US20230323594A1 - Artificial leather, production method therefor, and artificial leather backing material - Google Patents

Artificial leather, production method therefor, and artificial leather backing material Download PDF

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Publication number
US20230323594A1
US20230323594A1 US18/024,602 US202118024602A US2023323594A1 US 20230323594 A1 US20230323594 A1 US 20230323594A1 US 202118024602 A US202118024602 A US 202118024602A US 2023323594 A1 US2023323594 A1 US 2023323594A1
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United States
Prior art keywords
artificial leather
flame retardant
fiber
less
elastomer
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US18/024,602
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English (en)
Inventor
Takahiro Tsuchimoto
Tatsuya Hagiwara
Atsushi Shinozaki
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Toray Industries Inc
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Toray Industries Inc
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Publication of US20230323594A1 publication Critical patent/US20230323594A1/en
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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
    • D06N3/0002—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
    • D06N3/0006—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 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
    • D06N3/0009—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 knitted 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
    • D06N3/0036—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
    • D06N3/0054—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 mechanical perforations
    • 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
    • D06N3/007—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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • 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
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/186—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials one of the layers is on one surface of the fibrous web and the other layer is on the other surface of the fibrous web
    • 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
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0209—Elastomeric, elastic fibres, e.g. spandex, lycra
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/045—Vinyl (co)polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/06—Properties of the materials having thermal properties
    • D06N2209/067—Flame resistant, fire resistant
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Definitions

  • the present invention relates to an artificial leather which includes a fiber entanglement including ultrafine fibers, an elastomer, and a functional agent (flame retardant or the like), has moderate air permeability and a flexible texture, is excellent in flame retardancy, and has feels like natural suede and an elegant appearance.
  • the present invention also relates to an artificial leather backing material used for obtaining the artificial leather, and having good formability of an opening portion.
  • an artificial leather including a fiber entanglement formed of ultrafine fibers and an elastomer and having raised nap has excellent characteristics in air permeability, durability, uniformity of quality, and the like as compared with natural leather, and is used not only as a clothing material but also in various fields such as interior materials of public transporters such as aircrafts, ships, and railroad vehicles, interior materials for vehicles, interior materials, building materials, and miscellaneous goods.
  • artificial leather is often required to have high flame retardant performance, and in the fields where flame retardancy is required, it is common that the artificial leather includes a flame retardant.
  • the artificial leather in order to cope with a ventilation system particularly in an interior material for vehicles, moderate air permeability is required by the density and material configuration of artificial leather and control of an opening portion.
  • the elastomer such as polyurethane constituting the artificial leather and an ultrafine thermoplastic synthetic fiber constituting a nonwoven fabric, a woven fabric, or a knitted fabric are different from each other in a mechanism developing flame retardancy, and therefore, it is known that it is very difficult to make the entire artificial leather flame retardant.
  • an organic phosphorus component copolymerized polyester is used for ultrafine fibers of artificial leather (for example, see Patent Document 1)
  • a polyurethane elastomer obtained by copolymerizing an organic phosphorus component is used for an elastomer of artificial leather (for example, see Patent Document 2)
  • a diaryl phosphoramidate-based flame retardant is attached to ultrafine fibers and exhausted (for example, see Patent Document 3).
  • the organophosphorus component is copolymerized as compared with polyester usually used for ultrafine fibers, so that spinnability and dye dyeability at the time of production are deteriorated.
  • thread strength of ultrafine fibers and rubbing fastness of the artificial leather decrease, it is difficult to use the artificial leather for applications requiring high light resistance and high abrasion resistance.
  • the organophosphorus component is copolymerized with a polyurethane component that is an important constituent material for imparting strength and texture to the artificial leather without aged deterioration, and the design is such that texture and durability are lowered as compared with normal polyurethane.
  • Patent Document 4 it is necessary to have a sufficient basis weight of the flame-retardant heat-resistant fiber in order to secure a certain flame retardancy, and denseness of an entangled structure of the artificial leather is reduced, so that an elegant appearance and a flexible texture tend to be impaired.
  • a method of integrating by entanglement by inserting into the inside and intertwining and integrating the flame-retardant heat-resistant fiber and a method of mixing flame-retardant heat-resistant fiber with constituent fiber also have the same problem.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide an artificial leather having excellent functionality (flame retardancy and the like) while having moderate air permeability and a flexible texture, and having feels like natural suede and an elegant appearance.
  • Another object of the present invention is to provide an artificial leather backing material used for obtaining the artificial leather, and having good formability of an opening portion.
  • the present invention has been completed based on these findings.
  • the present invention provides the following inventions.
  • the artificial leather of the present invention is an artificial leather including a fiber entanglement including an ultrafine fiber having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and an elastomer, in which one surface is a napped surface having a raised nap, the other surface is a flame retardant surface having a flame retardant, and the following requirements 1 and 2 are satisfied.
  • Requirement 1 At least the flame retardant surface has a plurality of opening portions.
  • the flame retardant has a tackiness of 0.1 N/cm 2 or more and 2.0 N/cm 2 or less.
  • an opening ratio of the flame retardant surface is 1% or more and 40% or less.
  • the artificial leather has a plurality of opening portions in each of the napped surface and the flame retardant surface, and at least some of the opening portions are through opening portions formed to penetrate from the napped surface to the flame retardant surface.
  • the fiber entanglement is formed by integrating a fiber entanglement including the ultrafine fiber and a woven/knitted fabric (a).
  • the flame retardant surface is a surface formed by stacking a woven/knitted fabric (b).
  • a presence ratio of the flame retardant in a thickness direction satisfies the following formula:
  • W is a thickness (mm) from the flame retardant surface where the flame retardant is present, and W 0 is a thickness (mm) of the entire artificial leather.
  • the flame retardant contains a phosphorus-based compound.
  • the fiber entanglement including the elastomer has a density of 0.20 g/cm 3 or more and 0.50 g/cm 3 or less.
  • a flame retardant having a tackiness of 0.1 N/cm 2 or more and 2.0 N/cm 2 or less is applied to one surface of a napped sheet-shaped article including a fiber entanglement including ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less and an elastomer to form a flame retardant surface, and a plurality of opening portions are provided on at least the flame retardant surface.
  • An artificial leather backing material of the present invention is an artificial leather backing material including a fiber entanglement including an ultrafine fiber having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and an elastomer, in which one surface is a napped surface having a raised nap, the other surface is a functional surface having a functional agent, and the functional agent has a tackiness of 0.1 N/cm 2 or more and 2.0 N/cm 2 or less.
  • the artificial leather backing material can be used as the artificial leather of the present invention by forming an opening portion, and the artificial leather backing material itself can also be used as an artificial leather.
  • An artificial leather backing material of the present invention is an artificial leather backing material including a fiber entanglement including an ultrafine fiber having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and an elastomer, in which one surface is a napped surface having a raised nap, and the other surface is a functional surface having a functional agent, the functional surface has a Kinetic friction coefficient of 0.15 or more and 0.60 or less, and the artificial leather backing material has a stiffness of 30 mm or more and 150 mm or less.
  • An artificial leather backing material of the present invention is an artificial leather backing material including a fiber entanglement including an ultrafine fiber having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and an elastomer, in which one surface is a napped surface having a raised nap, the other surface is a functional surface having a functional agent, and an adhesion amount of the functional agent is 2 to 30% by mass with respect to the artificial leather backing material.
  • an artificial leather having excellent functionality flame retardancy and the like
  • an artificial leather backing material used for obtaining the artificial leather and having good formability of an opening portion.
  • the artificial leather of the present invention is an artificial leather including a fiber entanglement including an ultrafine fiber having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and an elastomer, in which one surface is a napped surface having a raised nap, the other surface is a flame retardant surface having a flame retardant, and the following requirements 1 and 2 are satisfied.
  • Requirement 1 At least the flame retardant surface has a plurality of opening portions.
  • Requirement 2 The flame retardant has a tackiness of 0.1 N/cm 2 or more and 2.0 N/cm 2 or less.
  • a ratio by weight of the ultrafine fiber contained in the fiber entanglement is preferably 60% or more, more preferably 80% or more.
  • An artificial leather backing material of the present invention is an artificial leather backing material including a fiber entanglement including an ultrafine fiber having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and an elastomer, in which one surface is a napped surface having a raised nap, the other surface is a functional surface having a functional agent, and the functional agent has a tackiness of 0.1 N/cm 2 or more and 2.0 N/cm 2 or less.
  • An artificial leather backing material of the present invention is an artificial leather backing material including a fiber entanglement including an ultrafine fiber having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and an elastomer, in which one surface is a napped surface having a raised nap, and the other surface is a functional surface having a functional agent, the functional surface has a Kinetic friction coefficient of 0.15 or more and 0.60 or less, and an artificial leather has a stiffness of 30 mm or more and 150 mm or less.
  • An artificial leather backing material of the present invention is an artificial leather backing material including a fiber entanglement including an ultrafine fiber having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and an elastomer, in which one surface is a napped surface having a raised nap, the other surface is a functional surface having a functional agent, and an adhesion amount of the functional agent is 2 to 30% by mass with respect to the artificial leather backing material.
  • the constituent elements will be described in detail, but the present invention is not limited to the scope described below at all as long as the gist thereof is not exceeded.
  • the fiber entanglement constituting the artificial leather of the present invention includes an ultrafine fiber, and the ultrafine fiber has an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the average single fiber diameter of the ultrafine fiber is 0.1 ⁇ m or more, preferably 1.5 ⁇ m or more, an excellent effect of coloring property after dyeing, light resistance, fastness to rubbing, and stability during spinning is exhibited, and strength of the artificial leather that withstands practical use can be obtained.
  • the average single fiber diameter is 10.0 ⁇ m or less, preferably 6.0 ⁇ m or less, more preferably 4.5 ⁇ m or less, it is possible to obtain an artificial leather that has flexibility, and dense and soft-to-the-touch surface quality.
  • the average single fiber diameter of ultrafine fiber is calculated by taking a scanning electron microscope (SEM) photograph of a cross-section of the artificial leather, randomly selecting 10 ultrafine fibers having a circular shape or an elliptical shape close to a circular shape, measuring the single fiber diameters, calculating the arithmetic average of the 10 fibers, and rounding the arithmetic average off to the first decimal place.
  • SEM scanning electron microscope
  • the cross-sectional area of the single fiber is measured, and the diameter of a hypothetical circle on the assumption that the cross-section was circular is calculated to obtain the diameter of the single fiber.
  • various synthetic fibers including polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylenedimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4′-dicarboxylate, polyamides such as polyamide 6 and polyamide 66, polymers such as acrylic polyethylene and polypropylene, and the like can be used.
  • polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylenedimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4′-dicarboxylate
  • polyamides such as polyamide 6 and polyamide 66
  • polymers such as acrylic polyethylene
  • polyester fibers formed of polymers such as polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate, and the like are excellent in strength, dimensional stability, light resistance and coloring properties and are thus preferably used. Ultrafine fibers formed of different materials can be mixed in the fiber entanglement as long as the object of the present invention is not impaired.
  • the cross-sectional shape of the ultrafine fiber is circular from the viewpoint of processing operability, and it is also possible to employ ultrafine fibers having a modified cross-sectional shape such as an ellipse, polygons such as a flattened polygon and a triangle, a fan shape, a cross shape, a hollow shape, a Y-shape, a T-shape, and a U-shape.
  • a modified cross-sectional shape such as an ellipse, polygons such as a flattened polygon and a triangle, a fan shape, a cross shape, a hollow shape, a Y-shape, a T-shape, and a U-shape.
  • Inorganic particles such as titanium oxide particles, a lubricant, a pigment, a thermal stabilizer, a UV absorber, a conductive agent, a heat storage agent, an antibacterial agent, and the like can be added to the ultrafine fibers forming the fiber entanglement according to various purposes.
  • a resin constituting the ultrafine fiber may be a polyester-based resin, and the polyester-based resin may contain a pigment having an average particle diameter of 0.05 ⁇ m or more and 0.20 ⁇ m or less.
  • the particle diameter referred to herein is a particle diameter in a state in which the pigment is present in the ultrafine fiber, and generally refers to a particle diameter referred to as a secondary particle diameter.
  • the average particle diameter is 0.05 ⁇ m or more, preferably 0.07 ⁇ m or more, the pigment is gripped inside the ultrafine fiber, and therefore, falling off from the ultrafine fiber is suppressed.
  • the average particle diameter is 0.20 ⁇ m or less, preferably 0.18 ⁇ m or less, more preferably 0.16 ⁇ m or less, stability during spinning and yarn strength are excellent.
  • the average particle diameter is calculated by the following method.
  • the content of the pigment contained in the polyester-based resin forming the ultrafine fiber is preferably 0.5% by mass or more and 2.0% by mass or less with respect to the mass of the ultrafine fiber.
  • the proportion of the pigment is 0.5% by mass or more, preferably 0.7% by mass or more, and more preferably 0.9% by mass or more, the deep color developability is excellent.
  • the proportion of the pigment is 2.0% by mass or less, preferably 1.8% by mass or less, and more preferably 1.6% by mass or less, an artificial leather having high physical properties such as strength can be obtained.
  • carbon-based black pigments such as carbon black and graphite, and oxide-based black pigments such as triiron tetraoxide and composite oxides of copper and chromium can be used.
  • the pigment is preferably carbon black from the viewpoint of easily obtaining a pigment having a small particle diameter and excellent dispersibility in a polymer.
  • a chromatic fine-particle oxide pigment a known pigment close to the target color can be used, and examples thereof include iron oxyhydroxide (e.g., “TM Yellow 8170” produced by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), iron oxide (e.g., “TM Red 8270” produced by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), and cobalt aluminate (e.g., “TM Blue 3490E” produced by Dainichiseika Color & Chemicals Mfg. Co., Ltd.).
  • iron oxyhydroxide e.g., “TM Yellow
  • a fiber entanglement including the ultrafine fiber is one of constituent elements.
  • the fiber entanglement include a woven fabric, a knitted fabric, and a nonwoven fabric, and the fiber entanglement further includes an elastomer inside or outside, and these may be properly used depending on the cost and properties required for each application and purpose.
  • Woven and knitted fabrics are preferably used from the viewpoint of cost, and nonwoven fabrics, fiber entanglements filled with an elastomer, and the like are preferably used from the viewpoint of texture with a sense of fulfillment and quality due to fine naps.
  • examples of the woven fabric include plain woven fabrics, twill woven fabrics, satin woven fabrics, and various woven fabrics based on these weave structures.
  • the knitted fabric any of warp knitted fabrics, weft knitted fabrics represented by tricot knit fabrics, lace knit fabrics, and various knitted fabrics based on these knitting structures may be adopted.
  • nonwoven fabrics described in various categories may be applied, such as general short fiber nonwoven fabrics, long fiber nonwoven fabrics, needle punch nonwoven fabrics, papermaking nonwoven fabrics, spunbond nonwoven fabrics, meltblown nonwoven fabrics, and electrospun nonwoven fabrics.
  • a nonwoven fabric is preferable from the viewpoint of the texture with a sense of fulfillment and the quality due to fine naps.
  • the inclusion of the elastomer inside or outside the fiber entanglement is more preferably used from the viewpoint of excellent durability and abrasion resistance of the artificial leather.
  • the elastomer is contained in the fiber entanglement from the viewpoint of flexibility.
  • the fiber entanglement is a nonwoven fabric, and the woven/knitted fabric (a) is contained therein. Still more preferably, a balance of appearance, flexibility, and strength is optimized when the fiber entanglement is a nonwoven fabric and the woven/knitted fabric (a) is a woven fabric.
  • the yarn that constitutes the woven/knitted fabric (a) integrated with the fiber entanglement as the yarn that constitutes the woven/knitted fabric (a), synthetic fibers formed of polyester, polyamide, polyethylene, polypropylene, copolymers thereof, or the like are preferably used. Among these, synthetic fibers formed of polyester, polyamide and copolymers thereof may be used singly or in combination or in mixture.
  • the yarn that constitutes the woven/knitted fabric (a) filament yarns, spun yarns, blended yarns of filaments and short fibers, and the like may be used. From the viewpoint of durability, particularly mechanical strength and the like, it is more preferable to use a multifilament including a polyester-based resin or a polyamide-based resin.
  • the average single fiber diameter of the fibers that constitute the woven/knitted fabric (a) is 50.0 ⁇ m or less, more preferably 15.0 ⁇ m or less, and still more preferably 13.0 ⁇ m or less, not only an artificial leather excellent in flexibility is obtained, but also even when the fibers of the woven/knitted fabric are exposed on the surface of the artificial leather, a hue difference from the ultrafine fiber containing the pigment after dyeing is reduced, so that uniformity of a hue of the surface is not impaired.
  • the average single fiber diameter of the fibers that constitute the woven/knitted fabric (a) is 1.0 ⁇ m or more, more preferably 8.0 ⁇ m or more, and still more preferably 9.0 ⁇ m or more, shape stability of a product as an artificial leather is improved.
  • the average single fiber diameter of the fibers that constitute the woven/knitted fabric (a) is calculated by taking a scanning electron microscope (SEM) photograph of the cross-section of the artificial leather, randomly selecting 10 fibers constituting the woven fabric, measuring the single fiber diameter of the fiber, calculating the arithmetic average of the 10 fibers, and rounding the arithmetic average off to the first decimal place.
  • a total fineness of the multifilaments is measured according to “8.3.1 Fineness based on corrected mass b) Method B (simple method)” in “8.3 Fineness” in JIS L 1013: 2010 “Chemical fiber filament yarn test method”, and is preferably 30 dtex or more and 170 dtex or less.
  • Method B simple method
  • JIS L 1013: 2010 “Chemical fiber filament yarn test method” is preferably 30 dtex or more and 170 dtex or less.
  • the fibers that constitute the woven/knitted fabric (a) are less likely to be exposed on the surface of the artificial leather when the woven/knitted fabric (a) is integrated by entanglement by needle punching or the like, which is preferable.
  • the woven/knitted fabric (a) is a woven fabric
  • the multifilaments of the warp and the weft preferably have the same total fineness.
  • the yarns constituting the woven fabric preferably have a twist count of 1000 T/m or more and 4000 T/m or less.
  • the twist count is 4000 T/m or less, more preferably 3500 T/m or less, and still more preferably 3000 T/m or less, an artificial leather excellent in flexibility is obtained.
  • the twist count is 1000 T/m or more, more preferably 1500 T/m or more, and still more preferably 2000 T/m or more, in a case where a nonwoven fabric and a woven fabric are integrated by entanglement by needle punching or the like, damage to fibers constituting the woven fabric can be prevented, and the mechanical strength of the artificial leather is excellent, which is preferable.
  • a woven/knitted fabric containing a composite fiber (hereinafter, described as a side-by-side composite fiber in some cases) in which two or more kinds of polymers are combined in a side-by-side or eccentric sheath-core type may also be used.
  • a side-by-side composite fiber formed of two or more kinds of polymers having different intrinsic viscosities (IV) different internal strains are generated between the two components by stress concentration on the high viscosity side during stretching.
  • a nonwoven fabric When the fiber entanglement is a nonwoven fabric, a nonwoven fabric can provide an appearance and a texture that are uniform and elegant when the surface of the nonwoven fabric is napped.
  • Examples of the form of the nonwoven fabric include a long fiber nonwoven fabric mainly composed of filaments and a short fiber nonwoven fabric mainly composed of fibers of 100 mm or less.
  • the long fiber nonwoven fabric is used as a fibrous substrate, an artificial leather having excellent strength can be obtained, which is preferable.
  • the short fiber nonwoven fabric the number of fibers oriented in the thickness direction of the artificial leather can be increased as compared with the case of the long fiber nonwoven fabric, and the surface of the artificial leather when napped can have a high dense feeling.
  • the fiber length of the ultrafine fibers in the case where a short fiber nonwoven fabric is used is preferably 25 mm or more and 90 mm or less.
  • the fiber length is 90 mm or less, more preferably 80 mm or less, and still more preferably 70 mm or less, good quality and texture are obtained.
  • the fiber length is 25 mm or more, more preferably 35 mm or more, and still more preferably 40 mm or more, an artificial leather with excellent abrasion resistance can be obtained.
  • the basis weight of the fiber entanglement including the ultrafine fiber that constitutes the artificial leather according to the present invention is measured according to “6.2 Mass per Unit Area (ISO method)” in “Test methods for nonwovens” of JIS L 1913: 2010, and is preferably in a range of 50 g/m 2 or more and 600 g/m 2 or less.
  • the basis weight of the nonwoven fabric is 50 g/m 2 or more, more preferably 100 g/m 2 or more, an artificial leather having a sense of fulfillment and an excellent texture can be obtained.
  • the basis weight is 600 g/m 2 or less, more preferably 450 g/m 2 or less, a soft artificial leather having excellent moldability can be obtained.
  • the basis weight of the fiber entanglement is preferably in the above-described basis weight range.
  • the artificial leather of the present invention has an elastomer.
  • the elastomer is contained in the fiber entanglement.
  • the softness, shape stability, and abrasion resistance of the artificial leather are improved.
  • the elastomer is required to have a purpose as a binder of the fiber entanglement.
  • polyurethane As the elastomer, polyurethane, styrene-butadiene rubber (SBR), nitrile rubber (NBR), acrylic resin, and the like may be used, and it is a preferred aspect to use polyurethane as the main component among these.
  • SBR styrene-butadiene rubber
  • NBR nitrile rubber
  • acrylic resin and the like may be used, and it is a preferred aspect to use polyurethane as the main component among these.
  • polyurethane can afford an artificial leather having touch having feels like natural suede, an elegant appearance, and physical properties enough to endure actual use.
  • the polyurethane forming the elastomer preferably contains a black pigment (b) having an average particle diameter of 0.05 ⁇ m or more and 0.20 ⁇ m or less and a coefficient of variation (CV) of 75% or less.
  • the particle diameter referred to herein is a particle diameter in a state in which the black pigment (b) is present in the elastomer, and generally refers to a particle diameter referred to as a secondary particle diameter.
  • the average particle diameter is 0.05 ⁇ m or more, preferably 0.07 ⁇ m or more, the black pigment (b) is gripped inside the elastomer, and therefore, falling off from the ultrafine fiber is suppressed.
  • the average particle diameter is 0.20 ⁇ m or less, preferably 0.18 ⁇ m or less, more preferably 0.16 ⁇ m or less, dispersibility is excellent when the elastomer is impregnated.
  • the coefficient of variation (CV) of the particle diameter is 75% or less, preferably 65% or less, more preferably 60% or less, still more preferably 55% or less, and most preferably 50% or less, a distribution of the particle diameter becomes small, and falling off of small particles from a surface of the elastomer, precipitation of significantly aggregated particles in an impregnation tank, and the like are suppressed.
  • the average particle diameter and the coefficient of variation (CV) are calculated by the following method.
  • Coefficient of variation of particle diameter (%) (standard deviation of particle diameter)/(arithmetic average of particle diameter) ⁇ 100.
  • black pigment (b) in the present invention carbon-based black pigments such as carbon black and graphite, and oxide-based black pigments such as triiron tetraoxide and composite oxides of copper and chromium can be used.
  • the black pigment is preferably carbon black from the viewpoint of easily obtaining a pigment having a small particle diameter and excellent dispersibility in a polymer.
  • polyurethane used in the present invention either organic solvent-based polyurethane used in the state of being dissolved in an organic solvent or water-dispersible polyurethane used in the state of being dispersed in water can be used.
  • Polyurethane obtained by reaction of a polymer diol, an organic diisocyanate, and a chain extender is preferably used as polyurethane to be used for the present invention.
  • a polycarbonate-based diol polyester-based diol, polyether-based diol, silicone-based diol, or fluorine-based diol can be used as the aforementioned polymer diol, and a copolymer of a combination of these diols can also be used.
  • a polycarbonate-based diol from the viewpoint of hydrolysis resistance and abrasion resistance.
  • a polycarbonate-based diol as described above can be produced, for example, through ester exchange reaction between alkylene glycol and ester carbonate or through reaction of phosgene or a chloroformate with alkylene glycol.
  • alkylene glycol examples include linear alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol, branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 2-methyl-1,8-octanediol, alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, and glycerin, trimethylolpropane, and pentaerythritol.
  • linear alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-
  • polyester-based diols examples include polyester diols produced by condensing one of various low molecular weight polyols and a polybasic acid.
  • one or a plurality selected from the following can be used as the low molecular weight polyol described above: ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butane diol, 1,4-butane diol, 2,2-dimethyl-1,3-propane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, 1,8-octane diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, and cyclohexane-1,4-dimethanol.
  • Adducts prepared by adding various alkylene oxides to bisphenol A are also usable.
  • one or a plurality selected from the following can be used as the polybasic acid: succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydroisophthalic acid.
  • polyether-based diols used in the present invention examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymerized diols which are formed by combining these substances.
  • the number average molecular weight of the polymer diol is preferably in a range of 500 or more and 4000 or less when the molecular weight of a polyurethane-based elastomer is constant.
  • the number average molecular weight is preferably 500 or more, more preferably 1,500 or more, it is possible to prevent the artificial leather from becoming hard.
  • the number average molecular weight is 4000 or less, or more preferably 3000 or less, the polyurethane can maintain its strength.
  • organic diisocyanate used in the present invention examples include aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and aromatic diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. These compounds can also be used in combination.
  • chain extender amine chain extenders such as ethylenediamine and methylenebisaniline, and diol chain extenders such as ethylene glycol can be preferably used. Furthermore, a polyamine which is obtained by reacting polyisocyanate and water can also be used as a chain extender.
  • the polyurethane used in the present invention may be used in combination with a crosslinker with the aim of improving waterproofness, abrasion resistance, hydrolysis resistance, and the like.
  • the crosslinker may be an external crosslinker that is added as a third component to polyurethane, or an internal crosslinker that introduces reaction points to form a crosslinked structure in advance into the polyurethane molecular structure. It is preferable to use an internal crosslinker from the viewpoint that crosslinking points can be formed more uniformly in the polyurethane molecular structure and that the decrease in flexibility can be mitigated.
  • the crosslinking agent used may be a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group and the like.
  • the elastomer may contain various additives including flame retardants such as “phosphorus, halogen, and inorganic flame retardants”; antioxidants such as “phenolic, sulfur, and phosphorus antioxidants”; ultraviolet absorbers such as “benzotriazole, benzophenone, salicylate, cyanoacrylate, and oxalic acid anilide UV absorbers”; light stabilizers such as “hindered amine and benzoate light stabilizers”; hydrolysis stabilizers such as polycarbodiimide; plasticizers; antistatic agents; surfactants; coagulation modifiers; and dyes according to purposes.
  • flame retardants such as “phosphorus, halogen, and inorganic flame retardants”
  • antioxidants such as “phenolic, sulfur, and phosphorus antioxidants”
  • ultraviolet absorbers such as “benzotriazole, benzophenone, salicylate, cyanoacrylate, and oxalic acid anilide UV absorbers”
  • light stabilizers such as “hindered amine
  • the content of the elastomer in the artificial leather can be appropriately adjusted in consideration of the type of the elastomer to be used, a production method for the elastomer, and the texture and physical properties; however, in the present invention, the content of the elastomer is preferably 10% by mass or more and 60% by mass or less with respect to the mass of the fiber entanglement.
  • the content of the elastomer is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, the bonding between the fibers by the elastomer can be enhanced, and the abrasion resistance of the artificial leather can be improved.
  • the content of the elastomer is preferably 60% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, the flexibility of the artificial leather can be further increased.
  • the density of the fiber entanglement including the elastomer is preferably 0.20 g/cm 3 or more and 0.50 g/cm 3 or less.
  • the density is 0.20 g/cm 3 or more, preferably 0.25 cm 3 .
  • the shape stability, dimensional stability, and strength of the artificial leather become sufficient.
  • the artificial leather becomes dense, and the opening portion becomes a clean opening portion without fraying or the like.
  • the density is 0.50 g/cm 3 or less, preferably 0.45 g/cm 3 or less, the air permeability and flexibility of the artificial leather are improved.
  • the functional agent used in the present invention refers to an agent that imparts functionality such as flame retardancy, antifouling properties, yellowing resistance, NOx resistance, grip properties, water repellency, oil repellency, color migration resistance, abrasion resistance, odor resistance, durability, flexibility, and stretchability to a fibrous product.
  • the functional agent (flame retardant or the like) used for the artificial leather of the present invention has tackiness of 0.1 N/cm 2 or more and 2.0 N/cm 2 or less.
  • the functional agent flame retardant or the like
  • the functional agent flame retardant or the like
  • the functional agent is secured to the fiber entanglement with sufficient adhesiveness during application and drying of the functional agent (flame retardant or the like), and the functional agent (flame retardant or the like) after drying does not fall off even in a high-temperature environment.
  • the tackiness of the functional agent is a value obtained by measurement and calculation as follows.
  • the tackiness when the functional agent (flame retardant or the like) is heated to 40° C. is preferably 0.05 N/cm 2 or more and 1.00 N/cm 2 or less, and the tackiness at 20° C. is preferably 0.01 N/cm 2 or more and 0.50 N/cm 2 or less.
  • the tackiness at 20° C. is preferable when the stickiness of the surface of the functional surface (surface of the flame retardant or the like) is small as handleability such as molding or sewing of an artificial leather sheet at room temperature.
  • the tackiness of the functional agent is within the above range, resistance is reduced when the artificial leather is unwound from the roll shape, and the handleability of the artificial leather is improved in the work of the next step.
  • the functional agent flame retardant or the like
  • the tackiness is measured in the same manner as described above except that the heating temperature in (1) is changed to 40° C. or 20° C.
  • the functional agent may be a resin itself composed of a polymer compound having an active functional group, in addition to a low molecular compound having a functional component (flame retardant component or the like), it is preferable to contain a resin in order to obtain durability of functionality, and the resin is selected from, for example, an acrylic resin, a urethane resin, a polyester resin, a vinyl acetate resin, and the like, is not particularly limited, and is preferably an acrylic resin having a good balance from the viewpoint of adhesiveness to a fiber entanglement and a woven/knitted fabric, heat resistance, and adhesiveness.
  • An amount of the binder resin to be blended is not limited to a specific value, and is preferably in a range of 5 to 50% by mass with respect to a total mass of the functional component (flame retardant component or the like) contained in the functional agent (flame retardant or the like).
  • the blending amount is 5% by mass or less, the flame retardant is likely to cause falling off of a powder component, and when the blending amount exceeds 50% by mass, the texture of the artificial leather may be impaired.
  • a resin having low rubber elasticity is preferably used.
  • an acrylamide-based acrylic resin is more preferable than an acrylonitrile-based acrylic resin because the tackiness is better.
  • many resins have a hard texture, and the texture can be softened by reducing the blending amount of the resin.
  • an ethylene-vinyl acetate resin having high adhesiveness is used, the adhesiveness and the tackiness are enhanced even in a small amount; therefore, when it is desired to reduce the blending amount of the resin, it is preferable to contain ethylene-vinyl acetate.
  • the functional agent is a flame retardant and a combustion mode is a carbonization type
  • resin of the flame retardant other resins such as acrylic resins, SBR resins, and MBR resins may also be used, provided they do not affect the carbide formation of vinyl acetate, vinyl acetate copolymer resins, or the like.
  • the flame retardant is made to further include an acrylic resin, the advantages of softened texture and improved water resistance of the flame retardant are obtained.
  • the type of the flame retardant component of the flame retardant is not particularly limited, and the flame retardant component is preferably water-insoluble or sparingly water-soluble from the viewpoint of water spot.
  • the “water spot” as used herein refers to a phenomenon in which, in the artificial leather to which a flame retardant is added, when moisture typified by water droplets adheres from either side of the front and back surfaces and the artificial leather is then naturally dried, the wet portion becomes a white spot or stain. From the viewpoint of adapting to recent environmental hormone regulations, it is preferable to use a dehalogenated flame retardant.
  • Examples of the dehalogenated flame retardant include phosphorus-containing compounds, nitrogen-containing compounds, phosphorus-nitrogen compounds, sulfoamide-based compounds, phosphorus-sulfoamide-based compounds, and sulfur-containing nitrogen-based compounds, and these can be used alone or in combination of two or more thereof.
  • a phosphorus-based compound is preferable, and examples of the phosphorus-based compound include guanidine-based compounds, carbamate-based compounds, phosphate ester-based compounds, phosphate ester-amide-based compounds, ammonium polyphosphate compounds, and aromatic phosphate ester-based compounds such as triphenyl phosphate and trixylenyl phosphate.
  • an ammonium polyphosphate flame retardant having a high phosphorus content is preferable, and a type covered with a melamine resin or a silicon oxide resin is preferable for further making the flame retardant sparingly water-soluble.
  • known flame retardants such as aluminum hydroxide, titanium oxide, zinc oxide, expandable graphite, magnesium hydroxide, calcium carbonate, zinc borate, ammonium polyphosphate, and red phosphorus can be used, and it is preferable to use a polyphosphate-based flame retardant excellent in processability and durability.
  • the combustion mode of the flame retardant there are a carbonization type for forming a carbonized film and a melting type for dropping a fire source, and although any mode is not limited, the melting type is preferable from the viewpoint of flame retardant stability in flame retardant evaluation in the case of sufficient flame retardancy.
  • a judgment classification is “non-combustible”, and the product is judged as acceptable.
  • the judgment classification is “self-extinguished”, and the product is judged as acceptable.
  • the judgment classification is “burning at rate not more than specified rate”, and the product is judged as acceptable.
  • the judgment classification is “burning at rate exceeding specified rate”, and the composite sheet product is judged as unacceptable.
  • the flame retardant when a carbonization type agent such as an antifouling agent is applied to the artificial leather, since the flame retardant is of the carbonization type, the carbonization amount increases, the flame retardancy improves, and the combustion mode can be selected according to the material configuration of the artificial leather.
  • the carbonization type is selected for the flame retardant, by selecting a resin that is easily carbonized for the resin of the flame retardant, the above-described flame retardant component can be reduced, which is preferable from the viewpoint of cost.
  • the vinyl group-containing resin contains at least one selected from a vinyl acetate resin, an ethylene-vinyl acetate copolymer resin, an acrylic vinyl acetate copolymer resin, a vinyl acetate vinyl copolymer resin, and a branched fatty acid vinyl acetate copolymer resin, since the formation of a carbide by using the vinyl acetate resin or the vinyl acetate copolymer resin in combination with a phosphorus-based compound promotes flame retardancy, and particularly exhibits an effect of improving flame retardant properties for horizontal burning of the artificial leather.
  • An adhesion amount of the flame retardant is required to be determined from the viewpoint of securing necessary flame retardant performance and reducing texture curing, and increases or decreases depending on the basis weight, thickness, and ultrafine fiber of the artificial leather, the polymer type of the elastomer, and the fiber entanglement type; however, it is preferable to contain the flame retardant in an amount of 2 to 30% by mass with respect to the artificial leather from the viewpoint of achieving both the flame retardancy and the texture.
  • An application amount of the flame retardant is preferably 10 to 200 g/m 2 , and more preferably within a range of 20 to 100 g/m 2 .
  • the adhesion amount of the flame retardant can be calculated by, for example, mass after application ⁇ mass after application, when the adhesion amount is calculated from the artificial leather after application, the adhesion amount can also be calculated using elemental peak analysis such as fluorescent X-rays.
  • the viscosity is 500 to 10000 mPa ⁇ s at normal temperature from the viewpoint of coating permeability, and a viscosity modifier may be contained as necessary.
  • the viscosity is more preferably 1500 to 9000 mPa ⁇ s, and still more preferably 2500 to 7000 mPa ⁇ s. In this way, a presence ratio of the flame retardant described later in the thickness direction falls within a suitable range, and an artificial leather that is more flexible and has high flame retardancy can be obtained.
  • the method for measuring the viscosity of the solution is not particularly limited, but a measurement method using a commonly used rotational viscometer is used.
  • the viscosity modifier used for adjusting the viscosity of the solution is preferably poorly soluble in water from the viewpoint of preventing occurrence of water spot, and is preferably, for example, an alkali-thickened acrylic resin or an ethylene oxide higher fatty acid ether.
  • aluminum hydroxide, magnesium hydroxide, a metal oxide, and the like can also be used as a flame retardant aid for the flame retardant.
  • the adhesion amount of the functional agent is required to be determined from the viewpoint of securing necessary functional performance and reducing texture curing, and the opening properties of the artificial leather backing material, and increases or decreases depending on the basis weight, thickness, and ultrafine fiber of the artificial leather, the polymer type of the elastomer, and the fiber entanglement type; however, it is preferable to contain the functional agent in an amount of 2 to 30% by mass with respect to the artificial leather from the viewpoint of satisfying the above characteristics.
  • An application amount of the functional agent (flame retardant or the like) is preferably 10 to 200 g/m 2 , and more preferably within a range of 20 to 100 g/m 2 .
  • the functional surface is preferably a surface formed by stacking the woven/knitted fabric (b). That is, by adopting an aspect in which the woven/knitted fabric (b) is further stacked to the fiber entanglement on the functional surface (surface of flame retardant or the like) side opposite to the napped surface of the artificial leather, the artificial leather has more strength and also has flexibility.
  • the fiber entanglement may include the woven/knitted fabric (a) as described above, and a suitable woven/knitted fabric can be selected according to the purpose of each of the woven/knitted fabric (a) and the woven/knitted fabric (b).
  • the kind of the woven/knitted fabric (b) used in the present invention it is possible to use any of various kinds of knitted fabrics such as warp knitted fabrics and weft knitted fabrics typified by tricot knitted fabrics, lace knitted fabrics, and knitted fabrics based on these knitting methods, and various kinds of woven fabrics such as plain weave fabrics, twill weave fabrics, satin weave fabrics, and woven fabrics based on these weaving methods.
  • a knitted fabric having high air permeability and high stretchability is used as the woven/knitted fabric (b).
  • the kind of the yarn that constitutes the woven/knitted fabric (b) for example, a filament yarn, a spun yarn, or a blended yarn of a filament yarn and short fibers can be used.
  • the density of the woven/knitted fabric (b) is preferably 0.10 g/cm 3 or more and 0.60 g/cm 3 or less.
  • the density of the woven/knitted fabric (b) is 0.10 g/cm 3 or more, more preferably 0.15 g/cm 3 or more, an artificial leather having good shape retention can be obtained.
  • the density of the woven/knitted fabric (b) is 0.60 g/cm 3 or less, more preferably 0.50 g/cm 3 or less, the functional agent (flame retardant or the like) can be penetrated to the inside, and an artificial leather excellent in flexibility can be obtained.
  • the thickness of the woven/knitted fabric (b) is preferably 0.10 to 2.50 mm, more preferably 0.15 to 1.50 mm, and still more preferably 0.20 to 1.00 mm. If the thickness of the woven/knitted fabric (b) is less than 0.10 mm, the processability and strength at the time of sticking with the fiber entanglement are deteriorated, and if the thickness exceeds 2.50 mm, the flexibility of the air permeability tends to be impaired.
  • the method of stacking the fiber entanglement and the woven/knitted fabric (b) is not limited, and a method of bonding the fiber entanglement and the woven/knitted fabric (b) with an adhesive interposed therebetween is common.
  • the adhesive include thermoplastic resins such as a polyester resin, a copolymerized polyester resin, a nylon resin, and an acrylic resin, and moisture-curable resins such as a silicone rubber, a polystyrene rubber, and a polyurethane resin.
  • a thermoplastic resin excellent in workability is preferably used and, in particular, a nylon resin excellent in hydrolysis resistance is preferably used.
  • a moisture-curable resin capable of being processed with a low thermal history is preferable from the viewpoint of improving rubbing fastness.
  • a thickness of an adhesive layer is preferably 1 to 300 ⁇ m as long as the adhesive layer has sufficient bondability and does not impair the flexibility and air permeability of the artificial leather.
  • the softening temperature of the thermoplastic resin is preferably 70 to 160° C., more preferably 80 to 120° C. If the softening temperature is lower than 70° C., the thermoplastic resin may be softened during the processing or actual use. If the softening temperature is higher than 160° C., the texture of the artificial leather and the rubbing fastness may be impaired by the softening treatment at the time of sticking.
  • the artificial leather of the present invention includes the fiber entanglement and the elastomer, and one surface is a napped surface having a raised nap, and the other surface is a flame retardant surface having the flame retardant.
  • one surface is the napped surface having the raised nap. That is, the raised nap may be provided only on the surface to be a product surface of the artificial leather, and is also allowed to be provided on both surfaces.
  • the raised nap in the case where the artificial leather has raised nap on the surface to be the product surface, the raised nap preferably has a length and direction flexibility to such an extent that traces remain when the artificial leather is stroked with a finger, that is, a so-called finger mark remain due to the change of direction of the raised nap from the viewpoint of design effects.
  • Examples of the form having raised nap on the other surface (back surface) with respect to the product surface of the artificial leather include imparting a flame retardant after forming raised nap on the back surface of the fiber entanglement.
  • the woven/knitted fabric (b) is stacked on the back surface of the fiber entanglement, the front and back surfaces of the fiber entanglement are napped, and the flame retardant is added to the surface of the stacked woven/knitted fabric (b), so that the flame retardant is present in the napped portion of the back surface of the fiber entanglement, and the flame retardant surface has raised nap.
  • the raised napped length on the surface is preferably 50 ⁇ m or more and 500 ⁇ m or less, and more preferably 100 ⁇ m or more and 450 ⁇ m or less.
  • the raised nap length is 50 ⁇ m or more, the raised nap covers the elastomer, and the exposure of the elastomer on the product surface of the artificial leather is suppressed, so that an elegant appearance can be obtained.
  • the woven/knitted fabric (a) When the woven/knitted fabric (a) is entangled and integrated with the fiber entanglement constituting the artificial leather, or when the fiber entanglement itself includes a woven/knitted fabric, setting the raised nap length within the above range can sufficiently cover a tissue of the woven/knitted fabric in the vicinity of the product surface of the artificial leather, which is preferable in that a naturally-like and elegant appearance can be obtained.
  • the raised nap length is 500 ⁇ m or less, an artificial leather excellent in design effect and abrasion resistance can be obtained.
  • the raised nap length of the artificial leather is calculated by the following method.
  • the “opening portion” in the present invention is not limited to a portion where a hole (through opening portion) formed by penetrating an artificial leather from the napped surface to the functional surface (surface of flame retardant or the like) is opened, and includes, for example, a case where the opening portion does not overlap the woven/knitted fabric (b) in a planar direction and is not the through opening portion.
  • Examples of the latter include a form in which an opening portion is formed in advance in the woven/knitted fabric (b) containing the functional agent (flame retardant or the like) and the woven/knitted fabric (b) is stacked on the fiber entanglement.
  • the shape of the opening portion can be any shape according to a desired design, and polygonal shapes such as a round shape, an elliptical shape, a flat shape, and a triangular shape, a fan shape, a cross shape, and deformed shapes such as a hollow shape, a Y shape, a T shape, and a U shape can be adopted.
  • An arrangement pattern of the opening portion is not particularly limited, and the opening portion may be regularly provided or irregularly provided; however, from the viewpoint of exhibiting uniform air permeability and strength throughout the artificial leather, the opening portions are preferably regularly arranged at predetermined intervals.
  • a hole diameter of the opening portion is preferably 0.1 to 3.0 mm and more preferably 0.5 to 2.5 mm from the viewpoint of achieving both air permeability and strength of the entire artificial leather.
  • an opening ratio of the functional surface is preferably 1% or more and 40% or less from the viewpoint of achieving both air permeability and strength of the entire artificial leather. That is, when the opening ratio is 1% or more, more preferably 2% or more, an artificial leather excellent in air permeability can be obtained. On the other hand, when the opening ratio is 40% or less, more preferably 20% or less, and still more preferably 15% or less, an artificial leather excellent in strength can be obtained.
  • the artificial leather of the present invention has a plurality of opening portions in each of the napped surface and the functional surface (surface of flame retardant or the like), and at least some of the opening portions are the through opening portions formed to penetrate from the napped surface to the functional surface (surface of flame retardant or the like). With this configuration, an artificial leather having more excellent air permeability can be obtained.
  • the shape of the through opening portion in the thickness direction may be, for example, a cylindrical through opening portion in which the hole diameters of the opening portion of the napped surface and the opening portion of the functional surface (surface of flame retardant or the like) are the same, or a mortar-shaped through opening portion in which the hole diameters of the opening portion of the napped surface and the opening portion of the functional surface (surface of flame retardant or the like) are different. That is, the shape of the through opening portion can be selected in consideration of the design and mechanical properties of the artificial leather.
  • the presence ratio of the functional agent (flame retardant or the like) in the thickness direction preferably satisfies the following formula:
  • W is the thickness (mm) from the functional surface (surface of flame retardant or the like) where the functional agent (flame retardant or the like) is present
  • W 0 is the thickness (mm) of the entire artificial leather.
  • the presence ratio of the functional agent (flame retardant or the like) in the thickness direction is 0.001 or more, more preferably 0.01 or more, still more preferably 0.05 or more, an artificial leather excellent in functionality (flame retardancy or the like) can be obtained.
  • the presence ratio of the functional agent (flame retardant or the like) in the thickness direction is 0.7 or less, more preferably 0.5 or less, and still more preferably 0.3 or less, an artificial leather excellent in air permeability and flexibility can be obtained.
  • the presence ratio of the functional agent (flame retardant or the like) in the thickness direction is obtained by collecting and preparing three SEM measurement samples, randomly selecting five points in an observation image of each cross section, measuring W and W 0 at each point, and calculating W/W 0 using an arithmetic average value.
  • the functional agent flame retardant or the like
  • calculation is performed using a method of determining a resin containing an element peak as the functional agent by SEM-EDX.
  • calculation is performed using a method of determining a resin containing a phosphorus element peak as the flame retardant.
  • the artificial leather As a preferred form of the artificial leather, a form in which the woven/knitted fabric (b) is stacked on the fiber entanglement and the functional agent (flame retardant or the like) is unevenly distributed in the woven/knitted fabric (b) is preferable from the viewpoint of functionality (flame retardancy or the like).
  • the functional agent flame retardant or the like
  • an area ratio of the functional agent (flame retardant or the like) of the functional surface (surface of flame retardant or the like) is 10 to 100%.
  • the area ratio is obtained by collecting and preparing three SEM measurement samples, randomly selecting five points in an observation image of 50 times of the surface of each functional surface (surface of flame retardant or the like), photographing a SEM image, binarizing the SEM image, and then performing calculation by using a value obtained by arithmetically averaging the area ratio in which the functional agent (flame retardant or the like) is present with respect to a total area obtained by excluding the opening portion from an image area of 50 times.
  • an artificial leather excellent in functionality (flame retardancy or the like) and functional (flame retardant, etc.) stability can be obtained, and for example, when a polyurethane foam is laminated on the back surface of an artificial leather such as an interior material for vehicles, smoothness of the functional surface (surface of flame retardant or the like) increases, so that e peel strength with the polyurethane foam increases.
  • the artificial leather of the present invention preferably has a thickness of 0.2 mm or more and 2.5 mm or less as measured according to “6.1.1 A method” in “6.1 Thickness (ISO method)” in “Test methods for nonwovens” of JIS L 1913: 2010
  • the thickness of the artificial leather is 0.2 mm or more, more preferably 0.3 mm or more, and still more preferably 0.4 mm or more, not only excellent processability at the time of production is obtained, but also a sense of fulfillment and excellent texture are obtained.
  • the thickness is 2.5 mm or less, more preferably 2.0 mm or less, and still more preferably 1.5 mm or less, a soft artificial leather having excellent moldability can be obtained.
  • the rubbing fastness measured by a “9.1 friction tester type I (clock meter) method” according to JIS L 0849: 2013 “Test methods for color fastness to rubbing” and light fastness measured by a “7.2 Exposure method a) First exposure method” according to JIS L 0843: 2006 “Test method for color fastness to light of xenon arc lamp” are each preferably grade 3 or higher. When the rubbing fastness and the light fastness are grade 3 or higher, it is possible to prevent color loss and contamination of clothes and the like during actual use.
  • the mass loss of the artificial leather after 20,000 times of abrasion under a pressing load of 12.0 kPa in an abrasion test measured in accordance with “8.19.5 Method E (Martindale method)” of “8.19 Abrasion strength and color change by rubbing” of JIS L 1096:2010 “Cloth experiment method of woven fabric and knitted fabric” is preferably 20 mg or less, more preferably 15 mg or less, still more preferably 10 mg or less. When the mass loss is 20 mg or less, fluff dropping during actual usage can be prevented.
  • the tensile strength as measured in accordance with “6.3.1 Tensile strength and percentage elongation (ISO method)” in “Test methods for nonwovens” of JIS L 1913: 2010 is preferably from 20 to 400 N/cm in arbitrary measurement direction.
  • the tensile strength is 20 N/cm or more, more preferably 30 N/cm or more, and still more preferably 40 N/cm or more
  • the artificial leather is excellent in shape stability and durability, which is preferable.
  • the tensile strength is 400 N/cm or less, more preferably 300 N/cm or less, and still more preferably 250 N/cm or less, an artificial leather excellent in moldability is obtained.
  • the artificial leather of the present invention preferably has a stiffness of 30 to 150 mm as measured by a cantilever method in “8.21 Stiffness” of JIS L 1096:2010 “Cloth experiment method of woven fabric and knitted fabric”, from the viewpoint of texture and flexibility, and more preferably 50 to 130 mm.
  • the air permeability is preferably 1 to 400 cm 3 /cm 2 /sec, more preferably 20 to 300 cm 3 /cm 2 /sec, and still more preferably 70 to 250 cm 3 /cm 2 /sec in order to achieve both flame retardancy and air permeability in Method A (Frazier type method) of “8.26 Air permeability” of JIS L 1096: 2010 “Cloth experiment method of woven fabric and knitted fabric”.
  • Method A Fastier type method
  • the air permeability is greatly affected by the opening; however, when the fiber entanglement has air permeability, the fiber entanglement is better from the viewpoint of sweatiness and multiplication of bacteria. Therefore, the air permeability of the fiber entanglement having no opening portion is preferably 1 to 100 cm 3 /cm 2 /sec, more preferably 2 to 50 cm 3 /cm 2 /sec.
  • the basis weight of the artificial leather of the present invention is measured according to “6.2 Mass per Unit Area (ISO method)” in “Test methods for nonwovens” of JIS L 1913: 2010, and is preferably in a range of 50 g/m 2 or more and 800 g/m 2 or less.
  • the basis weight of the nonwoven fabric is 50 g/m 2 or more, more preferably 100 g/m 2 or more, still more preferably 150 g/m 2 or more, an artificial leather having a sense of fulfillment and an excellent texture can be obtained.
  • the basis weight is 800 g/m 2 or less, more preferably 600 g/m 2 or less, and still more preferably 500 g/m 2 or less, a soft artificial leather having excellent moldability can be obtained.
  • the artificial leather backing material for producing the artificial leather having the opening portion according to the present invention preferably has a stiffness of 30 mm or more and 150 mm or less, more preferably 50 mm or more and 130 mm or less, as measured by the cantilever method in “8.21 Stiffness” of JIS L 1096: 2010 “Cloth experiment method of woven fabric and knitted fabric”.
  • an opening portion is easily formed in the artificial leather backing material, and for example, when the opening portion is formed with a hollow punch such as a hole piercing punch, waste of the artificial leather backing material hollowed out at the opening portion tends to come out from the hollow portion of the punch, so that productivity of opening forming processing is improved.
  • the Kinetic friction coefficient of the functional surface is preferably 0.15 or more and 0.60 or less in terms of the formability of the opening portion and the productivity of opening forming processing.
  • a friction coefficient affects slipperiness of the functional agent and an opening device (punch, hollow needle, drill, etc.), for example, in the case of an opening method is perforation (punch, hollow needle, etc.) and drilling.
  • the adhesion amount of the functional agent is preferably 2 to 30% by mass with respect to the artificial leather backing material in terms of the properties of the artificial leather described above, the formability of the opening, and the productivity of opening forming processing.
  • the adhesion amount of the functional agent is less than 2% by mass, fiber waste hollowed out at the opening portion of the artificial leather backing material is likely to be loosened, and for example, in the case of a punch, it is difficult to remove the fiber waste from the hollow portion.
  • the adhesion amount of the functional agent is more than 30% by mass, for example, in the case of the punch, the hollow portion is likely to be clogged with the waste.
  • the adhesion amount can be calculated from a weight change before and after application similarly to the adhesion amount, and can also be calculated by chemical analysis such as fluorescent X-ray.
  • the artificial leather of the present invention is preferably produced by applying a flame retardant having a tackiness of 0.1 N/cm 2 or more and 2.0 N/cm 2 or less to one surface of a napped sheet-shaped article including a fiber entanglement including ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less and an elastomer to form a flame retardant surface, and providing a plurality of opening portions on at least the flame retardant surface to have.
  • a flame retardant having a tackiness of 0.1 N/cm 2 or more and 2.0 N/cm 2 or less
  • a fiber entanglement including ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less and an elastomer
  • the ultrafine fiber constituting the artificial leather of the present invention can be produced by a conventionally known method, and examples of the method include a sea-island spinning method, a mixed spinning method, and a split type composite spinning method in synthetic fiber production. It is preferable to use ultrafine fiber-generating fibers including two or more kinds of polymer substances having different solubilities in a solvent in terms of productivity such as formation of the fiber entanglement.
  • an ultrafine fiber generation step an island portion formed of a resin to be an ultrafine fiber is formed, and an ultrafine fiber-generating fiber having a sea-island type composite structure in which an easily soluble polymer forms a sea portion is produced.
  • an islands-in-the-sea fiber is used in which thermoplastic resins having different solvent solubilities are used as a sea portion (easily soluble polymer) and an island portion (hardly soluble polymer), and the sea portion is dissolved and removed using a solvent or the like to cause the island portion to form an ultrafine fiber.
  • Use of the islands-in-the-sea fiber is favorable in view of the texture or surface quality of the artificial leather, because at the time of removing the sea portion, a suitable gap can be provided between island portions, that is, between ultrafine fibers inside a fiber bundle.
  • the method of spinning the ultrafine fiber-generating fiber having a sea-island composite structure a method using a mutually arranged polymer body in which a spinneret for sea-island composite fibers is used and the fiber is spun by mutually arranging a sea portion and an island portion is preferred from the viewpoint that ultrafine fibers having a uniform single fiber fineness are obtained.
  • any method can be adopted in which a master batch obtained by kneading the pigment with the resin is prepared in advance, and the master batch and chips of another resin are mixed and spun.
  • a copolymerized polyester obtained by copolymerizing polyethylene, polypropylene, polystyrene, sodium sulfoisophthalic acid, polyethylene glycol or the like, and polylactic acid can be used, but polystyrene or copolymerized polyester is preferably used from the viewpoint of yarn making property, easy elutability, and the like.
  • an islands-in-the-sea fiber in which the strength of the island portion is 2.5 cN/dtex or more is preferably used.
  • the strength of the island portion is 2.5 cN/dtex or more, more preferably 2.8 cN/dtex or more, still more preferably 3.0 cN/dtex or more, the abrasion resistance of the artificial leather is enhanced, and at the same time, reduction in the rubbing fastness due to falling off of the fiber can be suppressed.
  • the strength of the island portion of the islands-in-the-sea fibers is calculated by the following method.
  • a conventional production method for a fiber entanglement in which ultrafine fibers or islands-in-the-sea fibers are used as a woven/knitted fabric and a nonwoven fabric can be applied.
  • the spun-out ultrafine fiber-generating fiber is opened and passed through a cross wrapper, etc. to form a fiber web, and the fiber web is then entangled to obtain a nonwoven fabric.
  • a needle punching treatment, a water jet punching treatment, and the like can be used as the method for obtaining the nonwoven fabric by entangling the fiber web.
  • either a short-fiber nonwoven fabric or a long-fiber nonwoven fabric may be used as described above, and in the case of the short-fiber nonwoven fabric, the number of fibers oriented in the thickness direction of the artificial leather is larger than that in the long-fiber nonwoven fabric, and the surface of the artificial leather at the time of being napped can give a highly dense feeling.
  • the obtained ultrafine fiber-generating fibers are preferably crimped, cut to a predetermined length to obtain a raw cotton, then opened, stacked, and entangled, thereby obtaining a short-fiber nonwoven fabric.
  • crimping and cutting steps may be used for the crimping and cutting steps.
  • the obtained nonwoven fabric and the woven/knitted fabric (a) are stacked and then integrated by entanglement.
  • the woven/knitted fabric (a) is stacked on one surface or both surfaces of the nonwoven fabric, or the woven/knitted fabric (a) is sandwiched between a plurality of nonwoven fabric webs, and then the fibers of the nonwoven fabric and the woven/knitted fabric (a) can be interlaced by needle punching, water jet punching, or the like.
  • the apparent density of the nonwoven fabric including ultrafine fiber-generating fibers 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 sheet-shaped article should have sufficient shape stability and dimension stability.
  • a sufficient space can be kept such that the elastomer is imparted.
  • nonwoven fabric prefferably be subjected to heat shrinkage treatment with warm water or steam to improve the dense feeling of the fibers.
  • the nonwoven fabric may be impregnated with an aqueous solution of a water-soluble resin and dried to add the water-soluble resin to the nonwoven fabric. Adding the water-soluble resin to the nonwoven fabric fixes the fibers and improves the dimensional stability.
  • the obtained fibrous substrate is treated with a solvent to generate ultrafine fibers having an average single fiber diameter of single fibers of 0.1 ⁇ m or more and 10 ⁇ m or less.
  • ultrafine fibers is carried out by immersing the nonwoven fabric formed of islands-in-the-sea fibers in a solvent to ensure dissolution and removal of the sea portion of the islands-in-the-sea fibers.
  • the ultrafine fiber-generating fiber is an islands-in-the-sea fiber and the sea portion is polyethylene, polypropylene or polystyrene
  • an organic solvent such as toluene or trichloroethylene can be used as the solvent to dissolve and remove the sea portion.
  • An aqueous alkali solution of sodium hydroxide or the like can be used when the sea portion is copolymerized polyester or polylactic acid.
  • Hot water can be used when the sea portion is water-soluble thermoplastic polyvinyl alcohol-based resin.
  • a fiber entanglement including ultrafine fibers or ultrafine fiber-generating fibers as a main component is impregnated with a solution of an elastomer and solidified to add the elastomer.
  • the method of fixing the elastomer to the fiber entanglement may be a method of impregnating a solution of the elastomer into the fiber entanglement and then subjecting the resultant to wet coagulation or dry coagulation, and these methods can be appropriately selected according to the kind of the used elastomer.
  • N,N′-dimethylformamide, dimethyl sulfoxide, or the like is preferably used as the solvent used when polyurethane is added as the elastomer.
  • a water-dispersible polyurethane liquid in which polyurethane is dispersed as an emulsion in water may be used.
  • the elastomer may be applied to the fiber entanglement before generating ultrafine fibers from the ultrafine fiber-generating fibers, or after generating ultrafine fibers from the ultrafine fiber-generating fibers.
  • the fiber entanglement provided with the elastomer is cut in half in the thickness direction to form half-cut sheets as two fiber entanglements.
  • a napped surface can be formed by applying a napping treatment to the fiber entanglement provided with the elastomer or a half-cut sheet-shaped article obtained by cutting in half.
  • the napping treatment can be performed by grinding the surface using sandpaper or a roll sander.
  • the napping treatment can be applied to only one surface or both surfaces.
  • a lubricant such as a silicone emulsion can be added to the surface of the fiber entanglement before the napping treatment.
  • a ground powder generated by grinding is less likely to deposit on sandpaper. In this way, a napped sheet-shaped article having a napped surface is formed.
  • the napped sheet-shaped article prefferably be dyed.
  • the dyeing treatment include jet dyeing treatment using a jigger dyeing machine or a jet dyeing machine, dip dyeing treatment such as thermosol dyeing treatment using a continuous dyeing machine, and printing treatment to the napped surface, such as roller printing, screen printing, inkjet printing, sublimation printing, and vacuum sublimation printing.
  • a jet dyeing machine is preferably used from the viewpoint of quality and appearance from the viewpoint of obtaining a flexible texture. If necessary, the artificial leather may be subjected to various kinds of resin finishing after the dyeing.
  • the woven/knitted fabric (b) is stacked and integrated with an adhesive on a surface opposite to a napped surface (when both surfaces each have a napped surface, the napped surface on a side to be a product surface) of the napped sheet.
  • the method of adding the adhesive include a method of applying a predetermined amount of the adhesive using a device such as a rotary screen, a knife roll coater, a gravure roll coater, a kiss roll coater, or a calender coater.
  • a discontinuous adhesive layer using a rotary screen or a gravure roll coater because the artificial leather has a good texture.
  • the discontinuous adhesive layer means an adhesive layer including both a portion where an adhesive is present and a portion where an adhesive is absent with respect to an adhesion surface, that is, a horizontal surface of the woven/knitted fabric or raised nap sheet.
  • the discontinuous adhesive layer means an adhesive layer in which the adhesive is arranged in a dot pattern.
  • thermocompression bonding when a thermoplastic resin is used as an adhesive, the adhesive can be integrated by thermocompression bonding.
  • a method such as heat rolls can be used. In the case where heat rolls are used, it is preferable to set the temperature of the heat roll on the woven/knitted fabric side higher than the temperature of the heat roll on the skin sheet side.
  • a wet-curable resin is used as an adhesive, adhesion is promoted under a suitable temperature and humidity environment called curing.
  • the roll temperature on the woven/knitted fabric side in thermocompression bonding with heat rolls is preferably 80 to 180° C., more preferably 100 to 160° C. If the roll temperature on the woven/knitted fabric side is lower than 80° C., adhesion takes time, and a large load is imposed on the process. If the roll temperature on the woven/knitted fabric side is higher than 180° C., the texture of the artificial leather becomes coarse and hard.
  • a functional agent (flame retardant or the like) is added to one surface of the napped sheet-shaped article to form a functional surface (surface of flame retardant or the like), thereby obtaining an artificial leather backing material.
  • the functional agent flame retardant or the like
  • the functional surface has a Kinetic friction coefficient (JIS K 7125) of 0.15 or more and 0.60 or less
  • the artificial leather backing material has a stiffness of 30 mm or more and 150 mm or less.
  • the functional surface (surface of flame retardant or the like) is formed on a surface opposite to the napped surface (when both surfaces each have a napped surface, the napped surface on the side to be a product surface) of the napped sheet-shaped article.
  • Examples of the method of forming the functional surface include a method of applying the functional agent (flame retardant or the like) to a stacked sheet obtained by stacking the napped sheet-shaped article or the woven/knitted fabric (b) by using a device such as a rotary screen, a knife roll coater, a gravure roll coater, a kiss roll coater, or a calender coater.
  • the functional agent flame retardant or the like
  • the napping treatment may be further performed after the functional agent (flame retardant or the like) is applied and dried.
  • the functional agent flame retardant or the like
  • the woven/knitted fabric (b) may be applied to the woven/knitted fabric (b) in advance, and then the woven/knitted fabric (b) may be stacked on the surface opposite to the napped surface (when both surfaces each have the napped surface, the napped surface on the side to be a product surface) of the napped sheet-shaped article to form a functional surface (surface of flame retardant or the like).
  • the functional agent flame retardant or the like
  • the functional agent permeates the inside after being applied
  • the functional agent flame retardant or the like
  • the functional agent is permeated while adjusting the viscosity of the functional agent (flame retardant or the like), a mesh of a gravure roll, the application amount, an immersion amount, and the like.
  • the drying can be performed using a known dryer such as a tenter dryer.
  • the functional (flame retardant or the like) sheet including the functional surface (surface of flame retardant or the like) has a plurality of opening portions at least on the functional surface (surface of flame retardant or the like).
  • the means for providing the opening portion include methods such as boring such as perforation and drilling, and laser processing.
  • the opening portion may be formed not only on the functional surface (surface of flame retardant or the like) but also on the other surface.
  • the timing of opening is not limited, and for example, the fiber entanglement and the woven/knitted fabric (b) may be separately opened and then stacked and integrated.
  • the functional agent flame retardant or the like
  • a through opening portion is formed by a drill, a perforated needle, or a hole piercing punch.
  • the artificial leather is obtained by forming the opening portion.
  • the Kinetic friction coefficient of the functional surface decreases.
  • the Kinetic friction coefficient of the functional surface is preferably 0.10 to 0.55 as the artificial leather having the opening portion.
  • an artificial leather in which a design may be applied to its surface as necessary.
  • the surface may be subjected to post processing such as embossing, laser processing, pinsonic processing, and printing processing.
  • the artificial leather of the present invention obtained by the production method exemplified above is excellent in functionality (flame retardancy and the like) while having moderate air permeability and a flexible texture, has feels like natural suede and an elegant appearance, and can be widely used for an interior material for vehicles, interior materials, building materials, and miscellaneous goods, and in particular, the artificial leather is suitably used for the interior material for vehicles because of its excellent functionality (flame retardancy and the like).
  • the artificial leather backing material of the present invention obtained by the production method exemplified above is excellent in opening formability, and is suitably used for the production of the artificial leather.
  • the average single fiber diameter of ultrafine fibers was calculated by observing the ultrafine fibers by means of a scanning electron microscope, Model “VW-9000”, manufactured by Keyence Corp.
  • the appearance quality and feel of the artificial leather were evaluated by a total of 20 evaluators consisting of 10 healthy adult men and 10 healthy adult women and after visually deciding the following ratings, the most common rating was employed as the appearance quality and feel of the artificial leather. In the case of a tie between ratings, a higher rating was employed as the quality and feel of the artificial leather.
  • the acceptance level of the present invention was “A, B, or C”.
  • a 200 mm ⁇ 200 mm test piece was taken from five different positions and subjected to measurement according to Method A (Frazier type method) of “8.26 Air permeability” of JIS L 1096: 2010 “Cloth experiment method of woven fabric and knitted fabric”, followed by calculating the quantity of air (cm 3 /cm 2 /sec) passing through the test piece based on the conversion table attached to the test apparatus. In addition, the five calculations thus obtained were averaged to give a value to be adopted as the air permeability (cm 3 /cm 2 /sec).
  • test piece at this time was 350 mm ⁇ 100 mm.
  • the opening ratio refers to an area ratio of the opening portion in the entire area on one surface of the artificial leather, and refers to an area ratio on the surface.
  • a 20 cm ⁇ 20 cm sample of the artificial leather was scanned by image photographing, an operation of calculating the area ratio by binarization processing was performed on the sample at 5 points, and the area ratio was determined by arithmetic average.
  • the presence ratio of the flame retardant in the thickness direction was calculated by the above method after observing the cross section of the artificial leather by using the scanning electron microscope (SEM), Model “VW-9000”, manufactured by Keyence Corp.
  • the density of the fiber entanglement including the elastomer (the density of the woven/knitted fabric (b) and the artificial leather containing no flame retardant) shown in Examples and Comparative Examples was calculated by measuring the basis weight of the fiber entanglement to which the elastomer was added (including the woven/knitted fabric (a) when there was the woven/knitted fabric (a)) according to “6.2 Mass per Unit Area (ISO method)” in “Test methods for nonwovens” of JIS L 1913: 2010 as described above, and dividing the basis weight by the thickness of the fiber entanglement to which the elastomer was added. Five samples were randomly taken out from the fiber entanglement sample including the elastomer, and the average value was taken as the density.
  • Density (g/cm 3 ) basis weight (g/m 2 ) ⁇ thickness (mm) ⁇ 1000).
  • test pieces of 80 mm ⁇ 200 mm were taken from the artificial leather, and the functional surface was measured at a test speed of 100 mm/min, with a sliding piece of 63 mm ⁇ 63 mm, and at a load of 1.92 N according to JIS K 7125, and the average value was taken as the Kinetic friction coefficient.
  • the raw stock obtained as described above was used to form a laminated web via carding and cross wrapper steps.
  • the needle punching treatment was performed with a number of punches of 2,500 punches/cm 2 to obtain a nonwoven fabric having a basis weight of 540 g/m 2 and a thickness of 2.4 mm.
  • the nonwoven fabric obtained as described above was shrunk with hot water at 96° C. Thereafter, the nonwoven fabric shrunk with hot water was impregnated with a polyvinyl alcohol (hereinafter, may be abbreviated as PVA) aqueous solution having a saponification degree of 88%, which was prepared so as to have a concentration of 12% by mass. Furthermore, the nonwoven fabric was squeezed with rollers and dried by hot air having a temperature of 120° C. for 10 minutes while allowing for migration of PVA, to obtain a PVA-impregnated sheet in which the mass of PVA was 25% by mass relative to the mass of a sheet base.
  • PVA polyvinyl alcohol
  • the PVA-impregnated sheet thus obtained was immersed in trichloroethylene, and squeezed and compressed by a mangle ten times. Thus, dissolution removal of the sea portion and compression treatment of the PVA-impregnated sheet were performed to obtain a PVA-impregnated sheet in which the ultrafine fiber bundles to which PVA was applied were entangled.
  • the average single fiber diameter of the ultrafine fiber was 4.4 ⁇ m.
  • a dimethylformamide (hereinafter, may be abbreviated as DMF) solution of polyurethane prepared so that the concentration of a solid content mainly composed of polyurethane was 13% was immersed in the PVA-impregnated sheet obtained as described above. Thereafter, the sea-removing PVA-impregnated sheet immersed in DMF solution of polyurethane was squeezed with rollers. Then, the sheet was immersed in a DMF aqueous solution having a concentration of 30% by mass to solidify the polyurethane.
  • DMF dimethylformamide
  • the polyurethane-impregnated sheet obtained as described above was cut in half such that the thickness of each part was 1 ⁇ 2. Subsequently, a napping treatment was performed by grinding the surface layer portion of the half-cut surface by 0.3 mm with an endless sandpaper having a sandpaper grit size of 180 to obtain a napped sheet having a thickness of 0.6 mm.
  • the napped sheet obtained as described above was dyed with a black disperse dye at 120° C. using a jet dyeing machine, and reduction-cleaned. Thereafter, a drying treatment was performed at 100° C. for 7 minutes to obtain a dyed sheet having an average single fiber diameter of the ultrafine fiber of 4.4 ⁇ m, a basis weight of 220 g/m 2 , and a thickness of 0.70 mm.
  • a flame retardant A was obtained by mixing 20 parts by mass of ammonium polyphosphate treated with a silicon oxide resin (manufactured by Wellchem.com, phosphorus content: 28%, nitrogen content: 14%) as a flame retardant main component of the flame retardant, 0.2 parts by mass of polyoxyethylene sorbitan monostearate (nonionic surfactant) as a surfactant, 11 parts of methyl acrylate resin having a nonvolatile content of 50% as a binder resin, and 4 parts by mass of melamine cyanurate (nitrogen content: 49.4%), and using hydroxyethyl cellulose as a thickener.
  • Coating processing of applying a flame retardant processing agent solution (the viscosity was adjusted to 3000 mPa ⁇ s by the thickener) containing 70% by mass of the flame retardant A to one surface opposite to the product surface of the dyed sheet using a screen coater was performed, and then drying treatment was performed at a temperature of 100° C. for 7 minutes to obtain a sheet with a flame retardant in which the adhesion amount of the flame retardant with respect to the mass of the artificial leather after drying was 20% by mass.
  • a through opening portion was formed with a punching board in which needles were planted, thereby obtaining an artificial leather (needle diameter: 1.2 mm, longitudinal pitch: 5 mm, transverse pitch: 5 mm, opening ratio: 6%).
  • the through opening portion after the punching was not clogged with fiber waste, the flame retardant did not stick to an edge of the opening portion, a clean opening portion was formed, and the fiber waste and the flame retardant did not adhere to the punching board after the punching in which dust was blown off by air.
  • the obtained artificial leather had excellent flame retardancy while having moderate air permeability and a flexible texture, and had dense feels like natural suede and an elegant appearance.
  • the tackiness of the flame retardant was 0.45 N/cm 2 at 60° C., 0.20 N/cm 2 at 40° C., and 0.14 N/cm 2 at 20° C.
  • the basis weight of the artificial leather was 240 g/m 2 , and the thickness was 0.72 mm. The results are shown in Table 1.
  • An artificial leather was obtained in the same manner as in Example 1 except that an ultrafine fiber-generating fiber having a sea-island composite structure including an island component and a sea component was subjected to melt spinning using a sea-island composite spinneret having 16 islands under the conditions of an island/sea mass ratio of 55/45, a discharge amount of 1.0 g/(min ⁇ hole), and a spinning speed of 1100 m/min, and then the ratio of stretching in a spinning oil solution bath set at 90° C. was 3.4 times.
  • the average single fiber diameter of the ultrafine fiber was 2.9 ⁇ m. The results are shown in Table 1.
  • a laminated web was formed using the raw stock described in Example 1 via the carding and cross wrapper steps, and then a plain woven fabric (basis weight: 75 g/m 2 ) having a warp density of 95 yarns/2.54 cm and a weft density of 76 yarns/2.54 cm, in which a twisted yarn obtained by twisting a multifilament (average single fiber diameter: 11 ⁇ m, total fineness: 84 dtex, 72 filaments) containing polyethylene terephthalate having an intrinsic viscosity (IV value) of 0.65 at 2500 T/m was used for both wefts and warps, was stacked on and under the laminated web.
  • a plain woven fabric (basis weight: 75 g/m 2 ) having a warp density of 95 yarns/2.54 cm and a weft density of 76 yarns/2.54 cm, in which a twisted yarn obtained by twisting a multifilament (average single fiber diameter: 11 ⁇ m, total fineness
  • an artificial leather in which the average single fiber diameter of the ultrafine fiber was 4.4 ⁇ m, the basis weight was 360 g/m 2 , and the thickness was 1.0 mm was obtained in the same manner as in Example 1 except that the needle punching treatment was performed with a number of punches of 2,500 punches/cm 2 to obtain a nonwoven fabric of a fiber entanglement having a basis weight of 700 g/m 2 and a thickness of 3.0 mm.
  • a tough artificial leather having higher strength than that of Example 1 was obtained. The results are shown in Table 1.
  • a tricot fabric was prepared with a multifilament (total fineness: 48 dtex, 18 filaments) containing polyethylene terephthalate by using a single tricot machine, and dyed with a black disperse dye to prepare a dyed tricot fabric having a warp density of 32 yarns/2.54 cm and a weft density of 48 yarns/2.54 cm, and a low-melting-point nylon resin (softening temperature: 90° C.) as an adhesive was applied in an amount of 20 g/m 2 in the form of dots using a gravure roll coater, and then dried with hot air at a temperature of 100° C. to obtain a tricot with an adhesive.
  • a multifilament total fineness: 48 dtex, 18 filaments
  • a black disperse dye to prepare a dyed tricot fabric having a warp density of 32 yarns/2.54 cm and a weft density of 48 yarns/2.54 cm
  • a low-melting-point nylon resin softening
  • the tricot side was thermocompression-bonded to the dyed sheet of Example 3 with a heat roll heated to a temperature of 150° C. to obtain a composite sheet having a basis weight of 440 g/m 2 and a thickness of 1.1 mm.
  • the composite sheet was subjected to flame retardant processing and punched in the same manner as in Example 3 to obtain an artificial leather having a basis weight of 490 g/m 2 and a thickness of 1.2 mm.
  • An artificial leather having higher strength than that of Example 3 was obtained.
  • the flame retardant adhered to the entire tricot, and the tricot as a single component had high flame retardancy, so that the artificial leather had high flame retardancy.
  • Table 1 The results are shown in Table 1.
  • a circular knitted base fabric was knitted with a blister structure using an interlaced yarn containing a multifilament (84 dtex/25 f, average single fiber diameter of ultrafine fibers after sea removal: 9 ⁇ m) using a sea-island composite yarn using polyethylene terephthalate as the island component and polystyrene as the sea component and a multifilament (33 dtex/12 f) of polyethylene terephthalate.
  • An artificial leather including the fiber entanglement including the elastomer was obtained in the same manner as in Example 1 except that the fiber entanglement was a circular knitted base fabric.
  • the basis weight of the artificial leather was 240 g/m 2 , and the thickness was 0.72 mm.
  • the artificial leather which had a luxurious feeling in a lower zone as compared with Example 1 and a relatively hard texture, and was excellent in water spot and punching processability was obtained. The results are shown in Table 1.
  • An artificial leather having a basis weight of 490 g/m 2 and a thickness of 1.2 mm was obtained in the same manner as in Example 4 except that with respect to the flame retardant, 30 parts by mass of a dialkylphosphinic acid metal salt as a main component of the flame retardant and 15 parts by mass of an acrylic acid ester copolymer as a binder resin were used to obtain a flame retardant B, and a flame retardant processing agent solution containing 50% by mass of the flame retardant B was obtained.
  • the tackiness of the flame retardant was 1.50 N/cm 2 at 60° C., 0.50 N/cm 2 at 40° C., and 0.30 N/cm 2 at 20° C.
  • An artificial leather was obtained in the same manner as in Example 4 except that 5 parts by mass of a methyl acrylate resin and 10 parts by mass of an acrylonitrile resin were used as binder components for the flame retardant.
  • the tackiness was high, the opening portion was clogged during punching, and the air permeability was poor.
  • the results are shown in Table 1.
  • Example 2 Fiber Average single fiber 4.4 2.9 4.4 4.4 9.0 4.4 4.4 4.4 11.0 entangle- diameter of ultrafine ment fiber ( ⁇ m) Fiber Nonwoven Nonwoven Nonwoven Knitted Nonwoven Nonwoven Nonwoven Nonwoven Nonwoven entanglement fabric fabric fabric fabric fabric fabric fabric fabric fabric fabric fabric fabric fabric fabric fabric fabric fabric Woven/ — — Woven Woven — Woven Woven Woven Woven knitted fabric (a) fabric fabric fabric fabric fabric fabric Woven/ — — Tricot — Tricot Tricot Tricot Tricot knitted fabric (b) Elastomer Polyurethane Density of fiber 0.35 0.36 0.40 0.40 0.30 0.40 0.40 0.40 0.42 entanglement including elastomer (g/cm 3 ) Flame Flame retardant Ammonium polyphosphate Dialkylphos- Ammonium polyphosphate retardant main component phinic acid metal salt Main resin Methyl acrylate Acrylic acid Methyl Acrylon

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  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
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