WO2020029594A1 - 一种模拟天然头层皮的超纤革的制备方法及应用 - Google Patents

一种模拟天然头层皮的超纤革的制备方法及应用 Download PDF

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Publication number
WO2020029594A1
WO2020029594A1 PCT/CN2019/080853 CN2019080853W WO2020029594A1 WO 2020029594 A1 WO2020029594 A1 WO 2020029594A1 CN 2019080853 W CN2019080853 W CN 2019080853W WO 2020029594 A1 WO2020029594 A1 WO 2020029594A1
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Prior art keywords
leather
polyurethane
natural
fabric
slurry
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PCT/CN2019/080853
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English (en)
French (fr)
Inventor
王乐智
王晓磊
马金美
郭彦杰
李正奇
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山东同大海岛新材料股份有限公司
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Publication of WO2020029594A1 publication Critical patent/WO2020029594A1/zh

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial 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)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial 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 non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/26—Vehicles, transportation
    • D06N2211/261—Body finishing, e.g. headliners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/26—Vehicles, transportation
    • D06N2211/263—Cars

Definitions

  • the present application relates to the field of preparation methods of artificial synthetic leather, and in particular, to a preparation method and application of a super-fiber leather that simulates a natural scalp.
  • Microfiber synthetic leather is currently the closest product to natural leather in terms of internal microstructure, appearance and feel, surpassing natural leather in terms of physical and chemical properties.
  • Natural head skin has obvious density gradient ratio of upper and lower layers and uniform folds.
  • the goal of microfiber synthetic leather is to achieve the density gradient ratio and gradient structure of upper and lower layers of head skin.
  • the density of the upper and lower layers of the conventionally produced microfiber synthetic leather is uniform and there is no gradient structure of the natural scalp, which cannot truly replace the natural scalp.
  • the existing technology CN102304858B provides a super-fiber high-imitation scalp leather synthesis A method for preparing leather, and a synthetic leather with strong gradient feeling, full hand feeling, fine surface folds, and strong toughness after bending is obtained.
  • a first object of the present application is to provide a method for preparing a superfiber leather that simulates a natural head layer skin.
  • the preparation method of the present application can improve the simulation degree of the obtained ultrafine fiber synthetic leather, and achieve the density gradient, wrinkle effect of natural leather, and Feel.
  • the second object of the present application is to provide a microfiber leather that simulates the natural scalp leather obtained by the preparation method of the present application.
  • a third object of the present application is to provide an application of the microfiber leather that simulates a natural scalp.
  • a method for preparing a super-fiber leather simulating a natural scalp skin comprises: polyester and / or polyether polyurethane slurry adjusted with a solvent for viscosity adjustment, and 0-50% high-density filler.
  • the surface of one side of the non-woven fabric made of the ultra-fine ultra-fine composite fiber is once-bladed to form the upper dense layer, and a grey fabric is obtained; or, the water-based polyurethane slurry adjusted with a thickener or water for viscosity adjustment is matched with 0 ⁇ 50% high-density filler, one-time blade coating on one side surface of a non-woven fabric made of sea-island type ultra-fine composite fibers to form an upper dense layer, and obtain a grey fabric;
  • the polyester and / or polyether polyurethane slurry adjusted with the solid content of the solvent is mixed with the penetrant and the curing agent to obtain an impregnated slurry; the side of the obtained gray fabric which is not blade-coated is impregnated with the impregnated slurry To form a lower layer loose layer; or, use a thickening agent or water to adjust the viscosity of the aqueous resin slurry as an impregnating slurry, and impregnate the impregnated slurry on the side of the obtained gray fabric with the impregnating slurry to form a lower layer looseness Floor;
  • the semi-finished synthetic leather is treated with a hot toluene solution, and then subjected to extrusion treatment; after washing and drying, a microfiber leather that simulates a natural head skin is obtained; or, the semi-finished synthetic leather is treated with a hot alkaline solution, and then subjected to extrusion treatment and cleaning After being neutralized and dried, a microfiber leather simulating a natural scalp is obtained.
  • the sea-island type ultrafine composite fiber is obtained by melt-blending spinning of nylon 6 / PET and LLDPE / COPET; wherein the island component is nylon 6 / PET and the sea component is LLDPE or COPET; more preferably, the mass ratio of nylon 6 / PET to LLDPE / COPET is 50:50 to 65:35.
  • the preparation of the non-woven fabric includes: opening, carding, and laying the sea-island type ultra-fine composite fibers, and then needle-punching and strengthening the fabric to obtain a non-woven fabric;
  • the heat setting temperature is 110 to 150 ° C .; and / or, the apparent density of the obtained non-woven fabric is ⁇ 0.2 g / cm 3 .
  • the number of laying layers is 25 to 50 layers, the average weight is 300 to 900 g / m 2 ; and / or, the needling frequency is 400 to 1800 thorns / min and the needling density is 800. ⁇ 2000 thorns / m 2 ; non-woven vehicle speed is 1.5 to 5 m / min; and / or, the apparent density of the prepared non-woven fabric is 0.2 to 0.35 g / cm 3 .
  • the one-time doctor blade coating is performed under conditions of a temperature of 10 to 50 ° C. and a humidity of 5 to 50%; more preferably, the one-time doctor blade can be controlled by heating and blowing.
  • the ambient humidity of the coating further preferably, the heating includes: electric heating, natural gas heating, and thermal oil heating.
  • the high-density filler includes one or more of light calcium carbonate, heavy calcium carbonate, talc, elastic powder, wollastonite, or modified natural protein. .
  • the preparation method further includes a step of finishing the prepared microfiber leather that simulates a natural scalp; more preferably, the finishing includes: grinding One or more processes of wool, dyeing, softening, kneading, waterproofing, breathable, dry veneer, surface, polishing, water kneading, embossing and ironing.
  • the present application also provides a microfiber leather that mimics the natural scalp leather obtained by the preparation method described in the application.
  • the gradient density ratio of the upper dense layer to the lower loose layer is (1.15 to 1.8): 1.
  • the application also provides the application of the microfiber leather simulating the natural head layer leather in footwear, automobile interiors, luggage, apparel or decorative fabrics;
  • the clothing or decorative fabric comprising the microfiber leather that simulates the natural head skin as described in this application.
  • This application provides a new production method of ultra-fine fiber polyurethane synthetic leather; by redesigning the production process and technological scheme, the ultra-fine fiber polyurethane synthetic leather is completely simulated with the gradient structure, folds and feel of the natural head layer skin, and has surpassed The physical and chemical properties of the natural top leather fully meet the requirements for replacing natural leather, further expanding the application field of superfine fiber synthetic leather. At the same time, the synthesis of the synthetic leather of this application has positive significance in terms of reducing pollution and protecting animals.
  • this application provides a new process for preparing a superfiber leather that simulates natural head skin, especially in the early invention (CN102304858B)
  • CN102304858B On the basis of technology, a more advanced production scheme is proposed, which better solves the density gradient ratio and gradient structure of superfine fiber synthetic leather to simulate the natural head layer skin, which greatly improves the simulation degree and technical level of superfine fiber synthetic leather.
  • melt blending Using nylon 6 / PET and LLDPE (linear low density polyethylene) / COPET (alkali soluble polyester) as raw materials, spinning through melt blending (specifically, it can include steps such as melt extrusion, cooling and blowing, drawing and oiling) , Spinning different types of sea-island ultrafine composite fibers;
  • the mass ratio of the raw material nylon 6 / PET and LLDPE / COPET is: (50-65): (50-35) (based on the total weight of the raw materials being 100 parts);
  • the mass ratio of nylon 6 / PET to LLDPE / COPET may be, but is not limited to, 50:50, 55:45, 60:40, or 65:35.
  • the island component is nylon 6 or PET, and the sea component is linear low-density polyethylene or COPET.
  • the process parameters of the non-woven fabric are designed, and the grey fabric used in the post-production process is subjected to the setting treatment by heating and cold pressing.
  • a needling process is used to obtain a needling nonwoven fabric
  • the steps can be referred to as follows: after opening, carding and laying of sea-island type ultra-fine composite fibers, they are needle-punched and consolidated into a cloth, and then heat-set to obtain a non-woven fabric;
  • the number of layers is 25 to 50 (for example, it can be, but not limited to, 30, 35, 40, or 45), and the average weight is 300 to 900 g / m 2 (for example, it can be, but not limited to, 350, 400) , 450, 500, 550, 600, 650, 700, 750, 800 or 850g / m 2 etc.);
  • acupuncture frequency of 400 to 1800 acupuncture / min (for example, it can be, but not limited to, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, or 1700 Thorn / min, etc.);
  • Acupuncture density of 800-2000 thorns / m 2 (for example, but not limited to 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, or 1900 thorns / m 2, etc.);
  • the heat setting process parameters are: the heat setting temperature is 110 to 150 ° C (for example, it can be, but not limited to, 120, 125, 130, 135, 140, or 145 ° C, etc.);
  • the speed of the non-woven fabric is 1.5 to 5 m / min (for example, it can be, but is not limited to, 2, 2.5, 3, 3.5, 4, or 4.5 m / min).
  • the apparent density of the nonwoven fabric obtained in step (2) is ⁇ 0.2 g / cm 3 , and preferably 0.2 to 0.35 g / cm 3 (for example, it may be, but not limited to, 0.25 or 0.3 g / cm 3, etc.).
  • polyester polyurethane emulsion or polyether polyurethane emulsion with a solid content of 25-50% for example, it can be, but not limited to, 30, 35, 40, or 45%, etc.
  • dimethylformamide as the solvent to disperse the emulsion.
  • Adjust the viscosity to 20000 ⁇ 90,000CPS / 25 ° C (for example, it can be, but not limited to, 30,000, 40,000, 50000, 60,000, 70,000 or 80,000CPS / 25 ° C, etc.);
  • an aqueous polyurethane slurry as a raw material, and adjust the viscosity to 5000-70000CPS / 25 ° C by adding a thickener or water (for example, it can be, but not limited to, 10,000, 15000, 20000, 30,000, 40,000, 50,000, or 60,000 CPS / 25 °C);
  • step (2) use a high-precision coating knife to scrape the surface of one side of the non-woven fabric obtained in step (2), so that all the polyurethane enters the non-woven fabric through processes such as penetration and rolling. In the middle, an upper dense layer is formed.
  • the high-density filler used is any of the fillers that can be used for superfiber impregnation, such as light calcium carbonate, heavy calcium carbonate powder, microcrystalline cellulose, talc, elastic powder, wollastonite, and modified natural protein.
  • the fillers such as light calcium carbonate, heavy calcium carbonate powder, microcrystalline cellulose, talc, elastic powder, wollastonite, and modified natural protein.
  • the temperature and humidity of the environment need to be controlled during the blade coating process of any method.
  • the ambient temperature of the blade coating should be controlled at 10-50 ° C (for example, it can be, but not limited to, 15, 20, 25, 30, 35, 40, or 45 ° C, etc.)
  • the humidity should be controlled at 5-50% (for example, it can be For, but not limited to, 10, 15, 20, 25, 30, 35, 40, or 45%, etc.);
  • the humidity of the environment can be controlled by means of dehumidification by heating air, and specifically, heating by electric heating, natural gas heating, and heat-conducting oil heating can be adopted.
  • Dimethylformamide is added to the polyester or polyether polyurethane slurry, and the solid content of the slurry is adjusted to 3 to 26% (for example, it can be, but not limited to, 5, 10, 15, 20, or 25% Wait);
  • step (3) The side of the grey fabric obtained in step (3) that is not subjected to doctor blade coating is fully impregnated with the impregnating slurry to form a lower layer loose layer (the other surface opposite to the one-side surface of doctor blade coating).
  • water-based resin and adjust the viscosity to 500 ⁇ 20,000CPS / 25 °C by adding thickener or water (for example, it can be, but not limited to, 1000, 2000, 3000, 5000, 7000, 10000, 12000, 15000, 17000, or 19000CPS / 25 °C, etc.);
  • step (3) The side of the grey fabric obtained in step (3), which is not subjected to doctor blade coating, is fully impregnated with the impregnating slurry to form a lower layer loose layer.
  • the main component of the penetrant used is one or more of succinate sulfonate, higher fatty acid ester salt, sulfonate salt and sulfate ester salt, and compounded with polyol ester surfactant;
  • the main component of the curing agent used is: sorbitol oleate or silicone surfactant.
  • step (4) The impregnated grey fabric obtained in step (4) is again subjected to a high-precision coating knife to scrape the surface of the grey fabric once-scraped (that is, the upper surface after one-squeegee coating); for the blade coating liquid and the blade coating process, refer to Step (3) is performed.
  • polyester polyurethane emulsion or polyether polyurethane emulsion with a solid content of 25-50% for example, it can be, but not limited to, 30, 35, 40, or 45%, etc.
  • dimethylformamide as the solvent to disperse the emulsion.
  • Adjust the viscosity to 20,000 ⁇ 90,000CPS / 25 °C (for example, it can be, but not limited to, 30,000, 40,000, 50000, 60,000, 70,000 or 80,000CPS / 25 °C, etc.); then, match the viscosity-adjusted polyurethane emulsion with 0 ⁇ 50% ( (5 to 20%) of high-density filler is preferably applied on the surface (upper surface) of the non-woven fabric obtained in step (3) by one-time blade coating using a high-precision coating knife;
  • an aqueous polyurethane slurry as a raw material, and adjust the viscosity to 5000-70000CPS / 25 ° C by adding a thickener or water (for example, it can be, but not limited to, 10,000, 15000, 20000, 30,000, 40,000, 50,000, or 60,000 CPS / 25 °C);
  • a high-density filler of 0 to 50% (preferably 5 to 20%)
  • a high-precision coating knife is used to apply the non-woven fabric obtained in step (3) to one side of the surface (the upper surface) that has been subjected to one-time blade coating. ).
  • the high-density fillers used are any of the fillers that can be used in superfiber impregnation, such as light calcium carbonate, heavy calcium carbonate powder, microcrystalline cellulose, talc, elastic powder, wollastonite, and modified natural protein.
  • the fillers such as light calcium carbonate, heavy calcium carbonate powder, microcrystalline cellulose, talc, elastic powder, wollastonite, and modified natural protein.
  • the ambient temperature of the blade coating should be controlled at 10-50 ° C (for example, it can be, but not limited to, 15, 20, 25, 30, 35, 40, or 45 ° C, etc.), and the humidity should be controlled at 5-50% (for example, it can be (But not limited to 10, 15, 20, 25, 30, 35, 40, or 45%, etc.); further, heating blast dehumidification can be used to control the ambient humidity, and electric heating, natural gas heating, and Heating oil is used for heating.
  • the second-squeegee coated slurry enters the non-woven fabric and is fully combined with the first-squeegee coated slurry.
  • the grey cloth obtained by processing the polyester or polyether resin obtained in step (5) has a concentration of 10 to 45% (for example, it can be, but is not limited to, 15, 20, 25, 30, 35, or 40%, etc.) and the temperature is In a mixed aqueous solution of dimethylformamide at 15 to 50 ° C (for example, but not limited to 20, 30, 35, 40, or 45 ° C, etc.), the polyurethane is solidified, and the cell structure formed by adjusting the concentration and temperature of the polyurethane is used. And aperture size. After repeated backwashing of multiple channels of fresh water, the residual dimethylformamide in the base cloth is removed to obtain a semi-finished synthetic leather.
  • a concentration of 10 to 45% for example, it can be, but is not limited to, 15, 20, 25, 30, 35, or 40%, etc.
  • the temperature is In a mixed aqueous solution of dimethylformamide at 15 to 50 ° C (for example, but not limited to 20, 30, 35, 40, or 45 ° C, etc.), the polyure
  • the gray cloth processed by the aqueous resin obtained in step (5) is dried by using ultrasonic or heating and drying to obtain a semi-finished synthetic leather.
  • the semi-finished synthetic leather obtained in step (6) is impregnated with hot toluene at a temperature of 75 to 95 ° C (for example, it can be, but is not limited to, 80, 85, or 90 ° C, etc.), and then repeatedly extruded with a roller to make the island
  • the low-density polyethylene of the sea component in the fiber is dissolved and separated.
  • the island component in the sea-island fiber is opened into ultra-fine fibers and forms a certain gap and slip space with the polyurethane.
  • the residual toluene is removed by boiling water washing, and dried to obtain Microfiber leather with a highly natural head skin structure (for products based on nylon 6 / PET and LLDPE).
  • the semi-finished synthetic leather obtained in step (6) is repeatedly extruded through a roller through a NaOH aqueous solution having a temperature of 60 to 100 ° C. and a concentration of 5 to 15%, and the sea component COPET in the sea-island fiber is made for 15 to 60 minutes. Dissolved and separated, the island components in the sea island fibers are opened into ultra-fine fibers, and form a certain gap and slip space with the polyurethane. After sufficient washing and neutralization, and drying, ultra-high natural head skin structure is obtained. Fiber leather (for products made from nylon 6 / PET and COPET).
  • the finishing includes sanding, dyeing, softening, kneading, dry veneer, surface treatment, polishing, water rubbing, Embossed and scald. Processed into products required by customers.
  • microfiber leather that simulates the natural head layer leather produced by the above method can completely simulate the gradient structure, wrinkles and feel of the natural head layer leather, and has physicochemical properties that surpass the natural head layer leather, so it can completely replace natural leather. use;
  • the gradient density ratio of the upper dense layer (formed by primary and secondary blade coating) of the superfiber leather simulating natural head skin and the lower layer of loose layer is (1.15 to 1.8): 1 (for example, it can be , But not limited to 1.2, 1.3, 1.4, 1.5, 1.6, or 1.7: 1, etc.).
  • the microfiber leather that simulates the natural head layer leather produced in this application can be further applied to clothing or decorative fabrics, for example, it is used to prepare clothing, shoes, and hats , Gloves, and handbags, or use them as decorative fabrics for home improvement and car decoration.
  • the sea-island ultrafine composite fiber obtained in step (1) is used to make a non-woven fabric with a width of 1700 mm and a thickness of 1.9 to 2.0 mm.
  • the needling frequency is 800 to 1200 thorns / min, and the needling density is 1000 to 1500 thorns / m. 2
  • the number of paving layers is 40
  • the average weight is 500g / m 2
  • the non-woven speed is 2.5m / min.
  • Heat setting control thickness is 1.8mm
  • apparent density is 0.28g / m 3 .
  • step (3) The grey cloth is impregnated sufficiently with the impregnated slurry to form a lower loose layer.
  • step (4) The impregnated non-woven fabric obtained in step (4) was subjected to the same method as in step (3), and again passed a high-precision coating knife, and polyurethane and microcrystalline fibers were applied to scrape the upper surface of the non-woven fabric with a gap of 0.05 mm. After the large-arc scraper or the pair of rollers are pressed, the second-squeegee coated slurry enters the non-woven fabric and is fully combined with the first-squeegee coated slurry.
  • the gray cloth obtained in step (5) was passed through a mixed aqueous solution of dimethylformamide having a concentration of 18% and a temperature of 30 ° C. to coagulate the polyurethane. Then, after repeated backwashing through multiple channels of fresh water, the dimethylformamide remaining in the base cloth is removed to obtain a semi-finished synthetic leather.
  • the semi-finished synthetic leather obtained in step (6) is heated and heated at 85 ° C, and then repeatedly pressed by a roller to dissolve and separate the sea component low-density polyethylene in the sea-island fibers.
  • the ultrafine fiber is washed with boiling water to remove residual toluene, and dried to obtain a microfiber leather with a highly natural head skin structure.
  • the finishing includes sanding, dyeing, softening, kneading, dry veneer, surface treatment, polishing, water rubbing, Embossing and scalding to process into products that customers need.
  • the nylon 6 chips and COPET are mixed according to a mass ratio of 60:40, melt-extruded by a screw extruder, and the temperature range is controlled from 245 to 285 ° C. After cooling and blowing, drafting (draft ratio is 4 times), oiling ( The oil concentration was 5.5%), and 8D ⁇ 51mm sea-island type ultrafine composite fibers were produced.
  • COPET should be pretreated. The pre-crystallization temperature is 120 ° C, the crystallization time is 1.5 hours, the drying temperature is 150 ° C, and the drying time is 4 hours. A dry slice with a moisture content of ⁇ 0.03% is obtained.
  • the sea-island type ultra-fine composite fiber prepared in step (1) is used to produce a non-woven fabric with a width of 1650 mm and a thickness of 2.0 to 2.1 mm.
  • the needling frequency is 500 to 1000 thorns / min, and the needling density is 1000 to 1500 thorns / m. 2 , the number of laying layers is 45, the average weight is 560g / m 2 , and the non-woven fabric speed is 2.5m / min.
  • Heat setting control thickness is 1.85mm, apparent density is 0.3g / m 3 .
  • step (3) The obtained grey fabric was fully impregnated with the impregnating slurry to form a lower loose layer.
  • step (4) The impregnated non-woven fabric obtained in step (4) was subjected to the same method as in step (3) again with a high-precision coating knife, and the polyurethane slurry was mixed with light calcium carbonate, and the upper surface of the cloth was scraped with a gap of 0.1. mm, after passing through a large arc scraper or a pair of rollers, the second-squeegee coated slurry enters the non-woven fabric and is fully combined with the first-squeegee coated slurry.
  • the gray cloth obtained in step (5) was passed through a mixed aqueous solution of dimethylformamide having a concentration of 10% and a temperature of 35 ° C. to coagulate the polyurethane. After repeated backwashing of multiple channels of fresh water, the residual dimethylformamide in the base cloth is removed to obtain a semi-finished synthetic leather.
  • the semi-finished synthetic leather obtained in step (6) is dissolved and separated by adding the sea component COPET to the sea-island fiber through a hot alkali aqueous solution having a concentration of 10% and a temperature of 95 ° C. for about 40 minutes, and the sea-island fiber is opened. It becomes ultra-fine fiber, and after multiple passes of washing, acid neutralization and washing, the residual lye is removed, and after drying, a super-fiber leather with a highly natural head skin structure is prepared.
  • the finishing includes sanding, dyeing, softening, kneading, dry veneer, surface treatment, polishing, water rubbing, Embossed and scald. Processed into products required by customers.
  • the nylon 6 chip and the linear low density polyethylene are mixed according to a mass ratio of 55:45, and melt-extruded by a screw extruder to control the temperature range of 240-285 ° C. After cooling and blowing, the draft is drawn (the draft ratio is 5 times) , Oiling (oil concentration 6%), 6D ⁇ 51mm sea-island type ultra-fine composite fiber was produced.
  • the sea-island type ultrafine composite fiber obtained in step (1) is used to produce a non-woven fabric with a width of 1650 mm and a thickness of 1.7 to 1.8 mm.
  • the needling frequency is 500 to 1000 thorns / min, and the needling density is 800 to 1200 thorns / m. 2 , 25 layers, average weight 400g / m 2 , non-woven speed 3m / min.
  • Heat setting control thickness is 1.35mm, apparent density is 0.3g / m 3 .
  • step (4) The impregnated non-woven fabric obtained in step (4) was subjected to the same method as in step (3), and again passed a high-precision coating knife.
  • the polyurethane slurry was mixed with light calcium carbonate, and the upper surface of the cloth was scraped with a gap of 0.05. mm, after passing through a large arc scraper or a pair of rollers, the second-squeegee coated slurry enters the non-woven fabric and is fully combined with the first-squeegee coated slurry.
  • the grey cloth obtained in step (5) is dried in an environment of 120 to 140 ° C. for 10 to 15 minutes to completely cure and crosslink the aqueous resin to obtain a semi-finished synthetic leather.
  • the semi-finished synthetic leather obtained in step (6) is heated and heated at 90 ° C. and repeatedly pressed by a roller to dissolve and separate the low-density polyethylene in the sea component of the sea-island fiber. Fine fibers, washed with boiling water to remove residual toluene, and dried to obtain a microfiber leather with a highly natural head skin structure.
  • the finishing includes sanding, dyeing, softening, kneading, dry veneer, surface treatment, polishing, water rubbing, Embossed and scald. Processed into products required by customers.
  • microfiber leather samples that simulate the natural scalp skin prepared in Examples 1 and 2 of this application are compared with the dermis and the samples 1 and 2 obtained according to the method of the prior art CN102304858B example, and the results are shown in the following table:
  • microfiber leather simulating the natural head layer leather prepared by the method of the present application has good softness, tear resistance, and bending resistance performance, and the gradient of the upper and lower layers is closer to that of the dermis.

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  • Wood Science & Technology (AREA)
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Abstract

本申请提供了一种模拟天然头层皮的超纤革的制备方法及应用。本申请制备方法包括：海岛超细纤维的纺制、无纺布的制作、聚氨酯的刮涂、聚氨酯的含浸、聚氨酯的二次刮涂、凝固和水洗以及海岛纤维的减量开纤等步骤。本申请中，通过重新设计生产流程和工艺方案，实现超细纤维聚氨酯合成革完全模拟天然头层皮的梯度结构、褶皱和手感，并具有超越天然头层皮革的物理化学性能，完全具备替代天然皮革的条件，进一步扩大了超细纤维合成革的应用领域。

Description

一种模拟天然头层皮的超纤革的制备方法及应用
相关申请的交叉引用
本申请要求于2018年08月06日提交中国专利局的申请号为201810887585.1、名称为“一种模拟天然头层皮的超纤革的制备方法及应用”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
本申请涉及人工合成革的制备方法领域，具体而言，涉及一种模拟天然头层皮的超纤革的制备方法及应用。
背景技术
超细纤维合成革是目前内部微观结构、外观形态和手感上最接近天然皮革的产品，在物理化学性能等方面超过天然皮革。天然头层皮具有明显的上下层密度梯度比和均匀的褶皱，目前超细纤维合成革追求的目标也正是为了实现头层皮的上下层密度梯度比及梯度结构。然而，常规生产的超细纤维合成革上下层密度呈均一性并且没有天然头层皮的梯度结构，无法真正取代天然头层皮。
为了解决现有超纤维合成革所存在的上述问题，研究人员也进行了研发探索，并提出了新的制备工艺，例如，现有技术CN102304858B就提供了一种超细纤维高仿头层皮合成革的制备方法，并得到了一种梯度感强、手感丰满、表面折纹细腻并且弯折后韧性强的合成革。
虽然诸如如上示例的现有技术中通过工艺改良得到了具有一定天然头层皮质感的合成革材料，然而，这些合成材料在仿真度和质感等感官方面，仍然有待提升。
有鉴于此，特提出本申请。
发明内容
本申请的第一目的在于提供一种模拟天然头层皮的超纤革的制备方法，本申请制备方法能够提高所得到超细纤维合成革的仿真度，达到天然皮革的密度梯度、褶皱效果和手感。
本申请的第二目的在于提供一种由本申请制备方法所得到的模拟天然头层皮的超纤革。
本申请的第三目的在于提供一种本申请模拟天然头层皮的超纤革的应用。
为了实现本申请的上述目的，特采用以下技术方案：
一种模拟天然头层皮的超纤革的制备方法，包括：将以溶剂进行粘度调节后的聚酯和/或聚醚型聚氨酯浆料，搭配0～50％的高密度填料，在由海岛型超细复合纤维所制成无纺布的一侧表面进行一次刮涂以形成上层致密层，并得到坯布；或者，将以增稠剂或水进行粘 度调节后的水性聚氨酯浆料，搭配0～50％的高密度填料，在由海岛型超细复合纤维所制成无纺布的一侧表面进行一次刮涂以形成上层致密层，并得到坯布；
将以溶剂进行固含量调节后的聚酯和/或聚醚型聚氨酯浆料与渗透剂以及固化剂搅拌混匀，得到含浸浆料；将所得坯布未进行刮涂的一侧以含浸浆料浸渍，以形成下层疏松层；或者，将以增稠剂或水进行粘度调节后的水性树脂浆料为含浸浆料，将所得坯布未进行刮涂的一侧以含浸浆料浸渍，以形成下层疏松层；
在进行一次刮涂的一侧，再进行一次刮涂，得到聚氨酯加工的坯布；
将聚氨酯加工的坯布凝固水洗，得到半成品合成革；或者，将聚氨酯加工的坯布进行干燥处理，得到半成品合成革；
将半成品合成革以热甲苯溶液处理后，进行挤压处理；清洗干燥后，得到模拟天然头层皮的超纤革；或者，将半成品合成革以热碱液处理后，进行挤压处理，清洗并中和，干燥后，得到模拟天然头层皮的超纤革。
优选地，本申请所述的制备方法中，所述海岛型超细复合纤维由尼龙6/PET与LLDPE/COPET熔融共混纺丝得到；其中，所述岛成分为尼龙6/PET，海成分为LLDPE或COPET；更优选地，尼龙6/PET与LLDPE/COPET的质量比为50:50～65:35。
优选地，本申请所述的制备方法中，无纺布的制备包括：将海岛型超细复合纤维开松、梳理和铺网后，针刺加固成布，然后热定型，得到无纺布；其中，热定型的温度为110～150℃；和/或，所得无纺布的表观密度≥0.2g/cm 3。
优选地，本申请所述的制备方法中，铺网层数为25～50层，平均克重300～900g/m 2；和/或，针刺频率400～1800刺/min并且针刺密度800～2000刺/m 2；无纺布车速为1.5～5m/min；和/或，所制备的无纺布表观密度为0.2～0.35g/cm 3。
优选地，本申请所述的制备方法中，所述一次刮涂在温度为10～50℃，湿度为5～50％的条件下进行；更优选地，可以采用加热鼓风的方式控制一次刮涂的环境湿度；进一步优选地，所述加热包括：电加热、天然气加热以及导热油加热。
优选地，本申请所述的制备方法中，所述高密度填料包括：轻质碳酸钙、重质碳酸钙、滑石粉、弹力粉、硅灰石或者改性天然蛋白中的一种或几种。
优选地，本申请所述的制备方法中，所述制备方法还进一步包括将所制得的模拟天然头层皮的超纤革进行后整理的步骤；更优选地，所述后整理包括：磨毛、染色、化柔、揉皮、防水、透气、干法贴面、表处、抛光、水揉、压纹以及烫光中的一种或几种工序。
同时，本申请还提供了由本申请所述的制备方法得到的模拟天然头层皮的超纤革。
优选地，本申请所述的模拟天然头层皮的超纤革中，所述上层致密层与下层疏松层的梯度密度比为(1.15～1.8):1。
进一步地，本申请也提供了本申请所述的模拟天然头层皮的超纤革在鞋类、汽车内饰、箱包、服饰或装饰面料中的应用；
或者，包含本申请所述的模拟天然头层皮的超纤革的服饰或装饰面料。
与现有技术相比，本申请的有益效果为：
本申请提供了一种全新的超细纤维聚氨酯合成革生产方法；通过重新设计生产流程和工艺方案，实现超细纤维聚氨酯合成革完全模拟天然头层皮的梯度结构、褶皱和手感，并具有超越天然头层皮革的物理化学性能，完全具备替代天然皮革的条件，进一步扩大了超细纤维合成革的应用领域。同时，本申请合成革的合成在减少污染以及动物保护等方面具有积极意义。
具体实施方式
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，所描述的实施例仅是本申请的一部分，而不是全部实施例。同时，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
有鉴于现有仿皮超纤革在产品性能和感官上所存在的不足之处，本申请特提供了一种模拟天然头层皮的超纤革制备新工艺，特别是在前期发明(CN102304858B)技术的基础上，提出更为先进的生产方案，更好地解决了超细纤维合成革模拟天然头层皮密度梯度比和梯度结构，大大提高了超细纤维合成革的仿真度和技术水平。
具体地，本申请所提供的新工艺步骤参考如下：
(1)海岛超细纤维的纺制
以尼龙6/PET与LLDPE(线性低密度聚乙烯)/COPET(碱溶性聚酯)为原材料，通过熔融共混纺丝(具体地，可以包括熔融挤出、冷却吹风、牵引以及上油等步骤)，纺制出不同规格的海岛型超细复合纤维；
其中，原料尼龙6/PET与LLDPE/COPET的质量比为：(50～65):(50～35)(以原料质量总和为100份计)；
具体地，尼龙6/PET与LLDPE/COPET的质量比可以为，但不限于：50:50，55:45，60:40或者65:35等。
其中，所得到的海岛超细纤维中，岛组分为尼龙6或PET，海组分为线性低密度聚乙烯或COPET。
(2)无纺布的制作
以步骤(1)中得到的海岛超细纤维，根据成品要求，设计无纺布的工艺参数，制作后 工序使用的坯布，通过加热和冷压进行定型处理。
优选地，此步骤中，是采用针刺加固的工艺，以得到针刺无纺布；
其步骤可参考如下：海岛型超细复合纤维开松、梳理和铺网后，针刺加固成布，然后热定型，得到无纺布；
其中，铺网层数为25～50层(例如可以为，但不限于30、35、40或者45层等)，平均克重300～900g/m 2(例如可以为，但不限于350、400、450、500、550、600、650、700、750、800或者850g/m 2等)；
针刺加固的工艺参数为：针刺频率400～1800刺/min(例如可以为，但不限于500、600、700、800、900、1000、1100、1200、1300、1400、1500、1600或者1700刺/min等)；
针刺密度800～2000刺/m 2(例如可以为，但不限于900、1000、1100、1200、1300、1400、1500、1600、1700、1800或者1900刺/m 2等)；
热定型工艺参数为：热定型温度110～150℃(例如可以为，但不限于120、125、130、135、140或者145℃等)；
无纺布车速为：1.5～5m/min(例如可以为但不限于2、2.5、3、3.5、4或者4.5m/min等)。
由步骤(2)所得无纺布的表观密度≥0.2g/cm 3，优选为0.2～0.35g/cm 3(例如可以为，但不限于0.25或者0.3g/cm 3等)。
(3)聚氨酯的刮涂
选用固含量为25～50％(例如可以为，但不限于30、35、40或者45％等)的聚酯型聚氨酯乳液或聚醚型聚氨酯乳液，以二甲基甲酰胺为溶剂，将乳液调节粘度至20000～90000CPS/25℃(例如可以为，但不限于30000、40000、50000、60000、70000或者80000CPS/25℃等)；
然后，将如上粘度调节后的聚氨酯乳液搭配0～50％的高密度填料(根据产品最终功能要求，选择合适填料质量比，以起到调整PU微孔结构、赋予成品革一定的功能性、改善成品革手感、同时降低一定的生产成本的作用)，使用高精度涂刀，刮涂于步骤(2)得到的无纺布的一侧表面(上表面)，通过渗透和碾压等工序，使得聚氨酯全部进入无纺布中，形成上层致密层。
或者以水性聚氨酯浆料为原料，通过添加增稠剂或水，将浆料调节粘度至5000-70000CPS/25℃(例如可以为，但不限于10000、15000、20000、30000、40000、50000或者60000CPS/25℃)；
然后，搭配0～50％的高密度填料，使用高精度涂刀，刮涂于步骤(2)得到的无纺布的一侧表面，通过渗透和碾压等工序，使得聚氨酯全部进入无纺布中，形成上层致密层。
此步骤中，所用高密度填料为轻质碳酸钙、重质碳酸钙粉、微晶纤维素、滑石粉、弹力粉、硅灰石和改性天然蛋白等所有可用于超纤含浸的填料中的任一种或者两种及以上的组合。
同时，此步骤中，在任意方法的刮涂工艺过程中，都需要对于环境的温度和湿度进行控制。具体地，刮涂的环境温度要控制在10～50℃(例如可以为，但不限于15、20、25、30、35、40或者45℃等)，湿度控制在5～50％(例如可以为，但不限于10、15、20、25、30、35、40或者45％等)；
进一步地，可以采用加热鼓风除湿的方式对于环境湿度进行控制，具体可以采用电加热、天然气加热和导热油加热等方式进行加热。
(4)聚氨酯的含浸
将二甲基甲酰胺加入到聚酯型或聚醚型聚氨酯浆料中，将浆料的固含量调节至3～26％(例如可以为，但不限于5、10、15、20或者25％等)；
然后，加入0.5～3％(与固含量调节后聚氨酯浆料的质量占比；例如可以为，但不限于1、1.5、2或者2.5％等)的渗透剂以及0.5～4％的固化剂(与固含量调节后聚氨酯浆料的质量占比；例如可以为，但不限于1、1.5、2、2.5、3或者3.5％等)，搅拌均匀制得含浸浆料；
将步骤(3)中得到的坯布未进行刮涂的一侧由含浸浆料浸渍充分，形成下层疏松层(与刮涂的一侧表面相对的另一侧表面)。
或者使用水性树脂，通过添加增稠剂或水，调节粘度至500～20000CPS/25℃(例如可以为，但不限于1000、2000、3000、5000、7000、10000、12000、15000、17000或者19000CPS/25℃等)；
将步骤(3)中得到的坯布未进行刮涂的一侧由含浸浆料浸渍充分，形成下层疏松层。
此步骤中，所用渗透剂的主要成分为琥珀酸酯磺酸盐、高级脂肪酸酯盐、磺酸化盐和硫酸酯盐中的一种或几种，复配多元醇酯类表面活性剂；同时，所用固化剂的主要成分为：山梨糖醇油酸酯或有机硅表面活性剂。
(5)聚氨酯的二次刮涂
将步骤(4)得到的浸渍后坯布，再次经过高精度涂刀，涂刮于坯布一次刮涂侧的表面(即一次刮涂后的上表面)；所用刮涂液和刮涂工艺，可参照步骤(3)进行。
具体地，刮涂的具体步骤可参考如下：
选用固含量为25～50％(例如可以为，但不限于30、35、40或者45％等)的聚酯型聚氨酯乳液或聚醚型聚氨酯乳液，以二甲基甲酰胺为溶剂，将乳液调节粘度至20000～90000CPS/25℃(例如可以为，但不限于30000、40000、50000、60000、70000或者80000CPS/25℃ 等)；然后，将如上粘度调节后的聚氨酯乳液搭配0～50％(优选为5～20％)的高密度填料，使用高精度涂刀，刮涂于步骤(3)得到的无纺布进行过一次刮涂的一侧表面(上表面)；
或者以水性聚氨酯浆料为原料，通过添加增稠剂或水，将浆料调节粘度至5000-70000CPS/25℃(例如可以为，但不限于10000、15000、20000、30000、40000、50000或者60000CPS/25℃)；
然后，搭配0～50％(优选为5～20％)的高密度填料，使用高精度涂刀，刮涂于步骤(3)得到的无纺布进行过一次刮涂的一侧表面(上表面)。
如上步骤中，所用高密度填料为轻质碳酸钙、重质碳酸钙粉、微晶纤维素、滑石粉、弹力粉、硅灰石和改性天然蛋白等所有可用于超纤含浸的填料中的任一种或者两种及以上的组合。
同样地，在如上任意方法的刮涂工艺过程中，都需要对于环境的温度和湿度进行控制。具体地，刮涂的环境温度要控制在10～50℃(例如可以为，但不限于15、20、25、30、35、40或者45℃等)，湿度控制在5～50％(例如可以为，但不限于10、15、20、25、30、35、40或者45％等)；进一步地，可以采用加热鼓风除湿的方式对于环境湿度进行控制，具体可以采用电加热、天然气加热和导热油加热等方式进行加热。
然后，经过大圆弧刮刀或对辊挤压，使得二次刮涂的浆料进入无纺布坯布，与第一次刮涂的浆料充分结合。
(6)凝固和水洗
将步骤(5)得到的聚酯型或聚醚型树脂加工的坯布通过浓度为10～45％(例如可以为，但不限于15、20、25、30、35或者40％等)并且温度为15～50℃(例如可以为，但不限于20、30、35、40或者45℃等)的二甲基甲酰胺的混合水溶液中，使得聚氨酯凝固，利用浓度和温度调节聚氨酯形成的泡孔结构及孔径大小。经过多道淡水反复积压清洗，去除基布中残留的二甲基甲酰胺，得到半成品合成革。
或者采用超声波或加热烘干的方式，将步骤(5)得到的水性树脂加工的坯布进行干燥处理，得到半成品合成革。
(7)海岛纤维的减量开纤
将步骤(6)得到的半成品合成革，以温度为75～95℃(例如可以为，但不限于80、85或者90℃等)的热甲苯进行浸渍处理，然后以轧辊反复挤压，使海岛纤维中的海成分低密度聚乙烯溶解分离，海岛纤维中的岛成分开纤成为超细纤维，并与聚氨酯形成一定的空隙和滑移空间，经过沸水清洗除去残留甲苯，烘干后，制得具有高度天然头层皮结构的超纤革(针对于以尼龙6/PET和LLDPE为原料的产品)。
或者，将步骤(6)得到的半成品合成革，通过温度为60～100℃并且浓度为5～15％ 的NaOH水溶液，通过轧辊反复挤压，经15～60min，使海岛纤维中的海成分COPET溶解分离，海岛纤维中的岛成分开纤成为超细纤维，并与聚氨酯形成一定的空隙和滑移空间，经过充分水洗和中和，烘干后，制得具有高度天然头层皮结构的超纤革(针对于以尼龙6/PET和COPET为原料的产品)。
(8)后整理
对步骤(7)中制得的高度天然头层皮结构的超纤革进行后整理，后整理包括磨毛、染色、化柔、揉皮、干法贴面、表处、抛光、水揉、压纹和烫光。加工成客户需要的产品。
由如上方法所制得的模拟天然头层皮的超纤革能够完全模拟天然头层皮的梯度结构、褶皱和手感，并具有超越天然头层皮革的物理化学性能，因而完全可以替代天然皮革而使用；
进一步地，本申请模拟天然头层皮的超纤革的上层致密层(由一次刮涂和二次刮涂形成)与下层疏松层的梯度密度比为(1.15～1.8):1(例如可以为，但不限于1.2、1.3、1.4、1.5、1.6或者1.7:1等)。
由于具有高仿真度和优异的使用性能，也使得本申请所制得的模拟天然头层皮的超纤革能够进一步应用于服饰或装饰面料中，例如，将其用于制备服装、鞋、帽、手套和提包等服饰，或者将其作为家装和汽车装饰等装饰面料而使用。
实施例1
(1)海岛超细纤维的纺制
将尼龙6切片和线性低密度聚乙烯按照50:50的质量比进行混合，通过螺杆挤出机熔融挤出，控制温度范围240-280℃，经过冷却吹风，牵伸(牵伸比4.3倍)，上油(油剂浓度4.5％)，制出7D×51mm的海岛型超细复合纤维。
(2)无纺布的制作
以步骤(1)中制得的海岛型超细复合纤维制作幅宽1700mm和厚度为1.9～2.0mm的无纺布，针刺频率800～1200刺/min，针刺密度1000～1500刺/m 2，铺网层数40层，平均克重500g/m 2，无纺布车速2.5m/min。热定型控制厚度1.8mm，视密度0.28g/m 3。
(3)聚氨酯的刮涂
选用固含量为35％的聚醚型聚氨酯，以二甲基甲酰胺作为溶剂，调节粘度至70000CPS/25℃，搭配5％的微晶纤维素，使用高精度涂刀，刮涂于步骤(2)得到的定型无纺布上表面，涂覆间隙0.8mm，通过渗透和碾压等工序，经过5分钟，使得聚氨酯全部进入无纺布中，形成上层致密层。
(4)聚氨酯的含浸
将二甲基甲酰胺加入聚醚型聚氨酯浆料中，调节固含量至8％，加入2％的渗透剂以及 0.5％的固化剂，搅拌均匀制得含浸浆料；将步骤(3)中得到的坯布通过含浸浆料，浸渍充分，形成下层疏松层。
(5)聚氨酯的二次刮涂
将步骤(4)得到的浸渍后无纺布按照步骤(3)相同的方法，再次经过高精度涂刀，将聚氨酯搭配微晶纤维涂刮于无纺布的上表面，刮涂间隙0.05mm，经过大圆弧刮刀或对辊挤压，使二次刮涂的浆料进入无纺布坯布，与第一次刮涂的浆料充分结合。
(6)凝固和水洗
将步骤(5)得到的坯布通过浓度为18％以及温度为30℃的二甲基甲酰胺的混合水溶液中，使聚氨酯凝固。然后，经过多道淡水反复积压清洗，去除基布中残留的二甲基甲酰胺，得到半成品合成革。
(7)海岛纤维的减量开纤
将步骤(6)得到的半成品合成革，通过温度为85℃的热甲苯，然后通过轧辊反复挤压，使海岛纤维中的海成分低密度聚乙烯溶解分离，海岛纤维中的岛成分开纤成为超细纤维，经过沸水清洗除去残留甲苯，烘干后，制得具有高度天然头层皮结构的超纤革。
(8)后整理
对步骤(7)中制得的高度天然头层皮结构的超纤革进行后整理，后整理包括磨毛、染色、化柔、揉皮、干法贴面、表处、抛光、水揉、压纹和烫光，以加工成客户需要的产品。
实施例2
(1)海岛超细纤维的纺制
将尼龙6切片和COPET按照60:40的质量比进行混合，通过螺杆挤出机熔融挤出，控制温度范围245～285℃，经过冷却吹风，牵伸(牵伸比4倍)，上油(油剂浓度5.5％)，制出8D×51mm的海岛型超细复合纤维。COPET应经过预处理，预结晶温度120℃，结晶时间1.5小时，干燥温度150℃，干燥时间4小时，得到含水率≤0.03％的干切片。
(2)无纺布的制作
用步骤(1)中制得的海岛型超细复合纤维制作幅宽1650mm和厚度为2.0～2.1mm的无纺布，针刺频率500～1000刺/min，针刺密度1000～1500刺/m 2，铺网层数45层，平均克重560g/m 2，无纺布车速2.5m/min。热定型控制厚度1.85mm，视密度0.3g/m 3。
(3)聚氨酯的刮涂
选用固含量为30％的聚醚型聚氨酯，以二甲基甲酰胺作为溶剂，调节粘度至50000CPS/25℃，搭配15％的轻质碳酸钙，使用高精度涂刀，刮涂于步骤(2)得到的定型无纺布上表面，涂覆间隙0.9mm，通过渗透和碾压等工序，经过4分钟使得聚氨酯全部进入无纺布中，形成上层致密层。
(4)聚氨酯的含浸
将二甲基甲酰胺加入到聚醚型聚氨酯浆料中，调节固含量至15％，加入1.5％的渗透剂和1％的固化剂，搅拌均匀制得含浸浆料；将步骤(3)中得到的坯布通过含浸浆料，浸渍充分，形成下层疏松层。
(5)聚氨酯的二次刮涂
将步骤(4)得到的浸渍后无纺布按照步骤(3)相同的方法，再次经过高精度涂刀，将聚氨酯浆料搭配轻质碳酸钙，涂刮于布的上表面，刮涂间隙0.1mm，经过大圆弧刮刀或对辊挤压，使二次刮涂的浆料进入无纺布坯布，与第一次刮涂的浆料充分结合。
(6)凝固和水洗
将步骤(5)得到的坯布通过浓度为10％以及温度为35℃的二甲基甲酰胺的混合水溶液中，使聚氨酯凝固。经过多道淡水反复积压清洗，去除基布中残留的二甲基甲酰胺，得到半成品合成革。
(7)海岛纤维的减量开纤
将步骤(6)得到的半成品合成革，通过浓度为10％以及温度为95℃的热碱水溶液，添加经过40min左右，使海岛纤维中的海成分COPET溶解分离，海岛纤维中的岛成分开纤成为超细纤维，经过多道冲洗、酸中和以及冲洗，除去残留碱液，烘干后，制得具有高度天然头层皮结构的超纤革。
(8)后整理
对步骤(7)中制得的高度天然头层皮结构的超纤革进行后整理，后整理包括磨毛、染色、化柔、揉皮、干法贴面、表处、抛光、水揉、压纹和烫光。加工成客户需要的产品。
实施例3
(1)海岛超细纤维的纺制
将尼龙6切片和线性低密度聚乙烯按照55:45的质量比进行混合，通过螺杆挤出机熔融挤出，控制温度范围240～285℃，经过冷却吹风，牵伸(牵伸比5倍)，上油(油剂浓度6％)，制出6D×51mm的海岛型超细复合纤维。
(2)无纺布的制作
用步骤(1)中制得的海岛型超细复合纤维制作幅宽1650mm和厚度为1.7～1.8mm的无纺布，针刺频率500～1000刺/min，针刺密度800～1200刺/m 2，铺网层数25层，平均克重400g/m 2，无纺布车速3m/min。热定型控制厚度1.35mm，视密度0.3g/m 3。
(3)聚氨酯的刮涂
选用固含量为40％的水性聚氨酯，使用增稠剂或水，调节粘度至30000CPS/25℃，搭配20％的轻质碳酸钙，使用高精度涂刀，刮涂于步骤(2)得到的定型无纺布上表面，涂覆 间隙0.5mm，通过渗透和碾压等工序，经过3分钟使聚氨酯全部进入无纺布中，形成上层致密层。
(4)聚氨酯的含浸
选用固含量40％的软质水性聚氨酯，使用增稠剂或水，调节粘度至6000CPS/25℃，搅拌均匀制得含浸浆料；将步骤(3)中得到的坯布通过含浸浆料，浸渍充分，形成下层疏松层。
(5)聚氨酯的二次刮涂
将步骤(4)得到的浸渍后无纺布按照步骤(3)相同的方法，再次经过高精度涂刀，将聚氨酯浆料搭配轻质碳酸钙，涂刮于布的上表面，刮涂间隙0.05mm，经过大圆弧刮刀或对辊挤压，使二次刮涂的浆料进入无纺布坯布，与第一次刮涂的浆料充分结合。
(6)干燥凝固
将步骤(5)得到的坯布在120～140℃的环境下，干燥10～15min，使水性树脂完全固化和交联，得到半成品合成革。
(7)海岛纤维的减量开纤
将步骤(6)得到的半成品合成革，通过温度为90℃的热甲苯，通过轧辊反复挤压，使海岛纤维中的海成分低密度聚乙烯溶解分离，海岛纤维中的岛成分开纤成为超细纤维，经过沸水清洗除去残留甲苯，烘干后，制得具有高度天然头层皮结构的超纤革。
(8)后整理
对步骤(7)中制得的高度天然头层皮结构的超纤革进行后整理，后整理包括磨毛、染色、化柔、揉皮、干法贴面、表处、抛光、水揉、压纹和烫光。加工成客户需要的产品。
实验例1
分别将本申请实施例1和实施例2所制备模拟天然头层皮的超纤革样品与真皮以及按照现有技术CN102304858B实施例方法所得到样品1和2进行对比，结果如下表所示：
Figure PCTCN2019080853-appb-000001
Figure PCTCN2019080853-appb-000002
由如上表格数据可知，由本申请方法所制备的模拟天然头层皮的超纤革具有良好的柔软度和耐撕裂、耐弯折性能，且上下层梯度比与真皮更为接近。
尽管已用具体实施例来说明和描述了本申请，然而应意识到，在不背离本申请的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本申请范围内的所有这些变化和修改。

Claims (10)

  1. 一种模拟天然头层皮的超纤革的制备方法，其特征在于，包括：
    将以溶剂进行粘度调节后的聚酯和/或聚醚型聚氨酯浆料，搭配0～50％的高密度填料，在由海岛型超细复合纤维所制成无纺布的一侧表面进行一次刮涂以形成上层致密层，并得到坯布；或者，将以增稠剂或水进行粘度调节后的水性聚氨酯浆料，搭配0～50％的高密度填料，在由海岛型超细复合纤维所制成无纺布的一侧表面进行一次刮涂以形成上层致密层，并得到坯布；
    将以溶剂进行固含量调节后的聚酯和/或聚醚型聚氨酯浆料与渗透剂以及固化剂搅拌混匀，得到含浸浆料，将所得坯布未进行刮涂的一侧以含浸浆料浸渍，以形成下层疏松层；或者，将以增稠剂或水进行粘度调节后的水性树脂浆料为含浸浆料，将所得坯布未进行刮涂的一侧以含浸浆料浸渍，以形成下层疏松层；
    在进行一次刮涂的一侧，再进行一次刮涂，得到聚氨酯加工的坯布；
    将聚氨酯加工的坯布凝固水洗，得到半成品合成革；或者，将聚氨酯加工的坯布进行干燥处理，得到半成品合成革；
    将所述半成品合成革以热甲苯溶液处理后，进行挤压处理；清洗干燥后，得到模拟天然头层皮的超纤革；或者，将所述半成品合成革以热碱液处理后，进行挤压处理，清洗和中和，干燥后，得到模拟天然头层皮的超纤革。
  2. 根据权利要求1所述的制备方法，其特征在于，所述海岛型超细复合纤维由尼龙6/PET与LLDPE/COPET熔融共混纺丝得到；
    其中，所述岛成分为尼龙6或PET，海成分为LLDPE或COPET；
    优选地，尼龙6/PET与LLDPE/COPET的质量比为50:50～65:35。
  3. 根据权利要求1所述的制备方法，其特征在于，无纺布的制备包括：将所述海岛型超细复合纤维开松、梳理和铺网后，针刺加固成布，然后热定型，得到无纺布；
    其中，热定型的温度为110～150℃；
    和/或，所得无纺布的表观密度≥0.2g/cm 3。
  4. 根据权利要求3所述的制备方法，其特征在于，铺网层数为25～50层，平均克重300～900g/m 2；
    和/或，针刺频率400～1800刺/min并且针刺密度800～2000刺/m 2；无纺布车速为1.5～5m/min；
    和/或，所制备的无纺布表观密度为0.2～0.35g/cm 3。
  5. 根据权利要求1所述的制备方法，其特征在于，所述一次刮涂在温度为10～ 50℃，湿度为5～50％的条件下进行；
    优选地，能够采用加热鼓风的方式控制一次刮涂的环境湿度；
    更优选地，所述加热包括：电加热、天然气加热以及导热油加热。
  6. 根据权利要求1所述的制备方法，其特征在于，所述高密度填料包括：轻质碳酸钙、重质碳酸钙、滑石粉、弹力粉、硅灰石或者改性天然蛋白中的一种或几种。
  7. 根据权利要求1所述的制备方法，其特征在于，所述制备方法还进一步包括将所制得的模拟天然头层皮的超纤革进行后整理的步骤；
    优选地，所述后整理包括：磨毛、染色、化柔、揉皮、防水、透气、干法贴面、表处、抛光、水揉、压纹以及烫光中的一种或几种工序。
  8. 由权利要求1-7中任一项所述的制备方法得到的模拟天然头层皮的超纤革。
  9. 根据权利要求8所述的模拟天然头层皮的超纤革，其特征在于，所述上层致密层与下层疏松层的梯度密度比为(1.15～1.8):1。
  10. 权利要求8或9所述的模拟天然头层皮的超纤革在鞋类、汽车内饰、箱包、服饰或装饰面料中的应用；
    或者，包含权利要求8或9所述的模拟天然头层皮的超纤革的服饰或装饰面料。
PCT/CN2019/080853 2018-08-06 2019-04-01 一种模拟天然头层皮的超纤革的制备方法及应用 WO2020029594A1 (zh)

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CN116005462A (zh) * 2022-12-29 2023-04-25 江苏华峰超纤材料有限公司 一种仿真皮水性聚氨酯超纤基布的制备方法
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