TW201738060A - Sheet-shaped material and method for producing same - Google Patents

Abstract

Provided are: a sheet-shaped material having excellent appearance and feeling, and moreover having a high elongation rate and a high elongation recovery rate; and a method for producing the same. The sheet-shaped material is formed from ultra fine fibers and a porous elastic polymer, and is characterized in that: the sheet-shaped material comprises a substrate layer and a napped layer; the ultra fine fibers have a coil-shaped crimp, have an average single fiber diameter of 0.1-10 [mu]m, and include fibers having a fiber length of 8-90 mm; and the sheet-shaped material has an elongation rate of 10% or more, and an elongation recovery rate of 80% or more.

Description

Sheet and manufacturing method thereof

The present invention relates to a sheet having a beautiful appearance and excellent elongation by coiling a very fine fiber, and a method for producing the same.

In the past, sheets containing mainly fine fibers and polymeric elastomers have excellent characteristics not found in natural leather, and their use is expanding year by year in clothing and chair covers, and automotive interior materials. Further, recently, in particular, in the use of clothing, the feeling of wearing, and the use of materials, from the viewpoint of moldability, a sheet having excellent elongation is required. For the purpose of imparting the extensibility of the sheet, a study has been conducted to bond the fibers constituting the sheet into a side-by-side type.

For example, Patent Document 1 proposes an artificial leather which removes sea components by a bundle fiber-producing fiber adjacent to a sea-shell structure having an island component containing an inelastic polymer from a fiber component containing an elastic polymer. A fiber having a structure in which a non-elastic ultrafine fiber bundle-forming fiber having an island component is a non-elastic polymer and a fiber of an elastic fiber are adhered to each other, and an artificial leather of the fiber is used. However, in the case of spinning a polyurethane-based fiber of an elastic polymer, there is a polyurethane-based fiber which is inherent in texture and hard texture, texture or drape of the fabric. The problem of sexual decline. Furthermore, Polyurethane-based fibers are less likely to be dyed in terms of dyes for polyesters, and even when used together with polyester fibers, not only the dyeing step becomes complicated, but also it is difficult to dye into a desired color.

Patent Document 2 proposes a method of inserting a woven fabric into a yarn comprising a conjugate fiber having a side-by-side type formed by a polyethylene terephthalate copolymer having two kinds of inherent viscosity (IV). By concentrating the stress on the high-viscosity side at the time of stretching, the two components are different in internal deformation, and the crimping is exhibited. However, the ultrafine fibers constituting the sheet are not intended to be crimped and formed, but are merely crimped by the inserted woven fabric for the purpose of reinforcing the strength of the sheet, and although the stretch can be imparted to the sheet, However, the dense feeling of the ultrafine fibers on the surface of the sheet cannot be revealed.

Patent Document 3 proposes an artificial leather comprising a latent crimping-type fiber obtained by combining two types of polytrimethylene terephthalate having different intrinsic viscosities into a side-by-side type. However, since the ultrafine fiber length of the sheet is extremely short, for example, 5 mm or less, and the fiber bundle for the direct spinning method cannot be formed, it becomes a entanglement of the ultrafine fibers and a shrinkage of the ultrafine fibers, and a sheet having a lack of elongation. .

On the other hand, Patent Document 4 proposes a sheet-like material comprising a non-woven fabric of a side-by-side type ultrafine fiber formed of two kinds of polyethylene terephthalate having a difference in inherent viscosity, and containing water dispersion therein. A sheet of a polyurethane. In this patent document, since the water-dispersible polyurethane is impregnated into the non-woven fabric, it becomes a structure of the interlacing point of the water-dispersed polyurethane solid ultrafine fiber at the time of drying. also, Since the polyurethane has a non-porous structure, there is no degree of freedom of the ultrafine fibers. For this reason, the ultrafine fibers are crimped and the appearance of the surface of the sheet becomes dense, but the elongation is not exhibited.

That is, it has not been possible to obtain a sheet having a dense appearance and an elongation of elongation and stretch recovery.

Further, in general, in the pile-like artificial leather having the standing hair on the surface, the light reflection of the surface fiber changes depending on the direction of the standing hair, and the hue is different depending on the viewing angle, and is used for the clothing and the sheet. There is a need to pay attention to the direction.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent No. 03128333

Patent Document 2 Japanese Patent No. 05035117

Patent Document 3 Japanese Patent Laid-Open Publication No. 2003-286663

Patent Document 4 Japanese Patent Laid-Open Publication No. 2012-136800

Although the document for solving the above-mentioned problem has not been seen so far, the inventors of the present invention have solved the above-mentioned problems by imparting a change in the directivity of the surface fibers by using the potential crimping yarn.

The object of the present invention is to provide a sheet having both a dense appearance, an elongation ratio and an elongation of stretch recovery in view of the actual situation of the prior art described above, and has a high-grade feeling and a difference in color angle even if the angle is changed. Small sheets and methods of making the same.

The present invention is a sheet material comprising a sheet composed of an ultrafine fiber and a porous elastomeric polymer, characterized in that the sheet material comprises a substrate layer and a standing layer, and the ultrafine fiber has a coil shape. The crimping has an average single fiber diameter of 0.1 to 10 μm, and includes fibers having a fiber length of 8 to 90 mm, and the sheet has a stretch ratio of 10% or more and a tensile recovery ratio of 80% or more.

According to a preferred aspect of the sheet of the present invention, the ultrafine fibers constituting the sheet include a sheet of fibers having a fiber length of 25 to 90 mm.

Further, according to a preferred aspect of the sheet material of the present invention, a leather-like sheet material comprising a nonwoven fabric comprising a composite fiber having an average single fiber diameter of 0.3 μm or more and 7 μm or less, and a polymer elastomer therein, A leather-like sheet having a bristled layer on the surface, wherein the conjugate fiber has two or more kinds of polyethylene terephthalate polymers having a difference in inherent viscosity, which are laminated in the longitudinal direction of the fiber to form a side-by-side type or to form an eccentricity. The core-sheath structure is characterized in that, for the measurement target point on the surface of the leather-like sheet, the viewpoint from the upper side of the longitudinal direction of the leather-like sheet is inclined by 45° as the viewpoint 1, and the longitudinal direction is reversed. The viewpoint which is inclined upward by 45° in the direction is set as the viewpoint 2, the viewpoint which is inclined by 45° from the upper side of the horizontal direction is the viewpoint 3, and the color difference between the viewpoint 1 and the viewpoint 2 is ΔE*ab ₁₂ , viewpoint 2 and viewpoint 3 When the color difference is set to ΔE*ab ₂₃ and the color difference between the viewpoint 3 and the viewpoint 1 is ΔE*ab ₃₁ , the following formula is satisfied: 0.2 ≦ (ΔE*ab ₁₂ + ΔE*ab ₂₃ + ΔE*ab ₃₁ ) / 3 ≦ 1.5.

It can obtain a sheet with a dense appearance, stretchability and elongation of stretch recovery, and has a high-grade and varied expression of the pile-like artificial leather, and the color difference due to the viewing angle Small leather-like sheet, and the method of manufacturing the same. Thereby, the functionality of the moldability and the wearing comfort is improved, and even when the surface of the sheet is touched by hand or sitting on the surface of the sheet, it is difficult to see the sheet of the trace. .

1‧‧‧Leather-like sheet

2‧‧‧ Surface of leather-like sheet

3‧‧‧ longitudinal

4‧‧‧ Horizontal

5‧‧‧ Thickness direction

6‧‧‧立毛顺顺

Fig. 1 is a SEM photograph (100 magnifications) showing the shape of the fiber on the surface of the sheet obtained in Example 1.

Fig. 2 is a schematic view for explaining a method and apparatus for measuring a hue difference of a sheet.

Form of implementing the invention

The sheet material of the present invention is a sheet composed of an ultrafine fiber and a porous elastomeric polymer, characterized in that the sheet material comprises a substrate layer and a standing layer, and the ultrafine fiber has a coil-like crimp. The average single fiber diameter is 0.1 to 10 μm, and the fibers having a fiber length of 8 to 90 mm are included, and the stretch ratio of the sheet is 10% or more, and the tensile recovery is 80% or more.

The term "hair layer" as used in the present invention refers to a layer in which a sheet-like material is formed into fibers of a standing hair, and the term "base material layer" means a layer other than the pile layer of the sheet-like material.

In the present invention, the average single fiber diameter of the ultrafine fibers is important from 0.1 to 10 μm from the viewpoint of the flexibility of the sheet and the quality of the standing yarn. When the average single fiber diameter is increased, the sheet having a surface lacking in quality is preferably 7 μm or less, more preferably 5 μm or less. On the other hand, the color developability after dyeing is preferably 0.3 μm or more, and more preferably 0.5 μm or more from the viewpoint of dispersibility of the fibers during the raising treatment such as grinding of a sandpaper or the like. Further, in view of the fact that the flexibility, the quality of the standing yarn and the color development property at the time of dyeing are excellent, and the color difference due to the viewing angle is small, the preferable range is 0.3 μm to 0.7 μm.

In addition, the average fiber diameter of the ultrafine fibers is determined by scanning electron microscopy (SEM) photographs of the cross section of the photographic sheet, and 100 round or nearly circular elliptical fibers are randomly selected to measure the fiber diameter, and the average value is calculated. And calculate.

As the cross-sectional shape of the ultrafine fibers, for example, a polygon such as a circle, an ellipse, a flat or a triangle, a fan, a cross, a Y, H, X, W, C, and a π type can be used.

The ultrafine fibers constituting the fiber-wound body are in the form of an ultrafine fiber bundle. By forming the ultrafine fibers into a bundle, the tensile strength of the sheet and the physical strength of the tensile strength are enhanced, and the abrasion resistance can be further exhibited. In terms of the form of the ultrafine fiber bundle, the ultrafine fibers may be slightly separated from each other, and may be partially combined or agglomerated as the case may be. Examples of the ultrafine fiber-forming polymer used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polylactic acid. Melt-spinning of polyester, 6-nylon and 66-nylon, such as polyamide, acrylic, polyethylene, polypropylene, and thermoplastic cellulose Thermoplastic resin, etc. Among them, from the viewpoints of strength, dimensional stability, light resistance, and dyeability, it is preferred to use polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. Polyester fibers of polyester polymers. Further, at least two or more selected from these polymers may be combined.

Further, from the viewpoint of environmental considerations, it may be a fiber obtained by reusing raw materials and raw materials derived from plants. Moreover, the ultrafine fibers can be composed by mixing fibers of different materials.

Further, the polymer constituting the ultrafine fibers may be copolymerized with other components, and may contain additives such as organic particles, inorganic particles, a flame retardant, and an antistatic agent.

The ultrafine fibers constituting the sheet of the present invention may be a composite fiber in which two different polymers (A) and (B) are bonded together in the longitudinal direction of the fiber.

The combination of the polymer (A) and the polymer (B) may be appropriately selected from the group consisting of the polymer forming the above-mentioned ultrafine fibers, preferably a combination of polyester polymers having a poor intrinsic viscosity, and more preferably At least one of the polymer (A) or the polymer (B) is a polybutylene terephthalate polymer. In particular, the ultrafine fibers obtained by spinning and stretching the polymer obtained by laminating the combined polymer along the longitudinal direction of the fiber are concentrated on the high-viscosity side at the time of stretching, and the two components are different. The internal deformation is performed by heat treatment after sheeting, whereby the high-viscosity side is largely shrunk, deformation occurs in the single fiber, and coil-like crimping is exhibited. Due to the crimping, the entanglement of the fibers of the standing layer portion on the surface of the sheet becomes large, and the elongation is exhibited.

In the composite fiber of the side-by-side type, when the polymer (A) and the polymer (B) are a polyester-based copolymer, the difference in the inherent viscosity is preferably from 0.002 to 1.5. When the difference in the intrinsic viscosity is increased to 0.002 or more, a fiber excellent in crimping properties is obtained. On the other hand, when the intrinsic viscosity difference exceeds 1.5, the obtained fiber has a good crimping property, but since the spun fiber is excessively bent toward the high-viscosity component side, it is impossible to perform long-term stable spinning. Further, in view of the combination of the above polymers, at least one of them is a polybutylene terephthalate-based polymer. Since the polybutylene terephthalate-based polymer is a polymer having high crystallinity, for example, when the other is polyethylene terephthalate, a difference in crystallinity between the two polymers is caused, and it is easy to appear. Curl up.

The inherent viscosity of the polyester-based polymer in the present invention is preferably from 0.5 to 2.0 in the high viscosity component. By setting the intrinsic viscosity to 0.5 or more, it is possible to produce a fiber having sufficient strength and elongation. In addition, the upper limit of the intrinsic viscosity is preferably 2.0 or less from the viewpoints of ease of molding such as melt extrusion, production cost, and molecular weight drop due to molecular chain cutting due to heat and shear force in the middle of the step. . On the other hand, the low-viscosity component is stabilized by making the intrinsic viscosity 0.3 to 1.

Further, the composite ratio of the two components is preferably a high viscosity component: a low viscosity component = 75:25 to 35:65 (% by mass), more preferably 65:35 to 45:55 (% by mass). The scope of). In this range, the compounding ratio can be appropriately set in accordance with the elongation of the obtained sheet, and for example, the composite ratio of the high-viscosity component can be reduced in the sheet having excellent softness, and the high-viscosity component can be improved in the toughness. The composite ratio is better.

The intrinsic viscosity difference of the polyester-based polymer can be a desired viscosity by appropriately adjusting the polymerization time, temperature, amount of catalyst, and copolymerization component.

The intrinsic viscosity in the present invention is a value measured by dissolving a sample in o-chlorophenol at a temperature of 25 °C.

The polyester-based polymer in the present invention has a structure in which a dicarboxylic acid or a derivative thereof and a diol or a derivative thereof are copolymerized as a main component, and the main component herein means the whole The weight is more than 50% by weight. The polyester-based polymer may be a component containing a copolymerizable with other ester bonds. Examples of the copolymerizable compound include, for example, isophthalic acid, succinic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, sebacic acid, and 5-isophthalic acid. Carboxylic acids; glycols such as ethylene glycol, butylene glycol, neopentyl glycol, cyclohexane dimethanol, polyethylene glycol, and polypropylene glycol. Further, titanium dioxide as a matting agent, fine particles of vermiculite and alumina as a slip agent, a hindered phenol derivative as an antioxidant, and a coloring pigment may be added as needed.

The polybutylene terephthalate-based polymer in the present invention contains a structure in which terephthalic acid or a derivative thereof is copolymerized with 1,4-butanediol or a derivative thereof as a main component.

The nonwoven fabric constituting the sheet of the present invention may be any of a short fiber nonwoven fabric and a long fiber nonwoven fabric, and a short fiber nonwoven fabric is preferably used in terms of texture and quality.

In the case of the short fiber non-woven fabric used in the sheet of the present invention, the short fibers are formed by using a card and a cross wrapper to form a laminated net, and a needle punch and a water spray are applied. The water jet punching is obtained by a paper-making method, and the long-fiber nonwoven fabric can be suitably obtained by a spun bond method and a melt blown method.

The short fibers in the short fiber non-woven fabric are important to have a fiber length of 8 to 90 mm. By setting the fiber length to 8 mm or more, a sheet having excellent abrasion resistance can be obtained by winding. Moreover, by setting the fiber length to 90 mm or less, a sheet-like object excellent in compression characteristics and surface quality of the sheet can be obtained. The fiber length is preferably 25 to 90 mm.

Fibers having a fiber length of less than 8 mm are less likely to be entangled, and fiber detachment occurs in the manufacturing step of the sheet. Further, although the fiber longer than 90 mm is excellent in the wrapability, there is a tendency that the wear resistance is insufficient and the surface quality is deteriorated when the hair is formed.

The ultrafine fiber has a fiber length of 8 to 90 mm, and is preferably 50% by mass or more of the entire ultrafine fibers constituting the sheet.

In addition, the ratio of the fiber length of 8 to 90 mm is obtained by first extracting and removing the elastomeric polymer in the sheet material, and after forming only the ultrafine fibers, randomly extracting 100 fibers, measuring the fiber length, and making the fiber length straight. Calculated by the figure.

The nonwoven fabric obtained as described above can be subjected to shrinkage treatment by warm water and steam in order to enhance the dense feeling of the fibers. The temperature of the warm water and the vapor is preferably such that the ultrafine fibers described later are not curled, and the temperature of the sheet is less than 100 ° C. However, if the temperature of the sheet itself is kept less than 100 ° C, the temperature of warm water and steam imparted to shrink the sheet may be allowed to be 100 ° C or more. Moreover, in the shrinking treatment, the ultrafine fiber-forming fibers constituting the non-woven fabric are collected in boiling water. In the case where the shrinkage rate is high, even in the case where the shrinkage treatment temperature of the sheet is less than 100 ° C, there is a case where curling occurs after the shrinking treatment. Further, when the shrinkage ratio of the fiber is low, the denseness of the sheet material is not improved, and an excellent surface feeling as a leather-like sheet material cannot be obtained. Therefore, the shrinkage ratio of the ultrafine fiber-forming fibers constituting the nonwoven fabric in boiling water is preferably 5 to 25%.

The sheet of the present invention may contain a reinforcing layer for the purpose of improving the strength of the inner layer portion or the surface. As the reinforcing layer, a woven fabric, a knitted fabric, a non-woven fabric (including paper), a film of a plastic film and a metal film sheet, or the like can be used. In the case where the reinforcing layer is a woven fabric and a knitted fabric composed of fibers, the average single fiber diameter of the fibers is preferably from about 0.1 to 20 μm from the viewpoint of the texture of the sheet.

Examples of the type of the fiber sliver constituting the woven fabric used in the present invention include a filament yarn, a spun yarn, an innovative short fiber glazing yarn, and a filament yarn. Mixed yarn of short fiber plus burning yarn, etc. Since the short-fiber pulverized yarn has a large amount of fluff on the upper surface of the structure, when the non-woven fabric is entangled with the woven fabric, the filament yarn is preferably used because of the disadvantage that the pile is peeled off to expose the surface. When the filament yarns are roughly divided, a monofilament composed of one single fiber and a multifilament composed of a plurality of fibers are used, but in the woven fabric used in the present invention, The best use of multifilament fiber. Monofilament fibers sometimes impair the texture of the sheet due to the excessive rigidity of the fibers.

The total fineness of the fiber sliver constituting the woven fabric is preferably 50 to 150 dtex from the viewpoint of rigidity and mass per unit area.

The mass per unit area of the woven fabric is preferably 20 to 200 g/m ² , and more preferably 30 to 150 g/m ² . The quality per unit area of the woven fabric is less than 20 g/m ² , and the form of the woven fabric is lacking. When the woven fabric is inserted between the non-woven fabric and the non-woven fabric, or the woven fabric is superposed on the surface of the non-woven fabric, wrinkles are generated, and it becomes difficult to make the woven fabric uniform. Ground layer. Moreover, when the mass per unit area of the woven fabric exceeds 200 g/m ² , the structure of the woven fabric becomes dense, and the entanglement between the nonwoven fabric and the woven fabric tends to be difficult.

The basic structure of the woven fabric used in the present invention may be twill and satin, and it is preferable to use a flat structure which is less likely to occur such as a yarn slippage.

The sheet of the present invention has a standing layer on one or both sides of the sheet. Further, the ultrafine fibers can have a volumey feeling in a coil shape, and can give a sheet volume feeling and also exhibit extensibility.

The stretch ratio of the sheet of the present invention is preferably 10% or more, and the stretch recovery ratio is 80% or more. When the elongation is 10% or more and the tensile recovery is 80% or more, a sheet having excellent elongation can be obtained.

Further, the elongation was measured in JIS L 1096 (2010) 8.16.1 B method (fixed load method), and the elongation recovery ratio was measured in JIS L 1096 (2010) 8.16.2 B-1 method (fixed load method). Further, the nip interval was set to 10 cm, and the standing time after the load was removed was set to 1 hour.

The radius of the coil-like crimp of the ultrafine fibers constituting the bristles is preferably an arc of 5 to 100 μm, more preferably 90 μm or less, still more preferably 85 μm or less. If the radius is larger than 100 μm, the crimping becomes weak and the elongation is not easily obtained. On the other hand, from the viewpoint of surface quality, it is preferably 7 μm or more, and more preferably 20 μm or more. Radius When it is less than 5 μm, the crimp becomes strong and the surface quality deteriorates. By shrinking the ultrafine fibers into a coil shape, the coverage of the ultrafine fibers on the surface of the sheet is higher than that in the case where the ultrafine fibers are not crimped, and the nonwoven fabric itself under the standing hair is not seen, and the appearance of only the vertical hair is obtained. Compact and beautiful appearance. Further, in the internal structure of the sheet, the coil-like ultrafine fibers are entangled with each other to form an extended space for stretching, and the elongation is exhibited.

The sheet material of the present invention preferably contains 5 to 60% by mass of a porous elastomeric polymer with respect to the ultrafine fiber mass of the filament wound body. By containing 5% by mass or more of the elastomer polymer with respect to the mass of the ultrafine fibers, it is possible to impart appropriate compression characteristics to the sheet. In the case where the mass of the elastomeric polymer is more than 60% by mass, the fibers in the standing step become deficient in the fiber opening property, and the softness of the sheet is lowered. Further, in the case where the sheet is dyed and used, it is preferable that the fiber of the fiber-wound body after dyeing differs from the color tone of the elastomer polymer, and the elastomer polymer is small. In terms of environmental considerations, the elastomeric polymer is contained in a large amount, which is not preferable because the amount of the organic substance used in the production step is increased, and the elastomeric polymer is used in a small amount from the recycled raw material and the fiber derived from the plant. In the case, recycling and disposal become easy. The quality of the elastomeric polymer is more preferably in the range of 15 to 55% by mass.

The above-mentioned elastomer polymer may contain a pigment such as carbon black, a dye, an antifungal agent, an antioxidant, an ultraviolet absorber, and a light stabilizer, a flame retardant, a flame retardant, a penetrating agent, a lubricant, and the like. Anti-caking agent such as stone and titanium oxide, water repellent, viscosity adjuster, antistatic A surfactant such as a surfactant, an antifoaming agent such as polyfluorene oxide, a filler such as cellulose, a coagulation adjusting agent, and inorganic particles such as vermiculite and titanium oxide.

The elastomeric polymer in the present invention is important for porosity. By the porosity, the holding power of the fiber due to the elastomer polymer can be reduced, and the elongation due to the crimping of the fiber can be exhibited.

The elastomeric polymer used in the present invention may, for example, be a polyurethane elastomer, a polyurea, a polyacrylic acid or an ethylene. Vinyl acetate elastomer and acrylonitrile. Butadiene elastomer and styrene. A butadiene elastomer, polyvinyl alcohol, polyethylene glycol, or the like is preferably a polyurethane-based elastomer from the viewpoint of durability and compression properties. The polymeric elastomer may contain a plurality of polymeric elastomers.

2. The polyurethanes and polyurethanes which are particularly preferably used in the present invention are exemplified by polyurethanes and polyurethanes. Polyurea elastomer and the like.

A solvent-based polyurethane-based elastomer can be used as the polyurethane-based elastomer used in the present invention.

In the case of the polyurethane-based elastomer used in the present invention, a polyurethane-based elastomer obtained by a reaction of a polymer diol with an organic diisocyanate and a chain extender is preferably used.

For the above polymer diol, for example, a polycarbonate diol, a polyester diol, a polyether diol, a polyoxy diol, and a fluoro diol may be used, or a combination thereof may be used. Copolymer. Among them, polycarbonate diol and polyether diol are preferred from the viewpoint of hydrolysis resistance.

The above polycarbonate 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.

Further, examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol. a linear alkylene glycol such as 1,10-nonanediol, or neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentane a branched alkylene glycol such as an alcohol or 2-methyl-1,8-octanediol, an alicyclic diol such as 1,4-cyclohexanediol, an aromatic diol such as bisphenol A, or glycerin. Trimethylolpropane, pentaerythritol, and the like. In the present invention, any of a polycarbonate diol obtained by separately stretching an alkanediol and a copolymerized polycarbonate diol obtained from two or more kinds of alkylene glycols may be used.

Further, examples of the polyester diol include a polyester diol obtained by condensing various low molecular weight polyols with a polybasic acid.

As the low molecular weight polyol, for example, it is selected from, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 2,2-di Methyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, One or more of dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, and cyclohexane-1,4-dimethanol.

Further, an adduct of various alkylene oxides may be added to bisphenol A.

Further, examples of the polybasic acid include, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylate. One or more of acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydroisophthalic acid.

The polyether diol used in the present invention may, for example, be polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or a combination of these copolymerized diols.

The number average molecular weight of the polymer diol is preferably in the range of 500 to 4,000 when the molecular weight of the polyurethane elastomer is constant. By setting the number average molecular weight to preferably 500 or more, more preferably 1500 or more, it is possible to prevent the sheet from becoming hard. In addition, the strength of the polyurethane-based elastomer can be maintained by setting the number average molecular weight to 4,000 or less, more preferably 3,000 or less.

The organic diisocyanate used in the present invention may, for example, be an aliphatic diisocyanate such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate or benzodimethyl diisocyanate. Further, an aromatic diisocyanate such as diphenylmethane diisocyanate or toluene diisocyanate may be used in combination.

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

The polyurethane used in the present invention has a purpose of improving water resistance, abrasion resistance, hydrolysis resistance, and the like, and a crosslinking agent can be used in combination. The crosslinking agent may be an external crosslinking agent added as a third component to the polyurethane elastomer, or may be used to introduce a reaction point in which a crosslinked structure is formed in advance in the molecular structure of the polyurethane. Internal crosslinker. It is preferred to use an internal crosslinking agent from the viewpoint that the crosslinking point can be more uniformly distributed in the molecular structure of the polyurethane and the flexibility can be reduced.

In the case of a crosslinking agent, an isocyanate group can be used. A compound such as an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, or a sterol group.

The apparent density of the sheet of the present invention is preferably from 0.10 to 0.80 g/cm ³ , more preferably from 0.20 to 0.70 g/cm ³ . When the apparent density is 0.10 g/cm ³ or more, the denseness and mechanical properties of the sheet are good, and when it is 0.80 g/cm ³ or less, the texture can be prevented from becoming hard.

The thickness of the sheet is preferably from 0.1 to 7 mm. By setting the thickness to 0.1 mm or more, preferably 0.3 mm or more, the sheet shape is excellent in form stability and dimensional stability. On the other hand, when the thickness is 7 mm or less, more preferably 5 mm or less, the sheet formability is excellent.

The sheet of the present invention is characterized in that the difference in hue due to the viewing angle is small, that is, the L*, a*, and b* are measured from the three directions on the surface of the sheet, and the color difference ΔE* is obtained between the points. Ab, the average value is in the range of 0.2 to 1.5. In general, when ΔE*ab exceeds 1.5, the hue perception is more different, so that the chromatic phase difference is preferably 1.5 or less. On the other hand, if the color difference is 0.2 or less, the change in expression is small and the sense of high quality is lacking. Therefore, when the hue difference when the leather-like sheet is viewed from the three directions is in the range of 0.2 to 1.5, the following sheet can be obtained, which has a high-grade feeling and a changed expression, and the color due to the viewing angle The difference is small, that is, even in the case of forming a three-dimensional type such as a car seat and a sofa, the reflection of the portion that is exposed to light can be suppressed, the sewing feeling is less, and the discoloration is less likely to occur, even when the sheet is contacted by hand. It is also difficult to see the traces of the surface and the situation of sitting on the surface of the sheet.

The sheet of the present invention may contain functional agents such as dyes, pigments, softeners, texture modifiers, anti-pilling agents, antibacterial agents, deodorants, water repellents, light stabilizers, and weathering agents.

Next, a method of producing the sheet of the present invention will be described.

In order to obtain the means for forming the ultrafine fibers of the nonwoven fabric used in the sheet of the present invention, it is important to exhibit fibers of the ultrafine fibers. By pre-winding the ultrafine fiber-developing type fiber into a non-woven fabric, the fiber is extremely refined, and a non-woven fabric obtained by winding a bundle of ultrafine fibers can be obtained.

In the ultrafine fiber-developing type fiber, a thermoplastic polymer component having a different solubility in a solvent or the like can be used as a sea component and an island component, and in the subsequent step, a sea component can be dissolved and removed using a solvent to form an island component into a very fine fiber. The island-in-the-sea composite fiber or the peeling-divided fiber which is peeled and separated by the physical force of water spray or the like and the swelling of the solvent, preferably has a fine fiber diameter uniformly controlled, and the surface appearance of the sheet can be made beautiful. Island-type composite fiber. In the sea-island composite fiber, since the sea component is removed, an appropriate gap can be provided between the island components, that is, between the ultrafine fibers in the fiber bundle, and the fiber diameter can be efficiently found from each of the composite fibers. Small ultrafine fibers are preferably used because they impart a soft texture and bulkiness to the sheet.

In the sea-island type composite fiber, a sea-based composite nozzle can be used, and a sea-component and a two-component component of the island component are arranged to be mutually woven, and a sea-component and a sea-component component are mixed with two components of the island component to be spun. Mixed spinning method, etc., to obtain ultrafine fibers with uniform fineness In other words, it is more preferable to use an island-in-the-sea type composite fiber using a polymer alignment method.

Further, in the present invention, it is preferable that the ultrafine fiber-developing fiber is an island-in-sea type composite fiber, and the island component is a side-by-side type, and may be an eccentric core-sheath type. In the island component, a potential crimping type of island component fiber can be obtained by laminating two different polymers (A) and (B) in the longitudinal direction of the fiber into a side-by-side or eccentric core-sheath type. .

Moreover, the mass ratio of the sea component to the island component in the sea-island composite fiber used in the present invention is preferably in the range of sea component: island component = 5:95 to 80:20. When the mass ratio of the sea component is less than 5% by mass, the extreme refinement of the island component becomes insufficient. In addition, when the mass ratio of the sea component exceeds 80% by mass, the productivity is lowered because the ratio of the eluted component is large. The mass ratio of the sea component to the island component is better for the sea component: the island component = 10:90 to 60:40.

In the present invention, in the case of extending the ultrafine fiber-developing fiber typified by the sea-island type composite fiber, it is also possible to use the unstretched yarn to be temporarily wound, and to extend the yarn or to stretch the undrawn yarn directly. Any method. The stretching can be suitably carried out by a method of extending from 1 to 3 stages by moist heat or dry heat or both. Next, it is preferable to apply a crimping process to the extended sea-island type composite fiber, and cut it into a predetermined length to obtain a raw cotton which is not woven. The usual method can be used for crimping and cutting.

Examples of the sea component of the sea-island type fiber include polyethylene, polypropylene, polystyrene, copolymerized polyester obtained by copolymerizing sodium sulfoisophthalate or polyethylene glycol, polylactic acid, and PVA. .

The fiber ultrafine treatment (desealing treatment) of the sea-island type fiber can be carried out by immersing the sea-island type fiber in a solvent and extracting the liquid. In the case of the solvent in which the sea component is dissolved, when the sea component is polyethylene, polypropylene or polystyrene, an organic solvent such as toluene or trichloroethylene is used. Further, in the case where the sea component is a copolymerized polyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide or hot water is used.

As the fiber ultrafine treatment, a device such as a continuous dyeing machine, a vibration washing type sea-removing machine, a liquid flow dyeing machine, a wince dyeing machine, and a jigger dyeing machine can be used.

The dissolution of the sea component can be carried out at any time before impregnation of the elastomeric polymer, after impregnation, and after the raising process. When the demineralization treatment is carried out before the application of the elastomer polymer, since the direct elastomer polymer is in close contact with the ultrafine fibers, the ultrafine fibers can be strongly held, so that the wear resistance of the sheet is further improved. . On the other hand, if the sea-repellent treatment is carried out after the application of the elastomer polymer, the voids due to the sea component of the sea are generated between the elastomer polymer and the ultrafine fibers, so the direct elastomer polymer is not The ultrafine fibers are held to make the compression properties of the sheet good.

In the present invention, the number of fibers in the ultrafine fiber bundle is preferably from 10 to 9000 pieces/bundle, more preferably from 10 to 4,000 pieces/bundle. When the number of fibers is less than 10/bundle, the ultrafine fibers lack denseness, and mechanical properties such as abrasion tend to decrease. In addition, when the number of fibers is more than 9000/bundle, the fiber opening property at the time of standing is lowered, and the fiber distribution on the pile surface tends to be uneven.

From the viewpoint of fiber density, the fiber density in the ultrafine fiber bundle is preferably from 30 to 1,000, more preferably from 50 to 700. The degree of fiber density is calculated as (the number of fibers in the ultrafine fiber bundle) × (the diameter of the single fiber), and is an index of the size of the bundle of the ultrafine fibers. Therefore, by making the fiber density in the ultrafine fiber bundle 30 to 1000, the workability in the production of the fiber-wound body is good, and the denseness of the fiber bundle becomes good.

As a method of obtaining the fiber-wound body used in the present invention, a method of winding a fiber web by punching or water jet punching, a spunbonding method, a melt-blown method, a papermaking method, or the like can be employed. Among them, a method of forming a very fine fiber bundle as described above and subjecting to a treatment such as needle punching or water jet punching is preferably used.

The apparent density of the filament wound body composed of the fine fiber-expanding fibers after the needle punching treatment or the water jet punching treatment is preferably 0.15 to 0.40 g/cm ³ . By setting the apparent density to 0.15 g/cm ³ or more, a filament wound body excellent in form stability and dimensional stability can be formed. On the other hand, by setting the apparent density to 0.40 g/cm ³ or less, preferably 0.30 g/cm ³ or less, a sufficient space for imparting an elastic polymer can be maintained between the fibers.

The fiber-wound body composed of the ultrafine fiber-developing fiber thus obtained can be heat-shrinked by dry heat or moist heat or both, from the viewpoint of densification, and further increased in density to The preferred aspect. Further, the filament wound body may be compressed in the thickness direction by a rolling treatment or the like.

Further, in order to obtain the denseness and uniformity of the fiber distribution on the surface of the sheet, the elastomer polymer is attached to the fiber of the ultrafine fiber. The fiber-wound body such as a bundle of non-woven fabrics is substantially not present in the fiber bundle of the ultrafine fibers. If the elastomer polymer is present inside the fiber bundle, since the elastomer polymer becomes attached to each of the ultrafine fibers, it becomes incapable of opening property at the time of polishing treatment.

In the method of obtaining a form in which the polymeric elastomer is substantially not present inside the fiber bundle of the ultrafine fibers, it is preferred to use, for example, an elastomeric polymer as a solution. (1) In the filament wound body composed of the sea-island type fiber of the ultrafine fiber-developing type, after impregnating the above-mentioned elastomer polymer solution and solidifying it, the sea of the sea-island type fiber is dissolved in a solvent which does not dissolve the elastomeric polymer. a method of dissolving and removing the ingredients, or (2) A polyvinyl alcohol having a degree of saponification of preferably 80% or more is provided in the fiber-wound body composed of the sea-island type fiber of the ultrafine fiber-developing type, and the majority of the periphery of the fiber is protected, and the polyvinyl alcohol is not dissolved. The solvent removes the sea component of the sea-island type fiber, and then impregnates the above-described elastomer polymer solution and solidifies it, and then removes polyvinyl alcohol.

As the polyvinyl alcohol described above, polyvinyl alcohol having a degree of saponification of 80% or more is preferably used.

When the polyurethane-based elastomer liquid is impregnated into a filament winding or the like and solidified, it is important that the polyurethane-based elastomer is an organic solvent-based polyurethane-based elastomer. .

The organic solvent-based polyurethane can be coagulated by hot coagulation or wet coagulation or by combining them, and it is preferred to use a wet coagulation which is immersed in water to solidify it. By performing wet coagulation, the polyurethane does not concentrate at the interlacing point of the ultrafine fibers due to the polyurethane. Since it is also porous, the degree of freedom of the ultrafine fibers increases, and the sheet extensibility can be structurally imparted. On the other hand, in the case where the polyurethane-based elastomer is a water-dispersible polyurethane, dry solidification is carried out as a solidification method, but since the polyurethane is concentrated at the interlacing point of the ultrafine fibers The ultrafine fibers are strongly held, and the polyurethane itself does not form a non-porous structure, so the ultrafine fibers have no freedom and do not exhibit extensibility.

The temperature of the wet solidification is not particularly limited.

After the elastomeric polymer is applied to the filament wound body, the sheet material to which the elastomer polymer is obtained is cut into half in the thickness direction of the sheet or divided into a plurality of sheets, which is a preferable aspect in which the production efficiency is excellent.

It is important for the sheet of the present invention to have bristles on at least one side of the sheet.

The raising treatment of the bristles for forming the ultrafine fibers on the surface of the sheet of the present invention can be carried out by a method of grinding using a sandpaper, a roll sander or the like. A slip agent such as a polyoxyxide emulsion may be imparted to the sheet before the raising treatment.

Further, it is preferable that the antistatic agent is applied before the above-described raising treatment because the grinding powder generated from the sheet material is less likely to accumulate on the sandpaper.

The sheet may be obtained by cutting into half or dividing into a plurality of sheets in the thickness direction of the sheet before the raising treatment.

The sheet can be dyed according to the purpose. In the dyeing method of the sheet, since the sheet can be softened by imparting a enamel effect while dyeing the sheet, a liquid flow dyeing machine is preferably used. Staining of flakes If the temperature is too high, the polymer elastomer may be deteriorated. On the other hand, if the temperature is too low, the dyeing of the fiber may be insufficient, so that it is preferably set depending on the type of the fiber. The dyeing temperature is usually preferably from 80 to 150 ° C, more preferably from 110 to 130 ° C. The heat treatment of the dyeing step and the use of hydrazine become easy to exhibit the crimping of the ultrafine fibers.

In order to make the manufacturing process of the crimping of the ultrafine fibers, it is preferable to carry out the steps in the following (1) to (3).

(1) a step of exhibiting ultrafine fibers from a nonwoven fabric containing ultrafine fiber-developing fibers, (2) a step of raising a nonwoven fabric containing ultrafine fibers, and (3) after raising the hair at a temperature of 110 ° C or more and 150 ° C or less The non-woven fabric is subjected to a heat treatment, and the ultrafine fibers of the standing layer are subjected to a crimping step.

For example, when a heat treatment at a temperature of 100 ° C or higher is applied to the nonwoven fabric before the step of visualizing the ultrafine fibers from the nonwoven fabric containing the ultrafine fiber-developing fibers, the sea component is dissolved and the crimp is formed, and the curling process is performed in the subsequent step. The shape is stretched, and it becomes difficult to obtain the hair surface of the present invention.

Further, in the method for producing a leather-like sheet according to the present invention, the crimping of the ultrafine fibers in the pile layer is performed by applying a heat treatment at a temperature of 110 ° C to 150 ° C for the nonwoven fabric after the raising treatment of the ultrafine fibers. Achieved. By crimping the ultrafine fibers of the standing layer, an anisotropic standing surface can be obtained, and a sheet having a small difference in hue due to the viewing angle can be obtained.

The dye system can be selected in accordance with the type of the fibers constituting the sheet. For example, a disperse dye is used for the polyester fiber, and an acid dye and a gold-containing dye are used for the polyamine fiber, and these combinations can be further used.

Further, it is also preferred to use a dyeing aid in the dyeing of the sheet. By using a dyeing aid, the uniformity and reproducibility of dyeing can be improved. Further, after the same bathing or dyeing as the dyeing, a treatment 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 can be used.

The sheet of the present invention can be suitably used as a seat for a vehicle, a chair and a wall material, or a vehicle interior of a car, an electric car, and an airplane, as a roof and interior, because of its beautiful and compact appearance and stretchability (stretchability). The surface material of the garment has a very beautiful appearance, the upper, the shirt, the outerwear, the casual shoes, the sports shoes, the men's shoes and the ladies' shoes, the upper, the trim, the bag, the belt, the wallet, etc. It is used for industrial materials such as materials for clothing and wiping cloth. Further, in the sheet material of the present invention, a plurality of gaps of a few nm to 500 nm are generated in a single fiber or a wound portion of the fiber, and a specific property such as a porous material may be used, and it may be used as a filter or the like. Use for use.

The sheet of the present invention can also form a coating layer on its surface for use in artificial leather with silver. The method for forming the coating layer and the primer layer for forming the artificial leather with silver may be a dry surface forming method, a direct coating method, or the like, and various conventionally known methods may be employed, and are not particularly limited. For example, a reverse roll coater, a spray coater, a roll coater, a gravure coater, a roll coater, a knife coater, a notch coater, etc. are used. The method of the device. The thickness of each layer can be appropriately set according to the use. A preferred thickness is from 10 to 1000 μm, more preferably from 50 to 800 μm.

The resin used in the coating layer is most preferably a polyurethane. Other resins may be appropriately mixed and used in the above resin. In recent years, since durability is required in many applications, it is preferable to use a polyurethane having excellent durability such as polycarbonate. From the viewpoint of abrasion resistance, it is preferred to use a polyfluorene modified polyurethane. For the same reason, the polyurethane resin may be used in which the eucalyptus oil and the solid polyoxo compound are contained.

Example

Next, the sheet of the present invention and a method for producing the same will be specifically described using the examples. Next, the evaluation method used in the examples and the measurement conditions thereof will be described.

(1) Intrinsic viscosity IV

0.8 g of the sample polymer was dissolved in 10 mL of o-chlorophenol (hereinafter abbreviated as OCP), and the relative viscosity (ηr) was determined by the following formula using an Oswald viscometer at a temperature of 25 ° C to calculate the intrinsic viscosity (IV). ).

Ηr=η/η0=(t×d)/(t0×d0)

Intrinsic viscosity IV=0.0242ηr+0.2634

Here, η: viscosity of the polymer solution

Η0: viscosity of OCP

t: drop time of the solution (seconds)

d: density of solution (g/cm ³ )

T0: OCP drop time (seconds)

D0: density of OCP (g/cm ³ ).

(2) Average single fiber diameter

The cross section in which the sheet was cut in the thickness direction was used as an observation surface, and the average fiber diameter of the arbitrary 100 fine fibers was measured by a scanning electron microscope (SEM. VE-7800 model manufactured by Keyence Corporation) to calculate an average value. value.

(3) Curl radius

The surface of the sheet was photographed (magnification: 100 times) using a scanning electron microscope (SEM, model VE-7800, manufactured by Keyence Corporation), and the radius of the arc-shaped fiber indicating the crimp was measured. The n number is 20 and the average value is obtained. When the arc is regarded as a part of a circle, if the circumferential portion including the arc does not exceed 1/2 of the entire circle, the fiber is excluded from the measurement target if the fiber does not conform to the crimp.

(4) Quality per unit area of the sheet

It was measured by the method described in JIS L 1096 (1999) 8.4.2.

Five pieces of 20 cm × 20 cm test pieces were taken, and the respective masses (g) were weighed, and the average value was expressed per 1 m ² of mass (g/m ² ).

(5) Thickness of sheet

Using a thickness gauge of 0.01 mm (disk diameter of 9 mm or more), 5 points were measured at equal intervals in the sheet width direction under a load of 10 kPa, and the average value thereof was obtained.

(6) Extensibility

It is carried out by elongation and elongation recovery. In the case where both the elongation and the elongation recovery ratio exceeded the target value in each direction of the sheet, the evaluation was made "○", and either or both of them did not exceed the target, and it was "X", which was unacceptable.

. Elongation

The elongation of the sheet was measured in JIS L 1096 (2010) 8.16.1 B method (fixed load method).

Further, in the present invention, a good level (target value) is an elongation of 10% or more.

. Elongation recovery rate

The elongation recovery of the sheet was measured in JIS L 1096 (2010) 8.16.2 B-1 (fixed load method). Further, the nip interval was set to 10 cm, and the standing time after the load was removed was set to 1 hour.

Further, in the present invention, a good level (target value) is an elongation recovery ratio of 80% or more.

(7) The difference in hue of the leather-like sheet:

As shown in FIG. 2, the surface of the leather-like sheet 1 is 2, the vertical direction is 3, the lateral direction is 4, and the thickness direction is 5, using a color difference meter (CR-410 manufactured by KONICA MINOLTA Co., Ltd.). In the case where the direction in which the grading direction is set to 6, the measurement target point of the surface 2 of the leather-like sheet 1 is inclined at an angle of 45° from the vertical direction 6 of the longitudinal direction 3 of the leather-like sheet 1 Viewpoint 1, the viewpoint which is inclined by 45 degrees from the upper direction of the vertical direction of the vertical direction is set to the viewpoint 2, and the viewpoint which is inclined by 45 degrees from the upper side of the horizontal direction 4 is the viewpoint 3, and L* is measured at each viewpoint. a*, and b*. At the time of measurement, a cylindrical frame cut obliquely at 45° was formed so as not to leak light from the device, and the measurement was performed by fitting the tip of the device. When the color difference between the viewpoint 1 and the viewpoint 2 is ΔE*ab ₁₂ , the color difference between the viewpoint 2 and the viewpoint 3 is ΔE*ab ₂₃ , and the color difference between the viewpoint 3 and the viewpoint 1 is ΔE*ab ₃₁ , the measured L is obtained. *, a*, and b*, calculate the color difference ΔE*ab between points. ΔE*ab is obtained by the following calculation formula.

. △E*ab=(△L*^2+Δa*^2+△b*^2) ^1/2

(wherein ΔL* represents the difference in L* values between two points, Δa* represents the difference in a* values between two points, and Δb* represents the difference in b* values between two points)

[Example 1]

(raw cotton)

Polybutylene terephthalate having an intrinsic viscosity (IV) of 1.75 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 were each melted and used as a sea component. JIS K7206 (1999), a polystyrene (PSt) having a Vicat softening point of 100 ° C and a melt flow rate (hereinafter referred to as MFR) of 120, and an island-in-sea type composite nozzle having a number of islands of 24 islands, /The mass ratio of 80/20 of the melt-spun fiber was stretched by a normal condition and crimped by a rolling plate, and the fiber was cut into a length of 51 mm to obtain an island-in-the-sea type composite fiber having an average single fiber diameter of 26 μm. raw cotton.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 312 g/m ² and a thickness of 1.70 mm.

(sheet)

After the above non-woven fabric was shrunk in hot water at a temperature of 98 ° C, an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% was impregnated therein. The film was dried by hot air at a temperature of 120 ° C for 10 minutes to obtain a nonwoven fabric having a PVA mass of 30% by mass based on the mass of the nonwoven fabric. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a non-woven fabric (deseaping tablet) containing extremely fine fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of the polyurethane of 37% by mass based on the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.70 mm and an average single fiber diameter of 4.4 μm. As a result of observing the portion of the bristles, it was confirmed that the ultrafine fibers constituting the bristles exhibited curling, and the average radius of the crimp was 25 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Embodiment 2] (raw cotton)

In the same manner as in Example 1, except that polyethylene terephthalate having an intrinsic viscosity (IV) of 0.78 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 were used, respectively. Ground, the raw cotton of the island-type composite fiber is obtained.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 335 g/m ² and a thickness of 1.85 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 35 mass%. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a nonwoven fabric (deseaping tablet) containing extremely fine hollow fibers. The non-woven fabric (dehydrated sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (di-s-methylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, by removing PVA and DMF with hot water, drying with hot air at a temperature of 110 ° C for 10 minutes to obtain relative to The sheet having a mass of the polyurethane of 37% by mass in terms of the mass of the above-mentioned ultrafine fibers including the island component.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.70 mm and an average single fiber diameter of 4.4 μm. As a result of observing the bristles, it was confirmed that the ultrafine fibers constituting the bristles showed curling, and the average radius of the crimp was 30 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Example 3] (raw cotton)

In the same manner as in Example 1, except that polyethylene terephthalate having an intrinsic viscosity (IV) of 0.655 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.651 were used, respectively. Ground, the raw cotton of the island-type composite fiber is obtained.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 350 g/m ² and a thickness of 1.90 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 35 mass%. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a nonwoven fabric (deseaping tablet) containing extremely fine hollow fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of the polyurethane of 37% by mass based on the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.82 mm and an average single fiber diameter of 4.4 μm. As a result of observing the portion of the bristles, it was confirmed that the ultrafine fibers constituting the bristles showed curling, and the average radius of the crimp was 55 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Example 4] (raw cotton)

Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.780 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.654 were each melted and used as a sea component. JIS K7206 (1999), a polystyrene (PSt) having a Vicat softening point of 100 ° C and an MFR of 120, and an island-type composite nozzle having a island number of 24 islands, which is melted at an island/sea mass ratio of 80/20. The spun fiber was stretched by a rolling method by a normal condition and crimped, and the fiber was cut into a length of 51 mm to obtain a raw cotton of an island-in-the-sea type composite fiber having an average single fiber diameter of 52 μm.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 340 g/m ² and a thickness of 1.85 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 34% by mass. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a nonwoven fabric (deseaping tablet) containing extremely fine hollow fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of the polyurethane of 35 mass% with respect to the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.82 mm and an average single fiber diameter of 8.8 μm. As a result of observing the bristles, it was confirmed that the ultrafine fibers constituting the bristles showed curling, and the average radius of the crimp was 45 μm. Further, by SEM observation (500 times) of the cross section, it was confirmed that the polyamine group The formate is porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Example 5] (raw cotton)

Polybutylene terephthalate having an intrinsic viscosity (IV) of 1.75 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 are each melted and used as a sea component. 8 mol% copolymerized polyethylene terephthalate of sodium 5-sulfoisophthalate, using a sea-island composite nozzle with a island number of 24 islands, and a fiber spun-spun at an island/sea mass ratio of 80/20 The fiber was cut into a length of 51 mm by a rolling plate method under normal conditions and subjected to crimping, to obtain a raw cotton of an island-in-the-sea type composite fiber having an average single fiber diameter of 16 μm.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 310 g/m ² and a thickness of 1.70 mm.

(sheet)

The nonwoven fabric was shrunk in hot water at a temperature of 96 ° C, and then immersed in a sodium hydroxide aqueous solution having a concentration of 15 g/L heated to 80 ° C for 30 minutes to remove the sea component of the sea-island type fiber to obtain a microfiber. A sheet with a polyurethane. Next, it was immersed in a solid content concentration by drying with hot air at a temperature of 120 ° C for 10 minutes. The polycarbamate was solidified in a DMF solution of 12% polycarbonate-based polyurethane, followed by drying in a hot air of 110 ° C for 10 minutes in an aqueous solution having a DMF concentration of 30%. The mass of the polyurethane having a mass of 37% by mass relative to the mass of the aforementioned ultrafine fibers including the island component.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface. The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.70 mm and an average single fiber diameter of 2.8 μm. As a result of observing the portion of the bristles, it was confirmed that the ultrafine fibers constituting the bristles exhibited curling, and the average radius of the crimp was 30 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Embodiment 6] (spinning, making)

Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.780 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.654 are each melted and used as a sea component. JIS K7206 (1999), a polystyrene (PSt) having a Vicat softening point of 100 ° C and an MFR of 120, and an island-in-sea type composite nozzle having a number of islands of 24 islands, and having an island/sea mass ratio of 80/20 The way is spit out from the nozzle. The injection pressure was adjusted so that the spinning speed became 4000 m/min, and the sea-island type composite long fiber having an average single fiber diameter of 14 μm was collected by a net to obtain a long fiber nonwoven fabric sheet of 30 g/m ² .

(non-woven fabric containing very fine fiber-forming fibers)

Using the long-fiber nonwoven fabric sheet of the sea-island type composite fiber, a laminated fiber web was formed through a cross-wound step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle was punched at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 300 g/m ² and a thickness of 1.80 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 30% by mass. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a non-woven fabric (deseaping tablet) containing extremely fine fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of 38 mass% with respect to the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.80 mm and an average single fiber diameter of 2 μm. As a result of observing the portion of the bristles, it was confirmed that the ultrafine fibers constituting the bristles showed curling, and the average radius of the crimp was 70 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Embodiment 7] (spinning, making)

Each of the island components was used as a core component, and the polyethylene terephthalate having an intrinsic viscosity (IV) of 0.780 as a core component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 as a sheath component. Further, as a sea component, a sea-island composite having a Vicat softening point of 100 ° C, an MFR of 120, a island number of 24 islands, and an island component of an eccentric core sheath type measured in accordance with JIS K7206 (1999) was used. The nozzle was used to discharge from the nozzle so that the island/sea mass ratio became 80/20. The injection pressure was adjusted so that the spinning speed became 4000 m/min, and the sea-island type composite long fiber having an average single fiber diameter of 25 μm was collected by a net to obtain a long fiber nonwoven fabric sheet of 30 g/m ² .

(non-woven fabric containing very fine fiber-forming fibers)

Using the long-fiber nonwoven fabric sheet of the sea-island type composite fiber, a laminated fiber web was formed through a cross-wound step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle was punched at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 300 g/m ² and a thickness of 1.80 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 30% by mass. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a non-woven fabric (deseaping tablet) containing extremely fine fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of 40 mass% of the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.80 mm and an average single fiber diameter of 3.6 μm. As a result of observing the bristles, it was confirmed that the ultrafine fibers constituting the bristles showed curling, and the average radius of the crimp was 80 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Embodiment 8] (raw cotton)

Polybutylene terephthalate having an intrinsic viscosity (IV) of 1.75 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 were each melted and used as a sea component. JIS K7206 (1999), a polystyrene (PSt) having a Vicat softening point of 100 ° C and an MFR of 120, and an island-type composite nozzle having a island number of 24 islands, which is melted at an island/sea mass ratio of 80/20. The spun fiber was stretched by a normal rolling condition by a rolling method, and then the fiber was cut into a length of 10 mm to obtain a raw cotton of an island-in-the-sea type composite fiber having an average single fiber diameter of 26 μm.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 162 g/m ² and a thickness of 0.87 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 30% by mass. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a non-woven fabric (deseaping tablet) containing extremely fine fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of the polyurethane of 37% by mass based on the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.72 mm and an average single fiber diameter of 4.4 μm, and the result of observing the portion of the standing layer was confirmed. The ultrafine fibers of the bristles showed curling, and the average radius of the crimp was 20 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Embodiment 9] (raw cotton)

Polybutylene terephthalate having an intrinsic viscosity (IV) of 1.75 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 were each melted and used as a sea component. JIS K7206 (1999), a polystyrene (PSt) having a Vicat softening point of 100 ° C and an MFR of 120, and an island-type composite nozzle having a island number of 24 islands, which is melted at an island/sea mass ratio of 80/20. The spun fiber was stretched by a rolling method under normal conditions and crimped, and the fiber was cut into a length of 80 mm to obtain a raw cotton of an island-in-the-sea type composite fiber having an average single fiber diameter of 26 μm.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 172 g/m ² and a thickness of 0.94 mm.

(sheet)

After the above non-woven fabric was shrunk in hot water at a temperature of 98 ° C, an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% was impregnated therein. It was dried by hot air at a temperature of 120 ° C for 10 minutes to obtain a nonwoven fabric having a PVA mass of 35 mass% with respect to the quality of the nonwoven fabric. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a nonwoven fabric (deseaping tablet) containing extremely fine hollow fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of the polyurethane of 37% by mass based on the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.73 mm and an average single fiber diameter of 4.4 μm. As a result of observing the portion of the bristles, it was confirmed that the ultrafine fibers constituting the bristles showed curling, and the average radius of the crimp was 30 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The extensibility of the sheet was good. The results are shown in Table 1.

[Embodiment 10]

Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.78 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.48 were each melted and used as a sea component. Styrene, using a sea-island composite nozzle with a island number of 24 islands, the fiber melt-spun at an island/sea mass ratio of 80/20 is stretched by 3.2 times under normal conditions by a rolling plate, and after crimping, The fibers were cut to a length of 51 mm to obtain a sea-island type composite fiber having an average single fiber diameter of 4.4 μm and a raw water having a boiling water shrinkage of 14.5%.

Using the raw cotton of the sea-island type composite fiber thus obtained, a laminated fiber web was formed by a carding and cross-winding step, and after performing a needle punching with a number of punching holes of 600 pieces/cm ² , the number of punching holes of 3000 pieces/cm ² was carried out. Needle punch to obtain a sheet.

The sheet thus obtained was shrunk in hot water at a temperature of 96 ° C, and then dried by hot air at a temperature of 95 ° C for 15 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) to obtain a relative fiber sheet. The PVA mass was 20% by mass of the sheet in terms of the mass of the substrate. The sheet was immersed in trichloroethylene to dissolve and remove the sea component to obtain a sea-leaf sheet obtained by winding the ultrafine fibers and the woven fabric. The thus obtained sea-leaf piece was immersed in a DMF (dimethylformamide) solution having a solid content concentration adjusted to 12% of a polyurethane, followed by a polyamine group in an aqueous solution having a DMF concentration of 30%. The formate is solidified. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 95 ° C for 15 minutes to obtain a mass of the above-mentioned ultrafine fiber sheet containing an island component having a single fiber fineness of 0.21 dtex. A leather substrate sheet having a mass of polyurethane of 28% by mass.

The leather substrate sheet thus obtained was cut vertically in the thickness direction, and the half-cut surface was ground with an annular sandpaper having a sandpaper count of 180 pieces to form a standing surface. The leather base material sheet thus obtained was placed in a liquid flow dyeing machine, and dyed to a light brown color and a crimping treatment at a temperature of 120 ° C, and then dried in a dryer to obtain a leather-like sheet.

With respect to the leather-like sheet thus obtained, it was confirmed that the thickness of the bristles was 150 μm, and the standing bristles of the surface were curled into a coil shape, and the direction of the bristles was random. With respect to the surface of the obtained sheet, L*, a*, and b* were measured from the three directions by the above-described measurement method, and ΔE*ab between the respective points was obtained, and the average value of ΔE*ab at three points was 0.72, and there is no chromatic aberration caused by the angle of view. Moreover, the expression is rich and has a high-grade feeling, and there is no feeling of smearing and fading when formed into a sheet. The results are shown in Table 2.

[Example 11]

In the above-described Example 1, the number of islands was changed to 36 islands, and the island/sea mass ratio was changed to 60/40, and processing was performed under the same conditions as in Example 1 to obtain an average single fiber diameter of 2.1 μm. Leather-like sheet.

With respect to the leather-like sheet thus obtained, it was confirmed that the thickness of the bristles was 180 μm, and the standing bristles of the surface were curled into a coil shape, and the direction of the bristles was random. With respect to the surface of the obtained sheet, L*, a*, and b* were measured from the three directions by the above-described measurement method, and ΔE*ab between the respective points was obtained, and the average value of ΔE*ab at three points was 1.20. There is no chromatic aberration caused by the angle of view. Moreover, the expression is rich and has a high-grade feeling, and there is no feeling of smearing and fading when formed into a sheet. The results are shown in Table 2.

[Embodiment 12]

In addition to the above-mentioned Example 1, polyethylene terephthalate having an intrinsic viscosity (IV) of 1.21 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.48 were used to obtain an extension. The leather-like sheet was obtained under the same conditions as in Example 1 except that the raw cotton having a magnification of 3.7 times and a boiling water shrinkage ratio of 21.5% was used.

With respect to the leather-like sheet thus obtained, it was confirmed that the thickness of the bristles was 150 μm, and the standing bristles of the surface were curled into a coil shape, and the direction of the bristles was random. With respect to the surface of the obtained leather-like sheet, L*, a*, and b* were measured from the three directions by the above-described measurement method, and ΔE*ab between the respective points was obtained, and ΔE*ab at three points was obtained. The average value is 0.46 and there is no hue difference due to the angle of view. Moreover, the expression is rich and has a high-grade feeling, and there is no feeling of smearing and fading when formed into a sheet. The results are shown in Table 2.

[Comparative Example 1] (raw cotton)

Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.718 as an island component, and polystyrene having a Vicat softening point of 100 ° C and an MFR of 120 as a sea component according to JIS K7206 (1999) PSt), using a sea-island composite nozzle with a number of islands of 24 islands, the fibers that are melt-spun at an island/sea mass ratio of 80/20 are stretched by a normal method under a rolling condition, and then the fibers are cut. The length was 51 mm, and the raw cotton of the sea-island type composite fiber having an average single fiber diameter of 26 μm was obtained.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 560 g/m ² and a thickness of 3.15 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 33% by mass. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a nonwoven fabric (deseaping tablet) containing extremely fine hollow fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of the polyurethane of 32% by mass based on the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.90 mm and an average single fiber diameter of 4.4 μm. As a result of observing the portion of the standing layer, it was confirmed that the ultrafine fibers constituting the pile layer did not exhibit curling. Moreover, it was confirmed by the SEM observation (500 times) of the cross section that the polyurethane was porous, but the elongation of the sheet was poor. The results are shown in Table 1.

[Comparative Example 2] (spinning)

Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.718 was extruded from a spinning nozzle and stretched by a usual condition by a rolling plate to obtain a composite multifilament fiber (very fine fiber) of 74 dtex/350f.

On the other hand, a 56 dtex/12f multifilament fiber was obtained in the same manner as described above. The composite long fiber twisted yarn (1500/m) was used for warp yarns and weft yarns to produce a plain weave fabric.

First, the produced 74 dtex/350f composite multifilament fiber (very fine fiber) was cut into a length of 5 mm, and then dispersed in water to prepare a papermaking slurry for the surface layer and the inner layer. The surface unit area mass of the surface layer was set to 100 g/m ² , and the mass per unit area of the inner layer was set to 100 g/m ² , and the woven fabric was inserted to form a laminated structure fiber sheet, and the fibers constituting the sheet were three-dimensionally interlaced by spraying with a high-speed water stream. To get a non-woven fabric.

Then, it was immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%. Then, the polyurethane was solidified in an aqueous solution having a DMF concentration of 30%. Then, DMF was removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of the polyurethane of 33% by mass based on the mass of the above-mentioned ultrafine fibers.

Then, the surface of the sheet was polished using 240 mesh sandpaper at a polishing wheel speed of 500 m/min, a sheet conveying speed of 1.0 m/min, and a sheet contact angle of the polishing wheel and the sheet was set to 50° to form. Stand the rough surface.

The sheet thus obtained was dyed using a flow dyeing machine. The obtained sheet-like sheet had a thickness of 0.90 mm and an average single fiber diameter of 4.4 μm. As a result of observing the portion of the bristles, it was confirmed that the ultrafine fibers did not constitute the fiber bundle, and the ultrafine fibers constituting the bristles did not appear to be crimped. Moreover, it was confirmed by the SEM observation (500 times) of the cross section that the polyurethane was porous, but the elongation of the sheet was poor. The results are shown in Table 1.

[Comparative Example 3] (raw cotton)

In the same manner as in Example 1, except that polyethylene terephthalate having an intrinsic viscosity (IV) of 0.652 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.651 were used, respectively. , the raw cotton of the island-type composite fiber is obtained.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 340 g/m ² and a thickness of 1.80 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 33% by mass. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a nonwoven fabric (deseaping tablet) containing extremely fine hollow fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of 38 mass% with respect to the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.80 mm and an average single fiber diameter of 4.4 μm, and the result of observing the portion of the standing layer was confirmed to constitute a standing hair. The ultrafine fibers of the layer did not show curling, but the average radius of the crimp was 110 μm. Moreover, it was confirmed by the SEM observation (500 times) of the cross section that the polyurethane was porous, but the elongation of the sheet was poor. The results are shown in Table 1.

[Comparative Example 4] (raw cotton)

The raw cotton of the sea-island type composite fiber was obtained in the same manner as in Example 1 except that the island/sea mass ratio was 20/80.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 340 g/m ² and a thickness of 1.85 mm.

(sheet)

After the above-mentioned nonwoven fabric was shrunk in hot water at a temperature of 98 ° C, it was dried by hot air at a temperature of 120 ° C for 10 minutes by impregnating a 12% aqueous solution of PVA (polyvinyl alcohol) therein to obtain a quality relative to the nonwoven fabric. A non-woven fabric having a PVA mass of 34% by mass. The nonwoven fabric thus obtained was immersed in trichloroethylene to dissolve and remove the sea component, thereby obtaining a nonwoven fabric (deseaping tablet) containing extremely fine hollow fibers. The non-woven fabric (deseaping sheet) containing the ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then, Polyamine in an aqueous solution of 30% DMF concentration The carbamate is solidified. Then, PVA and DMF were removed by hot water, and dried by hot air at a temperature of 110 ° C for 10 minutes to obtain a sheet having a mass of the polyurethane of 35 mass% with respect to the mass of the above-mentioned ultrafine fibers including the island component. Shape.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.70 mm and an average single fiber diameter of 0.05 μm. As a result of observing the portion of the bristles, it was confirmed that the ultrafine fibers constituting the bristles showed curling, and the average radius of the crimp was 3 μm. Moreover, it was confirmed by the SEM observation (500 times) of the cross section that the polyurethane was porous, but the elongation of the sheet was poor. The results are shown in Table 1.

[Comparative Example 5] (raw cotton)

Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.780 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 were each melted and used as a sea component. 8 mol% of sodium 5-sulfoisophthalate copolymerized polyethylene terephthalate, using an island-in-sea composite nozzle with a island number of 24 islands, which will have an island/sea mass ratio The fiber of the 80/20 melt-spun yarn was stretched by a normal condition under a rolling condition, and the fiber was cut into a length of 51 mm to obtain a raw cotton of an island-in-the-sea type composite fiber having an average single fiber diameter of 26 μm.

(non-woven fabric containing very fine fiber-forming fibers)

Using the raw cotton of the sea-island type composite fiber, a laminated fiber web is formed by a carding and cross-winding step, and after needle punching with a number of punching holes of 600 pieces/cm ² , the needle is applied at a number of punching holes of 3000 pieces/cm ² The thorn was obtained to obtain a sheet having a mass per unit area of 340 g/m ² and a thickness of 1.83 mm.

(sheet)

The above non-woven fabric was shrunk in hot water at a temperature of 98 ° C, and then dried by hot air at a drying temperature of 100 ° C for 5 minutes. Then, it was dried by hot air drying at a drying temperature of 100 ° C for 10 minutes by impregnating a water-dispersed polyurethane solution (ether system) having a solid content of the polyurethane of 12% by mass to obtain a relative island. The mass of the above-mentioned ultrafine fibers of the component is a sheet having a mass of the polyurethane of 45% by mass.

Then, the sheet thus obtained was immersed in a sodium hydroxide aqueous solution having a concentration of 15 g/L heated to a temperature of 80 ° C, and the sea component of the sea-island type composite fiber was removed by treatment for 30 minutes to obtain an ultrafine fiber and a water-dispersed type. a sheet of polyurethane.

Then, the sheet was cut into half in the thickness direction, and the opposite side of the half-cut surface was made of 240 mesh sandpaper, and the polishing wheel was contacted with the sheet at a polishing wheel speed of 500 m/min and a sheet conveying speed of 1.0 m/min. The sheet contact angle was set to 50° for polishing to form a raised surface.

The sheet thus obtained was subjected to a crimping treatment and dyeing at a temperature of 130 ° C using a liquid flow dyeing machine, followed by drying using a dryer to obtain a sheet.

The obtained sheet-like sheet had a thickness of 0.75 mm and an average single fiber diameter of 4.4 μm. As a result of observing the portion of the bristles, it was confirmed that the ultrafine fibers constituting the bristles showed curling, and the average radius of the crimp was 60 μm. Further, by the SEM observation (500 times) of the cross section, the polyurethane was not porous, and the extensibility of the sheet was poor. The results are shown in Table 1.

[Comparative Example 6] (raw cotton)

In addition to the use of polybutylene terephthalate having an intrinsic viscosity (IV) of 1.750 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.025, respectively, In the same manner, the yarn is bent sharply when ejected from the nozzle, and the yarn breakage often occurs unsteadily.

[Comparative Example 7]

A leather-like sheet was obtained under the same conditions as in Example 1 except that the island component was a polyethylene terephthalate single component having an intrinsic viscosity (IV) of 0.78.

With respect to the leather-like sheet thus obtained, it was confirmed that the thickness of the bristles was 210 μm, the standing bristles were not crimped, and the direction of the bristles was consistent in one direction. With respect to the surface of the obtained sheet, L*, a*, and b* were measured from the three directions by the above-described measurement method, and ΔE*ab between each point was obtained, and the average value of ΔE*ab at three points was 2.51. The color difference is due to the angle of view, and the stitching feeling and the fading feeling are generated when formed into a sheet. The results are shown in Table 2.

[Comparative Example 8]

In addition to the above-mentioned Example 1, after the needled sheet was shrunk in hot water at a temperature of 96 ° C, it was impregnated with a 12% aqueous solution of PVA (polyvinyl alcohol) at a temperature of 120 ° C. A leather-like sheet was obtained under the same conditions as in Example 1 except that the drying was carried out for 15 minutes.

With respect to the leather-like sheet thus obtained, the thickness of the bristles was 195 μm, and the crepe of the surface was weak, and the crimp which appeared before the pilling treatment was stretched by the pilling process. With respect to the surface of the obtained sheet, L*, a*, and b* were measured from the three directions by the above-described measurement method, and ΔE*ab between the respective points was obtained, and the average value of ΔE*ab at the three points was 2.31. The color difference is due to the angle of view, and the stitching feeling and the fading feeling are generated when formed into a sheet. The results are shown in Table 2.

[Comparative Example 9]

In addition to the above Example 3, polybutylene terephthalate having an intrinsic viscosity (IV) of 1.21 as an island component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.48 were used. The leather sheet-like material was obtained under the same conditions as in Example 3 except for the raw cotton having a stretching ratio of 3.9 times and a boiling water shrinkage ratio of 25.2%.

With respect to the leather-like sheet thus obtained, the thickness of the standing layer is 170 μm, and the surface of the hair is weakened, and the curl which appears in the heat shrinking step before the raising treatment is stretched by the raising treatment. shape. With respect to the surface of the obtained sheet, L*, a*, and b* were measured from the three directions by the above-described measurement method, and ΔE*ab between the respective points was obtained, and the average value of ΔE*ab at three points was 1.98. The color difference is due to the angle of view, and the stitching feeling and the fading feeling are generated when formed into a sheet. The results are shown in Table 2.

[Comparative Example 10]

In the same manner as in the first embodiment, the leather sheet-like material was obtained in the same manner as in Example 1 except that the number of the counts was changed to 320 pieces of sandpaper in the sandpaper treatment in the thickness direction.

With respect to the leather-like sheet thus obtained, it was confirmed that the thickness of the bristles was 40 μm, and the standing bristles of the surface were curled into a coil shape, and the direction of the bristles was random. With respect to the surface of the obtained sheet, L*, a*, and b* were measured from the three directions by the above-described measurement method, and ΔE*ab between the respective points was obtained, and the average value of ΔE*ab at three points was 0.17. There is no chromatic aberration caused by the angle of view, but the expression lacks change and lacks a sense of quality. The results are shown in Table 2.

Claims (9)

a sheet comprising a sheet of ultrafine fibers and a porous elastomeric polymer, characterized in that the sheet comprises a substrate layer and a standing layer, the ultrafine fibers having a coil-like crimp. The average single fiber diameter is 0.1 to 10 μm, and the fiber having a fiber length of 8 to 90 mm is included, and the stretch ratio of the sheet is 10% or more, and the tensile recovery ratio is 80% or more. The sheet of claim 1, wherein the ultrafine fibers constituting the sheet comprise fibers having a fiber length of 25 to 90 mm. The sheet of claim 1 or 2, wherein the ultrafine fibers constituting the standing layer have a coil-like crimping radius of 5 to 100 μm. The sheet according to any one of claims 1 to 3, wherein the ultrafine fibers are formed by combining two different polymers (A) and (B) in a fiber lengthwise direction. The sheet of claim 4, wherein the polymer (A) and the polymer (B) are polyester-based polymers, and the difference in intrinsic viscosity (IV) is from 0.002 to 1.5. A sheet according to claim 4 or 5, wherein at least one of the polymer (A) or the polymer (B) is a polybutylene terephthalate-based polymer. A method for producing a sheet, which is a method for producing a sheet according to any one of claims 1 to 6, which is characterized in that the ultrafine fibers are made of a sheet comprising fibers of the ultrafine fiber-developing type. The method for producing a sheet according to claim 7, wherein the ultrafine fiber-forming fiber is an island-in-sea type composite fiber, and the island component is a side-by-side type. A leather-like sheet comprising a non-woven fabric comprising a composite fiber having an average single fiber diameter of 0.3 μm or more and 7 μm or less, a leather-like sheet having a polymer elastomer therein and a pile layer on the surface, and the composite fiber Two or more polyethylene terephthalate polymers having a difference in intrinsic viscosity are attached to the fiber length direction to form a side-by-side type or an eccentric core-sheath structure, which is characterized in that a leather-like sheet is used. The measurement target point on the surface is set to be the viewpoint point 1 from the upper side of the longitudinal direction of the leather-like sheet, and the viewpoint point is inclined by 45 degrees from the vertical direction of the vertical direction. The viewpoint in which one of the horizontal directions is inclined by 45° is set as the viewpoint 3, the color difference between the viewpoint 1 and the viewpoint 2 is ΔE*ab ₁₂ , and the color difference between the viewpoint 2 and the viewpoint 3 is ΔE*ab ₂₃ , the viewpoint 3 and the viewpoint When the color difference of 1 is set to ΔE*ab ₃₁ , the following formula is satisfied: 0.2 ≦ (ΔE*ab ₁₂ + ΔE*ab ₂₃ + ΔE*ab ₃₁ ) / 3 ≦ 1.5.