EP3812507B1 - Method of manufacturing sheet article - Google Patents

Method of manufacturing sheet article Download PDF

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Publication number
EP3812507B1
EP3812507B1 EP19823144.1A EP19823144A EP3812507B1 EP 3812507 B1 EP3812507 B1 EP 3812507B1 EP 19823144 A EP19823144 A EP 19823144A EP 3812507 B1 EP3812507 B1 EP 3812507B1
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EP
European Patent Office
Prior art keywords
polyvinyl alcohol
fibrous substrate
polyurethane
fibers
sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP19823144.1A
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German (de)
English (en)
French (fr)
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EP3812507A1 (en
EP3812507A4 (en
Inventor
Takanori Furui
Gen Koide
Makoto Nishimura
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Toray Industries Inc
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Toray Industries Inc
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Publication date
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Publication of EP3812507A1 publication Critical patent/EP3812507A1/en
Publication of EP3812507A4 publication Critical patent/EP3812507A4/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance
    • 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
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/045—Vinyl (co)polymers
    • 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
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1685—Wear resistance
    • 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
    • D06N2211/28—Artificial leather

Definitions

  • the present invention relates to a method of manufacturing a sheet article that uses water-dispersible polyurethane for a binder resin to reduce an amount of an organic solvent used in a manufacturing process, achieves both good flexibility and high-grade surface appearance in an environment-friendly sheet article, and has good wear resistance.
  • Sheet articles made up mainly of a fibrous substrate and polyurethane have excellent features that natural leathers do not have, and are widely utilized in various uses.
  • a leather-like sheet article that employs a polyester-based fibrous substrate is excellent in light resistance, and therefore its use has spread year by year to clothing, chair upholstery, automotive interior finishing material uses, etc.
  • a process in which a fibrous substrate is impregnated with an organic solvent solution of polyurethane, and then the obtained fibrous substrate is dipped in water or a mixed solution of organic solvent and water that is a non-dissolving medium for polyurethane, so as to cause polyurethane to undergo wet coagulation is generally adopted.
  • a water miscible organic solvent such as N,N-dimethylformamide (hereinafter referred to as "DMF" is used.
  • a conventional sheet article which is formed by impregnating a fibrous substrate with water-dispersible polyurethane and adding the polyurethane has a problem in that the feel tends to be hard because the polyurethane strongly adheres to fibers of the fibrous substrate.
  • Patent Document 2 in the method of adding polyvinyl alcohol to a fibrous substrate in advance, then adding polyurethane, and then removing the polyvinyl alcohol, the polyvinyl alcohol is water-soluble, and therefore, after the polyvinyl alcohol is added to the fibrous substrate, when the fibrous substrate is wetted with water, the polyvinyl alcohol may dissolved away and lost in the water.
  • Patent Document 2 it is attempted to suppress the loss of polyvinyl alcohol into water by using an aqueous solution of polyvinyl alcohol having a saponification degree of 98% or more and a degree of polymerization of 800 to 3500 and a small amount of impurities.
  • an object of the present invention is to provide a sheet article that reduces use of an organic solvent in a manufacturing process and thereby to consider the environment, achieves both an elegant, napped appearance and a flexible feel even when a polyvinyl alcohol aqueous solution having a low degree of polymerization and a low viscosity is used, and has good wear resistance.
  • the present invention aims to solve the above problems, and is a method of manufacturing a sheet article including a fibrous substrate including microfibers and polyurethane, and a method of manufacturing a sheet article including the following steps (1) to (4):
  • a degree of polymerization of the polyvinyl alcohol is 200 to 3500.
  • the fibrous substrate having the microfiber expression type fibers as its main constituent is treated with an alkaline aqueous solution.
  • heating is performed at 80 to 190°C.
  • the fibrous substrate having the microfiber expression type fibers as its main constituent in which the fibers and a woven fabric and/or a knitted fabric are integrated by entanglement is used.
  • the method of manufacturing a sheet article of the present invention is to perform the following steps (1) to (4):
  • a step for example, a dissolution step of adding the polyvinyl alcohol aqueous solution to a fibrous substrate having microfiber expression type fibers as its main constituent and then expressing microfibers from the microfiber expression type fibers (for example, islands-in-the-sea fibers) is performed. Then, a water-dispersible polyurethane liquid is added to the fibrous substrate having the microfibers as its main constituent and having the added polyvinyl alcohol. In addition, the polyvinyl alcohol is removed from the fibrous substrate.
  • microfibers are partially in direct contact with and held by the polyurethane, so that an elegant appearance, a flexible feel, and good wear resistance can be exhibited.
  • the resulting sheet article can give an elegant surface appearance where a raised nap is unlikely to be bundled but uniformly separated.
  • both voids derived by the removal of the polyvinyl alcohol and voids derived by the dissolved sea component are formed between the polyurethane and the microfibers.
  • the area where the surface of the microfibers is in direct contact with and held by the polyurethane is further reduced.
  • the polyvinyl alcohol-adding step of adding the polyvinyl alcohol aqueous solution, which is the aqueous solution of polyvinyl alcohol having the following characteristics, to the fibrous substrate having microfiber expression type fibers as its main constituent to add the polyvinyl alcohol in an amount of 0.1 to 50% by mass based on the mass of the fibers contained in the fibrous substrate.
  • the polyvinyl alcohol used here has a saponification degree of 90% or more and an rrr composition abundance ratio of 14.5% or more.
  • polyvinyl alcohol added to the fibrous substrate
  • a polyvinyl alcohol containing polyvinyl acetate as a raw material is preferable.
  • a polyvinyl alcohol containing poly(trifluorovinyl acetate) as a raw material is also preferable.
  • Polyvinyl alcohol has a saponification degree of 90% or more. The saponification degree is preferably 95% or more, and more preferably 98% or more.
  • the saponification degree of polyvinyl alcohol By setting the saponification degree of polyvinyl alcohol to a certain value or more, it is possible to prevent the polyvinyl alcohol from being dissolved in the water-dispersible polyurethane liquid when the water-dispersible polyurethane is added after the polyvinyl alcohol is added to the fibrous substrate.
  • the saponification degree is low, when the water-dispersible polyurethane liquid is added to the fibrous substrate, the polyvinyl alcohol is dissolved in the water-dispersible polyurethane liquid, and polyvinyl alcohol is taken into the polyurethane, which makes it difficult to remove the polyvinyl alcohol later.
  • an adhesive state between the polyurethane and the fibers cannot be controlled stably, and the feel is hard.
  • the saponification degree of polyvinyl alcohol can be calculated as follows as described in 3.5 "Saponification Degree” in JIS K 6726: 1994 "Polyvinyl Alcohol Test Method”.
  • the polyvinyl alcohol added to the fibrous substrate has an rrr composition abundance ratio of 14.5% or more in a heavy water solvent in the tacticity evaluation measured by 13 C-NMR.
  • a structure in which an "r" (racemo) structure having adjacent hydroxyl groups being in different directions is repeated is a partially syndiotactic structure.
  • hydroxyl groups are arranged alternately one above the other on a plane formed by a carbon chain in a polymer, so that the syndiotactic structure is a structure likely to form many hydrogen bonds due to a hydroxyl group in a molecule of polyvinyl alcohol in the syndiotactic structure.
  • the hydroxyl groups that contribute to the formation of hydrogen bonds with water molecules are reduced, solubility in water is reduced, and solubility in warm water is also reduced.
  • Polyvinyl alcohol having an abundance ratio of the rrr structure having the highest syndiotactic properties of 14.5% or more can effectively reduce the solubility in water.
  • the abundance ratio of the rrr structure is preferably 14.7% or more, and more preferably 15.0% or more.
  • a high abundance ratio of the rrr structure means a high ratio of the syndiotactic structure, and the solubility in water can be further reduced.
  • the abundance ratio of the rrr structure is less than 14.5%, the formation of hydrogen bonds between polyvinyl alcohols is reduced, and the polyvinyl alcohol is dissolved away and lost in water during the dissolution step, etc.
  • An area where fibers are in direct contact with and held by the polyurethane increases, and flexibility and surface appearance of the sheet article decrease.
  • the abundance ratio of the mrr structure is preferably 25% or more.
  • the abundance ratio is more preferably 25.5% or more, still more preferably 26% or more.
  • a total of the abundance ratio of the rrr structure and the abundance ratio of the mrr structure is preferably 39.5% or more.
  • the total is more preferably 40% or more, still more preferably 40.5% or more.
  • a total of the abundance ratio of the mmm structure and the abundance ratio of the mmr structure is preferably 50% or less.
  • the total is more preferably 48% or less, still more preferably 45% or less.
  • the upper limit is 28.0% or less, and preferably 20.0% or less, from the viewpoint of easy availability or easy production.
  • the rrr composition abundance ratio of polyvinyl alcohol is measured as follows, and the calculated value is adopted.
  • polyvinyl alcohol is dissolved in a heavy water solvent at a temperature of 80°C, and 13 C-NMR measurement at a measurement temperature of 80°C and a resonance frequency of 100 MHz is performed.
  • the group of peaks observed at 45 to 49 ppm is the group of peaks corresponding to methylene carbon in the polyvinyl alcohol skeleton.
  • the group of peaks on the low magnetic field side is a methine carbon peak group to which the hydroxyl group in the polyvinyl alcohol skeleton is bonded.
  • the carbon peak group constituting this methylene group in five peaks detected, if the peaks overlap, the peaks are vertically divided in a peak valley to calculate an integrated value, and the abundance ratio of each arrangement is calculated as a percentage.
  • the peak of the rrr structure is observed on the lowest magnetic field side of the group of peaks.
  • the abundance ratio of the rrr structure can be adjusted by appropriately changing the polymerization conditions and polymerization catalyst of polyvinyl alcohol or polyvinyl acetate which can be a raw material.
  • the solubility of polyvinyl alcohol in water and the viscosity of the polyvinyl alcohol aqueous solution change depending on the degree of polymerization.
  • the higher the degree of polymerization of polyvinyl alcohol the lower the solubility in water.
  • an average degree of polymerization of polyvinyl alcohol is preferably 200 or more, more preferably 300 or more, and still more preferably 400 or more.
  • the average degree of polymerization of polyvinyl alcohol is preferably 3500 or less, more preferably 2500 or less, still more preferably 1500 or less, and particularly preferably 1000 or less.
  • the degree of polymerization of polyvinyl alcohol By setting the degree of polymerization of polyvinyl alcohol to 3500 or less, it is possible to prevent the viscosity of the polyvinyl alcohol aqueous solution from becoming too high, and to improve the impregnation property into the fibrous substrate and the handleability of the polyvinyl alcohol aqueous solution.
  • the average degree of polymerization of polyvinyl alcohol is measured as shown in the following (1) to (7) according to 3.7 "Average Degree of Polymerization” in JIS K 6726: 1994 "Polyvinyl Alcohol Test Method” and refers to the average degree of polymerization calculated in the present invention in (8).
  • the viscosity of the polyvinyl alcohol aqueous solution refers to the viscosity at 20°C of the polyvinyl alcohol aqueous solution having a concentration of 4% by mass, which is measured as follows in 3.11.1 "Rotary Viscometer Method” in JIS K 6726: 1994 "Polyvinyl Alcohol Test Method”.
  • the polyvinyl alcohol preferably has a viscosity of a 4% by mass aqueous solution of the polyvinyl alcohol at 20°C of 2 to 70 mPa ⁇ s.
  • a viscosity of the polyvinyl alcohol is within this range, an appropriate migration structure can be obtained inside the fibrous substrate during drying, and it is possible to obtain a balance between the flexibility of the sheet article and the physical properties such as surface appearance and wear resistance.
  • the viscosity By setting the viscosity to 2 mPa ⁇ s or more, more preferably 3 mPa ⁇ s or more, and still more preferably 4 mPa ⁇ s or more, it is possible to suppress an extreme migration structure.
  • the fibrous substrate can be easily impregnated with polyvinyl alcohol.
  • a glass transition temperature (Tg) of polyvinyl alcohol is preferably 70 to 100°C or lower.
  • Tg glass transition temperature
  • the glass transition temperature of polyvinyl alcohol is preferably 70 to 100°C or lower.
  • a melting point of polyvinyl alcohol is preferably 200 to 250°C.
  • the melting point of polyvinyl alcohol is set to 200°C or higher, and more preferably 210°C or higher, softening in the drying step can be prevented, the dimensional stability of the fibrous substrate can be obtained, and deterioration of the surface appearance of the sheet article can be suppressed.
  • the melting point of polyvinyl alcohol is set to 250°C or lower, and more preferably 240°C or lower, it is possible to prevent the fibrous substrate from becoming too hard and thereby preventing deterioration in the handleability.
  • the glass transition point and melting point of polyvinyl alcohol refer to as, respectively, the glass transition temperature and the melting temperature measured in differential scanning calorimetry (DSC) in JIS K 7121: 1987 "Testing Methods for Transition Temperatures of Plastics”.
  • the polyvinyl alcohol-adding step of adding a polyvinyl alcohol aqueous solution to a fibrous substrate having microfiber expression type fibers as its main constituent to add the polyvinyl alcohol in an amount of 0.1 to 50% by mass based on the mass of the fibers contained in the fibrous substrate.
  • the fibrous substrate in the present invention typically has microfiber expression type fibers as its main constituent.
  • the content of the microfiber expression type fibers in the fibrous substrate is preferably 50 to 100% by mass.
  • the content of the microfiber expression type fibers in the fibrous substrate is more preferably 60% by mass or more, and still more preferably 70% by mass or more, because an elegant surface appearance of a sheet article can be obtained.
  • the microfiber expression type fibers are used to generate microfibers through the subsequent step of ultra-fining fibers, and an elegant surface appearance can be obtained.
  • the microfiber expression type fibers may be (a) "islands-in-the-sea fibers", which are prepared using two types of thermoplastic resins having different solvent solubilities as the sea and island components and which can generate microfibers from the island component through the dissolution and removal of the sea component with a solvent or the like.
  • the microfiber expression type fibers may be (b) "peelable composite fibers", which are prepared by alternately arranging two types of thermoplastic resins in radial segments or multi-layered segments in the cross-section and which generate microfibers through splitting the fibers by peeling and separating the segments.
  • the islands-in-the-sea fibers can give voids in an appropriate size between the island components, i.e., between the microfibers, through the removal of the sea component, and thus are preferably used from the viewpoint of the flexibility and feel of the sheet article.
  • the islands-in-the-sea fibers include, for example, islands-in-the-sea conjugated fiber prepared by using a nozzle for islands-in-the-sea conjugation, mutually aligning two components, namely, the sea component and the island component, and spinning the aligned sea and island components from the nozzle, and mix-spun fiber prepared by spinning a mixture of two components, namely, the sea component and the island component.
  • the islands-in-the-sea conjugated fiber described first is preferably used in view of producing microfibers having uniform fineness as well as the production of microfibers with sufficient length contributing for the strength of the resulting sheet article.
  • the island component of the islands-in-the-sea fibers is not particularly limited, and the following are exemplified.
  • Polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polylactic acid.
  • Polyamides such as polyamide 6 and polyamide 66; acryl; polyethylene; and polypropylene.
  • Thermoplastic resins that can be melt-spun such as thermoplastic cellulose.
  • polyester fibers from the viewpoint of strength, dimensional stability, and light resistance. Due to environmental concerns, the fibers are preferably fibers obtained from recycled materials or bio-base materials.
  • the fibrous substrate may include mixed fibers made from different materials.
  • the sea component of the islands-in-the-sea fibers is not particularly limited, and the following are exemplified.
  • Addition polymers of hydrocarbons such as polyethylene, polypropylene and polystyrene.
  • Copolymerized polyester prepared by copolymerizing sodium sulfoisophthalic acid, polyethylene glycol, etc.
  • Polylactic acid Polyvinyl alcohol.
  • copolymerized polyesters prepared by copolymerizing sodium sulfoisophthalate, polyethylene glycol, or the like, and polylactic acid, because these polymers are alkali-degradable and can be degraded without any organic solvent.
  • polyvinyl alcohol because it is soluble in hot water.
  • the cross-sectional shape of the fibers constituting the fibrous substrate is not particularly limited, and may be a circular shape, an oval shape, a flat shape, a polygonal shape such as a triangular shape, or a modified cross-sectional shape such as fan and cross shapes.
  • the fibrous substrate in the present invention may be a woven fabric, a knitted fabric, a nonwoven fabric, or the like.
  • a nonwoven fabric is preferably used because it gives a sheet article having a good surface appearance after buffing treatment on the surface.
  • the nonwoven fabric may be a staple nonwoven fabric or a filament nonwoven fabric.
  • a filament nonwoven fabric has a smaller amount of fibers which lie in the thickness direction of a resulting sheet article and which is to form a raised nap by buffing, as compared with a staple nonwoven fabric.
  • a filament nonwoven fabric thus tends to give a less dense nap, resulting in a poor surface appearance. Therefore, a staple nonwoven fabric is preferably used.
  • the fiber length of the staples in the staple nonwoven fabric is preferably 25 to 90 mm.
  • the fiber length is 25 mm or more, and more preferably 30 mm or more, the fibers can be entangled to yield a sheet article having an excellent wear resistance.
  • the fiber length is 90 mm or less, and more preferably 80 mm or less, the fibers can yield a sheet article having excellent feel and quality.
  • the method for entangling the fibers or fiber bundles to yield a nonwoven fabric may be needle punching or water jet punching.
  • the fibrous substrate including microfiber expression type fibers when the fibrous substrate including microfiber expression type fibers is a nonwoven fabric, a preferred embodiment of the nonwoven fabric is a nonwoven fabric having a structure in which microfiber expression type fibers are entangled with each other in advance. Consequently, the fibrous substrate including microfibers has a structure in which bundles of the microfibers are entangled, and the strength of the sheet article is improved by the entangled microfibers in the bundle state.
  • the fibrous substrate having microfiber expression type fibers as its main constituent is a nonwoven fabric
  • a woven fabric or a knitted fabric may be further integrated inside the nonwoven fabric by entanglement for the purpose of improving the strength and other properties.
  • the woven fabric include plain woven fabrics, twill woven fabrics, and satin woven fabrics, and preferred is plain woven fabrics in view of the cost.
  • the knitted fabric include circular knitted fabrics, tricot fabrics, and raschel fabrics.
  • the fibers constituting such woven and knitted fabrics preferably have an average single fiber diameter of 0.3 to 20 ⁇ m.
  • the addition of the polyvinyl alcohol before addition of the water-dispersible polyurethane reduces the area where the woven fabric or the knitted fabric is in direct contact with and held by the water-dispersible polyurethane, the feel of the resulting sheet article is unlikely to be hard.
  • the woven fabric and/or the knitted fabric to be used is made of fibers other than microfiber expression type fibers, a sheet article having remarkably excellent flexibility can be obtained.
  • the amount of polyvinyl alcohol to be added to the fibrous substrate is 0.1 to 50% by mass based on the total mass of the fibers in the fibrous substrate.
  • the amount of polyvinyl alcohol to be added is 0.1% by mass or more, preferably 1% by mass or more, a sheet article having good flexibility and feel is obtained.
  • the amount of polyvinyl alcohol to be added is 50% by mass or less, preferably 45% by mass or less, a sheet article having good processability and good physical properties including wear resistance is obtained.
  • the method of adding polyvinyl alcohol to the fibrous substrate is not particularly limited, and various methods commonly used in the art can be adopted. Among the methods, preferred is a method involving dissolving polyvinyl alcohol in water, impregnating the fibrous substrate with the polyvinyl alcohol solution, and heat-drying the substrate, so that the polyvinyl alcohol can be uniformly added. If the drying temperature is too low, a longer drying time is required, and if the drying temperature is too high, polyvinyl alcohol becomes completely insoluble, making it difficult to dissolve and remove the polyvinyl alcohol later. Thus, the drying temperature is preferably 80 to 140°C, and more preferably 110 to 130°C.
  • the drying time is usually 1 to 20 minutes, and is preferably 1 to 10 minutes and more preferably 1 to 5 minutes in view of the processability.
  • heat treatment may be performed after drying.
  • the heating treatment is preferably performed at 80 to 190°C.
  • insolubilization of polyvinyl alcohol proceeds simultaneously with thermal degradation of the polyvinyl alcohol, and thus the heating temperature is more preferably 90°C to 170°C.
  • microfiber expression step of expressing microfibers having an average single fiber diameter of 0.1 to 10 ⁇ m from a fibrous substrate including microfiber expression type fibers.
  • the microfiber expression type fiber is preferably an islands-in-the-sea fiber.
  • a microfiber expression treatment of a fibrous substrate having such fibers as its main constituent is a dissolution treatment.
  • the dissolution treatment can be performed by immersing the fibrous substrate in a solvent, dissolving a sea component in the solvent, and wringing out the fibrous substrate.
  • the solvent may be an organic solvent such as toluene and trichloroethylene.
  • the solvent may be an aqueous solution of alkali such as sodium hydroxide.
  • the sea component is polyvinyl alcohol
  • the solvent may be hot water. Due to environmental concerns regarding the process, dissolution treatment is preferably performed with an aqueous solution of alkali such as sodium hydroxide or with hot water.
  • the average single fiber diameter of the microfibers generated from the microfiber expression type fibers through the step of ultra-fining fibers is 0.1 to 10 ⁇ m.
  • the average single fiber diameter is 10 ⁇ m or less, more preferably 7 ⁇ m or less, and still more preferably 5 ⁇ m or less, a sheet article having excellent flexibility and an excellent nap quality can be obtained.
  • the resulting sheet article will exhibit an excellent chromogenic property for dyeing, an excellent separability of fibers aggregated into bundles during napping treatment by, for example, grinding with a sandpaper or the like, and an excellent loosening property of fibers.
  • the water-dispersible polyurethane includes (I) emulsified polyurethanes, which have been forced to be stably dispersed in water with use of a surfactant, and (II) self-emulsifying polyurethanes, which have hydrophilic structures in their molecular structures and are capable of being dispersed and then stabilized in water without use of any surfactant. Both types of polyurethanes can be used in the present invention.
  • the method of adding the water-dispersible polyurethane to the fibrous substrate is not particularly limited. Preferred is a method in which a water-dispersible polyurethane liquid is impregnated into or applied to the fibrous substrate, then coagulated and heat-dried, because the water-dispersible polyurethane is uniformly added by this method.
  • the concentration of polyurethane is preferably 10 to 50% by mass and more preferably 15 to 40% by mass in the water-dispersible polyurethane.
  • the water-dispersible polyurethane liquid used in the present invention may contain a water-soluble organic solvent in an amount of 40% by mass or less based on the total amount of the polyurethane liquid for the purpose of improving the storage stability of the polyurethane dispersion and the productivity of the sheet.
  • the amount of the organic solvent is preferably 1% by mass or less in view of the environmental safety at the production site for the sheet, and the like.
  • the water-dispersible polyurethane liquid used in the present invention preferably has a heat-sensitive coagulation property.
  • the polyurethane can be added uniformly in the thickness direction of the fibrous substrate.
  • the heat-sensitive coagulation property refers to a property that, when the polyurethane liquid is heated and reaches a certain temperature, reduces the flowability of the polyurethane liquid and then coagulates the polyurethane.
  • a temperature at which this occurs refers to as a heat-sensitive coagulation temperature.
  • the polyurethane liquid is added to the fibrous substrate, then coagulated by dry coagulation, wet-heat coagulation, wet coagulation, or any combination thereof, and dried to give the fibrous substrate having the added polyurethane.
  • a realistic method for coagulating a water-dispersible polyurethane liquid not exhibiting a heat-sensitive coagulation property is dry coagulation.
  • a migration phenomenon occurs in which the polyurethane concentrates in the surface layer of the fibrous substrate, and the feel of the resulting sheet article having the polyurethane added tends to be hardened.
  • the migration can be prevented by adjusting the viscosity of the water-dispersible polyurethane liquid by a thickener.
  • the migration can be prevented by the addition of a thickener and dry coagulation.
  • the heat-sensitive coagulation temperature of the water-dispersible polyurethane liquid is preferably 40 to 90°C.
  • the heat-sensitive coagulation temperature is 40°C or higher, the polyurethane liquid has good storage stability, and the adhesion of the polyurethane to the machines during operation can be prevented.
  • the heat-sensitive coagulation temperature is 90°C or lower, the migration phenomenon of the polyurethane toward the surface layer of the fibrous substrate can be suppressed.
  • a heat-sensitive coagulant in order to achieve the above heat-sensitive coagulation temperature, a heat-sensitive coagulant may be added, as appropriate.
  • the heat-sensitive coagulant include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate, calcium sulfate, and calcium chloride; and radical initiators such as sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and benzoyl peroxide.
  • the polyurethane liquid can be added to the fibrous substrate by impregnation, application, or other methods, and the polyurethane can be coagulated by dry coagulation, wet-heat coagulation, wet coagulation, or any combination thereof.
  • the temperature for the wet-heat coagulation is preferably equal to or higher than the heat-sensitive coagulation temperature of the polyurethane and is preferably 40 to 200°C.
  • the temperature for the wet-heat coagulation is 40°C or higher, and more preferably 80°C or higher, the polyurethane can coagulate in a shorter period of time, and the migration phenomenon can be more efficiently prevented.
  • the temperature for the wet-heat coagulation is 200°C or lower, and more preferably 160°C or lower, thermal degradation of the polyurethane and of the polyvinyl alcohol can be prevented.
  • the temperature for the wet coagulation is equal to or higher than the heat-sensitive coagulation temperature of the polyurethane and is preferably 40 to 100°C.
  • the temperature for the wet coagulation in hot water is 40°C or higher, and more preferably 80°C or higher, the polyurethane can coagulate in a shorter period of time, and the migration phenomenon can be more efficiently prevented.
  • the temperature for the dry coagulation and the drying temperature are preferably 80 to 140°C.
  • the temperature for the dry coagulation and the drying temperature are 80°C or higher, and more preferably 90°C or higher, the productivity is excellent.
  • the temperature for the dry coagulation and the drying temperature are 140°C or lower, and more preferably 130°C or lower, thermal degradation of the polyurethane and of the polyvinyl alcohol can be prevented.
  • the polyurethane after being subjected to the coagulation, may be subjected to heat treatment.
  • the heat treatment reduces the number of interfaces between the polyurethane molecules, thereby strengthening the polyurethane.
  • the heat treatment is performed after removing the polyvinyl alcohol from a sheet having water-dispersible polyurethane added.
  • the temperature for the heat treatment is preferably 80 to 170°C.
  • the polyurethane used in the present invention is preferably obtained by reaction of a polymer diol and an organic diisocyanate with a chain extender.
  • polymer diol examples include, but are not particularly limited to, polycarbonate diols, polyester diols, polyether diols, silicone diols, and fluorine diols, and copolymers obtained by combining them.
  • polycarbonate diols and polyether diols are preferably used.
  • polycarbonate diols and polyester diols are preferably used.
  • polycarbonate diols and polyester diols are more preferably used, and polycarbonate diols are particularly preferably used.
  • the polycarbonate diols can be produced by, for example, transesterification of an alkylene glycol and a carbonate or reaction of phosgene or a chloroformate with an alkylene glycol.
  • the alkylene glycol is not particularly limited, and examples thereof include the following alkylene glycols.
  • Linear alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol.
  • Branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 2-methyl-1,8-octanediol.
  • alicyclic diols such as 1,4-cyclohexanediol
  • aromatic diols such as bisphenol A
  • glycerin trimethylolpropane
  • pentaerythritol and the like.
  • the polycarbonate diol may be either a polycarbonate diol obtained from a single type of alkylene glycol or a copolymerized polycarbonate diol obtained from two or more types of alkylene glycols.
  • polyester diols are exemplified by polyester diols obtained by condensation of various low molecular weight polyols and polybasic acids.
  • low molecular weight polyols examples include, but are not particularly limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, and cyclohexane-1,4-dimethanol. These polyols may be used singly or in combination of two or more of them. Adducts prepared by adding various alkylene oxides to bisphenol A are also usable.
  • polybasic acids examples include, but are not particularly limited to, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydroisophthalic acid. These acids may be used singly or in combination of two or more of them.
  • polyether diols examples include, but are not particularly limited to, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymerized diols obtained by combining them.
  • a number average molecular weight of the polymer diol used in the present invention is preferably 500 to 4000.
  • the number average molecular weight is 500 or more, and more preferably 1500 or more, the feel of the sheet article is prevented from becoming hard.
  • the number average molecular weight is 4000 or less, or more preferably 3000 or less, the polyurethane can maintain its strength.
  • organic diisocyanate examples include, but are not particularly limited to, aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate; and aromatic diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. These diisocyanates may be used in combination. Among them, in view of light resistance, aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferably used.
  • chain extender examples include, but are not particularly limited to, amine chain extenders such as ethylenediamine and methylenebisaniline; and diol chain extenders such as ethylene glycol.
  • amine chain extenders such as ethylenediamine and methylenebisaniline
  • diol chain extenders such as ethylene glycol.
  • Polyamines prepared by reacting a polyisocyanate with water may also be used as the chain extender.
  • the polyurethane may be used in combination with a crosslinker for the purpose of improving water resistance, wear resistance, hydrolysis resistance, and other characteristics.
  • the crosslinker may be an external crosslinker, which is added to the polyurethane as a third component, or an internal crosslinker, which previously introduces reaction points into the molecular structure of the polyurethane to form crosslinked structure.
  • an internal crosslinker is preferably used because it can form crosslinking points uniformly throughout the molecular structure of the polyurethane and alleviates the reduction in flexibility.
  • crosslinker a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group and the like can be used.
  • a crosslinker having a silanol group is preferably used in view of the balance between reactivity and flexibility.
  • the polyurethane used in the present invention preferably has a hydrophilic group in the molecular structure.
  • a hydrophilic group exists in the molecular structure, dispersibility and stability as the water-dispersible polyurethane can be improved.
  • the hydrophilic group may be any hydrophilic groups including cationic groups such as quaternary amine groups; anionic groups such as a sulfonate group and a carboxylate group; nonionic groups such as a polyethylene glycol group; combinations of a cationic group and a nonionic group; and combinations of an anionic group and a nonionic group.
  • cationic groups such as quaternary amine groups
  • anionic groups such as a sulfonate group and a carboxylate group
  • nonionic groups such as a polyethylene glycol group
  • combinations of a cationic group and a nonionic group and combinations of an anionic group and a nonionic group.
  • particularly preferred are the nonionic hydrophilic groups, which are free from concerns of yellowing by light or harmful effects by a neutralizer.
  • a neutralizer is required.
  • the neutralizer used is a tertiary amine such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine, and dimethylethanolamine
  • the amine is generated and volatilized by heating during the sheet production or drying and is released outside the system.
  • a device for recovering the volatilized amine is required to be installed. If the amine is not volatilized by the heating but remains in a sheet article as the end product, the amine may be released in the environment when, for example, the product is burned.
  • the polyurethane having a nonionic hydrophilic group can be preferably used.
  • the neutralizer for the anionic hydrophilic group is a hydroxide of an alkali metal or an alkaline earth metal, such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, if a polyurethane portion is wetted with water, alkalinity is demonstrated.
  • the polyurethane having a nonionic hydrophilic group requires no neutralizer, there is no need for concerns about the deterioration of the polyurethane by hydrolysis.
  • the water-dispersible polyurethane used in the present invention may contain various additives, including pigments such as carbon black; flame retardants such as phosphoric flame retardants, halogen flame retardants, silicone flame retardants, and inorganic flame retardants; antioxidants such as phenol antioxidants, sulfur-containing antioxidants, and phosphorus-containing antioxidants; ultraviolet absorbers such as benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and oxalic acid anilide ultraviolet absorbers; light stabilizers such as hindered amine light stabilizers and benzoate light stabilizers; hydrolysis inhibitors such as polycarbodiimide; plasticizers; antistatic agents; surfactants; softening agents; water repellents; coagulation modifiers; viscosity modifiers; dyes; antiseptics; antimicrobials; deodorants; fillers such as cellulose particles and microballoons; and inorganic particles such as silica
  • the water-dispersible polyurethane may also contain inorganic foaming agents such as sodium hydrogen carbonate and organic foaming agents such as 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] in order to form large voids between the fibers and the polyurethane.
  • inorganic foaming agents such as sodium hydrogen carbonate
  • organic foaming agents such as 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]
  • the amount of the polyurethane contained in the fibrous substrate having microfibers as its main constituent according to the present invention is preferably 1 to 80% by mass.
  • the amount of the polyurethane contained in the sheet article is 1% by mass or more, and more preferably 5% by mass or more, the sheet strength can be obtained, and, at the same time, a loss of the fibers can be prevented.
  • the amount of the polyurethane contained in the sheet article is 80% by mass or less, and more preferably 70% by mass or less, the feel is prevented from becoming hard, and a good nap quality can be obtained.
  • the polyvinyl alcohol is removed from the fibrous substrate having the added polyurethane, and a flexible sheet article is obtained.
  • the method for removing the polyvinyl alcohol is not particularly limited, but in a preferred embodiment, the polyvinyl alcohol is dissolved and removed by, for example, immersing the sheet in hot water at 60 to 100°C, and wringing out the water from the sheet with a mangle or the like.
  • the method of manufacturing a sheet article of the present invention may include, after at least the addition of the water-dispersible polyurethane to the fibrous substrate having the added polyvinyl alcohol is performed, a step of cutting the fibrous substrate in half thickness-wise.
  • a large amount of the polyvinyl alcohol adheres to the surface layer of the fibrous substrate by migration, whereas a small amount of the polyvinyl alcohol adheres to the inside of the fibrous substrate.
  • the water-dispersible polyurethane is added and the fibrous substrate is cut in half thickness-wise to give a sheet article having a structure in which a small amount of the water-dispersible polyurethane adheres to the side to which a large amount of the polyvinyl alcohol has adhered, whereas a large amount of the water-dispersible polyurethane adheres to the side to which a small amount of the polyvinyl alcohol has adhered.
  • the side to which a large amount of the polyvinyl alcohol once adhered in other words, the side to which a small amount of the water-dispersible polyurethane has adhered is used as a nap face of the sheet article, the following effects can be obtained.
  • the side to which a small amount of the polyvinyl alcohol once adhered that is, the side to which a large amount of the water-dispersible polyurethane has adhered is used as a nap face of the sheet article
  • the nap-forming fibers are strongly held by the polyurethane. This provides a good surface appearance with a short nap with a more density and also provides a good wear resistance.
  • the process includes the step of cutting the sheet in half thickness-wise, the production efficiency can be improved.
  • At least one side of the sheet article may be subjected to buffing treatment to raise a nap on the surface.
  • the method of raising a nap is not particularly limited, and it is possible to use various methods usually performed in the art, such as buffing with a sandpaper or the like. An excessively short nap is unlikely to provide an elegant appearance, whereas an excessively long nap is likely to cause pilling. Therefore, the length of the raised nap is preferably 0.2 to 1 mm.
  • silicone or the like may be added as a lubricant to the sheet article.
  • a lubricant is preferred because it facilitates buffing by surface grinding and provides the surface with excellent quality.
  • An antistatic agent may also be added before the buffing treatment. The addition of an antistatic agent is preferred because a grinding powder generated from the sheet article by grinding is unlikely to deposit on the sandpaper.
  • the sheet article can be dyed.
  • various methods commonly used in the art can be adopted, and preferred is a method using a jet dyeing machine because, at the same time of dyeing the sheet article, the sheet article can be softened by kneading.
  • the dyeing temperature varies with the type of the fibers but is preferably 80 to 150°C.
  • the dyeing temperature is 80°C or higher, and more preferably 110°C or higher, the attachment of dye to the fibers is efficiently performed.
  • the dyeing temperature is 150°C or lower, and more preferably 130°C or lower, deterioration of the polyurethane can be prevented.
  • the dye used in the present invention is not particularly limited as long as the dye is appropriately selected depending on the type of the fibers constituting the fibrous substrate.
  • a disperse dye can be used.
  • the fibers are polyamide fibers, an acid dye, a metal complex dye, or a combination thereof may be used.
  • the sheet article is dyed with a disperse dye, the sheet article may be subjected to reduction cleaning after the dyeing.
  • a dyeing aid is used during the dyeing.
  • a dyeing aid is used, uniform dyeing is achieved and reproduction of color is improved.
  • finishing treatment can be performed using a fabric softener such as silicone, an antistatic agent, a water repellent, a flame retardant, a light stabilizer, an antimicrobial agent, or other finishing agents.
  • the sheet article obtained by the above-mentioned manufacturing method achieves an elegant appearance and a flexible feel and has good wear resistance.
  • the surface appearance of the sheet article will be evaluated by the following method.
  • the surface appearance of a sheet article is evaluated by 20 panelists including 10 healthy adult males and 10 healthy adult females. Visual evaluation and sensory evaluation are performed and scored based on the following criteria with 5 grades. The grade which had the largest number of the panelists is taken as the grade for the surface appearance of the sheet article. Grades 3 to 5 are regarded as good surface appearance.
  • Grade 5 a uniform nap of the fibers is observed, a scattered state of the fibers is good, and the appearance is good.
  • Grade 4 the material is evaluated as between Grade 5 and Grade 3.
  • Grade 3 as the scattered state of the fibers, some of the fibers are not well separated, but the fibers are napped and the appearance is rather good.
  • Grade 2 the material is evaluated as between Grade 3 and Grade 1.
  • Grade 1 the scattered state of the fibers is very poor throughout the whole surface or the napped fibers have a long length, and the appearance is poor.
  • the flexibility of the sheet article will be evaluated by the magnitude of stiffness (mm) measured as follows, based on 8.21 “Stiffness” and “A method (45° cantilever method)" described in 8.21.1 in JIS L 1096: 2010 "Fabric Testing Methods for Woven and Knit Fabrics”.
  • the stiffness of the sheet article is preferably 20 to 45 mm.
  • the stiffness of the sheet article is more preferably 25 mm or more. In places where the stiffness is high, 40 mm or less is preferable.
  • the wear resistance will be evaluated by a small amount of wear loss (mg) measured by the following method.
  • the wear loss of the sheet article is preferably 30 mg or less.
  • the wear loss is more preferably 25 mg or less.
  • the density of the sheet article obtained by the above-mentioned manufacturing method is preferably 0.2 to 0.7 g/cm 3 .
  • the density is 0.2 g/cm 3 or more, and more preferably 0.3 g/cm 3 or more, the surface is provided with density and high quality appearance.
  • the density is 0.7 g/cm 3 or less, and more preferably 0.6 g/cm 3 or less, the sheet article can be prevented from having a hard feel.
  • a sample obtained by dissolving 10 mg of polyvinyl alcohol in 1 mL of heavy water (D 2 O) at a temperature of 80°C was placed in a straight tube, and 13 C-NMR measurement was performed at a measurement temperature of 80°C, a resonance frequency of 100 MHz, and an integration number of 20000 times or more.
  • ECA400 manufactured by JEOL RESONANCE Inc. was used for the measurement.
  • VE-7800 type manufactured by KEYENCE CORPORATION was used as a scanning electron microscope.
  • a polyethylene terephthalate copolymerized with 8 mol % of sodium 5-sulfoisophthalate was provided as the sea component, and a polyethylene terephthalate was provided as the island component.
  • the sea and island components were used at a ratio of 45% : 55% by mass to give islands-in-the-sea composite fibers with 36 islands per filament and an average single fiber diameter of 17 ⁇ m.
  • the obtained islands-in-the-sea composite fibers were cut into a length of 51 mm to prepare staples.
  • the staples were subjected to carding and cross wrapping to form a fibrous web.
  • the fibrous web was needle punched to give a nonwoven fabric.
  • the thus obtained nonwoven fabric was shrunk by being immersed in hot water at a temperature of 98°C for 2 minutes and was dried at a temperature of 100°C for 5 minutes to give a nonwoven fabric for a fibrous substrate.
  • Polyvinyl alcohol having a saponification degree of 98%, an rrr composition abundance ratio of 15.5%, and a degree of polymerization of 450 obtained from polyvinyl acetate was provided.
  • the polyvinyl alcohol was added to water at 25°C, and the mixture was heated to 90°C.
  • the mixture was stirred for 2 hours while the temperature was maintained at 90°C to give a polyvinyl alcohol aqueous solution with a solid content of 10% by mass.
  • the nonwoven fabric for a fibrous substrate was impregnated with the polyvinyl alcohol aqueous solution, heat-dried at a temperature of 140°C for 10 minutes, and then heat-treated at a temperature of 160°C for 5 minutes.
  • a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained.
  • the sheet having the added polyvinyl alcohol was immersed in a 10 g/L aqueous sodium hydroxide solution heated to a temperature of 60°C and treated for 30 minutes to give a dissolution sheet from which the sea component of the islands-in-the-sea composite fibers was removed.
  • the average single fiber diameter of a cross section of the dissolution sheet was 3 ⁇ m.
  • Polyhexamethylene carbonate was used as a polyol and dicyclohexylmethane diisocyanate was used as an isocyanate to give a self-emulsifying polycarbonate polyurethane liquid.
  • To the self-emulsifying polycarbonate polyurethane liquid was added 1 part by mass of magnesium sulfate as a heat-sensitive coagulant relative to 100 parts by mass of the solid content of the polyurethane liquid. Water was then added to adjust the overall solid content to 20% by mass to give a water-dispersible polyurethane.
  • the heat-sensitive coagulation temperature was 65°C.
  • the dissolution sheet having the added polyvinyl alcohol was impregnated with the polycarbonate polyurethane liquid.
  • the sheet was treated in a dry-heat atmosphere at a temperature of 120°C for 10 minutes, then dried, and dry-heated at a temperature of 150°C for 2 minutes.
  • the sheet to which the polyurethane was adhered was immersed in water heated to 95°C and treated for 10 minutes to give a sheet from which the added polyvinyl alcohol was removed.
  • the polyvinyl alcohol-removed sheet was cut in half thickness-wise.
  • the surfaces opposite to the cut surfaces were subjected to buffing treatment by grinding with a 240-mesh abrasive belt. Thereafter, the sheet was dyed with a disperse dye by using a circular dyeing machine and subjected to reduction cleaning to give a sheet article.
  • the obtained sheet article had a good surface appearance and a flexible feel.
  • a polyethylene terephthalate copolymerized with 8 mol % of sodium 5-sulfoisophthalate was provided as the sea component, and a polyethylene terephthalate was provided as the island component.
  • the sea and island components were used at a ratio of 45% : 55% by mass to give islands-in-the-sea composite fibers with 16 islands per filament and an average single fiber diameter of 12 ⁇ m.
  • the obtained islands-in-the-sea composite fibers were cut into a length of 51 mm to prepare staples.
  • the staples were subjected to carding and cross wrapping to form a fibrous web.
  • the fibrous web was needle punched to give a nonwoven fabric.
  • the thus obtained nonwoven fabric was shrunk by being immersed in hot water at a temperature of 98°C for 2 minutes and was dried at a temperature of 100°C for 5 minutes to give a nonwoven fabric for a fibrous substrate.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Example 1.
  • Example 2 The same polyvinyl alcohol aqueous solution as in Example 1 was used, and a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained.
  • the nonwoven fabric for a fibrous substrate was treated in the same manner as in Example 1 to obtain a dissolution sheet from which the sea components of the islands-in-the-sea composite fibers were removed.
  • the average single fiber diameter of a cross section of the dissolution sheet was 2 ⁇ m.
  • the obtained sheet article had a good surface appearance, a flexible feel, and good wear resistance.
  • a polyethylene terephthalate copolymerized with 8 mol % of sodium 5-sulfoisophthalate was provided as the sea component, and a polyethylene terephthalate was provided as the island component.
  • the sea and island components were used at a ratio of 20% : 80% by mass to give islands-in-the-sea composite fibers with 16 islands per filament and an average single fiber diameter of 20 ⁇ m.
  • the obtained islands-in-the-sea composite fibers were cut into a length of 51 mm to prepare staples.
  • the staples were subjected to carding and cross wrapping to form a fibrous web.
  • the fibrous web was needle punched to give a nonwoven fabric.
  • the thus obtained nonwoven fabric was shrunk by being immersed in hot water at a temperature of 98°C for 2 minutes and was dried at a temperature of 100°C for 5 minutes to give a nonwoven fabric for a fibrous substrate.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Example 1.
  • Example 2 The same polyvinyl alcohol aqueous solution as in Example 1 was used, and a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained.
  • the nonwoven fabric for a fibrous substrate was treated in the same manner as in Example 1 to obtain a dissolution sheet from which the sea components of the islands-in-the-sea composite fibers were removed.
  • the average single fiber diameter of a cross section of the dissolution sheet was 4.4 ⁇ m.
  • the obtained sheet article had a good surface appearance, a flexible feel, and good wear resistance.
  • a polyethylene terephthalate copolymerized with 8 mol % of sodium 5-sulfoisophthalate was provided as the sea component, and a polyethylene terephthalate was provided as the island component.
  • the sea and island components were used at a ratio of 10% : 90% by mass to give islands-in-the-sea composite fibers with 16 islands per filament and an average single fiber diameter of 24 ⁇ m.
  • the obtained islands-in-the-sea composite fibers were cut into a length of 51 mm to prepare staples.
  • the staples were subjected to carding and cross wrapping to form a fibrous web.
  • the fibrous web was needle punched to give a nonwoven fabric.
  • the thus obtained nonwoven fabric was shrunk by being immersed in hot water at a temperature of 98°C for 2 minutes and was dried at a temperature of 100°C for 5 minutes to give a nonwoven fabric for a fibrous substrate.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Example 1.
  • Example 2 The same polyvinyl alcohol aqueous solution as in Example 1 was used, and a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained.
  • the nonwoven fabric for a fibrous substrate was treated in the same manner as in Example 1 to obtain a dissolution sheet from which the sea components of the islands-in-the-sea composite fibers were removed.
  • the average single fiber diameter of a cross section of the dissolution sheet was 5.5 ⁇ m.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • Example 2 In the same manner as in Example 1, a sheet article was obtained.
  • the obtained sheet article had a good surface appearance, a flexible feel, and good wear resistance.
  • Example 2 The same nonwoven fabric for a fibrous substrate as in Example 1 was used.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Example 1.
  • Example 2 The same polyvinyl alcohol aqueous solution as in Example 1 was used, and a sheet having the added polyvinyl alcohol was obtained in the same manner as in Example 1 except that the amount of the polyvinyl alcohol adhering was changed by controlling the degree of wringing after the impregnation. In the sheet, the amount of polyvinyl alcohol adhering was 20% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate.
  • Example 2 In the same manner as in Example 1, a dissolution sheet was obtained from the nonwoven fabric for a fibrous substrate.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the obtained sheet article had a good surface appearance, a flexible feel, and good wear resistance.
  • a polyethylene terephthalate copolymerized with 8 mol % of sodium 5-sulfoisophthalate was provided as the sea component, and a polyethylene terephthalate was provided as the island component.
  • the sea and island components were used at a ratio of 20% : 80% by mass to give islands-in-the-sea composite fibers with 16 islands per filament and an average single fiber diameter of 20 ⁇ m.
  • the obtained islands-in-the-sea composite fibers were cut into a length of 51 mm to prepare staples. The staples were subjected to carding and cross wrapping to form a fibrous web.
  • a plain woven fabric using a polyethylene terephthalate (PET) hard twist yarn of 84 dtex and 72 filaments with a twist of 2000 T/m was stacked, and needle punching was performed to give a nonwoven fabric.
  • the thus obtained nonwoven fabric was shrunk by being immersed in hot water at a temperature of 98°C for 2 minutes and was dried at a temperature of 100°C for 5 minutes to give a nonwoven fabric for a fibrous substrate.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Example 1.
  • Example 2 The same polyvinyl alcohol aqueous solution as in Example 1 was used, and a sheet having the added polyvinyl alcohol was obtained in the same manner as in Example 1 except that the amount of the polyvinyl alcohol adhering was changed by controlling the degree of wringing after the impregnation. In the sheet, the amount of polyvinyl alcohol adhering was 15% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate.
  • the nonwoven fabric for a fibrous substrate was treated in the same manner as in Example 1 to obtain a dissolution sheet from which the sea components of the islands-in-the-sea composite fibers were removed.
  • the average single fiber diameter of a cross section of the dissolution sheet was 4.4 ⁇ m.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • a sheet article was obtained in the same manner as in Example 1 except that the cut surface was ground and subjected to buffing.
  • the obtained sheet article had a good surface appearance, a flexible feel, and good wear resistance.
  • Example 2 The same nonwoven fabric for a fibrous substrate as in Example 1 was used.
  • Polyvinyl alcohol having a saponification degree of 98%, an rrr composition abundance ratio of 15.2%, and a degree of polymerization of 1000 obtained from polyvinyl acetate was provided.
  • the polyvinyl alcohol was added to water at 25°C, and the mixture was heated to 90°C.
  • the mixture was stirred for 2 hours while the temperature was maintained at 90°C to give a polyvinyl alcohol aqueous solution with a solid content of 10% by mass.
  • a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was used.
  • Example 2 In the same manner as in Example 1, a dissolution sheet was obtained from the nonwoven fabric for a fibrous substrate.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the obtained sheet article had a good surface appearance, a flexible feel, and good wear resistance.
  • a nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 6.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Example 7.
  • a sheet to which the polyvinyl alcohol was added in an amount of 15% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 6 except that the polyvinyl alcohol aqueous solution of Example 7 was used.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the obtained sheet article had a good surface appearance, a flexible feel, and good wear resistance.
  • Example 2 The same nonwoven fabric for a fibrous substrate as in Example 1 was used.
  • Polyvinyl alcohol having a saponification degree of 98%, an rrr composition abundance ratio of 14.1%, and a degree of polymerization of 400 obtained from polyvinyl acetate was provided.
  • the polyvinyl alcohol was added to water at 25°C, and the mixture was heated to 90°C.
  • the mixture was stirred for 2 hours while the temperature was maintained at 90°C to give a polyvinyl alcohol aqueous solution with a solid content of 10% by mass.
  • a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was used.
  • Example 2 In the same manner as in Example 1, a dissolution sheet was obtained from the nonwoven fabric for a fibrous substrate.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the polyvinyl alcohol was not uniformly added due to partial dissolution of the polyvinyl alcohol into the aqueous alkaline solution and the water-dispersible polyurethane liquid.
  • the sheet article had a poor surface appearance with a poor scattered state of the fibers and with no dense nap and had a hard feel.
  • a nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 6.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Comparative Example 1.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the polyvinyl alcohol was not uniformly added due to partial dissolution of the polyvinyl alcohol into the aqueous alkaline solution and the water-dispersible polyurethane liquid.
  • the sheet article had a poor surface appearance with a poor scattered state of the fibers and with no dense nap and had a hard feel.
  • Example 2 The same nonwoven fabric for a fibrous substrate as in Example 1 was used.
  • Polyvinyl alcohol having a saponification degree of 98%, an rrr composition abundance ratio of 13.9%, and a degree of polymerization of 500 obtained from polyvinyl acetate was provided.
  • the polyvinyl alcohol was added to water at 25°C, and the mixture was heated to 90°C.
  • the mixture was stirred for 2 hours while the temperature was maintained at 90°C to give a polyvinyl alcohol aqueous solution with a solid content of 10% by mass.
  • a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was used.
  • Example 2 In the same manner as in Example 1, a dissolution sheet was obtained from the nonwoven fabric for a fibrous substrate.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the polyvinyl alcohol was not uniformly added due to partial dissolution of the polyvinyl alcohol into the aqueous alkaline solution and the water-dispersible polyurethane liquid.
  • the sheet article had a poor surface appearance with a poor scattered state of the fibers and with no dense nap and had a hard feel.
  • Example 2 The same nonwoven fabric for a fibrous substrate as in Example 1 was used.
  • Polyvinyl alcohol having a saponification degree of 99%, an rrr composition abundance ratio of 14.4%, and a degree of polymerization of 500 obtained from polyvinyl acetate was provided.
  • the polyvinyl alcohol was added to water at 25°C, and the mixture was heated to 90°C. The mixture was stirred for 2 hours while the temperature was maintained at 90°C to give a polyvinyl alcohol aqueous solution with a solid content of 10% by mass.
  • a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was used.
  • Example 2 In the same manner as in Example 1, a dissolution sheet was obtained from the nonwoven fabric for a fibrous substrate.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the polyvinyl alcohol was not uniformly added due to partial dissolution of the polyvinyl alcohol into the aqueous alkaline solution and the water-dispersible polyurethane liquid.
  • the sheet article had a poor surface appearance with a poor scattered state of the fibers and with no dense nap and had a hard feel.
  • Example 2 The same nonwoven fabric for a fibrous substrate as in Example 1 was used.
  • Polyvinyl alcohol having a saponification degree of 88%, an rrr composition abundance ratio of 14.2%, and a degree of polymerization of 500 obtained from polyvinyl acetate was provided.
  • the polyvinyl alcohol was added to water at 25°C, and the mixture was heated to 90°C.
  • the mixture was stirred for 2 hours while the temperature was maintained at 90°C to give a polyvinyl alcohol aqueous solution with a solid content of 10% by mass.
  • a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was used.
  • Example 2 In the same manner as in Example 1, a dissolution sheet was obtained from the nonwoven fabric for a fibrous substrate.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the polyvinyl alcohol was not uniformly added due to partial dissolution of the polyvinyl alcohol into the aqueous alkaline solution and the water-dispersible polyurethane liquid.
  • the sheet article had a poor surface appearance with a poor scattered state of the fibers and with no dense nap and had a hard feel.
  • Example 2 The same nonwoven fabric for a fibrous substrate as in Example 1 was used.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Example 1.
  • the nonwoven fabric for a fibrous substrate obtained above was immersed in a 10 g/L aqueous sodium hydroxide solution heated to a temperature of 95°C and treated for 10 minutes to give a dissolution sheet from which the sea component of the islands-in-the-sea composite fibers was removed.
  • the average single fiber diameter of the surface of the dissolution sheet was 3 ⁇ m.
  • the above dissolution sheet was impregnated with the polyvinyl alcohol aqueous solution obtained in Example 1.
  • the sheet was heat-dried at a temperature of 140°C for 10 minutes to give a sheet to which the polyvinyl alcohol was added in an amount of 30% by mass to the dissolution sheet.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • the obtained sheet article had a good surface appearance and a flexible feel, but the wear loss was relatively large.
  • Example 2 The same nonwoven fabric for a fibrous substrate as in Example 1 was used.
  • a polyvinyl alcohol aqueous solution was obtained in the same manner as in Example 1.
  • Example 2 The same polyvinyl alcohol aqueous solution as in Example 1 was used, and a sheet to which the polyvinyl alcohol was added in an amount of 55% by mass relative to the mass of the fibers in the nonwoven fabric for a fibrous substrate was obtained in the same manner as in Example 1 except that the amount of the polyvinyl alcohol adhering was changed by controlling the degree of wringing after the impregnation.
  • Example 2 In the same manner as in Example 1, a dissolution sheet was obtained from the nonwoven fabric for a fibrous substrate.
  • Example 1 The same water-dispersible polyurethane liquid as in Example 1 was used.
  • Example 2 In the same manner as in Example 1, a sheet article was obtained.
  • the obtained sheet article had a flexible feel.
  • the excess amount of the polyvinyl alcohol resulted in insufficient holding of the fibers by the polyurethane.
  • the sheet article had a poor surface appearance with an excessively long nap and had a poor wear resistance.
  • Table 1 shows the test conditions and the evaluation results for the sheet articles in Examples and Comparative Examples.
  • Fibrous substrate Polyvinyl alcohol (PVA) Amount of PVA adhering relative to fibers of fibrous substrate Sheet article Average single fiber diameter Saponification degree Abundance ratio Degree of polymerization Viscosity Sheet density Feel Wear resistance Surface appearance rrr composition mrr composition Total of mmm composition and mmr composition Unit ( ⁇ m) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (-) (mPs ⁇ s) (mass%) (g/cm 3 ) (mm) (
  • the sheet articles had a poor surface appearance with a poor scattered state of the fibers and with no dense nap.
  • the bonding area between the fibers and the polyvinyl alcohol increased during the manufacturing process, and the holding of the fibers by the polyurethane was weakened, resulting in poor wear resistance.
  • the sheet article obtained according to the present invention is suitable as interior materials having a very elegant appearance, such as surface materials of furniture, chairs, walls, seats in vehicles including automobiles, trains, and aircrafts, ceiling, and interior decoration; clothing materials, such as shirts, jackets, upper and trim and the like of shoes including casual shoes, sports shoes, men's shoes and ladies' shoes, bags, belts, wallets, and a part of them; and industrial materials such as wiping cloth, abrasive cloth and CD curtains.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Paper (AREA)
EP19823144.1A 2018-06-20 2019-06-18 Method of manufacturing sheet article Active EP3812507B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018116758 2018-06-20
PCT/JP2019/024016 WO2019244862A1 (ja) 2018-06-20 2019-06-18 シート状物の製造方法

Publications (3)

Publication Number Publication Date
EP3812507A1 EP3812507A1 (en) 2021-04-28
EP3812507A4 EP3812507A4 (en) 2022-01-26
EP3812507B1 true EP3812507B1 (en) 2025-05-21

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EP19823144.1A Active EP3812507B1 (en) 2018-06-20 2019-06-18 Method of manufacturing sheet article

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EP (1) EP3812507B1 (https=)
JP (1) JP7163959B2 (https=)
KR (1) KR102708132B1 (https=)
CN (1) CN112262238A (https=)
TW (1) TWI807050B (https=)
WO (1) WO2019244862A1 (https=)

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CN120641615A (zh) * 2023-02-08 2025-09-12 株式会社可乐丽 人造革基材及人造革基材的制造方法
CN120641616A (zh) * 2023-02-08 2025-09-12 株式会社可乐丽 人造革基材及人造革基材的制造方法
KR20250052887A (ko) 2023-10-12 2025-04-21 주식회사 한국에너지 합성수지의 열분해 유화 장치

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Publication number Priority date Publication date Assignee Title
JPS5350302A (en) * 1976-10-15 1978-05-08 Toray Industries Production of suede like artificial leather
EP0389833B1 (en) * 1989-03-07 1994-01-05 Kuraray Co., Ltd. Vinyl alcohol polymers and a process for their production
WO1994028223A1 (en) * 1993-06-02 1994-12-08 Minnesota Mining And Manufacturing Company Nonwoven articles and methods of producing same
JP3875805B2 (ja) * 1998-12-24 2007-01-31 株式会社クラレ 皮革様シートの製造方法
JP2002030579A (ja) 2000-07-17 2002-01-31 Toray Ind Inc 立毛調皮革様シート状物およびその製造方法
JP5958060B2 (ja) * 2012-05-10 2016-07-27 東レ株式会社 シート状物およびその製造方法
EP2896741B1 (en) * 2012-09-14 2019-08-07 Toray Industries, Inc. Process for manufacturing a leather-like nonwoven fabric
EP2927368B1 (en) 2012-11-30 2017-10-11 Toray Industries, Inc. Process for producing a leather-like sheet-shaped object
US9354357B2 (en) * 2013-01-28 2016-05-31 Sekisui Specialty Chemicals America, Llc Water soluble high syndiotactic polyvinyl alcohol
JP6651849B2 (ja) * 2014-02-25 2020-02-19 東レ株式会社 海島複合繊維、複合極細繊維および繊維製品

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KR20210018998A (ko) 2021-02-19
CN112262238A (zh) 2021-01-22
JP7163959B2 (ja) 2022-11-01
JPWO2019244862A1 (ja) 2021-07-08
WO2019244862A1 (ja) 2019-12-26
TWI807050B (zh) 2023-07-01
TW202006200A (zh) 2020-02-01
KR102708132B1 (ko) 2024-09-19
EP3812507A1 (en) 2021-04-28
EP3812507A4 (en) 2022-01-26

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