WO2024070649A1 - Cuir artificiel - Google Patents

Cuir artificiel Download PDF

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Publication number
WO2024070649A1
WO2024070649A1 PCT/JP2023/033136 JP2023033136W WO2024070649A1 WO 2024070649 A1 WO2024070649 A1 WO 2024070649A1 JP 2023033136 W JP2023033136 W JP 2023033136W WO 2024070649 A1 WO2024070649 A1 WO 2024070649A1
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Prior art keywords
fiber
fibers
artificial leather
less
ultrafine
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PCT/JP2023/033136
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English (en)
Japanese (ja)
Inventor
孝之介 山本
俊 大根田
現 小出
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東レ株式会社
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Publication of WO2024070649A1 publication Critical patent/WO2024070649A1/fr

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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
    • 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

Definitions

  • the present invention relates to artificial leather that combines elegant appearance and high strength.
  • Suede-like artificial leather which contains nonwoven fabric mainly made of ultrafine fibers as a component, has a good appearance and is used in a wide range of fields such as automobile interior materials, furniture, miscellaneous goods, and clothing applications, and efforts are being made to improve its physical properties such as strength.
  • Patent Document 1 proposes a fibrous sheet-like material consisting of a fiber-entangled nonwoven fabric in which ultrafine fibers (A) and high-strength fibers (B) are mixed in a certain ratio and three-dimensionally entangled, and an elastic polymer that exists in the interstitial spaces between the fibers.
  • Patent Document 2 also proposes a nonwoven fabric that is a sheet-like material made of ultrafine fibers, in which a distribution of ultrafine fiber diameters created in increments of 0.1 ⁇ m has two or more different peaks, the center value of the peak located on the larger diameter side is greater than the center value of the peak adjacent to the smaller diameter side by a certain amount, and the total number of fibers present within a range of ⁇ 30% of the center value of each peak accounts for 90% or more of the total number of fibers.
  • the artificial leather obtained by the method disclosed in Patent Document 1 can achieve a certain degree of strength by blending ultrafine fibers with high-strength, thick fibers.
  • the artificial leather obtained by the method disclosed in Patent Document 2 uses a specially designed spinneret to simultaneously spin fine and thick fibers, achieving a uniform blend.
  • the uniformity of the appearance quality is impaired when the thick fibers are exposed on the surface of the artificial leather.
  • the present invention was made in consideration of the above circumstances, and its purpose is to provide artificial leather that combines high strength with the elegant appearance characteristic of artificial leather.
  • An artificial leather having a fiber-entangled body containing a nonwoven fabric as a component and a polymeric elastomer,
  • the nonwoven fabric is Ultrafine fibers A having a single fiber diameter of 1.0 ⁇ m or more and 8.0 ⁇ m or less; and fiber B having a single fiber diameter of 10.0 ⁇ m or more and 50.0 ⁇ m or less,
  • the fiber B is composed of at least two types of thermoplastic resins, At least one surface of the artificial leather has nap, The proportion of fiber B in the cross section of the artificial leather is 1% or more and 20% or less.
  • Artificial leather is a fiber-entangled body containing a nonwoven fabric as a component and a polymeric elastomer,
  • the nonwoven fabric is Ultrafine fibers A having a single fiber diameter of 1.0 ⁇ m or more and 8.0 ⁇ m or less; and fiber B having a single fiber diameter of 10.0 ⁇ m or more and 50.0 ⁇ m or less,
  • the fiber B is composed of at least two types of
  • a step of forming a fiber-entangled body including a nonwoven fabric composed of ultrafine fiber-developing fibers as a component (2) A step of immersing the fiber-entangled body in an alkaline aqueous solution and then heating it in a steam atmosphere at 90° C. or more and 100° C.
  • a method for producing an artificial leather comprising a step of performing a nap raising treatment on at least one surface of the polymer elastomer-applied sheet on which the ultrafine fibers A and the fibers B are developed, to form a napped sheet having nap on the surface.
  • ultrafine fibers are formed on the surface of the fiber entanglement by immersion and heat treatment while ultrafine fibers and thick fibers are simultaneously formed inside, resulting in a state in which fibers with different finenesses are mixed, and the nonwoven fabric constituting the artificial leather is made to contain ultrafine fibers A with a single fiber diameter of 1.0 ⁇ m to 8.0 ⁇ m and fibers B composed of at least two types of thermoplastic resins and with a single fiber diameter of 10.0 ⁇ m to 50.0 ⁇ m, and raised nap is provided on at least one surface of the artificial leather, and the proportion of fibers B in the cross section is 1% to 20%.
  • the artificial leather of the present invention can be used widely, from furniture, chairs, and vehicle interior materials to clothing applications, but since it has high strength as described above, it is particularly suitable for use in vehicle interior materials.
  • FIG. 1 is a cross-sectional view of an artificial leather for illustrating and explaining the nap length of the artificial leather of the present invention.
  • the artificial leather of the present invention is an artificial leather having a fiber entanglement containing a nonwoven fabric as a component, and a polymeric elastomer, the nonwoven fabric containing ultrafine fibers A with a single fiber diameter of 1.0 ⁇ m to 8.0 ⁇ m and fibers B with a single fiber diameter of 10.0 ⁇ m to 50.0 ⁇ m, the fibers B being composed of at least two types of thermoplastic resins. At least one surface of the artificial leather has nap, and the proportion of fibers B in the cross section of the artificial leather is 1% to 20%.
  • the components are described in detail below, but the present invention is not limited to the scope described below as long as it does not exceed the gist of the invention, and various modifications are possible within the scope of the invention.
  • the artificial leather of the present invention has a fiber-entangled body containing a nonwoven fabric as a component, and thus the artificial leather has a uniform nap on the surface and an elegant appearance.
  • nonwoven fabrics examples include short fiber nonwoven fabrics obtained by forming short fibers with a fiber length of approximately 100 mm or less into a laminated fiber web using a card or cross wrapper, and then needle punching or water jet punching the web; short fiber nonwoven fabrics obtained by subjecting the short fibers to a papermaking process; and long fiber nonwoven fabrics obtained by the spunbonding process or meltblowing process.
  • the nonwoven fabric contains ultrafine fibers A with a single fiber diameter of 1.0 ⁇ m or more and 8.0 ⁇ m or less, and fibers B with a single fiber diameter of 10.0 ⁇ m or more and 50.0 ⁇ m or less.
  • the lower limit of the range of the single fiber diameter of ultrafine fiber A By setting the lower limit of the range of the single fiber diameter of ultrafine fiber A to 1.0 ⁇ m or more, and preferably 1.5 ⁇ m or more, it is possible to obtain artificial leather with excellent light fastness and friction fastness.
  • the upper limit of the range of the single fiber diameter of ultrafine fiber A to 8.0 ⁇ m or less, and preferably 5.0 ⁇ m or less, it is possible to obtain artificial leather that is dense, has a soft surface feel, and has excellent surface quality.
  • the inclusion of ultrafine fibers A is determined by the following method. (1) Photographs of ten random locations on a cross section of the artificial leather in the thickness direction are taken at 2000x magnification using a scanning electron microscope (SEM: Keyence Corporation's "VHX-D500/D510 type"). (2) For each image, randomly select 10 circular or nearly circular elliptical fibers, measure the single fiber diameter, and round off to the nearest tenth. (However, when fibers with a modified cross section are used, the cross-sectional area of the single fiber is first measured, and the diameter (equivalent circle diameter) of the cross section as if it were a circle is calculated to obtain the single fiber diameter.) (3) The single fiber diameter is measured for all images. If there is at least one fiber that falls within the range of single fiber diameters of ultrafine fiber A, it is determined that the image contains ultrafine fiber A whose single fiber diameter falls within the range.
  • the ultrafine fibers A are preferably made of a thermoplastic resin.
  • the thermoplastic resin is preferably a polymer such as polyester, polyamide, polyolefin, or polyphenylene sulfide.
  • polyester or polyamide is more preferable from the viewpoint of strength, dimensional stability, and heat resistance.
  • Specific examples of polyester include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polylactic acid.
  • Specific examples of polyamide include polyamide 6, polyamide 66, and polyamide 12.
  • thermoplastic resin used for the ultrafine fibers A can contain inorganic particles such as titanium oxide, lubricants, heat stabilizers, UV absorbers, conductive agents, heat storage agents, antibacterial agents, etc., depending on the purpose, as long as the purpose of the present invention is not hindered.
  • the ultrafine fibers A are preferably formed into fiber bundles. This makes it possible to create voids inside the fiber bundles that are free of polymeric elastomers, resulting in an artificial leather with a good texture.
  • "ultrafine fibers A form fiber bundles” refers to a state in which, in the cross section of the artificial leather, three or more ultrafine fibers A are oriented in the same direction, and the spacing between adjacent ultrafine fibers is within 1/5 of the fiber diameter, forming an aggregate.
  • whether the ultrafine fibers A form fiber bundles is determined by the following method. (1) Photographs of ten random locations on a cross section of the artificial leather in the thickness direction are taken at 2000x magnification using a scanning electron microscope (SEM: Keyence Corporation's "VHX-D500/D510 type"). (2) For each image, randomly select 10 circular or nearly circular elliptical fibers, measure the single fiber diameter, and round off to the nearest tenth.
  • the cross-sectional area of the single fiber is first measured, and the diameter (equivalent circle diameter) of the cross section as if it were a circle is calculated to obtain the single fiber diameter.
  • the 10 fibers count the number of fibers (hereinafter sometimes referred to as reference fibers) that satisfy the range of the single fiber diameter of the ultrafine fiber A, that are oriented in the same direction as the reference fiber, that have an interval between the reference fiber and an adjacent fiber that is within 1/5 of the single fiber diameter, and that further satisfy the range of the single fiber diameter of the ultrafine fiber A.
  • the "interval” referred to here means the shortest distance between the outer periphery of the reference fiber and the outer periphery of the fiber adjacent to the reference fiber.
  • the CV value of the diameter of a single fiber in the fiber bundle is 0.0% or more and 10.0% or less.
  • the upper limit of the range of the CV value of the diameter of a single fiber in the fiber bundle is 10.0% or less, and preferably 8.0% or less, the appearance of the raised nap on the artificial leather surface can be made elegant and the dyeing can be made uniform and good.
  • the CV value of the single fiber diameter of the fiber bundle of the ultrafine fibers A refers to the coefficient of variation of the single fiber diameter measured and calculated by the following method.
  • the average ( ⁇ m) and standard deviation ( ⁇ m) of the single fiber diameter of the fibers that are determined to be "fibers that satisfy the range of the single fiber diameter of the ultrafine fibers A" are calculated.
  • the standard deviation ( ⁇ m) is divided by the average value ( ⁇ m), expressed as a percentage (%), and the value is rounded off to one decimal place to calculate the coefficient of variation of the single fiber diameter.
  • the CV value of the single fiber diameter of the fiber bundle of the ultrafine fiber A can be adjusted to the above range by adjusting the hole diameter of the nozzle hole of the spinneret, the spinning speed, etc.
  • the nonwoven fabric for the artificial leather of the present invention contains fiber B having a single fiber diameter of 10.0 ⁇ m or more and 50.0 ⁇ m or less.
  • the fiber B is composed of at least two types of thermoplastic resins.
  • fiber B is composed of at least two types of thermoplastic resins.
  • At least one of the thermoplastic resins is preferably a thermoplastic resin similar to that of ultrafine fiber A, for example, a polymer such as polyester, polyamide, polyolefin, and polyphenylene sulfide.
  • polyester and polyamide are more preferable from the viewpoint of strength, dimensional stability, and heat resistance.
  • Specific examples of polyester include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polylactic acid.
  • Specific examples of polyamide include polyamide 6, polyamide 66, and polyamide 12.
  • at least one of the thermoplastic resins used in fiber B can be the same thermoplastic resin as that used in ultrafine fiber A.
  • the thermoplastic resin different from the thermoplastic resin used in ultrafine fiber A is preferably a polymer such as a copolymer polyester copolymerized with polyethylene, polystyrene, sodium sulfoisophthalate, polyethylene glycol, etc., polylactic acid, and copolymerized polyvinyl alcohol.
  • polystyrene and copolymer polyester are more preferable from the viewpoint of the strength and heat resistance of the artificial leather.
  • these resins are preferably used as one type of thermoplastic resin used in fiber B, even if at least one of the thermoplastic resins used in fiber B is a thermoplastic resin different from the thermoplastic resin used in ultrafine fiber A.
  • the inclusion of fiber B is determined by the following method.
  • (1) For example, using an ultramicrotome "MT6000” manufactured by Sorvall, the artificial leather is cut in the thickness direction to produce five ultrathin slices with a thickness of 0.40 ⁇ m.
  • (2) Using a nanoscale infrared spectroscopic analyzer (AFM-IR, for example, "NanoIR1” manufactured by Anasys Instruments) equipped with an atomic force microscope (AFM), an AFM image is obtained from the ultrathin section prepared in (1) within an area of 80 ⁇ m square, and 10 fibers in the AFM image are randomly selected to measure the single fiber diameter ( ⁇ m), and the value is rounded off to one decimal place.
  • AFM-IR nanoscale infrared spectroscopic analyzer
  • the cross-sectional area of the single fiber is first measured, and the diameter (circle equivalent diameter) when the cross section is regarded as a circle is calculated to determine the diameter of the single fiber.
  • AFM-IR spectrum measurement is performed for each component at the interface between the multiple components in the fiber cross section. If the interface between the multiple components cannot be confirmed, the fiber is determined to be not fiber B.
  • the components of the thermoplastic resin constituting the fiber are identified from the AFM-IR spectrum, and if at least two types of thermoplastic resin are detected, the fiber is determined to be fiber B.
  • the fiber is composed of two types of thermoplastic resins, polyethylene terephthalate and copolymerized polyethylene terephthalate.
  • (5) (2) to (4) are carried out for all ultrathin sections, and if any ultrathin section contains at least one fiber that satisfies the range of single fiber diameter of fiber B and is made of at least two types of thermoplastic resin, it is deemed to contain fiber B whose single fiber diameter falls within the range and is made of at least two types of thermoplastic resin.
  • Thermoplastic resin used in fiber B can also contain inorganic particles such as titanium oxide, lubricants, heat stabilizers, UV absorbers, conductive agents, heat storage agents, antibacterial agents, etc., depending on various purposes, as long as the purpose of the present invention is not hindered.
  • the nonwoven fabric contains ultrafine fiber A and fiber B, and is not, for example, a nonwoven fabric made only of ultrafine fiber A, into which a woven or knitted fabric made of fiber B is inserted, layered, or backed.
  • the polymeric elastomer constituting the artificial leather of the present invention is a binder that holds the fibers constituting the artificial leather.
  • examples of the polymeric elastomer that can be used include polyurethane, silicone, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), acrylic resins such as ethylene-vinyl acetate resin, and polyester-based, polyamide-based, and polyolefin-based elastomer resins.
  • SBR styrene-butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • acrylic resins such as ethylene-vinyl acetate resin
  • polyester-based, polyamide-based, and polyolefin-based elastomer resins it is preferable to use polyurethane as the main component.
  • main component means that the mass of polyurethane is more than 50% by mass with respect to the mass of the entire polymeric elastomer.
  • Polyurethanes include those obtained by reacting a polymer diol, a diisocyanate, and a chain extender in a predetermined molar ratio, or modified products thereof.
  • polymer diols include polyester diols, polyether diols, polycarbonate diols, and mixtures thereof, each having an average molecular weight of 500 to 3000.
  • diisocyanates include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate and dicyclohexylmethane diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, or mixtures thereof.
  • chain extenders include low molecular weight compounds having two or more active hydrogen atoms, such as ethylene glycol, butanediol, ethylenediamine, and 4,4'-diaminodiphenylmethane, or mixtures thereof.
  • polyurethane When polyurethane is used in the present invention, either organic solvent-based polyurethane, which is used in a dissolved state in an organic solvent, or water-dispersed polyurethane, which is used in a dispersed state in water, can be used.
  • the polymer elastomer may contain various additives according to various purposes, within the scope of the present invention, such as pigments such as carbon black, flame retardants such as "phosphorus-based, halogen-based and inorganic" antioxidants such as "phenol-based, sulfur-based and phosphorus-based” antioxidants, ultraviolet absorbers such as "benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based and oxalic acid anilide-based” light stabilizers such as "hindered amine-based and benzoate-based” hydrolysis-resistant stabilizers such as polycarbodiimide, plasticizers, antistatic agents, surfactants, coagulation regulators, dispersants, softeners, antibacterial agents, deodorants and dyes.
  • additives such as carbon black
  • flame retardants such as "phosphorus-based, halogen-based and inorganic” antioxidants such as "phenol-based, sulfur-based and phosphorus-based” antioxidants
  • the content of the polymer elastomer in the artificial leather can be adjusted as appropriate taking into consideration the type of polymer elastomer used, the manufacturing method of the polymer elastomer, and the texture and strength, but in the present invention, the content of the polymer elastomer is preferably 15% by mass or more and 50% by mass or less relative to the mass of the artificial leather.
  • the lower limit of the polymer elastomer content range to 15% by mass or more, and more preferably 20% by mass or more, the bonds between the fibers by the polymer elastomer can be strengthened, and the abrasion resistance of the artificial leather can be improved.
  • the upper limit of the polymer elastomer content range to 50% by mass or less, and more preferably 45% by mass or less, the artificial leather can be made more flexible.
  • the artificial leather of the present invention is an artificial leather having the fiber entanglement and the polymeric elastomer as described above, at least one surface of which has nap, and the proportion of fiber B in the cross section of the artificial leather is 1% or more and 20% or less.
  • the proportion is preferably 3% or more and 15% or less, more preferably 5% or more and 10% or less.
  • the tensile strength of the artificial leather is improved by setting the lower limit of the range of the proportion of fiber B to 1% or more, preferably 3% or more, and more preferably 5% or more.
  • the upper limit of the range of the proportion of fiber B to 20% or less, preferably 15% or less, and more preferably 10% or less makes the artificial leather softer to the touch.
  • cross section of the artificial leather refers to a cross section in the thickness direction.
  • the proportion of fiber B in the artificial leather refers to a value measured and calculated by the following procedure. (1) For example, using an ultramicrotome "MT6000" manufactured by Sorvall, the artificial leather is cut in the thickness direction to produce five ultrathin slices with a thickness of 0.40 ⁇ m.
  • AFM-IR spectrum measurement is performed for each component at the interface between the multiple components in the fiber cross section. If the interface between the multiple components cannot be confirmed, the fiber is determined to be not fiber B.
  • the components of the thermoplastic resin constituting the fiber are identified from the AFM-IR spectrum. If at least two types of thermoplastic resin are detected, the fiber is determined to be fiber B.
  • the cross-sectional area is measured using, for example, a "VW-9000 Album" manufactured by Keyence Corporation, and the total cross-sectional area ( ⁇ m 2 ) is divided by the cross-sectional area ( ⁇ m 2 ) of the entire artificial leather in the AFM image to obtain a percentage, thereby calculating the proportion of fiber B in the cross section of the artificial leather.
  • (6) Repeat steps (2) to (5) for all ultrathin sections, calculate the arithmetic mean of the occupancy ratios (%) for the five sections, and round off to the nearest whole number.
  • the proportion of fiber B in the cross section of the artificial leather can be adjusted to the above range by adjusting the impregnation time when the ultrafine fiber-expressing fiber entanglement body described below is immersed in a solvent, the temperature of the solvent, the concentration of the solute dissolved in the solvent, etc.
  • the surface having the nap has an area coverage rate (hereinafter, sometimes simply referred to as area coverage rate) of fibers having a fiber diameter of 8.0 ⁇ m or less of 90% or more and 100% or less.
  • area coverage rate an area coverage rate of fibers having a fiber diameter of 8.0 ⁇ m or less of 90% or more and 100% or less.
  • the above-mentioned area coverage rate refers to a value measured and calculated by the following procedure: When both surfaces have nap, both surfaces are measured, and the arithmetic average value is regarded as the area coverage rate for the artificial leather.
  • Photographs of the napped surface of the artificial leather are taken at 10 random locations using a scanning electron microscope (SEM: for example, Keyence Corporation's "VHX-D500/D510 type") at 800x magnification.
  • SEM scanning electron microscope
  • the surface area of all fibers having a fiber diameter of more than 8.0 ⁇ m is measured, and the area coverage rate (%) of fibers having a fiber diameter of 8.0 ⁇ m or less is calculated from the area coverage rate (%) of the fibers in the entire image using the following formula.
  • Area coverage rate (%) of fibers having a fiber diameter of 8.0 ⁇ m or less 100 - (area coverage rate (%) of all fibers having a diameter of more than 8.0 ⁇ m) (3) Calculate the arithmetic average of the 10 sheets and round off to the first decimal place.
  • the area coverage rate can be adjusted to the above range by adjusting the impregnation time when the fiber entanglement is immersed in the solvent, the temperature of the solvent, the concentration of the solute dissolved in the solvent, etc.
  • the artificial leather of the present invention has nap on at least one surface.
  • the nap shape preferably has a nap length and directional flexibility to the extent that a mark is left when the nap direction changes when the leather is traced with a finger, that is, a so-called finger mark is left.
  • the nap length on the surface is preferably 100 ⁇ m or more and 400 ⁇ m or less.
  • the lower limit of the nap length range is preferably 100 ⁇ m or more, more preferably 150 ⁇ m or more, and even more preferably 200 ⁇ m or more, so that the artificial leather has an elegant appearance and quality.
  • the upper limit of the nap length range is preferably 400 ⁇ m or less, more preferably 350 ⁇ m or less, so that the artificial leather has high durability against friction.
  • the nap length refers to a value measured and calculated by the following method.
  • the nap is made to stand up using a lint brush or the like.
  • SEM scanning electron microscope
  • a layer consisting only of fibers oriented in the thickness direction is defined as a napped portion 2
  • the length from a line 3 connecting the intersection of the fibers oriented in the thickness direction and the fibers oriented in the surface direction of the artificial leather to the tip of the nap is defined as a nap length 4
  • 10 points are measured.
  • the weight per unit area of the artificial leather of the present invention is preferably 100 g/ m2 or more and 500 g/ m2 or less.
  • the lower limit of the weight per unit area is preferably 100 g/ m2 or more, more preferably 150 g/ m2 or more, so that sufficient shape stability and dimensional stability can be obtained.
  • the upper limit of the weight per unit area is preferably 500 g/ m2 or less, more preferably 300 g/ m2 or less, so that sufficient flexibility and texture can be obtained.
  • the basis weight refers to a value obtained by randomly taking five 250 mm x 250 mm test pieces from the artificial leather, measuring them in accordance with "6.2 Mass per unit area (ISO method)" of JIS L1913:2010 "General nonwoven fabric testing methods", and rounding off the calculated value to the first decimal place.
  • ISO method 6.2 Mass per unit area
  • JIS L1913:2010 General nonwoven fabric testing methods
  • the artificial leather of the present invention preferably has a thickness of 0.1 mm or more and 10.0 mm or less.
  • the lower limit of the thickness range preferably 0.1 mm or more, and more preferably 0.3 mm or more, sufficient shape stability and dimensional stability can be obtained.
  • the upper limit of the thickness range preferably 10.0 mm or less, and more preferably 5.0 mm or less, sufficient flexibility and texture can be obtained.
  • the thickness refers to the value obtained by randomly taking five 50 mm x 50 mm test pieces from the artificial leather, measuring the thickness using a thickness measuring device (such as the dial thickness gauge “H20” manufactured by Ozaki Manufacturing Co., Ltd.) in accordance with "6.1 Thickness (ISO method)" "6.1.1 A method” of JIS L1913:2010 “General nonwoven fabric test methods”, and rounding the calculated value to the nearest tenth.
  • a thickness measuring device such as the dial thickness gauge "H20” manufactured by Ozaki Manufacturing Co., Ltd.
  • the artificial leather of the present invention can be laminated with woven or knitted fabrics for the purpose of adjusting the thickness, etc.
  • woven fabrics plain weave, twill weave, and satin weave are examples, with plain weave being preferred due to its good dimensional stability.
  • plain weave being preferred due to its good dimensional stability.
  • knitted fabrics circular knit, tricot knit, and russell knit are examples.
  • the average single fiber diameter of the fibers constituting such woven or knitted fabrics is preferably about 0.3 ⁇ m to 10 ⁇ m.
  • the artificial leather of the present invention has high strength and an elegant appearance, so it can be used for a wide range of applications, from furniture, chairs, and vehicle interior materials to clothing, but it is particularly suitable for use in vehicle interior materials because it has high tensile strength.
  • the method for producing the artificial leather of the present invention preferably includes the following steps (1) to (4) or (1) to (5).
  • a step of performing post-processing on the napped sheet is carried out, the napped sheet becomes artificial leather.
  • an entangled body is formed from ultrafine fiber-developing fibers containing two or more types of thermoplastic resins having different solubilities in a solvent.
  • the ultrafine fiber-developing fibers for example, it is preferable to use islands-in-sea composite fibers in which thermoplastic resins having different solubilities in a solvent are used as a sea portion (easily soluble polymer) and an island portion (hardly soluble polymer), and the sea portion can be dissolved and removed using a solvent or the like.
  • the sea portion is not completely removed but is removed to a certain extent to be left, thereby making it possible to obtain fibers having a larger diameter than the island portion when the sea portion is completely removed, and to form voids between the remaining island portions. Therefore, by subjecting the entangled body made of such ultrafine fiber-developing fibers to an appropriate dissolution treatment, ultrafine fibers A and fibers B having different finenesses can be simultaneously formed inside the fiber-entangled body, and appropriate voids can be provided between the ultrafine fibers A on the surface of the fiber-entangled body, which is preferable from the viewpoint of the texture and surface quality of the artificial leather.
  • a method for spinning ultrafine fiber-producing fibers having an island-in-sea composite structure a method using a polymer mutual alignment body in which the sea and island parts are mutually aligned and spun using an island-in-sea composite spinneret is preferred from the viewpoint of obtaining ultrafine fibers with uniform single fiber fineness and a dense appearance.
  • the polymers described above in relation to ultrafine fiber A can be used.
  • polyester, polyamide, polyolefin, polyphenylene sulfide, etc. can be used.
  • polyester and polyamide are preferably used from the viewpoints of strength, dimensional stability, and heat resistance.
  • the above-mentioned easily soluble polymer can be a polymer described as "a thermoplastic resin different from the thermoplastic resin used in ultrafine fiber A" in the description of fiber B.
  • a thermoplastic resin different from the thermoplastic resin used in ultrafine fiber A in the description of fiber B.
  • polyethylene, polystyrene, copolymer polyesters copolymerized with sodium sulfoisophthalic acid or polyethylene glycol, polylactic acid, copolymer polyvinyl alcohol, etc. can be used.
  • polystyrene and copolymer polyesters are preferably used from the viewpoint of spinnability and easy elution.
  • Polystyrene is easily soluble in, for example, trichloroethylene, tetrahydrofuran, N,N-dimethylformamide, etc., and copolymer polyesters are easily soluble in hot water or alkaline aqueous solutions.
  • hot water refers to water heated to 90°C to 100°C.
  • the hole diameter of the nozzle outlet hole when spinning ultrafine fiber-producing fibers having an islands-in-sea composite structure is preferably 0.5 mm or more and 1.0 mm or less. More preferably, it is 0.6 mm or more and 0.8 mm or less.
  • the spinning speed is preferably 500 m/min or more and 2000 m/min or less. More preferably, it is 1000 m/min or more and 1500 m/min or less.
  • the formed ultrafine fiber-developing fibers prefferably subjected to a crimping process.
  • the ultrafine fiber-developing fibers are efficiently entangled with each other in the process of forming the fiber entanglement, and an artificial leather with a fine appearance and quality can be obtained.
  • the crimping process can be performed by a known method.
  • an ultrafine fiber-developing fiber entanglement is formed, containing a nonwoven fabric made of the ultrafine fiber-developing fibers as a component.
  • the nonwoven fabric may be in the form of a single fiber nonwoven fabric or a long fiber nonwoven fabric.
  • a short fiber nonwoven fabric obtained by cutting the ultrafine fiber-developing fibers to a fiber length of approximately 100 mm or less, forming the short fibers into a laminated fiber web using a card or cross wrapper, and then subjecting the short fibers to needle punching or water jet punching, or a short fiber nonwoven fabric obtained by subjecting the short fibers to a papermaking method.
  • the ultrafine fiber-expressing fiber entanglement may be made of such a nonwoven fabric alone, or may be made by adding another fiber base material to the laminated fiber web and entangling it by needle punching or water jet punching, but it is more preferable to make the ultrafine fiber-entanglement only from a nonwoven fabric made of ultrafine fiber-expressing fibers without including woven fabrics, knitted fabrics, etc.
  • ultrafine fibers A having a single fiber diameter of 1.0 ⁇ m or more and 8.0 ⁇ m or less and fibers B composed of at least two types of thermoplastic resins and having a single fiber diameter of 10.0 ⁇ m or more and 50.0 ⁇ m or less are expressed from the ultrafine fiber-expressing fiber-entangled body to form a fiber-entangled body containing, as a component, a nonwoven fabric containing the ultrafine fibers A and fibers B.
  • the ultrafine fiber-entangled fiber body can be immersed and treated in an organic solvent or an alkaline aqueous solution under specific conditions.
  • the easily soluble polymer in the ultrafine fiber-producing fiber is a polymer that is easily dissolved in an organic solvent such as polyethylene or polystyrene
  • the ultrafine fiber-producing fiber entanglement is immersed in a solvent such as trichloroethylene, tetrahydrofuran, or N,N-dimethylformamide at a solvent temperature below the boiling point of each solvent for 3 to 5 minutes.
  • a solvent such as trichloroethylene, tetrahydrofuran, or N,N-dimethylformamide
  • an alkaline aqueous solution in which sodium hydroxide or the like is dissolved is used as the solvent.
  • the ultrafine fiber-producing fiber entanglement is immersed in an alkaline aqueous solution with a sodium hydroxide concentration of 1.0 g/L for 1 to 2 minutes, and then is pulled out and heated in a steam atmosphere.
  • the temperature of the steam at this time is preferably 90°C to 100°C, and the time for leaving in the steam atmosphere is preferably 5 to 20 minutes, more preferably 10 to 15 minutes.
  • a hot water-soluble inhibitor that can inhibit adhesion between the ultrafine fibers A and B and the polymeric elastomer can be added.
  • the adhesion between the fibers and the polymeric elastomer can be reduced and a soft texture can be achieved, which is preferable.
  • polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) is preferably used because it has a high reinforcing effect on the fiber entanglement and is not easily dissolved in water.
  • PVA polyvinyl alcohol
  • high saponification degree refers to a saponification degree of 95% or more and 100% or less.
  • PVA polystyrene-maleic anhydride copolymer
  • PVA with a high degree of saponification it is preferable to use PVA with a degree of saponification of 98% or more and 100% or less.
  • the degree of polymerization of PVA is preferably 500 or more and 3500 or less, and more preferably 500 or more and 2000 or less.
  • the degree of polymerization of PVA 500 or more it is possible to suppress the dissolution of PVA when applying the water-dispersed polyurethane liquid.
  • the degree of polymerization of PVA 3500 or less the viscosity of the PVA solution does not become too high, and PVA can be applied stably to the fibrous substrate.
  • the amount of PVA added to the ultrafine fiber-expressing fiber entanglement, or to the fiber entanglement after ultrafine fiber A and fiber B are expressed is 0.1% by mass or more and 50% by mass or less, and preferably 1% by mass or more and 45% by mass or less, based on the fiber mass of the ultrafine fiber-entanglement.
  • Step of obtaining sheet provided with polymeric elastomer> a polymer elastomer is applied to the fiber-entangled body to obtain a sheet with the polymer elastomer applied thereto either before or after the ultrafine fibers A and fibers B are developed.
  • Methods for impregnating the fiber-entangled body with the polymer elastomer and solidifying it include a wet coagulation method in which the fiber-entangled body is impregnated with a solution of the polymer elastomer and then immersed in a coagulation bath to fix it, and a dry coagulation method in which the fiber-entangled body is impregnated with a solution of the polymer elastomer and then dried and fixed by applying hot air to the fiber-entangled body, and these methods can be appropriately selected depending on the type of polymer elastomer to be applied.
  • Preferred solvents for applying polyurethane as a polymeric elastomer include N,N'-dimethylformamide and dimethylsulfoxide.
  • a water-dispersed polyurethane liquid in which polyurethane is dispersed in water as an emulsion may also be used.
  • Step of forming napped sheet> at least one surface of the polymeric elastomer-imparted sheet is subjected to a nap raising treatment to form naps on the surface, thereby forming a napped sheet.
  • a nap raising treatment to form naps on the surface, thereby forming a napped sheet.
  • Methods for forming nap include grinding at least one surface of the polymer elastomer-imparted sheet using sandpaper or a roll sander. Naturally, nap can be formed on only one surface of the polymer elastomer-imparted sheet, or on both surfaces.
  • the leather is cut in half, it is preferable to form nap on the surface opposite to the surface that was cut in half. This makes it possible to obtain artificial leather with a uniform and elegant appearance.
  • a lubricant such as a silicone emulsion can be applied to the surface of the polymer elastomer-applied sheet before the nap-forming process. Also, by applying an antistatic agent to the surface of the polymer elastomer-applied sheet before forming the nap, grinding dust generated from the polymer elastomer-applied sheet during grinding is less likely to accumulate on the surface of sandpaper or other materials used for grinding.
  • the polymeric elastomer may be applied to the entangled fiber body before the ultrafine fibers A and fibers B are developed, but the nap raising process is performed on the sheet to which the polymeric elastomer has been applied and in which the ultrafine fibers A and fibers B are developed.
  • the napped sheet can be subjected to a dyeing process.
  • the dyeing process include flow dyeing using a jigger dyeing machine or a flow dyeing machine, immersion dyeing such as thermosol dyeing using a continuous dyeing machine, or printing of the napped surface by roller printing, screen printing, inkjet printing, sublimation printing, vacuum sublimation printing, etc.
  • a flow dyeing machine which provides a soft texture and is superior in terms of quality and grade.
  • various resin finishing processes can be performed after dyeing, if necessary.
  • the surface of the napped sheet or the napped sheet that has been dyed can be given a design depending on the desired form of artificial leather.
  • post-processing such as perforation, embossing, laser processing, pinsonic processing, and printing can be performed.
  • the artificial leather of the present invention will be described in more detail using examples. However, the present invention is not limited to these examples. However, in the measurement of each physical property, unless otherwise specified, the measurement was performed according to the method described above.
  • Pile length ( ⁇ m) In measuring the nap length, a scanning electron microscope (SEM) "VHX-D500/D510 type" manufactured by Keyence Corporation was used, and the measurement and calculation were performed according to the above-mentioned method.
  • Appearance quality of artificial leather A total of 20 people, 10 healthy adult males and 10 healthy adult females, were used as evaluators to make the following visual and tactile judgments, and the average of the 20 evaluations was rounded off to the first decimal place to determine the appearance quality of the artificial leather.
  • a good level in the present invention was set to "3 or higher.”
  • ⁇ 5 An appearance quality in which the density of the standing pile is very uniform and the ground is not visible (ground area is less than 2%).
  • ⁇ 4 An appearance quality in which the density of the standing pile is uniform and the ground is almost invisible (ground area is 2% to 10%).
  • ⁇ 3 An appearance quality in which the density of the standing pile varies slightly and the ground is visible in some areas (ground area is 10% to 30%).
  • ⁇ 2 An appearance quality in which the standing pile is not dense and the ground is visible in many areas (ground area is 30% to 50%).
  • ⁇ 1 An appearance quality in which there is no standing pile and the ground is visible (ground area is more than 50%).
  • Example 1 ⁇ (1) Step of forming ultrafine fiber-entangled body> First, an islands-in-sea type composite fiber consisting of island parts and sea parts was melt spun under the following conditions.
  • Island component Polyethylene terephthalate A (PET) with an intrinsic viscosity (IV value) of 0.73
  • Sea component Polyethylene terephthalate copolymerized with 8 mol% sodium 5-sulfoisophthalate (copolymerized PET)
  • Spinneret A spinneret for islands-in-the-sea composite fibers with 16 islands/hole and a discharge hole diameter of 0.7 mm.
  • the islands-in-the-sea composite fiber obtained as described above was subjected to a crimping process using a push-in crimping machine, and then cut to a length of 51 mm to form islands-in-the-sea composite fiber raw cotton with a single fiber fineness of 4.2 dtex.
  • a laminated fiber web (nonwoven fabric) was formed using a card and a cross wrapper, and needle punching was performed to obtain a fiber entanglement that develops ultrafine fibers.
  • the shrunk fiber entanglement was impregnated with an aqueous solution of polyvinyl alcohol (PVA) with a degree of saponification of 98% and a degree of polymerization of 550, which had been adjusted to a concentration of 12% by mass.
  • PVA polyvinyl alcohol
  • the fiber entanglement was then squeezed with a roll, heated and dried with hot air at a temperature of 140°C for 10 minutes, and then heated at a temperature of 160°C for 5 minutes to obtain a sheet with PVA in which the mass of PVA relative to the mass of the nonwoven fabric was 25% by mass.
  • the sheet with PVA obtained as described above was immersed in a 1.0 g/L aqueous sodium hydroxide solution for 1 minute, then removed and heated in a steam atmosphere at 95°C for 10 minutes. It was then washed with water and dried at 120°C for 5 minutes to partially remove the sea component of the islands-in-the-sea composite fiber, forming a fiber entanglement containing a nonwoven fabric containing ultrafine fiber A and fiber B as its constituent elements.
  • the fiber entanglement obtained was immersed in hot water at 95° C. for 10 minutes to remove the PVA, and then dried by blowing hot air at a temperature of 120° C. for 10 minutes to obtain a polymer elastomer-applied sheet in which the mass ratio of polyurethane in the artificial leather was 30 mass%.
  • Example 2 In (1) the step of forming an ultrafine fiber-entangled body, an artificial leather was obtained in the same manner as in Example 1, except that a spinneret for islands-in-sea type composite fiber having an island number of 16 islands/hole and an outlet hole diameter of 0.7 mm was used instead of a spinneret for islands-in-sea type composite fiber having an island number of 32 islands/hole and an outlet hole diameter of 0.7 mm. The results are shown in Table 1.
  • Example 3 In (1) the step of forming an ultrafine fiber-entangled body, an artificial leather was obtained in the same manner as in Example 1, except that a spinneret for islands-in-sea type composite fiber having an island number of 16 islands/hole and an outlet hole diameter of 0.7 mm was used instead of the spinneret for islands-in-sea type composite fiber having an island number of 8 islands/hole and an outlet hole diameter of 0.7 mm. The results are shown in Table 1.
  • Example 4 An artificial leather was obtained in the same manner as in Example 1, except that in ⁇ (1) Step of forming ultrafine fiber-entangled body>, the discharge amount was changed from 1.2 g/(min. hole) and the mass ratio of island component/sea component was changed from 80/20 to 1.1 g/(min. hole) and 90/10. The results are shown in Table 1.
  • Example 5 An artificial leather was obtained in the same manner as in Example 1, except that in ⁇ (1) Step of forming ultrafine fiber-entangled body>, the discharge amount was 1.2 g/(min. hole) and the mass ratio of island component/sea component was 80/20, but was changed to 2.4 g/(min. hole) and 40/60. The results are shown in Table 1.
  • Example 6 An artificial leather was obtained in the same manner as in Example 1, except that in the step (2) of forming a fiber-entangled body including, as a component, a nonwoven fabric containing ultrafine fibers A and fibers B, the time for which the PVA-attached sheet was placed in a steam atmosphere was changed from 10 minutes to 20 minutes. The results are shown in Table 1.
  • Example 7 An artificial leather was obtained in the same manner as in Example 1, except that in the step (2) of forming a fiber-entangled body including, as a component, a nonwoven fabric containing ultrafine fibers A and fibers B, the time for which the PVA-attached sheet was placed in a steam atmosphere was changed from 10 minutes to 5 minutes. The results are shown in Table 2.
  • Example 8 In the step (1) of forming an ultrafine fiber-entangled body, the sea component was polyethylene terephthalate copolymerized with 8 mol% sodium 5-sulfoisophthalate, but the sea component was changed to polystyrene (PST).
  • the step (2) of forming a fiber-entangled body including a nonwoven fabric containing ultrafine fibers A and fibers B as components the fiber was immersed in a sodium hydroxide aqueous solution having a concentration of 1.0 g/L for 1 minute, then pulled out and placed in a steam atmosphere at 95°C for 10 minutes, and then washed with water and dried at 120°C for 5 minutes. However, the procedure was changed to immersing the fiber in trichloroethylene at room temperature for 5 minutes and then drying at 100°C for 3 minutes. Except for these, an artificial leather was obtained in the same manner as in Example 1. The results are shown in Table 2.
  • Example 9 In the step (1) of forming an ultrafine fiber-entangled body, the island component was polyethylene terephthalate A and the sea component was polyethylene terephthalate copolymerized with 8 mol % of sodium 5-sulfoisophthalate, but the island component was changed to polyamide 6 (PA6) and the sea component to polystyrene (PST).
  • PA6 polyamide 6
  • PST polystyrene
  • the step (2) of forming a fiber-entangled body including a nonwoven fabric containing ultrafine fibers A and fibers B as components the fabric was immersed in a 1.0 g/L sodium hydroxide aqueous solution for 1 minute, then removed and placed in a steam atmosphere at 95°C for 10 minutes, and then washed with water and dried at 120°C for 5 minutes. Except for this, an artificial leather was obtained in the same manner as in Example 1. The results are shown in Table 2.
  • Example 10 In the step (4) of forming a napped sheet, the nap-raising treatment was applied to the surface (non-cut surface) opposite to the surface (cut surface) obtained by cutting in half, but instead, the nap-raising treatment was applied to the surface (cut surface) obtained by cutting in half.
  • An artificial leather was obtained in the same manner as in Example 1. The results are shown in Table 2.
  • Example 11 In ⁇ (1) Step of forming ultrafine fiber-entangled body> of Example 1, a spinneret for islands-in-sea type composite fiber having 16 islands/hole and a discharge hole diameter of 0.7 mm was used and the spinning speed was 1,100 m/min, but in this example, a spinneret for islands-in-sea type composite fiber having 16 islands/hole and a discharge hole diameter of 0.8 mm was used and the spinning speed was 900 m/min, respectively, and an artificial leather was obtained in the same manner as in Example 1. The results are shown in Table 2.
  • Example 12 An artificial leather was obtained in the same manner as in Example 1, except that the order of ⁇ (2) the step of forming a fiber-entangled body containing, as a component, a nonwoven fabric containing ultrafine fibers A and fibers B> and ⁇ (3) the step of obtaining a sheet with polymeric elastomer> in Example 1 was reversed, and the step of shrinking with hot water and the step of applying PVA were omitted in ⁇ (2) the step of forming a fiber-entangled body containing, as a component, a nonwoven fabric containing ultrafine fibers A and fibers B>. The results are shown in Table 2.
  • Example 1 An artificial leather was obtained in the same manner as in Example 1, except that in ⁇ (1) Step of forming an ultrafine fiber-entangled body> of Example 1, a spinneret for islands-in-sea type composite fiber with 16 islands/hole and an outlet hole diameter of 0.7 mm was used instead of the spinneret for islands-in-sea type composite fiber with 64 islands/hole and an outlet hole diameter of 0.7 mm.
  • the results are shown in Table 3.
  • the fiber diameter of the ultrafine fibers A was reduced, the strength of the fiber-entangled body was reduced, and the obtained artificial leather was inferior in tensile strength.
  • Example 3 An artificial leather was obtained in the same manner as in Example 1, except that in ⁇ (1) Step of forming an ultrafine fiber-entangled body>, the discharge amount was 1.2 g/(min.hole) and the mass ratio of island component/sea component was 80/20, but was changed to 1.0 g/(min.hole) and the mass ratio of island component/sea component was 95/5. The results are shown in Table 3. When the fiber diameter of fiber B was reduced, the strength of the fiber-entangled body was reduced, and the obtained artificial leather had poor tensile strength.
  • Example 4 An artificial leather was obtained in the same manner as in Example 1, except that in ⁇ (1) Step of forming ultrafine fiber-entangled body>, the discharge amount was 1.2 g/(min.hole) and the mass ratio of island component/sea component was 80/20, but was changed to 3.0 g/(min.hole) and 30/70. The results are shown in Table 3. When the fiber diameter of fiber B was increased, the area of fiber B exposed to the surface was increased, and the obtained artificial leather had poor appearance quality.
  • Example 5 An artificial leather was obtained in the same manner as in Example 1, except that in ⁇ (2) Step of forming a fiber-entangled body including, as a component, a nonwoven fabric containing ultrafine fiber A and fiber B>, the time for which the PVA-attached sheet was placed in a steam atmosphere was changed from 10 minutes to 25 minutes. The results are shown in Table 3. When the occupancy rate of fiber B in the cross section was reduced, the strength of the fiber-entangled body was reduced, and the obtained artificial leather had inferior tensile strength.
  • Example 6 An artificial leather was obtained in the same manner as in Example 1, except that in the step (2) of forming a fiber-entangled body including a nonwoven fabric containing ultrafine fiber A and fiber B as a component, the time for which the PVA-attached sheet was placed in a steam atmosphere was changed from 10 minutes to 2 minutes. The results are shown in Table 3. When the occupancy rate of fiber B in the cross section was increased, the proportion of fiber B in the entirety increased, and as a result, the proportion of fiber B exposed to the surface increased, and the obtained artificial leather had inferior appearance quality.
  • Example 7 An artificial leather was obtained in the same manner as in Example 1, except that in ⁇ (2) step of forming a fiber-entangled body including a nonwoven fabric containing ultrafine fiber A and fiber B as a component> of Example 1, the sheet with PVA was immersed in an aqueous sodium hydroxide solution having a concentration of 4.0 g/L instead of immersed in an aqueous sodium hydroxide solution having a concentration of 1.0 g/L. The results are shown in Table 4. In the absence of fiber B, the strength of the fiber-entangled body was low, and the obtained artificial leather had poor tensile strength.
  • Example 8 An artificial leather was obtained in the same manner as in Example 1, except that the step (2) of forming a fiber-entangled body including a nonwoven fabric containing ultrafine fibers A and fibers B as a component was not performed. The results are shown in Table 4. In the absence of ultrafine fibers A, the fiber diameter of the fibers exposed to the surface was large, and the obtained artificial leather had poor appearance quality.
  • Comparative Example 9 The ⁇ (1) step of forming an ultrafine fiber-entangled fiber body> in Example 1 was changed to the following ⁇ (1') step of forming an ultrafine fiber-entangled fiber body>.
  • the time for which the sheet with PVA was placed in a steam atmosphere was changed from 10 minutes to 30 minutes. Except for these changes, artificial leather was obtained in the same manner as in Example 1.
  • polyethylene terephthalate fibers with single fiber diameters of 18.7 ⁇ m to 20.7 ⁇ m were confirmed (however, this was not fiber B because it was composed of one type of thermoplastic resin).
  • Table 4 Note that in this comparative example only, "fiber B" in Table 4 was changed to "fiber with a single fiber diameter of 10.0 ⁇ m to 50.0 ⁇ m" and the corresponding part was marked with an asterisk.
  • a first islands-in-sea type composite fiber consisting of island parts and a sea part was melt spun under the following conditions.
  • Island component Polyethylene terephthalate A (PET) with an intrinsic viscosity (IV value) of 0.73
  • Sea component Polyethylene terephthalate copolymerized with 8 mol% sodium 5-sulfoisophthalate (copolymerized PET)
  • Spinneret A spinneret for islands-in-the-sea composite fibers with 16 islands/hole and a discharge hole diameter of 0.7 mm.
  • a second islands-in-sea type composite fiber consisting of island parts and sea parts was melt spun under the following conditions.
  • Island component Polyethylene terephthalate A (PET) with an intrinsic viscosity (IV value) of 0.73
  • Sea component Polyethylene terephthalate copolymerized with 8 mol% sodium 5-sulfoisophthalate (copolymerized PET)
  • Spinneret A spinneret for islands-in-the-sea composite fibers with 8 islands per hole and a discharge hole diameter of 0.7 mm.
  • Spinning temperature 285°C Island/sea mass ratio: 80/20 Discharge rate: 1.5g/min (whole) Spinning speed: 1100 m/min.
  • the islands-in-sea type composite fiber was then stretched 2.1 times in a steam box at 150° C.
  • the second islands-in-sea type composite fiber thus obtained was then subjected to a crimping process using a push-in crimper and then cut to a length of 51 mm to obtain an islands-in-sea type composite fiber having a single fiber fineness of 14.6 dtex.
  • the cut first sea-island type composite fiber and the cut second sea-island type composite fiber obtained above were mixed in a blender at a mass ratio of 90/10 to form a sea-island type composite fiber raw cotton.
  • a laminated fiber web (nonwoven fabric) was formed using a card and a cross wrapper, and needle punching was performed to obtain a fiber entanglement that develops ultrafine fibers.
  • the artificial leathers of Examples 1 to 11 are able to form fibers of different fineness simultaneously during the formation of ultrafine fibers, making it possible to create a uniform cotton blend. Furthermore, when carrying out the above-mentioned ultrafine fiber formation process, the fiber entanglement is immersed in the treatment liquid and then heated, which creates a difference in treatment speed between the surface and the interior, forming uniform ultrafine fibers on the surface while allowing ultrafine and thick fibers to be mixed inside, resulting in a product that has both an elegant appearance and high strength.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

En vue de fournir un cuir artificiel qui présente une résistance élevée tout en ayant la caractéristique de présentation élégante de cuir artificiel, l'invention concerne un cuir artificiel ayant un corps élastique polymère et une masse de fibres enchevêtrées qui contient un non-tissé en tant qu'élément constitutif, le non-tissé contenant une fibre ultrafine A ayant un diamètre de monofilament situé dans la plage allant de 1,0 à 8,0 µm et une fibre B ayant un diamètre de monofilament situé dans la plage allant de 10,0 à 50,0 µm. La fibre B est composée d'au moins deux résines thermoplastiques ; au moins une surface du cuir artificiel est une surface porteuse de grain ; et la proportion de fibre B dans une section transversale du cuir artificiel est située dans la plage allant de 1 à 20 %.
PCT/JP2023/033136 2022-09-28 2023-09-12 Cuir artificiel WO2024070649A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11269775A (ja) * 1998-03-18 1999-10-05 Kuraray Co Ltd スエード調人工皮革およびその製造法
JP2007177382A (ja) * 2005-11-30 2007-07-12 Toray Ind Inc 皮革様シート状物、その製造方法、並びにそれを用いてなる内装材、衣料用資材及び工業用資材
JP2008285807A (ja) * 2006-01-26 2008-11-27 Toray Ind Inc 皮革様シート状物の製造方法
JP2008297673A (ja) * 2007-06-01 2008-12-11 Kuraray Co Ltd 長繊維不織布および人工皮革用基材の製造方法
JP2014019983A (ja) * 2012-07-20 2014-02-03 Toray Ind Inc シート状物およびその製造方法
WO2021085427A1 (fr) * 2019-10-30 2021-05-06 旭化成株式会社 Cuir artificiel et son procédé de production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11269775A (ja) * 1998-03-18 1999-10-05 Kuraray Co Ltd スエード調人工皮革およびその製造法
JP2007177382A (ja) * 2005-11-30 2007-07-12 Toray Ind Inc 皮革様シート状物、その製造方法、並びにそれを用いてなる内装材、衣料用資材及び工業用資材
JP2008285807A (ja) * 2006-01-26 2008-11-27 Toray Ind Inc 皮革様シート状物の製造方法
JP2008297673A (ja) * 2007-06-01 2008-12-11 Kuraray Co Ltd 長繊維不織布および人工皮革用基材の製造方法
JP2014019983A (ja) * 2012-07-20 2014-02-03 Toray Ind Inc シート状物およびその製造方法
WO2021085427A1 (fr) * 2019-10-30 2021-05-06 旭化成株式会社 Cuir artificiel et son procédé de production

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