EP3951047A1 - Article en forme de feuille et procédé de fabrication associé - Google Patents

Article en forme de feuille et procédé de fabrication associé Download PDF

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Publication number
EP3951047A1
EP3951047A1 EP20783144.7A EP20783144A EP3951047A1 EP 3951047 A1 EP3951047 A1 EP 3951047A1 EP 20783144 A EP20783144 A EP 20783144A EP 3951047 A1 EP3951047 A1 EP 3951047A1
Authority
EP
European Patent Office
Prior art keywords
elastic body
polymer elastic
sheet
shaped article
hydrophilic group
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.)
Pending
Application number
EP20783144.7A
Other languages
German (de)
English (en)
Other versions
EP3951047A4 (fr
Inventor
Ryuji SHIKURI
Koki ISHII
Takuya SHIBANO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Publication of EP3951047A1 publication Critical patent/EP3951047A1/fr
Publication of EP3951047A4 publication Critical patent/EP3951047A4/fr
Pending legal-status Critical Current

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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
    • D06N3/0002—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
    • D06N3/12—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
    • D06N3/146—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 characterised by the macromolecular diols used
    • 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
    • D06N3/0011—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
    • D06N3/0002—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
    • D06N3/0015—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 fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
    • D06N3/0031—Retractable fibres; Shrinking of fibres during manufacture
    • 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
    • D06N3/0015—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 fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0036—Polyester fibres
    • 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
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0052—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by leaching out of a compound, e.g. water soluble salts, fibres or fillers; obtained by freezing or sublimation; obtained by eliminating drops of sublimable fluid
    • 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
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • 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
    • D06N3/0056—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
    • D06N3/0065—Organic pigments, e.g. dyes, brighteners
    • 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
    • D06N3/0075—Napping, teasing, raising or abrading of the resin coating
    • 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
    • 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
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • 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
    • D06N2209/1635—Elasticity
    • 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
    • D06N2211/14—Furniture, upholstery
    • 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
    • D06N2211/18—Medical, e.g. bandage, prostheses, catheter
    • 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
    • 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
    • D06N2211/265—Trains
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    • 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
    • D06N2211/267—Aircraft
    • D—TEXTILES; PAPER
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    • 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 sheet-shaped article and a method for manufacturing the sheet-shaped article, and particularly preferably to a sheet-shaped article having a raised nap and a method for manufacturing the sheet-shaped article.
  • Sheet-shaped articles mainly including a fibrous substrate and polyurethane such as a nonwoven fabric have superior characteristics not shared with natural leather, and are widely used for various applications such as artificial leather.
  • sheet-shaped articles using a polyester-based fibrous substrate have superior lightfast, so that their usage as clothing, chair covering, and automobile interior material has increasingly been extended year by year.
  • a combination of steps has been generally adopted, including: impregnating a fibrous substrate with a polyurethane-containing organic solvent solution; and then immersing the resulting fibrous substrate in an aqueous solution containing water or an organic solvent in which polyurethane is not dissolved, thereby subjecting the polyurethane to wet coagulation.
  • a water miscible organic solvent such as N,N-dimethylformamide is used as the organic solvent that is a solvent for polyurethane.
  • the organic solvents are highly harmful to the environment in general, a procedure without using any organic solvent has been strongly sought in manufacturing the sheet-shaped article.
  • a method has been considered in which a water-dispersible polyurethane prepared by dispersing a polyurethane resin into water is used as an alternative for the conventional organic solvent-based polyurethane.
  • a method has been proposed in which a thickener is added to a solution containing a water-dispersible polyurethane, and a fibrous substrate impregnated with the solution is treated with hot water, thereby reducing the domain size of polyurethane and reducing retaining forces of entangled portions of fibers by the water-dispersible polyurethane (Patent Document 1).
  • an object of the present invention is to provide a sheet-shaped article having both a supple texture and superior wear resistance, and a method for manufacturing the sheet-shaped article.
  • a sheet-shaped article manufactured by impregnating a fibrous substrate with a water-dispersible polyurethane dispersion in which a water-dispersible polyurethane has been dispersed in the liquid and coagulating the polyurethane tends to have a hard texture.
  • a water-dispersible polyurethane dispersion in which a water-dispersible polyurethane has been dispersed in the liquid and coagulating the polyurethane tends to have a hard texture.
  • the coagulated form of the organic solvent-based polyurethane liquid is a coagulated form obtained by replacing the solvent for a polyurethane molecule, which has been dissolved in the organic solvent, by water, and is generally obtained by using a so-called wet coagulation process.
  • this polyurethane when a film was formed and the structure after coagulation was observed, a porous film having a low density was formed in the organic solvent-based polyurethane film coagulated by the wet coagulation process.
  • This low-density porous structure causes the contact area between fibers and the polyurethane at the time of coagulation to be reduced even in the case where the polyurethane is soaked in a fibrous substrate, and thus a soft sheet-shaped article is considered to be obtained.
  • a so-called dry coagulation process including disintegrating the hydration state of a water-dispersible polyurethane dispersion mainly by heating to cause polyurethane emulsions to be aggregated to one another for coagulation.
  • a nonporous film having a high density was formed in the film of the water-dispersible polyurethane coagulated by the dry coagulation process. This enhances the adhesion between a fibrous substrate and the polyurethane, thereby strongly retaining entangled portions of fibers. Accordingly, it is considered that this makes the texture hard.
  • the inventors have found that a specific amount of a monovalent positive ion-including inorganic salt and a crosslinker is used in coagulation of a hydrophilic group-having polymer elastic body, whereby it is possible to manufacture not only a sheet-shaped article in consideration of the environment, but also a sheet-shaped article having superior texture and wear resistance as compared with a conventional sheet-shaped article.
  • the present invention has been completed.
  • the present invention is intended to solve the above-described problems, and the sheet-shaped article of the present invention is a sheet-shaped article including a fibrous substrate including ultrafine fibers with an average individual fiber fineness of 0.1 ⁇ m or more and 10 ⁇ m or less, the fibrous substrate containing a hydrophilic group-having polymer elastic body, in which an inside of the polymer elastic body has N-acylurea bonding and/or isourea bonding, and a monovalent positive ion-including inorganic salt is present at a rate of 0.1 mass% or more and 5 mass% or less, with regard to a mass of the polymer elastic body.
  • the monovalent positive ion-including inorganic salt is sodium chloride and/or sodium sulfate.
  • the polymer elastic body contains a polyether diol as a constituent.
  • the polymer elastic body includes a hydrophilic group-having polymer elastic body A containing a polyether diol as a constituent, and a hydrophilic group-having polymer elastic body B containing a polycarbonate diol as a constituent.
  • a bending resistance as specified in JIS L 1096: 2010 (a 45° cantilever method) is 50 mm or more and 180 mm or less, and an abrasion loss after 20,000 times of rubbing by a Martindale abrasion test as specified in JIS L 1096: 2010 is 10 mg or less.
  • a method for manufacturing a sheet-shaped article includes: impregnating a fibrous substrate including ultrafine fibers with an average individual fiber fineness of 0.1 ⁇ m or more and 10 ⁇ m or less with an aqueous dispersion containing a hydrophilic group-having polymer elastic body, a monovalent positive ion-including inorganic salt, and a crosslinker; and subjecting the fibrous substrate to a heat treatment at a temperature of 100°C or more and 180°C or less, in which a content of the monovalent positive ion-including inorganic salt in the aqueous dispersion is 10 mass% or more and 50 mass% or less with regard to a mass of a solid content of the hydrophilic group-having polymer elastic body.
  • the monovalent positive ion-including inorganic salt is sodium chloride and/or sodium sulfate.
  • the crosslinker is a carbodiimide-based crosslinker.
  • the hydrophilic group-having polymer elastic body contains a polyether diol as a constituent.
  • a hydrophilic group-having polymer elastic body X and a hydrophilic group-having polymer elastic body Y having compositions different from each other are contained in the aqueous dispersion liquid, and the hydrophilic group-having polymer elastic body Y is coagulated after the hydrophilic group-having polymer elastic body X is coagulated.
  • a sheet-shaped article having both a supple texture and superior wear resistance is obtained.
  • the sheet-shaped article of the present invention is a sheet-shaped article including a fibrous substrate including ultrafine fibers with an average individual fiber fineness of 0.1 ⁇ m or more and 10 ⁇ m or less, the fibrous substrate containing a hydrophilic group-having polymer elastic body, in which an inside of the polymer elastic body has N-acylurea bonding and/or isourea bonding, and a monovalent positive ion-including inorganic salt is present at a rate of 0.1 mass% or more and 5 mass% or less, with regard to a mass of the polymer elastic body.
  • 0.1 mass% or more and 5 mass% or less with regard to the mass of the polymer elastic body means that the mass of the monovalent positive ion-including inorganic salt is 0.1 or more and 5 or less with regard to 100 mass of the polymer elastic body. That is, in this case, the total mass of the polymer elastic body and the monovalent positive ion-including inorganic salt is 100.1 or more and 105 or less.
  • this constituent element will be described in detail, but the present invention is not limited to the scope described below at all as long as it is not beyond the gist of the present invention.
  • a polyester-based resin can be used as the ultrafine fiber used in the present invention.
  • the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate.
  • the polyester-based resin can be obtained from, for example, a dicarboxylic acid and/or an ester-forming derivative thereof and a diol.
  • Examples of the dicarboxylic acid and/or the ester-forming derivative thereof used for the polyester-based resin include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, and an ester-forming derivative thereof.
  • the ester-forming derivative referred in the present invention is a lower alkyl ester of a dicarboxylic acid, an acid anhydride, an acyl chloride, and the like. Specifically, a methyl ester, an ethyl ester, a hydroxyethyl ester, and the like are preferably used.
  • a more preferred embodiment of a dicarboxylic acid and/or an ester-forming derivative thereof used in the present invention is a terephthalic acid and/or a dimethyl ester thereof.
  • diol used in the polyester-based resin examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and cyclohexanedimethanol. Among them, ethylene glycol is preferably used.
  • the polyester-based resin may contain particles of metal oxides, pigments, and the like that are usually used, and additives such as a flame retardant and an antistatic agent as long as the effects of the present invention are not impaired.
  • the cross-sectional shape of the ultrafine fiber may be either a round cross section or a modified cross section.
  • the modified cross section include an elliptical shape, a flat shape, a polygonal shape such as a triangular shape, a fan-like shape, and a cross shape.
  • the average individual fiber fineness of the ultrafine fibers is 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the average individual fiber fineness of the ultrafine fibers is 10 ⁇ m or less, preferably 7 ⁇ m or less, and more preferably 5 ⁇ m or less, it is possible to cause the sheet-shaped article to be more supple. In a case where the sheet-shaped article has a raised nap, the raised nap quality can be improved.
  • the average individual fiber fineness of the ultrafine fibers is 0.1 ⁇ m or more, preferably 0.3 ⁇ m or more, and more preferably 0.7 ⁇ m or more, it is possible to obtain a sheet-shaped article superior in color developability after dyeing. Further, in a case where the sheet-shaped article has a raised nap, when napped by buffing, bundled ultrafine fibers can be easy to disperse and handle.
  • the average individual fiber fineness referred to in the present invention is measured by the following method. That is:
  • the fibrous substrate used in the present invention is made of the ultrafine fiber.
  • it is allowed that ultrafine fibers of different raw materials are mixed in the fibrous substrate.
  • a nonwoven fabric in which the above ultrafine fibers are interlaced or a nonwoven fabric in which fiber bundles of ultrafine fibers are interlaced.
  • a nonwoven fabric in which fiber bundles of ultrafine fibers are interlaced is preferably used, from the viewpoints of the strength and texture of a sheet-shaped article. From the viewpoints of flexibility and texture, it is particularly preferable to use a nonwoven fabric in which ultrafine fibers constituting fiber bundles of ultrafine fibers are appropriately spaced from one another to form spaces.
  • the nonwoven fabric in which fiber bundles of ultrafine fibers are interlaced, may be obtained by, for example, beforehand interlacing ultrafine fiber-generating fibers and then generating ultrafine fibers. Further, the nonwoven fabric, in which ultrafine fibers constituting fiber bundles of ultrafine fibers are appropriately spaced from one another to form spaces, may be obtained by, for example, using islands-in-the-sea fibers in which a sea component may be removed to make a space between island components.
  • the nonwoven fabric may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric. From the viewpoint of the texture and quality of the sheet-shaped article, the short fiber nonwoven fabric is more preferably used.
  • the fiber length of the short fibers in the case of using the short fiber nonwoven fabric is in a range of 25 mm or more and 90 mm or less.
  • the fiber length is 25 mm or more, more preferably 35 mm or more, and still more preferably 40 mm or more, a sheet-shaped article with superior wear resistance is obtained by interlacing.
  • the fiber length is set to 90 mm or less, more preferably 80 mm or less, and still more preferably 70 mm or less, so that it is possible to obtain a sheet-shaped article having more superior texture and quality.
  • a nonwoven fabric when used as the fibrous substrate, a woven fabric or a knitted fabric may be inserted into or laminated on the nonwoven fabric, or the nonwoven fabric may be lined with a woven fabric or a knitted fabric, for the purpose of improving strength or the like.
  • the average individual fiber fineness of the fibers constituting the woven fabric and the knitted fabric is more preferably 0.3 ⁇ m or more and 10 ⁇ m or less, because damage during needle punching can be reduced and the strength can be maintained.
  • the fibers constituting the woven fabric and the knitted fabric it is possible to use a polyester such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, or polylactic acid, a synthetic fiber such as a polyamide such as 6-nylon or 66-nylon, a regenerated fiber such as cellulosic polymer, and a natural fiber such as cotton or hemp.
  • a polyester such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, or polylactic acid
  • a synthetic fiber such as a polyamide such as 6-nylon or 66-nylon
  • a regenerated fiber such as cellulosic polymer
  • a natural fiber such as cotton or hemp.
  • examples of the hydrophilic group-having polymer elastic body include water-dispersible silicone resins, water-dispersible acrylic resins, water-dispersible urethane resins, and copolymers thereof.
  • water-dispersible polyurethane resins are preferably used from the viewpoint of texture.
  • the water-dispersible polyurethane resin a resin obtained by a reaction of a polymeric polyol having a number average molecular weight of preferably 500 or more and 5000 or less, an organic polyisocyanate, and a chain extender is preferably used. Further, in order to enhance the stability of the water-dispersible polyurethane dispersion, it is preferable to use an active hydrogen component-containing compound having a hydrophilic group in combination.
  • the number average molecular weight of the polymeric polyol is set to 500 or more, and more preferably 1500 or more, so that it is possible to easily prevent the texture from becoming hard.
  • the number average molecular weight is set to 5000 or less, and more preferably 4000 or less, so that it is possible to easily maintain the strength of the polyurethane as a binder.
  • a water-dispersible polyurethane resin is used as the polymer elastic body will be described.
  • polymeric polyol examples include polyether polyol, polyester polyol, and polycarbonate polyol.
  • polyether polyol examples include polyols obtained by adding and polymerizing a monomer such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, or cyclohexylene using a polyhydric alcohol or a polyamine as an initiator, and polyols obtained by ring-opening polymerization of the monomer using a protic acid, a Lewis acid, a cationic catalyst, or the like as a catalyst.
  • Specific examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymerized polyol obtained by combining these glycols.
  • polyester polyol examples include polyester polyols obtained by condensing various low-molecular-weight polyols with a polybasic acid, and polyols obtained by ring-opening polymerization of lactones.
  • low-molecular-weight polyols include one or more selected from linear alkylene glycols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1.8-octanediol, 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; and aromatic dihydric alcohols such as 1,4-bis( ⁇ -hydroxyethoxy)benzene. Adducts obtained by adding various linear al
  • polybasic acid examples include one or more selected from the group consisting of 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.
  • polycarbonate polyol examples include compounds obtained by reacting a polyol with a carbonate compound such as a dialkyl carbonate or a diaryl carbonate.
  • the polyol as a raw material for manufacturing the polycarbonate polyol the polyols exemplified in the raw materials for manufacturing the polyester polyol can be used.
  • the dialkyl carbonate a dimethyl carbonate, a diethyl carbonate, or the like can be used, and as the diaryl carbonate, a diphenyl carbonate or the like can be listed.
  • the polymer elastic body preferably contains a polyether diol as a constituent.
  • the term "contain as a constituent” refers to containing as a monomer component or an oligomer component constituting the polymer elastic body.
  • the polyether diol has a high degree of freedom of the ether bond, and thus has a low glass transition temperature and a weak cohesive force. Accordingly, a polyurethane having superior flexibility is easily obtained.
  • the polymer elastic body preferably includes a hydrophilic group-having polymer elastic body A containing a polyether diol as a constituent, and a hydrophilic group-having polymer elastic body B containing a polycarbonate diol as a constituent.
  • a hydrophilic group-having polymer elastic body A containing a polyether diol as a constituent superior in flexibility and the hydrophilic group-having polymer elastic body B containing a polycarbonate diol as a constituent superior in durability against external stimuli such as light and heat are contained in the sheet-shaped article, whereby a sheet-shaped article superior in flexibility and durability is easily obtained.
  • Examples of the organic diisocyanate used in the present invention include a C6-20 aromatic diisocyanate (excluding carbon atoms in an NCO group; the same applies to the following), a C2-18 aliphatic diisocyanate, a C4-15 alicyclic diisocyanate, a C8-15 aroaliphatic diisocyanate, a modified product of these diisocyanates (e.g., a carbodiimide-modified product, a urethane-modified product, a uretdione-modified product), or a mixture of two or more kinds thereof.
  • a C6-20 aromatic diisocyanate excluding carbon atoms in an NCO group; the same applies to the following
  • a C2-18 aliphatic diisocyanate excluding carbon atoms in an NCO group
  • C4-15 alicyclic diisocyanate e.g., a C4-15 alicyclic diisocyanate
  • C6-20 aromatic diisocyanate examples include 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate, 2,4'- and/or 4,4'-diphenylmethane diisocyanate (hereinafter, abbreviated as MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, and 1,5-naphthylene diisocyanate.
  • MDI 1,3- and/or 1,4-phenylene diisocyanate
  • 2,4- and/or 2,6-tolylene diisocyanate 2,4'- and/or 4,4'-diphenylmethane diisocyanate
  • MDI 4,4'-diisocyanatobiphenyl
  • C2-18 aliphatic diisocyanate examples include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis(2-isocyanatoethyl)carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexaate.
  • C4-15 alicyclic diisocyanate examples include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexylene-1,2-dicarboxylate, and 2,5- and/or 2,6-norbornane diisocyanate.
  • C8-15 aroaliphatic diisocyanate examples include m- and/or p-xylylene diisocyanate, and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate.
  • a preferred organic diisocyanate is an alicyclic diisocyanate.
  • a particularly preferred organic diisocyanate is dicyclohexylmethane-4,4'-diisocyanate.
  • Examples of the chain extender used in the present invention include water, a low-molecular-weight diol such as "ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, or neopentyl glycol", an alicyclic diol such as "1,4-bis(hydroxymethyl)cyclohexane", an aromatic diol such as "1,4-bis(hydroxyethyl)benzene", an aliphatic diamine such as "ethylenediamine", an alicyclic diamine such as “isophoronediamine", an aromatic diamine such as "4-4-diaminodiphenylmethane", an aroaliphatic diamine such as "xylenediamine", an alkanolamine such as "ethanolamine", hydrazine, a dihydrazide such as “adipic acid dihydrazide”, and a mixture of two or
  • preferred chain extenders are water, low molecular weight diols, and aromatic diamines, and more preferred examples thereof include water, ethylene glycol, 1,4-butanediol, 4,4'-diaminodiphenylmethane, and a mixture of two or more kinds thereof.
  • a colorant such as titanium oxide
  • various stabilizers such as a UV absorber (e.g., a benzophenone-based or benzotriazole-based UV absorber) and an antioxidant [e.g., a hindered phenol such as 4,4-butylidene-bis(3-methyl-6-1-butylphenol); an organic phosphite such as triphenylphosphite or trichloroethylphosphite]
  • an inorganic filler e.g., calcium carbonate
  • examples of the component for imparting a hydrophilic group include a hydrophilic group-containing active hydrogen component.
  • examples of the hydrophilic group-containing active hydrogen component include a compound containing a nonionic group and/or an anionic group and/or a cationic group and active hydrogen.
  • Examples of the compound having a nonionic group and active hydrogen include compounds containing two or more active hydrogen components or two or more isocyanate groups and having a polyoxyethylene glycol group with a molecular weight of 250 to 9000 or the like in a side chain, and triols such as trimethylol propane and trimethylol butane.
  • Examples of the compound having an anionic group and active hydrogen include carboxyl group-containing compounds such as 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid and 2,2-dimethylol valeric acid and derivatives thereof, sulfonic group-containing compounds such as 1,3-phenylenediamine-4,6-disulfonic acid and 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid and derivatives thereof, and salts obtained by neutralizing these compounds with a neutralizer.
  • carboxyl group-containing compounds such as 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid and 2,2-dimethylol valeric acid and derivatives thereof
  • sulfonic group-containing compounds such as 1,3-phenylenediamine-4,6-disulfonic acid and 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid and derivatives thereof, and salts obtained by neutralizing these compounds with
  • Examples of the compound containing a cationic group and active hydrogen include tertiary amino group-containing compounds such as 3-dimethylaminopropanol, N-methyldiethanolamine, and N-propyldiethanolamine, and derivatives thereof.
  • the hydrophilic group-containing active hydrogen component can also be used in the form of salt neutralized with a neutralizer.
  • hydrophilic group-containing active hydrogen component used in the polyurethane molecule 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, and neutralized salts thereof are preferably used from the viewpoints of the mechanical strength and dispersion stability of the water-dispersible polyurethane resin.
  • the hydrophilic group in the hydrophilic group-having polymer elastic body is a group having active hydrogen.
  • Specific examples of the hydrophilic group include a hydroxyl group, a carboxyl group, a sulfonic acid group, and an amino group.
  • an inside of the hydrophilic group-having polymer elastic body has N-acylurea bonding and/or isourea bonding.
  • the term "inside of the polymer elastic body has N-acylurea bonding and/or isourea bonding" means that the polymer elastic body has N-acylurea bonding and/or isourea bonding.
  • the hydrophilic group-having polymer elastic body has N-acylurea bonding and/or isourea bonding.
  • N-acylurea bonding and/or the isourea bonding can be formed, for example, by reacting a hydroxyl group and/or a carboxyl group present as the hydrophilic group-containing active hydrogen component with a carbodiimide-based crosslinker.
  • N-acylurea bonding and/or isourea bonding which is superior in physical properties, such as lightfast, heat resistance and wear resistance, and flexibility, is imparted into the molecule of the hydrophilic group-having polymer elastic body, and physical properties such as wear resistance can be dramatically improved while maintaining the flexibility of the sheet-shaped article.
  • the presence of the N-acylurea group or the isourea group in the polymer elastic body can be analyzed by performing a mapping process such as TOF-SIMS analysis on the cross section of the sheet-shaped article.
  • the number average molecular weight of the hydrophilic group-having polymer elastic body used in the present invention is preferably 20,000 or more from the viewpoint of resin strength, and is preferably 500,000 or less from the viewpoint of viscosity stability and workability.
  • the number average molecular weight is more preferably 30,000 or more and 150,000 or less.
  • the number average molecular weight of the hydrophilic group-having polymer elastic body can be determined by gel permeation chromatography, and is measured under, for example, the following conditions:
  • the hydrophilic group-having polymer elastic body used in the present invention appropriately retains fibers in the sheet-shaped article, and is preferably present in the fibrous substrate from the viewpoint of providing at least one raised nap surface of the sheet-shaped article, which is a preferred embodiment.
  • a monovalent positive ion-including inorganic salt is present in the polymer elastic body at a rate of 0.1 mass% or more and 5 mass% or less, with regard to a mass of the polymer elastic body.
  • the presence of the monovalent positive ion-including inorganic salt in the polymer elastic body means that the polymer elastic body contains a monovalent positive ion-including inorganic salt.
  • the content is 5 mass% or less, a sufficient film strength of the polymer elastic body can be obtained, and the polymer elastic body is superior in physical properties.
  • the presence of the inorganic salt in the polymer elastic body can be analyzed by performing a mapping process such as TOF-SIMS analysis on the cross section of the sheet-shaped article.
  • the monovalent positive ion-including inorganic salt is preferably sodium chloride and/or sodium sulfate. The significance of using these monovalent positive ion-including inorganic salts is as described later.
  • a bending resistance as specified in JIS L 1096: 2010 (a 45° cantilever method) is 50 mm or more and 180 mm or less, and an abrasion loss after 20,000 times of rubbing by a Martindale abrasion test as specified in JIS L 1096: 2010 is 10 mg or less.
  • the bending resistance is within the above range, a sheet-shaped article having moderate flexibility and repulsive feeling is easily obtained.
  • the abrasion loss after 20,000 times of rubbing by the Martindale abrasion test is 10 mg or less, it is possible to suppress fall-off of fluff in actual use, deterioration of appearance, and the like.
  • the method for manufacturing a sheet-shaped article of the present invention is a method for manufacturing a sheet-shaped article, including: impregnating a fibrous substrate including ultrafine fibers having an average individual fiber fineness of 0.1 ⁇ m or more and 10 ⁇ m or less with an aqueous dispersion containing a hydrophilic group-having polymer elastic body, a monovalent positive ion-including inorganic salt, and a crosslinker; and subjecting the fibrous substrate to a heat treatment at a temperature of 100°C or more and 180°C or less, in which a content of the monovalent positive ion-including inorganic salt in the aqueous dispersion is 10 mass% or more and 50 mass% or less with regard to a mass of a solid content of the hydrophilic group-having polymer elastic body.
  • Direct fiber spinning and ultrafine fiber-generating fibers may be used as a production unit of ultrafine fibers used in the present invention.
  • ultrafine fiber-generating fibers are used in a preferred embodiment.
  • the ultrafine fiber-generating fibers employed include: islands-in-the-sea fibers in which a sea component and an island component are made of two thermoplastic resin components with different solvent solubilities are used as a sea component and an island component, and only the sea component is dissolved and removed using a solvent to yield ultrafine fibers as the island component; or peelable composite fibers or multi-layer composite fibers in which two thermoplastic resin components are alternately arranged to make a fiber cross section radiated or layered, and each component is peeled or split into ultrafine fibers. Since the product quality can be uniform, the sea-island composite fibers are preferably used.
  • sea component of the islands-in-the-sea fibers examples include a polyolefin such as polyethylene or polypropylene, polystyrene, sodium sulfoisophthalate, a copolymerized polyester obtained by copolymerizing polyethylene glycol, polylactic acid, or polyvinyl alcohol, or a copolymer thereof.
  • a polyolefin such as polyethylene or polypropylene, polystyrene, sodium sulfoisophthalate
  • a copolymerized polyester obtained by copolymerizing polyethylene glycol, polylactic acid, or polyvinyl alcohol, or a copolymer thereof.
  • An ultrafine fiber-generating process (sea-removing process) for the islands-in-the-sea fibers may be carried out by immersing the islands-in-the-sea fibers in a solvent and by squeezing them.
  • a solvent for dissolving the sea component it is possible to use an organic solvent such as toluene or trichlorethylene, an alkaline aqueous solution such as sodium hydroxide, or hot water.
  • the ultrafine fiber-generating process may be implemented by using a machine such as a continuous dyeing machine, a vibro washer type sea remover, a jet dyeing machine, a wins dyeing machine, or a jigger dyeing machine.
  • a machine such as a continuous dyeing machine, a vibro washer type sea remover, a jet dyeing machine, a wins dyeing machine, or a jigger dyeing machine.
  • the sea component may be dissolved and removed at any of the timing before or after the polymer elastic body is imparted.
  • the ultrafine fibers can be strongly retained by the structure of the polymer elastic body directly and tightly attached to the ultrafine fibers.
  • this allows the wear resistance of the sheet-shaped article to be more favorable.
  • the sea-removing process is carried out after the polymer elastic body is imparted, a space caused by removing the sea component occurs between the polymer elastic body and the ultrafine fibers. Accordingly, the polymer elastic body does not directly retain the ultrafine fibers, so the texture of the sheet-shaped article becomes more supple.
  • the mass ratio of the sea component is 10 mass% or more, the island component tends to be made sufficiently ultrafine.
  • the mass ratio of the sea component is 80 mass or less, the proportion of the eluted component is small and the productivity is thus improved.
  • an unstretched yarn may be once wound and then stretched in another time or an unstretched yarn may be withdrawn and stretched continuously as they are. Either method can be adopted.
  • the stretching may be conducted, if appropriate, by a one-to-three stretching step using wet heat or dry heat or both.
  • the stretched islands-in-the-sea fibers may be preferably crimped and cut into a predetermined length to obtain raw stock for a nonwoven fabric.
  • a usual method can be used for the crimping and/or cutting.
  • a buckling crimp is given to a composite fiber such as islands-in-the-sea fibers used in the present invention. This is because the buckling crimp can cause interlacing between the fibers to be improved when a short fiber nonwoven fabric is formed, thereby achieving high density and high degree of interlacing.
  • a usual stuffing box-type crimper is preferably used.
  • the processed fiber fineness, the crimper temperature, the crimper load, the pushing pressure, and the like are adjusted, if appropriate, in a preferred embodiment.
  • the crimp retention coefficient of the ultrafine fiber-generating fibers subjected to a buckling crimp is preferably in a range of 3.5 or more and 15 and less and more preferably in a range of 4 or more and 10 or less.
  • the crimp retention coefficient is 3.5 or more, the stiffness of nonwoven fabric in the thickness direction when the nonwoven fabric is formed is increased. This makes it possible to maintain interlacing performance during an interlacing step such as needle punching.
  • the crimp retention coefficient is 15 or less, crimps are not too strong and the fiber-opening performance for fiber web is superior during carding.
  • the crimp retention coefficient is expressed by the following equation.
  • a load of 100 mg/dtex is first applied to a sample. Next, the load is incremented by 10 mg/dtex. Then, the resulting crimp state is checked. The load is increased until the crimp is maximally stretched. When the crimp is in a maximally stretched state, the marking length (the distance from 30.0 cm) is measured.
  • the single fiber fineness of each composite fiber used in the present invention is preferably in a range of 2 dtex or more and 10 dtex or less, and more preferably in a range of 3 dtex or more and 9 dtex or less from the viewpoint of interlacing performance in a needle punching step or the like.
  • Each composite fiber that can be used in manufacturing the sheet-shaped article of the present invention preferably has a contraction rate, at a temperature of 98°C, of 5% or more and 40% or less and more preferably 10% or more and 35% or less.
  • hydrothermal treatment can cause the fiber density to increase, thereby realizing a touch inspiring real leather.
  • a load of 50 mg/dtex is first applied to a composite fiber bundle.
  • 30.0 cm is marked (L 0 ).
  • 10-min treatment in hot water at a temperature of 98°C is carried out, lengths (L 1 ) before and after the treatment are measured, and (L 0 -L 1 )/L 0 ⁇ 100 is calculated.
  • the measurement is performed three times, and the average value of the measurements is defined as the contraction rate.
  • the number of fibers in the ultrafine fiber bundle is preferably 8 fibers/bundle or more and 1000 fibers/bundle or less, and more preferably 10 fibers/bundle or more and 800 fibers/bundle or less.
  • the number of fibers is 8 fibers/bundle or more, the ultrafine fibers tend to have sufficient compactness.
  • the mechanical property such as abrasion tends to increase.
  • the number of fibers is 1000 fibers/bundle or less, the fiber-opening performance at the time of napping is improved, the fiber distribution on the raised nap surface becomes uniform, and a favorable product quality is easily obtained.
  • a method for producing a nonwoven fabric that can be used for a fibrous substrate constituting a sheet-shaped article of the present invention it is possible to use a method for interlacing a composite fiber web by needle punching or water-jet punching, spun bonding, melt-blowing, or papermaking. Among them, it is preferable to use a method undergoing treatment such as needle punching or water-jet punching so as to provide the previously mentioned ultrafine fiber bundle form.
  • the nonwoven fabric may be prepared such that a nonwoven fabric and a woven or knitted fabric are layered and integrated as described above. It is preferable to use a method for integrating them by needle punching or water-jet punching.
  • the number of needle barbs (notches) of a needle used for the needle punching is preferably 1 or more and 9 or less.
  • the number of needle barbs is preferably set to 1 or more, the fibers can be interlaced efficiently. Meanwhile, the number of needle barbs is preferably set to 9 or less, so that damage on the fibers can be reduced.
  • each barb of a needle used during the needle punching step is preferably shaped such that the kick-up is 0 ⁇ m or more and 50 ⁇ m or less, the undercut angle is 0° or more and 40° or less, the throat depth is 40 ⁇ m or more and 80 ⁇ m or less, and the throat length is 0.5 mm or more and 1.0 mm or less.
  • the number of punching is preferably 1000 sites/cm 2 or more and 8000 sites/cm 2 or less.
  • the number of punching is preferably set to 1000 sites/cm 2 or more, so that the compactness can be obtained, and the finishing can be achieved with high precision.
  • the number of punching is preferably set to 8000 sites/cm 2 or less, so that it is possible to prevent deterioration of processability, damage on the fibers, and a decrease in the strength.
  • water is in a pillar-shaped stream state. Specifically, water is jetted from nozzles with a diameter of 0.05 mm or more and 1.0 mm or less at a pressure of 1 MPa to 60 MPa in a preferred embodiment.
  • the apparent density of the nonwoven fabric after needle punching or water-jet punching is preferably 0.15 g/cm 3 or more and 0.45 g/cm 3 or less.
  • the apparent density is preferably set to 0.15 g/cm 3 or more, whereby the sheet-shaped article is likely to have sufficient shape stability and dimension stability. Meanwhile, the apparent density is preferably set to 0.45 g/cm 3 or less, so that a sufficient space for imparting polyurethane can be easily maintained.
  • the nonwoven fabric thus obtained may be contracted and further highly compacted by dry heat or wet heat or by both in a preferred embodiment. Further, the nonwoven fabric may be compressed in the thickness direction by calendaring or the like.
  • the sea-removing process for removing the sea component of the islands-in-the-sea fibers in the case of using the islands-in-the-sea fibers may be carried out before or/and after the aqueous dispersion containing the hydrophilic group-having polymer elastic body is imparted to the fibrous substrate.
  • the sea-removing process is carried out before the aqueous dispersion is imparted, there is a tendency of forming a structure of the polymer elastic body directly and tightly attached to the ultrafine fibers, causing the ultrafine fibers to be strongly retained.
  • this allows the wear resistance of the sheet-shaped article to be more favorable.
  • the ultrafine fibers and an inhibitor such as a cellulose derivative or polyvinyl alcohol are imparted before the aqueous dispersion is imparted, and then the aqueous dispersion is imparted, whereby the adhesion between the ultrafine fibers and the polymer elastic body can be reduced, and a more supple texture can be achieved.
  • PVA polyvinyl alcohol
  • the inhibitor may be added either before or after the sea-removing process of a fiber having an islands-in-the-sea structure.
  • the inhibitor is imparted before the sea-removing process, so that the shape retention capacity of the fibrous substrate can be enhanced even when the basis weight of the fiber decreases and the tensile strength of the sheet decreases.
  • a thin sheet can also be stably processed, and the thickness retention of the fibrous substrate in the step of the sea-removing process can be increased. Consequently, it is possible to prevent the fibrous substrate from being highly compacted.
  • the inhibitor is imparted after the sea-removing process, so that it is possible to allow the fibrous substrate to be highly compacted. Therefore, appropriate adjustment is carried out according to the purpose in a preferred embodiment.
  • PVA is preferably used because it has a high reinforcing effect on the fibrous substrate and is hardly eluted in water.
  • highly saponified polyvinyl alcohol that is more poorly soluble in water is used in a more preferred embodiment, from the viewpoint that it is possible to cause the inhibitor to be hardly eluted at the time of imparting the aqueous dispersion containing the hydrophilic group-having polymer elastic body, and inhibit the adhesion between the ultrafine fibers and the polymer elastic body.
  • the highly saponified polyvinyl alcohol has a saponification degree of preferably 95% or more and 100% or less, and more preferably 98% or more and 100% or less.
  • the saponification degree is set to 95% or more, so that it is possible to reduce elution at the time of imparting the hydrophilic group-having polymer elastic body dispersion.
  • the polymerization degree of PVA is preferably 500 or more and 3500 or less, and more preferably 500 or more and 2000 or less.
  • the polymerization degree of PVA is set to 500 or more, so that it is possible to reduce the elution of highly saponified polyvinyl alcohol at the time of imparting the polymer elastic body dispersion.
  • the polymerization degree of PVA is set to 3500 or less, so that the viscosity of the highly saponified polyvinyl alcohol liquid does not become excessively high, and it is possible to stably impart the highly saponified polyvinyl alcohol to the fibrous substrate.
  • the amount of PVA imparted to the fibrous substrate with regard to the fiber mass of the fibrous substrate is 0.1 mass% or more and 50 mass% or less, and preferably 1 mass% or more and 45 mass% or less.
  • the amount of PVA imparted is set to 0.1 mass% or more, so that it is possible to obtain a sheet-shaped article with favorable flexibility and texture.
  • the amount of PVA imparted is set to 50 mass% or less, so that it is possible to obtain a sheet-shaped article with favorable processability and more favorable physical characteristics such as wear resistance.
  • a fibrous substrate is impregnated with an aqueous dispersion containing a hydrophilic group-having polymer elastic body, a monovalent positive ion-including inorganic salt, and a crosslinker, and then heat treatment is performed at a temperature of 100°C or more and 180°C or less.
  • the hydrophilic group-having polymer elastic body is imparted to the fibrous substrate.
  • the hydrophilic group-having polymer elastic body can be imparted to both a nonwoven fabric made of composite fibers and a nonwoven fabric in which fibers are made ultrafine.
  • a dry-heat coagulation method in which heat treatment is performed at a temperature of 100°C or more and 180°C or less is used for coagulation after imparting the hydrophilic group-having polymer elastic body.
  • a hot water coagulation method in which the hydrophilic group-having polymer elastic body is coagulated in hot water, the polymer elastic body is diffused into hot water and partially falls off, whereby there is a concern about processability.
  • the dry-heat coagulation method used in the present invention is a very simple procedure of heat-treating a sheet impregnated with the hydrophilic group-having polymer elastic body using a hot-air dryer or the like, and is a procedure superior in processability without concern of falling off of the polymer elastic body.
  • the heating temperature in dry heat coagulation is 100°C or more and 180°C or less.
  • the heating temperature is set to 100°C or more, so that it is possible to cause the hydrophilic group-having polymer elastic body to rapidly coagulate, and reduce uneven distribution of the polymer elastic body on the lower surface of the sheet due to its own weight.
  • the temperature is set to the above temperature, so that the crosslinking reaction can be sufficiently promoted, and the physical properties can be improved.
  • the heating temperature is set to 180°C or less, so that it is possible to suppress the heat deterioration of the polymer elastic body. From the viewpoint of curing the polymer, the heating temperature is more preferably 120°C or more and 160°C or less. Within such a temperature range, the wear resistance and heat resistance are easily improved.
  • the concentration of the aqueous dispersion of the hydrophilic group-having polymer elastic body is preferably 10 mass% or more and 50 mass% or less, and more preferably 15 mass% or more and 40 mass% or less, from the viewpoint of the storage stability of the aqueous dispersion of the hydrophilic group-having polymer elastic body.
  • the aqueous dispersion of the hydrophilic group-having polymer elastic body used in the present invention may contain a water-soluble organic solvent in an amount of 40 mass% or less with regard to the aqueous dispersion of the hydrophilic group-having polymer elastic body in order to improve storage stability and film formability.
  • the content of the water-soluble organic solvent is preferably 1 mass% or less in view of protecting a film-forming environment, and the like.
  • the aqueous dispersion of the hydrophilic group-having polymer elastic body contains a monovalent positive ion-including inorganic salt.
  • the monovalent positive ion-including inorganic salt is contained, thereby making it possible to impart thermosensitive coagulability to the aqueous dispersion of the hydrophilic group-having polymer elastic body.
  • thermosensitive coagulability refers to a property of decreasing fluidity of the aqueous dispersion of the hydrophilic group-having polymer elastic body and coagulating the aqueous dispersion after a certain temperature (thermosensitive coagulation temperature) is reached at the time of heating the aqueous dispersion of the hydrophilic group-having polymer elastic body.
  • the aqueous dispersion of the hydrophilic group-having polymer elastic body is imparted to the fibrous substrate, and the resulting product is dry-heat coagulated by heat treatment at a temperature of 100°C or more and 180°C or less so as to impart the polymer elastic body to the fibrous substrate.
  • hydrophilic group-having polymer elastic body does not have thermosensitive coagulability
  • migration occurs in which the hydrophilic group-having polymer elastic body migrates to the sheet surface along with evaporation of moisture.
  • coagulation proceeds in a state in which the polymer elastic body is unevenly distributed around the fiber as moisture evaporates, whereby the polymer elastic body covers the periphery of the fiber and strongly restricts the movement. As a result, the texture of the sheet-shaped article becomes significantly hard.
  • the thermosensitive coagulation temperature of the aqueous dispersion of the hydrophilic group-having polymer elastic body is preferably 55°C or more and 80°C or less, more preferably 60°C or more and 70°C or less.
  • the thermosensitive coagulation temperature is set to 55°C or more, so that the stability of the aqueous dispersion of the hydrophilic group-having polymer elastic body during storage is improved, and the adhesion of the polymer elastic body to a machine during operation or the like can be suppressed.
  • the thermosensitive coagulation temperature is set to 80°C or less, so that the migration phenomenon of the polymer elastic body to the surface layer of the fibrous substrate can be suppressed.
  • the coagulation of the polymer elastic body proceeds before moisture evaporates from the fibrous substrate, so that a structure similar to that obtained by wet coagulation of a solvent-based polymer elastic body, i.e., a structure in which the polymer elastic body does not strongly retain fibers can be formed, thereby achieving favorable flexibility, repulsive feeling, and heat resistance.
  • an inorganic salt used as a thermosensitive coagulant it is important to use a monovalent positive ion-including inorganic salt.
  • the monovalent positive ion-including inorganic salt is preferably sodium chloride and/or sodium sulfate.
  • a divalent positive ion-including inorganic salt such as magnesium sulfate or calcium chloride has been preferably used as the thermosensitive coagulant.
  • the additive amount is adjusted, as a result of which the thermosensitive coagulation temperature of the aqueous dispersion can be strictly controlled while ensuring the stability of the aqueous dispersion.
  • the content of the monovalent positive ion-including inorganic salt in the aqueous dispersion is 10 mass% or more and 50 mass% or less with regard to the solid content of the hydrophilic group-having polymer elastic body.
  • the content is 10 mass% or more, ions present in a large amount in the aqueous dispersion of the hydrophilic group-having polymer elastic body uniformly act on the polymer elastic body particles, as a result of which coagulation can be rapidly completed at a specific thermosensitive coagulation temperature.
  • a more remarkable effect can be obtained by allowing the coagulation of the polymer elastic body to proceed in a state where a large amount of moisture is contained in the fibrous substrate as described above.
  • the content is set as described above, as a result of which the inorganic salt serves as an inhibitor in the fusion of the polymer elastic body particles, and it is also possible to prevent the polymer elastic body from being hardened due to the continuous film formation. Meanwhile, the content is set to 50 mass% or less, as a result of which it is possible to cause a continuous film structure of an appropriate polymer elastic body to be remained, and suppress a decrease in physical properties. In addition, it is possible to maintain the stability of the aqueous dispersion of the hydrophilic group-having polymer elastic body.
  • the sheet-shaped article of the present invention preferably has a L value retention of 90% to 100% when the napped surface of the sheet-shaped article is placed on a hot plate heated to 150°C and pressed at a pressing load of 2.5 kPa for 10 seconds (hereinafter, sometimes simply abbreviated as L value retention).
  • L value retention is 90% or more, more preferably 92% or more, and still more preferably 95% or more
  • the sheet-shaped article has high heat resistance.
  • the "napped surface of the sheet-shaped article” refers to a surface obtained by napping the sheet-shaped article.
  • the L value is an L value defined by the International Commission on Illumination (CIE).
  • CIE International Commission on Illumination
  • the L value retention in the present invention is an index indicating that a rate of change in brightness under heating and pressing conditions is small, that is, to what extent a sheet-shaped article having a dark color before heating and pressing does not become bright after heating and pressing.
  • the L value retention refers to a value measured and calculated by the following procedure.
  • Examples of the method for setting the L value retention to the above range include a method in which uneven distribution (migration) of polyurethane to the surface of the sheet-shaped article due to moisture evaporation is suppressed by setting the thermosensitive coagulation temperature to a range of 55 to 80°C, and deterioration of polyurethane due to hot pressing is suppressed, and/or a method in which heat treatment (curing treatment) is performed at a temperature of 120°C or more and 160°C or less in a drying step in dry heat coagulation.
  • uneven distribution (migration) of polyurethane to the surface of the sheet-shaped article due to moisture evaporation is suppressed by setting the thermosensitive coagulation temperature to a range of 55 to 80°C, and deterioration of polyurethane due to hot pressing is suppressed
  • heat treatment curing treatment
  • an aqueous dispersion of a hydrophilic group-having polymer elastic body contains a crosslinker.
  • the content of the crosslinker is preferably 1 mass% or more, and more preferably 2 mass% or more, with regard to the mass of the solid content of the polymer elastic body.
  • the content of the crosslinker is set to 1 mass% or more, so that more three-dimensional network structures can be introduced into the polymer elastic body by the crosslinker, and physical properties such as wear resistance can be further improved.
  • the content of the crosslinker is preferably 10 mass% or less and more preferably 7 mass% or less, with regard to the mass of the solid content of the polymer elastic body.
  • the content of the crosslinker is set to 10 mass% or less, whereby fusion inhibition of the polymer elastic body by an excess of the crosslinker hardly occurs, and deterioration of physical properties such as wear resistance is easily suppressed.
  • the monovalent positive ion-including inorganic salt described above is used in combination, the sheet-shaped article is made supple by controlling the adhesive structure between the polymer elastic body and the fiber, and at the same time, high physical properties and high heat resistance of the sheet-shaped article are easily achieved.
  • the crosslinker is preferably a carbodiimide-based crosslinker because the polymer elastic body obtained after the reaction is superior in lightfast, heat resistance, and wear resistance, and has favorable flexibility, and the L value retention of the napped surface before and after hot pressing is low.
  • the polymer elastic body contains a polyether diol as a constituent in a preferred embodiment.
  • the reason is as described in the section of (1-1) Polymeric Polyol.
  • a hydrophilic group-having polymer elastic body X and a hydrophilic group-having polymer elastic body Y having compositions different from each other are contained in the aqueous dispersion, and the hydrophilic group-having polymer elastic body Y is coagulated after the hydrophilic group-having polymer elastic body X is coagulated.
  • the content of the monovalent positive ion-including inorganic salt is adjusted, as a result of which it is possible to adjust each thermosensitive coagulation temperature so that the hydrophilic group-having polymer elastic body B is coagulated after the hydrophilic group-having polymer elastic body A is coagulated, and to control the distribution of the two kinds of polymer elastic bodies in the sheet-shaped article.
  • the hydrophilic group-having polymer elastic body X is a polymer elastic body having superior flexibility such as a polyether-based polymer elastic body
  • the hydrophilic group-having polymer elastic body Y is a polycarbonate-based polymer elastic body having superior physical properties such as durability
  • a step of removing PVA from the fibrous substrate to which the hydrophilic group-having polymer elastic body has been imparted may be included, if necessary.
  • a supple sheet-shaped article is obtained by removing PVA from the fibrous substrate to which the hydrophilic group-having polymer elastic body has been imparted.
  • the method for removing PVA is not particularly limited.
  • the sheet is immersed in hot water at a temperature of 60°C or more and 100°C or less and then squeezed using a mangle or the like, if necessary, to dissolve and remove PVA. This is a preferred embodiment.
  • the sheet-shaped article may be subjected to a napping treatment to form a raised nap on the surface.
  • the method for forming the raised nap is not particularly limited, and various methods usually performed in the art such as buffing with sandpaper or the like can be used.
  • the length of the raised nap is preferably 0.2 mm or more and 1 mm or less.
  • a lubricant such as silicone may be imparted to the sheet-shaped article.
  • a lubricant such as silicone
  • napping can be made easy by surface grinding. This is preferable because the surface quality is very favorable.
  • an antistatic agent may be imparted before the napping. When an antistatic agent is imparted, grinding powder generated from a sheet-shaped article by grinding is unlikely to be deposited on a sandpaper. This is thus a preferred embodiment.
  • the sheet-shaped article may be dyed.
  • various methods usually used in the art may be adopted. Since the sheet-shaped article may be made supple by adding a softening effect at the same time of dyeing of the sheet-shaped article, a method using a jet dyeing machine is preferable.
  • the dyeing temperature is preferably set to 80°C or more and 150°C or less.
  • the dyeing temperature is set to 80°C or more, and more preferably 110°C or more, so that it is possible to efficiently dye the fiber.
  • the dyeing temperature is set to 150°C or less, and more preferably 130°C or less, so that it is possible to prevent deterioration of the polymer elastic body.
  • a dye used in the present invention may be selected according to the kind of fibers included in the fibrous substrate, and is not particularly limited.
  • any disperse dye may be used in the case of a polyester-based fiber.
  • an acidic dye or a gold-containing dye may be used in the case of a disperse dye.
  • reduction cleaning may be performed after the dyeing.
  • a dyeing auxiliary is used during dyeing in a preferred embodiment.
  • the dyeing auxiliary is used, so that the evenness and reproducibility of dyeing can be improved.
  • a finishing agent such as a softener such as silicone, an antistatic agent, a water repellent, a flame retardant, a lightfast agent, and/or an antimicrobial agent.
  • a prepolymer was prepared in a toluene solvent using polytetramethylene ether glycol (designated as PTMG in the table) having a number average molecular weight (Mn) of 2,000 as a polyol, MDI as an isocyanate, and 2,2-dimethylol propionic acid as a component for imparting a hydrophilic group.
  • Ethylene glycol and ethylenediamine as chain extenders, polyoxyethylene nonylphenyl ether as an external emulsifier, and water were added and stirred.
  • Toluene was removed under reduced pressure to obtain an aqueous dispersion Wa of a hydrophilic group-having polymer elastic body a.
  • the polymer elastic body a is a polymer elastic body corresponding to the polymer elastic body A.
  • a prepolymer was prepared in an acetone solvent using polyhexamethylene carbonate (designated as PHC in the table) having Mn of 2,000 as a polyol, hydrogenated MDI as an isocyanate, and a diol compound having polyethylene glycol in a side chain and 2,2-dimethylol propionic acid as components for imparting a hydrophilic group.
  • PHC polyhexamethylene carbonate
  • MDI hydrogenated MDI as an isocyanate
  • diol compound having polyethylene glycol in a side chain and 2,2-dimethylol propionic acid as components for imparting a hydrophilic group.
  • Ethylene glycol and ethylenediamine as chain extenders and water were added, and the mixture was stirred.
  • Acetone was removed under reduced pressure to obtain an aqueous dispersion Wb of a hydrophilic group-having polymer elastic body b.
  • the polymer elastic body b is a polymer elastic body corresponding to the polymer elastic body B
  • aqueous dispersions Wa and Wb of the polymer elastic bodies in Reference Examples 1 and 2 two kinds of aqueous dispersions were mixed so that the solid content of each polymer elastic body was 20 mass%, thereby obtaining an aqueous dispersion Wc containing hydrophilic group-having polymer elastic bodies a and b with a solid content of 40 mass%.
  • a branched (self-crosslinking) prepolymer was prepared in a toluene solvent using polytetramethylene ether glycol (designated as PTMG in the table) having a number average molecular weight (Mn) of 2,000 as a polyol, HDI biuret as an isocyanate, and 2,2-dimethylol propionic acid as a component for imparting a hydrophilic group.
  • PTMG polytetramethylene ether glycol
  • Mn number average molecular weight
  • HDI biuret as an isocyanate
  • 2,2-dimethylol propionic acid as a component for imparting a hydrophilic group.
  • Ethylene glycol and ethylenediamine as chain extenders
  • polyoxyethylene nonylphenyl ether as an external emulsifier
  • water were added and stirred.
  • Toluene was removed under reduced pressure to obtain an aqueous dispersion Wd of a hydrophilic group-
  • a copolymerized polyester containing 8 mol% SSIA (sodium 5-sulfoisophthalate) was used as a sea component, and polyethylene terephthalate was used as an island component to obtain islands-in-the-sea fibers with an average individual fiber fineness of 20 ⁇ m in which the composite ratio of the sea component : the island component was 20 mass% : 80 mass% and the number of islands was 16 islands/1 filament.
  • the resulting islands-in-the-sea fibers were cut into a fiber length of 51 mm to obtain a staple, which went through a carding machine and a cross wrapper to form a fiber web.
  • This fiber web was subjected to needle punching to manufacture a nonwoven fabric with a basis weight of 700 g/m 2 and a thickness of 3.1 mm.
  • the nonwoven fabric thus obtained was immersed and contracted in hot water at a temperature of 98°C for 2 minutes, and was then dried at a temperature of 100°C for 5 minutes to obtain a nonwoven fabric for fibrous substrate.
  • the above nonwoven fabric for fibrous substrate was impregnated with an aqueous solution containing 10 mass% of PVA (NM-14, manufactured by Nippon Chemical Industrial CO., LTD.) with a saponification degree of 99% and a polymerization degree of 1400, and heated and dried at a temperature of 140°C for 10 minutes to obtain a PVA-imparted sheet in which the amount of PVA imparted per fiber mass of the nonwoven fabric for fibrous substrate was 30 mass%.
  • PVA NM-14, manufactured by Nippon Chemical Industrial CO., LTD.
  • the resulting PVA-imparted sheet was immersed and treated for 30 minutes in a sodium hydroxide aqueous solution that was heated to a temperature of 95°C and was at a concentration of 8 g/L. Then, a sheet (PVA-imparted ultrafine fiber nonwoven fabric) composed of ultrafine fibers, in which the sea component had been removed from the islands-in-the-sea fibers, was obtained.
  • thermosensitive coagulation temperature was 70°C.
  • the resulting PVA-imparted ultrafine fiber nonwoven fabric was immersed in the aqueous dispersion, and then dried with hot air at a temperature of 150°C for 15 minutes to obtain a 1.9 mm-thick polymer elastic body-imparted sheet in which 25 mass% of polymer elastic body A was imparted with regard to the fiber weight.
  • the resulting polymer elastic body-imparted sheet was submerged and treated for 10 minutes in water heated to 95°C to obtain a sheet from which the imparted PVA had been removed.
  • the resulting PVA-removed, polymer elastic body-imparted sheet was cut in half in a direction perpendicular to the thickness direction.
  • the side opposite to the half-cutting surface was subjected to grinding with an endless sandpaper of sandpaper count No. 240 to obtain a sheet-shaped article having a raised nap with a thickness of 0.7 mm.
  • the resulting sheet-shaped article having a raised nap was dyed with a black dye by using a jet dyeing machine under conditions at a temperature of 120°C. Then, drying was performed with a dryer to obtain a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance. Further, it was confirmed that N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 1.2 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 95%, and the napped surface had superior heat resistance.
  • the resulting nonwoven fabric for fibrous substrate was immersed and treated for 25 minutes in a sodium hydroxide aqueous solution heated to a temperature of 95°C and was at a concentration of 10 g/L and, thereby obtaining a sea-removed sheet from which the sea component of the islands-in-the-sea fibers had been removed.
  • thermosensitive coagulation temperature was 68°C.
  • the resulting sea-removed sheet was immersed in the aqueous dispersion, and then dried with hot air at a temperature of 160°C for 15 minutes to obtain a 1.8 mm-thick polymer elastic body-imparted sheet in which 25 mass% of polymer elastic body was imparted with regard to the fiber weight.
  • the cutting in half process and the finishing process were performed in a similar manner to Example 1 to obtain a sheet-shaped article including ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance. Further, it was confirmed that N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 1.8 mass% of sodium chloride was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 94%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that the aqueous dispersion containing the hydrophilic group-having polymer elastic body was changed (specifically, changed to the aqueous dispersion Wb of the hydrophilic group-having polymer elastic body b) in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 2.0 mass% of sodium chloride was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 96%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 2 except that sodium chloride as a thermosensitive coagulant was added in an amount of 40 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 2, and the thermosensitive coagulation temperature was adjusted to 60°C.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 3.5 mass% of sodium chloride was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 92%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 2 except that the aqueous dispersion liquid containing the hydrophilic group-having polymer elastic body was changed (specifically, changed to the aqueous dispersion Wc containing hydrophilic group-having polymer elastic bodies a and b, 50 mass% of sodium chloride was added as a thermosensitive coagulant, the thermosensitive coagulation temperature of the hydrophilic group-having polymer elastic body a was adjusted to 60°C, and the thermosensitive coagulation temperature of the hydrophilic group-having polymer elastic body b was adjusted to 70°C) in (To Impart Polymer Elastic Body) of Example 2. Similarly to Fig.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance. Further, it was confirmed that N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 4.8 mass% of sodium chloride was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 97%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that sodium sulfate as a thermosensitive coagulant was added in an amount of 45 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1, and the thermosensitive coagulation temperature was adjusted to 60°C.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 3.7 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 94%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that sodium sulfate as a thermosensitive coagulant was added in an amount of 12 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1, and the thermosensitive coagulation temperature was adjusted to 75°C.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 0.7 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 94%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that a carbodiimide-based crosslinker was added in an amount of 1 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 1.3 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 92%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that a carbodiimide-based crosslinker was added in an amount of 8 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 1.2 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 96%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that a carbodiimide-based crosslinker was added in an amount of 0.5 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 1.2 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 91%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that a carbodiimide-based crosslinker was added in an amount of 12.0 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 1.2 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 90%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that a blocked isocyanate-based crosslinker was added in an amount of 3 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded as shown in Fig. 1 , and had a supple texture and superior wear resistance.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 1.2 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 91%, and the napped surface had superior heat resistance.
  • Example 2 The process was performed in a similar manner to Example 1 except that calcium chloride was used as a thermosensitive coagulant in (To Impart Polymer Elastic Body) of Example 1, an aqueous dispersion containing a hydrophilic group-having polymer elastic body gelled during processing, and a polymer elastic body-imparted sheet was not able to be obtained.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that an additive amount of sodium sulfate was 1.0 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the entire fiber bundle was covered with the polymer elastic body as shown in Fig. 2 , and had superior wear resistance, but had a hard texture. Further, N-acylurea bonding and isourea bonding were present in the polymer elastic body, but sodium sulfate was not present in the sheet-shaped article. Furthermore, the L value retention of the napped surface before and after hot pressing was 87%, and the heat resistance was poor.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that an additive amount of sodium sulfate was 55 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded, but the size of the lump of the polymer elastic body was very small.
  • the sheet-shaped article was supple, but the wear resistance was poor.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, and 8.0 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 94%, and the napped surface had superior heat resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 2 except that no crosslinker was added to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 2.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded, and was supple but had poor wear resistance. Further, it was confirmed that 2.5 mass% of sodium chloride was contained with regard to the solid content of the polymer elastic body, but N-acylurea bonding and isourea bonding were not able to be confirmed in the polymer elastic body. Furthermore, the L value retention of the napped surface before and after hot pressing was 84%, and the heat resistance was poor.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that an oxazoline-based crosslinker was added in an amount of 4.0 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the fiber and the polymer elastic body were partially bonded, and was supple but had poor wear resistance.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that calcium chloride was added in an amount of 1.2 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the entire fiber bundle was covered with the polymer elastic body as shown in Fig. 2 , and had superior wear resistance, but had a hard texture.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, but sodium sulfate was not present in the sheet-shaped article. Furthermore, the L value retention of the napped surface before and after hot pressing was 85%, and the heat resistance was poor.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that "VA-086" (manufactured by Wako Pure Chemical Industries, Ltd., 2,2'-azobis[2-methyl-N-(2-hydroxyester)propionamide] as a foaming agent was added in an amount of 3.0 mass% with regard to 100 mass% of the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1. Similarly to Fig.
  • the resulting sheet-shaped article formed a structure in which the entire fiber bundle was covered with the polymer elastic body, but had poor wear resistance and also had a hard texture. Further, N-acylurea bonding and isourea bonding were present in the polymer elastic body, but sodium sulfate was not present in the sheet-shaped article. Furthermore, the L value retention of the napped surface before and after hot pressing was 80%, and the heat resistance was poor.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that no thermosensitive coagulant was used with regard to the solid content of the aqueous dispersion Wa of the hydrophilic group-having polymer elastic body a in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article formed a structure in which the entire fiber bundle was covered with the polymer elastic body, but had poor wear resistance and also had a hard texture.
  • N-acylurea bonding and isourea bonding were present in the polymer elastic body, but sodium sulfate was not present in the sheet-shaped article.
  • the L value retention of the napped surface before and after hot pressing was 87%, and the heat resistance was poor.
  • a sheet-shaped article having ultrafine fibers with an average individual fiber fineness of 4.4 ⁇ m was obtained in a similar manner to Example 1 except that the hydrophilic group-having polymer elastic body d was used in place of the hydrophilic group-having polymer elastic body a and no crosslinker was added in (To Impart Polymer Elastic Body) of Example 1.
  • the resulting sheet-shaped article had favorable wear resistance and formed a structure in which the fiber and the polymer elastic body were partially bonded, but had a hard texture. Further, it was confirmed that 1.2 mass% of sodium sulfate was contained with regard to the solid content of the polymer elastic body, but N-acylurea bonding and isourea bonding were not able to be confirmed in the polymer elastic body.
  • the sheet-shaped article of the present invention can be fit for furniture, chairs and wall coverings, seats in cabins of vehicles such as cars, trains and aircrafts, skin materials for ceilings and interiors, interior materials with a very elegant appearance, and clothing and industrial materials, and so on.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
EP20783144.7A 2019-03-29 2020-03-19 Article en forme de feuille et procédé de fabrication associé Pending EP3951047A4 (fr)

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DE2436740A1 (de) * 1974-07-30 1976-02-12 Bayer Ag Verfahren zur herstellung von polyharnstoffen
DE3523856A1 (de) * 1985-07-04 1987-01-08 Bayer Ag Waessrige loesungen oder dispersionen von polyisocyanat-additionsprodukten, ein verfahren zu ihrer herstellung, sowie ihre verwendung als beschichtungsmittel oder als leimungsmittel fuer papier
GB9418329D0 (en) * 1994-09-12 1994-11-02 Stahl International Bv Functionalised polymers
JPH10199699A (ja) 1997-01-11 1998-07-31 Tokyo Electron Ltd プラズマ処理装置
US8076445B2 (en) * 2000-01-11 2011-12-13 Robert Shane Porzio Oligocarbodiimides for the formation of crosslinked latex films
JP4617591B2 (ja) * 2001-03-30 2011-01-26 東レ株式会社 立毛調皮革様シート状物およびその製造方法
JP3971770B2 (ja) * 2005-04-18 2007-09-05 三菱鉛筆株式会社 着色剤組成物及び着色方法
CN101654550A (zh) * 2009-09-09 2010-02-24 福建宝利特集团有限公司 一种改进聚氨酯耐老化性能的复合添加剂及其应用
KR101892303B1 (ko) * 2010-03-16 2018-08-27 도레이 카부시키가이샤 시트상물 및 그의 제조 방법
JP2013112905A (ja) * 2011-11-28 2013-06-10 Toray Ind Inc シート状物
US9382442B2 (en) * 2012-05-24 2016-07-05 Basf Se Aqueous binder compositions
JP6225917B2 (ja) * 2012-11-30 2017-11-08 東レ株式会社 シート状物及びそのシート状物の製造方法
CN105745375A (zh) * 2013-11-21 2016-07-06 东丽株式会社 片状物
EP3101172B1 (fr) * 2014-01-30 2024-01-17 Toray Industries, Inc. Cuir artificiel en feuille et son procédé de fabrication
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US20220186431A1 (en) 2022-06-16
CN113474509A (zh) 2021-10-01
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