TW201329312A - Sheet-like article and production method thereof - Google Patents

Abstract

The present invention provides a sheet-like article, such as a leather-like sheet, having both of a flexible texture and a good wrinkle recovery without generating a wrinkle and having a high durability such as leather-like sheet article; and a production method thereof. Moreover, the present invention provides a method for producing a sheet-like article without using environmentally unfriendly organic solvents in a producing process. The sheet-like article contains a water-dispersible polyurethane within the inside of a fibrous base comprising an ultra-fine fiber having an average single fiber diameter of 0.3-7 &mgr; m. A portion of the water-dispersible polyurethane misdistributes and adheres to the periphery of the ultra-fine fiber and comprises a material having an amide bond. The water-dispersible polyurethane excluding the portion being misdistributed and adhered to the periphery of the ultra-fine fiber comprises a polycarbonate-based polyurethane. The method for producing the sheet-like article is for applying a water-dispersible polyurethane liquid comprising a blowing agent to the fibrous base comprising ultra-fine fiber-generating fibers, and then for generating an ultra-fine fiber having an average single fiber diameter of 0.3-7 &mgr; m from the ultra-fine fiber-generating fibers and applying the water-dispersible polycarbonate-based polyurethane liquid.

Description

Sheet and manufacturing method thereof

The present invention relates to a sheet, in particular, an organic solvent which does not use an organic solvent in a manufacturing step, and which has a soft touch and wrinkle-free good wrinkle recovery property, and has high durability. Sheet and its method of manufacture.

The leather-like sheet mainly composed of a fibrous substrate and a polyurethane has excellent characteristics not found in natural leather, and is widely used for various purposes. In particular, the use of a leather-like sheet-like material of a polyester-based fibrous base material is excellent in light resistance, and its use has been increasing year by year in the use of clothing materials, chair decoration, and automotive interior materials.

The manufacture of such a leather-like sheet is generally carried out by a combination of the following two steps: a step of impregnating a fibrous substrate with an organic solvent solution of a polyurethane, and a fibrous substrate obtained in the step. The step of immersing in a water or an organic solvent aqueous solution which is not a solvent of a polyurethane to wet-solidify the polyurethane. As the organic solvent which is a solvent of such a polyurethane, a water-miscible organic solvent such as N,N-dimethylformamide can be used. However, in general, the use of an organic solvent has a strong influence on the human body or the environment, and it is strongly desired to use an organic solvent at the time of manufacture of a sheet.

Regarding the specific solution, for example, a method of replacing the organic solvent type of polyurethane with a water-dispersible polyurethane obtained by dispersing a polyurethane in water is reviewed. However, the fibrous substrate is impregnated with a sheet of water-dispersed polyurethane, and Compared with the sheet imparted by the organic solvent type of the polyurethane, there is a problem that the touch is hard.

That is, in the case where the organic solvent type polyurethane was previously used, since the fibrous substrate is impregnated and generally solidified by wet coagulation by immersion in water, the polyamine group The acid ester is replaced with water by an organic solvent to form a porous structure. Thereby, the polyurethane does not strongly hold the fiber entangled portion of the fibrous substrate, and the touch of the sheet becomes soft. However, in the case of using a water-dispersible polyurethane, since the fibrous substrate is solidified after impregnation, it is generally a dry heat coagulation method by heating and drying, and the polyurethane has a non-porous structure. As a result, since the polyurethane strongly holds the fiber entangled portion of the fibrous substrate, the touch of the sheet becomes hard.

Therefore, in the method of using a water-dispersible polyurethane, a soft water-dispersible polyurethane is suitably used to weaken the anchoring force of the fiber entangled point of the polyurethane so that Various methods of softening the touch are conducted.

For example, in the case of a water-dispersible polyurethane to which a fibrous substrate is imparted, it is proposed to use a polyimide having a sensitizing gelation property which is dried at a temperature of 50 ° C to obtain a film having a thickness of 100 μm. The modulus of elasticity at a temperature of 90 ° C is 2.0 × 10 ⁷ to 5.0 × 10 ⁸ dyn / cm ² , the modulus of elasticity at 160 ° C is 1.0 × 10 ⁷ dyn / cm ² or more, and the temperature of α dispersion (Tα) is -30. °C or less (refer to Patent Document 1). However, according to the method of this proposal, a sheet having a soft touch can be obtained. However, if a soft polyurethane is proposed as such, the abrasion resistance of the sheet is deteriorated, and grinding and grinding are performed. The sandpaper or the like used in the raising process is liable to cause clogging, and therefore there is a problem that it is difficult to obtain a good standing grade and the productivity is deteriorated.

Further, a method of adding polyfluorene to a polyurethane to improve the slipperiness of the fiber and the polyurethane has been proposed (see Patent Document 2). However, in the case of this proposal, although the touch of the sheet becomes soft, there is a problem that the residual elongation after stretching becomes large and it is difficult to return to the original shape.

Further, a method in which a soft water-dispersible polyurethane is imparted to a fibrous substrate, and then the fiber of the fibrous substrate is subjected to an extremely fine step, and then a polyurethane is re-applied (refer to Patent Document 3). However, the proposed method, while softening by the soft polyurethane to hold the fiber entanglement point of the fibrous substrate, is rendered durable by the subsequent imparting of the polyurethane. However, since the polyurethane is imparted to the inside of the fibrous substrate at a high density, the sheet becomes heavy. In addition, since the water-dispersed polyurethane is applied to the fibrous base material, the step of extremely thinning the fibers of the fibrous base material is performed. Therefore, the efficiency of the extremely fine treatment of the fibers is low, and the thickness of the sheet is increased. Or in the case where a large amount of a polyurethane is contained, it is difficult to make the fiber extremely fine.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4074377

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-174868

[Patent Document 3] Japanese Patent No. 4216111

That is, in the prior art, a sheet having a soft touch and high durability as a sheet produced by the step of not using an organic solvent, and a method for producing the same have not been obtained so far.

Accordingly, an object of the present invention is to provide a sheet having a soft touch and high durability in a sheet-like sheet, particularly a leather-like sheet, and further exhibiting good wrinkle recovery.

Another object of the present invention is to provide a method for producing the above-mentioned sheet, which is a method for producing a sheet which does not use an organic solvent in the production step and which is concerned with the environment.

In order to achieve the above object, the sheet of the present invention is characterized in that a water-dispersed polyurethane is contained in a fibrous substrate having an ultrafine fiber having an average single fiber diameter of 0.3 to 7 μm; One of the water-dispersible polyurethanes is partially present and adhered to the outer periphery of the bundle containing the ultrafine fibers, and contains a substance having a guanamine bond; and is biased to exist and adheres to a portion other than the outer periphery of the ultrafine fiber bundle The water-dispersible polyurethane contains a water-dispersible polycarbonate-based polyurethane.

In addition, the "outer peripheral portion of the ultrafine fiber bundle" means a shape which can be formed by connecting the centers of the ultrafine fibers existing along the outer circumference in a straight line in the cross section of the ultrafine fiber bundle. Further, "the partial presence and adhesion to the outer peripheral portion of the ultrafine fiber bundle" means that the water-dispersible polyurethane enters and adheres to the inner side of the ultrafine fiber bundle with respect to the area enclosed by the outer peripheral portion (i.e., The ratio of the area of the inner side of the outer peripheral portion is 20% or less.

According to a preferred aspect of the sheet of the present invention, the aforementioned guanamine The molecular weight of the bond material is 100~500.

Further, according to a preferred aspect of the sheet of the present invention, the water-dispersible polyurethane which is present and adhered to the outer peripheral portion of the ultrafine fiber bundle is a polycarbonate-based polyurethane, Or ether based polyurethanes.

Further, according to a preferred aspect of the sheet of the present invention, the water-dispersed polyurethane which is present and adhered to the outer periphery of the ultrafine fiber bundle is biased and/or biased to exist and adhered to the microfiber bundle The water-dispersible polycarbonate-based polyurethane other than the outer peripheral portion contains polyfluorene oxide, and the polyfluorene oxide is preferably a film-forming polyfluorene oxide.

Moreover, the method for producing a sheet of the present invention is characterized in that a water-dispersed polyurethane solution containing a foaming agent is applied to a fibrous substrate comprising an ultrafine fiber-presenting fiber, and then is finely pulverized. The fiber-extended fiber is expressed by an ultrafine fiber having an average single fiber diameter of 0.3 to 7 μm, and then a water-dispersible polycarbonate-based polyurethane solution is supplied.

According to a preferred aspect of the method for producing a sheet according to the present invention, the water-dispersed polyurethane solution containing the foaming agent previously imparted to the ultrafine fiber is a polycarbonate-based polyamine group. The formate or the ether-based polyurethane solution preferably contains inorganic particles, and the inorganic particles-based porous vermiculite is more preferable.

Further, according to a preferred aspect of the method for producing a sheet according to the present invention, the water-dispersed polyurethane solution containing a foaming agent and/or the water imparted by the above-mentioned ultrafine fibers are expressed. The dispersion-type polycarbonate-based polyurethane solution contains a poly-hydrogen peroxide aqueous dispersion, and the poly-hydrogen peroxide aqueous dispersion is more preferably a film-forming polyhydric oxygen aqueous dispersion.

According to the present invention, it is possible to provide a soft touch and a good wrinkle recovery property (i.e., wrinkle-free when unfolded after folding) by using an organic solvent in the production step without considering the use of the environment. It is also a durable sheet that can be applied to applications requiring high durability such as automatic vehicle use.

[Formation of the Invention]

The sheet of the present invention is a sheet having a water-dispersed polyurethane containing a water-dispersed polyurethane in a fibrous substrate comprising an ultrafine fiber having an average single fiber diameter of 0.3 to 7 μm; One of the urethanes is partially present and adhered to the outer periphery of the bundle containing the above-mentioned ultrafine fibers, and contains a substance having a guanamine bond; and a water-dispersed type which is present in a portion other than the outer peripheral portion of the ultrafine fiber bundle The polyurethane contains a water-dispersible polycarbonate-based polyurethane.

As the fibers constituting the fibrous substrate used in the present invention, fibers containing a thermoplastic resin which can be melt-spun can be used. The thermoplastic resin is not limited to a specific one, and examples thereof include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate or polylactic acid; Polyamide, 6-nylon or 66-nylon, polyacrylic acid, polyethylene or polypropylene, and thermoplastic cellulose. Among them, polyester fibers are preferred from the viewpoints of strength, dimensional stability, and light resistance. Further, the fibrous base material may be composed of fibers in which the raw materials are different from each other.

The cross-sectional shape of the fiber constituting the fibrous base material may be Circular section, however, it is also possible to use polygons such as ellipse, flat and triangular, or fan-shaped and cross-shaped profiles. The fiber comprises ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm. By setting the average single fiber diameter of the ultrafine fibers to 7 μm or less, preferably 6 μm or less, more preferably 5 μm or less, an excellent softness or a rose-like sheet can be obtained. On the other hand, the average single fiber diameter of the ultrafine fibers is set to 0.3 μm or more, preferably 0.7 μm or more, more preferably 1 μm or more, and the color development property after dyeing or the beaming treatment such as grinding with a sandpaper or the like is performed. The dispersibility of the fibers and the ease of finishing are excellent.

As the form of the above fibrous substrate including the ultrafine fibers, a woven fabric, a knitted fabric, a non-woven fabric, or the like can be used. Among them, since the surface quality of the sheet is good when the non-woven fabric is subjected to the surface raising treatment, it is preferable to use a non-woven fabric. Although it is possible to use either of a staple fiber nonwoven fabric and a long fiber nonwoven fabric for the nonwoven fabric, it is preferable to use a staple fiber nonwoven fabric from the viewpoint of touch or grade.

The fiber length of the short fibers used in the above-mentioned short fiber nonwoven fabric is preferably 25 to 90 mm, more preferably 30 to 80 mm. By setting the fiber length of the short fibers to 25 mm or more, a sheet having excellent abrasion resistance can be obtained based on the entanglement. Further, by setting the fiber length of the short fibers to 90 mm or less, a sheet having a better touch and grade can be obtained.

In the case where the fibrous base material is a non-woven fabric, the nonwoven fabric is preferably a structure having a structure in which a bundle of extremely fine fibers (a very fine fiber bundle) is entangled. The strength of the sheet can be increased by the fact that the ultrafine fibers are entangled in the state of the bundle. Such a non-woven fabric, as described later, can be The fine fiber constituting fibers are obtained by preliminarily entanglement with each other and then expressing the ultrafine fibers.

The ultrafine fiber or the ultrafine fiber bundle thereof may be formed into a non-woven fabric, and a fabric or a knitted fabric may be inserted into the nonwoven fabric for the purpose of improving strength and the like. The average single fiber diameter of the fibers constituting the woven fabric or the knitted fabric is preferably about 0.3 to 10 μm.

When the mass per unit area of the fibrous base material is too low, physical properties such as tensile strength and tear strength of the sheet are weak, and if it is too high, the touch of the sheet becomes hard, so that 50 ~2000 g/m ² is preferred.

Further, when the thickness of the fibrous base material is too thin, physical properties such as tensile strength and tear strength of the sheet are weak, and if it is too thick, the touch of the sheet becomes hard, so that it is 0.1 to 5 mm. It is better.

The polyurethane which can be used in the present invention is preferably a polyurethane obtained by a reaction of a polymer diol with an organic diisocyanate and a chain extender; a so-called ether polyamine The carbamate means that 70% by mass or more of the polymer diol constituting the polyurethane is an ether system; the polycarbonate-based polyurethane means a polymer constituting the polyurethane. 70% by mass or more of the diol is a polycarbonate system. Ether-based polyurethanes are generally soft and have good hydrolysis resistance, but are poor in light resistance and heat resistance; polycarbonate-based polyurethanes are generally used. It is a polyurethane which is harder than ether urethanes, such as hydrolysis resistance, light resistance and heat resistance; it can also be used in different systems without affecting various good characteristics. Polymer diol copolymerization.

Examples of the ether polymer diol include polyethylene glycol and poly Propylene glycol, polytetramethylene glycol, and a combination of these copolymerized diols.

The polycarbonate-based polymer diol can be produced by a transesterification reaction of an alkylene glycol with a carbonate, or a reaction of phosgene or a chloroformate with an alkylene glycol.

As the alkylene glycol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol or a linear alkylene glycol such as 1,10-nonanediol; or neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol or a branched alkylene glycol such as 2-methyl-1,8-octanediol; an alicyclic diol such as 1,4-cyclohexanediol; an aromatic diol such as bisphenol A, glycerin or trimethylol Propane and neopentyl alcohol. The polycarbonate diol obtained from each of the individual alkylene glycols may be either a copolymerized polycarbonate diol obtained from two or more kinds of alkylene glycols.

The number average molecular weight of the polymer diol is preferably from 500 to 4,000. By setting the number average molecular weight to 500 or more, more preferably 1500 or more, it is possible to prevent the touch from becoming hard. Further, by setting the number average molecular weight to 4,000 or less, more preferably 3,000 or less, the strength of the polyurethane can be maintained.

The organic diisocyanate may, for example, be an aliphatic diisocyanate such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate or xylylene diisocyanate; or diphenylmethane II. An aromatic diisocyanate such as an isocyanate or a tolyl diisocyanate may be used in combination. Among them, from the viewpoint of light resistance, hexamethylene diisocyanate and dicyclohexyl are used. An aliphatic diisocyanate such as a methane diisocyanate or an isophorone diisocyanate is preferred.

As the chain extender, an amine chain extender such as ethylenediamine or methylenebisaniline or a glycol chain extender such as ethylene glycol can be used. Further, as the chain extender, a polyamine obtained by reacting a polyisocyanate with water may also be used.

In the case of the polyurethane, a crosslinking agent may be used in combination in order to improve water resistance, abrasion resistance, hydrolysis resistance, and the like. The crosslinking agent may be an external crosslinking agent added as a third component in the polyurethane, or may be an internal crosslinking agent, which is introduced in advance in the molecular structure of the polyurethane. There are reaction sites that form a crosslinked structure. In the case of a crosslinking agent, it is suitable to use an isocyanate group, A compound such as an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, or a stanol group.

The polyurethane used in the present invention is preferably a hydrophilic group in a molecular structure. By having a hydrophilic group in the molecular structure, the dispersion and stability of the water-dispersible polyurethane can be improved.

The hydrophilic group may be, for example, any of the following hydrophilic groups: a cationic system such as a quaternary ammonium salt, an anion such as a sulfonate or a carboxylate, or a nonionic system such as polyethylene glycol. And a combination of a cationic type and a nonionic hydrophilic group, and a combination of an anionic type and a nonionic hydrophilic group. Among them, it is particularly preferable to use a nonionic hydrophilic group which does not require the yellowing caused by light or the disadvantage caused by the neutralizing agent.

That is, in the case where the above hydrophilic group is an anionic system, although a neutralizing agent is necessary, for example, the neutralizing agent is ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine or dimethyl. Grade 3 amine such as ethanolamine In the case of film formation, the heat during drying will cause the amine to be produced and volatilized and discharged to the outside of the system. Therefore, in order to suppress the deterioration of the discharge to the atmosphere or the working environment, it is necessary to introduce a device for recovering volatile amines. Further, in the case where the above-mentioned amine is not volatilized by heating and remains in the sheet form of the final product, the amine is also discharged into the environment when the product is incinerated.

On the other hand, when the above hydrophilic group is a nonionic system, since the neutralizing agent is not used, it is not necessary to introduce an amine recovery device, and there is no fear that the amine remains in the sheet.

Further, 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 portion is alkaline if it is wetted by water. I am afraid that it will be deteriorated by hydrolysis. However, in the case of a nonionic hydrophilic group, since the neutralizing agent is not used, there is no fear of deterioration due to hydrolysis of the polyurethane.

In the present invention, a water-dispersible polyurethane is contained in the interior of the fibrous substrate, and a part of the water-dispersible polyurethane is partially present and adhered to the outer periphery of the bundle containing the above-mentioned ultrafine fibers. Further, it contains a substance having a guanamine bond; and the water-dispersible polyurethane having a portion other than the portion which is present and adhered to the outer peripheral portion of the ultrafine fiber bundle contains a water-dispersible polycarbonate-based polyurethane.

The above-mentioned substance having a guanamine bond is a decomposition product of the organic foaming agent in the method for producing a sheet to be described later, and examples thereof include 2,2'-azobis[2-methyl-N-(2). -hydroxyethyl)propanamide] (for example, "VA-086" manufactured by Wako Pure Chemical Industries, Ltd.), or 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxyl) A decomposition product of a water-soluble foaming agent such as methyl-2-hydroxyethyl]propanamide (for example, "VA-080" manufactured by Wako Pure Chemical Industries, Ltd.).

The "water-dispersed polyurethane" contains a foaming agent decomposition product, that is, a substance having a guanamine bond, meaning that the water-dispersed polyurethane exhibits a gas generated by decomposition of a foaming agent. Foamer.

The molecular weight of the above-mentioned substance having a guanamine bond is vaporized by heating at the time of foaming if it is too low, so there is a problem of odor or safety of the operator or even environmental efflux in the manufacturing step; if the molecular weight is too high Therefore, the ratio of the amount of gas generated to the added mass of the water-dispersible polyurethane decreases, and the foaming effect becomes low. Therefore, the molecular weight of the substance is preferably from 100 to 500, and more preferably from 150 to 450. good.

The content of the substance having a guanamine bond contained in the water-dispersed polyurethane having the outer peripheral portion of the bundle containing the above-mentioned ultrafine fibers is proportional to the ratio of the solid content of the polyurethane In other words, 0.5 to 20% by mass is preferred. Since the substance having a guanamine bond is a decomposition product of the foaming agent, by adjusting the content thereof to 0.5% by mass or more, preferably 1% by mass or more, the touch feeling by the foamed sheet can be effectively obtained. The effect of the transformation. On the other hand, when the content of the substance having a guanamine bond is adjusted to 20% by mass or less, preferably 15% by mass or less, the abrasion resistance of the sheet due to excessive foaming can be suppressed from being lowered.

A polycarbonate-based polyurethane is present in a type which is present in a peripheral portion of the bundle containing the above-mentioned ultrafine fibers and which contains a water-dispersed polyurethane having a substance having a guanamine bond. Or an ether type polyurethane is preferred.

a case where the water-dispersed ester-based polyurethane is present and adhered to the outer peripheral portion of the bundle containing the above-mentioned ultrafine fibers, and the type of the water-dispersible polyurethane containing a substance having a guanamine bond is a water-dispersed ester-based polyurethane. Due to fiber intersection The binding force of the wrap is weakened, so the touch of the sheet can be softened. However, when only the water-dispersible ether-based polyurethane is contained in the interior of the fibrous base material, it is not able to exhibit good wrinkle recovery, and durability such as light resistance or heat resistance is difficult to express.

In the present invention, the water-dispersed ether-based polyamine-based group is present in the outer peripheral portion of the bundle containing the above-mentioned ultrafine fibers, and the water-dispersible polyurethane having a substance having a guanamine bond is a water-dispersible ether-based polyamine group. In the case of an acid ester, the water-dispersed ether-based polyurethane retains the fiber entanglement point of the fibrous substrate, and the touch of the sheet can be softened; further, by the presence and attachment of the bias The water-dispersible polyurethane other than the outer peripheral portion of the ultrafine fiber bundle contains a water-dispersible polycarbonate-based polyurethane, which exhibits good wrinkle recovery, and such as light resistance and heat resistance. Durable.

On the other hand, the type of the water-dispersible polyurethane which is present in the outer peripheral portion of the bundle containing the above-mentioned ultrafine fibers and which contains a substance having a guanamine bond is a water-dispersed polycarbonate-based polyamine group. In the case of a formate, it exhibits wrinkle recovery, and durability such as light resistance and heat resistance. Further, as described later, the water-dispersible polycarbonate-based polyaminocarboxylic acid containing a substance having a guanamine bond The ester is present in a biased manner and adheres to the outer peripheral portion of the ultrafine fiber bundle, and the touch of the sheet can be softened and the wrinkle recovery property is good.

It is assumed that in the case where the inside of the fibrous substrate contains only a water-dispersible polycarbonate-based polyurethane which does not contain a substance having a guanamine bond, it can exhibit wrinkle recovery or light resistance and heat resistance. Durability, however, due to the direct retention of water-dispersible polycarbonate-based polyurethanes The fine fiber bundle is attached in a manner, and the touch of the sheet becomes hard and is not practical.

In the present invention, the water-dispersed polycarbonate polycondensate is present in the outer peripheral portion of the bundle of the ultrafine fibers described above, and the water-dispersed polyurethane having a substance having a guanamine bond is dispersed. In the case of a urethane, the water-dispersible polycarbonate-based polyurethane containing a substance having a guanamine bond forms an attachment structure of a fiber interlacing point which does not directly hold the fibrous substrate. The touch feeling of the sheet is softened, and the water-dispersible polycarbonate-based polyurethane which is present and adhered to the outer peripheral portion of the ultrafine fiber bundle is preferably combined. Wrinkle recovery, while showing good durability such as light resistance and heat resistance.

In the present invention, the water-dispersible polyurethane which is present in the interior of the fibrous substrate and which is attached to the outer peripheral portion of the above-mentioned ultrafine fiber bundle, and which are biased to exist and adhere to the outer periphery of the ultrafine fiber bundle The water-dispersible polycarbonate-based polyurethane other than the above is not limited to a specific content, but is also finely contained in the fibrous substrate with respect to the quality of the ultrafine fibers forming the fibrous substrate. In the case where the woven fabric or the knitted fabric is inserted into the non-woven fabric of the fiber or the ultrafine fiber bundle, the total mass is preferably 10 to 50% by mass, and preferably 15 to 40% by mass. good. If the content of the polyurethane is too small, the tensile strength, tear strength and abrasion resistance of the sheet are lowered; if too large, the touch of the sheet becomes hard, because the unit area is The quality has become heavier.

Moreover, all of the water-dispersible polyamine contained in the interior of the fibrous substrate The mass (U) of the carbamate, or the mass (U1) of the water-dispersed polyurethane which is present and attached to the outer periphery of the ultrafine fiber bundle and contains a substance having a guanamine bond, and is biased to exist and The mass (U2) of the water-dispersible polycarbonate-based polyurethane which is adhered to the outer peripheral portion of the ultrafine fiber bundle is not limited to a specific value, but is completely aggregated with respect to the fibrous substrate. The urethane is 10 to 50% by mass, and the water-dispersed polyurethane having the above-mentioned partial tendency and adhered to the outer peripheral portion of the ultrafine fiber bundle is 1 to 35% by mass, and is biased to adhere to the microfiber bundle. The water-dispersible polycarbonate-based polyurethane other than the outer peripheral portion is preferably 1 to 40% by mass.

Further, with respect to the mass (U) of all the water-dispersible polyurethanes, the mass (U1) of the water-dispersed polyurethane which is present and adhered to the outer peripheral portion of the ultrafine fiber bundle, and the bias The individual ratio of the mass (U2) of the water-dispersible polycarbonate-based polyurethane present and adhered to the outer peripheral portion of the ultrafine fiber bundle is 1 to 90% in terms of (U1)/(U) It is preferable that (U2)/(U) is 1 to 99%.

In addition, the mass (U1) of the water-dispersible polyurethane which is present and adhered to the outer peripheral portion of the ultrafine fiber bundle, and the water-dispersed type other than the portion which is biased and adhered to the outer peripheral portion of the ultrafine fiber bundle The ratio of the mass (U2) of the polycarbonate-based polyurethane is not limited to a specific value, but it is preferably (U1) / (U2) = 1 / 0.1 to 1/10, and (U1) /(U2)=1/0.5~1/5 is better.

This is because the above-mentioned polycarbonate is high in the ratio of the mass (U1) of the water-dispersed polyurethane having a substance having a guanamine bond and being attached to the outer peripheral portion of the ultrafine fiber bundle. Polyurethane If the ratio of the mass (U2) is too low, the wrinkle recovery or durability of the sheet is lowered; if it is biased to exist and adheres to the periphery of the ultrafine fiber bundle and contains a substance having a guanamine bond, the water-dispersed polyamine group When the mass ratio of the mass of the formate (U1) is low, and the ratio of the mass (U2) of the polycarbonate-based polyurethane is too high, the flexibility of the sheet is lowered.

Furthermore, the "inside of the fibrous substrate" in the present invention means a range from the surface of one side to the surface of the other side, but in the case where the fibrous substrate has a standing layer, it means The range of the hair layer. For example, the case where the surface of one side has a bristles means the range from the bristles to the surface of the other side when the fibrous substrate is viewed from the cross section; both surfaces have a bristles, meaning When the fibrous substrate is viewed in section, the range from the upper bristles to the underlying bristles.

The water-dispersible polyurethane which is present in the present invention and which is present in the outer peripheral portion of the ultrafine fiber bundle and which contains a substance having a guanamine bond, is a foaming structure by a foaming agent. The person. The blowing agent means that it decomposes upon heating to produce an additive such as nitrogen or carbon dioxide. By using a water-dispersible polyurethane solution containing a foaming agent, the water-dispersed polyurethane solution imparted to the fibrous substrate is foamed while being heated, and the obtained water-dispersed type The polyurethane forms a porous structure from the foaming. The porous structure is formed by the water-dispersible polyurethane, and the touch of the sheet containing the polyurethane becomes soft. This is because the bonding area between the fibers and the polyurethane in the sheet is reduced, whereby the binding force of the fibers is weakened. Further, after the foaming agent is foamed, the water-dispersible polyurethane has a residue containing a guanamine bond.

As the foaming agent to be added to the above water-dispersible polyurethane solution, for example, azoisobutyronitrile or dinitrosopentamethylenetetramine can be used (for example, Sanxie Chemical Co., Ltd.) "Cellmic (registered trademark) A"), azodimethylamine (for example, "Cellmic (registered trademark) CAP" manufactured by Sankyo Chemical Co., Ltd.), p, p'-oxybisbenzenesulfonide (for example) "Cellmic (registered trademark) S" manufactured by Sankyo Chemical Co., Ltd.), N, N'-dinitrosopentamethylenetetramine (for example, "Cellular GX" manufactured by Yonghe Chemical Industry Co., Ltd.), or 2, 2' -Azobis[2-methyl-N-(2-hydroxyethyl)propanamide] (for example, "VA-086" manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azo double {2- Organic-based foaming agent such as methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide} (for example, "VA-080" manufactured by Wako Pure Chemical Industries, Ltd.); An inorganic foaming agent such as sodium hydride (for example, "Cellmic (registered trademark) 266" manufactured by Sankyo Chemical Co., Ltd.), in which a foaming agent having a guanamine bond is water-soluble, and can be uniformly dissolved in a water-dispersible polyamine. It is preferred in the carboxylic acid ester solution.

A part of the above-mentioned water-dispersible polyurethane used in the present invention is a material which is biased to exist and adheres to the outer periphery of the ultrafine fiber bundle and contains a guanamine bond. A water-dispersible polyurethane containing a substance having a guanamine bond is present in a peripheral portion of the ultrafine fiber bundle by being biased and does not adhere thereto, and is more inner than the outer portion of the ultrafine fiber bundle. At the point where the restraining force of the fiber is weakened, the touch of the sheet becomes soft.

Since the water-dispersible polyurethane having a substance having a guanamine bond is soft, when the water-dispersible polyurethane is applied, the sea component of the sea-island fiber is removed, and dyeing is performed. Step, by physically compressing ‧ in this step, the above water-dispersible polyamine group One part of the acid ester sometimes adheres to the inner side of the outer portion of the ultrafine fiber bundle. However, in the present invention, since the water-dispersed polyurethane having the above-mentioned biased and adhered to the outer peripheral portion of the ultrafine fiber bundle is porously structured by a foaming agent as described above, it is ensured that the guanamine is contained. The gap between the water-dispersible polyurethane and the ultrafine fiber bundle of the substance of the bond is broad, and the water-dispersible polyurethane is clearly biased and adheres to the outer periphery of the ultrafine fiber bundle.

In the present invention, the "outer peripheral portion of the ultrafine fiber bundle" means a shape obtained by connecting the centers of the extremely fine single fibers existing along the outer circumference in a straight line in the cross section of the ultrafine fiber bundle. However, in the case of inserting a reinforcing fabric or a knitted fabric in addition to a nonwoven fabric containing ultrafine fibers or an ultrafine fiber bundle, the fibers of the reinforcing weave are excluded from the object. Further, "the water-dispersed polyurethane is biased and adhered to the outer peripheral portion of the ultrafine fiber bundle" means that the water-dispersible polyurethane enters the ultrafine fiber bundle with respect to the area enclosed by the outer peripheral portion. The ratio of the area of the inner side (that is, the inner side when compared with the outer peripheral portion) is 20% or less.

In the present invention, the water-dispersible polycarbonate-based polyurethane which is present and adhered to the outer peripheral portion of the ultrafine fiber bundle is attached to a water-dispersed type containing a substance having a guanamine bond. On the polyurethane, the water-dispersible polyurethane containing a substance having a guanamine bond forms a porous structure inside the fibrous substrate. When focusing on the water-dispersible polycarbonate-based polyurethane, it is assumed that a porous structure is formed inside the fibrous substrate in the same manner as the water-dispersible polyurethane containing the substance having a guanamine bond. Even hard for polyurethanes The water-dispersible polycarbonate-based polyurethane can also exhibit a soft touch in the form of a sheet. The water-dispersed polyurethane having a substance having a guanamine bond present in the outer peripheral portion of the ultrafine fiber bundle, and the water dispersion which is present in a portion other than the outer peripheral portion of the ultrafine fiber bundle The polycarbonate-based polyurethanes are present in such a manner that they do not mix with each other.

In addition, the water-dispersible polycarbonate-based polyurethane which is present in the outer peripheral portion of the ultrafine fiber bundle, which is present in the outer peripheral portion of the ultrafine fiber bundle, may be contained in order to soften the touch of the sheet. The substance of the guanamine bond is preferable because it does not contain a substance having a guanamine bond, and the durability of the sheet can be improved.

The water-dispersed polyurethane which is present in the outer peripheral portion of the ultrafine fiber bundle and/or the polycarbonate which is present in the outer periphery of the ultrafine fiber bundle and which is attached to the outer peripheral portion of the ultrafine fiber bundle The ester type polyurethane is preferably one containing polyfluorene oxide. By the polyurethane containing polyfluorene, the friction between the polyurethane and the fibers of the fibrous substrate is reduced, and the touch of the sheet is softer. Further, since it is easy to grind by sandpaper or the like in the raising step, the length of the standing hair can be lengthened, and the grinding powder is less likely to be clogged with the grinding powder, and the workability is improved.

The polyoxo-oxygen content of the above-mentioned polyurethane is not limited to a specific value, but the mass ratio to the polyurethane is preferably 0.1 to 10% by mass, and preferably 0.5 to 8 by mass. % is better. In this case, if the polypyrene content is too small, the softening effect of the sheet is insufficient, and if it is too large, the force of the polyurethane-holding fiber in the sheet is changed. Weak, wear resistance is reduced.

In the above polyfluorene oxide, polydimethyl methoxy oxane, amine modified poly fluorene oxide, epoxy modified poly fluorene oxide, or polyester modified poly fluorene can be used, wherein a film is used. Sexual polyoxygen is preferred. The film-forming polyfluorene means that a three-dimensional crosslinked structure is formed by heating and is film-formed, and is not dispersed in water, and that it has a film-forming property, even after imparting film-forming polyfluorene. The sheet is washed or dyed, washed, or the like in water, or subjected to external factors such as friction, and also prevents the polypoxy oxygen from falling off the sheet and maintaining the softness of the sheet.

Further, after impregnating the fibrous substrate with the water-dispersible polyurethane solution containing the film-forming polyhydric oxygen aqueous dispersion, the sheet is treated with hot water and/or an aqueous alkali solution to refine the fibers. In this case, the flexibility of the sheet can be maintained by the film forming property of polyoxymethylene. In the present invention, "the film-forming polyfluorene oxide also remains in the sheet after the extremely fine treatment of the fiber" means that the measured value of the weight of the sheet after the ultra-fine treatment is compared with the theoretically calculated value, and the difference is 30. Less than %.

The water-dispersed polyurethane which is present in the outer peripheral portion of the ultrafine fiber bundle and which is present in the present invention, and the water-dispersed polycondensation which is present in the outer peripheral portion of the ultrafine fiber bundle Carbonate-based polyurethanes may contain various additives such as pigments such as carbon black; flame retardants such as phosphorus, halogen, polyfluorene, and inorganic; phenol, sulfur, and phosphorus resistant Oxidizing agents; ultraviolet absorbers such as benzotriazole, diphenylketone, salicylate, cyanoacrylate, or oxalic acid anilide; hindered amine or benzoate Light stabilizer, polycarbodiimide and other hydrolysis-resistant stabilizer; plasticizer; Antistatic agent; surfactant; softener; water repellent; coagulation modifier; dye; preservative; antibacterial agent; deodorant; cellulose particles and other fillers; or vermiculite, titanium oxide and other inorganic particles, etc. They may be contained singly or in any combination.

When the thickness of the sheet obtained in the present invention is too thin, physical properties such as tensile strength or tear strength of the sheet are weak, and if it is too thick, the touch of the sheet becomes hard. Therefore, 0.1 to 5 mm is preferred.

Next, a method of producing the sheet of the present invention will be described. The method for producing a sheet according to the present invention is to impart a specific water-dispersible polyamine to a fibrous substrate by expressing a specific water-dispersible polyurethane solution, and then expressing the ultrafine fibers from the fibrous substrate. Carbamate solution.

As the form of the above fibrous substrate including the ultrafine fibers, a woven fabric, a knitted fabric, a non-woven fabric, or the like can be used. Among them, since the surface quality of the sheet is good when the non-woven fabric is subjected to the surface raising treatment, it is preferable to use a non-woven fabric. Although it is possible to use either of a staple fiber nonwoven fabric and a long fiber nonwoven fabric for the nonwoven fabric, it is preferable to use a staple fiber nonwoven fabric from the viewpoint of touch or grade.

In the nonwoven fabric used as the fibrous substrate, the method of entanglement of the fibers or the fiber bundles is not limited to a specific method, and for example, a needle punch or a water jet punch can be employed.

In order to form a very fine fiber of a fibrous base material, it is preferable to use an ultrafine fiber constituting fiber. By using the ultrafine fiber characterization fiber, the form in which the ultrafine fiber bundle is entangled can be stably obtained.

In the case of the ultrafine fiber characterization fiber, an island-in-the-sea type fiber or a peel-off type composite fiber or the like may be used, wherein the sea-island type fiber system does not dissolve the solvent. The thermoplastic resin of the same two components is divided into a sea component and an island component, and the sea component is dissolved and removed by using a solvent or the like, and the remaining island component is made into an ultrafine fiber; and the peeling type composite fiber is a thermoplastic resin of two components in the fiber. The surfaces are alternately arranged in a radial or multi-layered shape, and the components are peeled and divided into fine fibers. Among them, in the sea-island type fiber, since the sea component is removed, an appropriate gap can be provided between the island components, that is, between the ultrafine fibers, so that it is used from the viewpoint of flexibility or touch of the sheet-like material. It is better.

Among the island-in-the-sea type fibers, there are sea-island type composite fibers and mixed-spun fibers, and the sea-island type composite fibers are formed by using an island-in-sea type composite nozzle, and the sea component and the island component 2 are alternately arranged and spun; The spun fiber is obtained by mixing and spinning a sea component and an island component 2 component. From the viewpoint of obtaining a fine fiber having a uniform fineness, it is also preferable to use an island-in-the-sea type composite fiber from the viewpoint of obtaining a very fine fiber of a sufficient length to favor the strength of the sheet.

For the sea component of the sea-island type fiber, polyethylene, polypropylene, polystyrene, copolymerized polyester obtained by copolymerizing sodium sulfonate isophthalic acid and polyethylene glycol, polylactic acid, and poly Vinyl alcohol and the like. Among them, a copolymerized polyester or polylactic acid obtained by copolymerization of sodium sulfoisophthalate and polyethylene glycol which is decomposable in an organic solvent without using an organic solvent, or a seawater which can be removed in hot water The polyvinyl alcohol of the composition is preferred.

The sea-removing treatment of the sea-island type fiber is carried out, and the sea-removing treatment is carried out by immersing the sea-island type fiber in a solvent and extracting the liquid. As the solvent for dissolving the sea component, in the case where the sea component is polyethylene, polypropylene or polystyrene, an organic solvent such as toluene or trichloroethylene can be used. also, In the case where the sea component is a copolymerized polyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide can be used; and in the case where the sea component is polyvinyl alcohol, hot water can be used.

The sea-removal treatment in the case of using the sea-island type fiber is carried out after the water-dispersible polyurethane containing the foaming agent is applied to the fibrous substrate. When the seawater treatment is carried out before the application of the polyurethane, the structure in which the polyurethane is directly adhered to the ultrafine fibers strongly holds the ultrafine fibers, and the touch of the sheet becomes hard. On the other hand, when the water-dispersed polyurethane containing a foaming agent is subjected to the sea-removal treatment, the water-dispersible polyurethane and the ultrafine fiber containing the substance having a guanamine bond are contained. Between the gaps caused by the components of the sea of the sea, the water-dispersed polyurethane is formed to adhere to and adhere to the outer periphery of the ultrafine fiber bundle. Thereby, since the water-dispersed polyurethane containing the substance having a guanamine bond does not directly hold the structure of the ultrafine fibers, the touch of the sheet becomes soft. Further, the water-dispersible polyurethane has a porous structure inside the fibrous substrate by containing a foaming agent as will be described later. The voids caused by the foaming of the foaming agent are formed between the sea-island fiber and the water-dispersed polyurethane, and the permeability of the sea component extraction solvent is improved in the sea removal step, and the sea-removing efficiency becomes high even if the unit area is A fibrous substrate having a high quality or a tablet having a large amount of polyurethane adhesion can also be easily removed from the sea.

Further, in the present invention, the water-dispersible polycarbonate-based solution containing the foaming agent is applied to the fibrous substrate, and then the ultrafine fibers are expressed from the fibrous substrate, and then the water-dispersible polycarbonate is polymerized. Aminoformate solution. The water-dispersed polyurethane solution containing a foaming agent is an ether-based polyamine group In the case of the formic acid ester solution, a water-dispersible polycarbonate-based polyurethane solution is provided by imparting a water-dispersible ether-based polyurethane solution containing a foaming agent and then expressing the ultrafine fibers. It exhibits durability such as light resistance and heat resistance which are hard to be expressed when only an ether-based polyurethane is used, and imparts good abrasion resistance to the sheet.

In the case where the water-dispersed polyurethane solution containing a foaming agent is a polycarbonate-based polyurethane solution, a water-dispersible polycarbonate-based polyamine containing a foaming agent is imparted. The carboxylic acid ester solution, which is then subjected to the expression of the ultrafine fibers, imparts a water-dispersible polycarbonate-based polyurethane solution, and can exhibit a water-dispersible polycarbonate-based polyurethane containing a foaming agent. When the water-dispersible polycarbonate-based polyurethane imparted by the ultrafine fibers is imparted with durability such as soft touch, light resistance, heat resistance, and the like, the surface appearance of the sheet can be imparted. And good wear resistance.

In addition, a water-dispersed polyurethane having a substance having a guanamine bond imparted before the formation of the ultrafine fiber is formed into a porous structure inside the fibrous substrate by containing a foaming agent, and then borrows By expressing the ultrafine fibers, a water-dispersible polycarbonate-based polyurethane solution is attached, and the polycarbonate-based polyurethane is attached to a polyurethane containing a substance having a guanamine bond. Porous structure. That is, if only the polycarbonate-based polyurethane to which the ultrafine fibers are expressed is focused, it is assumed that the polyurethane having a substance having a hydrazine bond imparted before the performance of the ultrafine fibers is present. Similarly, a porous structure is formed inside the fibrous base material, whereby even if the polyurethane is a rigid polycarbonate-based polyurethane, the sheet can exhibit a soft touch. .

The polyurethane-based solution containing a foaming agent which is imparted before the ultrafine fiber is used in the present invention, and the polycarbonate-based polyurethane solution which is imparted after the formation of the ultrafine fibers are used. A water-dispersed polyurethane solution which is dispersed in water and stabilized is used. Such water-dispersible polyurethanes can be classified into forced-dispersed polyurethanes which are forcibly dispersed by a surfactant, and have a hydrophilicity in the molecular structure of the polyurethane. The structure is such that the self-emulsifying polyurethane can be dispersed in water even if the surfactant is not present, but any of them can be used in the present invention.

The concentration of the above-mentioned water-dispersible polyurethane (relative to the polyurethane content of the water-dispersed polyurethane solution), from the storage of water-dispersed polyurethane solution From the viewpoint of properties, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

In addition, the water-dispersible polyurethane solution has a water-soluble organic content of 40% by mass or less based on the water-dispersible polyurethane solution as long as it is contained in order to improve the storage stability or the film-forming property. The solvent may be used. However, the content of the organic solvent is preferably 1% by mass or less from the viewpoint of preservation of the film formation environment.

Further, the water-dispersible polyurethane solution used in the present invention is preferably one having thermal coagulability. By using a water-dispersible polyurethane solution having thermotropic coagulability, a uniform polyurethane can be imparted in the thickness direction of the fibrous substrate. The thermosetting coagulation means that when the water-dispersed polyurethane solution is heated, if a certain temperature (sensible heat setting temperature) is reached, the fluidity of the water-dispersed polyurethane solution is reduced, and solidification is performed. nature. In the form of a sheet of the present invention to which a polyurethane is attached In the production of the material, after the water-dispersed polyurethane solution is applied to the fibrous substrate, it can be coagulated by dry heat coagulation, moist heat coagulation, wet coagulation, or a combination thereof, and Drying imparts the polyurethane to the fibrous substrate.

In the method of solidifying a water-dispersible polyurethane solution which does not exhibit thermosensitive coagulability, dry heat setting is practical in industrial production, but in this case, polyamine is formed on the surface of the fibrous substrate. In the phenomenon of migration of carbamate concentration, the touch of the sheet with the polyurethane attached tends to be hardened.

The sensible heat setting temperature of the water-dispersed polyurethane solution is not limited to a specific temperature, but is preferably 40 to 90 °C. By setting the thermosensitive solidification temperature to 40° C. or more, the stability of the polyurethane solution during storage is improved, and problems such as adhesion of the polyurethane to the machine during the operation can be suppressed. Further, by setting the thermosensitive solidification temperature to 90 ° C or lower, the transfer phenomenon of the polyurethane in the fibrous substrate can be suppressed. The thermosensitive solidification temperature is preferably from 50 ° C to 80 ° C.

In order to adjust the thermosensitive solidification temperature as described above, an appropriate thermosensitive coagulant may be added. Examples of the thermosensitive coagulant include inorganic salts such as sodium sulfate, magnesium sulfate, calcium sulfate, and calcium chloride; or sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and peroxidation. A free radical reaction initiator such as benzamidine.

The water-dispersible polyurethane solution used in the present invention preferably contains a foaming agent. The blowing agent means that it decomposes upon heating to produce an additive such as nitrogen or carbon dioxide. Water-dispersed polypolymer in a fibrous substrate by using a water-dispersible polyurethane solution containing a blowing agent The urethane solution is foamed upon heating, and the obtained water-dispersible polyurethane forms a porous structure derived from the foaming. The porous structure is formed by the water-dispersible polyurethane, and the touch of the sheet with the polyurethane is soft. This is because the bonding area between the fibers and the polyurethane in the sheet is small, whereby the binding force of the fibers is weakened.

As the foaming agent to be added to the water-dispersed polyurethane solution, for example, azoisobutyronitrile or dinitrosopentamethylenetetramine can be used (for example, manufactured by Sankyo Chemical Co., Ltd.) "Cellmic (registered trademark) A"), azodimethylamine (for example, "Cellmic (registered trademark) CAP" manufactured by Sankyo Chemical Co., Ltd.), p, p'-oxybisbenzenesulfonide (for example, "Cellmic (registered trademark) S" manufactured by Sankyo Chemical Co., Ltd.), N, N'-dinitrosopentamethylenetetramine (for example, "Cellular GX" manufactured by Yonghe Chemical Industry Co., Ltd.), or 2, 2'- Azobis[2-methyl-N-(2-hydroxyethyl)propanamide] (for example, "VA-086" manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis {2-A Organic-based foaming agent such as base-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide} (for example, "VA-080" manufactured by Wako Pure Chemical Industries, Ltd.); hydrogencarbonate An inorganic foaming agent such as sodium (for example, "Cellmic (registered trademark) 266" manufactured by Sankyo Chemical Co., Ltd.), in which a foaming agent having a guanamine bond is water-soluble, and can be uniformly dissolved in a water-dispersible polyamine group. It is preferred in the formic acid ester solution.

The amount of the foaming agent added to the water-dispersible polyurethane solution is preferably 0.5 to 20% by mass based on the ratio of the solid content of the polyurethane. By setting the amount of the foaming agent to be 0.5% by mass or more, more preferably 1% by mass or more, the effect of softening the touch of the sheet by foaming can be effectively obtained. On the other hand, by setting the amount of the foaming agent to be 20% by mass or less, more preferably 15% by mass or less, it is possible to suppress The abrasion resistance of the sheet caused by excessive foaming is lowered.

In the preferred embodiment of the above water-dispersible polyurethane solution, as described above, in the case of thermo-coagulation, the foaming agent is thermally decomposed to generate a gas foaming temperature, which is higher than the polyamine base. The sensible heat setting temperature of the acid ester is preferably high. In this way, the gas generated by the foaming does not escape from the polyurethane, and the porous structure can be stably formed.

The foaming temperature of the foaming agent is not limited to a specific temperature, but is preferably 50 to 200 °C. By setting the foaming temperature to 50° C. or more, more preferably 60° C. or more, it is easy to adjust the time of foaming after the polyurethane is solidified, and the porous structure can be effectively formed. 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 thermal decomposition of the polyurethane caused by heating for foaming.

Further, in order to prevent the gas generated by the above-mentioned foam from escaping from the polyurethane, a porous structure is formed stably, and it is preferred to add inorganic particles to the water-dispersed polyurethane solution. The water-dispersed polyurethane solution containing a foaming agent is held in a fine state by the inorganic particles before the gas is dispersed from the water-dispersible polyurethane solution by containing the inorganic particles, so that even if it is released The difference between the foaming temperature of the foaming agent and the thermosensitive solidification temperature of the polyurethane is small, and the porous structure of the polyurethane can be formed well. For the inorganic particles, for example, an oxide such as porous vermiculite, titanium oxide, aluminum oxide, or zinc oxide can be used, but it is used from the viewpoint of being porous and easily generating a gas generated by foaming. Porous vermiculite is particularly good.

The average particle diameter of the above inorganic particles is not limited to a specific value, but If the water is too large, the water dispersibility is deteriorated. If it is too small, the gas generated by the foaming cannot be maintained. Therefore, it is preferably from 1 to 10,000 nm, more preferably from 10 to 1,000 nm.

In the present invention, the water-dispersed polyurethane solution containing the foaming agent and the polymerized water-dispersed polycarbonate obtained by the performance of the ultrafine fibers are used to express the ultrafine fibers. The urethane solution is preferably a polyhydrazide aqueous dispersion. By containing the polyhydric oxygen aqueous dispersion, the friction between the polyurethane and the fibers of the fibrous substrate can be reduced, and the touch of the sheet can be made softer. Further, in the raising step by sandpaper or the like, the grinding property can be improved, and a uniform standing length can be obtained, and clogging of the sandpaper can be further suppressed.

The content of the polyhydrazine aqueous dispersion of the water-dispersed polyurethane solution is 0.1 to 10 in terms of the mass of the solid content of the polyoxyl of the mass of the water-dispersible polyurethane. The mass % is preferably, and more preferably 0.5 to 8 mass%. In this case, if the polyoxyl content is too small, the softening effect of the sheet becomes insufficient. When the amount is too large, the strength of the polyurethane-holding fiber in the sheet is weakened, and the abrasion resistance is lowered.

In the above polyoxymethylene, polydimethyl methoxy oxane, amine modified poly fluorene oxide, epoxy modified poly argon, or polyester modified poly argon can be used, among which Membrane polyfluorene is preferred.

The above-mentioned film-forming polyfluorene oxide means a film which is formed by heating to form a three-dimensional crosslinked structure, and which becomes redispersible in water. By imparting film-forming properties, after the film-forming polyfluorene is imparted, the film can be prevented from falling off the sheet even if the sheet is washed, dyed, washed, or the like, or subjected to external factors such as friction. And can maintain the softness of the piece. Further, after the sheet is impregnated with the water-dispersible polyurethane solution containing the film-forming polyhydric oxygen aqueous dispersion, the sheet is treated with hot water and/or an aqueous alkaline solution to make the fiber extremely fine. The flexibility of the sheet can be maintained by making the polysiloxane having film forming properties. In addition, "the film-forming polyfluorene remains in the sheet after the extremely fine treatment of the fiber" means that the measured value of the weight of the sheet after the ultra-fine treatment is compared with the theoretically calculated value, and the difference is within 30%.

In the present invention, a water-dispersible polycarbonate-based polyhydric acid solution containing a foaming agent and a water-dispersed polycarbonate-based polyamine group imparted by the ultrafine fibers are used. The formic acid ester solution may contain various additives such as carbon black, etc.; a flame retardant such as a pigment, a phosphorus system, a halogen system, a polyfluorene system or an inorganic system; an antioxidant such as a phenol system, a sulfur system or a phosphorus system; And a UV absorber such as a triazole-based, diphenylketone-based, salicylate-based, cyanoacrylate-based or oxalic acid-based benzoic acid; a light stabilizer such as a hindered amine or benzoate; and a polycarbodiene Amine and other hydrolysis-resistant stabilizer; plasticizer; antistatic agent; surfactant; foaming agent; softener; water repellent; coagulation modifier; dye; preservative; antibacterial agent; deodorant, cellulose particles and other fillers Or inorganic particles such as vermiculite or titanium oxide, etc., which may be contained singly or in any combination.

The water-dispersible polyurethane solution described above may be solidified by dry heat coagulation, moist heat coagulation, wet coagulation, or a combination thereof after impregnation or coating of the fibrous substrate.

In the case of the above wet heat setting, the solidification temperature is set to be higher than the thermosensitive solidification temperature of the water-dispersible polyurethane, and preferably 40 to 200 °C. By setting the temperature of the moist heat setting to 40 ° C or higher, more preferably 80 ° C or higher, the time to solidification of the polyurethane can be shortened, and the inhibition can be more suppressed. Transfer phenomenon. On the other hand, by setting the temperature at which the moist heat is solidified to 200 ° C or lower, preferably 160 ° C or lower, thermal deterioration of the polyurethane can be prevented.

In the case of the above wet solidification, the solidification temperature is set to be higher than the thermosensitive solidification temperature of the water-dispersible polyurethane, and preferably 40 to 100 °C. By setting the temperature of the wet solidification in hot water to 40 ° C or higher, more preferably 80 ° C or higher, the time to solidification of the polyurethane can be shortened, and the transfer phenomenon can be more suppressed.

The solidification temperature and the drying temperature in the case of the above dry heat setting are preferably from 80 to 180 °C. The dry heat setting temperature and the drying temperature are set to 80 ° C or higher, more preferably 90 ° C or higher, and the productivity is excellent. On the other hand, by setting the dry heat setting 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 a standing hair on the surface of the above-mentioned sheet, a raising treatment can also be performed. This raising treatment can be carried out by a method of grinding using a sandpaper or a roll sander or the like. It is preferable that the antistatic agent is applied before the raising process, and it is difficult to deposit the grinding powder generated from the sheet by grinding on the sandpaper.

The above-mentioned sheet can also be dyed. As for the dyeing method, it is preferred to use a liquid flow dyeing machine because it imparts a crepe effect while dyeing the sheet, and the sheet can be softened.

The temperature at the time of the above dyeing varies depending on the type of the fiber, but it is preferably 80 to 150 °C. By setting the dyeing temperature to 80 ° C or higher, more preferably 110 ° C or higher, the dyeing of the fibers can be performed efficiently. On the other hand, by setting the dyeing temperature to 150 ° C or lower, more preferably 130 ° C Hereinafter, deterioration of the polyurethane can be prevented.

The dye used in the dyeing may be selected together with the type of the fiber constituting the fibrous substrate. For example, if it is a polyester fiber, a disperse dye may be used; and if it is a polyamide fiber, an acid dye or Gold-containing dyes can be used in combination. When dyeing with a disperse dye, it may be subjected to reduction washing after dyeing.

Further, it is also preferred to use a dyeing aid during dyeing. The uniformity or reproducibility of dyeing can be improved by using a dyeing aid. Further, after the same bathing or dyeing with the dyeing, it can be treated with a finishing agent such as a softening agent such as polyfluorene oxide, an antistatic agent, a water repellent, a flame retardant, a light stabilizer, and an antibacterial agent.

[Examples]

Further, the sheet material of the present invention and the method for producing the same are described in more detail by way of examples, but the invention is not limited to the examples.

[Evaluation method] (1) Average single fiber diameter

The average single fiber diameter is a scanning electron micrograph (SEM) photograph of the surface of the fibrous substrate or sheet at a magnification of 2,000 times, and 100 fibers are randomly selected, and the diameter of the single fiber is measured, and the average value is calculated. . In this case, the ultrafine fibers constituting the fibrous base material or the sheet material have different cross-sections, and the diameters of the rounds other than the cross-sections of different shapes are calculated as the single fiber diameter. Further, in the case where the circular cross section is mixed with the different shape cross sections, or when the single fiber diameters are greatly different, the number of samples is selected in accordance with each of the existing count ratios and the total is made 100. Calculated by means of support. However, in the case where a woven fabric or a knitted fabric is inserted in addition to the non-woven fabric containing the ultrafine fibers or the fiber bundles thereof, the fibers of the woven fabric for reinforcement are measured in the average single fiber diameter of the ultrafine fibers. Excluded from sampling objects.

(2) Sensible solidification temperature of water-dispersed polyurethane solution

20 g of a water-dispersed polyurethane solution having a solid content concentration of a polyurethane of 10% by mass was placed in a test tube having an inner diameter of 12 mm, and the thermometer was inserted in such a manner that the front end was placed below the liquid surface. The test tube was sealed and immersed in a warm water bath at a temperature of 95 ° C so that the liquid surface of the polyurethane solution was below the liquid surface of the warm water bath. The temperature inside the test tube is confirmed by a thermometer, and the test tube should be lifted once every 5 seconds, and shaken to the extent that the liquid surface of the water-dispersed polyurethane solution is confirmed to have fluidity. In the test tube, the temperature at which the liquid surface of the water-dispersed polyurethane solution loses fluidity is defined as the thermosensitive solidification temperature. The measurement was carried out three times for each of the polyurethane solutions, and the average value was calculated.

(3) Structure inside the sheet

The inside structure of the sheet was observed by scanning a scanning electron micrograph (SEM) photograph of a sheet section at a magnification of 500 times.

(4) Touch of the sheet

According to JIS L 1096:2010 "Method for Testing Fabrics and Fabrics", the A method (45° cantilever method) described in 8.21.1 of "Softness" of 8.21 "softness" is produced from the longitudinal direction and the transverse direction. Five test pieces of 20 mm × 150 mm were placed on a water platform having a temperature of 45 ° C and inclined, and the test piece was slid, and the scale at which the center point of one end of the test piece was in contact with the inclined surface was read, and the average value of the five pieces was obtained.

(5) Wrinkle recovery of sheet

According to JIS L 1059-1:2009 "Test method for anti-wrinkle properties of fiber products - Part 1: Determination of wrinkle recovery of tatami mats in horizontal folding (Monsanto method)", 5 pieces were measured using a 10N load device The wrinkle recovery angle of the test piece was calculated from the wrinkle resistance formula described in 10 "Calculation of the wrinkle recovery angle and the wrinkle prevention rate", and the average value of the wrinkles was calculated.

(6) Evaluation of wear resistance of sheet

A nylon fiber having a diameter of 0.4 mm including nylon 6 was cut perpendicularly in the longitudinal direction of the fiber to a length of 11 mm, and bundled into 100 bundles, and 97 bundles were arranged in a concentric manner at a diameter of 110 mm. Within the circle (one at the center, six at a diameter of 17 mm, 13 at a diameter of 37 mm, 19 at a diameter of 55 mm, 26 at a diameter of 74 mm, and 32 at a diameter of 90 mm) The round brush (9700 pieces of nylon wire) was subjected to abrasion on the surface of a circular sample (diameter 45 mm) of the sheet under the conditions of a load of 8 lbs (about 3629 g), a rotation speed of 65 rpm, and a number of rotations of 50 times. The mass change of the sample before and after the measurement was measured, and the average value of the 5 samples was taken as the wear reduction.

(7) Evaluation of hydrolysis resistance

The above-mentioned abrasion resistance evaluation was carried out by performing a forced deterioration treatment in a gas atmosphere having a temperature of 70 ° C and a relative humidity of 95% for 5 weeks using a constant temperature and humidity chamber manufactured by ESPEC.

(8) Light resistance evaluation

Using the X-ray arc weathering tester manufactured by Suga Test Equipment Co., Ltd., according to the B method of JIS L 0843:2006 "Testing methods for dyeing fastness of xenon arc lighting", the wavelength is 300~ The light of 400 nm was irradiated for 3.8 hours and turned off for 1 hour under the conditions of radiation illuminance 150 W/m ² , black panel temperature 73±3 ° C, in-tank temperature 38 ° C, relative humidity 50 ± 5%, and so on. After 38 times, the irradiation time was 144 hours in total, and after the forced deterioration treatment was performed, the above-described abrasion resistance evaluation was performed.

(9) Appearance grade of sheet

The appearance grade of the sheet was 10 in each of the adult males and the females in good health, and a total of 20 were evaluated as visual evaluators. The visual evaluation and the functional evaluation were carried out in accordance with the following five-stage evaluation, with the most evaluation. As a look and feel. The appearance grade is considered to be good from grades 3 to 5.

Grade 5: There are even fibers of the fibers, the fibers are well dispersed and have a good appearance.

Level 4: An evaluation between level 5 and level 3.

Grade 3: Although the dispersion state of the fiber has a slightly poor portion, the fiber has a standing hair and the appearance is also good.

Level 2: An evaluation between level 3 and level 1.

Grade 1: The fibers have few vertical hairs, and overall, the dispersion of the fibers is very poor and the appearance is poor.

(non-woven fabric for fibrous substrate)

Next, regarding the three nonwoven fabric base materials used in the examples and the comparative examples, the production procedures are described in Reference Examples 1 to 3, respectively.

[Reference Example 1] Production of Nonwoven Fabric A

For the sea component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used; for the island component, polyethylene terephthalate is used; The composite ratio of 45 mass% of sea component and 55 mass% of island component obtained island-in-sea type composite fiber having an island number of 36 islands/1 filament and an average single fiber diameter of 17 μm. The polyethylene terephthalate which is an island component has an average single fiber diameter of 2 μm. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, and a fiber web was formed by a card and a cross lapper, and by a needle punch. The treatment forms a non-woven fabric. 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 form a nonwoven fabric A for a fibrous substrate (mass per unit area: 300 g/m ² , thickness: 1 mm) ).

[Reference Example 2] Production of Nonwoven Fabric B

For the sea component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used; for the island component, polyethylene terephthalate is used; The composite ratio of 20% by mass of the sea component and 80% by mass of the island component was obtained from the island-in-sea type composite fiber having an island number of 16 islands/1 filament and an average single fiber diameter of 30 μm. The polyethylene terephthalate which is an island component has an average single fiber diameter of 4 μm. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form short fibers, and a fiber web was formed by a roughing machine and a cross-lapper, and a non-woven fabric was formed by needling treatment. The non-woven 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 serve as a non-woven fabric B for a fibrous substrate (mass per unit area: 350 g/m ² , thickness) : 1.1mm).

[Reference Example 3] Production of Non-woven Cloth C

For the sea component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfonate isophthalate is used; for the island component, 6-nylon is used; and sea component is 30% by mass. The composite ratio of 70% by mass of the island component was obtained by the island-type composite fiber having an island number of 200 islands/1 filament and an average single fiber diameter of 27 μm. The average single fiber diameter of 6-nylon which is an island component is 1.5 μm. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form short fibers, and a fiber web was formed by a roughing machine and a cross-lapper, and a non-woven fabric was formed by needling treatment. The non-woven fabric was immersed in hot water having a temperature of 97 ° C for 2 minutes to be shrunk, and dried at a temperature of 140 ° C for 5 minutes to serve as a non-woven fabric C for a fibrous substrate (mass per unit area: 430 g/m ² , thickness) : 1.2mm).

(Water-dispersed polyurethane solution)

Next, the production procedures of the above-described 11 kinds of water-dispersible polyurethane liquids used in the examples and the comparative examples are described in Reference Examples 4 to 14, respectively.

[Reference Example 4] Production of water-dispersed ether-based polyurethane-based solution a

In the ether-based forced emulsification polyurethane solution (polytetramethylene glycol is preferably used for the polyol, and isophorone diisocyanate is preferably used for the isocyanate), relative to the polyamine group. 100 parts by mass of the solid content of the acid ester liquid, and 2 parts by mass of magnesium sulfate as a heat-sensitive coagulant and 3 parts by mass of azo-isobutyronitrile (AIBN) (foaming temperature: 120 ° C) as a foaming agent were added as "IE-7170" manufactured by Toray Dow Corning Co., Ltd., which is 3 parts by mass of a film-forming polysiloxane, was prepared to have a solid content of 10% by mass in water to obtain a water-dispersible ether-based polyurethane solution a. The thermosensitive solidification temperature was 56 °C.

[Reference Example 5] Production of water-dispersed ether-based polyurethane solution b

In the water-dispersed ether-based polyurethane solution a of the reference example 4, 5 parts by mass of sodium hydrogencarbonate (Cellmic (registered trademark) 266, manufactured by Sankyo Chemical Co., Ltd., foaming temperature: 140 ° C) was added. In the same manner as in Reference Example 4, in place of the film-forming polyfluorene oxide, in place of the film-forming polyfluorene oxide, 3 parts by mass of dimethylpolyoxymethylene latex, which is a foaming agent, was added in an amount of 3 parts by mass. A water-dispersible ether-based polyurethane solution b was obtained. The thermosensitive solidification temperature was 61 °C.

[Reference Example 6] Production of water-dispersed ether-based polyurethane liquid c

In the water-dispersed ether-based polyurethane solution a of Reference Example 4, a water-dispersed ether-based polyamine group was obtained in the same manner as in Reference Example 4 except that the film-forming polyfluorene was not added. Acid ester c. The thermosensitive solidification temperature was 55 °C.

[Reference Example 7] Production of water-dispersed ether-based polyurethane liquid d

In the water-dispersed ether-based polyurethane solution a of Reference Example 4, a water-dispersed ether system was obtained in the same manner as in Reference Example 4 except that a foaming agent and a film-forming polyfluorene gas were not added. Polyurethane solution d. The thermosensitive solidification temperature was 55 °C.

[Reference Example 8] Production of water-dispersed polycarbonate-based polyurethane solution e

Polycarbonate-based self-emulsifying polyurethane solution containing polyoxyethylene-extended ethyl chain (polyhexamethylene carbonate should be used for polyol, dicyclohexylmethane diisocyanate should be used for isocyanate) In the above, with respect to 100 parts by mass of the solid content of the polyurethane solution, 2 parts by mass of ammonium persulfate (APS) as a thermosetting coagulant and 5 parts by mass of the film-forming polyphosphonium are added. "IE-7170" manufactured by Li Dow Corning Co., Ltd., all prepared by water to a solid content of 20% by mass to obtain a water-dispersible type Polycarbonate polyurethane solution e. The thermosensitive solidification temperature was 74 °C.

[Reference Example 9] Production of Water-Dispersible Polycarbonate Polyurethane Solution F

In the water-dispersed polycarbonate-based polyurethane liquid e of Reference Example 8, in addition to adding 3 parts by mass of dimethyl polyfluorene latex, "SM7036EX" manufactured by Toray Dow Corning Co., Ltd. was used instead of film forming property. A water-dispersible polycarbonate-based polyurethane solution f was obtained in the same manner as in Reference Example 8 except for polyoxymethylene. The thermosensitive solidification temperature was 75 °C.

[Reference Example 10] Production of Water-Dispersible Polycarbonate Polyurethane Solution G

In the water-dispersible polycarbonate-based polyurethane liquid e of Reference Example 8, a water-dispersed polycarbonate system was obtained in the same manner as in Reference Example 8 except that the film-forming polyfluorene oxide was not added. Polyurethane solution g. The thermosensitive solidification temperature was 73 °C.

[Reference Example 11] Production of water-dispersed ether-based polyurethane liquid

In the water-dispersed ether-based polyurethane solution a of the reference example 4, "VA-080" (2,2'-azo double {2-A) manufactured by Wako Pure Chemical Industries, Ltd. was added in addition to 3 parts by mass. Base-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide}; the molecular weight of the substance having a guanamine bond after decomposition is 380) instead of AIBN as a foaming agent, added 3 parts by mass of "Brian (registered trademark) SL-100N" (porous vermiculite, average particle diameter: 100 nm) manufactured by Matsumoto Oil & Fats Co., Ltd., which is an inorganic particle, and the amount of film-forming polyxylene added is adjusted to 5 masses. In the same manner as in Reference Example 4, a water-dispersible ether-based polyurethane liquid h was obtained. The thermosensitive solidification temperature was 54 °C.

[Reference Example 12] Production of water-dispersed ether-based polyurethane liquid i

In the water-dispersed ether type polyurethane solution liquid of Reference Example 11, except Water dispersion was obtained in the same manner as in Reference Example 11 except that 5 parts by mass of "TECNADIS-TI-120-1KG" (titanium oxide, average particle diameter: 15 nm) manufactured by TECNAN Co., Ltd. was added instead of the porous vermiculite as the inorganic particles. Type ether polyurethane solution i. The thermosensitive solidification temperature was 58 °C.

[Reference Example 13] Production of Water-Dispersible Polycarbonate Polyurethane Solution j

In the water-dispersed polycarbonate-based polyurethane liquid e of Reference Example 8, in place of 5 parts by mass of "Dripon (registered trademark) 600E" manufactured by Nikko Chemical Co., Ltd., instead of film-forming polyoxyl "IE-7170" manufactured by Toray Dow Corning Co., Ltd., and added 3 parts by mass of "VA-086" (2,2'-azobis[2-methyl-N" manufactured by Wako Pure Chemical Industries Co., Ltd. as a foaming agent. -(2-hydroxyethyl)propanamide], the molecular weight of the substance having a guanamine bond after decomposition is 260), and 3 parts by mass of "Brian (registered trademark) SL-100N manufactured by Matsumoto Oil & Fats Co., Ltd. as an inorganic particle A water-dispersible polycarbonate-based polyurethane solution j was obtained in the same manner as in Reference Example 8 except that (porous vermiculite, average particle diameter: 100 nm). The thermosensitive solidification temperature was 72 °C.

[Reference Example 14] Production of Water-Dispersible Polycarbonate Polyurethane Solution K

In the water-dispersible polycarbonate-based polyurethane solution j of Reference Example 13, except for adding 5 parts by mass of "TECNADIS-AL-120-1KG" (alumina, average particle diameter 25 nm) manufactured by TECNAN Co., Ltd. A water-dispersible polycarbonate-based polyurethane solution k was obtained in the same manner as in Reference Example 13 except for the porous vermiculite of the inorganic particles. The thermosensitive solidification temperature was 76 °C.

[Example 1] (Before sea removal: the addition of ether based polyurethane)

The fibrous substrate prepared in the above Reference Example 1 was impregnated with the non-woven fabric A in the water-dispersible ether-based polyurethane solution a prepared in the above Reference Example 4 by a hot humid gas atmosphere at a temperature of 100 ° C. After the treatment for 5 minutes, hot air drying was carried out at a drying temperature of 120 ° C for 5 minutes to obtain an ether-based polyamine group which was obtained by massing the mass of the polyurethane to 15 mass % with respect to the mass of the island material of the nonwoven fabric. Tablets of acid esters.

(off sea)

The sheet to which the ether-based polyurethane was applied was immersed in an aqueous sodium hydroxide solution heated to a temperature of 95 ° C and having a concentration of 10 g/L, and subjected to sea-removal treatment for 30 minutes to obtain a sea component in which sea-island-type fibers were removed. Take off the sea.

(After the sea removal: the addition of polycarbonate-based polyurethane)

The above-mentioned dehydrated tablet was impregnated with the water-dispersible polycarbonate-based polyurethane liquid e prepared in the above Reference Example 8, and subjected to a treatment in a hot humid gas atmosphere at a temperature of 100 ° C for 5 minutes at a drying temperature. The hot air drying was carried out for 5 minutes at a temperature of 120 °C. In this way, a polycarbonate-based polyurethane-coated sheet having a mass of the polyurethane imparted after the sea removal of 15% by mass was obtained with respect to the mass of the island material of the nonwoven fabric.

(hairing, dyeing, reduction and washing)

The surface of the sheet of the above polycarbonate-based polyurethane was applied, and the hair was raised by grinding using an endless sandpaper of 180 mesh, and then dispersed by using a circular dyeing machine. The dye is dyed and subjected to reduction washing to obtain a sheet.

(the obtained sheet)

When the obtained sheet was observed in cross section, a void was clearly observed between the ultrafine fiber bundle and the water-dispersible ether-based polyurethane. Again Good grade and abrasion resistance, soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Embodiment 2] (Before sea removal: the addition of ether based polyurethane)

The water-dispersible ether-based polyurethane solution B produced in the above Reference Example 5 was used as the polyurethane solution impregnated with the nonwoven fabric A for the fibrous substrate, and was compared with the island component of the nonwoven fabric. A sheet to which an ether-based polyurethane was imparted was obtained in the same manner as in Example 1 except that the mass of the polyurethane was 10% by mass.

(off sea)

The sheet to which the ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

The same procedure as in Example 1 was carried out, except that the water-dispersible polycarbonate-based polyurethane liquid f produced in the above Reference Example 9 was used as the polyurethane solution impregnated in the above-mentioned sea-leaf sheet. In the form, a polycarbonate-based polyurethane-coated sheet having a mass of the polyurethane imparted after the sea removal was obtained in an amount of 15% by mass based on the mass of the non-woven island.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing treatment in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, in the ultrafine fiber bundle and water A void is clearly seen between the dispersed ester-based polyurethanes. Moreover, the appearance grade and abrasion resistance are good, and it has a soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Example 3] (Before sea removal: the addition of ether based polyurethane)

In the same manner as in Example 1, the fibrous substrate was impregnated with a water-dispersible ether-based polyamine-based base fabric in the same manner as in Example 1 except that the mass of the mass of the non-woven island was 20% by mass. The ester liquid a was obtained as a sheet to which an ether-based polyurethane was added.

(off sea)

The sheet to which the above-mentioned ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

The water-dispersed polycarbonate-based polyurethane liquid g produced in the above Reference Example 10 was used as the polyurethane solution impregnated in the above-mentioned sea-leaf sheet, and the mass of the island component relative to the nonwoven fabric was used. A sheet to which a polycarbonate-based polyurethane was imparted was obtained in the same manner as in Example 1 except that the mass of the polyurethane to be imparted after the sea was 20% by mass.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, in the ultrafine fiber bundle and water A void is clearly seen between the dispersed ether-based polyurethanes. Moreover, the appearance grade and abrasion resistance are good, and it has a soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Example 4] (Before sea removal: the addition of ether based polyurethane)

The polyurethane-based solution impregnated with the non-woven fabric A for the fibrous substrate is used in addition to the water-dispersed ether-based polyurethane solution c prepared in the above Reference Example 6. In the same manner as in Example 1, a sheet obtained by providing an ether-based polyurethane with a mass of the polyurethane of 15% by mass based on the mass of the island material of the nonwoven fabric was obtained.

(off sea)

The tablet to which the above-mentioned ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

In addition to using the water-dispersible polycarbonate-based polyurethane solution g as the polyurethane solution impregnated in the above-mentioned sea-leaf sheet, and the mass of the component of the non-woven island is made, the poly A sheet to which a polycarbonate-based polyurethane was imparted was obtained in the same manner as in Example 1 except that the mass of the urethane was 30% by mass.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, in the ultrafine fiber bundle and water A void is clearly seen between the dispersed ether-based polyurethanes. Moreover, the appearance grade and abrasion resistance are good, and it has a soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Example 5] (Before sea removal: the addition of ether based polyurethane)

In addition to the use of the nonwoven fabric B for the fibrous substrate produced in the above Reference Example 2 as the fibrous substrate, and the mass of the polyurethane component was 20% by mass based on the mass of the island component of the nonwoven fabric, In the same manner, the fibrous base material is impregnated with the water-dispersible ether-based polyurethane solution a to obtain a sheet having an ether-based polyurethane.

(off sea)

The above-mentioned sheet to which the ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

In the same manner as in the first embodiment, the dehydrated sheet was impregnated with the water-dispersible polycarbonate-based polyurethane liquid e to obtain the mass of the island component of the non-woven fabric, and the polyamine-based group was given after the sea-removal. A sheet obtained by imparting a polycarbonate-based polyurethane to an ester mass of 15% by mass.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, a void was clearly observed between the ultrafine fiber bundle and the water-dispersible ether-based polyurethane. Again Good grade and abrasion resistance, soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Embodiment 6] (Before sea removal: the addition of ether based polyurethane)

The nonwoven fabric C for a fibrous substrate produced in the above Reference Example 3 was used as the fibrous base material, and the mass of the polyurethane was 10% by mass based on the mass of the island component of the nonwoven fabric. In the same manner as in the first embodiment, the fibrous base material was impregnated with the water-dispersible ether-based polyurethane solution a to obtain a sheet having an ether-based polyurethane.

(off sea)

The above-mentioned sheet to which the ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

The above-mentioned sea-leaching sheet was impregnated with water-dispersed polycarbonate in the same manner as in Example 1 except that the mass of the polyurethane to be imparted after the sea-off was 20% by mass. The polyaminoester solution e was obtained, and a sheet to which a polycarbonate-based polyurethane was imparted was obtained.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, a void was clearly observed between the ultrafine fiber bundle and the water-dispersible ether-based polyurethane. Again, appearance Good grade and abrasion resistance, soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Embodiment 7] (Before sea removal: the addition of ether based polyurethane)

The same procedure as in Example 1 was carried out, except that the water-dispersible ether-based polyurethane solution h was used as the polyurethane solution impregnated in the nonwoven fabric A for the fibrous substrate produced in the above Reference Example 1. In the manner of obtaining an ether-based polyurethane, the mass of the polyurethane component was 15% by mass based on the mass of the non-woven island.

(off sea)

The above-mentioned sheet to which the ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

In the same manner as in Example 1, the above-mentioned sea-leaching sheet was impregnated with the water-dispersible polycarbonate-based polyurethane liquid e, and the mass of the island component of the nonwoven fabric was obtained, and the polyamine group imparted after the sea-removal was obtained. The polycarbonate-based polyurethane-coated sheet was obtained in an amount of 15% by mass of the formate.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, a void was clearly observed between the ultrafine fiber bundle and the water-dispersible ether-based polyurethane. Moreover, the appearance grade and wear resistance are good, and it has a soft touch and good wrinkles. Refolding. Further, hydrolysis resistance and light resistance are also good.

[Embodiment 8] (Before sea removal: the addition of ether based polyurethane)

In the same manner as in Example 1, except that the water-dispersible ether-based polyurethane solution I was used as the polyurethane solution impregnated in the nonwoven fabric A for the fibrous substrate produced in the above Reference Example 1. The sheet obtained with an ether-based polyurethane was obtained in an amount of 15% by mass based on the mass of the island material of the nonwoven fabric.

(off sea)

The above-mentioned sheet to which the ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

In the same manner as in the first embodiment, the dehydrated sheet was impregnated with the water-dispersible polycarbonate-based polyurethane liquid e to obtain the mass of the island component of the non-woven fabric, and the polyamine-based group was given after the sea-removal. A sheet obtained by imparting a polycarbonate-based polyurethane to an ester mass of 15% by mass.

(hairing, dyeing, reduction and washing)

The polycarbonate-based polyurethane-coated sheet was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, a void was clearly observed between the ultrafine fiber bundle and the water-dispersible ether-based polyurethane. Moreover, the appearance grade and abrasion resistance are good, and it has a soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Embodiment 9] (Before sea removal: the addition of polycarbonate-based polyurethane)

A water-dispersible polycarbonate-based polyurethane solution was used as the polyurethane solution impregnated in the nonwoven fabric A for the fibrous substrate produced in the above Reference Example 1, and compared with the island component of the nonwoven fabric. A sheet to which a polycarbonate-based polyurethane was imparted was obtained in the same manner as in Example 1 except that the mass of the polyurethane was 25% by mass.

(off sea)

The pellets to which the polycarbonate-based polyurethane was applied were subjected to sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

In the same manner as in Example 1, the above-mentioned sea-leaf-containing water-dispersed polycarbonate was obtained in the same manner as in Example 1 except that the mass of the polyurethane component after the sea-off was 5% by mass. The ester-based polyurethane solution e was obtained as a sheet to which a polycarbonate-based polyurethane was imparted.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, a void was clearly observed between the ultrafine fiber bundle and the water-dispersible polycarbonate-based polyurethane. Moreover, the appearance grade and abrasion resistance are good, and it has a soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Embodiment 10] (Before sea removal: the addition of polycarbonate-based polyurethane)

The water-dispersed polycarbonate-based polyurethane solution k was used as the polyurethane solution impregnated in the nonwoven fabric A for the fibrous substrate produced in the above Reference Example 1, and compared to the island of non-woven fabric. A polycarbonate-based polyurethane-based sheet was obtained in the same manner as in Example 1 except that the mass of the component was changed to 25% by mass.

(off sea)

The pellets to which the polycarbonate-based polyurethane was applied were subjected to sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

The above-mentioned sea-leaching sheet was impregnated with water-dispersed polycarbonate in the same manner as in Example 1 except that the mass of the polyurethane to be imparted after the sea-off was 5% by mass. The polyaminoester solution e was obtained, and a sheet to which a polycarbonate-based polyurethane was imparted was obtained.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

From the cross section of the obtained sheet, a void was clearly observed between the ultrafine fiber bundle and the water-dispersible polycarbonate-based polyurethane. Moreover, the appearance grade and abrasion resistance are good, and it has a soft touch and good wrinkle recovery. Further, hydrolysis resistance and light resistance are also good.

[Comparative Example 1] (Before sea removal: the addition of ether based polyurethane)

In the same manner as in Example 1, the fibrous substrate was impregnated with a water-dispersible ether-based polyamine-based base fabric in the same manner as in Example 1 except that the mass of the mass of the non-woven island was 20% by mass. The ester liquid a was obtained as a sheet to which an ether-based polyurethane was added.

(off sea)

The above-mentioned sheet to which the ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(hairing, dyeing, reduction and washing)

A sheet-like product was obtained in the same manner as in Example 1 except that the above-mentioned dehydrated sheet was omitted, except that the polycarbonate-based polyurethane was omitted.

(the obtained sheet)

In the obtained sheet-like article of Comparative Example 1, the polycarbonate-based polyurethane was not imparted to the kelp sheet, and the touch was soft, but the light resistance was low.

[Comparative Example 2] (off sea)

The sea-removal treatment was carried out in the same manner as in Example 1 except that the nonwoven fabric A for the fibrous substrate was omitted and the addition of the polyurethane was omitted.

(After the sea removal: the addition of polycarbonate-based polyurethane)

In addition to using a water-dispersible polycarbonate-based polyurethane solution g as a polyurethane solution impregnated in the above-mentioned sea-leaf sheet, and relative to the non-woven A sheet to which a polycarbonate-based polyurethane was imparted was obtained in the same manner as in Example 1 except that the mass of the component of the island was 30% by mass.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

In the obtained sheet-like article of Comparative Example 2, since the ether-based polyurethane was not imparted to the nonwoven fabric nonwoven fabric, the wrinkle recovery property and durability were good, but the touch was hard and the surface appearance was poor. .

[Comparative Example 3] (Before sea removal: the addition of ether based polyurethane)

In addition to the use of the water-dispersible ether-based polyurethane solution d to which the foaming agent produced in the above Reference Example 7 is not added, other than the polyurethane solution impregnated with the nonwoven fabric A for the fibrous substrate In the same manner as in Example 1, a sheet obtained by providing an ether-based polyurethane with a mass of the polyurethane of 15% by mass based on the mass of the island material of the nonwoven fabric was obtained.

(off sea)

The above-mentioned sheet to which the ether-based polyurethane was applied was subjected to a sea-removal treatment in the same manner as in Example 1 to obtain a sea-leaf tablet.

(After the sea removal: the addition of polycarbonate-based polyurethane)

The same method as in Example 1 except that the water-dispersed polyurethane solution g was used as the polyurethane solution impregnated in the above-mentioned sea-leaf tablet In the formula, a polycarbonate-based polyurethane-coated sheet having a mass of the polyurethane imparted after the sea removal was obtained in an amount of 15% by mass based on the mass of the non-woven island.

(hairing, dyeing, reduction and washing)

The sheet to which the polycarbonate-based polyurethane was applied was subjected to raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

(the obtained sheet)

In the obtained sheet of Comparative Example 3, since the foaming agent was not added to the ether-based polyurethane, the ultrafine fiber bundle and the ether-based polyamine group were observed from the cross section of the sheet. No clear voids were observed between the acid esters, and the etheric polyurethane was locally observed to adhere to the inside of the ultrafine fiber bundle. Further, since the sheet-like material does not contain a foaming agent in the ether-based polyurethane, the wrinkle recovery property is low and the touch is hard.

The composition of the polyurethane solution shown in each of the above Reference Examples is shown in Table 1. Moreover, the evaluation results of the sheet obtained in each Example and each comparative example are shown in Table 2.

[Industrial availability]

The sheet obtained according to the present invention can be suitably used as a seat for furniture, a chair and a wall material, or a vehicle interior such as a car, a tram, and an airplane; and has a very beautiful appearance on a skin material such as a ceiling and a interior. Materials; or uppers, decorations, etc. for shirts, jackets, casual shoes, sports shoes, gentlemen's shoes, and women's shoes; luggage, belts, purses, etc.; and materials for use in one of these parts; Industrial materials such as cloth, abrasive cloth, and CD curtain. In particular, it can be applied to the effects of the present invention, that is, the soft touch and the excellent wrinkle recovery and durability which are not wrinkled, and are strongly required for the use of the interior material.

Claims (11)

A sheet-like material comprising: a water-dispersible polyurethane in a fibrous substrate comprising an ultrafine fiber having an average single fiber diameter of 0.3 to 7 μm; the water-dispersible polyaminocarboxylic acid One of the esters is partially present and adhered to the outer periphery of the bundle containing the ultrafine fibers, and contains a substance having a guanamine bond; a water-dispersed polyamine group which is present and attached to a portion other than the outer periphery of the ultrafine fiber bundle The acid ester contains a water-dispersible polycarbonate-based polyurethane. The sheet of claim 1, wherein the substance having the guanamine bond has a molecular weight of 100 to 500. A sheet according to claim 1 or 2, wherein the water-dispersible polyurethane having the bias and being attached to the outer periphery of the ultrafine fiber bundle is a polycarbonate-based polyurethane or ether. It is a polyurethane. The sheet of any one of claims 1 to 3, wherein the water-dispersed polyurethane having a bias applied to and attached to the outer periphery of the ultrafine fiber bundle and/or the bias exists and adheres to The water-dispersible polycarbonate-based polyurethane other than the outer peripheral portion of the ultrafine fiber bundle contains polyfluorene oxide. The sheet of claim 4, wherein the polyfluorene is a film-forming polyfluorene. A method for producing a sheet, characterized in that a water-dispersed polyurethane solution containing a foaming agent is applied to a fibrous substrate comprising an ultrafine fiber phenotype fiber, and then averaged from an ultrafine fiber phenotype fiber After the ultrafine fibers having a single fiber diameter of 0.3 to 7 μm are expressed, a water-dispersible polycarbonate-based polyurethane solution is supplied. The method for producing a sheet according to claim 6, wherein the water-dispersible polyurethane-based polycarbonate-based polyurethane or ether-based polyamine-based polymer containing a foaming agent Acid ester solution. The method for producing a sheet according to claim 6 or 7, wherein the water-dispersible polyurethane solution containing a foaming agent contains inorganic particles. The method for producing a sheet according to the eighth aspect of the invention, wherein the inorganic particles are porous vermiculite. The method for producing a sheet according to any one of claims 6 to 9, wherein the water-dispersed polyurethane solution containing a foaming agent and/or the water imparted by the ultrafine fibers The dispersion type polycarbonate-based polyurethane solution contains a polyhydrazine aqueous dispersion. The method for producing a sheet according to claim 10, wherein the polyhydrazide aqueous dispersion is a film-forming polyhydric oxygen aqueous dispersion.