WO2013065608A1 - Article de type feuille et son procédé de fabrication - Google Patents

Article de type feuille et son procédé de fabrication Download PDF

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Publication number
WO2013065608A1
WO2013065608A1 PCT/JP2012/077767 JP2012077767W WO2013065608A1 WO 2013065608 A1 WO2013065608 A1 WO 2013065608A1 JP 2012077767 W JP2012077767 W JP 2012077767W WO 2013065608 A1 WO2013065608 A1 WO 2013065608A1
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WIPO (PCT)
Prior art keywords
polyurethane
water
sheet
dispersed
polycarbonate
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PCT/JP2012/077767
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English (en)
Japanese (ja)
Inventor
現 小出
俊一郎 中井
行博 松崎
西村　誠
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東レ株式会社
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Priority to JP2013510814A priority Critical patent/JP6007900B2/ja
Publication of WO2013065608A1 publication Critical patent/WO2013065608A1/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
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • 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 is a sheet-like material, particularly a leather-like sheet-like material that does not use an organic solvent in the production process, and has both a soft texture and good wrinkle recovery property that does not cause wrinkles, and has high durability.
  • the present invention relates to a sheet-like material and a manufacturing method thereof.
  • a leather-like sheet mainly composed of a fibrous base material and polyurethane has excellent characteristics not found in natural leather and is widely used in various applications.
  • a leather-like sheet-like material using a polyester-based fibrous base material is excellent in light resistance, and therefore its use has been expanded year by year for clothing, chair upholstery, automobile interior materials, and the like.
  • a step of impregnating a fibrous base material with an organic solvent solution of polyurethane, and the fibrous base material obtained in this step in water or an organic solvent aqueous solution which is a non-solvent of polyurethane is generally employed.
  • a water-miscible organic solvent such as N, N-dimethylformamide is used as the organic solvent that is a solvent for such polyurethane.
  • N, N-dimethylformamide is used as the organic solvent that is a solvent for such polyurethane.
  • the polyurethane in the case of using a conventional organic solvent type polyurethane, since the fiber base material is impregnated and then solidified by a wet coagulation method generally immersed in water, the polyurethane is obtained by replacing the organic solvent with water. It becomes a porous structure. Thereby, polyurethane does not strongly hold the entangled portion of the fibers of the fibrous base material, and the texture of the sheet-like material becomes flexible.
  • the solidification after impregnation of the fibrous base material is generally a dry heat coagulation method in which it is dried by heating, so that the polyurethane has a nonporous structure. As a result, polyurethane strongly grips the entangled portions of the fibers of the fibrous base material, so that the texture of the sheet-like material becomes hard.
  • the elastic modulus at a temperature of 90 ° C. of a 100 ⁇ m-thick film having heat-sensitive gelation property and dried at a temperature of 50 ° C. is 2.0 ⁇
  • T ⁇ ⁇ dispersion temperature
  • the proposed method can obtain a sheet-like material having a soft texture
  • the use of a flexible polyurethane as in this proposal deteriorates the wear resistance of the sheet-like material, and when the material is ground and brushed. Since sandpaper or the like used for clogging is easily clogged, it is difficult to obtain good napped quality, and productivity is also poor.
  • an object of the present invention is to provide a sheet-like material that has a soft texture and high durability in a sheet-like material, particularly a leather-like sheet-like material, and that can exhibit good wrinkle recovery properties.
  • Another object of the present invention is to provide a method for producing an environmentally friendly sheet-like material that does not use an organic solvent in the production process in the method for producing the sheet-like material.
  • the present invention is to achieve the above-mentioned object, and the sheet-like material of the present invention is a water-dispersed type inside a fibrous base material comprising ultrafine fibers having an average single fiber diameter of 0.3 to 7 ⁇ m. It contains polyurethane, and a part of the water-dispersed polyurethane is unevenly attached to the outer peripheral portion of the bundle of ultrafine fibers and contains a substance having an amide bond, and this ultrafine fiber bundle
  • the water-dispersed polyurethane other than the part that is unevenly distributed on the outer peripheral part of the water-containing polyurethane contains water-dispersed polycarbonate-based polyurethane.
  • the “outer peripheral portion of the ultrafine fiber bundle” refers to a shape formed by connecting the centers of the ultrafine single fibers existing along the outer periphery in a straight line in the cross section in the thickness direction of the ultrafine fiber bundle.
  • distributed unevenly on the outer peripheral portion of the ultrafine fiber bundle means that the water-dispersed polyurethane is attached to the area surrounded by the outer peripheral portion by entering inside the ultrafine fiber bundle from the outer peripheral portion.
  • the area ratio is 20% or less.
  • the substance having an amide bond has a molecular weight of 100 to 500.
  • the water-dispersed polyurethane adhering to the outer peripheral portion of the ultrafine fiber bundle is a polycarbonate-based polyurethane or an ether-based polyurethane.
  • the water-dispersed polyurethane adhering to and adhering to the outer peripheral part of the ultrafine fiber bundle and / or adhering to and adhering to the outer peripheral part of the ultrafine fiber bundle contains silicone, and more preferably, the silicone is a film-forming silicone.
  • a water-dispersed polyurethane liquid containing a foaming agent is applied to a fibrous base material containing ultrafine fiber-expressing fibers, and then averaged from the ultrafine fiber-expressing fibers.
  • the present invention is characterized in that after an ultrafine fiber having a single fiber diameter of 0.3 to 7 ⁇ m is expressed, a water-dispersed polycarbonate polyurethane liquid is applied.
  • the water-dispersed polyurethane liquid containing a foaming agent to be applied before the development of the ultrafine fibers is a polycarbonate-based polyurethane or an ether-based polyurethane liquid. More preferably, it contains inorganic particles, and more preferably, the inorganic particles are porous silica.
  • the water dispersion-type polycarbonate-type polyurethane provided after making the water dispersion-type polyurethane liquid containing the said foaming agent and / or the said ultrafine fiber express.
  • the liquid contains a silicone water dispersion, and more preferably, the silicone water dispersion is a film-forming silicone water dispersion.
  • a soft texture and a good wrinkle recovery property that does not wrinkle when expanded after folding in a sheet-like material obtained by an environment-friendly manufacturing method that does not use an organic solvent in the manufacturing process, a soft texture and a good wrinkle recovery property that does not wrinkle when expanded after folding.
  • a sheet-like material having durability that can be applied to applications that require high durability such as automobile applications can be obtained.
  • the sheet-like material of the present invention contains water-dispersible polyurethane inside a fibrous base material comprising ultrafine fibers having an average single fiber diameter of 0.3 to 7 ⁇ m, and a part of this water-dispersible polyurethane is
  • the water-dispersed polyurethane other than the portion that is unevenly distributed and attached to the outer peripheral portion of the bundle made of the above-mentioned ultrafine fibers and contains a substance having an amide bond and that is unevenly distributed and attached to the outer peripheral portion of this ultrafine fiber bundle is A sheet-like product containing water-dispersed polycarbonate polyurethane.
  • a fiber made of a thermoplastic resin that can be melt-spun can be used.
  • the thermoplastic resin is not limited to a specific one.
  • polyester such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate or polylactic acid, polyamide such as 6-nylon and 66-nylon, polyacryl, polyethylene And polypropylene, and thermoplastic cellulose.
  • polyester fibers are preferably used from the viewpoints of strength, dimensional stability, and light resistance.
  • the fibrous base material may be configured by mixing fibers of different materials.
  • the cross-sectional shape of the fibers constituting the fibrous base material may be a round cross section, but a polygonal shape such as an ellipse, a flat shape, and a triangle, or a deformed cross section such as a sector shape and a cross shape may be employed.
  • These fibers are made of ultrafine fibers, and the average single fiber diameter is 0.3 to 7 ⁇ m. By setting the average single fiber diameter of the ultrafine fibers to 7 ⁇ m or less, more preferably 6 ⁇ m or less, and even more preferably 5 ⁇ m or less, a sheet-like product having excellent flexibility and napping quality can be obtained.
  • the coloring property after dyeing or the napping treatment such as grinding with sandpaper can be used. Excellent dispersibility of bundled fibers and ease of judgment.
  • the form of the fibrous base material composed of the above ultrafine fibers woven fabrics, knitted fabrics, non-woven fabrics and the like can be employed.
  • a nonwoven fabric is used preferably.
  • the nonwoven fabric may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric, but a short fiber nonwoven fabric is preferably used in terms of texture and quality.
  • the fiber length of the short fibers used in the above-mentioned short fiber nonwoven fabric is preferably 25 to 90 mm, more preferably 30 to 80 mm.
  • the fiber length of the short fibers is preferably 25 to 90 mm, more preferably 30 to 80 mm.
  • the non-woven fabric When the fibrous base material is a non-woven fabric, the non-woven fabric preferably has a structure in which bundles of ultrafine fibers (ultrafine fiber bundles) are entangled. Since the ultrafine fibers are entangled in a bundle state, the strength of the sheet-like material is improved. As will be described later, the nonwoven fabric of this aspect can be obtained by expressing the ultrafine fibers after entanglement of the ultrafine fiber-expressing fibers in advance.
  • ultrafine fibers ultrafine fiber bundles
  • the ultrafine fiber or the ultrafine fiber bundle constitutes a nonwoven fabric
  • a woven fabric or a knitted fabric may be inserted into the nonwoven fabric for the purpose of improving the strength.
  • the average single fiber diameter of the fibers constituting the woven or knitted fabric is preferably about 0.3 to 10 ⁇ m.
  • the basis weight of the fibrous base material is too low, physical properties such as tensile strength and tearing strength of the sheet-like material are weakened. If it is too high, the texture of the sheet-like material is hardened, so 50 to 2000 g / m 2. It is preferable that Further, if the thickness of the fibrous base material is too thin, physical properties such as tensile strength and tearing strength of the sheet-like material will be weak, and if it is too thick, the texture of the sheet-like material will be hard. It is preferable that
  • the polyurethane used in the present invention is preferably a polyurethane obtained by a reaction of a polymer diol, an organic diisocyanate, and a chain extender.
  • Ether-based polyurethane is an ether-based polymer in which 70% by mass or more of the polymer diol constituting the polyurethane is ether-based.
  • the polycarbonate-based polyurethane means that 70% by mass or more of the polymer diol constituting the polyurethane is polycarbonate-based.
  • Ether-based polyurethanes are generally flexible and have good hydrolysis resistance, but are poor in light resistance and heat resistance.
  • Polycarbonate-based polyurethanes are generally harder than ether-based polyurethanes and are resistant to hydrolysis. Although the polyurethane has good durability such as degradability, light resistance and heat resistance, different types of polymer diols may be copolymerized as long as each good characteristic is not affected.
  • ether-based polymer diol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymerized diols obtained by combining them.
  • the polycarbonate-based polymer diol can be produced by an ester exchange reaction between an alkylene glycol and a carbonate ester, or a reaction between phosgene or chloroformate ester and an alkylene glycol.
  • alkylene glycols examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol.
  • Chain alkylene glycols branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol or 2-methyl-1,8-octanediol, Alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol. Either a polycarbonate diol obtained from a single alkylene glycol or a copolymerized polycarbonate diol obtained from two or more types of alkylene glycols may be used.
  • the number average molecular weight of the polymer diol is preferably 500 to 4000. By setting the number average molecular weight to 500 or more, more preferably 1500 or more, it is possible to prevent the texture from becoming hard. Moreover, the intensity
  • organic diisocyanates examples include aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and aromatic diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. You may use it in combination.
  • aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferably used from the viewpoint of light resistance.
  • chain extender amine chain extenders such as ethylenediamine and methylenebisaniline, or diol chain extenders such as ethylene glycol can be used.
  • the polyamine obtained by making polyisocyanate and water react can also be used as a chain extender.
  • a crosslinking agent may be used in combination for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like.
  • the cross-linking agent may be an external cross-linking agent added as a third component to the polyurethane, or may be an internal cross-linking agent that introduces a reaction point that becomes a cross-linked structure in advance in the polyurethane molecular structure.
  • a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, or a silanol group can be suitably used.
  • the polyurethane used in the present invention preferably has a hydrophilic group in the molecular structure.
  • a hydrophilic group in the molecular structure it is possible to improve dispersion / stability as a water-dispersed polyurethane.
  • hydrophilic group examples include cationic systems such as quaternary amine salts, anionic systems such as sulfonates and carboxylates, nonionic systems such as polyethylene glycol, and combinations of cationic and nonionic hydrophilic groups. And any hydrophilic group of a combination of anionic and nonionic hydrophilic groups can be employed. Of these, nonionic hydrophilic groups that are free from yellowing caused by light and harmful effects caused by a neutralizing agent are particularly preferably used.
  • the hydrophilic group is anionic
  • a neutralizing agent is tertiary, such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine, or dimethylethanolamine.
  • the amine is generated and volatilized by heat during film formation and drying, and is released out of the system. For this reason, in order to suppress the release of air and the deterioration of the working environment, it is essential to introduce a device for recovering volatile amines.
  • the above amine does not volatilize by heating and remains in the final product sheet, the amine may be discharged into the environment when the product is incinerated.
  • the hydrophilic group is a nonionic system, no neutralizer is used, so there is no need to introduce an amine recovery device, and there is no concern about remaining amine in the sheet.
  • the neutralizing agent is an alkali metal such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or a hydroxide of an alkaline earth metal
  • the polyurethane part exhibits alkalinity when wet.
  • a water-dispersible polyurethane is contained inside the fibrous base material, and a part of this water-dispersible polyurethane is unevenly attached to the outer peripheral portion of the bundle of the above-mentioned ultrafine fibers and has an amide bond.
  • the water-dispersed polyurethane other than the portion that is unevenly distributed and attached to the outer peripheral portion of the ultrafine fiber bundle contains water-dispersed polycarbonate-based polyurethane.
  • the substance having an amide bond is a decomposition product of an organic foaming agent in a method for producing a sheet-like material described later.
  • an organic foaming agent for example, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) Propionamide] (for example, “VA-086” manufactured by Wako Pure Chemical Industries, Ltd.) and 2,2′-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propion Amide ⁇ (for example, “VA-080” manufactured by Wako Pure Chemical Industries, Ltd.)
  • the fact that the water-dispersible polyurethane contains a substance having an amide bond, which is a decomposition product of the foaming agent indicates that the water-dispersible polyurethane is foamed by the gas generated by the decomposition of the foaming agent.
  • the molecular weight of the substance having an amide bond is too low, it is vaporized by heating at the time of foaming.Therefore, there are problems such as odor and safety of workers in the process, and environmental outflow, and if the molecular weight is too high, Since the ratio of the amount of gas generated relative to the mass added to the water-dispersed polyurethane is small and the foaming effect is low, the molecular weight of this substance is preferably 100 to 500, more preferably 150 to 450.
  • the content of the substance having an amide bond contained in the water-dispersed polyurethane adhering to and adhering to the outer periphery of the bundle of ultrafine fibers is 0.5 to 20% by mass relative to the polyurethane solid content. Is preferred. Since the substance having an amide bond is a decomposition product of the foaming agent, the texture of the sheet-like material due to foaming has a softening effect by setting its content to 0.5 mass% or more, more preferably 1 mass% or more. Can be effectively obtained. On the other hand, by setting the content of the substance having an amide bond to 20% by mass or less, more preferably 15% by mass or less, it is possible to suppress a decrease in wear resistance of the sheet-like material due to excessive foaming.
  • the type of water-dispersed polyurethane containing a substance having an amide bond that is unevenly distributed and attached to the outer peripheral portion of the bundle of ultrafine fibers is preferably polycarbonate polyurethane or ether polyurethane.
  • the water-dispersed polyurethane containing a substance having an amide bond is unevenly attached to the outer peripheral portion of the bundle of the ultrafine fibers and the water-dispersed ether-based polyurethane is used, this water
  • the dispersed ether-based polyurethane grips the fiber entanglement point of the fibrous base material to soften the texture of the sheet-like material, and the water-dispersed polyurethane other than the part that is unevenly distributed and attached to the outer peripheral portion of the ultrafine fiber bundle is water.
  • a dispersed polycarbonate polyurethane good wrinkle recovery and durability such as light resistance and heat resistance are exhibited.
  • the wrinkle recovery property, Durability such as light resistance and heat resistance can be expressed, and as will be described later, the water-dispersed polycarbonate polyurethane containing a substance having an amide bond is unevenly distributed on the outer peripheral portion of the ultrafine fiber bundle, The texture of the sheet can be softened and good wrinkle recovery can be achieved.
  • the type of the water-dispersed polyurethane containing a substance having an amide bond that is unevenly distributed and attached to the outer peripheral portion of the bundle composed of the ultrafine fibers is a water-dispersed polycarbonate polyurethane
  • the amide bond The texture of the sheet-like material is softened as an adhesion structure that does not directly grip the fiber entanglement point of the fibrous base material with a water-dispersible polycarbonate-based polyurethane containing a substance having a property, and further added to the outer peripheral portion of this ultrafine fiber bundle Together with the water-dispersed polycarbonate polyurethane other than the part that is unevenly distributed, it exhibits good wrinkle recovery and also exhibits good durability such as light resistance and heat resistance.
  • Water-dispersed polyurethane adhering to and adhering to the outer peripheral part of the above-mentioned ultrafine fiber bundle, and a part other than the part adhering to and adhering to the outer peripheral part of this extrafine fiber bundle
  • Water-dispersed polycarbonate polyurethane is not limited to a specific content, but is reinforced to the mass of the ultrafine fibers that form the fibrous base material, and the fibrous base material is reinforced to a non-woven fabric made of ultrafine fibers or bundles of ultrafine fibers.
  • the content is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, based on the total mass. If the polyurethane content is too small, the tensile strength, tear strength, wear resistance, etc. of the sheet-like material will decrease, and if it is too high, the texture of the sheet-like material will become hard and the basis weight will become heavier.
  • the water-dispersed polyurethane containing the mass (U) of the entire water-dispersible polyurethane contained inside the fibrous base material and a substance having an amide bond that is unevenly attached to the outer peripheral portion of the ultrafine fiber bundle The mass (U2) of the water-dispersed polycarbonate-based polyurethane other than the portion that is unevenly distributed and attached to the outer peripheral portion of the ultrafine fiber bundle (U2) is not limited to a specific value.
  • the entire polyurethane is 10 to 50% by mass, and the water-dispersed polyurethane adhering to and adhering to the outer peripheral part of the ultrafine fiber bundle is 1 to 35% by mass, and the polyurethane is unevenly distributed to the outer peripheral part of the ultrafine fiber bundle.
  • the water-dispersed polycarbonate-based polyurethane other than the adhering part is preferably 1 to 40% by mass. Further, the mass (U1) of the water-dispersed polyurethane adhering to and adhering to the outer peripheral portion of the ultrafine fiber bundle and the outer peripheral portion of the extrafine fiber bundle with respect to the mass (U) of the entire water-dispersible polyurethane.
  • the ratio of the mass (U2) of the water-dispersed polycarbonate polyurethane other than the adhering part is 1 to 90% for (U1) / (U) and 1 to 99% for (U2) / (U). Preferably there is.
  • the ratio of the mass (U1) of the water-dispersed polyurethane containing a substance having an amide bond that is unevenly distributed and attached to the outer peripheral portion of the ultrafine fiber bundle is high, and the ratio of the mass (U2) of the polycarbonate-based polyurethane is low. If it is too much, the wrinkle recovery property and durability of the sheet are lowered, and the mass ratio of the mass (U1) of the water-dispersed polyurethane containing a substance having an amide bond that is unevenly distributed and attached to the outer peripheral portion of the ultrafine fiber bundle is low, This is because if the ratio of the mass (U2) of the polycarbonate-based polyurethane is too high, the flexibility of the sheet is lowered.
  • the above “inside of the fibrous base material” refers to a range from one surface to the other surface, and when the fibrous base material has a raised layer, the raised layer is included.
  • a range For example, when one surface has a raised layer, it means the range from the raised layer to the other surface when the fibrous base material is viewed from a cross section, and when both surfaces have a raised layer. It means the range from the upper surface raised layer to the lower surface raised layer when the fibrous base material is viewed from the cross section.
  • the water-dispersed polyurethane containing a substance having an amide bond that is unevenly distributed and attached to the outer peripheral portion of the above-described ultrafine fiber bundle used in the present invention employs a foamed structure with a foaming agent.
  • the foaming agent refers to an additive that decomposes when heated to generate nitrogen gas, carbon dioxide gas, or the like.
  • the texture of the sheet-like material containing the polyurethane becomes flexible. This is because the binding force between the fibers in the sheet-like material is reduced and the binding force between the fibers is weakened.
  • said water dispersion type polyurethane contains the substance which has an amide bond as a residue which remains after a foaming agent foams.
  • foaming agent added to the water-dispersed polyurethane liquid examples include azoisobutylnitrile, dinitrosopentamethylenetetramine (for example, “Cermic (registered trademark) A” manufactured by Sankyo Kasei Co., Ltd.), azodicarbonamide (for example, “Cermic (registered trademark) CAP” manufactured by Sankyo Kasei Co., Ltd.), p, p′-oxybisbenzenesulfonyl hydrazide (for example, “Cermic® (registered trademark) S” manufactured by Sankyo Kasei), N, N′-dinitroso Pentamethylenetetramine (for example, “Cellular GX” manufactured by Eiwa Chemical Industries) or 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (for example, manufactured by Wako Pure Chemical Industries, Ltd.) VA-086 "), 2,2'-azobis ⁇ 2-methyl-N- [
  • a part of the water-dispersed polyurethane used in the present invention is unevenly distributed on the outer peripheral portion of the ultrafine fiber bundle and contains a substance having an amide bond.
  • a water-dispersed polyurethane containing a substance having an amide bond is unevenly attached to the outer peripheral portion of the ultrafine fiber bundle, and does not adhere to the inner side of the outer peripheral portion of the ultrafine fiber bundle, thereby reducing the binding force of the fiber and the sheet The texture of the material becomes flexible.
  • the water-dispersible polyurethane containing the above-mentioned substance having an amide bond is flexible, this water-dispersible polyurethane is applied to remove sea components of sea-island fibers and then subjected to a process such as dyeing. Due to physical compression / stagnation in the process, a part of the water-dispersed polyurethane may adhere to the inner side of the outer periphery of the ultrafine fiber bundle.
  • the water-dispersed polyurethane that is unevenly distributed and attached to the outer peripheral portion of the above-mentioned ultrafine fiber bundle is made porous by a foaming agent, the water-dispersed polyurethane containing the substance having this amide bond It is possible to ensure a wide gap between the fiber bundle and the ultrafine fiber bundle, and clearly this water-dispersed polyurethane is unevenly distributed on the outer peripheral portion of the ultrafine fiber bundle.
  • the “outer peripheral portion of the ultrafine fiber bundle” refers to a shape formed by connecting the centers of the ultrafine single fibers existing along the outer periphery with a straight line in the cross section in the thickness direction of the ultrafine fiber bundle.
  • the fibers of the reinforcing woven or knitted fabric are excluded from the object.
  • the water-dispersed polyurethane is unevenly distributed and adhered to the outer peripheral portion of the ultrafine fiber bundle means that the above water is disposed inside the ultrafine fiber bundle with respect to the area surrounded by the outer peripheral portion. A state in which the proportion of the area where the dispersed polyurethane is contained is 20% or less.
  • the water-dispersed polycarbonate polyurethane used in the present invention is a substance having an amide bond that forms a porous structure inside the fibrous base material. It adheres to the water-dispersed polyurethane contained. Focusing only on this water-dispersed polycarbonate-based polyurethane, a porous structure similar to the water-dispersed polyurethane containing the above-mentioned substance having an amide bond is formed inside the fibrous base material. Even a dispersion-type polycarbonate-based polyurethane can exhibit a soft texture as a sheet-like material.
  • Polyurethane exists without being mixed with each other.
  • the water-dispersed polycarbonate polyurethane other than the portion that is unevenly distributed and attached to the outer peripheral portion of the ultrafine fiber bundle may contain a substance having an amide bond in order to make the texture of the sheet-like material flexible. Although it does not contain a substance having an amide bond, it is more preferable because the durability of the sheet-like material can be improved.
  • the water-dispersed polyurethane that is unevenly attached to the outer peripheral portion of the ultrafine fiber bundle used in the present invention and / or the polycarbonate polyurethane other than the portion that is unevenly attached to the outer peripheral portion of the ultrafine fiber bundle is silicone. It is preferable to contain.
  • the polyurethane contains silicone, the frictional force between the polyurethane and the fibers of the fibrous base material can be reduced, and the texture of the sheet can be made more flexible. Further, since grinding with sandpaper or the like can be easily performed in the raising step, the length of napping can be increased, and clogging of the grinding powder into the sandpaper is less likely to occur, and the operability is improved.
  • the silicone content relative to the polyurethane is not limited to a specific value, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass relative to the mass of polyurethane. This is because if the silicone content is too low, the effect of softening the sheet-like material becomes insufficient, and if it is too high, the force with which the polyurethane grips the fibers is weakened in the sheet-like material, resulting in a decrease in wear resistance. .
  • a film-forming silicone is a silicone that becomes a three-dimensional cross-linked structure when heated and cannot be redispersed in water. The film-forming property allows the sheet to be washed and dyed after application of the film-forming silicone. Even when there are external factors such as handling in water such as washing and friction, the silicone is prevented from falling off the sheet, and the flexibility of the sheet can be maintained.
  • the fiber base material is impregnated with a water-dispersible polyurethane liquid containing a film-forming silicone water dispersion, and then the sheet is treated with hot water and / or an alkaline aqueous solution to make the fibers extremely fine. Further, the flexibility of the sheet can be maintained due to the film-forming property of silicone.
  • “the film-forming silicone remains in the sheet even after the fiber ultrafine treatment” means that the measured weight value of the sheet after the ultrafine treatment is compared with the theoretical calculation value, and the difference is 30%. It is within.
  • the water-dispersed polyurethane used in the present invention other than the water-dispersed polyurethane adhering to and adhering to the outer peripheral portion of the ultrafine fiber bundle and the portion adhering to and adhering to the outer peripheral portion of the ultrafine fiber bundle, Various additives such as pigments such as carbon black, flame retardants such as phosphorus, halogen, silicone and inorganic, antioxidants such as phenol, sulfur and phosphorus, benzotriazole, benzophenone and salicylate UV absorbers such as cyanoacrylates, oxalic acid anilides, light stabilizers such as hindered amines and benzoates, hydrolysis stabilizers such as polycarbodiimides, plasticizers, antistatic agents, surfactants, Softeners, water repellents, coagulation regulators, dyes, preservatives, antibacterial agents, deodorants, fillers such as cellulose particles, There is a like inorganic particles such as silica or titanium oxide may contain singly or in
  • the thickness of the sheet-like material obtained in the present invention is too thin, physical properties such as tensile strength and tearing strength of the sheet-like material are weakened, and when too thick, the texture of the sheet-like material becomes hard. 5 mm is preferable.
  • a method for producing the sheet-like material of the present invention will be described.
  • a specific water-dispersed polyurethane liquid is applied to the fibrous base material, and then the ultrafine fibers are expressed from the fibrous base material, and then the specific water-dispersed polyurethane liquid is applied. To do.
  • the form of the fibrous base material composed of the above ultrafine fibers woven fabrics, knitted fabrics, non-woven fabrics and the like can be employed.
  • a nonwoven fabric is used preferably.
  • the nonwoven fabric may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric, but a short fiber nonwoven fabric is preferably used in terms of texture and quality.
  • the method for entanglement of fibers or fiber bundles is not limited to a specific method, and for example, a needle punch or a water jet punch can be employed.
  • the ultrafine fiber expression type fiber As a means for forming the ultrafine fiber of the fibrous base material, it is preferable to use an ultrafine fiber expression type fiber.
  • the ultrafine fiber expression type fiber By using the ultrafine fiber expression type fiber, a form in which the ultrafine fiber bundles are entangled can be stably obtained.
  • the ultra-fine fiber development type fiber is a sea island in which two component thermoplastic resins with different solvent solubility are used as a sea component and an island component, and the remaining island component is dissolved and removed using a solvent or the like, and the remaining island component is used as an ultra-fine fiber. It is possible to employ a release type composite fiber that splits into ultrafine fibers by alternately disposing a mold fiber or a two-component thermoplastic resin in a radial or multilayered manner on the fiber cross section and separating and separating each component.
  • the sea-island type fiber can be preferably used also from the viewpoint of flexibility and texture of the sheet-like material because it can provide an appropriate gap between the island components, that is, between the ultrafine fibers, by removing the sea component.
  • sea-island type fiber a sea-island type compound base is used, and the sea-island type composite fiber that spins the sea component and the island component by mutual arrangement and the sea component and the island component are mixed and spun.
  • Sea-island type composite fibers are preferably used from the viewpoint that ultrafine fibers having a uniform fineness can be obtained, and that a sufficiently long ultrafine fiber is obtained and contributes to the strength of the sheet-like material.
  • polyethylene, polypropylene, polystyrene, copolymer polyester obtained by copolymerizing sodium sulfoisophthalic acid or polyethylene glycol, polylactic acid, polyvinyl alcohol, or the like can be used.
  • alkali-degradable, copolyester or polylactic acid copolymerized with sodium sulfoisophthalic acid or polyethylene glycol, which can be decomposed without using an organic solvent, and polyvinyl alcohol capable of removing sea components with hot water are preferable. Used.
  • the sea removal treatment for eluting and removing the sea components of the sea-island fibers can be performed by immersing the sea-island fibers in a solvent and squeezing it.
  • a solvent for dissolving the sea component when the sea component is polyethylene, polypropylene, or polystyrene, an organic solvent such as toluene or trichloroethylene can be used.
  • an alkaline aqueous solution such as sodium hydroxide can be used, and when the sea component is polyvinyl alcohol, hot water can be used.
  • Sea removal treatment when sea-island type fibers are used is performed after application of water-dispersed polyurethane containing a foaming agent to the fibrous base material.
  • the texture of the sheet-like material becomes hard because the polyurethane is in close contact with the ultrafine fibers and strongly grips the ultrafine fibers.
  • the sea removal treatment is performed after the application of the water-dispersible polyurethane containing the foaming agent, the void caused by the sea component removed from the water-dispersible polyurethane containing the substance having an amide bond and the ultrafine fibers
  • the water-dispersed polyurethane is unevenly distributed and attached to the outer peripheral portion of the ultrafine fiber bundle.
  • the structure becomes such that the water-dispersed polyurethane containing the substance having a direct amide bond does not grip the ultrafine fiber, the texture of the sheet-like material becomes flexible. Furthermore, as will be described later, the water-dispersed polyurethane forms a porous structure inside the fibrous base material by containing a foaming agent. By creating voids due to foaming of the foaming agent between the sea-island fibers and the water-dispersed polyurethane, the permeability of the sea component extraction solvent in the sea removal process is improved, and the sea removal efficiency is increased. Even a porous substrate or a sheet with a large amount of polyurethane can be easily removed from the sea.
  • a water-dispersed polyurethane liquid containing a foaming agent is applied to the fibrous base material, and then after the ultrafine fibers are expressed from the fibrous base material, the water-dispersed polycarbonate-based polyurethane liquid is applied.
  • the water-dispersed polyurethane liquid containing the foaming agent is an ether-based polyurethane liquid
  • the water-dispersed polycarbonate-based polyurethane liquid is applied after the water-dispersed ether-based polyurethane liquid containing the foaming agent is applied and then the ultrafine fibers are expressed.
  • the water-dispersible polyurethane liquid containing the foaming agent is a polycarbonate-based polyurethane liquid
  • the water-dispersible polycarbonate-based polyurethane liquid containing the foaming agent is applied, and then the ultrafine fibers are expressed, and then the water-dispersible polycarbonate-based liquid is used.
  • a dense surface appearance and good wear resistance can be imparted to the sheet-like material by the polyurethane.
  • the water-dispersed polyurethane containing a substance having an amide bond that has been imparted before the development of ultrafine fibers will be described later.
  • a foaming agent By containing a foaming agent, a porous structure is formed inside the fibrous base material.
  • the polycarbonate-based polyurethane liquid thereto the polycarbonate-based polyurethane adheres to the porous structure of the polyurethane containing a substance having an amide bond.
  • the polyurethane liquid containing a foaming agent that is applied before the development of ultrafine fibers and the polycarbonate-based polyurethane liquid that is applied after the development of ultrafine fibers are used in the present invention as water dispersed and stabilized in water.
  • a dispersed polyurethane liquid is used.
  • This water-dispersible polyurethane is a forced emulsification type polyurethane that is forcibly dispersed and stabilized using a surfactant, and has a hydrophilic structure in the polyurethane molecular structure, and even in the absence of a surfactant, Although classified into the self-emulsifying type polyurethane which is dispersed and stabilized, any of them may be used in the present invention.
  • the concentration of the water-dispersible polyurethane (content of polyurethane relative to the water-dispersible polyurethane liquid) is preferably 5 to 50% by mass, more preferably 10% from the viewpoint of storage stability of the water-dispersible polyurethane liquid. ⁇ 40% by weight.
  • the water-dispersed polyurethane liquid may contain a water-soluble organic solvent in an amount of 40% by mass or less based on the water-dispersed polyurethane liquid in order to improve storage stability and film-forming property.
  • the content of the organic solvent is preferably 1% by mass or less.
  • the water-dispersed polyurethane liquid used in the present invention preferably has heat-sensitive coagulation properties.
  • heat-sensitive coagulation property refers to a property in which, when a water-dispersed polyurethane liquid is heated, the fluidity of the water-dispersible polyurethane liquid is reduced and solidified when a certain temperature (heat-sensitive coagulation temperature) is reached.
  • the sheet with polyurethane of the present invention after applying the water-dispersed polyurethane liquid to the fibrous base material, it is solidified by dry heat coagulation, wet heat coagulation, wet coagulation, or a combination thereof, and dried.
  • polyurethane can be imparted to the fibrous base material.
  • the heat-sensitive coagulation temperature of the water-dispersed polyurethane liquid is not limited to a specific temperature, but is preferably 40 to 90 ° C.
  • the heat-sensitive coagulation temperature is more preferably 50 ° C. to 80 ° C.
  • a heat-sensitive coagulant may be added as appropriate.
  • the heat-sensitive coagulant include inorganic salts such as sodium sulfate, magnesium sulfate, calcium sulfate, calcium chloride, and radical reactions such as sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and benzoyl peroxide. Initiators are mentioned.
  • the water-dispersed polyurethane liquid used in the present invention preferably contains a foaming agent.
  • the foaming agent refers to an additive that decomposes when heated to generate nitrogen gas, carbon dioxide gas, or the like.
  • a water-dispersed polyurethane liquid containing a foaming agent By using a water-dispersed polyurethane liquid containing a foaming agent, the polyurethane liquid applied to the fibrous base material foams when heated, and the resulting polyurethane has a porous structure derived from this foaming.
  • the texture of the sheet with polyurethane becomes flexible. This is because the binding force between the fibers in the sheet with polyurethane and the polyurethane is reduced, and the binding force of the fibers becomes weak.
  • foaming agent added to the water-dispersed polyurethane liquid examples include azoisobutylnitrile, dinitrosopentamethylenetetramine (for example, “Cermic (registered trademark) A” manufactured by Sankyo Kasei Co., Ltd.), and azodicarbonamide (for example, Sankyo Kasei).
  • VA-080 and other organic foaming agents, and sodium hydrogen carbonate (eg, Sankyo Kasei Co., Ltd. “Cermic (registered trademark) 266”).
  • a foaming agent having an amide bond is preferable because it is water-soluble and can be uniformly dissolved in a water-dispersed polyurethane liquid.
  • the amount of the foaming agent added to the water-dispersed polyurethane liquid is preferably 0.5 to 20% by mass relative to the polyurethane solid content.
  • the addition amount of the foaming agent 0.5% by mass or more, more preferably 1% by mass or more, the texture of the sheet-like material by foaming can effectively obtain the effect of softening.
  • the addition amount of the foaming agent is set to 20% by mass or less, more preferably 15% by mass or less, it is possible to suppress a decrease in wear resistance of the sheet-like material due to excessive foaming.
  • the foaming temperature at which the foaming agent is thermally decomposed to generate gas is higher than the thermal coagulation temperature of polyurethane. preferable. By doing so, the gas due to foaming does not escape from the polyurethane, and the porous structure can be formed stably.
  • the foaming temperature of the foaming agent is not limited to a specific temperature, but is preferably 50 to 200 ° C.
  • the foaming temperature is set to 50 ° C. or higher, more preferably 60 ° C. or higher, it is easy to adjust the timing of foaming, such as foaming after the start of coagulation of polyurethane, and a porous structure can be formed effectively.
  • the foaming temperature is set to 200 ° C. or lower, more preferably 180 ° C. or lower, it is possible to prevent the polyurethane from being thermally decomposed by heating for foaming.
  • inorganic particles to the water-dispersed polyurethane liquid in order to stably form a porous structure without letting the gas caused by the foaming escape from the polyurethane. Since the water-dispersed polyurethane liquid containing the foaming agent contains inorganic particles, the foamed gas is held in a fine state by the inorganic particles before escaped from the water-dispersed polyurethane liquid. Even if the difference in thermal coagulation temperature between polyurethane and polyurethane is small, a porous structure of polyurethane can be formed satisfactorily.
  • the inorganic particles for example, porous silica, titanium oxide, aluminum oxide, oxide such as zinc oxide, or the like can be used. Silica is particularly preferably used.
  • the average particle diameter of the inorganic particles is not limited to a specific value, but if it is too large, the water dispersibility deteriorates, and if it is too small, the foamed gas cannot be retained, and is preferably 1 to 10,000 nm, more preferably. Is 10 to 1000 nm.
  • the water-dispersed polyurethane liquid containing a foaming agent applied before developing the ultrafine fibers and / or the water-dispersed polycarbonate polyurethane liquid applied after developing the ultrafine fibers used in the present invention is silicone water. It is preferable to contain a dispersion. By containing this silicone aqueous dispersion, the frictional force between the polyurethane and the fibers of the fibrous base material can be reduced, and the texture of the sheet can be made more flexible. Moreover, in the raising process by sandpaper etc., grindability becomes favorable and uniform nap length can be obtained, and also clogging of sandpaper can be suppressed.
  • the silicone aqueous dispersion content of the water-dispersible polyurethane liquid is preferably 0.1 to 10% by mass, more preferably 0.5%, as the mass of the solid content of silicone with respect to the mass of the water-dispersible polyurethane. ⁇ 8% by mass. If the silicone content is too small, the effect of softening the sheet becomes insufficient. If the silicone content is too large, the force with which the polyurethane grips the fibers in the sheet-like material is weakened and wear resistance is lowered.
  • silicone polydimethylsiloxane, amino-modified silicone, epoxy-modified silicone, polyether-modified silicone, or the like can be used, and among these, film-forming silicone is preferably used.
  • the above-mentioned film-forming silicone is a silicone that becomes a three-dimensional crosslinked structure by heating and becomes a film and cannot be redispersed in water. Due to the film-forming properties, even if there are external factors such as handling in water such as washing and dyeing, washing, etc. and friction after the film-forming silicone is applied, the silicone is prevented from falling off the sheet, The flexibility of the sheet can be maintained. In the case where the sheet is impregnated with a water-dispersed polyurethane liquid containing a film-forming silicone water dispersion, and then the sheet is treated with hot water and / or an aqueous alkali solution to make the fibers extremely fine, the film is formed on the silicone. Therefore, the flexibility of the sheet can be maintained. In addition, the film-forming silicone remains in the sheet even after the fiber ultrafine treatment, comparing the actual measured value with the theoretical calculation value of the sheet after ultrafine treatment, and the difference is within 30%. Say.
  • the water-dispersed polyurethane liquid containing a foaming agent that is applied before developing ultrafine fibers and the water-dispersed polycarbonate-based polyurethane liquid that is imparted after developing ultrafine fibers are used in the present invention.
  • Agents for example, pigments such as carbon black, phosphorus-based, halogen-based, silicone-based, inorganic-based flame retardants, phenol-based, sulfur-based, phosphorus-based antioxidants, benzotriazole-based, benzophenone-based, salicylate-based, UV absorbers such as cyanoacrylates and oxalic acid anilides, light stabilizers such as hindered amines and benzoates, hydrolysis stabilizers such as polycarbodiimides, plasticizers, antistatic agents, surfactants, foaming agents , Softeners, water repellents, coagulation modifiers, dyes, preservatives, antibacterial agents, deodorants, cellulose particles, etc.
  • the water-dispersed polyurethane liquid can be coagulated by dry heat coagulation, wet heat coagulation, wet coagulation, or a combination thereof after impregnating and coating the fibrous base material.
  • the coagulation temperature is not less than the heat-sensitive coagulation temperature of the water-dispersed polyurethane, and is preferably 40 to 200 ° C.
  • the wet heat solidification temperature is set to 40 ° C. or higher, more preferably 80 ° C. or higher, the time to solidification of the polyurethane can be shortened to further suppress the migration phenomenon.
  • the wet heat solidification temperature is set to 200 ° C. or lower, more preferably 160 ° C. or lower, it is possible to prevent thermal degradation of the polyurethane.
  • the coagulation temperature is not less than the heat-sensitive coagulation temperature of the water-dispersed polyurethane, and is preferably 40 to 100 ° C.
  • the solidification temperature and the drying temperature in the dry heat solidification described above are preferably 80 to 180 ° C.
  • the productivity is excellent.
  • the dry heat solidification temperature and the drying temperature is set to 180 ° C. or lower, more preferably 160 ° C. or lower, thermal deterioration of the polyurethane can be prevented.
  • raising treatment may be performed.
  • This raising process can be performed by a method of grinding using a sandpaper or a roll sander. Giving an antistatic agent before the raising treatment is a preferable embodiment in order to make it difficult for the grinding powder generated from the sheet-like material to be deposited on the sandpaper by grinding.
  • the above sheet-like material may be dyed.
  • a dyeing method it is preferable to use a liquid dyeing machine because the sheet-like material can be softened by dyeing the sheet-like material and at the same time giving a stagnation effect.
  • the temperature at the time of dyeing is preferably 80 to 150 ° C., although it depends on the type of fiber.
  • the temperature at the time of dyeing is preferably 80 to 150 ° C., although it depends on the type of fiber.
  • the dyeing temperature is preferably 80 ° C. or higher, more preferably 110 ° C. or higher, it is possible to efficiently dye the fibers.
  • the deterioration of the polyurethane can be prevented by setting the dyeing temperature to 150 ° C. or lower, more preferably 130 ° C. or lower.
  • the dye used for the above dyeing may be selected according to the type of fiber constituting the fibrous base material.
  • a disperse dye is used for a polyester fiber
  • an acid dye or a metal-containing dye is used for a polyamide fiber.
  • a combination of dyes can be used. When dyed with disperse dyes, reduction washing may be performed after dyeing.
  • a dyeing assistant during dyeing.
  • a dyeing assistant By using a dyeing assistant, the uniformity and reproducibility of dyeing can be improved.
  • a finishing treatment using a softening agent such as silicone, an antistatic agent, a water repellent, a flame retardant, a light proofing agent, and an antibacterial agent can be performed in the same bath or after dyeing.
  • Average single fiber diameter The average single fiber diameter is obtained by taking a scanning electron microscope (SEM) photograph of the surface of a fibrous base material or sheet-like material at a magnification of 2000 times, randomly selecting 100 fibers, and the single fiber diameter was calculated by calculating the average value. At this time, when the ultrafine fibers constituting the fibrous base material or the sheet-like material had an irregular cross section, the diameter of the circumscribed circle of the irregular cross section was calculated as a single fiber diameter. In addition, when the circular cross section and the irregular cross section are mixed, or when the single fiber diameters are greatly different, etc., the sampling number corresponding to each existing number ratio is selected to be 100 in total. Calculated.
  • the fibers of the reinforcing woven or knitted fabric are measured by measuring the average single fiber diameter of the ultrafine fibers. Excluded from sampling.
  • Appearance quality of the sheet-like material is as follows by visual and sensory evaluation with 20 adult men and 10 adult women each in good health as a total of 20 evaluators. Five-stage evaluation was performed, and the highest evaluation was defined as appearance quality. Appearance quality was good from grade 3 to grade 5. Grade 5: There is uniform fiber napping, the fiber dispersion state is good, and the appearance is good. Grade 4: Evaluation between grade 5 and grade 3. Third grade: The dispersion state of the fibers is slightly poor, but there are fiber nappings and the appearance is reasonably good. Second grade: An evaluation between the third grade and the first grade. First grade: There are few raised fibers, and the overall dispersion state of the fibers is very poor, and the appearance is poor.
  • Nonwoven fabric for fibrous base materials Next, the preparation procedures for the three types of nonwoven fabrics for fibrous base materials used in Examples and Comparative Examples will be described as Reference Examples 1 to 3, respectively.
  • This nonwoven fabric was immersed in hot water at a temperature of 97 ° C. for 2 minutes to shrink and dried at a temperature of 140 ° C. for 5 minutes to obtain a nonwoven fabric A for fibrous base material (weight per unit: 300 g / m 2 , thickness: 1 mm). .
  • This nonwoven fabric is immersed in hot water at a temperature of 97 ° C. for 2 minutes to shrink, dried at a temperature of 140 ° C. for 5 minutes, and nonwoven fabric B for a fibrous base material (weight per unit: 350 g / m 2 , thickness: 1.1 mm). It was.
  • This nonwoven fabric is immersed in hot water at a temperature of 97 ° C. for 2 minutes to shrink, dried at a temperature of 140 ° C. for 5 minutes, and nonwoven fabric C for a fibrous base material (weight per unit: 430 g / m 2 , thickness: 1.2 mm). It was.
  • Propionamide The molecular weight of the substance having an amide bond after decomposition 260) 3 parts by mass and “Brian (registered trademark) SL-100N” (porous silica, average particle diameter 100 nm) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. as inorganic particles
  • a water-dispersed polycarbonate polyurethane liquid j was obtained in the same manner as in Reference Example 8 except that 3 parts by mass was added.
  • the thermal coagulation temperature was 72 ° C.
  • Example 1 (Before sea removal: ether polyurethane addition)
  • the nonwoven fabric A for fibrous base material prepared in the above Reference Example 1 was impregnated with the water-dispersed ether-based polyurethane liquid a prepared in the above Reference Example 4, and treated for 5 minutes in a humid heat atmosphere at a temperature of 100 ° C. Then, the sheet
  • seat which provided the polycarbonate-type polyurethane so that the polyurethane mass provided after the sea removal with respect to the island component mass of a nonwoven fabric might be 15 mass% was obtained.
  • the surface of the sheet provided with the polycarbonate-based polyurethane was subjected to raising treatment by grinding using a 180-mesh endless sandpaper, then dyed with a disperse dye using a circular dyeing machine, subjected to reduction cleaning, and a sheet-like material was obtained. .
  • Obtained sheet In cross-sectional observation of the obtained sheet-like material, a clear gap was observed between the ultrafine fiber bundle and the water-dispersed ether polyurethane. Moreover, the appearance quality and wear resistance were good, and it had a soft texture and good wrinkle recovery. Furthermore, hydrolysis resistance and light resistance were also good.
  • Example 2 Before sea removal: ether polyurethane addition
  • the water-dispersed ether-based polyurethane liquid b created in Reference Example 5 was used, and the polyurethane mass relative to the island component mass of the nonwoven fabric was 10 mass%. Except for this, a sheet provided with an ether-based polyurethane was obtained in the same manner as in Example 1.
  • the sheet provided with the ether polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • Example 3 Before sea removal: ether polyurethane addition: Except that the mass of polyurethane with respect to the mass of the island component of the non-woven fabric was 20% by mass, the non-woven fabric A for fibrous base material was impregnated with the water-dispersed ether-based polyurethane liquid a, and the ether type A sheet provided with polyurethane was obtained. (Sea removal) The sheet provided with the ether polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • the water-dispersed polycarbonate-based polyurethane liquid g prepared in Reference Example 10 is used, and the polyurethane mass given after sea removal relative to the island component mass of the nonwoven fabric is 20% by mass.
  • a sheet provided with a polycarbonate-based polyurethane was obtained in the same manner as in Example 1 except that this was achieved. (Raising, dyeing, reducing cleaning)
  • the sheet provided with the polycarbonate-based polyurethane was subjected to brushing / dying / reduction cleaning treatment in the same manner as in Example 1 to obtain a sheet-like material.
  • Example 4 Before sea removal: ether polyurethane addition: Except for using the water-dispersed ether-based polyurethane liquid c prepared in Reference Example 6 as the polyurethane liquid to be impregnated into the nonwoven fabric A for fibrous base material, the same as in Example 1, with respect to the island component mass of the nonwoven fabric
  • Sa removal The sheet provided with the ether polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • Example 5 Before sea removal: ether polyurethane addition
  • the nonwoven fabric B for fibrous substrates created in Reference Example 2 was used as the fibrous substrate, and the polyurethane mass relative to the island component mass of the nonwoven fabric was 20 mass%.
  • the above-mentioned fibrous base material was impregnated with the water-dispersed ether polyurethane liquid a to obtain a sheet provided with ether polyurethane.
  • Sa removal The sheet provided with the ether polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • Example 6 Before sea removal: ether polyurethane addition
  • the nonwoven fabric C for fibrous substrate created in Reference Example 3 was used as the fibrous substrate, and the polyurethane mass relative to the island component mass of the nonwoven fabric was 10 mass%.
  • the above-mentioned fibrous base material was impregnated with the water-dispersed ether polyurethane liquid a to obtain a sheet provided with ether polyurethane.
  • the sheet provided with the ether polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • Example 7 Before sea removal: ether polyurethane addition: Except for using the water-dispersed ether-based polyurethane liquid h as the polyurethane liquid to be impregnated into the nonwoven fabric A for fibrous base material prepared in Reference Example 1 above, with respect to the island component mass of the nonwoven fabric, in the same manner as in Example 1.
  • Sa removal The sheet provided with the ether polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • Example 8 Before sea removal: ether polyurethane addition
  • the polyurethane liquid impregnated into the nonwoven fabric A for fibrous base material prepared in Reference Example 1 above is the same as in Example 1 except that the water-dispersed ether polyurethane liquid i is used.
  • seat which provided the ether type polyurethane so that the polyurethane mass might be 15 mass% was obtained.
  • the sheet provided with the ether polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • Example 9 (Before sea removal: Polycarbonate-based polyurethane)
  • the water-dispersed polycarbonate-based polyurethane liquid j was used so that the polyurethane mass relative to the island component mass of the nonwoven fabric was 25% by mass. Except for the above, a sheet provided with polycarbonate polyurethane was obtained in the same manner as in Example 1. (Sea removal) The sheet provided with the polycarbonate-based polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • Example 10 (Before sea removal: Polycarbonate-based polyurethane)
  • a water-dispersed polycarbonate-based polyurethane liquid k was used so that the polyurethane mass relative to the island component mass of the nonwoven fabric was 25 mass%.
  • a sheet provided with polycarbonate polyurethane was obtained in the same manner as in Example 1.
  • the sheet provided with the polycarbonate-based polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • Example 1 (Before sea removal: ether polyurethane addition) The nonwoven fabric A for fibrous base material was impregnated with water-dispersed ether-based polyurethane liquid a in the same manner as in Example 1 except that the mass of polyurethane relative to the mass of the island component of the non-woven fabric was 20% by mass. A sheet provided with a polyurethane was obtained. (Sea removal) The sheet provided with the ether polyurethane was subjected to sea removal treatment in the same manner as in Example 1 to obtain a sea removal sheet.
  • the above sea removal sheet was subjected to raising / dying / reduction washing treatment in the same manner as in Example 1 except that the addition of the polycarbonate-based polyurethane was omitted to obtain a sheet-like material.
  • the obtained sheet-like material of Comparative Example 1 had a soft texture but low light resistance due to the fact that the polyurethane-based polyurethane was not added to the sea removal sheet.
  • the sheet provided with the polycarbonate-based polyurethane was subjected to brushing / dying / reduction cleaning treatment in the same manner as in Example 1 to obtain a sheet-like material.
  • the obtained sheet-like material of Comparative Example 2 had good wrinkle recovery and durability because it did not impart ether polyurethane to the nonwoven fabric for fibrous base material, but the texture became hard and the surface The appearance was also poor.
  • the polyurethane weight applied after sea removal relative to the island component mass of the nonwoven fabric was 15% by mass in the same manner as in Example 1 except that the water-dispersed polyurethane liquid g was used.
  • seat which provided the polycarbonate-type polyurethane so that it might become was obtained.
  • the sheet provided with the polycarbonate-based polyurethane was subjected to brushing / dying / reduction cleaning treatment in the same manner as in Example 1 to obtain a sheet-like material.
  • Table 1 shows the composition of the polyurethane liquid shown in each of the above reference examples.
  • Table 2 shows the evaluation results of the sheet-like materials obtained in each example and each comparative example.
  • the sheet-like material obtained by the present invention includes furniture, chairs and wall materials, interior materials having a very elegant appearance as a skin material such as seats, ceilings and interiors in vehicle interiors such as automobiles, trains and aircraft, shirts, Jackets, casual shoes, sports shoes, uppers and trims for shoes such as men's shoes and women's shoes, bags, belts, wallets, etc., and clothing materials, wiping cloths, abrasive cloths and CD curtains used for some of them It can use suitably as industrial materials, such as.
  • the soft texture and the good wrinkle recovery and durability that do not cause wrinkles which are the effects of the present invention, can be suitably used for interior material applications that strongly require these functions.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne : un article de type feuille comme un cuir ou similaire, qui présente à la fois une texture flexible et de bonnes propriétés de récupération des plis (à savoir, sans froissage) et a également une durabilité élevée ; un procédé de fabrication de l'article de type feuille ; et un procédé de fabrication d'un article de type feuille, qui ne nécessite pas l'utilisation d'un quelconque solvant organique dans le procédé de fabrication de l'article de type feuille et est par conséquent respectueux de l'environnement. L'article de type feuille comprend : une matière de base fibreuse comprenant des microfibres ayant un diamètre moyen de fibre individuelle de 0,3-7 µm ; et un polyuréthane dispersé dans l'eau contenu dans l'intérieur de la matière de base fibreuse. Une partie du polyuréthane dispersé dans l'eau adhère de façon dominante sur la périphérie externe des faisceaux de microfibres et contient une substance ayant une liaison amide. La partie restante du polyuréthane dispersé dans l'eau, qui n'adhère pas de façon dominante sur la périphérie externe des faisceaux de microfibres, contient un polyuréthane de type polycarbonate. Le procédé de fabrication d'un article de type feuille comprend : appliquer une solution de polyuréthane dispersé dans l'eau contenant un agent moussant sur une matière de base fibreuse qui comprend des fibres aptes à développer des microfibres ; puis développer des microfibres ayant un diamètre moyen de fibre individuelle de 0,3-7 µm à partir des fibres aptes à développer des microfibres ; puis appliquer une solution de polyuréthane de type polycarbonate dispersé dans l'eau sur les microfibres résultantes.
PCT/JP2012/077767 2011-10-31 2012-10-26 Article de type feuille et son procédé de fabrication WO2013065608A1 (fr)

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WO2018110280A1 (fr) 2016-12-13 2018-06-21 株式会社クラレ Cuir artificiel gratté, fibres de polyester, et tissu non-tissé
CN110951028A (zh) * 2019-11-12 2020-04-03 合肥科天水性科技有限责任公司 一种聚氨酯树脂及其制备方法和用途
KR20200078345A (ko) 2018-12-21 2020-07-01 닛카 가가쿠 가부시키가이샤 피혁 용재의 제조 방법
WO2021125029A1 (fr) * 2019-12-20 2021-06-24 東レ株式会社 Matériau en feuille et son procédé de production
WO2021251053A1 (fr) * 2020-06-11 2021-12-16 Dic株式会社 Procédé de fabrication de produit coagulé
WO2022024760A1 (fr) * 2020-07-31 2022-02-03 セーレン株式会社 Matériau en forme de feuille de type cuir poncé et procédé de fabrication associé

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CN110951028B (zh) * 2019-11-12 2022-08-19 合肥科天水性科技有限责任公司 一种聚氨酯树脂及其制备方法和用途
CN114829701A (zh) * 2019-12-20 2022-07-29 东丽株式会社 片状物及其制造方法
KR20220111272A (ko) 2019-12-20 2022-08-09 도레이 카부시키가이샤 시트상물 및 그 제조 방법
JP6904494B1 (ja) * 2019-12-20 2021-07-14 東レ株式会社 シート状物およびその製造方法
WO2021125029A1 (fr) * 2019-12-20 2021-06-24 東レ株式会社 Matériau en feuille et son procédé de production
CN114829701B (zh) * 2019-12-20 2023-10-20 东丽株式会社 片状物及其制造方法
JP7070805B1 (ja) * 2020-06-11 2022-05-18 Dic株式会社 凝固物の製造方法
WO2021251053A1 (fr) * 2020-06-11 2021-12-16 Dic株式会社 Procédé de fabrication de produit coagulé
CN115461507A (zh) * 2020-06-11 2022-12-09 Dic株式会社 凝固物的制造方法
CN115461507B (zh) * 2020-06-11 2024-03-19 Dic株式会社 凝固物的制造方法
WO2022024760A1 (fr) * 2020-07-31 2022-02-03 セーレン株式会社 Matériau en forme de feuille de type cuir poncé et procédé de fabrication associé

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