WO2012024875A1 - 一种提高定岛超细纤维合成革卫生性能的方法 - Google Patents

一种提高定岛超细纤维合成革卫生性能的方法 Download PDF

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WO2012024875A1
WO2012024875A1 PCT/CN2010/079988 CN2010079988W WO2012024875A1 WO 2012024875 A1 WO2012024875 A1 WO 2012024875A1 CN 2010079988 W CN2010079988 W CN 2010079988W WO 2012024875 A1 WO2012024875 A1 WO 2012024875A1
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synthetic leather
collagen
water
microfiber
fiber
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PCT/CN2010/079988
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English (en)
French (fr)
Inventor
张飞跃
马兴元
张晓镭
牛建民
刘东辉
许旭辉
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厦门泓信超细纤维材料有限公司
陕西科技大学
中国皮革和制鞋工业研究院
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Publication of WO2012024875A1 publication Critical patent/WO2012024875A1/zh

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03Polysaccharides or derivatives thereof
    • D06M15/11Starch or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/15Proteins or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423Amino-aldehyde resins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53Polyethers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/12Permeability or impermeability properties
    • D06N2209/121Permeability to gases, adsorption
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/12Permeability or impermeability properties
    • D06N2209/121Permeability to gases, adsorption
    • D06N2209/123Breathable
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/12Permeability or impermeability properties
    • D06N2209/126Permeability to liquids, absorption
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/14Properties of the materials having chemical properties
    • D06N2209/141Hydrophilic

Definitions

  • the present invention relates to synthetic leather, and in particular to a method for improving the hygienic performance of a fixed island microfiber synthetic leather. Background technique
  • Natural leather resources are limited, and there is a large pollution in the production process. Therefore, the development of simulated synthetic leather with excellent performance has become a human pursuit.
  • the microfiber synthetic leather obtained by impregnating polyurethane with a microfiber nonwoven fabric having a three-dimensional network structure is close to the internal microstructure, appearance texture, physical properties and wearing comfort. Natural leather. According to statistics, as of 2009, the production capacity of China's microfiber synthetic leather is about 80 million square meters, and the actual output is about 50 million square meters. More than 90% of high-end sports shoes in the world use microfiber synthesis
  • hygienic properties are usually characterized by water vapor permeability and gas permeability.
  • the water vapor permeability as described herein refers to the ability to allow water vapor to pass through the sample through the sample with high humidity to the air with less humidity;
  • the gas permeability described herein refers to the test under a certain pressure and for a certain period of time. The amount of air per unit area is expressed.
  • the moisture permeability and the permeability of the material determine the wearing comfort of the material, which is an important indicator of the hygienic performance of the microfiber synthetic leather.
  • the main components of the island-type microfiber synthetic leather include ultrafine fibers and polyurethane filled between fibers, ultrafine Fibers and polyurethanes have few hydrophilic groups on the polymer chain, which are difficult to interact with water molecules. Hydrogen bonds and other intermolecular forces, through the adsorption of water on the high humidity side, through the hydrophilic groups on the polymer chain. Pass to the low humidity side to desorb. Therefore, there are few hydrophilic groups in the island-type ultrafine fiber synthetic leather, which is a cause of poor water vapor permeability.
  • the island-type microfiber synthetic leather does not have grain similar to natural leather. To obtain the beautiful appearance of natural leather, it is necessary to make artificial dough. That is to say, the island-type microfiber synthetic leather needs to be artificially coated on the microfiber synthetic leather base fabric, and processed into a mouth o
  • Low-temperature plasma fiber modification technology which relies mainly on a specific low-temperature plasma device.
  • gas molecules such as nitrogen and ammonia are broken down to generate electrons, ions, a mixture of atoms and free radicals, which has high activity and can undergo graft reaction with the surface of ultrafine fibers to increase the hydrophilic groups on the ultrafine fibers and improve their water vapor permeability.
  • Technology is difficult to control, high energy consumption, and difficult to industrialize.
  • Coating perforation technology which includes physical acupuncture and laser drilling methods, and perforates the artificial grain coating to increase the permeability of the coating. This technique destroys the appearance of the synthetic leather and the performance of the coating, and the effect is poor. The process is currently in the laboratory research stage. Summary of the invention
  • the problem to be solved by the present invention is to provide a method for improving the hygienic performance of a fixed island microfiber synthetic leather.
  • the treated leather of the present invention has good water vapor permeability and gas permeability as compared with the prior art.
  • the present invention provides a method for improving the hygienic performance of a fixed island microfiber synthetic leather, comprising:
  • the step a) comprises:
  • the crosslinking agent in the step a2) is one or more of glutaraldehyde, acrylic acid graft modified glutaraldehyde, dicyandiamide resin or oxazolidine oxime.
  • the step c) comprises:
  • top layer slurry applying a top layer slurry on the release paper, and drying to form a top layer slurry, wherein the top layer slurry is mixed from the powdered collagen powder and the surface layer aqueous polyurethane in a ratio of 10 to 30:90 to 70 by weight. to make;
  • the surface layer with an adhesive layer paste, attaching the release paper with the adhesive layer slurry to the synthetic leather treated in step b), drying, peeling off the release paper
  • the ultrafine fiber synthetic leather containing the top coat layer is obtained; the adhesive layer slurry is obtained by mixing the powdered collagen powder and the adhesive layer aqueous polyurethane in a weight ratio of 10 to 30:90 to 70.
  • the modified collagen with hydrophilic group in the step a) is modified by grafting modified collagen, acrylic graft modified collagen, amino resin modified collagen or castor oil. sexual collagen.
  • the hydrophilic material in the step b) is one or more of polyethylene glycol, oxidized modified starch, melamine resin, and acrylic resin.
  • the ultrafine fiber synthetic leather is treated with collagen in a water bath environment, and the temperature of the water bath environment is 50 ° C to 80 ° C.
  • the microfiber synthetic leather is first washed with water before the step b).
  • the temperature of the first water washing is from 50 ° C to 80 ° C.
  • the ultrafine fiber synthetic leather is subjected to a second water washing after the step b), and the temperature of the second water washing is 50 ° C to 80 ° C.
  • the ultrafine fiber synthetic leather is a fixed island type microfiber synthetic leather.
  • the invention provides a method for improving the hygienic performance of the island microfiber synthetic leather.
  • the invention first treats the ultrafine fiber synthetic leather with the modified collagen, so that the modified collagen is uniformly infiltrated into the microfiber synthetic leather base.
  • the cloth is adsorbed on the ultrafine fibers, and then the ultrafine fibers are cross-linked and fixed by a crosslinking agent, so that the modified collagen is wrapped on the ultrafine fibers to form a microfiber core, and the modified collagen is used as a shell.
  • the composite fiber, the modified collagen coated on the surface of the composite fiber has many hydrophilic groups, such as an amino group and a carboxyl group, so that the hydrophilicity of the surface is equivalent to the hydrophilic property of the collagen fiber of the natural leather, thereby improving
  • the water vapor permeability of the microfiber synthetic leather the present invention further uses a hydrophilic material to be filled into the ultrafine fiber synthetic leather, and the hydrophilic material can further improve the water vapor permeability of the ultrafine fiber synthetic leather; finally, the present invention is directed to the ultrafine fiber.
  • Synthetic leather is subjected to face-forming treatment to form a coating with collagen fibers, which can form a microporous structure on the surface of the synthetic leather, and can improve the overall ultrafine The gas permeable dimensional synthetic leather and gas permeability.
  • Fig. 1 is a scanning electron micrograph of a microfiber synthetic leather treated in accordance with the present invention. detailed description
  • the invention provides a method for improving the hygienic performance of a fixed island microfiber synthetic leather, comprising: a) taking a microfiber synthetic leather treated with collagen to fix the collagen cross-linking to the superfine fiber synthetic leather. Fine fiber
  • the ultrafine fiber synthetic leather is preferably a fixed island type ultrafine fiber synthetic leather, such as a polyester Dingdao fiber polyurethane synthetic leather or a nylon Dingdao fiber polyurethane synthetic leather, but is not limited thereto.
  • said step a) preferably comprises:
  • the modified collagen with a hydrophilic group is preferably a polyurethane graft modified collagen, an acrylic graft modified collagen, an amino resin graft modified collagen, and a castor oil graft modified collagen protein.
  • the modified collagen of the present invention can be produced according to a method well known to a person skilled in the art or commercially available, and the present invention is not particularly limited.
  • the reaction of the step a) is preferably carried out in a water bath environment, specifically: loading the ultrafine fiber synthetic leather into a water simmering machine to add hot water and modified collagen, the amount of which is added to the hot water
  • the ultrafine fiber synthetic leather is 100% to 600%, preferably 100% to 550%, more preferably 100% to 500%, still more preferably 100% to 400%, and the hot water temperature is preferably 55 ° C to 75 °.
  • the ultrafine fiber synthetic leather is treated in a water mashing machine, and the hydrazine treatment time is preferably 20 to 100 minutes, more preferably It is 30 minutes to 80 minutes, more preferably 35 minutes to 65 minutes, and still more preferably 40 minutes to 60 minutes.
  • the step a2) is preferably carried out in a water bath environment, specifically: after the ultrafine fiber synthetic leather is treated in a water bath machine containing collagen, a cross-linking agent is added to the water mashing machine to mix the cross-linking agent and the collagen. After the protein acts, the collagen can be fixed into the microfiber synthetic leather.
  • the crosslinking agent is preferably added in an amount of from 1 wt% to 5 wt%, more preferably from 2 wt% to 4 wt%, still more preferably from 2.5 wt% to 3.5 wt%, of the ultrafine fiber synthetic leather.
  • the crosslinking agent may use a crosslinking agent well known to those skilled in the art, and specific examples may be glutaraldehyde, acrylic acid graft modified glutaraldehyde, dicyandiamide resin, and oxazolidine oxime.
  • the ultrafine fiber synthetic leather is subjected to the first washing treatment.
  • the weight ratio first accounts for the ultrafine fiber
  • the first washing of the hot water is preferably from 50% to 400%, preferably from 150% by weight to 350% by weight, more preferably from 200% by weight to 300% by weight, and the hot water temperature is preferably from 50 ° C to 80 ° C. It is more preferably 55 ° C to 75 ° C, still more preferably 60 ° C to 70 ° C.
  • the washing time is not particularly limited, and is preferably at least 5 minutes, more preferably 5 minutes to 20 minutes, still more preferably 5 minutes to 15 minutes, still more preferably 5 minutes to 10 minutes.
  • the hydrophilic material may be selected from hydrophilic materials well known to those skilled in the art, and the hydrophilic material is preferably one or more of polyethylene glycol, oxidized modified starch, melamine resin or acrylic resin.
  • the hot water temperature is preferably 50 ° C to 80 ° C, more preferably 55 ° C to 75 ° C, and the hot water addition amount is preferably It accounts for 100% to 500% by weight of the ultrafine synthetic leather, more preferably 100% to 400%, still more preferably 100% to 300%, still more preferably 150% to 280%.
  • the water jet machine is started, preferably for at least 5 minutes, more preferably for 5 minutes to 10 minutes.
  • the hydrophilic material is added and the rotation is continued, preferably for 30 minutes to 90 minutes, more preferably for 40 minutes to 80 minutes, more preferably for 50 minutes to 70 minutes.
  • the amount of the hydrophilic material added is from 10% to 30%, more preferably from 10% to 25%, still more preferably from 15% to 20% by weight based on the weight of the microfiber synthetic leather.
  • the hot water is discharged, and then the hot water is added for the second time to wash the microfiber synthetic leather, and the second hot water is preferably added to the superfine fiber synthetic leather.
  • the weight is from 100% to 400%, more preferably from 150% to 300%, still more preferably from 200% to 260%.
  • the temperature at which hot water is added during the second washing is preferably from 50 ° C to 80 ° C, more preferably from 55 ° C to 75 ° C, still more preferably from 60 ° C to 70 ° C.
  • the rotation time of the water jet machine is preferably at least 5 minutes, more preferably 5 minutes to 20 minutes, still more preferably 10 minutes to 15 minutes.
  • the hot water is discharged from the water smashing machine.
  • the microfiber synthetic leather base fabric is then removed from the water shovel and used.
  • the surface treatment is preferably as follows:
  • the surface layer slurry is uniformly mixed to be coated on a release paper, and the coating amount of the top layer slurry is 50 g/m 2 synthetic leather to 300 g/m 2 synthetic leather, preferably 100 g/m 2 synthetic leather to 200 g/ m 2 synthetic leather;
  • the drying temperature is preferably 130 ° C ⁇ 180 ° C, more preferably 135 ° C ⁇ 170 ° C, more preferably 140 ° C ⁇ 160 ° C;
  • the powdered collagen fiber and the adhesive layer aqueous polyurethane are uniformly mixed in a ratio of 10 to 30:90 to 70 by mass ratio to obtain an adhesive layer slurry coated on the release paper, and the coating ratio of the adhesive layer slurry is as follows. a ratio of 50 g / m 2 synthetic leather ⁇ 400 g / m 2 synthetic leather;
  • the release paper with the adhesive layer slurry is bonded to the ultrafine fiber synthetic leather filled with the hydrophilic material, and the surface layer is bonded to the adhesive layer by the adhesive force of the adhesive layer aqueous polyurethane.
  • the ultrafine fiber synthetic leather to which the release paper is attached is dried, and the drying temperature is preferably 130 ° C to 180 ° C, more preferably 135 ° C to 170 ° C, and still more preferably 140 ° C to 160 ° C. ;
  • the release paper is peeled off to obtain a microfiber synthetic leather with a coating of collagen fibers and a polyurethane composite.
  • the granular collagen fibers have a particle size of 100 ⁇ m to 500 ⁇ m;
  • the surface layer aqueous polyurethane may use an aqueous polyurethane for the surface layer well known to those skilled in the art, and the specific example may be Zhejiang Lishui.
  • the surface waterborne polyurethanes supplied by Nike Group are UNK PU-200, UNK PU-600, UNK PU-230, UNK PU-5050, but are not limited to this.
  • the adhesive layer aqueous polyurethane may use an aqueous polyurethane for the adhesive layer which is well known to those skilled in the art, and specific examples may be provided by the Zhejiang Lishui You Nike Group as UNK PU-350, UNK PU-150, UNK PU-
  • the adhesive layer of 320 is an aqueous polyurethane, but is not limited thereto.
  • the ultrafine fiber synthetic leather of the present invention uses a fixed island type ultrafine fiber synthetic leather supplied by Xiamen Yuxin Group, wherein the ultrafine fiber is nylon and the resin is polyurethane.
  • Polyurethane graft modified collagen, amino resin graft modified collagen, castor oil resin modified collagen was provided by Bayer Wuxi Leather Chemical Co., Ltd.; acrylic graft modified collagen was provided by Shijiazhuang Yafu Chemical Co., Ltd.
  • the surface layer aqueous polyurethane and the adhesive layer waterborne polyurethane used in the surface reaction are provided by Zhejiang Lishui You Nike Group Co., Ltd.;
  • Powdered collagen fibers with a particle size of 100 ⁇ m to 200 ⁇ m are used in the surface reaction; oxidized modified starch XX-369 oxidized starch supplied by Fuyang Xinxing Chemical Co., Ltd.
  • the hot water addition amount is 300% of the weight of the microfiber synthetic leather base fabric, and the water shovel is turned on for 6.5 minutes to discharge the liquid in the water shovel;
  • 11 parts of powdered collagen fibers and 74 parts of the adhesive layer water-based polyurethane UNKPU-380 were mixed as an adhesive layer slurry, and the adhesive layer slurry was coated at an amount of 72 g of the adhesive layer slurry per square meter of synthetic leather.
  • the release paper was dried at 145 ° C, and the release paper was peeled off to obtain a coated microfiber synthetic leather.
  • the first washing process is a washing process
  • the hot water added amount is 350% of the weight of the microfiber synthetic leather base cloth, and the water smashing machine is turned on for 6.5 minutes to discharge the liquid in the water boring machine;
  • the first washing process is a washing process
  • the second washing process Add 65 °C hot water to the water simmering machine, the hot water added amount is 340% of the weight of the microfiber synthetic leather base cloth, and the water smashing machine is turned on for 6.5 minutes to discharge the liquid in the water smashing machine;
  • the ultrafine fiber synthetic leather treated with Examples 1 to 4 and the untreated ultrafine fiber synthetic leather were tested for water vapor permeability and gas permeability, wherein the thickness of the synthetic leather and the mass per unit area were in accordance with industry standard QB. /T2888 test, synthetic leather permeability according to industry standard QB/T2799 test, synthetic leather water vapor permeability according to industry standard QB/T1811 test, all test results are listed in Table 1:

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Description

一种提高定岛超细纤维合成革卫生性能的方法
本申请要求于 2010 年 8 月 25 日提交中国专利局、 申请号为 201010262234.5、 发明名称为"一种提高定岛超细纤维合成革卫生性能的方法" 的中国专利申请的优先权, 其全部内容通过引用结合在本申请中。 技术领域
本发明涉及合成革,具体涉及一种提高定岛超细纤维合成革卫生性能的方 法。 背景技术
天然皮革资源有限, 而且生产过程中会产生较大的污染, 因此, 具有优良 性能的仿真合成革的开发成为人类的追求。在仿真皮革中, 以具有三维网状结 构的超细纤维非织造布为增强材料通过浸渍聚氨酯得到的超细纤维合成革从 内部微观结构、外观质感、物理特性和人们穿着舒适性方面都接近了天然皮革。 据统计, 截至 2009年, 中国超细纤维合成革的产能约为 8000万平方米, 实际 产量约为 5000万平方米。 全球已有 90%以上的高档运动鞋采用超细纤维合成
可以和天然皮革相媲美, 成为天然皮革的最佳替代品。但是定岛型超细纤维合 成革的卫生性能和天然皮革有较大的差距,导致定岛型超细纤维合成革难以作 为高品质的服装和鞋用材料。如何提高定岛型高超纤纤维的合成革的卫生性能 就是其尚未突破的瓶颈技术之一。
对于定岛型超细纤维合成革, 卫生性能通常用透水气性和透气性来表征。 本文所述透水气性是指让水蒸气由湿度较大的空气中通过试样透过到湿度较 小空气中的能力; 本文所述透气性是指以在一定压力下和一定时间内, 试样单 位面积所透过的空气量来表示。透水气性和透气性的大小, 决定了材料的穿用 舒适性, 是超细纤维合成革的卫生性能的重要指标。 目前,造成定岛型超细纤维合成革卫生性能差的主要原因有以下两点: 首 先, 定岛型超细纤维合成革的主要组分包括超细纤维和填充在纤维间的聚氨 酯, 超细纤维和聚氨酯的高分子链上的亲水基团很少, 难以和水分子作用, 借 助氢键和其它分子间作用力,在高湿度一侧吸附水分后,通过高分子链上亲水 基团传递到低湿度一侧解吸。 所以, 定岛型超细纤维合成革中亲水基团很少, 是造成透水气性能差的原因。 而对于天然皮革来说, 由于其主要成分为胶原纤 维,胶原纤维上则具有大量的氨基和羧基,这些氨基和羧基具有良好的亲水性, 是水传递的 "阶梯石", 天然皮革能够很好的将水分吸附, 并完成水分的传递。 所以天然皮革具有良好的透水气性。其次, 定岛型超细纤维合成革没有类似天 然皮革的粒面, 要得到天然皮革美丽外观, 就必须进行人工造面。 也就是说, 定岛型超细纤维合成革需要在超细纤维合成革基布上制造人工涂层,加工成成 口口 o
在现有技术中, 为了提高超细纤维合成革的透水气性和透气性, 已经公开 了多种提高定岛型超细纤维合成革方法, 比较常用的有: (1 )采用纤维水解改 性技术, 这种技术主要是依靠酸或碱的作用, 对超细纤维进行适度水解, 增加 超细纤维上的亲水基团,改善其透水气性。但是水解会造成纤维分子链的断裂, 使纤维的强度降低,从而对定岛型超细纤维合成革的物理机械性能产生较大的 不良影响, 该工艺目前仅仅处于实验室的研究阶段。 (2 )低温等离子纤维改性 技术, 这种技术主要依靠特定的低温等离子装置, 当外加电压达到气体的着火 电压时, 氮气、 氨气等气体分子被击穿, 产生包括电子、 各种离子、 原子和自 由基在内的混合体, 这个混合体具有很高的活性, 可以和超细纤维表面发生接 枝反应, 增加超细纤维上的亲水基团, 改善其透水气性, 但是这种技术难于控 制、 能耗高, 难于工业化生产。 (3 )涂层打孔技术, 这种技术包括物理的针刺 打孔和激光打孔方法, 在人工粒面的涂层上打孔, 增加涂层的透气性。 这种技 术会破坏合成革的外观和涂层的性能, 效果差, 该工艺目前也处于实验室的研 究阶段。 发明内容
本发明要解决的问题在于提供一种提高定岛超细纤维合成革卫生性能的 方法,与现有技术相比,本发明处理后的合成革具有良好的透水气性和透气性。 为了解决以上技术问题,本发明提供一种提高定岛超细纤维合成革卫生性 能的方法, 包括:
a )取超细纤维合成革用带有亲水基团的改性胶原蛋白处理, 使带有亲水 基团的改性胶原蛋白交联固定到所述超细纤维合成革中的超细纤维上;
b )将亲水材料渗入到所述经过胶原蛋白处理后的超细纤维合成革中; c )对所述经过渗有亲水材料的超细纤维合成革进行造面处理, 形成带有 胶原纤维的涂层。
优选的, 所述步骤 a ) 包括:
al )在超细纤维合成革中渗入带有亲水基团的改性胶原蛋白,使带有亲水 基团的改性胶原蛋白吸附到所述超细纤维合成革中的超细纤维上;
a2 )在交联剂的作用下, 使所述胶原蛋白交联固定到所述的超细纤维上。 优选的, 所述步骤 a2 ) 中的交联剂为戊二醛、 丙烯酸接枝改性戊二醛、 双氰胺树脂或恶唑烷鞣剂中的一种或多种。
优选的, 所述步骤 c ) 包括:
cl )在离型纸上涂覆面层浆料, 干燥形成面层, 所述面层浆料由粉状胶原 蛋白粉末与面层水性聚氨酯按照重量比为 10〜30:90〜70的比例混合而成;
c2 )在所述面层上涂覆粘合层浆料, 将所述带有粘合层浆料的离型纸贴合 到步骤 b )处理后的合成革上, 干燥处理, 剥离离型纸得到含有面层涂层的超 细纤维合成革;所述粘合层浆料由粉状胶原蛋白粉末与粘合层水性聚氨酯按照 重量比为 10〜30:90〜70的比例混合而成。
优选的, 所述步骤 a ) 中的带有亲水基团的改性胶原蛋白为聚氨酯接枝改 性胶原蛋白、 丙烯酸接枝改性胶原蛋白、氨基树脂改性胶原蛋白或蓖麻油接枝 改性胶原蛋白。
优选的, 所述步骤 b ) 中亲水材料为聚乙二醇、 氧化改性淀粉、 三聚氰胺 树脂、 丙烯酸树脂中的一种或多种。
优选的, 所述步骤 a ) 中在水浴环境中用胶原蛋白处理超细纤维合成革, 所述水浴环境的温度为 50°C〜80°C。
优选的, 在所述步骤 b )之前对所述超细纤维合成革进行第一次水洗, 所 述第一次水洗的温度为 50°C〜80°C。
优选的, 在所述步骤 b )之后对所述超细纤维合成革进行第二次水洗, 所 述第二次水洗的温度为 50°C〜80°C。
优选的, 所述超细纤维合成革为定岛型超细纤维合成革
本发明提供一种提高定岛超细纤维合成革卫生性能的方法,本发明先用改 性胶原蛋白对超细纤维合成革进行处理,使改性胶原蛋白均匀的渗入到超细纤 维合成革基布吸附在超细纤维上, 然后通过交联剂对超细纤维进行交联固定, 从而使改性胶原蛋白包裹在超细纤维上, 形成以超细纤维为核, 以改性胶原蛋 白为壳的复合纤维,这种复合纤维表面包覆的改性胶原蛋白具有很多的亲水基 团,如氨基和羧基,因此表面的亲水性和天然皮革的胶原纤维的亲水性能相当, 从而提高了超细纤维合成革的透水气性;本发明进一步使用亲水材料填充到超 细纤维合成革中,亲水材料可以进一步提高超细纤维合成革的透水气性;最后, 本发明对超细纤维合成革进行造面处理, 形成带有胶原纤维的涂层, 这样可以 在合成革的表面形成微孔结构,可以整体改善超细纤维合成革的透水气性和透 气性。 附图说明
图 1为本发明处理后的超细纤维合成革的扫描电镜照片。 具体实施方式
为了进一步了解本发明, 下面结合实施例对本发明优选实施方案进行描 述, 但是应当理解, 这些描述只是为进一步说明本发明的特征和优点, 而不是 对本发明权利要求的限制。
本发明提供一种提高定岛超细纤维合成革卫生性能的方法, 包括: a )取超细纤维合成革用胶原蛋白处理, 使胶原蛋白交联固定到所述超细 纤维合成革中的超细纤维上;
b )将亲水材料渗入到所述经过胶原蛋白处理后的超细纤维合成革中; c )对所述经过渗有亲水材料的超细纤维合成革进行造面处理, 形成带有 胶原纤维的涂层。 按照本发明, 对于所述超细纤维合成革, 优选为定岛型超细纤维合成革, 例子如涤纶定岛纤维聚氨酯合成革,锦纶定岛纤维聚氨酯合成革,但不限于此。
按照本发明, 所述步骤 a )优选包括:
al )在超细纤维合成革中渗入带有亲水基团的改性胶原蛋白,使带有亲水 基团的改性胶原蛋白吸附到所述超细纤维合成革中的超细纤维上;
a2 )在交联剂的作用下, 使所述胶原蛋白交联固定到所述的超细纤维上。 所述带有亲水基团的改性胶原蛋白优选为聚氨酯接枝改性胶原蛋白、丙烯 酸接枝改性胶原蛋白、 氨基树脂接枝改性胶原蛋白和蓖麻油接枝改性胶原蛋 白。对于本发明所述的改性胶原蛋白, 可以按照本领域技术人员熟知的方法制 备, 或者从市场上购得, 对此本发明并无特别限制。
按照本发明, 所述步骤 al ) 的反应优选在水浴环境中进行, 具体为: 将 超细纤维合成革装入水揉机加入热水和改性胶原蛋白,所述热水的添加量占所 述超细纤维合成革的 100%〜600%,优选为 100%〜550%,更优选为 100%〜500%, 更优选为 100%〜400%, 热水温度优选为 55 °C〜75 °C , 更优选为 60°C〜70°C , 更 优选为 65 °C〜70°C ; 所述改性胶原蛋白的添加量优选占所述超细纤维合成革的 lwt%〜4wt%, 更优选为 1.5wt%〜3.5wt%, 更优选为 2wt%〜3wt%, 加入胶原蛋 白后, 将超细纤维合成革在水揉机中揉搓处理, 揉搓处理时间优选为 20〜100 分钟, 更优选为 30分钟〜 80分钟, 更优选为 35分钟〜 65分钟, 更优选为 40 分钟〜 60分钟。
所述步骤 a2 )优选在水浴环境中进行, 具体为: 将超细纤维合成革在含 有胶原蛋白的水揉机中进行处理后,在水揉机中加入交联剂混合, 交联剂与胶 原蛋白作用后, 可以将胶原蛋白固定到超细纤维合成革中。 按照本发明, 所述 交联剂的添加量优选占所述超细纤维合成革的 lwt%〜5wt% , 更优选为 2wt%〜4wt%, 更优选为 2.5wt%〜3.5wt%。 所述交联剂可以使用本领域技术人 员熟知的交联剂, 具体例子可以为戊二醛、 丙烯酸接枝改性戊二醛、 双氰胺树 脂和恶唑烷鞣剂。
按照本发明, 采用交联剂将胶原蛋白交联固定到超细纤维合成革表面以 后, 对超细纤维合成革进行第一次洗涤处理。 优选的, 先加入重量比占超细纤 维合成革重量比的 100%〜400%、 优选为 150wt%〜350wt% , 更优选为 200wt%〜300wt%的热水进行第一次洗涤, 热水温度优选为 50°C〜80°C , 更优选 为 55 °C〜75 °C , 更优选为 60°C〜70°C。 对于洗涤时间, 本发明并无特别限制, 优选为至少 5分钟, 更优选为 5分钟〜 20分钟, 更优选为 5分钟〜 15分钟, 更 优选为 5分钟〜 10分钟。
按照本发明, 进行第一次洗涤处理后, 需要在超细纤维合成革表面填充亲 水材料, 填充的亲水材料能够吸收水分, 进一步提到超细纤维合成革的透水气 性。 按照本发明, 亲水材料可以选择本领域技术人员熟知的亲水材料, 亲水材 料优选为聚乙二醇、氧化改性淀粉、三聚氰胺树脂或丙烯酸树脂中的一种或多 种。
在超细纤维合成革表面填充亲水材料具体按照如下步骤进行:
在第一次洗涤之后, 将水排出, 然后向水揉机中加入热水, 热水温度优选 为 50°C〜80°C , 更优选为 55 °C〜75 °C , 热水添加量优选占超细纤维合成革重量 的 100%〜500%, 更优选为 100%〜400%, 更优选为 100%〜300%, 更优选为 150%〜280%。 加入热水后, 开动水揉机, 优选转动至少 5分钟, 更优选转动 5 分钟〜 10分钟。 加入热水转动后, 加入亲水材料, 继续转动, 优选转动 30分 钟〜 90分钟, 更优选转动 40分钟〜 80分钟, 更优选转动 50分钟〜 70分钟。 亲 水材料的添加量占所述超细纤维合成革重量的 10%〜30% , 更优选为 10%〜25%, 更优选为 15%〜20%。
加入亲水材料在水揉机中转动后,将热水排出, 然后加入热水第二次洗涤 超细纤维合成革,第二次洗涤时热水的添加量优选占所述超细纤维合成革重量 的 100%〜400%, 更优选为 150%〜300%, 更优选为 200%〜260%。 按照本发明, 第二次洗涤时加入热水的温度优选为 50°C〜80°C , 更优选为 55 °C〜75 °C , 更优 选为 60°C〜70°C。 第二次洗涤时, 水揉机的转动时间优选为至少 5分钟, 更优 选为 5分钟〜 20分钟, 更优选为 10分钟〜 15分钟。 第二次洗涤后, 将热水从水 揉机中排出。 然后从水揉机中去除超细纤维合成革基布, 备用。 纤维和水性聚氨酯的复合材料, 造面处理优选如下步骤:
取粉状胶原纤维和面层水性聚氨酯树脂按照质量比为 10〜30: 90〜70的比 例混合均匀得到面层浆料涂覆在离型纸上, 面层浆料的涂覆量按照 50g/m2合 成革〜 300g/m2合成革, 优选按照 100g/m2合成革〜 200g/m2合成革;
将离型纸表面的面层浆料干燥, 干燥温度优选为 130°C〜180°C , 更优选为 135°C〜170°C , 更优选为 140°C〜160°C ;
取粉状胶原纤维和粘结层水性聚氨酯按照质量比为 10〜30: 90〜70的比例 混合均匀得到粘合层浆料涂覆在离型纸上, 粘合层浆料的涂覆比例按照 50 g /m2合成革〜 400g/m2合成革的比例涂覆;
将所述带有粘合层浆料的离型纸与所述填充有亲水性材料的超细纤维合 成革进行贴合,依靠粘结层水性聚氨酯的粘结力,将面层贴合到超细纤维合成 革的表面;
将所述贴合有离型纸的超细纤维合成革干燥, 干燥温度优选为 130°C〜180 °C , 更优选为 135°C〜170°C , 更优选为 140°C〜160°C ;
将离型纸剥离,即可得到带有胶原纤维和聚氨酯复合材料涂层的超细纤维 合成革。
按照本发明, 所述粉状胶原纤维的粒度为 100 μ ηι〜500 μ ηι; 所述面层水 性聚氨酯可以使用本领域技术人员熟知的用于面层的水性聚氨酯,具体例子可 以为浙江丽水优耐克集团提供的型号为 UNK PU-200、 UNK PU-600、 UNK PU-230、 UNK PU-5050的面层水性聚氨酯, 但不限于此。 所述粘合层水性聚 氨酯可以使用本领域技术人员熟知的用于粘合层的水性聚氨酯,具体例子可以 为浙江丽水优耐克集团提供的型号为 UNK PU-350、 UNK PU-150、 UNK PU-320的粘合层水性聚氨酯, 但不限于此。
以下以具体实施例说明本发明的技术方案,但是本发明的保护范围不受以 下实施例的限制。
本发明以下实施例使用以下原料:
本发明超细纤维合成革使用由厦门泓信集团提供的定岛型超细纤维合成 革, 其中超细纤维为尼龙, 树脂为聚氨酯。
聚氨酯接枝改性胶原蛋白、氨基树脂接枝改性胶原蛋白、 蓖麻油树脂改性 胶原蛋白由拜耳无锡皮革化工有限公司提供;丙烯酸接枝改性胶原蛋白由石家 庄市亚富化工有限公司提供。 造面反应中使用的面层水性聚氨酯和粘合层水性聚氨酯由浙江丽水优耐 克集团公司提供;
造面反应中使用粒度为 100 μ m〜200 μ m的粉状胶原纤维; 氧化改性淀粉 由沁阳市新兴化工有限公司提供的 XX-369氧化淀粉。
实施例 1
基布改性处理工序
取 3平方米定岛超细纤维基布, 称量;
将定岛超细纤维基布放在水揉机中, 加入温度为 60°C的热水, 热水添加 量为基布重量的 320%,然后在向水揉机中加入占基布重量 6.5%的聚氨酯接枝 改性胶原蛋白, 开启水揉机转动 35分钟; 向水揉机中加入占基布重量 1.1%的 戊二醛树脂交联剂, 开启水揉机转动 35分钟, 然后将水揉机内的液体排出; 第一次水洗工序:
向水揉机中添加 55 °C的热水, 热水添加量占超细纤维合成革基布重量的 300%, 开启水揉机转动 6.5分钟, 将水揉机中的液体排出;
填充亲水材料工序:
向水揉机中加入 55 °C的热水, 热水添加量占超细纤维合成革基布重量的 290%, 开启水揉机转动 6.5分钟, 向水揉机内加入 12%的聚乙二醇, 开启水 揉机转动 40分钟, 将水揉机中的液体排出;
第二次水洗工序:
向水揉机中加入 55 °C的热水, 热水添加量占超细纤维合成革基布重量的
320%, 开启水揉机转动 6分钟, 将水揉机中的液体排出; 从水揉机中取出定 岛超细纤维合成革基布, 加热至 150°C烘干备用;
造面工序:
取 10份粉状胶原纤维和 72份面层水性聚氨酯 UNKPU-200混合作为面层 浆料,、按照每平方米定岛纤维合成革 60克的面层浆料量将面层浆料涂覆在离 型纸上, 然后在 150°C干燥;
取 12份粉状胶原纤维和 72份粘合层水性聚氨酯 UNKPU-380混合作为粘 合层浆料, 按照每平方米合成革 72克的粘合层浆料量将粘合层浆料涂覆在离 型纸上, 然后在 145 °C干燥, 将离型纸剥离下来得到带有涂层的超细纤维合成 革, 扫描电镜照片如图 1所示。
实施例 2
基布改性处理工序
取 3平方米定岛超细纤维基布, 称量;
将定岛超细纤维基布放在水揉机中, 加入温度为 60°C的热水, 热水添加 量为基布重量的 320%,然后在向水揉机中加入占基布重量 6.5%的丙烯酸接枝 改性胶原蛋白, 开启水揉机转动 35分钟; 向水揉机中加入占基布重量 1.1%的 双氰胺树脂交联剂, 开启水揉机转动 35分钟, 然后将水揉机内的液体排出; 第一次水洗工序:
向水揉机中添加 55 °C的热水, 热水添加量占超细纤维合成革基布重量的
300%, 开启水揉机转动 6.5分钟, 将水揉机中的液体排出;
填充亲水材料工序:
向水揉机中加入 55 °C的热水, 热水添加量占超细纤维合成革基布重量的 290%, 开启水揉机转动 6.5分钟, 向水揉机内加入 12%的 XX-369氧化改性淀 粉, 开启水揉机转动 40分钟, 将水揉机中的液体排出;
第二次水洗工序:
与实施例 1相同;
造面工序:
取 15份粉状胶原纤维和 70份面层水性聚氨酯 UNKPU-200混合作为面层 浆料, 按照每平方米定岛纤维合成革 60克的面层浆料量将面层浆料涂覆在离 型纸上, 然后在 150°C干燥;
取 11份粉状胶原纤维和 74份粘合层水性聚氨酯 UNKPU-380混合作为粘 合层浆料, 按照每平方米合成革 72克的粘合层浆料量将粘合层浆料涂覆在离 型纸上, 然后在 145 °C干燥, 将离型纸剥离下来得到带有涂层的超细纤维合成 革。
实施例 3
基布改性处理工序
取 3平方米定岛超细纤维基布, 称量;
将定岛超细纤维基布放在水揉机中, 加入温度为 60°C的热水, 热水添加 量为基布重量的 320%,然后在向水揉机中加入占基布重量 6.5%的脲酸树脂接 枝改性胶原蛋白, 开启水揉机转动 35分钟; 向水揉机中加入占基布重量 1.1% 的丙烯酸介质改性戊二醛交联剂, 开启水揉机转动 35分钟, 然后将水揉机内 的液体排出;
第一次水洗工序:
向水揉机中添加 60°C的热水, 热水添加量占超细纤维合成革基布重量的 350%, 开启水揉机转动 6.5分钟, 将水揉机中的液体排出;
填充亲水材料工序:
向水揉机中加入 55 °C的热水, 热水添加量占超细纤维合成革基布重量的 290%, 开启水揉机转动 6.5分钟, 向水揉机内加入 15%三聚氰胺树脂, 开启 水揉机转动 40分钟, 将水揉机中的液体排出;
第二次水洗工序:
与实施例 1相同;
造面工序:
与实施例 1相同。
实施例 4
基布改性处理工序:
取 3平方米定岛超细纤维基布, 称量;
将定岛超细纤维基布放在水揉机中, 加入温度为 60°C的热水, 热水添加 量为基布重量的 320%,然后在向水揉机中加入占基布重量 6.5%的蓖麻油接枝 改性胶原蛋白, 开启水揉机转动 35分钟; 向水揉机中加入占基布重量 1.1%的 恶唑烷交联剂, 开启水揉机转动 35分钟, 然后将水揉机内的液体排出;
第一次水洗工序:
与实施例 1相同
填充亲水材料工序:
向水揉机中加入 55 °C的热水, 热水添加量占超细纤维合成革基布重量的 290%, 开启水揉机转动 6.5分钟, 向水揉机内加入 15%丙烯酸树脂, 开启水 揉机转动 40分钟, 将水揉机中的液体排出;
第二次水洗工序: 向水揉机中添加 65 °C的热水, 热水添加量占超细纤维合成革基布重量的 340%, 开启水揉机转动 6.5分钟, 将水揉机中的液体排出;
造面工序:
与实施例 1相同。
对实施例 1〜实施例 4处理后的超细纤维合成革与未经处理的超细纤维合 成革进行透水气性和透气性的性能测试, 其中,合成革厚度和单位面积质量按 照行业标准 QB/T2888测试, 合成革透气性按照行业标准 QB/T2799测试, 合 成革透水气性按照行业标准 QB/T1811测试, 所有测试结果列于表 1 :
表 1 本发明处理后和处理前的超细纤维合成革性能测试结果
Figure imgf000013_0001
表 1的结果表明, 与未处理的超细纤维合成革相比, 本发明处理后的超细 纤维合成革的透水气性和透气性能得到明显的改善。
以上对本发明所提供的超细纤维合成革的方法进行了详细介绍。本文中应 用了具体个例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是 用于帮助理解本发明的方法及其核心思想。应当指出, 对于本技术领域的普通 技术人员来说, 在不脱离本发明原理的前提下, 还可以对本发明进行若干改进 和修饰, 这些改进和修饰也落入本发明权利要求的保护范围内。

Claims

权 利 要 求
1、 一种提高定岛超细纤维合成革卫生性能的方法, 其特征在于, 包括: a )取超细纤维合成革用胶原蛋白处理, 使胶原蛋白交联固定到所述超细 纤维合成革中的超细纤维上;
b )将亲水材料渗入并吸附到所述经过胶原蛋白处理后的超细纤维合成革 中;
c )对所述经过渗有亲水材料的超细纤维合成革进行造面处理, 形成带有 胶原纤维的涂层。
2、 根据权利要求 1所述的方法, 其特征在于, 所述步骤 a ) 包括: al )在超细纤维合成革中渗入胶原蛋白, 使胶原蛋白吸附到所述超细纤维 合成革中的超细纤维上;
a2 )在交联剂的作用下, 使所述胶原蛋白交联固定到所述的超细纤维上。
3、 根据权利要求 2所述的方法, 其特征在于, 所述步骤 a2 ) 中的交联剂 为戊二醛、丙烯酸接枝改性戊二醛、双氰胺树脂或恶唑烷鞣剂中的一种或多种。
4、 根据权利要求 1所述的方法, 其特征在于, 所述步骤 c ) 包括: cl )在离型纸上涂覆面层浆料, 干燥形成面层, 所述面层浆料由粉状胶原 纤维与面层水性聚氨酯按照重量比为 10〜30:90〜70的比例混合而成;
c2 )在所述面层上涂覆粘合层浆料, 将所述带有粘合层浆料的离型纸贴合 到步骤 b )处理后的合成革上, 干燥处理, 剥离离型纸得到含有面层涂层的超 细纤维合成革;所述粘合层浆料由粉状胶原蛋白粉末与粘合层水性聚氨酯按照 重量比为 10〜30:90〜70的比例混合而成。
5、 根据权利要求 1 所述的方法, 其特征在于, 所述步骤 a ) 中胶原蛋白 为聚氨酯接枝改性胶原蛋白、 丙烯酸接枝改性胶原蛋白、氨基树脂改性胶原蛋 白或蓖麻油接枝改性胶原蛋白。
6、 根据权利要求 1至 5任一项所述的方法, 其特征在于, 所述步骤 b ) 中亲水材料为聚乙二醇、 氧化改性淀粉、 三聚氰胺树脂、 丙烯酸树脂中的一种 或多种。
7、 根据权利要求 1 所述的方法, 其特征在于, 所述步骤 a ) 中在水浴环 境中用胶原蛋白处理超细纤维合成革, 所述水浴环境的温度为 50°C〜80°C。
8、 根据权利要求 1至 5任一项所述的方法, 其特征在于, 在所述步骤 b ) 之前对所述超细纤维合成革进行第一次水洗, 所述第一次水洗的温度为 50°C〜80°C。
9、 根据权利要求 8所述的方法, 其特征在于, 在所述步骤 b )之后对所 述超细纤维合成革进行第二次水洗, 所述第二次水洗的温度为 50°C〜80°C。
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