JP6838602B2 - Sheet-shaped material and its manufacturing method - Google Patents

Description

The present invention relates to a sheet-like material having an elegant appearance and excellent stretchability due to the ultrafine fibers having coil-like crimps, and a method for producing the same.

Conventionally, sheet-like materials mainly composed of ultrafine fibers and polymer elastic bodies have excellent characteristics not found in natural leather, and their use has been expanding year by year for clothing, chair upholstery, automobile interior materials, and the like. Recently, there has been a demand for a sheet-like material having excellent stretchability, particularly from the viewpoint of wearing feeling in clothing applications and moldability in material applications. For the purpose of imparting stretchability to the sheet-like material, studies have been made to have a structure in which the fibers constituting the sheet-like material are attached side-by-side.

For example, in Patent Document 1, the island component is an inelastic polymer by removing the sea component from the focused fiber-generating fiber in which the fiber component made of an elastic polymer and the sea-island structure having an island component made of an inelastic polymer are adjacent to each other. Fibers having a structure in which two types of fibers, a non-elastic ultrafine fiber bundle generation type fiber and an elastic fiber, are attached side by side are obtained, and artificial leather using the fibers has been proposed. However, when spinning polyurethane-based fibers, which are elastic polymers, the polyurethane-based fibers have a problem that the texture is hard as a property peculiar to polyurethane, and the texture and drapeability of the woven fabric are deteriorated. Further, the polyurethane fiber is difficult to be dyed with a dye for polyester, and even when used in combination with the polyester fiber, not only the dyeing process becomes complicated but also it is difficult to dye the desired color.

Patent Document 2 proposes a method of inserting a woven or knitted fabric containing a yarn containing a side-by-side type composite fiber formed from two types of polyethylene terephthalate copolymers having different intrinsic viscosity (IV). Due to the stress concentration on the high viscosity side during stretching, different internal strains occur between the two components, and crimping occurs. However, since the ultrafine fibers constituting the sheet-like material are not latent crimp-expressing fibers and only the woven or knitted material inserted for the purpose of reinforcing the strength of the sheet-like material is crimped, the sheet-like material is imparted with stretchability. However, the feeling of fineness of the ultrafine fibers on the surface of the sheet-like material is not exhibited.

Patent Document 3 proposes an artificial leather containing latent crimp-expressing fibers obtained by compound-spinning two types of polytrimethylene terephthalates having different intrinsic viscosities in a side-by-side manner. However, the length of the ultrafine fibers forming this sheet is very short, 5 mm or less, and since the fiber bundle cannot be formed due to the direct spinning method, the entanglement between the ultrafine fibers and the crimping of the ultrafine fibers are small. It becomes a sheet-like material with poor stretchability.

On the other hand, Patent Document 4 proposes a non-woven fabric made of side-by-side type ultrafine fibers formed of two types of polyethylene terephthalates having different intrinsic viscosities, and a sheet-like material containing water-dispersible polyurethane inside. In the present patent document, since the non-woven fabric is impregnated with the water-dispersible polyurethane, the water-dispersible polyurethane has a structure in which the entanglement points of the ultrafine fibers are solidified when dried. Moreover, since polyurethane has a non-porous structure, there is no degree of freedom in ultrafine fibers. Therefore, the ultrafine fibers are crimped and the appearance of the surface of the sheet-like material becomes dense, but the stretchability is not exhibited.

That is, until now, a sheet-like material having both a precise appearance and stretchability such as a stretch rate and a stretch recovery rate has not been obtained.

In addition, in suede-like artificial leather that generally has fluff on the surface, the reflection of light on the surface fibers changes depending on the direction of the fluff, and the hue differs depending on the viewing angle. I had to pay attention to the direction.

Japanese Patent No. 03128333 Japanese Patent No. 0503517 Japanese Unexamined Patent Publication No. 2003-286663 Japanese Unexamined Patent Publication No. 2012-136800

Although no literature has been found on a proposal for solving the above-mentioned problems, the present inventors have solved the above-mentioned problems by changing the direction of the fibers on the surface using latent crimped yarn. We were able to.

An object of the present invention is a sheet-like material having both a precise appearance and stretchability such as a stretch rate and a stretch recovery rate in view of the actual conditions of the above-mentioned prior art, and a hue difference even if the viewing angle is changed while maintaining a high-class feeling. Provides small sheet-like materials and methods for producing them.

The present invention is a sheet-like material composed of ultrafine fibers and a porous elastic polymer, wherein the sheet-like material is composed of a base material layer and a napped layer, and the ultrafine fibers have coil-like crimps. The average single fiber diameter is 0.1 to 10 μm, the fiber length is 8 to 90 mm, the sheet-like material has an elongation rate of 10% or more, and a elongation recovery rate is 80% or more. It is a sheet-like material characterized by.

According to a preferred embodiment of the sheet-like material of the present invention, the ultrafine fibers constituting the sheet-like material are sheet-like materials containing fibers having a fiber length of 25 to 90 mm.

Further, according to a preferred embodiment of the sheet-like material of the present invention, two or more kinds of polyethylene terephthalate-based polymers having an intrinsic viscosity difference are bonded side-by-side in a fiber length direction, or an eccentric core. A non-woven fabric made of composite fibers having an average single fiber diameter of 0.3 μm or more and 7 μm or less forming a sheath structure, and a leather-like sheet-like material containing a polymer elastic body inside and having a napped layer on the surface. With respect to the measurement target point on the surface of the leather-like sheet-like material, the viewpoint from the upward oblique 45 ° in the vertical direction of the leather-like sheet-like material in the vertical direction of the fluffing forward is the viewpoint 1, and the viewpoint in the vertical direction is 45 ° upward in the opposite direction of the fluffing. The viewpoint from the viewpoint is the viewpoint 2, the viewpoint from any one of the horizontal directions diagonally upward 45 ° is 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 defined as the viewpoint 3. When ΔE * ab ₂₃ and the color difference between the viewpoint 3 and the viewpoint 1 are ΔE * ab ₃₁ , the leather-like sheet-like material is characterized by satisfying the following equation.
0.2 ≦ (ΔE * ab ₁₂ + ΔE * ab ₂₃ + ΔE * ab ₃₁ ) / 3 ≦ 1.5

A sheet-like material that has both a precise appearance and stretchability such as stretch rate and stretch recovery rate, and a leather-like sheet-like material that has a luxurious feel and a changing look of suede-like artificial leather, but has a small hue difference depending on the viewing angle. Goods and methods of manufacturing them can be obtained. As a result, it is possible to obtain a sheet-like material which is excellent in functionality such as moldability and comfort, and whose traces are hard to see even when the surface of the sheet-like material is touched by hand or when sitting.

FIG. 1 is an SEM photograph (100 times) showing the shape of fibers on the surface of the sheet-like material obtained in Example 1. FIG. 2 is a schematic view for explaining a method and an apparatus for measuring a hue difference of a sheet-like object.

The sheet-like material of the present invention is a sheet-like material composed of ultrafine fibers and a porous elastic polymer, the sheet-like material is composed of a base material layer and a napped layer, and the ultrafine fibers are coiled. It has crimping, has an average single fiber diameter of 0.1 to 10 μm, contains fibers having a fiber length of 8 to 90 mm, has a stretch rate of 10% or more, and a stretch recovery rate of 80%. It is a sheet-like material characterized by the above.

The fluffy layer in the present invention is a layer formed by fluffy fibers of a sheet-like material, and the base material layer refers to a layer other than the fluffy layer of a sheet-like material.

In the present invention, it is important that the average single fiber diameter of the ultrafine fibers is 0.1 to 10 μm from the viewpoint of the flexibility of the sheet-like material and the nap quality. When the average single fiber diameter is increased, a sheet-like material having poor surface quality is obtained, so that the average single fiber diameter is preferably 7 μm or less, more preferably 5 μm or less. On the other hand, from the viewpoints of color development after dyeing, dispersibility of fibers during brushing treatment such as grinding with sandpaper, and ease of handling, the thickness is preferably 0.3 μm or more, more preferably 0.5 μm or more. Further, the preferable range is 0.3 μm to 0.7 μm in consideration of the characteristics that the flexibility, the nap quality, the color development property at the time of dyeing are excellent, and the hue difference depending on the viewing angle is small.

The average single fiber diameter of the ultrafine fibers is obtained by taking a scanning electron microscope (SEM) photograph of a cross section of a sheet-like object, randomly selecting 100 circular or nearly circular elliptical fibers, measuring the fiber diameter, and averaging the fibers. It is calculated by calculating the value.

As the cross-sectional shape of the ultrafine fiber, for example, polygons such as round, elliptical, flat and triangular, fan, cross, Y, H, X, W, C, and π type can be used.

The ultrafine fibers constituting the fiber entanglement are in the form of ultrafine fiber bundles. By bundling the ultrafine fibers, physical strength such as tensile strength and tear strength of the sheet-like material can be improved, and wear resistance can also be exhibited. As the form of the ultrafine fiber bundle, the ultrafine fibers may be slightly separated from each other, or may be partially bonded or agglomerated in some cases. Examples of the polymer forming the ultrafine fibers used in the present invention include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polylactic acid, polyamides such as 6-nylon and 66-nylon, acrylic, polyethylene and polypropylene. , And a thermoplastic resin that can be melt-spun, such as thermoplastic cellulose. Among them, polyester fibers made of polyester-based polymers such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate are preferably used from the viewpoints of strength, dimensional stability, light resistance, and dyeability. In addition, at least two or more kinds selected from these polymers may be combined.

Further, from the viewpoint of environmental consideration, fibers obtained from recycled raw materials or plant-derived raw materials may be used. Further, the ultrafine fibers can be formed 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, flame retardants, and antistatic agents.

The ultrafine fibers constituting the sheet-like material of the present invention may be composite fibers in which two different types of polymers (A) and (B) are bonded side by side along the fiber length direction.

The combination of the polymer (A) and the polymer (B) can be appropriately selected from the above-mentioned polymers forming ultrafine fibers, but is preferably a combination of polyester-based polymers having an intrinsic viscosity difference, and is more preferable. Is a polybutylene terephthalate-based polymer in which at least one of the polymer (A) or the polymer (B) is. In particular, the ultrafine fibers obtained by spinning and stretching the polymer of such a combination so as to form a side-by-side type bonded structure along the fiber length direction have two components due to stress concentration on the high viscosity side during drawing. Different internal strains are generated between the fibers, and by heat-treating the fibers after forming the sheets, the high-viscosity side contracts significantly, strains occur in the single fibers, and coil-like crimps occur. Due to this crimping, the entanglement of the fibers in the napped layer portion on the surface of the sheet-like material becomes large, and stretchability is exhibited.

When the polymer (A) and the polymer (B) are polyester-based copolymers in the composite fibers bonded in a side-by-side type, the intrinsic viscosity difference is preferably 0.002 to 1.5. When the intrinsic viscosity difference is increased by 0.002 or more, fibers having excellent crimping characteristics can be obtained. On the other hand, when the intrinsic viscosity difference exceeds 1.5, the obtained fibers have good crimping characteristics, but the spun fibers are excessively bent toward the high viscosity component side, so that stable spinning is performed for a long time. Can't. Further, as the combination of the polymers, it is preferable that at least one of them is a polybutylene terephthalate-based polymer. Since the polybutylene terephthalate polymer is a polymer having high crystallinity, for example, when polyethylene terephthalate is used on the other side, a difference in crystallinity is generated between the two polymers, and crimping is likely to occur.

The intrinsic viscosity of the polyester polymer in the present invention is preferably 0.5 to 2.0 in the high viscosity component. By setting the intrinsic viscosity to 0.5 or more, it becomes possible to produce a fiber having sufficient strength and elongation. The upper limit of the intrinsic viscosity is preferably 2.0 or less from the viewpoints of ease of molding such as melt extrusion, manufacturing cost, and reduction of molecular weight due to molecular chain breakage caused by heat or shearing force during the process. On the other hand, the low viscosity component enables stable spinning by setting the intrinsic viscosity to 0.3 to 1.

The composite ratio of both components is preferably in the range of high viscosity component: low viscosity component = 75:25 to 35:65 (mass%), more preferably 65:35 to 45:55 (mass%). ). Within this range, the composite ratio can be appropriately set according to the stretchability of the obtained sheet-like material. For example, in order to obtain a sheet-like material having an excellent soft feeling, the composite ratio of the high-viscosity component is lowered. In order to obtain toughness, the composite ratio of high-viscosity components may be increased.

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

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

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 is the main component with respect to the total weight. It means that it is more than 50% by weight. The polyester-based polymer may contain other copolymerizing components capable of ester bonding. Examples of copolymerizable compounds include dicarboxylic acids such as isophthalic acid, succinic acid, cyclohexanedicarboxylic acid, adipic acid, dimaic acid, sebacic acid and 5-isophthalic acid, ethylene glycol, butanediol, neopentyl glycol and cyclohexanedi. Examples thereof include diols such as methanol, polyethylene glycol and polypropylene glycol. Further, if necessary, titanium dioxide as a matting agent, fine particles of silica or alumina as a lubricant, a hindered phenol derivative as an antioxidant, a coloring pigment and the like may be added.

The polybutylene terephthalate-based polymer in the present invention is mainly composed of a structure in which terephthalic acid or a derivative thereof is copolymerized with 1,4-butanediol or a derivative thereof.

The non-woven fabric constituting the sheet-like material of the present invention may be either a short-fiber non-woven fabric or a long-fiber non-woven fabric, but the short-fiber non-woven fabric is preferably used in terms of texture and quality.

The short fiber non-woven fabric used for the sheet-like material of the present invention is obtained by forming a laminated web of short fibers using a card and a cloth wrapper and then performing needle punching or water jet punching, or by a papermaking method. As the long-fiber non-woven fabric, those obtained by the spunbond method, the melt blow method, or the like can be appropriately adopted.

It is important that the short fibers in the short fiber non-woven fabric contain a fiber length of 8 to 90 mm. By setting the fiber length to 8 mm or more, a sheet-like material having excellent wear resistance can be obtained by entanglement. Further, by setting the fiber length to 90 mm or less, a sheet-like material having excellent compression characteristics and surface quality can be obtained. The fiber length is more preferably 25 to 90 mm.

Fibers having a fiber length of less than 8 mm are less likely to be entangled, and fibers fall off during the manufacturing process of the sheet-like material. Further, fibers longer than 90 mm have excellent entanglement, but when the napped portion is formed, the wear resistance is poor and the surface quality tends to be inferior.

The ratio of the fiber length of the ultrafine fibers to 8 to 90 mm is preferably 50% by mass or more of the total amount of the ultrafine fibers constituting the sheet-like material.

For the ratio of fiber lengths of 8 to 90 mm, first, the elastic polymer in the sheet-like material was extracted and removed to make only ultrafine fibers, and then 100 fibers were randomly extracted, the fiber length was measured, and the fiber length histogram was obtained. Is calculated by creating.

The non-woven fabric obtained as described above can be shrink-treated with warm water or steam in order to improve the denseness of the fibers. The temperature of the hot water or steam is preferably treated so that the temperature of the sheet-like material is less than 100 ° C. so that the crimping of the ultrafine fibers described later does not occur. However, if the temperature of the sheet-like material itself is kept below 100 ° C., it is permissible that the temperature of hot water or steam applied to shrink the sheet-like material is 100 ° C. or higher. Further, during this shrinkage treatment, when the shrinkage rate of the ultrafine fiber-expressing fibers constituting the non-woven fabric in boiling water is high, crimping occurs after the shrinkage treatment even when the shrinkage treatment temperature of the sheet-like material is less than 100 ° C. It may end up. Further, when the shrinkage rate of the fiber is low, the denseness of the sheet-like material does not increase, and an excellent surface feeling as a leather-like sheet-like material cannot be obtained. As a result, the shrinkage rate of the ultrafine fiber-expressing fibers constituting the non-woven fabric in boiling water is preferably 5 to 25%.

The sheet-like material of the present invention may include a reinforcing layer in the inner layer portion or the surface thereof for the purpose of improving the strength. As the reinforcing layer, a woven fabric, a knitted fabric, a non-woven fabric (including paper), a film-like material such as a plastic film or a metal thin film sheet, or the like can be adopted. In the case of a woven fabric or knitted fabric in which the reinforcing layer is made of fibers, the average single fiber diameter of the fibers is preferably about 0.1 to 20 μm from the viewpoint of the texture of the sheet-like material.

Examples of the types of fibrous yarns constituting the woven and knitted fabric used in the present invention include filament yarns, spun yarns, innovative spun yarns, and mixed composite yarns of filament yarns and spun yarns. Since a large number of fluffs are present on the surface of the spun yarn due to its structure, it is a drawback if the fluffs fall off and are exposed on the surface when the non-woven fabric and the woven fabric are entangled. Therefore, it is preferable to use filament yarn. Filament yarns are roughly classified into monofilaments composed of one single fiber and multifilaments composed of a plurality of fibers. In the woven and knitted fabric used in the present invention, it is preferable to use multifilaments. In the case of monofilament, the rigidity of the fiber becomes too high, which may impair the texture of the sheet-like material.

The total fineness of the fibrous threads constituting the woven or knitted fabric is preferably 50 to 150 dtex for reasons such as rigidity and basis weight.

The basis weight of the woven or knitted fabric ^{is preferably 20} to 200 g / m 2, and more preferably 30 to 150 g / m ² . If the basis weight ^{of the woven or knitted fabric is less than 20 g / m 2} , the form of the woven or knitted fabric becomes poor, and wrinkles occur when the woven or knitted fabric is inserted between the non-woven fabrics or when the woven or knitted fabric is laminated on the surface of the non-woven fabric. It becomes difficult to stack them uniformly. Further, when the basis weight of the woven or knitted fabric ^{exceeds 200 g / m 2} , the structure of the woven or knitted fabric becomes dense, and it tends to be difficult to entangle the non-woven fabric and the woven or knitted fabric.

As the basic structure of the woven fabric used in the present invention, twill or satin may be used, but a flat structure in which misalignment is unlikely to occur is preferably used.

The sheet-like material of the present invention has a napped layer on one side or both sides of the sheet-like material. Further, since the ultrafine fibers have coil-like crimps, a feeling of bulkiness can be given to the sheet-like material, and stretchability can also be exhibited.

It is important that the stretch rate of the sheet-like material of the present invention is 10% or more and the stretch recovery rate is 80% or more. When the stretch rate is 10% or more and the stretch recovery rate is 80% or more, a sheet-like material having excellent stretchability can be obtained.

The elongation rate is based on JIS L 1096 (2010) 8.16.1 B method (constant load method), and the elongation recovery rate is based on JIS L 1096 (2010) 8.16.2 B-1 method (constant load method). It was measured. The gripping interval was 10 cm, and the leaving time after removing the load was 1 hour.

The radius of coil-shaped crimping of the ultrafine fibers constituting the napped layer is preferably an arc shape of 5 to 100 μm, more preferably 90 μm or less, still more preferably 85 μm or less. When the radius is larger than 100 μm, the crimping becomes weak and it is difficult to obtain stretchability. On the other hand, from the viewpoint of surface quality, it is preferably 7 μm or more, more preferably 20 μm or more. When the radius is smaller than 5 μm, the crimp becomes stronger and the surface quality deteriorates. By crimping the ultrafine fibers in a coil shape, the coverage of the ultrafine fibers on the surface of the sheet-like material is higher than when there is no crimping, and the non-woven fabric itself under the fluff is not visible and only the fluff appears. , It has a precise and elegant appearance. Further, as the internal structure of the sheet-like material, the coil-shaped ultrafine fibers are entangled with each other to form a stretch margin with respect to tension, and stretchability is exhibited.

The sheet-like material of the present invention preferably contains 5 to 60% by mass of a porous elastic polymer with respect to the mass of the ultrafine fibers of the fiber entangled product. By containing 5% by mass or more of the elastic polymer with respect to the mass of the ultrafine fibers, it is possible to impart appropriate compression characteristics to the sheet-like material. When the mass of the elastic polymer is more than 60% by mass, the fiber opening property in the fluffing step is poor, and the suppleness of the sheet-like material may be lowered. Further, when the sheet-like material is dyed and used, it may be preferable that the amount of the elastic polymer is small because the color tone of the dyed fiber entangled fiber and the elastic polymer is different. From the viewpoint of environmental consideration, it is not preferable to contain a large amount of elastic polymer because the amount of organic substances used in the manufacturing process increases, and the smaller the amount of elastic polymer, the more fibers obtained from recycled raw materials and plant-derived raw materials. When used, it is easy to recycle and collect and dispose of. A more preferable range of the mass of the elastic polymer is 15 to 55% by mass.

The above-mentioned elastic polymers include pigments such as carbon black, dyes, antifungal agents and antioxidants, ultraviolet absorbers, and lightfasteners such as light stabilizers, flame retardants, penetrants and lubricants, and silica, if necessary. Anti-blocking agents such as titanium oxide, water repellents, viscosity modifiers, surfactants such as antistatic agents, defoamers such as silicone, fillers such as cellulose, and coagulation modifiers, silica, titanium oxide, etc. Inorganic particles and the like can be contained.

It is important that the elastic polymer in the present invention is porous. By making the fibers porous, the gripping force of the fibers by the elastic polymer can be reduced, and the stretchability due to the crimping of the fibers can be exhibited.

Examples of the elastic polymer used in the present invention include polyurethane elastomers, polyureas, polyacrylic acids, ethylene / vinyl acetate elastomers and acrylonitrile / butadiene elastomers and styrene / butadiene elastomers, polyvinyl alcohols, polyethylene glycols and the like, and have durability. From the viewpoint of compression characteristics, a polyurethane elastomer is preferably used. The polymer elastic body can contain a plurality of polymer elastic bodies.

Examples of the polyurethane-based elastomer particularly preferably used in the present invention include polyurethane and polyurethane / polyurea elastomers.

As the polyurethane-based elastomer used in the present invention, a solvent-based polyurethane-based elastomer can be used.

As the polyurethane-based elastomer used in the present invention, a polyurethane-based elastomer obtained by reacting a polymer diol, an organic diisocyanate, and a chain extender is preferably used.

As the above polymer diol, for example, a polycarbonate-based diol, a polyester-based diol, a polyether-based diol, a silicone-based diol, and a fluorine-based diol can be adopted, and a copolymer in which these are combined can also be used. Above all, from the viewpoint of hydrolysis resistance, it is preferable to use a polycarbonate-based diol and a polyether-based diol.

The above-mentioned polycarbonate-based diol can be produced by a transesterification reaction of an alkylene glycol and a carbonic acid ester, a reaction of a phosgene or a chloraterate with an alkylene glycol, or the like.

Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol. Linear alkylene glycols and branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and 2-methyl-1,8-octanediol. , Alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, pentaerythritol and the like. In the present invention, either a polycarbonate-based diol obtained from each of the alkylene glycols alone or a copolymerized polycarbonate-based diol obtained from two or more types of alkylene glycols can be adopted.

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

Examples of low molecular weight polyols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,2-dimethyl-1,3-propane. Diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, and One or more selected from cyclohexane-1,4-dimethanol can be used.

Further, an adduct in which various alkylene oxides are added to bisphenol A can also be used.

Examples of polybasic acids include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydro. One or more selected from isophthalic acid can be mentioned.

Examples of the polyether diol used in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and a copolymer diol in which they are combined.

The number average molecular weight of the polymer diol is preferably in the range of 500 to 4000 when the molecular weight of the polyurethane-based elatomer 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-like material from becoming hard. Further, by setting the number average molecular weight to 4000 or less, more preferably 3000 or less, the strength as a polyurethane-based elastomer can be maintained.

Examples of the organic diisocyanate used in the present invention include aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and aromatic diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. However, these can also be used in combination.

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

The polyurethane used in the present invention can be used in combination with a cross-linking agent for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like. The cross-linking agent may be an external cross-linking agent added as a third component to the polyurethane-based elastomer, or an internal cross-linking agent that introduces a reaction point having a cross-linked structure in advance in the polyurethane molecular structure can also be used. It is preferable to use an internal cross-linking agent from the viewpoint that cross-linking points can be formed more uniformly in the polyurethane molecular structure and the decrease in flexibility can be reduced.

As the cross-linking agent, a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group and the like can be used.

The apparent density of the sheet of this invention is preferably 0.10~0.80g / cm ^3, more preferably 0.20~0.70g / cm ^3. When the apparent density is 0.10 g / cm ³ or more, the fineness and mechanical properties of the sheet-like material are good, and when it is 0.80 g / cm ³ or less, it is possible to avoid the texture becoming hard.

The thickness of the sheet-like material is preferably 0.1 to 7 mm. By setting the thickness to 0.1 mm or more, preferably 0.3 mm or more, the sheet-like material is excellent in morphological stability and dimensional stability. On the other hand, by setting the thickness to 7 mm or less, more preferably 5 mm or less, the moldability of the sheet-like product is excellent.

The sheet-like material of the present invention has a small hue difference depending on the viewing angle, that is, L *, a *, and b * are measured from three directions with respect to the surface of the sheet, and the hue difference ΔE * is measured between the points. The ab is obtained, and the average value thereof is in the range of 0.2 to 1.5. Generally, when ΔE * ab exceeds 1.5, the hue is perceptibly different. Therefore, the hue difference is preferably 1.5 or less. On the other hand, when the hue difference is 0.2 or less, there is little change in facial expression and the feeling of luxury is poor. Therefore, by setting the hue difference when the leather-like sheet-like object is viewed from three directions in the range of 0.2 to 1.5, the hue difference depending on the viewing angle is small while having a high-class feeling and a changing expression. That is, even when molded into a three-dimensional shape such as an automobile seat or sofa, the reflection of the part exposed to light can be suppressed, the feeling of patching is small, blurring is unlikely to occur, and the surface of the sheet-like object is touched by hand. Even when sitting down, a sheet-like object whose traces are hard to see can be obtained.

The sheet-like material of the present invention contains, for example, functional agents such as dyes, pigments, fabric softeners, texture modifiers, anti-pilling agents, antibacterial agents, deodorants, water repellents, lightfasteners, and weatherproofing agents. You may.

Next, a method for producing the sheet-like material of the present invention will be described.

As a means for obtaining the ultrafine fibers constituting the non-woven fabric used for the sheet-like material of the present invention, it is important that the ultrafine fibers are phenotypic fibers. By entwining the ultrafine fiber-expressing fibers in advance to form a non-woven fabric and then performing ultrafineness of the fibers, a non-woven fabric formed by entwining bundles of ultrafine fibers can be obtained.

As the ultrafine fiber expression type fiber, the thermoplastic polymer component having different solubility in a solvent or the like is used as a sea component and an island component, and the island component is dissolved and removed by using a solvent or the like in a subsequent step to remove the island component. It is possible to adopt a sea-island type composite fiber or a peeling split type fiber that peels and splits by physical force such as a water jet or swelling of a solvent, but preferably, the ultrafine fiber diameter can be uniformly controlled and a sheet-like material can be used. It is a sea-island type composite fiber that can make the surface appearance of the solvent graceful. The sea-island type composite fiber can provide an appropriate void between the island components, that is, between the ultrafine fibers inside the fiber bundle by removing the sea component, and the fiber diameter is particularly small from the composite fiber per fiber. It is preferably used because the fibers can be efficiently expressed and the sheet-like material can be imparted with a soft texture and bulkiness.

For the sea-island type composite fiber, a polymer mutual arrangement method in which two components of the sea component and the island component are mutually arranged and spun using a sea-island type composite base, and a mixture of the two components of the sea component and the island component are mixed. A mixed spinning method for spinning or the like can be used, but a sea-island type composite fiber based on the polymer array method is more preferably used in that ultrafine fibers having a uniform fineness can be obtained.

Further, in the present invention, it is preferable that the ultrafine fiber-expressing type fiber is a sea-island type composite fiber and the island component is a side-by-side type, but an eccentric core-sheath type may also be used. In the island component, two different types of polymers (A) and polymer (B) are bonded to a side-by-side type or an eccentric core-sheath type along the fiber length direction to form a latent crimp-type island component fiber. can get.

Further, the mass ratio of the sea component and the island component in the sea-island type composite fiber used in the present invention is preferably in the range of sea component: island component = 5:95 to 80:20. If the mass ratio of the sea component is less than 5% by mass, the ultrafineness of the island component becomes insufficient. Further, 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 more preferably in the range of sea component: island component = 10:90 to 60:40.

In the present invention, when an ultrafine fiber-expressing fiber represented by a sea-island type composite fiber is drawn, the undrawn yarn is once wound and then separately drawn, or the undrawn yarn is taken up and continuously drawn as it is. Either method can be adopted. Stretching can be appropriately performed by a method of stretching in 1 to 3 steps by moist heat, dry heat, or both. Next, the stretched sea-island type composite fiber is preferably crimped and cut to a predetermined length to obtain a non-woven raw cotton. Ordinary methods can be used for crimping and cutting.

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

The fiber ultrafine treatment (desealing treatment) of the sea-island type fiber can be performed by immersing the sea-island type fiber in a solvent and squeezing the liquid. As the solvent for dissolving the sea component, when the sea component is polyethylene, polypropylene or polystyrene, an organic solvent such as toluene or trichlorethylene is used. When the sea component is copolymerized polyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide or hot water is used.

For the fiber ultrafine processing, an apparatus such as a continuous dyeing machine, a vibro washer type dewatering machine, a liquid flow dyeing machine, a Wins dyeing machine and a Jigger dyeing machine can be used.

The dissolution and removal of the sea component can be carried out at any timing before, after the impregnation of the elastic polymer, and after the raising treatment. If the desealing treatment is performed before the elastic polymer is applied, the elastic polymer is in direct contact with the ultrafine fibers and the ultrafine fibers can be strongly gripped, so that the abrasion resistance of the sheet-like material becomes better. On the other hand, when the desea treatment is performed after the elastic polymer is applied, voids due to the desea component are generated between the elastic polymer and the ultrafine fibers, so that the elastic polymer does not directly grip the ultrafine fibers. In addition, the compression characteristics of the sheet-like material are improved.

In the present invention, the number of fibers in the ultrafine fiber bundle is preferably 10 to 9000 fibers / bundle, more preferably 10 to 4000 fibers / bundle. When the number of fibers is less than 10 fibers / bundle, the fineness of the ultrafine fibers is poor, and the mechanical properties such as wear tend to decrease. Further, when the number of fibers is more than 9000 fibers / bundle, the fiber opening property at the time of nap is lowered, and the fiber distribution on the nap surface tends to be uneven.

From the viewpoint of fiber density, the degree of fiber density in the ultrafine fiber bundle is preferably 30 to 1000, more preferably 50 to 700. The degree of fiber density is calculated by (the number of fibers in the ultrafine fiber bundle) × (single fiber diameter), and is an index of the size of the ultrafine fiber bundle. By setting the degree of fiber density in the ultrafine fiber bundle to 30 to 1000 in this way, the processing operability at the time of forming the fiber entangled body is good, and the fineness of the fiber bundle is improved.

As a method for obtaining the fiber entanglement used in the present invention, a method of entwining the fiber web with a needle punch or a water jet punch, a spunbond method, a melt blow method, a papermaking method and the like can be adopted. Above all, a method that undergoes treatment such as needle punching or water jet punching is preferably used in order to achieve the above-mentioned aspect of the ultrafine fiber bundle.

The apparent density of the fiber entangled body composed of the ultrafine fiber-generating 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 fiber entangled body having excellent morphological stability and dimensional stability can be obtained. 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 the elastic polymer can be maintained between the fibers.

From the viewpoint of densification, it is preferable that the fiber entangled body composed of the ultrafine fiber-generating fibers thus obtained is heat-shrinked by dry heat, moist heat, or both to further increase the density. Is. Further, the fiber entanglement can be compressed in the thickness direction by a calendar process or the like.

Further, in order to obtain the denseness and uniformity of the fiber distribution on the surface of the sheet-like material, the elastic polymer is used for the fiber entanglement such as the non-woven fabric in which the fiber bundles of the ultrafine fibers are entangled, and the inside of the fiber bundles of the ultrafine fibers. It is a preferred embodiment that it is substantially absent from. If the elastic polymer exists even inside the fiber bundle, the elastic polymer adheres to each of the ultrafine fibers and exists, so that the fiber opening property at the time of buffing treatment becomes poor.

As a method for obtaining a form in which the polymer elastic body is substantially not present inside the fiber bundle of the ultrafine fibers, for example, an elastic polymer is used as a solution.
(1) After impregnating a fiber entangled body composed of ultrafine fiber-generating type sea-island type fibers with the above-mentioned elastic polymer solution and coagulating it, the sea component of the sea-island type fibers is mixed with a solvent in which the elastic polymer does not dissolve. How to dissolve and remove
(2) Polyvinyl alcohol having a saponification degree of preferably 80% or more is added to a fiber entanglement composed of ultrafine fiber-generating type sea-island type fibers to protect most of the periphery of the fibers, and then the sea-island type fibers are formed. A method of dissolving and removing the sea component with a solvent that does not dissolve polyvinyl alcohol, then impregnating and coagulating the above-mentioned elastic polymer solution, and then removing polyvinyl alcohol, or the like can be preferably used.

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

When the fiber entangled body is impregnated with the polyurethane-based elastomer solution and solidified, it is important that the polyurethane-based elastomer is an organic solvent-based polyurethane elastomer.

The organic solvent-based polyurethane can be coagulated by dry heat coagulation, wet coagulation, or a combination thereof, and among them, wet coagulation in which the polyurethane is immersed in water to coagulate is preferably used. By wet coagulation, polyurethane does not concentrate at the entanglement points of the ultrafine fibers, and the polyurethane itself becomes porous, so that the degree of freedom between the ultrafine fibers increases and structurally imparts stretchability to the sheet-like material. be able to. On the other hand, when the polyurethane-based elastomer is a water-dispersible polyurethane, there is dry heat coagulation as a coagulation method, but the polyurethane concentrates at the entanglement point of the ultrafine fibers and strongly grips the ultrafine fibers, and the polyurethane itself has a non-porous structure. Therefore, the ultrafine fibers do not have a degree of freedom and stretchability cannot be exhibited.

The temperature of wet solidification is not particularly limited.

After applying the elastic polymer to the fiber entangled body, it is preferable to divide the obtained elastic polymer-imparted sheet-like material into halves or several sheets in the sheet thickness direction because of excellent production efficiency.

It is important that the sheet-like material of the present invention has naps on at least one surface of the sheet-like material.

The raising treatment for forming fluff of ultrafine fibers on the surface of the sheet-like material of the present invention can be performed by a method of grinding using sandpaper, a roll sander, or the like. Prior to the brushing treatment, a lubricant such as a silicone emulsion may be applied to the sheet.

Further, it is a preferable mode to apply an antistatic agent before the above-mentioned raising treatment because the grinding powder generated from the sheet-like material by grinding tends to be difficult to be deposited on the sandpaper.

The sheet-like material may be obtained by halving or dividing into several sheets in the thickness direction of the sheet-like material before the raising treatment is performed.

The sheet-like material can be dyed depending on the intended use. As a method for dyeing the sheet-like material, it is preferable to use a liquid flow dyeing machine because the sheet-like material can be dyed and at the same time a kneading effect can be given to soften the sheet-like material. If the dyeing temperature of the sheet-like material is too high, the polymer elastic body may deteriorate, and if it is too low, the dyeing to the fibers becomes insufficient. Therefore, it is preferable to set the dyeing temperature according to the type of fiber. The dyeing temperature is generally preferably 80 to 150 ° C, more preferably 110 to 130 ° C. The heat treatment and kneading in the dyeing step facilitate the development of crimping of ultrafine fibers.

As the manufacturing process for developing the crimping of the ultrafine fibers, it is preferable to carry out in the following order (1) to (3).
(1) A step of expressing ultrafine fibers from a non-woven fabric made of ultrafine fiber-expressing fibers.
(2) A process of raising a non-woven fabric made of ultrafine fibers,
(3) A step of causing the ultrafine fibers of the napped layer to develop crimp by heat-treating the non-woven fabric after the raising treatment at a temperature of 110 ° C. or higher and 150 ° C. or lower.

For example, if the non-woven fabric is heat-treated at a temperature of 100 ° C. or higher before the step of expressing the fine fibers from the non-woven fabric made of the fine fiber-expressing fibers, crimping occurs after the sea component is dissolved, and the raising treatment is performed in the subsequent step. When processed, the crimps are stretched, making it difficult to obtain the fluffy surface that is the object of the present invention.

Further, in the method for producing a leather-like sheet-like material of the present invention, the crimping of the ultrafine fibers in the napped layer is performed by subjecting the non-woven fabric made of the ultrafine fibers to a brushed treatment at a temperature of 110 ° C. or higher and 150 ° C. or lower. Achieved. By crimping the ultrafine fibers of the nap layer, an anisotropic fluff surface can be obtained, and a sheet-like material having little difference in hue depending on the viewing angle can be obtained.

The dye can be selected according to the type of fiber constituting the sheet-like material. For example, if it is a polyester fiber, a disperse dye can be used, if it is a polyamide fiber, an acid dye or a gold-containing dye can be used, and a combination thereof can be used.

It is also a preferred embodiment to use a dyeing aid when dyeing the sheet-like material. By using a dyeing aid, the uniformity and reproducibility of dyeing can be improved. In addition, a finishing agent treatment using a softener such as silicone, an antistatic agent, a water repellent agent, a flame retardant, a light resistant agent, an antibacterial agent, or the like can be applied in the same bath or after dyeing.

Since the sheet-like material of the present invention has both a graceful and precise appearance and stretchability (stretchability), furniture, chairs and wall materials, and seats, ceilings and interiors in vehicle interiors such as automobiles, trains and aircraft. Interior materials, shirts, jackets, casual shoes, sports shoes, men's shoes, women's shoes, and other shoes that have a very elegant appearance as skin materials such as uppers, trims, bags, belts, wallets, etc., and one of them. It can be suitably used as an industrial material such as a clothing material used for a part and a wiping cloth. Further, in the sheet-like material of the present invention, since a large number of gaps of several nm to 500 nm are formed between the single fibers or in the entangled portion of the fibers, the sheet-like material may exhibit specific properties like a porous material, and the filter It can also be used for such purposes.

The sheet-like material of the present invention can also be used for silver-coated artificial leather by forming a coating layer on its surface. As a method for forming the coating layer and the undercoat layer for making the artificial leather with silver, there are a dry surface forming method, a direct coating method and the like, and various conventionally known methods can be adopted and are particularly limited. is not it. For example, a method using a device such as a reverse roll coater, a spray coater, a roll coater, a gravure coater, a kiss roll coater, a knife coater, and a comma coater can be mentioned. The thickness of each layer can be appropriately set according to the application. The preferred thickness is 10 to 1000 μm, more preferably 50 to 800 μm.

Polyurethane is the most suitable resin used for the coating layer. Other resins may be appropriately mixed and used with the resin. In recent years, durability is required in many applications, so it is preferable to use polyurethane having excellent durability such as polycarbonate. From the viewpoint of abrasion resistance, silicone-modified polyurethane is preferably used. For the same reason, it is also possible to use a polyurethane resin containing a silicone oil or a solid silicone-based compound.

Next, the sheet-like material of the present invention and the method for producing the same will be described in more detail with reference to Examples. Next, the evaluation method used in the examples and the measurement conditions thereof will be described.

(1) Intrinsic viscosity IV
Dissolve 0.8 g of the sample polymer in 10 mL of orthochlorophenol (hereinafter abbreviated as OCP), determine the relative viscosity (ηr) using an Ostwald viscometer at a temperature of 25 ° C., and determine the relative viscosity (ηr) by the following formula to obtain the intrinsic viscosity (IV). Was calculated.
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: falling time of the solution (seconds)
d: Solution density (g / cm ³ )
t0: OCP fall time (seconds)
d0: OCP density (g / cm ³ ).

(2) Average single fiber diameter A cross section of a sheet-like material cut in the thickness direction is used as an observation surface and observed with a scanning electron microscope (SEM. VE-7800 type manufactured by Keyence Co., Ltd.). The fiber diameter was measured and the average value was calculated.

(3) Curly radius Using a scanning electron microscope (SEM, VE-7800 type manufactured by KEYENCE CORPORATION), the surface of the sheet-like material is photographed (magnification 100 times), and the radius of the crimped arc-shaped fiber is measured. did. The n number was 20, and the average value was calculated. When the arc shape is a part of a circle, if the circumference of the arc shape does not exceed 1/2 of the entire circle, the fiber is excluded from the measurement target as it does not correspond to a crimped fiber. And said.

(4) Metsuke of sheet-like material Measured by the method described in JIS L 1096 (1999) 8.4.2.
Five 20 cm × 20 cm test pieces were collected, the mass (g) of each was measured, and the average value was expressed as ^{the mass per 1 m 2} (g / m ^2).

(5) Thickness of sheet-like material Using a thickness meter with a scale 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 was calculated.

(6) Stretchability The stretching rate and the stretching recovery rate were used. In each direction of the sheet, if both the elongation rate and the elongation recovery rate exceed the target value, the evaluation is evaluated as "○" and passed, and if either or both do not exceed the target value, it is evaluated as "×" and rejected. And said.
-Elongation rate JIS L 1096 (2010) 8.16.1 The elongation rate of the sheet-like material was measured by the B method (constant load method).
A good level (target value) in the present invention is an elongation rate of 10% or more.
-Elongation recovery rate The elongation recovery rate of the sheet-like material was measured by the JIS L 1096 (2010) 8.16.2 B-1 method (constant load method). The gripping interval was 10 cm, and the leaving time after removing the load was 1 hour.
A good level (target value) in the present invention is an elongation recovery rate of 80% or more.

(7) Color difference of leather-like sheet-like material:
Using a color difference meter (CR-410 manufactured by Konica Minolta), as shown in FIG. 2, the surface of the leather-like sheet 1 is 2, the vertical direction is 3, the horizontal direction is 4, the thickness direction is 5, and so on. When the fluffy forward direction is 6, the viewpoint is viewed from an oblique 45 ° upward of the fluffy forward direction 6 of the leather-like sheet-like object 1 in the vertical direction 3 with respect to the measurement target point on the surface 2 of the leather-like sheet-like object 1. Assuming that the viewpoint 2 is the viewpoint from the upward diagonal 45 ° in the opposite direction of the fluff in the vertical direction 3 and the viewpoint from any one upward diagonal 45 ° in the horizontal direction 4 is the viewpoint 3, each viewpoint is L. *, A *, and b * were measured. At the time of measurement, a cylindrical frame cut diagonally at 45 ° was created so that the light of the device did not leak, and the measurement was performed by fitting it on 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 . From the measured L *, a *, and b *, the color difference ΔE * ab between each point was calculated. ΔE * ab is calculated by the following formula.
・ ΔE * ab = (ΔL * ^ 2 + Δa * ^ 2 + Δb * ^ 2) ^1/2
(In the formula, ΔL * represents the difference in L * value between two points, Δa * represents the difference in a * value between two points, and Δb * represents the difference in b * value between two points. )
[Example 1]
(raw cotton)
Polybutylene terephthalate having an intrinsic viscosity (IV) of 1.75 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 are separately melted and used as island components, and are used as sea components according to JIS K7206 (1999). Using polystyrene (PSt) with a measured Vicat softening point of 100 ° C. and a melt flow rate (hereinafter referred to as MFR) of 120, and using a sea-island type composite base with 24 islands, an island / sea mass ratio of 80 The fibers melt-spun at / 20 were drawn by a roller plate method under normal conditions and crimped, and then the fibers were cut to a length of 51 mm to obtain raw cotton of sea-island type composite fiber having an average single fiber diameter of 26 μm.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 312 g / m ^{2 and a thickness of 1.70 mm was obtained.}

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 30% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 37 mass% with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.70 mm and an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 25 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 2]
(raw cotton)
Sea islands in the same manner as in Example 1 except that polyethylene terephthalate having an intrinsic viscosity (IV) of 0.78 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 were separately melted and used as island components. Raw cotton of mold composite fiber was obtained.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 335 g / m ^{2 and a thickness of 1.85 mm was obtained.}

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 35% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine hollow fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 37 mass% with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.70 mm and an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 30 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 3]
(raw cotton)
Sea islands in the same manner as in Example 1 except that polyethylene terephthalate having an intrinsic viscosity (IV) of 0.655 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.651 were separately melted and used as island components. Raw cotton of mold composite fiber was obtained.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 350 g / m ^{2 and a thickness of 1.90 mm was obtained.}

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 35% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine hollow fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 37 mass% with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.82 mm and an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 55 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 4]
(raw cotton)
Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.780 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.654 are separately melted and used as island components, and measured according to JIS K7206 (1999) as a sea component. Using polystyrene (PSt) with a Vicat softening point of 100 ° C. and an MFR of 120, and a sea-island type composite base with 24 islands, the fibers were melt-spun at an island / sea mass ratio of 80/20. After stretching under normal conditions by a roller plate method and crimping, the fibers were cut to a length of 51 mm to obtain raw cotton of a sea-island type composite fiber having an average single fiber diameter of 52 μm.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 340 g / m ^{2 and a thickness of 1.85 mm was obtained.}

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 34% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine hollow fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 35% by mass with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.82 mm and an average single fiber diameter of 8.8 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 45 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 5]
(raw cotton)
Polybutylene terephthalate having an intrinsic viscosity (IV) of 1.75 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 are separately melted and used as island components, and 8 mol of sodium 5-sulfoisophthalate is used as a sea component. Using a% copolymerized polyethylene terephthalate and a sea-island type composite base having 24 islands, fibers melt-spun at an island / sea mass ratio of 80/20 are drawn by a roller plate method under normal conditions. After the crimping process, the fibers were cut to a length of 51 mm to obtain raw cotton of a sea-island type composite fiber having an average single fiber diameter of 16 μm.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 310 g / m ^{2 and a thickness of 1.70 mm was obtained.}

(Sheet)
After shrinking the above non-woven fabric with hot water at a temperature of 96 ° C., the non-woven fabric is immersed in an aqueous solution of sodium hydroxide 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. , A sheet-like material composed of ultrafine fibers and polyurethane was obtained. Next, it was dried with hot air at a temperature of 120 ° C. for 10 minutes, immersed in a DMF solution of polycarbonate-based polyurethane having a solid content concentration adjusted to 12%, and then the polyurethane was solidified in an aqueous solution having a DMF concentration of 30% to solidify the polyurethane at 110 ° C. By drying with hot air at the same temperature for 10 minutes, a sheet-like product having a polyurethane mass of 37 mass% with respect to the mass of the ultrafine fibers composed of island components was obtained.
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface. The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.70 mm and an average single fiber diameter of 2.8 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 30 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 6]
(Spinning, cloth making)
Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.780 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.654 are separately melted and used as island components, and measured according to JIS K7206 (1999) as a sea component. Using polystyrene (PSt) with an MFR of 120 and a Viscosity softening point of 100 ° C., and using a sea-island type composite base with 24 islands, discharge from the base so that the island / sea mass ratio is 80/20. did. The ejector pressure was adjusted so that the spinning speed was 4000 m / min, and sea-island type composite long fibers having an average single fiber diameter of 14 μm were collected with a net to obtain a long fiber non-woven fabric sheet of ^{30 g / m 2.}

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this sea-island type composite fiber long fiber non-woven fabric sheet, a laminated fiber web is formed through a cross wrapper process ^{, needle punches are performed with a punch number of 600 lines / cm 2} , and then needles are punched with a punch number of 3000 lines / cm ^2. Punching was performed to obtain a sheet-like material having a grain size of 300 g / m ^{2 and a thickness of 1.80 mm.}

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 30% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 38% by mass with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.80 mm and an average single fiber diameter of 2 μm, and as a result of observing the napped layer portion, it was confirmed that crimps were exhibited in the ultrafine fibers constituting the napped layer. The average radius of crimp was 70 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 7]
(Spinning, cloth making)
Of the island components, 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 are separately melted and used, and JIS as a sea component. Using polystyrene (PSt) with a Viscosity softening point of 100 ° C. and an MFR of 120 measured according to K7206 (1999), and using a sea-island type composite mouthpiece with 24 islands and an eccentric core sheath type island component. Then, the mixture was discharged from the mouthpiece so that the island / sea mass ratio was 80/20. The ejector pressure was adjusted so that the spinning speed was 4000 m / min, and sea-island type composite long fibers having an average single fiber diameter of 25 μm were collected with a net to obtain a long fiber non-woven fabric sheet of ^{30 g / m 2.}

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this sea-island type composite fiber long fiber non-woven fabric sheet, a laminated fiber web is formed through a cross wrapper process ^{, needle punches are performed with a punch number of 600 lines / cm 2} , and then needles are punched with a punch number of 3000 lines / cm ^2. Punching was performed to obtain a sheet-like material having a grain size of 300 g / m ^{2 and a thickness of 1.80 mm.}

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 30% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet having a polyurethane mass of 40% by mass with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.80 mm and an average single fiber diameter of 3.6 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 80 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 8]
(raw cotton)
Polybutylene terephthalate having an intrinsic viscosity (IV) of 1.75 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 are separately melted and used as island components, and are used as sea components according to JIS K7206 (1999). Fibers melt-spun at an island / sea mass ratio of 80/20 using polystyrene (PSt) with a measured Vicat softening point of 100 ° C. and an MFR of 120 and a sea-island type composite base with 24 islands. After stretching under normal conditions by a roller plate method and crimping, the fibers were cut to a length of 10 mm to obtain raw cotton of a sea-island type composite fiber having an average single fiber diameter of 26 μm.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this sea-island type composite fiber raw cotton, a laminated fiber web is formed through a card and cross wrapper process, needle punching is performed with a punching number of 600 / cm2, and then needle punching is performed with a punching number of 3000 / cm2. A sheet-like material having a basis weight of 162 g / m2 and a thickness of 0.87 mm was obtained.

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 30% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 37 mass% with respect to the mass of the ultrafine fibers composed of island components. ..

After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.72 mm and an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 20 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 9]
(raw cotton)
Polybutylene terephthalate having an intrinsic viscosity (IV) of 1.75 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 are separately melted and used as island components, and are used as sea components according to JIS K7206 (1999). Fibers melt-spun at an island / sea mass ratio of 80/20 using polystyrene (PSt) with a measured Vicat softening point of 100 ° C. and an MFR of 120 and a sea-island type composite base with 24 islands. After stretching under normal conditions by a roller plate method and crimping, the fibers were cut to a length of 80 mm to obtain raw cotton of a sea-island type composite fiber having an average single fiber diameter of 26 μm.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this sea-island type composite fiber raw cotton, a laminated fiber web is formed through a card and cross wrapper process, needle punching is performed with a punching number of 600 / cm2, and then needle punching is performed with a punching number of 3000 / cm2. A sheet-like material having a basis weight of 172 g / m2 and a thickness of 0.94 mm was obtained.

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 35% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine hollow fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 37 mass% with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.73 mm and an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 30 μm. Moreover, it was confirmed that the polyurethane was porous by SEM observation (500 times) of the cross section. The stretchability of the sheet-like material was good. The results are shown in Table 1.

[Example 10]
Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.78 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.48 are separately melted and used as island components, and polystyrene is used as a sea component, and the number of islands is 24. Fibers melt-spun at an island / sea mass ratio of 80/20 are stretched 3.2 times under normal conditions by a roller plate method using the sea-island type composite base, and after crimper treatment, the fibers have a length of 51 mm. The raw cotton was cut into pieces to obtain raw cotton having an average single fiber diameter of 4.4 μm and a boiling water shrinkage rate of 14.5%.

Using the raw cotton of the sea-island type composite fiber thus obtained, a laminated fiber web is formed through a card and cross wrapper process, and after needle punching with a punching number of ^{600 fibers / cm 2, 3000 fibers /} Needle punching was performed with the number of punches of cm ^{2 to obtain a sheet-like material.}

The sheet-like product thus obtained is shrunk with hot water at a temperature of 96 ° C., impregnated with a PVA (polyvinyl alcohol) aqueous solution having a concentration of 12%, and dried with hot air at a temperature of 95 ° C. for 15 minutes. A sheet-like material having a PVA mass of 20% by mass with respect to the mass of the fiber sheet-like material substrate was obtained. This sheet-like material was immersed in trichlorethylene to dissolve and remove the sea component, and a desea sheet formed by entwining ultrafine fibers and a woven fabric was obtained. The desea sheet thus obtained was immersed in a DMF (dimethylformamide) solution of polyurethane having a solid content concentration adjusted to 12%, and then the polyurethane was solidified in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF are removed with hot water and dried with hot air at a temperature of 95 ° C. for 15 minutes with respect to the mass of the sheet-like material composed of the above-mentioned ultrafine fibers composed of island components having a single fiber fineness of 0.21 dtex. A leather base sheet having a polyurethane mass of 28% by mass was obtained.

The leather base material sheet thus obtained was cut in half perpendicular to the thickness direction, and the half-cut surface was ground with sandpaper count 180 endless sandpaper to form a fluffy surface. The leather base sheet thus obtained was put into a liquid flow dyeing machine, dyed in beige and crimped at the same time under the condition of a temperature of 120 ° C., and then dried in a dryer to make leather. A sheet-like material was obtained.

Regarding the leather-like sheet-like material thus obtained, it was confirmed that the thickness of the fluff layer was 150 μm, the fluff on the surface was coiled and crimped, and the direction of the fluff was random. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-mentioned measuring method, ΔE * ab between each point was obtained, and the average of ΔE * ab of the three points was obtained. The value was 0.72, and there was no difference in hue depending on the viewing angle. In addition, the expression was rich and luxurious, and there was no patchy or blurred feeling when molded into a sheet. The results are shown in Table 2.

[Example 11]
In Example 1 above, the average single fiber diameter was 2.1 μm after processing under the same conditions as in Example 1 except that the number of islands was 36 and the island / sea mass ratio was changed to 60/40. A leather-like sheet was obtained.

Regarding the leather-like sheet-like material thus obtained, it was confirmed that the thickness of the fluff layer was 180 μm, the fluff on the surface was coiled and crimped, and the direction of the fluff was random. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-mentioned measuring method, ΔE * ab between each point was obtained, and the average of ΔE * ab of the three points was obtained. The value was 1.20, and there was no difference in hue depending on the viewing angle. In addition, the expression was rich and luxurious, and there was no patchy or blurred feeling when molded into a sheet. The results are shown in Table 2.

[Example 12]
In Example 1 above, polybutylene terephthalate having an intrinsic viscosity (IV) of 1.21 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.48 are used as island components, the draw ratio is 3.7 times, and boiling water shrinkage. A leather-like sheet-like material was obtained by processing under the same conditions as in Example 1 except that raw cotton having a ratio of 21.5% was obtained.

Regarding the leather-like sheet-like material thus obtained, it was confirmed that the thickness of the fluff layer was 150 μm, the fluff on the surface was coiled and crimped, and the direction of the fluff was random. With respect to the surface of the obtained leather-like sheet-like material, L *, a *, and b * were measured from three directions by the above-mentioned measuring method, ΔE * ab between each point was obtained, and ΔE * ab between the three points was obtained. The average value of E * ab was 0.46, and there was no difference in hue depending on the viewing angle. In addition, the expression was rich and luxurious, and there was no patchy or blurred feeling when molded 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 (PSt) having a Vicat softening point of 100 ° C. and an MFR of 120 as a sea component measured according to JIS K7206 (1999) are used. Using a sea-island type composite mouthpiece with 24 islands, fibers melt-spun at an island / sea mass ratio of 80/20 are stretched under normal conditions by a roller plate method, and after crimping, the fibers are reduced to a length of 51 mm. It was cut to obtain raw cotton of sea-island type composite fiber having an average single fiber diameter of 26 μm.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 560 g / m ^{2 and a thickness of 3.15 mm was obtained.}
(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 33% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine hollow fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 32% by mass with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.90 mm and an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it was found that no crimping was exhibited in the ultrafine fibers constituting the napped layer. confirmed. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous, but the stretchability of the sheet-like material 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 spinneret and stretched under normal conditions by a roller plate method to obtain a composite multifilament (ultrafine fiber) of 74 dtex / 350 f.

On the other hand, in the same manner as described above, a 56dtex / 12f multifilament was obtained. A plain weave woven fabric was produced by using a twisted yarn (1500 / m) of this composite filament as a warp yarn and a weft yarn.

The 74dtex / 350f composite multifilament (ultrafine fiber) produced earlier was cut to a length of 5 mm and then dispersed in water to prepare papermaking slurries for the surface layer and the back layer. The surface layer weight is 100 g / m ² and the back layer weight is 100 g / m ² , and the above-mentioned woven fabric is inserted to form a laminated structure fiber sheet, and the fibers constituting the papermaking sheet are three-dimensionally entangled with each other by jetting a high-speed water flow. Obtained a non-woven fabric.

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

After that, the surface of the sheet-like material was buffed using 240 mesh sandpaper with a baflor speed of 500 m / min, a sheet transport speed of 1.0 m / min, and a sheet contact angle of contact between the baflor and the sheet of 50 °. Was formed.

The sheet-like material thus obtained was dyed using a liquid flow dyeing machine. The obtained sheet-like material had a sheet thickness of 0.90 mm and an average single fiber diameter of 4.4 μm. As a result of observing the napped layer portion, the ultrafine fibers did not form a fiber bundle and also formed a napped layer. It was confirmed that no crimping was expressed in the ultrafine fibers. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous, but the stretchability of the sheet-like material was poor. The results are shown in Table 1.

[Comparative Example 3]
(raw cotton)
Sea islands in the same manner as in Example 1 except that polyethylene terephthalate having an intrinsic viscosity (IV) of 0.652 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.651 were separately melted and used as island components. Raw cotton of mold composite fiber was obtained.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 340 g / m ^{2 and a thickness of 1.80 mm was obtained.}

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 33% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine hollow fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 38% by mass with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.80 mm and an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. As confirmed, the average radius of crimp was 110 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous, but the stretchability of the sheet-like material was poor. The results are shown in Table 1.

[Comparative Example 4]
(raw cotton)
Raw cotton of sea-island type composite fiber was obtained in the same manner as in Example 1 except that the island / sea mass ratio was set to 20/80.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 340 g / m ^{2 and a thickness of 1.85 mm was obtained.}

(Sheet)
The above-mentioned non-woven fabric is shrunk with hot water at a temperature of 98 ° C., impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 120 ° C. for 10 minutes to obtain the non-woven fabric. A non-woven fabric having a PVA mass of 34% by mass with respect to mass was obtained. The non-woven fabric thus obtained was immersed in trichlorethylene to dissolve and remove sea components to obtain a non-woven fabric (desea sheet) made of ultrafine hollow fibers. The non-woven fabric (desea sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of a polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. The polyurethane was solidified with. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet-like product having a polyurethane mass of 35% by mass with respect to the mass of the ultrafine fibers composed of island components. ..
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.70 mm and an average single fiber diameter of 0.05 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 3 μm. Further, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous, but the stretchability of the sheet-like material was poor. The results are shown in Table 1.

[Comparative Example 5]
(raw cotton)
Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.780 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 were separately melted and used as island components, and 8 mol% of sodium 5-sulfoisophthalate was used as a sea component. Using copolymerized polyethylene terephthalate and a sea-island type composite base with 24 islands, fibers melt-spun at an island / sea mass ratio of 80/20 are stretched and crimped under normal conditions by a roller plate method. After processing, the fibers were cut to a length of 51 mm to obtain raw cotton of a sea-island type composite fiber having an average single fiber diameter of 26 μm.

(Non-woven fabric made of ultrafine fiber-expressing fibers)
Using this raw cotton of a sea-island type composite fiber, card and a laminated fiber web was formed through the cross-wrapper process, and needle-punched at a punching number of 600 pieces / cm ^2, needle-punched at a punching number of 3000 / cm ² A sheet-like material having a grain size of 340 g / m ^{2 and a thickness of 1.83 mm was obtained.}

(Sheet)
The above non-woven fabric was shrunk with hot water at a temperature of 98 ° C., and then dried with hot air at a drying temperature of 100 ° C. for 5 minutes. Then, it is impregnated with an aqueous dispersion type polyurethane liquid (ether type) having a polyurethane solid content concentration of 12% by mass and dried with hot air at a drying temperature of 100 ° C. for 10 minutes to obtain a polyurethane mass with respect to the mass of the ultrafine fibers composed of island components. Obtained a sheet-like product having a mass content of 45% by mass.

Next, the sheet-like material 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 treated for 30 minutes to remove the sea component of the sea-island type composite fiber. Then, a sheet-like material composed of ultrafine fibers and water-dispersible polyurethane was obtained.
After that, the sheet-like material is cut in half in the thickness direction, and the surface opposite to the half-cut surface is sandpaper of 240 mesh, and the baflor speed is 500 m / min, the sheet transport speed is 1.0 m / min, and the baflor and the sheet come into contact with each other. Buffing was performed with the sheet contact angle set to 50 ° to form a fluffy surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing at the same time under a temperature condition of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to form a sheet-like material. I got something.

The obtained sheet-like material had a sheet thickness of 0.75 mm and an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it was found that crimps were exhibited in the ultrafine fibers constituting the napped layer. After confirmation, the average radius of crimp was 60 μm. Further, by SEM observation (500 times) of the cross section, the polyurethane was non-porous, and the stretchability of the sheet-like material was poor. The results are shown in Table 1.

[Comparative Example 6]
(raw cotton)
The same as in Example 1 except that polybutylene terephthalate having an intrinsic viscosity (IV) of 1.750 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.025 were separately melted and used as island components. , Thread bending was remarkable when the mouthpiece was discharged, and thread breakage occurred frequently, making stable production impossible.

[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.

Regarding the leather-like sheet-like material thus obtained, the thickness of the fluff layer was 210 μm, the fluff on the surface was not crimped, and the fluff directions were aligned in one direction. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-mentioned measuring method, ΔE * ab between each point was obtained, and the average of ΔE * ab of the three points was obtained. The value was 2.51, and there was a difference in hue depending on the viewing angle, and a feeling of patching and blurring occurred when the sheet was molded. The results are shown in Table 2.

[Comparative Example 8]
In Example 1 above, the sheet-like material after needle punching is shrunk with hot water at a temperature of 96 ° C., impregnated with a 12% aqueous solution of PVA (polyvinyl alcohol), and dried with hot air at a temperature of 120 ° C. for 15 minutes. A leather-like sheet-like material was obtained under the same conditions as in Example 1.

Regarding the leather-like sheet-like material thus obtained, the thickness of the fluff layer was 195 μm, the fluff on the surface was weakly crimped, and the crimp developed before the brushing treatment was stretched by the brushing treatment. It became. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-mentioned measuring method, ΔE * ab between each point was obtained, and the average of ΔE * ab of the three points was obtained. The value was 2.31, and there was a difference in hue depending on the viewing angle, and a feeling of patching and blurring occurred when the sheet was molded. The results are shown in Table 2.

[Comparative Example 9]
In Example 3 above, polybutylene terephthalate having an intrinsic viscosity (IV) of 1.21 and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.48 are used as island components, the draw ratio is 3.9 times, and boiling water shrinkage. A leather-like sheet was obtained by processing under the same conditions as in Example 3 except that raw cotton having a rate of 25.2% was obtained.

With respect to the leather-like sheet-like material thus obtained, the thickness of the nap layer is 170 μm, the naps on the surface are weakly crimped, and the crimps developed in the heat shrinkage step before the nap treatment are raised. It became a stretched shape. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-mentioned measuring method, ΔE * ab between each point was obtained, and the average of ΔE * ab of the three points was obtained. The value was 1.98, and there was a difference in hue depending on the viewing angle, and a feeling of patching and blurring occurred when the sheet was molded. The results are shown in Table 2.

[Comparative Example 10]
In the above-mentioned Example 1, in the sandpaper treatment after half-cutting in the thickness direction, a leather-like sheet-like material was obtained by processing under the same conditions as in Example 1 except that the count was changed to 320 sandpaper.

Regarding the leather-like sheet-like material thus obtained, it was confirmed that the thickness of the fluff layer was 40 μm, the fluff on the surface was coiled and crimped, and the direction of the fluff was random. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-mentioned measuring method, ΔE * ab between each point was obtained, and the average value of ΔE * ab of the three points was obtained. Was 0.17, and there was no difference in hue depending on the viewing angle, but there was little change in facial expression and the feeling of luxury was lacking. The results are shown in Table 2.

1: Leather-like sheet-like material 2: Surface of leather-like sheet-like material 3: Vertical direction 4: Horizontal direction 5: Thickness direction 6: Standing forward direction

Claims (7)

A sheet-like material composed of ultrafine fibers and a porous elastic polymer.
The sheet-like material is composed of a base material layer and a napped layer.
The ultrafine fibers have coiled crimps, have an average single fiber diameter of 0.1 to 10 μm, and include fibers having a fiber length of 8 to 90 mm, and two different types of polymers (A) and polymers (B). ) Are attached side by side along the fiber length direction, and at least one of the polymer (A) or the polymer (B) is a polybutylene terephthalate polymer, and
A sheet-like material having a stretch rate of 10% or more and a stretch recovery rate of 80% or more. The sheet-like material according to claim 1, wherein the ultrafine fibers constituting the sheet-like material include fibers having a fiber length of 25 to 90 mm. The sheet-like material according to claim 1 or 2, wherein the coil-shaped crimp radius of the ultrafine fibers constituting the nap layer is an arc shape of 5 to 100 μm. Any one of claims 1 to 3, wherein the polymer (A) and the polymer (B) are polyester-based polymers, and the difference in intrinsic viscosity (IV) is 0.002 to 1.5. The described sheet-like material. The method for producing a sheet-like product according to any one of claims 1 to 4 , wherein the ultra-fine fibers are expressed from the sheet-like material made of ultra-fine fiber-expressing fibers. The method for producing a sheet-like product according to claim 5 , wherein the ultrafine fiber-expressing type fiber is a sea-island type composite fiber, and the island component is a side-by-side type. A nonwoven fabric flat Hitoshitan fiber diameter made of 7μm or less of the composite fibers above 0.3 [mu] m, containing elastic polymer therein, a sheet over preparative like material having a napped layer on the surface, shea over preparative shape viewpoint to measured points on the surface of the object, viewpoint 1 viewpoint from obliquely upward 45 ° napped forward in the longitudinal direction of the sheet over preparative like material, the viewpoint from obliquely upward 45 ° napped reverse longitudinal direction 2. The viewpoint from any one of the horizontal directions at an angle of 45 ° upward is defined 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 sheet-like material according to claim 1, wherein when the color difference between the viewpoint 3 and the viewpoint 1 is ΔE * ab ₃₁ , the following equation is satisfied.
0.2 ≦ (ΔE * ab ₁₂ + ΔE * ab ₂₃ + ΔE * ab ₃₁ ) / 3 ≦ 1.5