JP6007900B2 - Sheet material and method for producing the same - Google Patents

Description

  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-like material mainly composed of a fibrous base material and polyurethane has excellent characteristics not found in natural leather, and is widely used for various applications. In particular, 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.

  For the production of such a leather-like sheet, 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 A combination with a step of wet coagulating polyurethane by dipping in 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. However, since the use of an organic solvent generally needs to consider the influence on the human body and the environment, a method that does not use an organic solvent is strongly demanded when manufacturing a sheet-like material.

  As a specific solution, for example, a method using water-dispersed polyurethane in which polyurethane is dispersed in water instead of the organic solvent-type polyurethane has been studied. However, a sheet-like material impregnated with a water-based polyurethane impregnated on a fibrous base material has a problem in the hardness of the texture as compared with a sheet-like material impregnated with an organic solvent type polyurethane.

  That is, 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. However, when water-dispersed polyurethane is used, 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.

  In view of this, various methods have been studied for applying a water-dispersible polyurethane to soften the texture by applying a flexible water-dispersible polyurethane to weaken the gripping force at the fiber entanglement point of the polyurethane.

For example, as a water-dispersed polyurethane to be applied to a fibrous base material, the elastic modulus at a temperature of 90 ° C. of a 100 μm-thick film having heat-sensitive gelation property and dried at a temperature of 50 ° C. is 2.0 ×. Use a polyurethane having an elastic modulus at 10 ^{7 to} 5.0 × 10 ⁸ dyn / cm ² and 160 ° C. of 1.0 × 10 ⁷ dyn / cm ² or more and an α dispersion temperature (Tα) of −30 ° C. or less. Has been proposed (see Patent Document 1). However, although 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.

  In addition, a method has been proposed in which silicone is added to polyurethane to increase the slipping property between fibers and polyurethane (see Patent Document 2). However, in the case of this proposal, the texture of the sheet-like material becomes flexible, but there is a problem that the residual elongation after pulling becomes large and it is difficult to return to the original shape.

  Furthermore, a method has been proposed in which a flexible water-dispersible polyurethane is applied to a fibrous base material, and then the polyurethane is applied again after the step of ultrafinening the fibers of the fibrous base material (see Patent Document 3). ). However, this proposed method expresses flexibility by gripping the fiber entanglement point of the fibrous base material with flexible polyurethane, and expresses durability of the sheet-like material with polyurethane to be applied later. However, since polyurethane is applied at a high density inside the fibrous base material, the sheet-like material becomes heavy. In addition, since water-dispersible polyurethane is applied to the fibrous base material, and then the fiber base fiber is made ultrafine, the efficiency of the ultrafine fiber treatment is low and the sheet thickness is high. When a large amount of is contained, there is a problem that it is difficult to make the fiber extremely fine.

Japanese Patent No. 4074377 JP 2008-174868 A Japanese Patent No. 4216111

That is, in the prior art, a sheet-like material having a soft texture and high durability and a method for producing the sheet-like material produced in a process not using an organic solvent have not been obtained so far.
Accordingly, 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 μm. It contains polyurethane, and a part of the above 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. 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.

  Here, 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. In addition, “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.

  According to a preferred embodiment of the sheet-like material of the present invention, the substance having an amide bond has a molecular weight of 100 to 500.

  According to a preferred embodiment of the sheet-like material of the present invention, 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.

  Further, according to a preferred embodiment of the sheet-like material of the present invention, 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. The water-dispersed polycarbonate polyurethane other than the portion contains silicone, and more preferably, the silicone is a film-forming silicone.

  Further, in the method for producing a sheet-like product of the present invention, 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. A water-dispersed polycarbonate-based polyurethane liquid is applied after developing ultrafine fibers having a single fiber diameter of 0.3 to 7 μm.

  According to a preferred embodiment of the method for producing a sheet-like product of the present invention, 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.

  Moreover, according to the preferable aspect of the manufacturing method of the sheet-like material of this invention, 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.

  According to the present invention, 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. In addition, 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-dispersed polyurethane inside a fibrous base material comprising ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm, and part of this water-dispersed 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.

  As a fiber constituting the fibrous base material used in the present invention, 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. For example, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate or polylactic acid or other polyester, 6-nylon or 66-nylon polyamide, polyacryl, polyethylene, etc. And polypropylene, and thermoplastic cellulose. Among these, 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 may be a polygonal shape such as an ellipse, a flat shape, or a triangular shape, or a deformed cross section such as a sector shape or a cross shape. This fiber consists of a very fine fiber, The average single fiber diameter is 0.3-7 micrometers. By setting the average single fiber diameter of the ultrafine fibers to 7 μm or less, more preferably 6 μm or less, and even more preferably 5 μm or less, a sheet-like product having excellent flexibility and napping quality can be obtained. On the other hand, by setting the average single fiber diameter of the ultrafine fibers to 0.3 μm or more, more preferably 0.7 μm or more, and even more preferably 1 μm or more, 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.

  A woven fabric, a knitted fabric, a nonwoven fabric, etc. are employable as a form of the fibrous base material which consists of said ultrafine fiber. Especially, since the surface quality of the sheet-like thing at the time of surface raising treatment is favorable, 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 short fiber nonwoven fabric is preferably 25 to 90 mm, and more preferably 30 to 80 mm. By setting the fiber length of the short fibers to 25 mm or more, a sheet-like material having excellent wear resistance can be obtained by entanglement. Further, by setting the fiber length of the short fibers to 90 mm or less, it is possible to obtain a sheet-like product with better texture and quality.

  When said fibrous base material is a nonwoven fabric, it is a preferable aspect that the nonwoven fabric has a structure formed by a bundle of ultrafine fibers (ultrafine fiber bundle) intertwined. 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.

  When the above ultrafine fibers or the ultrafine fiber bundles constitute 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 μm.

If the basis weight of the fibrous base material is too low, physical properties such as tensile strength and tear strength of the sheet-like material are weakened, and 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 are weakened, and if it is too thick, the texture of the sheet-like material is hardened. 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. It means that 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.

Examples of the ether-based polymer diol 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.

  Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol. Chain alkylene glycol, branched alkylene glycol 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 | strength as a polyurethane is maintainable by making a number average molecular weight into 4000 or less, More preferably, 3000 or less.

  Examples of organic diisocyanates 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. Among these, aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferably used from the viewpoint of light resistance.

  As the chain extender, amine chain extenders such as ethylenediamine and methylenebisaniline, or diol chain extenders such as ethylene glycol can be used. Moreover, the polyamine obtained by making polyisocyanate and water react can also be used as a chain extender.

  In the polyurethane, 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. As the crosslinking agent, 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. By having a hydrophilic group in the molecular structure, it is possible to improve dispersion / stability as a water-dispersed polyurethane.

  Examples of the hydrophilic group 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.

That is, when the hydrophilic group is anionic, a neutralizing agent is required. For example, the neutralizing agent is tertiary, such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine, or dimethylethanolamine. In the case of an amine, 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. In addition, when 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.
On the other hand, when 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.

  In addition, when 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. Although there is a risk of degradation due to hydrolysis, there is no need to worry about degradation due to hydrolysis of polyurethane because a neutralizing agent is not used in the case of a nonionic hydrophilic group.

  In the present invention, 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. 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.) and the like.
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.

  If 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% by mass or more, more preferably 1% by 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 that contains 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.

When the type of water-dispersed polyurethane containing a substance having an amide bond is unevenly distributed and attached to the outer peripheral portion of the bundle of ultrafine fibers, the binding force of the fiber entanglement point is Since it weakens, the texture of the sheet can be softened. However, when only the water-dispersed ether-based polyurethane is contained in the fibrous base material, good wrinkle recovery properties cannot be expressed, and durability such as light resistance and heat resistance is hardly expressed.
In the present invention, when 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. By containing a dispersed polycarbonate polyurethane, good wrinkle recovery and durability such as light resistance and heat resistance are exhibited.

  On the other hand, if the type of water-dispersed polyurethane containing a substance having an amide bond is unevenly distributed and attached to the outer peripheral portion of the bundle of ultrafine fibers, 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.

If only the water-dispersed polycarbonate polyurethane containing no amide bond substance is contained inside the fibrous base material, wrinkle recovery, durability such as light resistance and heat resistance can be expressed. Since the water-dispersed polycarbonate polyurethane adheres so as to directly grip the ultrafine fiber bundle, the texture of the sheet-like material becomes hard and unpractical.
In the present invention, when 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.

  In the present invention, contained in the inside of the fibrous base material, 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. When the woven or knitted fabric is inserted, it is preferable to contain 10 to 50% by mass, and more preferably 15 to 40% by mass with respect to 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.

Also, 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. It is preferable that the water-dispersed polycarbonate polyurethane other than the adhering part is 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.
Also, the mass (U1) of the water-dispersed polyurethane adhering to and adhering to the outer peripheral portion of the ultrafine fiber bundle and the mass of the water-dispersing polycarbonate polyurethane other than the portion adhering to the outer peripheral portion of the ultrafine fiber bundle. The ratio with (U2) is not limited to a specific value, but is preferably (U1) / (U2) = 1 / 0.1 to 1/10, more preferably (U1) / (U2) = 1. /0.5 to 1/5.
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.

  In the present invention, 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.

  As 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, a foam-structured polyurethane foam is used. The foaming agent refers to an additive that decomposes when heated to generate nitrogen gas, carbon dioxide gas, or the like. By using a water-dispersible polyurethane liquid containing a foaming agent, the water-dispersible polyurethane liquid applied to the fibrous base material foams when heated, and the obtained water-dispersible polyurethane is derived from this foaming. It becomes a porous structure. By making the water-dispersible polyurethane porous, 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. Moreover, said water dispersion type polyurethane contains the substance which has an amide bond as a residue which remains after a foaming agent foams.

  Examples of the foaming agent added to the water-dispersed polyurethane liquid 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, Ltd.) 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- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propiyl. Namide} (for example, “VA-080” manufactured by Wako Pure Chemical Industries, Ltd.) and inorganic foams such as sodium hydrogen carbonate (for example, “Cermic (registered trademark) 266” manufactured by Sankyo Kasei Co., Ltd.) Among them, 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.

  A part of the water-dispersed polyurethane used in the present invention contains a substance having an amide bond while being unevenly attached to the outer peripheral portion of the ultrafine fiber bundle. 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.

  Since 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. However, in the present invention, as described above, since 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.

  In the present invention, 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. However, in the case where a reinforcing woven fabric or knitted fabric is inserted in addition to the nonwoven fabric composed of the ultrafine fibers or the ultrafine fiber bundle, the fibers of the reinforcing woven or knitted fabric are excluded from the object. In addition, “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, other than the portion that is unevenly distributed and attached to the outer peripheral portion of the above-mentioned ultrafine fiber bundle, 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. A water-dispersed polyurethane containing a substance having an amide bond that is unevenly attached to the outer peripheral portion of the ultrafine fiber bundle, and a water-dispersed polycarbonate system other than the portion that is unevenly attached to the outer peripheral portion of the ultrafine fiber bundle. Polyurethane exists without being mixed with each other.

  Note that 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. When 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.

  Although silicone content with respect to said polyurethane is not limited to a specific value, it is preferable that it is 0.1-10 mass% with respect to polyurethane mass, More preferably, it is 0.5-8 mass%. 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. .

  As the silicone, polydimethylsiloxane, amino-modified silicone, epoxy-modified silicone, polyether-modified silicone, or the like can be used. Among them, a film-forming silicone is preferably used. 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.

  In the case where 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. In the present invention, “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, or Is an inorganic particles such as silica or titanium oxide may contain singly or in any combination.

  If the thickness of the sheet-like material obtained in the present invention is too thin, physical properties such as tensile strength and tear strength of the sheet-like material will be weak, and if too thick, the texture of the sheet-like material will be hard. 5 mm is preferable.

  Next, the manufacturing method of the sheet-like material of this invention is described. In the method for producing a sheet-like product of the present invention, 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.

  A woven fabric, a knitted fabric, a nonwoven fabric, etc. are employable as a form of the fibrous base material which consists of said ultrafine fiber. Especially, since the surface quality of the sheet-like thing at the time of surface raising treatment is favorable, 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.

  In the nonwoven fabric used as the fibrous base material, the method of 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.

  As a means for forming the ultrafine fiber of the fibrous base material, it is preferable to use an 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. Among them, 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.

  For the 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. There are spinning fibers. 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.

  As the sea component of the sea-island fiber, polyethylene, polypropylene, polystyrene, copolymer polyester obtained by copolymerizing sodium sulfoisophthalic acid, polyethylene glycol, or the like, polylactic acid, polyvinyl alcohol, or the like can be used. Among them, 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. As the 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. Further, when the sea component is a copolyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide can be used, and when the sea component is polyvinyl alcohol, hot water can be used.

  The sea removal treatment using the sea-island fibers is performed after applying the water-dispersed polyurethane containing the foaming agent to the fibrous base material. When the sea removal treatment is performed before the polyurethane is applied, 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. On the other hand, when 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. Thereby, since 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.

  In the present invention, a water-dispersed polyurethane liquid containing a foaming agent is applied to the fibrous base material, and then the ultrafine fibers are expressed from the fibrous base material, and then the water-dispersed polycarbonate-based polyurethane liquid is applied. When 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. By imparting, it is possible to develop durability such as light resistance and heat resistance, which is difficult to be expressed only with ether-based polyurethane, and it is possible to impart good abrasion resistance to the sheet-like material.

  Further, when 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 water-dispersed polycarbonate that exhibits the soft texture and durability such as light resistance and heat resistance that are manifested in water-dispersed polycarbonate-based polyurethane containing a foaming agent by applying a polyurethane liquid, and has developed ultrafine fibers. A dense surface appearance and good wear resistance can be imparted to the sheet-like material by the polyurethane.

  In addition, 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. By containing a foaming agent, a porous structure is formed inside the fibrous base material. By forming an ultrafine fiber and then applying a water-dispersed polycarbonate-based polyurethane liquid thereto, the polycarbonate-based polyurethane adheres to the porous structure of the polyurethane containing a substance having an amide bond. That is, when focusing on only the polycarbonate-based polyurethane imparted after the development of ultrafine fibers, a porous structure similar to that of a polyurethane containing a substance having an amide bond imparted before the manifestation of ultrafine fibers is formed inside the fibrous base material. Thus, even if the polyurethane is a hard polyurethane polyurethane, a soft texture can be expressed as a sheet.

  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 (polyurethane content 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 mass%.

  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. From the viewpoint of environmental conservation, the content of the organic solvent is preferably 1% by mass or less.

  Further, the water-dispersed polyurethane liquid used in the present invention preferably has heat-sensitive coagulation properties. By using a water-dispersed polyurethane liquid having heat-sensitive coagulation properties, polyurethane can be uniformly applied in the thickness direction of the fibrous base material. The 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. In the production of 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. Thus, polyurethane can be imparted to the fibrous base material.

  As a method of coagulating a water-dispersed polyurethane solution that does not exhibit heat-sensitive coagulation, dry heat coagulation is practical in industrial production, but in this case, there is a migration phenomenon in which polyurethane concentrates on the surface layer of the fibrous base material. And the texture of the polyurethane sheet has a tendency to harden.

  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. By setting the heat-sensitive coagulation temperature to 40 ° C. or higher, stability during storage of the polyurethane liquid is improved, and adhesion of polyurethane to the machine during operation can be suppressed. Moreover, the migration phenomenon of the polyurethane in a fibrous base material can be suppressed by making a thermal coagulation temperature into 90 degrees C or less. The heat-sensitive coagulation temperature is more preferably 50 ° C to 80 ° C.

  In order to set the heat-sensitive coagulation temperature as described above, a heat-sensitive coagulant may be added as appropriate. Examples of 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. 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. By making the water-dispersible polyurethane a porous structure, 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.

  Examples of the foaming agent added to the water-dispersed polyurethane liquid include azoisobutylnitrile, dinitrosopentamethylenetetramine (for example, “Cermic (registered trademark) A” manufactured by Sankyo Kasei Co., Ltd.), and azodicarbonamide (for example, Sankyo Kasei). "Cermic (registered trademark) CAP", p, p'-oxybisbenzenesulfonyl hydrazide (for example, "Cermic (registered trademark) S" manufactured by Sankyo Kasei Co., Ltd.), N, N'-dinitrosopentamethylenetetramine (For example, “Cellular GX” manufactured by Eiwa Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (for example, “VA-086” manufactured by Wako Pure Chemical Industries, Ltd.) ), Or 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionami } (For example, “VA-080” manufactured by Wako Pure Chemical Industries, Ltd.) and inorganic foaming agents such as sodium hydrogen carbonate (for example, “Cermic (registered trademark) 266” manufactured by Sankyo Kasei Co., Ltd.) Among them, 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. By making 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. On the other hand, by setting the addition amount of the foaming agent 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.

  As a preferred embodiment of the above water-dispersed polyurethane liquid, when the thermal coagulation property is exhibited as described above, 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.

  Although the foaming temperature of said foaming agent is not limited to specific temperature, it is preferable that it is 50-200 degreeC. By setting the foaming temperature 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. On the other hand, by setting the foaming temperature 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.

  In addition, it is preferable to add inorganic particles to the water-dispersed polyurethane liquid in order to form the porous structure stably 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. As 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. 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-dispersed polyurethane liquid is preferably 0.1 to 10% by mass, more preferably 0.5% as the mass of the solid content of the silicone with respect to the mass of the water-dispersible polyurethane. It is -8 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.

  As the silicone, polydimethylsiloxane, amino-modified silicone, epoxy-modified silicone, polyether-modified silicone, or the like can be used. Among them, a film-forming silicone is preferably used.

  The 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 Filling with softeners, water repellents, coagulation regulators, dyes, preservatives, antibacterial agents, deodorants, cellulose particles, etc. Or the like inorganic particles such as silica or titanium oxide may contain singly or in any combination.

  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.

  In the case of the wet heat coagulation, the coagulation temperature is not less than the heat-sensitive coagulation temperature of the water-dispersed polyurethane, and is preferably 40 to 200 ° C. By setting the wet heat solidification temperature 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. On the other hand, by setting the wet heat solidification temperature to 200 ° C. or lower, more preferably 160 ° C. or lower, it is possible to prevent thermal degradation of the polyurethane.

  In the case of the above wet coagulation, the coagulation temperature is not less than the heat-sensitive coagulation temperature of the water-dispersed polyurethane, and is preferably 40 to 100 ° C. By setting the temperature of wet coagulation in hot water to 40 ° C. or higher, more preferably 80 ° C. or higher, the time to solidification of polyurethane can be shortened to further suppress the migration phenomenon.

  In the case of the above-mentioned dry heat solidification, the solidification temperature and the drying temperature are preferably 80 to 180 ° C. By setting the dry heat solidification temperature and the drying temperature to 80 ° C. or higher, more preferably 90 ° C. or higher, the productivity is excellent. On the other hand, by setting the dry heat solidification temperature and the drying temperature to 180 ° C. or lower, more preferably 160 ° C. or lower, thermal deterioration of the polyurethane can be prevented.

  In order to form napping on the surface of the sheet-like material, napping 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 sheet-like material may be dyed. As 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. By setting the dyeing temperature to 80 ° C. or higher, more preferably 110 ° C. or higher, it is possible to efficiently dye the fibers. On the other hand, 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. For example, a disperse dye is used for a polyester fiber, and 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.

  It is also a preferred embodiment to use a dyeing assistant during dyeing. By using a dyeing assistant, the uniformity and reproducibility of dyeing can be improved. In addition, 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.

  Next, the sheet-like material and the method for producing the same according to the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[Evaluation method]
(1) 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. However, in the case where a reinforcing woven fabric or knitted fabric is inserted in addition to the non-woven fabric composed of ultrafine fibers or fiber bundles thereof, 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.

(2) Heat-sensitive coagulation temperature of water-dispersed polyurethane liquid 20 g of water-dispersed polyurethane liquid prepared to a polyurethane solid content concentration of 10% by mass is placed in a test tube having an inner diameter of 12 mm, and the tip of the thermometer is below the liquid level. Then, the test tube was sealed, and immersed in a warm water bath at a temperature of 95 ° C. so that the liquid level of the polyurethane liquid was lower than the liquid level of the warm water bath. While checking the temperature rise in the test tube with a thermometer, the test tube is pulled up for a time within 5 seconds at a time, and shaken to the extent that the liquid surface of the water-dispersed polyurethane liquid can be checked for fluidity. The temperature at which the liquid level of the dispersed polyurethane liquid lost fluidity was defined as the thermal coagulation temperature. This measurement was performed three times for each type of polyurethane liquid, and the average value was calculated.

(3) Structure inside the sheet-like material The structure inside the sheet-like material was observed by taking a scanning electron microscope (SEM) photograph of a cross-section of the sheet-like material at a magnification of 500 times.

(4) Texture of sheet-like material According to method A (45 ° cantilever method) described in 8.21.1 of 8.21 “Bending softness” of JIS L 1096: 2010 “Testing methods for fabrics and knitted fabrics” Based on the above, make 5 x 20 mm x 150 mm test pieces in the vertical and horizontal directions, place them on a horizontal table with a slope of 45 ° C, slide the test piece, and the center point of one end of the test piece The scale when touched was read and the average value of 5 sheets was calculated.

(5) Wrinkle recoverability of sheet-like material JIS L 1059-1: 2009 "Wrinkle resistance test method for textile products-Part 1: Measurement of horizontal folding wrinkle recovery (Monsanto method)" Using a 10N load device, the wrinkle recovery angle of 5 test pieces was measured, and the wrinkle recovery property was calculated by the formula of wrinkle prevention rate described in 10 “Calculation of wrinkle recovery angle and wrinkle prevention rate”. The average value of the sheet was obtained.

(6) Evaluation of abrasion resistance of sheet-like material Nylon 6 made of nylon fiber 0.4 mm in diameter cut into a length of 11 mm perpendicular to the longitudinal direction of the fiber is made into a bundle, and this bundle is made 110 mm in diameter. 97 in a 6-fold concentric circle (1 in the center, 6 in the 17 mm diameter circle, 13 in the 37 mm diameter circle, 19 in the 55 mm diameter circle, 26 in the 74 mm diameter circle, Using a circular brush (9700 nylon threads) arranged in a circle with a diameter of 90 mm, under a load of 8 pounds (about 3629 g), a rotational speed of 65 rpm, and a number of rotations of 50, a circular sample (45 mm in diameter) ) Was worn, the change in mass of the samples before and after that was measured, and the average value of the five samples was taken as the weight loss.

(7) Evaluation of hydrolysis resistance After using the constant temperature and humidity chamber manufactured by Espec, forcibly deteriorating for 5 weeks in an atmosphere at a temperature of 70 ° C. and a relative humidity of 95%, the above-mentioned wear resistance evaluation is performed. went.

(8) Light resistance evaluation Based on B method of 4 “Test types” described in JIS L 0843: 2006 “Dye fastness test method for xenon arc lamp” using a xenon weather meter manufactured by Suga Test Instruments Co., Ltd. , Irradiance 150W / m ² , Irradiance 150W / m ² , Black panel temperature 73 ± 3 ° C, In-vessel temperature 38 ° C, Relative humidity 50 ± 5%, Irradiation 3.8 hours and extinction 1 hour 38 times After performing the forced deterioration treatment by performing the irradiation time for a total of 144 hours, the above-described wear resistance evaluation was performed.

(9) Appearance quality of the sheet-like material The 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. As for the appearance quality, Grade 3 to Grade 5 were considered good.
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, about the 3 types of nonwoven fabrics for fibrous base materials used by an Example and a comparative example, those preparation procedures are demonstrated as Reference Examples 1-3, respectively.

[Reference Example 1] Preparation of Nonwoven Fabric A Using polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate as the sea component and using polyethylene terephthalate as the island component, sea component 45 mass%, island component 55 mass A sea-island type composite fiber having 36 islands / 1 filament and an average single fiber diameter of 17 μm was obtained at a composite ratio of%. The average single fiber diameter of polyethylene terephthalate which is an island component was 2 μm. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. The 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 a fibrous base material (weight per unit: 300 g / m ² , thickness: 1 mm). .

[Reference Example 2] Preparation of nonwoven fabric B As sea component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate was used, and as the island component, polyethylene terephthalate was used. A sea-island type composite fiber having 16 islands / 1 filament and an average single fiber diameter of 30 μm was obtained at a composite ratio of%. The average single fiber diameter of polyethylene terephthalate which is an island component was 4 μm. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. 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.

[Reference Example 3] Preparation of nonwoven fabric C Polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate was used as the sea component, and 6-nylon was used as the island component. A sea-island type composite fiber having 200 islands / 1 filament and an average single fiber diameter of 27 μm was obtained at a composite ratio of mass%. The average single fiber diameter of 6-nylon, which is an island component, was 1.5 μm. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. 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.

(Water-dispersed polyurethane liquid)
Next, for 11 types of water-dispersed polyurethane liquids used in Examples and Comparative Examples, their preparation procedures will be described as Reference Examples 4 to 14, respectively.

[Reference Example 4] Preparation of water-dispersed ether polyurethane liquid a 100 mass of solid content of this polyurethane liquid was added to an ether-based forced emulsification type polyurethane liquid in which polytetramethylene glycol was applied to polyol and isophorone diisocyanate was applied to isocyanate. 2 parts by weight of magnesium sulfate as a heat-sensitive coagulant, 3 parts by weight of azoisobutyronitrile (AIBN) (foaming temperature 120 ° C.) as a foaming agent, and “IE-” manufactured by Toray Dow Corning as a film-forming silicone 3170 parts by weight of 7170 ″ were added, respectively, and the whole was adjusted to a solid content of 10% by mass with water to obtain a water-dispersed ether-based polyurethane liquid a. The thermal coagulation temperature was 56 ° C.

[Reference Example 5] Preparation of water-dispersed ether-based polyurethane liquid b In the water-dispersed ether-based polyurethane liquid a of Reference Example 4, sodium hydrogen carbonate ("Cermic" manufactured by Sankyo Kasei Co., Ltd.) was used instead of AIBN as a foaming agent. 266 ″, foaming temperature 140 ° C.) 5 parts by mass, and in the same manner as Reference Example 4 except that 3 parts by mass of “SM7036EX” manufactured by Toray Dow Corning, which is a dimethyl silicone emulsion, was added in place of the film-forming silicone. Thus, a water-dispersed ether-based polyurethane liquid b was obtained. The thermal coagulation temperature was 61 ° C.

[Reference Example 6] Preparation of water-dispersed ether-based polyurethane liquid c Water-dispersed in the same manner as in Reference Example 4 except that no film-forming silicone was added to water-dispersed ether-based polyurethane liquid a of Reference Example 4. Type ether polyurethane liquid c was obtained. The thermal coagulation temperature was 55 ° C.

[Reference Example 7] Preparation of water-dispersed ether-based polyurethane liquid d In the water-dispersed ether-based polyurethane liquid a of Reference Example 4, the same procedure as in Reference Example 4 was carried out except that no foaming agent and film-forming silicone were added. Thus, a water-dispersed ether-based polyurethane liquid d was obtained. The thermal coagulation temperature was 55 ° C.

[Reference Example 8] Preparation of water-dispersed polycarbonate-based polyurethane liquid e This polyurethane liquid was added to a polyoxyethylene chain-containing polycarbonate-based self-emulsifying polyurethane liquid in which polyhexamethylene carbonate was applied to the polyol and dicyclohexylmethane diisocyanate was applied to the isocyanate. 2 parts by mass of ammonium persulfate (APS) as a heat-sensitive coagulant and 5 parts by mass of “IE-7170” manufactured by Toray Dow Corning as a film-forming silicone are added to 100 parts by mass of the solid content of The whole was adjusted to a solid content of 20% by mass to obtain a water-dispersed polycarbonate polyurethane liquid e. The thermal coagulation temperature was 74 ° C.

[Reference Example 9] Preparation of water-dispersed polycarbonate-based polyurethane liquid f "SM7036EX" manufactured by Toray Dow Corning Co., Ltd., which is a dimethyl silicone emulsion instead of a film-forming silicone in water-dispersed polycarbonate-based polyurethane liquid e of Reference Example 8. A water-dispersed polycarbonate polyurethane liquid f was obtained in the same manner as in Reference Example 8 except that 3 parts by mass was added. The thermal coagulation temperature was 75 ° C.

[Reference Example 10] Preparation of water-dispersed polycarbonate-based polyurethane liquid g Water-dispersed polycarbonate-based polyurethane liquid e in Reference Example 8 was prepared in the same manner as in Reference Example 8 except that no film-forming silicone was added. Dispersed polycarbonate-based polyurethane liquid g was obtained. The thermal coagulation temperature was 73 ° C.

[Reference Example 11] Preparation of water-dispersed ether-based polyurethane liquid h In the water-dispersed ether-based polyurethane liquid a of Reference Example 4, instead of AIBN as a foaming agent, “VA-080” (2, 2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} 3 parts by mass of a molecular weight 380 of a substance having an amide bond after decomposition; and inorganic particles Except that 3 parts by mass of “Brian (registered trademark) SL-100N” (porous silica, average particle diameter of 100 nm) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. was added, and the amount of the film-forming silicone added was 5 parts by mass. In the same manner as in Example 4, a water-dispersed ether polyurethane liquid h was obtained. The thermal coagulation temperature was 54 ° C.

[Reference Example 12] Preparation of water-dispersed ether-based polyurethane liquid i In the water-dispersed ether-based polyurethane liquid h of Reference Example 11, "TECNADIS-TI-120-1KG" manufactured by TECNAN instead of porous silica as inorganic particles. (Titanium oxide, average particle diameter 15 nm) A water-dispersed ether-based polyurethane liquid i was obtained in the same manner as in Reference Example 11 except that 5 parts by mass was added. The thermal coagulation temperature was 58 ° C.

[Reference Example 13] Preparation of water-dispersed polycarbonate polyurethane liquid j In the water-dispersed polycarbonate polyurethane liquid e of Reference Example 8, instead of “IE-7170” manufactured by Toray Dow Corning Co., Ltd. as a film-forming silicone, Nikka “VA-086” (2,2′-azobis [2-methyl-N- (2-hydroxyethyl) manufactured by Wako Pure Chemical Industries, Ltd. was used as a foaming agent using 5 parts by mass of “Drypon (registered trademark) 600E” manufactured by Kagaku Co., Ltd. ) 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.

[Reference Example 14] Preparation of water-dispersed polycarbonate-based polyurethane liquid k In water-dispersed polycarbonate-based polyurethane liquid j of Reference Example 13, "TECNADIS-AL-120-1KG" manufactured by TECNAN was used instead of porous silica as inorganic particles. (Aluminum oxide, average particle diameter 25 nm) A water-dispersed polycarbonate polyurethane liquid k was obtained in the same manner as in Reference Example 13 except that 5 parts by mass was added. The thermal coagulation temperature was 76 ° 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 ether type polyurethane so that the polyurethane mass with respect to the island component mass of a nonwoven fabric might be 15 mass% was obtained by making it dry with hot air at the temperature of 120 degreeC for 5 minutes.
(Sea removal)
The above-mentioned ether-based polyurethane-coated sheet is immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and subjected to sea removal treatment for 30 minutes to remove sea components from sea-island fibers. A sheet was obtained.
(After sea removal: addition of polycarbonate polyurethane)
The sea removal sheet is impregnated with the water-dispersed polycarbonate polyurethane liquid e prepared in Reference Example 8 above, treated in a moist heat atmosphere at a temperature of 100 ° C. for 5 minutes, and then dried at a temperature of 120 ° C. for 5 minutes. Dry with hot air for a minute. Thereby, 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.
(Raising, dyeing, reducing cleaning)
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)
As the polyurethane liquid to be impregnated into the nonwoven fabric A for fibrous base material, 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.
(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.
(After sea removal: addition of polycarbonate polyurethane)
The seawater removal with respect to the island component mass of the nonwoven fabric was performed in the same manner as in Example 1 except that the water-dispersed polycarbonate-based polyurethane liquid f prepared in Reference Example 9 was used as the polyurethane liquid impregnated in the seawater-removal sheet. The sheet | seat which provided the polycarbonate-type polyurethane so that the polyurethane mass provided later might be 15 mass% was obtained.
(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.
(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 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.
(After sea removal: addition of polycarbonate polyurethane)
As the polyurethane liquid impregnated in the 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.
(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 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 The sheet | seat which provided the ether type polyurethane so that the polyurethane mass might be 15 mass% 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.
(After sea removal: addition of polycarbonate polyurethane)
As the polyurethane liquid to be impregnated in the sea removal sheet, water dispersion type polycarbonate polyurethane liquid g was used, and the polyurethane mass given after sea removal relative to the island component mass of the nonwoven fabric was 30% by mass. In the same manner as in Example 1, a sheet provided with polycarbonate-based polyurethane was obtained.
(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.
(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 5]
(Before sea removal: ether polyurethane addition)
The same procedure as in Example 1 was conducted except that 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.
(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.
(After sea removal: addition of polycarbonate polyurethane)
In the same manner as in Example 1, the sea removal sheet was impregnated with the water-dispersed polycarbonate-based polyurethane liquid e, and the polycarbonate was added so that the mass of polyurethane applied after sea removal relative to the island component mass of the nonwoven fabric was 15% by mass. A sheet provided with a polyurethane was obtained.
(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.
(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 6]
(Before sea removal: ether polyurethane addition)
The same procedure as in Example 1 was conducted except that 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.
(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.
(After sea removal: addition of polycarbonate polyurethane)
Except for the mass of polyurethane applied after sea removal relative to the island component mass of the nonwoven fabric being 20% by mass, the seawater-removed polycarbonate polyurethane liquid e was impregnated in the seawater removal sheet as in Example 1. Thus, a sheet provided with polycarbonate-based polyurethane was obtained.
(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.
(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 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. The sheet | seat which provided the ether type polyurethane so that the polyurethane mass might be 15 mass% 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.
(After sea removal: addition of polycarbonate polyurethane)
In the same manner as in Example 1, the sea removal sheet was impregnated with the water-dispersed polycarbonate-based polyurethane liquid e, and the polycarbonate was added so that the mass of polyurethane applied after sea removal relative to the island component mass of the nonwoven fabric was 15% by mass. A sheet provided with a polyurethane was obtained.
(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.
(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 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. The sheet | seat which provided the ether type polyurethane so that the polyurethane mass might be 15 mass% 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.
(After sea removal: addition of polycarbonate polyurethane)
In the same manner as in Example 1, the sea removal sheet was impregnated with the water-dispersed polycarbonate-based polyurethane liquid e, and the polycarbonate was added so that the mass of polyurethane applied after sea removal relative to the island component mass of the nonwoven fabric was 15% by mass. A sheet provided with a polyurethane was obtained.
(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.
(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 9]
(Before sea removal: Polycarbonate-based polyurethane)
As the polyurethane liquid to be impregnated into the nonwoven fabric A for a fibrous base material prepared in Reference Example 1, 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.
(After sea removal: addition of polycarbonate polyurethane)
In the same manner as in Example 1, except that the mass of polyurethane applied after sea removal relative to the island component mass of the nonwoven fabric was 5% by mass, the above-mentioned sea-sealed sheet was impregnated with the water-dispersed polycarbonate polyurethane liquid e. Thus, a sheet provided with polycarbonate-based polyurethane was obtained.
(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.
(Obtained sheet)
In the cross-sectional observation of the obtained sheet-like material, a clear gap was observed between the ultrafine fiber bundle and the water-dispersed polycarbonate 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 10]
(Before sea removal: Polycarbonate-based polyurethane)
As the polyurethane liquid to be impregnated into the nonwoven fabric A for fibrous base material prepared in the above Reference Example 1, 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%. 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.
(After sea removal: addition of polycarbonate polyurethane)
In the same manner as in Example 1, except that the mass of polyurethane applied after sea removal relative to the island component mass of the nonwoven fabric was 5% by mass, the above-mentioned sea-sealed sheet was impregnated with the water-dispersed polycarbonate polyurethane liquid e. Thus, a sheet provided with polycarbonate-based polyurethane was obtained.
(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.
(Obtained sheet)
In the cross-sectional observation of the obtained sheet-like material, a clear gap was observed between the ultrafine fiber bundle and the water-dispersed polycarbonate 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.

[Comparative 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.
(Raising, dyeing, reducing cleaning)
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.
(Obtained sheet)
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.

[Comparative Example 2]
(Sea removal)
The nonwoven fabric A for fibrous base material was subjected to sea removal treatment in the same manner as in Example 1 except that polyurethane was omitted to obtain a sea removal sheet.
(After sea removal: addition of polycarbonate polyurethane)
As the polyurethane liquid to be impregnated into the sea removal sheet, a water-dispersed polycarbonate-based polyurethane liquid g was used, and the polyurethane mass relative to the island component mass of the nonwoven fabric was set to 30 mass%. Then, a sheet provided with polycarbonate-based polyurethane was obtained.
(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.
(Obtained sheet)
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.

[Comparative Example 3]
(Before sea removal: ether polyurethane addition)
As the polyurethane liquid impregnated into the nonwoven fabric A for fibrous base material, the same procedure as in Example 1 was used except that the water-dispersed ether-based polyurethane liquid d to which the foaming agent prepared in Reference Example 7 was not added was used. Then, a sheet provided with ether-based polyurethane was obtained so that the polyurethane mass relative to the island component mass of the nonwoven fabric was 15 mass%.
(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.
(After sea removal: addition of polycarbonate polyurethane)
As the polyurethane liquid impregnated in the sea removal sheet, 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. The sheet | seat which provided the polycarbonate-type polyurethane so that it might become was obtained.
(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.
(Obtained sheet)
In the obtained sheet-like material of Comparative Example 3, no foaming agent was added to the ether-based polyurethane, and therefore, in the cross-sectional observation of this sheet-like material, a clear gap was observed between the ultrafine fiber bundle and the ether-based polyurethane. In some cases, ether polyurethane adhered to the inside of the ultrafine fiber bundle. In addition, this sheet-like product was low in wrinkle recovery and hard in texture because no foaming agent was added to the ether polyurethane.

  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. In particular, 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.

Claims (11)

It contains water-dispersible polyurethane inside a fibrous base material comprising ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm,
A part of the water-dispersible polyurethane contains a substance having an amide bond, while being unevenly attached to the outer peripheral portion of the bundle of the ultrafine fibers,
A sheet-like product characterized in that the water-dispersed polyurethane other than the part that is unevenly distributed and adhered to the outer peripheral part of the ultrafine fiber bundle contains water-dispersed polycarbonate polyurethane.   The sheet-like material according to claim 1, wherein the substance having an amide bond has a molecular weight of 100 to 500.   The sheet-like product according to claim 1 or 2, wherein the water-dispersed polyurethane adhering to and 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 that is unevenly distributed on the outer peripheral portion of the ultrafine fiber bundle and / or 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 contains silicone. The sheet-like article according to any one of claims 1 to 3, wherein the sheet-like article is provided.   The sheet-like material according to claim 4, wherein the silicone is a film-forming silicone.   A water-dispersed polyurethane solution containing a foaming agent is applied to a fibrous base material comprising an ultrafine fiber expression type fiber, and then an ultrafine fiber having an average single fiber diameter of 0.3 to 7 μm is expressed from the ultrafine fiber expression type fiber. A method for producing a sheet-like product, comprising applying a water-dispersed polycarbonate-based polyurethane solution after the treatment.   The method for producing a sheet-like product according to claim 6, wherein the water-dispersed polyurethane liquid containing the foaming agent is a polycarbonate-based polyurethane or an ether-based polyurethane liquid.   The method for producing a sheet-like material according to claim 6 or 7, wherein the water-dispersed polyurethane liquid containing the foaming agent contains inorganic particles.   9. The method for producing a sheet-like product according to claim 8, wherein the inorganic particles are porous silica.   The water-dispersed polyurethane liquid containing the foaming agent and / or the water-dispersed polycarbonate-based polyurethane liquid to be applied after developing the ultrafine fibers contains a silicone water dispersion. The method for producing a sheet-like material according to any one of 9.   The method for producing a sheet-like material according to claim 10, wherein the silicone water dispersion is a film-forming silicone water dispersion.