得到厚度为1.0mm回收纤维涂层。
实施例4：一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法
制备回收纤维：用木质素纤维低浓磨机将废旧灰色麻布进行破碎，破碎时废旧布料的进料速度为60～300kg/h，木质素纤维低浓磨机的蒸汽压力为4～16bar，并过40目筛子，得到平均粒径小于或等于40目回收纤维；
制备回收纤维涂层浆料：将40目回收纤维与水性聚氨酯混合均匀后，加入异氰酸酯固化剂并搅拌均匀，得到含有回收纤维的浆料，其中回收纤维、 水性聚氨酯、异氰酸酯固化剂的质量比为8:110:4；
将所述回收纤维涂层浆料抽真空除泡，真空度为-0.095～0.1mPa；
刮涂印刷：将制备的回收纤维浆料在2h内刮涂在塑料材质的基板上，控制刮涂厚度为0.5mm，将刮涂的涂层在60～80℃烘干，得到厚度为0.5mm回收纤维涂层。
实施例5：一种含废旧布料的回收纤维涂层浆料、涂层及其制备方法
制备回收纤维：用木质素纤维中浓磨机将废旧混纺布料进行破碎，破碎时废旧布料的进料速度为60～300kg/h，木质素纤维中浓磨机蒸汽压力为4～16bar，并过30目筛子，得到平均粒径为小于或等于30目的回收纤维；
制备回收纤维涂层浆料：将30目回收纤维与水性聚氨酯混合均匀后，加入异氰酸酯固化剂并搅拌均匀，得到回收纤维涂层浆料，其中回收纤维、水性聚氨酯、异氰酸酯固化剂的质量比为5:110:4；
将所述回收纤维涂层浆料抽真空除泡，真空度为-0.095～0.1mPa；
印刷：将制备的回收纤维涂层浆料在2h内薄涂0.5mm在金属基板上，在60～80℃烘干，得到厚度为0.5mm回收纤维涂层。
对比例1：空白涂层制备
对比例1与实施例1的不同之处为：涂层浆料中未加入回收纤维，全部为水性聚氨酯和异氰酸酯固化剂以质量比为115:5混合均匀而成。
将实施例1-5所制备的含有废旧布料的回收纤维涂层布料、对比例1制备的空白涂层布料与涂层前的布料基材进行涂层织物撕裂强力测试和耐磨性能测试。
撕裂强力测试方法为：根据GB/T3917.3-2009《纺织品织物撕破性能第3部分梯形试样撕破强力的测定》进行，采用YG0268型电子织物强力仪测定涂层织物撕裂强力。
耐磨性能测试方法为：根据GB/T 21196.3-2007《纺织品马丁代尔法织物耐磨性的测定第3部分质量损失的测定》进行，采用GT-7012-M耐磨仪测试。
实施例1-5及对比例1的涂层织物以及不含涂层的布料撕裂强力和耐磨仪测试结果见表1所示。
表1 实施例1-5及对比例1的涂层织物撕裂强力和耐磨指数测试结果
样品 涂层前布料 对比例1 实施例1 实施例2 实施例3 实施例4 实施例5
撕裂强力/N 59.23 66.27 74.90 69.01 83.36 82.90 67.59
耐磨指数(次/mg) 无 32 29 23 18 11 20
从表1的结果可知，实施例1-5因采用了含废旧布料的回收纤维，含回收纤维涂层织物的撕裂强力大于对比例1和使用涂层前的布料，并且实施例3所得到的涂层织物的撕裂强度优于其他实施例，说明废旧布料在涂层浆料中的含量及涂层的厚度对于撕裂强力都有影响。由于废旧布料破碎之后的回收纤维在水性聚氨酯的分散体系中均匀分散，有助于受力分散，实现纤维对水性聚氨酯涂层的增强，拓展了废旧布料的回收利用技术领域，为废旧布料物理法回收利用提供一种良好的途径。
需要说明的是，尽管在本文中已经对上述各实施例进行了描述，但并非因此限制本发明的专利保护范围。因此，基于本发明的创新理念，对本文所述实施例进行的变更和修改，或利用本发明说明书及附图内容所作的等效结构或等效流程变换，直接或间接地将以上技术方案运用在其他相关的技术领域，均包括在本发明的专利保护范围之内。

Claims (10)

  1. 一种含废旧布料的回收纤维涂层浆料，其特征在于，以重量份数计，含有：0.5～8份废旧布料的回收纤维、95～110份水性聚氨酯和4～6份固化剂。
  2. 根据权利要求1所述的含废旧布料的回收纤维涂层浆料，其特征在于，所述废旧布料为化纤、棉、麻、丝绸、呢绒和混纺中的一种或多种。
  3. 根据权利要求1所述的含废旧布料的回收纤维涂层浆料，其特征在于，所述固化剂为异氰酸酯。
  4. 一种含废旧布料的回收纤维涂层的制备方法，其特征在于，包括以下步骤：
    制备回收纤维：将废旧布料破碎，过筛，得到回收纤维，所述废旧布料为化纤、棉、麻、丝绸、呢绒和混纺布料中的一种或多种；
    制备回收纤维涂层浆料：将0.5～8重量份所述回收纤维、95～110重量份水性聚氨酯和4～6重量份固化剂混合均匀，得到回收纤维涂层浆料，所述固化剂为异氰酸酯；
    印刷：将所述回收纤维涂层浆料印刷在基布或基板上，烘干，得到含废旧布料的回收纤维涂层。
  5. 根据权利要求4所述的制备方法，其特征在于，所述将废旧布料破碎采用纤维磨浆机，废旧布料的进料速度为60～300kg/h，纤维磨浆机的蒸汽压力为4～16bar。
  6. 根据权利要求4所述的制备方法，其特征在于，所述过筛采用20～40目筛子。
  7. 根据权利要求4所述的制备方法，其特征在于，所述水性聚氨酯的粒径为0.001～0.1μm。
  8. 根据权利要求4所述的制备方法，其特征在于，所述印刷为丝网印刷、制版印刷、辊涂、薄涂和刮涂中的一种，且印刷涂层浆料的厚度为0.1～1mm，烘干温度为60～80℃。
  9. 根据权利要求4所述的制备方法，其特征在于，所述制备回收纤维涂层浆料步骤之后还包括抽真空除泡，真空度为-0.095～0.1mPa。
  10. 一种含废旧布料的回收纤维涂层，其特征在于，根据权利要求4-9中任一项所述制备方法制备得到，所述回收纤维涂层的厚度为0.1～1.0mm。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104480733A (zh) * 2014-10-23 2015-04-01 合肥金伶俐服饰有限公司 一种pu球面革及其生产方法
CN106868896A (zh) * 2017-03-17 2017-06-20 福建华峰运动用品科技有限公司 一种织物上立体标识的制备方法
CN109517363A (zh) * 2018-11-12 2019-03-26 金陵科技学院 一种尼龙纤维增强聚氨酯复合材料及其制备方法
CN110644252A (zh) * 2019-10-28 2020-01-03 广东省建言智能系统有限公司 一种弹性面料及其制备方法
CN111235922A (zh) * 2020-01-16 2020-06-05 福建华峰运动用品科技有限公司 一种颗粒涂层布料及其制备方法
WO2020131026A1 (en) * 2018-12-18 2020-06-25 Hewlett-Packard Development Company, L.P. Fabric coating compositions

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2645303B2 (ja) * 1988-04-01 1997-08-25 王子製紙株式会社 コート印刷故紙の脱墨方法
JP3811895B2 (ja) * 2002-05-28 2006-08-23 株式会社大本組 ダイオキシン類を含む排水の処理方法
US20070048526A1 (en) * 2005-08-31 2007-03-01 Hoffman William F Iii Recycling compatible hard coating
CA2676961A1 (en) * 2009-08-26 2011-02-26 Carlo Fascio Resin pellet from recycled waste
CN101838471A (zh) 2009-12-30 2010-09-22 上海新天和树脂有限公司 纺织纤维增强树脂基复合材料及其生产工艺
CN106221547B (zh) * 2016-08-19 2018-02-09 汕头市龙湖昌丰化工有限公司 随机分布有纤维的可转移涂层及含有该涂层的防伪标签
CN108838191A (zh) * 2018-06-13 2018-11-20 四川大学 一种成品革废料纤维化的处理方法
CN110511428A (zh) * 2019-07-10 2019-11-29 广东省测试分析研究所（中国广州分析测试中心） 一种将废旧涤丝等含丝混纺织物分离回收的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104480733A (zh) * 2014-10-23 2015-04-01 合肥金伶俐服饰有限公司 一种pu球面革及其生产方法
CN106868896A (zh) * 2017-03-17 2017-06-20 福建华峰运动用品科技有限公司 一种织物上立体标识的制备方法
CN109517363A (zh) * 2018-11-12 2019-03-26 金陵科技学院 一种尼龙纤维增强聚氨酯复合材料及其制备方法
WO2020131026A1 (en) * 2018-12-18 2020-06-25 Hewlett-Packard Development Company, L.P. Fabric coating compositions
CN110644252A (zh) * 2019-10-28 2020-01-03 广东省建言智能系统有限公司 一种弹性面料及其制备方法
CN111235922A (zh) * 2020-01-16 2020-06-05 福建华峰运动用品科技有限公司 一种颗粒涂层布料及其制备方法

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