WO2024009907A1 - 立毛人工皮革及びその製造方法 - Google Patents

立毛人工皮革及びその製造方法 Download PDF

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Publication number
WO2024009907A1
WO2024009907A1 PCT/JP2023/024418 JP2023024418W WO2024009907A1 WO 2024009907 A1 WO2024009907 A1 WO 2024009907A1 JP 2023024418 W JP2023024418 W JP 2023024418W WO 2024009907 A1 WO2024009907 A1 WO 2024009907A1
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Prior art keywords
artificial leather
napped
fibers
napped artificial
web
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PCT/JP2023/024418
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English (en)
French (fr)
Japanese (ja)
Inventor
公男 中山
将司 目黒
明久 岩本
弘行 菱田
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to KR1020247043338A priority Critical patent/KR20250029811A/ko
Priority to US18/878,936 priority patent/US20250382742A1/en
Priority to CN202380050478.2A priority patent/CN119365651A/zh
Priority to EP23835439.3A priority patent/EP4553219A1/en
Priority to JP2024532097A priority patent/JPWO2024009907A1/ja
Publication of WO2024009907A1 publication Critical patent/WO2024009907A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—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
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/4383—Composite fibres sea-island
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—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
    • D06N3/12—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
    • D06N3/121—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 polyesters, polycarbonates, alkyds
    • D06N3/123—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 polyesters, polycarbonates, alkyds with polyesters
    • 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
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/36—Matrix structure; Spinnerette packs therefor
    • 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 napped artificial leather and a method for producing the same.
  • Napped artificial leather which has a suede-like appearance and is used as a surface material for clothing, shoes, furniture, car seats, miscellaneous goods, etc., has a napped surface formed by raising microfibers by raising them.
  • Such napped artificial leather is usually used after being colored, and conventionally dyeing using dyes that can be colored in a wide range of colors from light to deep colors has been widely carried out.
  • Patent Document 1 proposes an artificial leather substrate in which the average area of the polymer elastic body exposed on the sheet surface is 0.1 mm 2 or less.
  • Patent Document 3 proposes suede-like artificial leather that uses pigment-colored fibers and pigment-colored elastomer polymers and has an average napped tone of 10 to 200 ⁇ m.
  • Patent Document 4 discloses that a nonwoven fabric made of short fibers with a single fiber fineness of 0.0001 to 0.5 dtex and an apparent density of 0.300 to 0.700 g/cm 3 and a nap length of A nubuck-like leather-like sheet material has been proposed, which has a particle size of 5 to 500 ⁇ m and is characterized by the absence of a film made of an elastic polymer.
  • Patent Document 5 proposes artificial leather in which the average fiber length of the ultrafine fibers in the napped layer is 250 ⁇ m or more and 500 ⁇ m or less, and the surface coverage of the ultrafine fibers in the napped layer is 60% or more and 100% or less. Further, in Patent Document 6, a resin layer is intermittently formed on the raised surface, the area ratio of the resin portion to the fabric surface is 10 to 90%, and the resin layer is composed of two or more layers. A similar fabric has been proposed.
  • JP2016-69790A Japanese Patent Application Publication No. 2016-11477 Japanese Patent Application Publication No. 2004-143654 JP2006-241620A International Publication No. 2020/003866 International Publication No. 2017/22387
  • the artificial leathers described in Cited Documents 1 and 2 suppress the occurrence of color unevenness, they do not have sufficient mechanical strength such as friction abrasion resistance or tensile strength, and there is room for improvement. Furthermore, the artificial leathers described in Patent Documents 3, 4, and 6 also did not have sufficient mechanical strength such as tensile strength, and there was room for improvement. Furthermore, the leather described in Patent Document 5 does not have a fully satisfactory texture, that is, the texture is rough, and there is room for improvement.
  • the present invention was made in view of the above situation, and an object of the present invention is to provide a raised artificial leather that suppresses the occurrence of color unevenness and has both high mechanical strength and excellent texture.
  • excellent feel means that the texture is close to that of natural leather, such as excellent denseness, flexibility, and good feel.
  • the present invention suppresses the occurrence of color unevenness by setting the content of the polymer elastic body imparted to the nonwoven fabric, the area ratio of the polymer elastic body present on the napped surface, and the napped fiber length to predetermined values. This is based on the discovery that napped artificial leather having both high mechanical strength and excellent texture can be obtained.
  • a napped artificial leather comprising a nonwoven fabric containing ultrafine fibers and a polymeric elastomer and having a napped surface, wherein the content of the polymeric elastomer is 15 to 35% by mass, and the napped surface has a napped surface.
  • the napped artificial leather according to [1] above, wherein the ultrafine fibers are polyester fibers.
  • the napped artificial leather according to [1] or [2] above, wherein the ultrafine fibers have an average fineness of 0.01 to 1.0 dtex.
  • a raised artificial leather that suppresses the occurrence of color unevenness and has both high mechanical strength and excellent texture, and a method for producing the same.
  • FIG. 2 is a conceptual diagram illustrating a method for measuring the napped fiber length of napped artificial leather according to the present invention.
  • the napped artificial leather of the present embodiment includes a nonwoven fabric containing ultrafine fibers and a polymeric elastomer, and has a napped surface, and the content of the polymeric elastomer is 15 to 35% by mass.
  • the area ratio of the polymeric elastic body present on the napped surface is 17% or less, and the napped fiber length is 250 ⁇ m or less.
  • the raised artificial leather of the present embodiment suppresses the occurrence of color unevenness and has high mechanical strength and excellent texture.
  • the napped fiber length means the length of the napped fibers present on the napped surface of napped artificial leather, and the uneven coloring refers to the uneven coloring that occurs when the napped artificial leather is colored. means.
  • the fibers constituting the nonwoven fabric and the polymeric elastomer use different components.
  • polyester fibers may be used as the fibers
  • polyurethane resins may be used as the polymeric elastomer.
  • the fibers and the polymeric elastic material have different coloring properties, resulting in differences in tone and color density between the fibers and the polymeric elastic material.
  • the content of the polymeric elastic material is 15 to 35% by mass, and the area ratio of the polymeric elastic material present on the napped surface is 17% or less, so that the napped surface is It is thought that exposure of the polymeric elastic body is suppressed, and as a result, color unevenness is suppressed.
  • the raised artificial leather of this embodiment has a polymer elastic material content of 15 to 35% by mass, which not only suppresses color unevenness but also has excellent denseness, flexibility, etc., and a good feel to the touch. , the texture becomes similar to natural leather. In other words, it has a good texture.
  • the content of the polymeric elastomer is preferably 16 to 34% by mass, more preferably 16.5 to 33.5% by mass, and still more preferably 17 to 33% by mass, from the viewpoint of obtaining napped artificial leather with a better texture. Mass%.
  • the area ratio of the polymer elastic body present on the napped surface is 17% or less.
  • the area ratio of the polymer elastic body is preferably 15% or less, more preferably 14% or less, still more preferably 13% or less, from the viewpoint of further suppressing uneven dyeing.
  • the area ratio of the polymeric elastic body is preferably 5% or more, more preferably 6% or more, still more preferably 7% or more, from the viewpoint of obtaining napped artificial leather with better flexibility and elasticity.
  • the area ratio of the polymeric elastic body existing on a nape surface is measured and calculated by the following method.
  • the raised surface of the raised artificial leather is photographed at three different locations using a scanning electron microscope (SEM) at a magnification of 50 times.
  • SEM scanning electron microscope
  • calculate the total area of the region in which the polymeric elastic material is present in each of the obtained images and calculate the area ratio of the polymeric elastic material from the obtained total area and the total area of the entire image region. is calculated using the following formula.
  • Area ratio of elastic polymer total area of area where elastic polymer exists / total area of entire image area x 100 (%) Specifically, it is measured and calculated by the method described in the Examples described later.
  • the napped artificial leather of this embodiment has a napped fiber length of 250 ⁇ m or less.
  • the napped fibers When the napped fiber length is 250 ⁇ m or less, the napped fibers have a uniform length in a finely dispersed state, and a napped surface with excellent flexibility and a smooth feel can be formed.
  • the napped fiber length is preferably 150 ⁇ m or less, more preferably 120 ⁇ m or less, and even more preferably 100 ⁇ m or less, from the viewpoint of forming a napped surface with better flexibility and smooth feel.
  • the length of the napped fibers is preferably 40 ⁇ m or more, more preferably 50 ⁇ m or more, and even more preferably 40 ⁇ m or more, from the viewpoint of preventing exposure of the polymeric elastic material at the bottom of the napped fibers, which would cause a decrease in appearance, and maintaining the soft feel of the ultrafine fibers. is 60 ⁇ m or more.
  • the thickness of the napped artificial leather of this embodiment is not particularly limited, but from the viewpoint of obtaining napped artificial leather having both high mechanical strength and excellent texture, it is preferably 0.1 to 1.5 mm, More preferably, it is 0.3 to 1.0 mm.
  • the basis weight of the napped artificial leather is not particularly limited, but from the viewpoint of obtaining napped artificial leather having both high mechanical strength and excellent texture, it is preferably 100 to 1000 g/m 2 , more preferably 150 g/m 2 . ⁇ 800/ m2 .
  • the apparent density of the napped artificial leather of this embodiment is preferably 0.35 g/cm 3 or more, more preferably 0.37 g/cm 3 or more, even more preferably 0.38 g/cm 3 or more, and preferably 0.35 g/cm 3 or more. It is 70 g/cm 3 or less, more preferably 0.50 g/cm 3 or less, even more preferably 0.48 g/cm 3 or less.
  • the apparent density is 0.35 g/cm 3 or more, it has excellent elasticity, and the fibers are prevented from being dragged out when the napped surface is rubbed, making it easy to obtain an elegant napped appearance.
  • the apparent density is 0.70 g/cm 3 or less, it has excellent flexibility.
  • the nonwoven fabric of this embodiment contains ultrafine fibers and an elastic polymer.
  • Nonwoven fabric has a texture similar to natural leather, and from the viewpoint of obtaining high mechanical strength, it has a structure in which multiple ultrafine fibers form fiber bundles and the fiber bundles are entangled (three-dimensional entangled body).
  • the nonwoven fabric is preferably a spunbond nonwoven fabric, and more preferably a spunbond nonwoven fabric containing long ultrafine fibers, from the viewpoint of easily obtaining high mechanical strength and simplifying the production process.
  • long fibers mean continuous fibers that are not short fibers that are intentionally cut after spinning.
  • the nonwoven fabric refers to filaments or continuous fibers that are not short fibers that have been intentionally cut to have a fiber length of about 3 to 80 mm.
  • the nonwoven fabric is preferably one obtained by spinning sea-island type (matrix domain type) composite fibers to obtain a web, subjecting the web to entanglement treatment, and further subjecting it to ultrafine fiber treatment.
  • the ultrafine fibers of the present invention are multicomponent fibers (composite fibers) made of at least two types of spinnable polymers with different chemical or physical properties, which are processed in an appropriate manner before or after being impregnated with a polymeric elastic material. This refers to fibers made into ultra-fine fibers by extracting and removing at least one type of polymer in a step.
  • the multicomponent fiber that generates this ultrafine fiber is an ultrafine fiber generation type fiber. Typical examples thereof include sea-island composite fibers, multilayer laminated composite fibers, radial laminated composite fibers, etc. obtained using methods such as chip blending (mixed spinning) and composite spinning. Among these, sea-island composite fibers are preferable because they cause less damage to the fibers when subjected to entanglement treatment by needle punching or the like, and the average fineness of the ultrafine fibers is uniform.
  • Examples of the resin constituting the ultrafine fibers contained in the nonwoven fabric of this embodiment include polyethylene terephthalate (hereinafter sometimes referred to as "PET”), isophthalic acid-modified PET, sulfoisophthalic acid-modified PET, and cationic dyes.
  • PET polyethylene terephthalate
  • isophthalic acid-modified PET isophthalic acid-modified PET
  • sulfoisophthalic acid-modified PET examples of the resin constituting the ultrafine fibers contained in the nonwoven fabric of this embodiment.
  • Modified PET such as dyeable PET and aromatic polyesters such as polybutylene terephthalate and polyhexamethylene terephthalate; polylactic acid, polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalerate Aliphatic polyesters such as resins; nylons such as nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, and nylon 6-12; fibers such as polypropylene, polyethylene, polybutene, polymethylpentene, and chlorinated polyolefin.
  • modified PET is PET in which at least a portion of the ester-forming dicarboxylic acid monomer units or diol monomer units of unmodified PET are replaced with substitutable monomer units.
  • modified monomer units that replace dicarboxylic acid monomer units include isophthalic acid that replaces terephthalic acid units, sodium sulfoisophthalic acid, sodium sulfonaphthalene dicarboxylic acid, adipic acid, etc. Units are listed. Specific examples of modified monomer units that replace diol monomer units include units derived from diols such as butanediol and hexanediol that replace ethylene glycol units. Among these, polyester resins such as aromatic polyesters and aliphatic polyesters are preferred from the viewpoint of obtaining raised artificial leather having colorability, high mechanical strength, and excellent texture.
  • modified PET such as polyethylene terephthalate (PET), isophthalic acid-modified PET, sulfoisophthalic acid-modified PET, cationic dye-dyeable PET, polybutylene terephthalate, and Aromatic polyesters such as hexamethylene terephthalate; aliphatic polyesters such as polylactic acid, polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalerate resin; nylon 6, nylon 66, nylon Preferred are nylons such as 10, nylon 11, nylon 12, and nylon 6-12; polyolefins such as polypropylene, polyethylene, polybutene, polymethylpentene, and chlorinated polyolefin.
  • PET polyethylene terephthalate
  • isophthalic acid-modified PET isophthalic acid-modified PET
  • sulfoisophthalic acid-modified PET cationic dye-dyeable PET
  • the ultrafine fibers preferably have an average fineness (average fiber diameter) of 0.01 to 1.0 dtex, more preferably from the viewpoint of obtaining napped artificial leather with excellent napped surface density and excellent flexibility and elasticity. is 0.05 to 0.7 dtex, more preferably 0.1 to 0.5 dtex.
  • the resin constituting the ultrafine fibers of this embodiment may contain various additives as long as the effects of the present invention are not impaired.
  • additives include catalysts, colorants, heat resistant agents, flame retardants, lubricants, antifouling agents, optical brighteners, matting agents, gloss improvers, antistatic agents, fragrances, deodorants, and antibacterial agents. , anti-mite agents, inorganic fine particles, etc.
  • Examples of the polymeric elastomer contained in the nonwoven fabric of this embodiment include polyurethane resins, acrylonitrile elastomers, olefin elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, modified products and copolymers thereof, Examples include mixtures. Among these, polyurethane resins are preferred from the viewpoint of obtaining napped artificial leather with excellent flexibility and elasticity.
  • polyurethane resins include various polyurethane resins obtained by reacting a polymer polyol with a weight average molecular weight of 200 to 6,000, an organic polyisocyanate, and, if necessary, a chain extender at a predetermined molar ratio. Can be mentioned.
  • polymeric polyols include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(methyltetramethylene glycol), and copolymers thereof; polybutylene adipate diol, polybutylene sebacate; polyester polyols such as diol, polyhexamethylene adipate diol, poly(3-methyl-1,5-pentylene adipate) diol, poly(3-methyl-1,5-pentylene sebacate) diol, polycaprolactone diol; Copolymers thereof; polycarbonate polyols such as polyhexamethylene carbonate diol, poly(3-methyl-1,5-pentylene carbonate) diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and copolymers thereof; polyester Examples include carbonate polyols. Further, if necessary, a polyfunctional alcohol such as a trifluor
  • organic polyisocyanates include non-yellowing diisocyanates such as aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; Examples include aromatic diisocyanates such as diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate polyurethane. Further, if necessary, a polyfunctional isocyanate such as a trifunctional isocyanate or a tetrafunctional isocyanate may be used in combination. These may be used alone or in combination of two or more.
  • non-yellowing diisocyanates such as aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate,
  • chain extenders include diamines such as hydrazine, ethylenediamine, propylene diamine, hexamethylene diamine, nonamethylene diamine, xylylene diamine, isophorone diamine, piperazine and its derivatives, adipic acid dihydrazide, isophthalic acid dihydrazide; Triamines such as diethylenetriamine; tetramines such as triethylenetetramine; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis( ⁇ -hydroxyethoxy)benzene, 1,4 - Diols such as cyclohexanediol; triols such as trimethylolpropane; pentaols such as pentaerythritol; amino alcohols such as aminoethyl alcohol and aminopropyl alcohol.
  • diamines such as hydrazine, ethylenediamine, propylene
  • monoamines such as ethylamine, propylamine, butylamine; carboxyl group-containing monoamine compounds such as 4-aminobutanoic acid and 6-aminohexanoic acid; methanol, ethanol, propanol, butanol, etc.
  • Monools may be used in combination.
  • polyurethane resins include polycarbonate urethane, polyether urethane, polyester urethane, polyether ester urethane, polyether carbonate urethane, polyester carbonate urethane, and the like.
  • polycarbonate urethane is preferred from the viewpoint of obtaining napped artificial leather with excellent flexibility and elasticity.
  • the polymeric elastomer may include pigments such as carbon black, colorants such as dyes, coagulation regulators, antioxidants, ultraviolet absorbers, fluorescent agents, antifungal agents, penetrants, Additives such as antifoaming agents, lubricants, water repellents, oil repellents, thickeners, bulking agents, curing accelerators, foaming agents, water-soluble polymer compounds such as polyvinyl alcohol and carboxymethyl cellulose, inorganic fine particles, and conductive agents. May include. However, when production of raised artificial leather is required in small quantities and in many brands, high-quality It is preferable that the molecular elastomer does not contain a colorant such as a pigment or dye.
  • the method for producing napped artificial leather of the present embodiment preferably includes the following steps 1 to 5 from the viewpoint of obtaining napped artificial leather that suppresses the occurrence of color unevenness and has both high mechanical strength and excellent texture.
  • Step 1 Obtaining a web
  • Step 2 Obtaining an entangled web by subjecting the web to an entangling process
  • Step 3 Obtaining an entangled web containing an elastic polymeric material
  • Step 4 Obtaining an entangled web containing an elastic polymeric material
  • Step 1 is a step of obtaining a web.
  • the process of obtaining the web involves melt-spinning sea-island composite fibers to form the web.
  • Methods for obtaining a web by melt-spinning sea-island composite fibers include a method in which the sea-island composite fibers are spun using a spunbond method and then collected on a net without being cut to obtain a web of long fibers; Examples include a method of crimping and cutting the sea-island composite fibers obtained by carding the short fibers of the sea-island composite fibers to obtain a web of short fibers.
  • spunbond method is used to spin the sea-island composite fibers, which are collected on a net without cutting.
  • a method of forming a web of long fibers (hereinafter sometimes referred to as "a method of forming a web of long fibers") is preferred.
  • the spunbond method refers to a method in which a molten strand of sea-island composite fiber is continuously ejected from a spinning nozzle at a predetermined speed using a composite spinning nozzle in which a large number of nozzle holes are arranged in a predetermined pattern.
  • This refers to a method in which the material is discharged from a composite spinning nozzle, stretched while being cooled using high-speed airflow, and deposited on a moving net in the form of a conveyor belt.
  • the web of long fibers formed by the spunbond method may be subjected to a fusing treatment in order to impart stability to its shape. The details of the method for forming a web of long fibers will be described below.
  • the fiber length of the sea-island composite fibers before melt spinning and before being made into ultra-fine fibers is 100 mm or more.
  • the fiber length may be several meters, several hundred meters, several kilometers, or more, as long as it is not unavoidably cut.
  • some of the long fibers may be unavoidably cut and become short fibers.
  • Examples of the island component resin included in the sea-island type composite fiber and which later becomes ultrafine fibers include the same resins as those constituting the ultrafine fibers in the above-mentioned "ultrafine fibers.”
  • As the sea component resin contained in the sea-island composite fiber and removed by extraction or decomposition it is preferable to use a resin that has a different solubility or degradability from the island component resin and has low compatibility. . It is preferable that such a resin is appropriately selected depending on the type of resin of the island component and the manufacturing method.
  • Sea component resins include, for example, olefin resins such as polyethylene, polypropylene, ethylene propylene copolymer, and ethylene vinyl acetate copolymer, and polystyrene, styrene-acrylic copolymer, and styrene-ethylene copolymer dissolved in organic solvents.
  • the resin include resins that have properties and can be dissolved and removed with organic solvents, and water-soluble resins such as water-soluble polyvinyl alcohol. Among these, resins that can be dissolved and removed with organic solvents are preferred from the viewpoint of melt-spinning island component resins with high intrinsic viscosity, and polyethylene is more preferred.
  • the mass ratio of the sea component to the island component (sea component/island component) contained in the sea-island type composite fiber is preferably 10/90 to 60/40, more preferably 20/80 to 50 from the viewpoint of mechanical strength. /50.
  • the number of island components that later become ultrafine fibers in the cross section of the sea-island composite fiber during melt spinning is preferably 5 to 200, more preferably 5 to 200, from the viewpoint of forming a fiber bundle of ultrafine fibers with appropriate voids.
  • the number is 10 to 50, more preferably 10 to 30.
  • the sea-island type composite fibers may be prepared with, for example, dark pigments such as carbon black, white pigments such as zinc white, lead white, lithopone, titanium dioxide, precipitated barium sulfate, and barite powder, weathering agents, and antifungal agents. , hydrolysis inhibitors, lubricants, fine particles, frictional resistance modifiers, etc., may be contained within the range that does not impair the effects of the present invention.
  • the web obtained by melt-spinning the sea-island composite fibers may be subjected to shrinkage treatment by immersing it in hot water of about 60 to 150°C to make the entangled state of the web dense in advance.
  • Step 2 is a step of subjecting the web to an entanglement treatment to obtain an entangled web.
  • the web obtained in step 1 is laminated in multiple layers and then subjected to an entangling treatment such as needle punching or hydroentangling treatment to form an entangled web in which long fibers are entangled in the thickness direction.
  • an entangling treatment such as needle punching or hydroentangling treatment to form an entangled web in which long fibers are entangled in the thickness direction.
  • the number of layers of webs to be stacked is not particularly limited, but from the viewpoint of mechanical strength, it is preferably 4 or more layers, more preferably 8 or more layers, and from the viewpoint of ease of manufacture, preferably 20 or less layers, more preferably It has 16 layers or less.
  • the type of felt needle used is not particularly limited, but from the viewpoint of sufficiently increasing the intertwining of fibers in the thickness direction and obtaining artificial leather with excellent mechanical strength, thin felt needles or It is preferable to use a felting needle with a small number of barbs, such as a one-barb needle. Further, from the viewpoint of suppressing cutting of fibers, the number of barbs in the felt needle is preferably 3 or more, more preferably 5 or more, and still more preferably 6. Further, the number of felt needles used in the needle punch per unit area is not particularly limited, but is preferably 200 to 5,500 needles/cm 2 .
  • An oil agent or an antistatic agent may be applied to the web or the entangled web at any stage from the spinning of the sea-island composite fiber to the entanglement treatment.
  • the basis weight of the entangled web is preferably 100 to 2000 g/m 2 from the viewpoint of obtaining napped artificial leather having both high mechanical strength and excellent texture.
  • heat shrinkage treatment may be performed.
  • fix the form of the entangled web, and smoothen the surface for example, when the surface temperature is 100 to 150 °C It may be pressed with hot rolls, or heated above the softening point of the resin constituting the fibers (island components) in the entangled web, and pressed using cooling rolls whose surface temperature is below the softening point of the resin.
  • the surface temperature of the cooling roll is preferably 30° C. or more lower than the softening point of the resin.
  • Step 3 is a step of impregnating the entangled web with an elastic polymer to obtain an entangled web containing the elastic polymer.
  • an elastomer is impregnated with a polymeric elastomer before removing the sea component. It is preferable that In this way, by impregnating and applying a polymeric elastic material before removing the sea component, the voids formed by removing the sea component can be created between the ultrafine fibers that form the fiber bundle after the sea component is removed. It is formed. As a result, the ultrafine fibers inside the fiber bundle are less likely to be restrained by the elastic polymer, that is, the ultrafine fibers are less likely to be affected by the elastic polymer, and a napped artificial leather with excellent flexibility can be obtained.
  • step 3 the entangled web is impregnated with the elastic polymer using an emulsion or solution containing the elastic polymer, and then the elastic polymer is coagulated to form the entangled web containing the elastic polymer. obtain.
  • the polymeric elastic material By solidifying the polymeric elastic material, the polymeric elastic material can be applied to the voids of the fibers of the entangled web.
  • the method of impregnating the entangled web with the polymer elastomer using an emulsion or solution containing the polymer elastomer is not particularly limited, but a dip-nip method is preferred.
  • Examples of the elastic polymer include those described in ⁇ Elastic Polymer> above, and polyurethane resins are preferred.
  • a solution containing the polymeric elastomer it is preferable to use a solution containing the polymeric elastomer, and use a solvent-based polyurethane in which a polyurethane resin is dissolved in a solvent such as N,N-dimethylformamide (DMF). It is more preferable to obtain an entangled web containing an elastomer polymer.
  • a solvent-based polyurethane in which a polyurethane resin is dissolved in a solvent such as N,N-dimethylformamide (DMF). It is more preferable to obtain an entangled web containing an elastomer polymer.
  • DMF N,N-dimethylformamide
  • the entangled web may be pretreated before being impregnated with the polymeric elastic material. After impregnation, the polymeric elastomer may be selectively removed from the entangled web.
  • Pretreatment of the entangled web includes, for example, a method of coating or impregnating a thermoplastic resin such as polyvinyl alcohol, or a method of coating or impregnating the thermoplastic resin with a gravure coater method, a knife coater method, a pipe coater method, a comma coater method, etc. Examples include a method in which it is present on the surface of an intertwined web or in an intertwined web.
  • Examples of a method for selectively removing the elastic polymer include a method in which the elastic polymer is removed by applying contact pressure to the surface of the entangled web using a nip roll, a squeeze bar, a doctor knife, or the like.
  • the entangled web is impregnated with the polymeric elastic material so that the content of the polymeric elastic material is 15 to 35% by mass in the napped artificial leather, and the entangled web containing the polymeric elastic material is After obtaining the web, it is preferable to selectively remove the elastic polymer from the entangled web so that the area ratio of the elastic polymer present on the napped surface is 17% or less.
  • Examples of methods for coagulating the polymeric elastomer include a method of drying and removing water contained in an emulsion or solution and coagulating it, a method of wet coagulation, and the like.
  • Methods for drying and solidifying include heat treatment in a dryer at 50 to 200°C, infrared heating followed by heat treatment in a dryer, steam treatment followed by heat treatment in a dryer, or ultra-high heat treatment in a dryer. Examples include a method in which heat treatment is performed using a dryer after sonic heating, and a method in which these methods are combined.
  • the entangled web containing the elastomer polymer is immersed in a treatment bath containing a poor solvent for the elastomer polymer, and the elastomer polymer is coagulated into a porous state.
  • Water is preferably used as a poor solvent for the polymeric elastomer, but for example, when polyurethane resin is used as the polymeric elastomer, a good solvent for the polymeric elastomer such as dimethylformamide (DMF) is mixed with water.
  • DMF dimethylformamide
  • It is preferable to use a treatment bath because it is possible to control the solidification state, that is, the size, number, shape, etc. of the large number of pores formed, by appropriately setting the mixing ratio.
  • a heat-sensitive gelling agent When applying a polymer elastomer using an emulsion containing a polymer elastomer, if a heat-sensitive gelling agent is added, it is possible to use a dry method or a combination of methods such as steaming or far-infrared heating. More uniform solidification is possible in the thickness direction. Furthermore, when an elastic polymer is applied using a solution containing an organic solvent and an elastic polymer, more uniform pores can be obtained by using a coagulation modifier in combination. Furthermore, examples of the organic solvent include dimethylformamide, dimethylacetamide, dimethylsulfoxide, and the like. By coagulating the polymer elastic body contained in the entangled web into a porous state, a texture similar to that of natural leather can be obtained. Among these, a method of wet coagulation is preferable, and a method of coagulating the entangled web by immersing it in a treatment solution of water mixed with dimethylformamide as an organic solvent is more preferable.
  • Step 4 is a step of removing sea components from the entangled web containing the elastomer polymer.
  • the microfibers are converted into fiber bundles of microfibers. That is, the fibers in the entangled web are made into ultrafine fibers, and a nonwoven fabric containing ultrafine fibers and an elastic polymer (hereinafter sometimes referred to as a nonwoven fabric containing an elastic polymer) is obtained.
  • Examples of the method for removing the sea component resin include a method using a solvent or a decomposing agent that can selectively remove only the sea component resin.
  • a solvent or a decomposing agent that can selectively remove only the sea component resin.
  • polyethylene from the viewpoint of melt-spinning the resin of the island component having a high intrinsic viscosity, and from this point of view, it is preferable to dissolve and remove the sea component with an organic solvent.
  • the organic solvent for dissolving and removing the sea component include toluene, trichlorethylene, tetrachloroethylene, etc. when the resin of the island component is a polyamide resin or polyester resin and the resin of the sea component is polyethylene.
  • the sea-island composite fibers are melt-spun to obtain a web and before the sea component is removed, the fibers are densified by applying heat shrinkage treatment (fiber shrinkage treatment) using steam, hot water, dry heat, etc. You may let them.
  • heat shrinkage treatment fiber shrinkage treatment
  • the nonwoven fabric containing the polymeric elastomer is dried after removing the sea component resin.
  • the nonwoven fabric containing the polymer elastic body may be cut to a predetermined thickness, if necessary.
  • the basis weight of the nonwoven fabric containing the polymeric elastic material is preferably 140 to 3000 g/m 2 , more preferably 200 to 2000 g/m 2 from the viewpoint of mechanical strength.
  • Step 5 is a step of buffing the nonwoven fabric containing the polymer elastic body obtained in Step 4.
  • the fibers present on the surface of the nonwoven fabric are napped, and napped artificial leather having a napped surface is obtained.
  • the buffing process is preferably carried out using sandpaper or emery paper of 120 to 600 grit, more preferably 320 to 600 grit. In this way, napped artificial leather having napped surfaces on one or both sides can be obtained.
  • the napped fiber length can be adjusted. Fiber length can be shortened.
  • raised artificial leather is subjected to shrinkage processing to add flexibility, kneading to soften it, brushing for reverse sealing, antifouling treatment, hydrophilic treatment, lubricant treatment, softener treatment, and anti-oxidation treatment. Finishing treatments such as agent treatment, ultraviolet absorber treatment, fluorescent agent treatment, and flame retardant treatment may be performed.
  • the napped artificial leather in this embodiment can be colored, and is preferably colored using a dye or a pigment.
  • a dye or a pigment Unlike pigments, which need to be used in combination with resins to make them stick, and whose texture tends to harden, pigments penetrate into the fibers, so there is no need to use resins in combination, there is less concern about deterioration of texture, and it is easy to create a variety of colors by adjusting the type and concentration of the dye. From the viewpoint of easy coloring, it is preferable to dye using a dye.
  • the dye for example, when the ultrafine fiber is formed from a polyester resin, it is preferable to dye it with a disperse dye or a cationic dye.
  • disperse dyes include benzene azo dyes (monoazo, disazo, etc.), heterocyclic azo dyes (thiazole azo, benzothiazo azo, quinoline azo, pyridine azo, imidazole azo, thiophene azo, etc.), anthraquinone dyes, and condensed dyes.
  • examples include dyes such as quinophthalin, styryl, coumarin, etc. These are, for example, commercially available as dyes with the prefix "Disperse”. These may be used alone or in combination of two or more.
  • a dyeing method such as a high-pressure jet dyeing method, a jigger dyeing method, a thermosol continuous dyeing method, a sublimation printing method, etc. can be used.
  • ⁇ Nap-pilled fiber length> After cutting the napped artificial leather in the thickness direction and aligning the napped fibers present on the napped side of the napped artificial leather in the opposite direction using a hair straightening brush, the cross section of the napped artificial leather was examined using a scanning electron microscope (SEM). Photographed at 40x magnification. In the obtained image, draw a line L1 at the root of the ultrafine fibers in the nonwoven fabric, or at the upper limit where the polymeric elastic film is present if an elastic polymeric film exists, and draw the line L1 at the point closest to the observation surface. A line L2 was drawn at the upper limit where the fibers were raised.
  • SEM scanning electron microscope
  • FIG. 3 A conceptual diagram illustrating a method for measuring the napped fiber length of napped artificial leather is shown in FIG. 3.
  • ⁇ Area ratio of elastic polymer> Three images of the raised surface of the raised artificial leather were taken at 50x magnification using a scanning electron microscope (SEM), and each of the obtained images was printed on A4 size paper. Then, the printed paper was placed on an OHP (overhead projector) sheet, and the portion of the polymeric elastic body was painted black and transferred onto the OHP sheet. A pattern on an OHP sheet in which the portion of the polymeric elastic body was painted black was captured by a scanner and an image was formed. Subsequently, using image processing software Image-Pro Premier 9.2 (image-pro plus, manufactured by Media Cybernetics), the total area of the region where the polymeric elastic body existed in the obtained image was determined.
  • SEM scanning electron microscope
  • the area ratio of the polymer elastic body was calculated using the following formula.
  • Area ratio of elastic polymer total area of area where elastic polymer exists / total area of entire image area x 100 (%)
  • Figure 1 is an image of the raised surface taken with a scanning electron microscope (SEM) at a magnification of 50x
  • Figure 2 is a transfer of the polyurethane part of the polymeric elastic material from the image in Figure 1 to an OHP sheet by painting it black. Show images.
  • ⁇ Apparent density> The thickness (mm) and basis weight (g/cm 2 ) were measured in accordance with JIS L 1096:2010, and the apparent density (g/cm 3 ) was determined from these values.
  • ⁇ Tensile strength> Using a 2.5 cm x 16 cm test piece cut from napped artificial leather, a stress-strain curve was obtained according to JIS L1096:2010 8.14.1 "Tensile strength test". The test pieces used were three test pieces cut out along the longitudinal direction of the napped artificial leather and three test pieces cut out along the horizontal direction. The stress at break is read from the stress-strain curve obtained using each test piece, and the average value of the stress of three test pieces cut along the length in the vertical direction and the long length in the horizontal direction are calculated. The average stress value of three test pieces cut along the length was calculated, and the lower value (average value) was taken as the tensile strength.
  • ⁇ Denseness> The denseness of the napped artificial leather was judged visually and by touch using the following criteria.
  • ⁇ Texture> The feel of the napped artificial leather when folded was evaluated visually and by touch using the following criteria. A: Excellent flexibility, elasticity, etc. B: At least one of flexibility and elasticity is poor.
  • Example 1 Prepare polyethylene terephthalate (PET) as the island component and polyethylene as the sea component, and use a melting composite nozzle so that the number of islands is 12, and pressurize so that the mass ratio of the sea component/island component is 35/65. After adjustment, the spinneret temperature was set at 280° C., single-hole discharge was performed at 1.2 g/min, and sea-island composite fibers with a fineness of 3 dtex were spun at a spinning speed of 4000 m/min. The obtained sea-island composite fibers were continuously deposited on a movable net and lightly pressed with a heated metal roll to prevent surface fluffing. The sea-island composite fibers were then peeled from the net and passed between a heated metal roll and a back roll under pressure to produce a web of long fibers with a basis weight of 40 g/m 2 .
  • PET polyethylene terephthalate
  • the laminated web was subjected to needle punching using a 6-barb needle at a punching density of 2050 punches/cm 2 to form an entangled web with a basis weight of 600 g/m 2 .
  • the resulting entangled web was subjected to shrinkage treatment with hot water at 90°C, dried, and then hot pressed to obtain a heat-shrinkable entangled web with a basis weight of 800 g/m 2 .
  • a DMF solution solid content 15% by mass of a polycarbonate polyurethane having a 100% modulus of 4.5 MPa, which is a polymeric elastic material, was added so that the content of the polymeric elastic material in the napped artificial leather was 18% by mass. was impregnated with a heat-shrinked entangled web. After impregnation, the polycarbonate polyurethane present on the surface of the entangled web is selectively removed by applying contact pressure so that the area ratio of the polycarbonate polyurethane present on the napped surface is 5%, and then water is applied.
  • the entangled web to which the polyurethane resin has been applied is dipped in toluene at 85°C while being nipped to dissolve and remove the polyethylene, which is a sea component, and then dried.
  • a nonwoven fabric to which a polyurethane resin was applied as a polymeric elastomer was obtained.
  • the fabric weight of the obtained nonwoven fabric was 600 g/m 2 .
  • the obtained nonwoven fabric was cut in half in the thickness direction to make artificial leather raw material, and the half-cut side was buffed with #180 and #240 sandpaper, and then the non-half-cut side was ground with #320 and #600 sandpaper.
  • a napped artificial leather having a napped surface was obtained by buffing one side of the material.
  • the obtained raised artificial leather was colored by adjusting the disperse dye to a dye concentration of 6% owf, performing high-pressure dyeing at 130 ° C in a circular dyeing machine, and then performing reduction cleaning, oxidation treatment, and water washing.
  • a raised artificial leather was obtained. Table 1 shows the evaluation results of the colored raised artificial leather.
  • Example 2 In Example 1, instead of selectively removing by applying contact pressure so that the area ratio of polycarbonate-based polyurethane existing on the raised surface was 5%, the area ratio of polycarbonate-based polyurethane existing on the raised surface was 9%. Colored napped artificial leather was obtained in the same manner, except that it was selectively removed by applying contact pressure so that the concentration was 0.3%. The evaluation results are shown in Table 1.
  • Example 3 Colored napped artificial leather was obtained in the same manner as in Example 1, except that buffing treatment was performed to obtain napped artificial leather of 0.4 mm. The evaluation results are shown in Table 1.
  • Example 4 In Example 1, a DMF solution (solid content 15%) of polycarbonate polyurethane having a 100% modulus of 4.5 MPa, which is a polymeric elastic material, was added such that the content of the polymeric elastic material in the napped artificial leather was 18% by mass. Instead of impregnating a heat-shrink-treated entangled web, napped artificial leather is impregnated with a DMF solution (solid content 18.5%) of polycarbonate polyurethane, which is a polymeric elastomer and has a 100% modulus of 4.5 MPa. Colored napped artificial leather was obtained in the same manner except that a heat-shrinkable entangled web was impregnated so that the content of the polymeric elastic material therein was 32% by mass. The evaluation results are shown in Table 1.
  • Example 5 In Example 1, one side of the obtained nonwoven fabric was buffed with #180 and #240 sandpaper in order to make it into an artificial leather raw material, and then the untreated side was ground with #320 and #600 sandpaper. A colored napped artificial leather was obtained in the same manner except that a napped artificial leather having a napped surface and a thickness of 1.0 mm was obtained by buffing the surface. The evaluation results are shown in Table 1.
  • Example 6 Prepare polyethylene terephthalate (PET) as the island component and polyethylene as the sea component, and use a melting composite nozzle so that the number of islands is 16, and pressurize so that the mass ratio of the sea component/island component is 35/65. After adjusting the nozzle temperature setting to 280°C and discharging at a single hole discharge rate of 1.2 g/min, and spinning at a spinning speed of 820 m/min, stretching and crimping are performed to obtain sea islands, which are short fibers with a fineness of 4.0 dtex. A composite fiber was obtained. The sea-island composite fibers were then passed through a card to produce a short fiber web.
  • PET polyethylene terephthalate
  • a plurality of the obtained webs were laminated to form a laminated web. Then, the laminated web was subjected to needle punching using a 1-barb needle at a punching density of 2050 punches/cm 2 to form an entangled web with a basis weight of 600 g/m 2 . The resulting entangled web was subjected to shrinkage treatment with hot water at 90°C, dried, and then hot pressed to obtain a heat-shrinkable entangled web with a basis weight of 800 g/m 2 .
  • a DMF solution solid content 15% by mass of a polycarbonate polyurethane having a 100% modulus of 4.5 MPa, which is a polymeric elastic material, was added so that the content of the polymeric elastic material in the napped artificial leather was 18% by mass. was impregnated with a heat-shrinked entangled web. After impregnation, the polycarbonate polyurethane present on the surface of the entangled web is selectively removed by applying contact pressure so that the area ratio of the polycarbonate polyurethane present on the napped surface is 5%, and then water is applied.
  • :DMF was immersed in a DMF aqueous solution having a mass ratio of 70:30 to coagulate the polycarbonate-based polyurethane, thereby imparting polycarbonate-based polyurethane (polyurethane-based resin) to the entangled web.
  • the entangled web to which the polyurethane resin has been applied is dipped in toluene at 85°C while being nipped to dissolve and remove the polyethylene, which is a sea component, and then dried.
  • a nonwoven fabric to which a polyurethane resin was applied as a polymeric elastomer was obtained.
  • the fabric weight of the obtained nonwoven fabric was 820 g/m 2 .
  • Example 1 In Example 1, instead of selectively removing by applying contact pressure so that the area ratio of the polycarbonate-based polyurethane existing on the raised surface was 5%, the area ratio of the polycarbonate-based polyurethane existing on the raised surface was 17%. Colored napped artificial leather was obtained in the same manner, except that it was selectively removed by applying contact pressure so that the concentration was .6%. The evaluation results are shown in Table 1.
  • Example 2 In Example 1, instead of selectively removing by applying contact pressure so that the area ratio of polycarbonate-based polyurethane existing on the raised surface was 5%, the area ratio of polycarbonate-based polyurethane existing on the raised surface was 14%. Coloring was carried out in the same manner except that contact pressure was applied to selectively remove the fibers so that the fiber concentration was 8%, and the length of the napped fibers was adjusted to 250 ⁇ m during the buffing process. Napped artificial leather was obtained. The evaluation results are shown in Table 1.
  • Example 3 In Example 1, instead of the DMF solution (solid content 15%) of polycarbonate polyurethane with a 100% modulus of 4.5 MPa, carbon black was added and colored so that the content was 1.0% by mass. A DMF solution (solid content 15%) of polycarbonate polyurethane with a modulus of 4.5 MPa was used, and the area ratio of polycarbonate polyurethane present on the napped surface was 5%. Instead of selectively removing the polycarbonate polyurethane present in the entangled web by applying contact pressure, the polycarbonate polyurethane present in the entangled web was removed by contact pressure such that the area ratio of the polycarbonate polyurethane present on the napped surface was 18.4%. Colored napped artificial leather was obtained in the same manner, except that 20% of the product was added and selectively removed. The evaluation results are shown in Table 1.
  • Example 4 In Example 1, polyvinyl alcohol was used instead of polyethylene as the sea component, and instead of being immersed in toluene to dissolve and remove polyethylene as a sea component, it was immersed in hot water to dissolve and remove polyethylene. Then, a DMF solution (solid content 15%) of polycarbonate-based polyurethane with a 100% modulus of 4.5 MPa was heat-shrinked so that the content of the polymeric elastomer in the napped artificial leather was 18% by mass.
  • DMF solution solid content 15%
  • (Comparative example 5) Prepare polyethylene terephthalate (PET) as the island component and polyethylene as the sea component, and use a melting composite nozzle so that the number of islands is 16, and pressurize so that the mass ratio of the sea component/island component is 35/65. After adjusting the nozzle temperature setting to 280°C and discharging at a single hole discharge rate of 1.2 g/min, and spinning at a spinning speed of 820 m/min, stretching and crimping are performed to obtain sea islands, which are short fibers with a fineness of 3.6 dtex. A composite fiber was obtained. The obtained sea-island composite fibers were passed through a card to produce a short fiber web.
  • PET polyethylene terephthalate
  • a plurality of sheets of the obtained web were laminated to form a laminated web. Then, the laminated web was subjected to needle punching using a 1-barb needle at a punching density of 2050 punches/cm 2 to form an entangled web with a basis weight of 600 g/m 2 . The resulting entangled web was subjected to shrinkage treatment with hot water at 90°C, dried, and then hot pressed to obtain a heat-shrinkable entangled web with a basis weight of 800 g/m 2 .
  • a DMF solution solid content 15% by mass of a polycarbonate polyurethane having a 100% modulus of 4.5 MPa, which is a polymeric elastic material, was added so that the content of the polymeric elastic material in the napped artificial leather was 40% by mass.
  • :DMF was immersed in a DMF aqueous solution having a mass ratio of 70:30 to coagulate the polycarbonate-based polyurethane, thereby imparting polycarbonate-based polyurethane (polyurethane-based resin) to the entangled web.
  • the entangled web to which the polyurethane resin has been applied is dipped in toluene at 85°C while being nipped to dissolve and remove the polyethylene, which is a sea component, and then dried.
  • a nonwoven fabric to which a polyurethane resin was applied as a polymeric elastomer was obtained.
  • the fabric weight of the obtained nonwoven fabric was 654 g/m 2 .
  • the obtained nonwoven fabric was cut in half in the thickness direction to make artificial leather raw material, and the half-cut side was buffed with #180 and #240 sandpaper, and then the non-half-cut side was ground with #320 and #600 sandpaper.
  • a napped artificial leather having a napped surface was obtained by buffing one side of the material.
  • the obtained raised artificial leather was colored by adjusting the disperse dye to a dye concentration of 6% owf, performing high-pressure dyeing at 130 ° C in a circular dyeing machine, and then performing reduction cleaning, oxidation treatment, and water washing.
  • a raised artificial leather was obtained. Table 1 shows the evaluation results of the colored raised artificial leather.
  • the napped artificial leather obtained in Comparative Example 1 has a polymer elastomer content in the range of 15 to 35% by mass and a napped fiber length of 250 ⁇ m or less;
  • the area ratio of the body was more than 17%, and the polymeric elastic material (polyurethane resin) was visible unevenly from the raised surface, causing uneven dyeing.
  • the napped artificial leather obtained in Comparative Example 2 has an elastic polymer content in the range of 15 to 35% by mass, and the area ratio of the elastic polymer present on the napped surface is 17% or less.
  • the napped fiber length was more than 250 ⁇ m, and the napped fibers were coarsely scattered and had non-uniform lengths, giving a rough feel and no writing.
  • the napped artificial leather obtained in Comparative Example 3 has a polymer elastomer content in the range of 15 to 35% by mass, and a napped fiber length of 250 ⁇ m or less.
  • the area ratio is over 17%. Since the polymeric elastomer contained carbon black, uneven dyeing was somewhat suppressed, but it still occurred to a visible degree.
  • the area ratio of the polymeric elastomer present on the napped surface is 17% or less, and the napped fiber length is 250 ⁇ m or less. did not satisfy the lower limit of the range of 15 to 35% by mass, and this napped artificial leather had poor flexibility and elasticity, and had a hard texture.
  • the napped artificial leather obtained in Comparative Example 5 is a napped artificial leather with a thickness of 0.4 mm using staple fibers, and the napped fiber length is 250 ⁇ m or less. Since the amount exceeds the upper limit of the range of 15 to 35% by mass, and the area ratio of the polymeric elastic material present on the napped surface is more than 17%, the polymeric elastic material (polyurethane resin) is uneven from the napped surface. It was visually recognized that uneven dyeing had occurred, and it did not have sufficient mechanical strength.

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JP2008280643A (ja) * 2007-05-11 2008-11-20 Kuraray Co Ltd スエード調人工皮革およびその製造方法
JP2015509149A (ja) * 2012-01-17 2015-03-26 アルカンターラ エス．ピー．エー．Ａｌｃａｎｔａｒａ Ｓ．Ｐ．Ａ． 極細繊維製品と、カバーおよび容器の製造のためのその使用方法
WO2020003866A1 (ja) * 2018-06-29 2020-01-02 東レ株式会社 シート状物およびその製造方法
WO2020189592A1 (ja) * 2019-03-20 2020-09-24 東レ株式会社 シート状物
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JP2016011477A (ja) 2014-06-30 2016-01-21 東レ株式会社 人工皮革用基体およびその製造方法
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JP2004143654A (ja) * 2002-09-30 2004-05-20 Kuraray Co Ltd スエード調人工皮革およびその製造方法
JP2008280643A (ja) * 2007-05-11 2008-11-20 Kuraray Co Ltd スエード調人工皮革およびその製造方法
JP2015509149A (ja) * 2012-01-17 2015-03-26 アルカンターラ エス．ピー．エー．Ａｌｃａｎｔａｒａ Ｓ．Ｐ．Ａ． 極細繊維製品と、カバーおよび容器の製造のためのその使用方法
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