WO2017164162A1

WO2017164162A1 - Sheet-shaped material and method for producing same

Info

Publication number: WO2017164162A1
Application number: PCT/JP2017/011194
Authority: WO
Inventors: 吉水邦典; 石倉康弘; 金子誠; 松崎行博; 西村誠
Original assignee: 東レ株式会社
Priority date: 2016-03-24
Filing date: 2017-03-21
Publication date: 2017-09-28
Also published as: KR20180122336A; TW201738060A; JPWO2017164162A1; JP6838602B2; KR102337556B1

Abstract

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

Description

Sheet material and method for producing the same

The present invention relates to a sheet-like material having an elegant appearance and excellent stretchability, and a method for producing the same, because the ultrafine fiber has a coiled crimp.

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 increasing year by year for clothing, chair upholstery, and automotive interior materials. Recently, a sheet-like material excellent in stretchability has been demanded from the viewpoint of a feeling of wear especially for clothing and from a moldability viewpoint for materials. For the purpose of imparting stretch properties to a sheet-like material, studies have been made to have a structure in which fibers constituting the sheet-like material are attached in a side-by-side manner.

For example, in Patent Document 1, an island component is an inelastic polymer by removing a sea component from a converging fiber generating fiber in which a fiber component composed of an elastic polymer and an island-island structure having an island component composed of an inelastic polymer are adjacent to each other. A fiber having a structure in which two types of fibers, a non-elastic ultrafine fiber bundle generation type fiber and an elastic fiber, are attached in a side-by-side manner is obtained, and an artificial leather using the fiber has been proposed. However, when a polyurethane fiber that is an elastic polymer is spun, the polyurethane fiber has a hard texture as a characteristic property of polyurethane, and there is a problem that the texture and drape of the fabric is lowered. Furthermore, polyurethane fibers are difficult to dye with polyester dyes, and even when used in combination with polyester fibers, the dyeing process is complicated and it is difficult to dye them in a desired color.

Patent Document 2 proposes a method of inserting a woven or knitted fabric including a yarn including a side-by-side type composite fiber formed from two types of polyethylene terephthalate copolymers having a difference in intrinsic viscosity (IV). Stress concentration on the high viscosity side during stretching causes different internal strains between the two components, and crimps are developed. However, the ultra-fine fibers that make up the sheet-like material are not latent crimped fibers, and only the woven or knitted fabric that is inserted for the purpose of reinforcing the strength of the sheet-like material is crimped. However, the fineness of the ultrafine fibers on the surface of the sheet-like material is not expressed.

Patent Document 3 proposes an artificial leather containing latent crimped fibers obtained by composite spinning of two types of polytrimethylene terephthalate having different intrinsic viscosities in a side-by-side manner. However, the ultrafine fiber length forming this sheet is very short as 5 mm or less, and since a fiber bundle cannot be formed by the direct spinning method, the entanglement between the ultrafine fibers and the crimp 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 composed of side-by-side ultrafine fibers formed from two types of polyethylene terephthalate having a difference in intrinsic viscosity, and a sheet-like material containing water-dispersible polyurethane therein. In this patent document, since the nonwoven fabric is impregnated with the water-dispersed polyurethane, the water-dispersed polyurethane has a structure in which the entanglement points of the ultrafine fibers are hardened when drying. Moreover, since polyurethane has a nonporous structure, there is no degree of freedom for ultrafine fibers. Therefore, the ultrafine fibers are crimped to make the surface of the sheet-like material dense, but do not exhibit stretch properties.

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

In addition, in the suede-like artificial leather generally having napped on the surface, the reflection of the light of the surface fiber changes depending on the napped direction, and there is a characteristic that the hue varies depending on the viewing angle, when used for clothing and sheet materials, It was necessary to pay attention to the direction.

Japanese Patent No. 03128333 Japanese Patent No. 0535117 JP 2003-286663 A JP 2012-136800 A

Although no literature on proposals for solving the above problems has been found so far, the present inventors solved the above problems by changing the direction of the fibers on the surface using latent crimped yarns. We were able to.

The object of the present invention is to take into account the actual state of the above-mentioned prior art, a sheet-like material that has both a dense appearance and stretch properties such as a stretch rate and a stretch recovery rate, and a hue difference even when the viewing angle is changed while maintaining a high-class feeling. Provides a small sheet-like material and a method for producing them.

The present invention is a sheet-like material composed of an ultrafine fiber and a porous elastic polymer, the sheet-like material comprising a base material layer and a raised layer, and the ultrafine fiber has a coiled crimp. The average single fiber diameter is 0.1 to 10 μm, the fiber length is 8 to 90 mm, and the sheet material has an elongation rate of 10% or more and an elongation recovery rate of 80% or more. It is a sheet-like thing characterized by these.

According to a preferred aspect of the sheet-like material of the present invention, the ultrafine fiber constituting the sheet-like material is a sheet-like material characterized by 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 types of polyethylene terephthalate polymers having a difference in intrinsic viscosity are bonded to a side-by-side type along the fiber length direction, or an eccentric core. A leather-like sheet-like material containing a nonwoven fabric composed of a composite fiber having an average single fiber diameter of 0.3 μm or more and 7 μm or less forming a sheath structure, a polymer elastic body inside, and a napped layer on the surface. From the point of measurement of the surface of the leather-like sheet material, the viewpoint from the upper 45 ° oblique direction of the napping forward direction of the leather-like sheet material is the viewpoint 1, the upper oblique direction 45 ° of the napping reverse direction of the vertical direction The viewpoint from the viewpoint 2 is the viewpoint 2, the viewpoint from any one of 45 degrees above the horizontal direction 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 △ E * ab ₂₃ , viewpoint 3 And the viewpoint 1 is a leather-like sheet characterized by satisfying the following equation when ΔE * ab ₃₁ is satisfied.
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 stretch properties such as stretch rate and stretch recovery rate, and a leather-like sheet shape that has a high-quality and varied expression of suede-like artificial leather and has a small hue difference depending on the viewing angle. Products, and methods for their production. As a result, it is possible to obtain a sheet-like material that is excellent in functionality such as moldability and improved feeling of comfort, and in which a trace is hardly visible even when the surface of the sheet-like material is touched by hand or sitting.

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

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

In the present invention, the raised layer is a layer formed by the fibers in which the sheet-like material is raised, and the base material layer is a layer other than the raised layer of the 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 napped quality. When the average single fiber diameter is increased, a sheet-like product having poor surface quality is obtained. Therefore, the average single fiber diameter is preferably 7 μm or less, more preferably 5 μm or less. On the other hand, it is preferably 0.3 μm or more, and more preferably 0.5 μm or more, from the viewpoints of color development after dyeing, dispersibility of fibers during raising treatment such as grinding with sandpaper, and ease of spreading. In addition, a preferable range is 0.3 μm to 0.7 μm in consideration of characteristics such as excellent flexibility, napped quality and color development at the time of dyeing, and a small hue difference depending on the viewing angle.

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

As the cross-sectional shape of the ultrafine fibers, for example, polygons such as circles, ellipses, flats and triangles, fans, crosses, Y, H, X, W, C, and π-types can be used.

The ultrafine fibers constituting the fiber entangled body are in the form of ultrafine fiber bundles. When the ultrafine fibers are bundled, physical strength such as tensile strength and tear strength of the sheet-like material can be improved, and furthermore, wear resistance can be expressed. As a form of the ultrafine fiber bundle, the ultrafine fibers may be somewhat separated from each other, and may be partially bonded or agglomerated in some cases. Examples of the polymer forming the ultrafine fiber used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polylactic acid and other polyesters, polyamides such as 6-nylon and 66-nylon, acrylic, polyethylene, and polypropylene. And thermoplastic resins that can be melt-spun such as thermoplastic cellulose. Of these, polyester fibers made of a polyester polymer 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 2 or more types 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 configured by mixing fibers of different materials.

Further, the polymer constituting the ultrafine fiber may be copolymerized with other components, and may contain additives such as organic particles, inorganic particles, flame retardants and antistatic agents.

The ultrafine fiber constituting the sheet-like product of the present invention may be a composite fiber 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 polymers forming the ultrafine fibers, but is preferably a combination of polyester polymers having a difference in intrinsic viscosity, more preferably At least one of the polymer (A) or the polymer (B) is a polybutylene terephthalate polymer. In particular, the ultrafine fiber obtained by spinning and stretching so as to form a structure in which a polymer of such a combination is bonded to the side-by-side type along the fiber length direction has two components due to stress concentration on the high viscosity side during stretching. Different internal strains occur between them, and heat treatment after forming into a sheet thereby causes the high-viscosity side to shrink significantly, producing strain within the single fiber and developing coiled crimps. By this crimp, the fiber entanglement of the napped layer portion on the surface of the sheet-like material becomes large, and stretch properties are expressed.

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

In the present invention, the intrinsic viscosity of the polyester polymer is preferably 0.5 to 2.0 for the high viscosity component. By setting the intrinsic viscosity to 0.5 or more, a fiber having sufficient strength and elongation can be produced. The upper limit of the intrinsic viscosity is preferably 2.0 or less from the viewpoint of ease of molding such as melt extrusion, production cost, and molecular weight reduction due to molecular chain breakage caused by heat or shear force during the process. On the other hand, the low viscosity component can be stably spun 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 the high viscosity component may be increased.

The inherent viscosity difference of the polyester polymer can be set 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 by dissolving a sample in orthochlorophenol at a temperature of 25 ° C.

The polyester 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, where the main component is based on the total weight. More than 50% by weight. The polyester polymer may contain a copolymer component capable of forming another ester bond. Examples of the copolymerizable compound include dicarboxylic acids such as isophthalic acid, succinic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, sebacic acid and 5-isophthalic acid, ethylene glycol, butanediol, neopentyl glycol, cyclohexanedi Examples include diols such as methanol, polyethylene glycol, and polypropylene glycol. Further, if necessary, titanium dioxide serving as a matting agent, silica or alumina fine particles as a lubricant, hindered phenol derivatives as an antioxidant, and coloring pigments may be added.

The polybutylene terephthalate-based polymer in the present invention is mainly composed of a structure obtained by copolymerizing terephthalic acid or a derivative thereof and 1,4-butanediol or a derivative thereof.

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

The short fiber nonwoven fabric used in the sheet-like material of the present invention is obtained by forming a laminated web using short fibers with a card and a cross wrapper and then applying a needle punch or a water jet punch or obtained by a papermaking method. As the obtained non-woven fabric, those obtained from a spunbond method, a melt blow method or the like can be appropriately employed.

It is important that the short fibers in the short fiber nonwoven fabric have 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. Moreover, by setting the fiber length to 90 mm or less, it is possible to obtain a sheet-like material excellent in compression characteristics and surface quality of the sheet-like material. The fiber length is more preferably 25 to 90 mm.

Fibers with a fiber length of less than 8 mm are less likely to be entangled, and fiber dropout occurs during the manufacturing process of the sheet-like material. Moreover, although the fiber longer than 90 mm is excellent in entanglement property, when a napped part is comprised, it is inferior to abrasion resistance and tends to be inferior to surface quality.

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

The ratio of the fiber length of 8 to 90 mm is determined by first extracting and removing the elastic polymer in the sheet to make only ultrafine fibers, then randomly extracting 100 fibers, measuring the fiber length, and measuring the fiber length histogram. Is calculated by creating

The nonwoven fabric obtained as described above can be subjected to shrinkage treatment with warm water or steam in order to improve the fineness 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 crimp of the ultrafine fiber described later does not appear. However, if the temperature of the sheet-like material itself is kept below 100 ° C., the temperature of hot water or steam applied to shrink the sheet-like material is allowed to be 100 ° C. or higher. In addition, when the shrinkage in the boiling water of the ultrafine fiber-expressing fiber constituting the nonwoven fabric is high during this shrinkage treatment, crimping is manifested after the shrinkage treatment even when the shrinkage treatment temperature of the sheet-like material is less than 100 ° C. 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 material cannot be obtained. Thus, the shrinkage ratio of the ultrafine fiber-expressing fiber constituting the nonwoven fabric in boiling water is preferably 5 to 25%.

The sheet-like material of the present invention can include a reinforcing layer for the purpose of improving the strength of the inner layer portion or the surface thereof. As the reinforcing layer, woven fabrics, knitted fabrics, nonwoven fabrics (including paper), and film-like materials such as plastic films and metal thin film sheets can be employed. In the case of a woven or knitted fabric in which the reinforcing layer is composed 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 fiber yarns constituting the woven or knitted fabric used in the present invention include filament yarn, spun yarn, innovative spun yarn, and mixed composite yarn of filament yarn and spun yarn. Since many yarns are present on the surface of the spun yarn due to its structure, when the nonwoven fabric and the woven fabric are entangled with each other, it becomes a drawback if the yarn falls off and is exposed on the surface. Therefore, it is preferable to use a filament yarn. The filament yarn is roughly classified into a monofilament composed of a single fiber and a multifilament composed of a plurality of filament yarns. In the woven or knitted fabric used in the present invention, it is preferable to use a multifilament. In the case of monofilaments, the stiffness of the fiber becomes too high, and the texture of the sheet-like material may be impaired.

The total fineness of the fiber yarns 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 , more preferably 30 to 150 g / m ² . When the basis weight of the woven or knitted fabric is less than 20 g / m ² , the form as the woven or knitted fabric becomes poor, and wrinkles are generated when the woven or knitted fabric is inserted between the nonwoven fabric and the woven or knitted fabric is stacked on the surface of the nonwoven fabric, It becomes difficult to laminate uniformly. On the other hand, 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 the entanglement between the nonwoven fabric and the woven or knitted fabric tends to be difficult.

As the basic structure of the fabric used in the present invention, twill or satin may be used, but a plain structure in which misalignment or the like hardly occurs is preferably used.

The sheet-like material of the present invention has a raised layer on one side or both sides of the sheet-like material. Moreover, when the ultrafine fiber has a coiled crimp, the sheet-like material can be given a bulky feeling, and stretch properties can also be expressed.

It is important that the stretch rate of the sheet 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 stretch properties can be obtained.

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

The radius of the coiled crimp of the ultrafine fiber constituting the nap layer is preferably an arc shape of 5 to 100 μm, more preferably 90 μm or less, and still more preferably 85 μm or less. When the radius is larger than 100 μm, the crimp is weakened 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 strong and the surface quality deteriorates. Since the ultrafine fibers are crimped 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 crimp, and the non-woven fabric under the raised fibers is not visible, and only the raised fibers appear. It has a precise and elegant appearance. In addition, as the internal structure of the sheet-like material, the coiled ultrafine fibers are entangled with each other, so that an elongation margin with respect to tension is formed, and stretch properties are 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 body. By containing 5% by mass or more of the elastic polymer with respect to the mass of the ultrafine fiber, it becomes possible to impart an appropriate compression property to the sheet-like material. When the mass of the elastic polymer is more than 60% by mass, the fiber opening property in the napping process may be poor, and the flexibility of the sheet-like material may be reduced. Furthermore, when the sheet-like material is used after being dyed, there is a difference in the color tone between the fibers of the fiber entangled body after dyeing and the elastic polymer. In terms of environmental considerations, it is not preferable to add a large amount of elastic polymer because the amount of organic matter used in the production process increases, and the smaller the amount of elastic polymer, the more the fibers obtained from recycled materials and plant-derived materials. When used, it can be easily recovered and discarded. A more preferable range of the mass of the elastic polymer is 15 to 55% by mass.

For the above-mentioned elastic polymer, pigments such as carbon black, dyes, antifungal agents and antioxidants, UV absorbers, light stabilizers such as light stabilizers, flame retardants, penetrants and lubricants, silica Antiblocking agents such as water and titanium oxide, water repellents, viscosity modifiers, surfactants such as antistatic agents, antifoaming agents such as silicone, fillers such as cellulose, and coagulation regulators, and silica and titanium oxide, etc. Inorganic particles or the like can be contained.

It is important that the elastic polymer in the present invention is porous. By making it porous, the gripping force of the fiber by the elastic polymer can be lowered, and the stretch property by the crimping of the fiber can be expressed.

Examples of the elastic polymer used in the present invention include polyurethane elastomer, polyurea, polyacrylic acid, ethylene / vinyl acetate elastomer, acrylonitrile / butadiene elastomer and styrene / butadiene elastomer, polyvinyl alcohol, and polyethylene glycol. From the viewpoint of compression characteristics, polyurethane elastomers are preferably used. The polymer elastic body can contain a plurality of polymer elastic bodies.

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

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

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

As the polymer diol, for example, a polycarbonate diol, a polyester diol, a polyether diol, a silicone diol and a fluorine diol can be employed, and a copolymer combining these can also be used. Among these, from the viewpoint of hydrolysis resistance, it is preferable to use a polycarbonate diol and a polyether diol.

The above polycarbonate diol can be produced by transesterification of alkylene glycol and carbonate or reaction of phosgene or chloroformate with alkylene glycol.

Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol. 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, and pentaerythritol. In the present invention, both polycarbonate-based diols obtained from individual alkylene glycols and copolymerized polycarbonate-based diols obtained from two or more types of alkylene glycols can be employed.

Further, examples of the polyester diol include polyester diols obtained by condensing various low molecular weight polyols and polybasic acids.

Examples of the low molecular weight polyol 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.

Also, adducts obtained by adding various alkylene oxides to bisphenol A can be used.

Polybasic acids include, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydro One kind or two or more kinds selected from isophthalic acid can be mentioned.

Examples of the polyether-based diol used in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymerized diols combining them.

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 elastomer is constant. By making the number average molecular weight preferably 500 or more, more preferably 1500 or more, it is possible to prevent the sheet-like material from becoming hard. Moreover, the intensity | strength as a polyurethane-type elastomer is maintainable by making a number average molecular weight into 4000 or less, More preferably, 3000 or less.

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. These can also be used in combination.

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

The polyurethane used in the present invention can be used in combination with a crosslinking 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 that becomes a cross-linked structure in advance in the polyurethane molecular structure. From the viewpoint that the cross-linking points can be formed more uniformly in the polyurethane molecular structure and the reduction in flexibility can be reduced, it is preferable to use an internal cross-linking agent.

As the crosslinking agent, compounds 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-like material of the present invention is preferably 0.10 to 0.80 g / cm ³ , more preferably 0.20 to 0.70 g / cm ³ . When the apparent density is 0.10 g / cm ³ or more, the denseness and mechanical properties of the sheet-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 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 form has excellent form stability and dimensional stability. On the other hand, when the thickness is 7 mm or less, more preferably 5 mm or less, the sheet-like product is excellent in moldability.

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 * between each point. Ab is obtained, and the average value thereof is in the range of 0.2 to 1.5. In general, when ΔE * ab exceeds 1.5, it is considered that the hue is different enough to be perceived. Therefore, the hue difference is preferably 1.5 or less. On the other hand, when the hue difference is 0.2 or less, the change in facial expression is small and the sense of quality is poor. Therefore, when the leather-like sheet-like material is viewed from three directions, the hue difference is in the range of 0.2 to 1.5, so that the hue difference depending on the viewing angle is small while maintaining a high-class feeling and a changing expression. In other words, even when it is molded into a three-dimensional shape such as an automobile seat or sofa, the reflection of the part that is exposed to light can be suppressed, there is little patchy feeling, blurring is difficult to occur, and the surface of the sheet-like object is touched Even when sitting down, it is possible to obtain a sheet-like material in which traces are difficult to see.

The sheet-like material of the present invention contains functional agents such as dyes, pigments, softeners, texture modifiers, anti-pilling agents, antibacterial agents, deodorants, water repellents, light proofing agents, and weathering agents. May be.

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

As a means for obtaining ultrafine fibers constituting the non-woven fabric used in the sheet-like material of the present invention, it is important that the fibers are ultrafine fiber expression type fibers. After the ultrafine fiber expression type fiber is entangled in advance to obtain a non-woven fabric, the non-woven fabric formed by entanglement of a bundle of ultrafine fibers can be obtained by performing ultrafine fiber formation.

As ultra-fine fiber expression type fiber, thermoplastic polymer component with different solubility in solvent etc. is used as sea component and island component, and the sea component is dissolved and removed by using solvent etc. in the later process to remove island component from ultra fine fiber. The sea-island type composite fiber and the separation-dividing fiber that is separated by physical force such as water jet or swelling of the solvent can be employed, but preferably the ultrafine fiber diameter can be controlled uniformly, and the sheet-like material It is a sea-island type composite fiber that can make the surface appearance of The sea-island type composite fiber can provide an appropriate gap between island components, that is, between the ultrafine fibers in the fiber bundle by removing the sea component, and the ultrafine fiber having a particularly small fiber diameter from each composite fiber. It is preferably used because the fibers can be efficiently expressed and a soft texture or bulkiness can be imparted to the sheet-like material.

For the sea-island type composite fiber, a sea-island type composite base is used, and a polymer inter-array system in which two components, the sea component and the island component, are spun together, and the two components, the sea component and the island component, are mixed. A mixed spinning method for spinning can be used, but a sea-island type composite fiber by a polymer array system is more preferably used in that an ultrafine fiber having a uniform fineness can be obtained.

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

In addition, the mass ratio of the sea component to the island component in the sea-island composite fiber used in the present invention is preferably in the range of sea component: island component = 5: 95 to 80:20. When the mass ratio of the sea component is less than 5% by mass, the island component is not sufficiently thinned. Further, when the mass ratio of the sea component exceeds 80 mass%, the productivity is lowered because the ratio of the eluted component is large. The mass ratio of the sea component and the island component is more preferably in the range of sea component: island component = 10: 90 to 60:40.

In the present invention, when drawing an ultrafine fiber expression type fiber typified by a sea-island type composite fiber, after winding the undrawn yarn once, it is drawn separately, or the undrawn yarn is taken up and drawn continuously. Any method can be employed, such as. Stretching can be appropriately performed by a method of stretching in one to three stages by wet heat, dry heat, or both. Next, the stretched sea-island type composite fiber is preferably crimped and cut into a predetermined length to obtain a raw nonwoven fabric. A usual method can be used for crimping and cutting.

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

Sea-island type fiber ultrafine treatment (sea removal treatment) can be performed by immersing the sea-island type fiber in a solvent and squeezing the solution. As the solvent for dissolving the sea component, when the sea component is polyethylene, polypropylene, or polystyrene, an organic solvent such as toluene or trichloroethylene is used. Further, when the sea component is a copolyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide or hot water is used.

For the ultrafine fiber treatment, devices such as a continuous dyeing machine, a vibro-washer type seawater removal machine, a liquid dyeing machine, a Wins dyeing machine, and a jigger dyeing machine can be used.

The dissolution and removal of the sea component can be performed at any timing before the impregnation with the elastic polymer, after the impregnation, and after the raising treatment. When the sea removal treatment is performed before the elastic polymer is applied, the elastic polymer is in close contact with the ultrafine fibers so that the ultrafine fibers can be strongly gripped, so that the abrasion resistance of the sheet-like material becomes better. On the other hand, when sea removal treatment is performed after the elastic polymer is applied, voids due to the sea component removed from the sea are generated between the elastic polymer and the ultrafine fibers. In addition, the compression property of the sheet-like material is 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 / bundle, the fineness of the ultrafine fibers is poor, and for example, mechanical properties such as wear tend to be reduced. Moreover, when there are more than 9000 fibers / bundle, the openability at the time of napping falls, and there exists a tendency for fiber distribution of a napped surface to become non-uniform | heterogenous.

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 (number of fibers in the ultrafine fiber bundle) × (single fiber diameter) and is an index of the size of the ultrafine fiber bundle. As described above, when the fiber density in the ultrafine fiber bundle is set to 30 to 1000, the processing operability when the fiber entangled body is obtained is improved, and the denseness of the fiber bundle is improved.

As a method of obtaining a fiber entangled body used in the present invention, a method of entanglement of a fiber web with a needle punch or a water jet punch, a spun bond method, a melt blow method, a paper making method, or the like can be employed. Among them, a method that undergoes a treatment such as a needle punch or a water jet punch is preferably used in order to obtain an ultrafine fiber bundle as described above.

The apparent density of the fiber entangled body composed of the ultrafine fiber generating fibers after the needle punching process or the water jet punching process 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 shape stability and dimensional stability can be obtained. On the other hand, when the apparent density is 0.40 g / cm ³ or less, preferably 0.30 g / cm ³ or less, a sufficient space for applying the elastic polymer can be maintained between the fibers.

The fiber entangled body composed of the ultrafine fiber-generating fibers thus obtained is preferably subjected to heat shrinkage treatment with dry heat or wet heat, or both from the viewpoint of densification, and further densified. It is. Further, the fiber entangled body can be compressed in the thickness direction by calendaring or the like.

In addition, in order to obtain denseness and uniformity of the fiber distribution on the surface of the sheet-like material, the elastic polymer is a fiber entanglement such as a nonwoven fabric in which a fiber bundle of ultrafine fibers is entangled. It is a preferred embodiment that it is not substantially present in. If the elastic polymer is present even inside the fiber bundle, the elastic polymer is adhered to each ultrafine fiber, so that the opening property during the buffing process is poor.

As a method of obtaining a form in which the macromolecular elastic body does not substantially exist inside the fiber bundle of ultrafine fibers, for example, an elastic polymer is used as a solution,
(1) After impregnating the elastic polymer solution with the fiber entangled body composed of ultra-fine fiber-generating sea-island fiber and solidifying it, the sea component of the sea-island fiber is a solvent that does not dissolve the elastic polymer. How to dissolve and remove,
(2) A fiber entangled body composed of ultra-fine fiber-generating sea-island fibers is provided with polyvinyl alcohol having a saponification degree of preferably 80% or more to protect most of the surroundings of the sea-island fibers. A method in which the sea component is dissolved and removed with a solvent that does not dissolve polyvinyl alcohol, then impregnated with the elastic polymer solution and solidified, and then the polyvinyl alcohol is removed can be preferably used.

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

When the fiber entanglement is impregnated with a polyurethane elastomer liquid and solidified, it is important that the polyurethane elastomer is an organic solvent polyurethane elastomer.

The organic solvent-based polyurethane can be coagulated by dry heat coagulation, wet coagulation, or a combination of these, and wet coagulation in which it is coagulated by immersion in water is preferably used. By wet coagulation, polyurethane does not concentrate at the entanglement point of the ultrafine fibers, and the polyurethane itself also becomes porous, so the degree of freedom between the ultrafine fibers increases and structurally imparts stretch properties to the sheet-like material. be able to. On the other hand, when the polyurethane elastomer is water-dispersed polyurethane, there is dry heat coagulation as a coagulation method, but the polyurethane concentrates at the entanglement point of the ultrafine fiber and strongly grips the ultrafine fiber. Therefore, the ultrafine fiber does not have a degree of freedom and cannot exhibit stretch properties.

The temperature of wet solidification is not particularly limited.

It is a preferable aspect that is excellent in production efficiency to divide the obtained elastic polymer-added sheet material into half or several sheets in the sheet thickness direction after applying the elastic polymer to the fiber entangled body.

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

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

Also, applying an antistatic agent before the above-mentioned raising treatment tends to make it difficult for the grinding powder generated from the sheet-like material to be deposited on the sandpaper by grinding, which is a preferable embodiment.

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

The sheet-like material can be dyed depending on the application. As a method for dyeing a sheet-like material, it is preferable to use a liquid dyeing machine because the sheet-like material can be softened by simultaneously giving a stagnation effect. If the dyeing temperature of the sheet-like material is too high, the polymer elastic body may be deteriorated. On the other hand, if it is too low, the dyeing to the fiber becomes insufficient. The dyeing temperature is generally preferably 80 to 150 ° C, more preferably 110 to 130 ° C. The heat treatment and stagnation by the dyeing process tend to cause crimping of ultrafine fibers.

It is preferable to carry out the following manufacturing steps (1) to (3) as production steps for expressing crimps of ultrafine fibers.
(1) a step of expressing ultrafine fibers from a nonwoven fabric composed of ultrafine fiber-expressing fibers,
(2) a step of raising a nonwoven fabric made of ultrafine fibers,
(3) A step of causing crimps to appear in the ultrafine fibers of the napped layer by subjecting the nonwoven fabric after the raising treatment to heat treatment at a temperature of 110 ° C. to 150 ° C.

For example, if the nonwoven fabric is subjected to a heat treatment at a temperature of 100 ° C. or higher before the step of expressing the ultrafine fiber from the nonwoven fabric composed of the ultrafine fiber-expressing type fibers, crimping occurs after the sea component is dissolved, and the raising process is performed in the subsequent step. When processed, the crimps are stretched and the napped surface targeted by the present invention is hardly obtained.

In the method for producing a leather-like sheet according to the present invention, the crimp of the ultrafine fibers in the raised layer is performed by performing a heat treatment at a temperature of 110 ° C. or more and 150 ° C. or less on the raised nonwoven fabric made of the ultrafine fibers. Achieved. When the ultrafine fibers of the napped layer are crimped, an napped surface having anisotropy can be obtained, and a sheet-like material with little hue difference depending on the viewing angle can be obtained.

Dye can be selected according to the type of fiber constituting the sheet. For example, disperse dyes can be used for polyester fibers, acidic dyes or metal-containing dyes can be used for polyamide fibers, and combinations thereof can be used.

In addition, it is also a preferable aspect to use a dyeing assistant when dyeing the sheet-like material. By using a dyeing assistant, the uniformity and reproducibility of dyeing can be improved. In addition, a finishing treatment using a softening agent such as silicone, an antistatic agent, a water repellent, a flame retardant, a light proofing agent, and an antibacterial agent can be performed in the same bath or after dyeing.

Since the sheet-like material of the present invention has both an elegant and precise appearance and stretchability (stretchability), the seat, ceiling, and interior in furniture, chairs and wall materials, and vehicle interiors such as automobiles, trains and aircraft Interior materials that have a very elegant appearance as a skin material such as shirts, jackets, casual shoes, sports shoes, shoes uppers such as men's shoes and women's shoes, trims, bags, belts, wallets, etc., and one of them It can be suitably used as industrial materials such as clothing materials and wiping cloths used for the parts. Furthermore, in the sheet-like material of the present invention, a large number of gaps of about several nm to 500 nm are created between single fibers or at the intertwined portion of the fibers. It can also be used for other purposes.

The sheet-like material of the present invention can also be used for artificial leather with silver by forming a coating layer on the surface thereof. As a method for forming a coating layer or an undercoat layer for making an artificial leather with silver, there are a dry surface forming method, a direct coating method, etc., and various conventionally known methods can be adopted and are particularly limited. is not. For example, the method using apparatuses, such as a reverse roll coater, a spray coater, a roll coater, a gravure coater, a kiss roll coater, a knife coater, 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.

The resin used for the coating layer is most preferably polyurethane. Other resins can be appropriately mixed and used for the resin. In recent years, since durability is required for many applications, it is preferable to use polyurethane having excellent durability such as polycarbonate. From the viewpoint of wear resistance, silicone-modified polyurethane is preferably used. For the same reason, the polyurethane resin can be used by containing silicone oil or a solid silicone compound.

Next, the sheet-like material of the present invention and the manufacturing method thereof will be described more specifically using examples. Next, the evaluation methods used in the examples and the measurement conditions will be described.

(1) Intrinsic viscosity IV
0.8 g of sample polymer is dissolved in 10 mL of orthochlorophenol (hereinafter abbreviated as OCP), and the relative viscosity (ηr) is obtained by the following equation using an Ostwald viscometer at a temperature of 25 ° C., and the intrinsic viscosity (IV) Was calculated.
ηr = η / η0 = (t × d) / (t0 × d0)
Intrinsic viscosity IV = 0.0242ηr + 0.2634
Where η: viscosity of the polymer solution η0: OCP viscosity t: solution drop time (seconds)
d: density of the solution (g / cm ³ )
t0: OCP fall time (seconds)
d0: OCP density (g / cm ³ ).

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

(3) Crimp radius Using a scanning electron microscope (SEM, VE-7800 manufactured by Keyence Corporation), the surface of the sheet is photographed (magnification 100 times), and the radius of the crimped and arc-shaped fiber is measured. did. The n number was 20, and the average value was obtained. When the arc shape is a part of a circle and the circumferential portion of the arc shape does not exceed 1/2 of the entire circle, the fiber is excluded from the measurement subject as not being a crimped fiber. It was.

(4) Fabric weight of sheet-like material Measured by the method described in JIS L 1096 (1999) 8.4.2.
A test piece of 20 cm × 20 cm to 5 sheets collected, weighed respective mass (g), representing the average value in 1 m ² per mass (g / ^{m 2).}

(5) Thickness of sheet-like material Using a thickness gauge with a 0.01-mm scale (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 obtained.

(6) Stretchability It was carried out according to the elongation rate and elongation recovery rate. For each direction of the sheet, if both the stretch rate and stretch recovery rate exceed the target values, the evaluation is "○", and the evaluation is "good", if either or both do not exceed the target, "X", fail It was.
-Elongation rate The elongation rate of the sheet-like material was measured in JIS L 1096 (2010) 8.16.1 B method (constant load method).
In the present invention, a good level (target value) is an elongation rate of 10% or more.
Elongation recovery rate The elongation recovery rate of the sheet-like material was measured according to JIS L 1096 (2010) 8.16.2 B-1 method (constant load method). The holding interval was 10 cm, and the standing time after removing the load was 1 hour.
In the present invention, a good level (target value) is an elongation recovery rate of 80% or more.

(7) Hue difference of leather-like sheet:
Using a color difference meter (CR-410 manufactured by Konica Minolta Co., Ltd.), 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, When the napped forward direction is set to 6, the viewpoint from the diagonal 45 ° above the napped forward direction 6 in the vertical direction 3 of the leather-like sheet 1 with respect to the measurement target point on the surface 2 of the leather-like sheet 1 is viewed. 1 is the viewpoint from a diagonal direction 45 ° above the nap in the vertical direction 3 and the viewpoint 2 is a viewpoint from any one diagonal 45 ° in the horizontal direction 4, the viewpoint 3 is L at each viewpoint. *, A *, and b * were measured. At the time of measurement, a cylindrical frame cut obliquely at 45 ° was prepared so as not to leak light from the device, and measurement was performed by fitting it to 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 obtained by the following formula.
ΔE * ab = (ΔL * ^ 2 + Δa * ^ 2 + Δb * ^ 2) ^1/2
(In the formula, ΔL * represents a difference in L * value between two points, Δa * represents a difference in a * value between two points, and Δb * represents a difference in b * value between two points, respectively. )
[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 used separately as island components, and in accordance with JIS K7206 (1999) as sea components. An island / sea mass ratio of 80 using polystyrene (PSt) having a measured Vicat softening point of 100 ° C., a melt flow rate (hereinafter referred to as MFR) of 120, and a number of islands of 24 islands. The fiber melt-spun at / 20 was stretched by a roller plate method under normal conditions and crimped, and then the fiber was cut to a length of 51 mm to obtain a sea-island composite fiber raw cotton having an average single fiber diameter of 26 μm.

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm ² , and then needle punched at a punch number of 3000 / cm ^2. As a result, a sheet-like material having a basis weight of 312 g / m ² and a thickness of 1.70 mm was obtained.

(Sheet)
After shrinking the nonwoven fabric with hot water at a temperature of 98 ° C., the nonwoven fabric was impregnated with an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% and dried with hot air at a temperature of 120 ° C. for 10 minutes. A non-woven fabric having a PVA mass of 30 mass% with respect to the mass was obtained. The nonwoven fabric obtained in this manner was immersed in trichlorethylene to dissolve and remove sea components to obtain a nonwoven fabric (sea removal sheet) made of ultrafine fibers. The nonwoven fabric (sea removal sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. To solidify the polyurethane. Thereafter, 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 material having a polyurethane mass of 37% by mass with respect to the mass of the ultrafine fibers comprising the island components. .
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

The sheet-like material thus obtained is subjected to crimping treatment and dyeing simultaneously under a temperature condition of 130 ° C. using a liquid dyeing machine, and then dried using a drier to obtain a sheet-like material. I got a thing.

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

[Example 2]
(raw cotton)
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, A raw cotton of type composite fiber was obtained.

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm ² , and then needle punched at a punch number of 3000 / cm ^2. As a result, a sheet-like material having a basis weight of 335 g / m ² and a thickness of 1.85 mm was obtained.

(Sheet)
After shrinking the nonwoven fabric with hot water at a temperature of 98 ° C., the nonwoven fabric was impregnated with an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% and dried with hot air at a temperature of 120 ° C. for 10 minutes. A non-woven fabric having a PVA mass of 35 mass% relative to the mass was obtained. The nonwoven fabric obtained in this way was immersed in trichlorethylene to dissolve and remove sea components, and a nonwoven fabric (sea removal sheet) made of ultrafine hollow fibers was obtained. The nonwoven fabric (sea removal sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. To solidify the polyurethane. Thereafter, 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 material having a polyurethane mass of 37% by mass with respect to the mass of the ultrafine fibers comprising the island components. .
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

The sheet-like material thus obtained is subjected to simultaneous crimping treatment and dyeing using a liquid dyeing machine under a temperature condition of 130 ° C., and then dried using a dryer. I got a thing.

The obtained sheet-like material has 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 is confirmed that crimps are expressed in the ultrafine fibers constituting the napped layer. As confirmed, the average radius of crimp was 30 μm. Moreover, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The stretchability of the sheet was good. The results are shown in Table 1.

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

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm ² , and then needle punched at a punch number of 3000 / cm ^2. As a result, a sheet-like material having a basis weight of 350 g / m ² and a thickness of 1.90 mm was obtained.

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

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

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm ² , and then needle punched at a punch number of 3000 / cm ^2. As a result, a sheet-like material having a basis weight of 340 g / m ² and a thickness of 1.85 mm was obtained.

(Sheet)
After shrinking the nonwoven fabric with hot water at a temperature of 98 ° C., the nonwoven fabric was impregnated with an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% and dried with hot air at a temperature of 120 ° C. for 10 minutes. A nonwoven fabric having a PVA mass of 34 mass% with respect to the mass was obtained. The nonwoven fabric obtained in this way was immersed in trichlorethylene to dissolve and remove sea components, and a nonwoven fabric (sea removal sheet) made of ultrafine hollow fibers was obtained. The nonwoven fabric (sea removal sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. To solidify the polyurethane. Thereafter, 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 material having a polyurethane mass of 35% by mass with respect to the mass of the ultrafine fibers comprising the island components. .
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

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

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

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm ² , and then needle punched at a punch number of 3000 / cm ^2. As a result, a sheet-like material having a basis weight of 310 g / m ² and a thickness of 1.70 mm was obtained.

(Sheet)
The above nonwoven fabric is shrunk with hot water at a temperature of 96 ° C. and then immersed in a 15 g / L sodium hydroxide aqueous solution heated to 80 ° C. for 30 minutes to remove sea components of the sea-island fibers. A sheet-like material made 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 polyurethane adjusted to a solid content concentration of 12%, and then the polyurethane was coagulated in an aqueous solution with a DMF concentration of 30%. By drying with hot air at a temperature of 10 minutes for 10 minutes, a sheet-like material having a polyurethane mass of 37 mass% relative to the mass of the ultrafine fiber made of the island component was obtained.
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface. The sheet-like material thus obtained is subjected to crimping treatment and dyeing simultaneously under a temperature condition of 130 ° C. using a liquid dyeing machine, and then dried using a drier to obtain a sheet-like material. I got a thing.

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

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

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber long-fiber nonwoven fabric sheet, a laminated fiber web is formed through a cross-wrapper process, needle punched with a punch number of 600 / cm ² , and then needles with a punch number of 3000 / cm ^2. Punching was performed to obtain a sheet-like material having a basis weight of 300 g / m ² and a thickness of 1.80 mm.

(Sheet)
After shrinking the nonwoven fabric with hot water at a temperature of 98 ° C., the nonwoven fabric was impregnated with an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% and dried with hot air at a temperature of 120 ° C. for 10 minutes. A non-woven fabric having a PVA mass of 30 mass% with respect to the mass was obtained. The nonwoven fabric obtained in this manner was immersed in trichlorethylene to dissolve and remove sea components to obtain a nonwoven fabric (sea removal sheet) made of ultrafine fibers. The nonwoven fabric (sea removal sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. To solidify the polyurethane. Thereafter, 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 material having a polyurethane mass of 38% by mass with respect to the mass of the ultrafine fibers comprising the island components. .
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

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

[Example 7]
(Spinning, fabric making)
Among the island components, polyethylene terephthalate having an intrinsic viscosity (IV) of 0.780 as the core component and polyethylene terephthalate having an intrinsic viscosity (IV) of 0.510 as the sheath component are separately melted and used as JIS as the sea component. Using a sea-island type composite base with polystyrene (PSt) having a Vicat softening point of 100 ° C. and an MFR of 120 measured according to K7206 (1999), having 24 islands and an eccentric core-shell type island component. Then, it was discharged from the base 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 the sea-island composite long fibers having an average single fiber diameter of 25 μm were collected by a net to obtain a 30 g / m ² long fiber nonwoven fabric sheet.

(Sheet)
After shrinking the nonwoven fabric with hot water at a temperature of 98 ° C., the nonwoven fabric was impregnated with an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% and dried with hot air at a temperature of 120 ° C. for 10 minutes. A non-woven fabric having a PVA mass of 30 mass% with respect to the mass was obtained. The nonwoven fabric obtained in this manner was immersed in trichlorethylene to dissolve and remove sea components to obtain a nonwoven fabric (sea removal sheet) made of ultrafine fibers. The nonwoven fabric (sea removal sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. To solidify the polyurethane. Thereafter, 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 material having a polyurethane mass of 40 mass% with respect to the mass of the ultrafine fibers comprising the island components. .
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

The obtained sheet-like material has 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 is confirmed that crimps are expressed in the ultrafine fibers constituting the napped layer. As a result, the average radius of crimp was 80 μm. Moreover, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The stretchability of the sheet 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 used separately as island components, and in accordance with JIS K7206 (1999) as sea components. Using a polystyrene (PSt) having a measured Vicat softening point of 100 ° C., an MFR of 120, and using a sea-island type composite base having 24 islands, a melt-spun fiber at an island / sea mass ratio of 80/20 is obtained. Then, after drawing and crimping by a roller plate method under normal conditions, the fiber was cut to a length of 10 mm to obtain a raw material of sea-island type composite fiber having an average single fiber diameter of 26 μm.

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm2, and then needle punched at a punch number of 3000 / cm2. Thus, a sheet-like material having a basis weight of 162 g / m 2 and a thickness of 0.87 mm was obtained.

(Sheet)
After shrinking the nonwoven fabric with hot water at a temperature of 98 ° C., the nonwoven fabric was impregnated with an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% and dried with hot air at a temperature of 120 ° C. for 10 minutes. A non-woven fabric having a PVA mass of 30 mass% with respect to the mass was obtained. The nonwoven fabric obtained in this manner was immersed in trichlorethylene to dissolve and remove sea components to obtain a nonwoven fabric (sea removal sheet) made of ultrafine fibers. The nonwoven fabric (sea removal sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. To solidify the polyurethane. Thereafter, 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 material having a polyurethane mass of 37% by mass with respect to the mass of the ultrafine fibers comprising the island components. .

Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

The obtained sheet-like material has a sheet thickness of 0.72 mm, an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it is confirmed that crimps are expressed in the ultrafine fibers constituting the napped layer. As confirmed, the average radius of crimp was 20 μm. Moreover, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The stretchability of the sheet 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 used separately as island components, and in accordance with JIS K7206 (1999) as sea components. Using a polystyrene (PSt) having a measured Vicat softening point of 100 ° C., an MFR of 120, and using a sea-island type composite base having 24 islands, a melt-spun fiber at an island / sea mass ratio of 80/20 is obtained. The fiber was cut into a length of 80 mm after being stretched under a normal condition by a roller plate method, and a fiber was cut into a length of 80 mm to obtain a raw cotton of a sea-island type composite fiber having an average single fiber diameter of 26 μm.

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm2, and then needle punched at a punch number of 3000 / cm2. Thus, a sheet-like material having a basis weight of 172 g / m 2 and a thickness of 0.94 mm was obtained.

The obtained sheet-like material has a sheet thickness of 0.73 mm and an average single fiber diameter of 4.4 μm. As a result of observing the napped layer portion, it is confirmed that crimps are expressed in the ultrafine fibers constituting the napped layer. As confirmed, the average radius of crimp was 30 μm. Moreover, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous. The stretchability of the sheet 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 melted separately as island components, and polystyrene is used as a sea component. Using a sea-island type composite die, a fiber that was melt-spun at an island / sea mass ratio of 80/20 was stretched 3.2 times by a roller plate method under normal conditions. After crimping, the fiber was 51 mm long. Then, a raw cotton having a sea-island type composite fiber having an average single fiber diameter of 4.4 μm and a boiling water shrinkage of 14.5% was obtained.

Using the raw cotton of the sea-island type composite fiber thus obtained, a laminated fiber web is formed through a card and cross wrapping process, and needle punching is performed at a punch number of 600 / cm ² , and 3000 / A needle punch was applied with a number of cm ² punches to obtain a sheet-like material.

The sheet-like material thus obtained is shrunk with hot water at a temperature of 96 ° C., then impregnated with a 12% concentration PVA (polyvinyl alcohol) aqueous solution, and dried with hot air at a temperature of 95 ° C. for 15 minutes. Thus, a sheet-like material having a PVA mass of 20% by mass relative to the mass of the fiber sheet-like substrate was obtained. This sheet-like material was immersed in trichlorethylene to dissolve and remove sea components, and a sea-removal sheet formed by intertwining ultrafine fibers and fabrics was obtained. The sea removal sheet thus obtained was immersed in a DMF (dimethylformamide) solution of polyurethane adjusted to a solid content concentration of 12%, and then the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF are removed with hot water and dried with hot air at a temperature of 95 ° C. for 15 minutes, so that 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 sheet thus obtained was cut in half perpendicular to the thickness direction, and the cut surface was ground with an endless sandpaper with sandpaper count 180 to form a raised surface. The leather base sheet thus obtained was put into a liquid dyeing machine, dyed in a beige color and crimped at the same time under a temperature of 120 ° C., and then dried in a dryer. A sheet-like product was obtained.

It was confirmed that the leather-like sheet-like material thus obtained had a nap layer thickness of 150 μm, the nap on the surface was crimped, and the napping direction was random. About the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-described measurement method, ΔE * ab between each point was obtained, and ΔE * ab average of the three points The value was 0.72, and there was no hue difference depending on the viewing angle. In addition, the expression was rich and high-class, and when molded into a sheet, there was no patchy or blurred feeling. The results are shown in Table 2.

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

It was confirmed that the leather-like sheet-like material thus obtained had a nap layer thickness of 180 μm, the nap on the surface was crimped, and the napping direction was random. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-described measurement method, ΔE * ab between each point was obtained, and ΔE * ab average of the three points was obtained. The value was 1.20, and there was no hue difference depending on the viewing angle. In addition, the expression was rich and high-class, and when molded into a sheet, there was no patchy or blurred feeling. 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 were used as island components, and the draw ratio was 3.7 times and the boiling water shrinkage A leather-like sheet was obtained by processing under the same conditions as in Example 1 except that raw cotton having a rate of 21.5% was obtained.

It was confirmed that the leather-like sheet-like material thus obtained had a nap layer thickness of 150 μm, the napped surface was crimped, and the napped direction was random. About the surface of the obtained leather-like sheet-like material, L *, a *, and b * are measured from three directions by the above-described measurement method, and ΔE * ab between each point is obtained. The average value of E * ab was 0.46, and there was no hue difference depending on the viewing angle. In addition, the expression was rich and high-class, and when molded into a sheet, there was no patchy or blurred feeling. 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 MFR of 120 measured as a sea component according to JIS K7206 (1999) Using a sea-island type composite base of 24 islands, the fiber melt-spun at an island / sea mass ratio of 80/20 is drawn by a roller plate method under normal conditions and crimped, and then the fiber is 51 mm long. Cut to obtain raw cotton of sea-island type composite fiber having an average single fiber diameter of 26 μm.

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm ² , and then needle punched at a punch number of 3000 / cm ^2. As a result, a sheet-like material having a basis weight of 560 g / m ² and a thickness of 3.15 mm was obtained.
(Sheet)
After shrinking the nonwoven fabric with hot water at a temperature of 98 ° C., the nonwoven fabric was impregnated with an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% and dried with hot air at a temperature of 120 ° C. for 10 minutes. A nonwoven fabric having a PVA mass of 33 mass% relative to the mass was obtained. The nonwoven fabric obtained in this way was immersed in trichlorethylene to dissolve and remove sea components, and a nonwoven fabric (sea removal sheet) made of ultrafine hollow fibers was obtained. The nonwoven fabric (sea removal sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. To solidify the polyurethane. Thereafter, 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 material having a polyurethane mass of 32 mass% with respect to the mass of the ultrafine fibers comprising the island components. .
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

The obtained sheet-like material has a sheet thickness of 0.90 mm, an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it is confirmed that crimps are not expressed in the ultrafine fibers constituting the napped layer. confirmed. Moreover, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous, but the stretchability of the sheet was poor. The results are shown in Table 1.

[Comparative Example 2]
(spinning)
Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.718 was extruded from a spinneret, and stretched by a roller plate method under ordinary conditions to obtain a 74 dtex / 350 f composite multifilament (ultrafine fiber).

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

The previously produced 74 dtex / 350 f composite multifilament (ultrafine fiber) was cut to a length of 5 mm, and then dispersed in water to produce a papermaking slurry for the surface layer and the back layer. The surface fabric weight is 100 g / m ² , the back fabric weight is 100 g / m ² , the above fabric is inserted to form a laminated fiber sheet, and the fibers constituting the paper sheet are three-dimensionally entangled by jetting high-speed water flow. To obtain a nonwoven fabric.

Thereafter, the polyurethane was immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content concentration adjusted to 12%, and then the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Then, 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 material having a polyurethane mass of 33 mass% relative to the mass of the ultrafine fibers.

Thereafter, the surface of the sheet-like material was buffed using a 240 mesh sandpaper, buffing speed of 500 m / min, sheet conveyance speed of 1.0 m / min, and the sheet contact angle between the bafrol and the sheet was 50 °, and the raised surface Formed.

The sheet-like material thus obtained was dyed using a liquid flow dyeing machine. The obtained sheet-like material has 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 do not constitute a fiber bundle, and constitute a napped layer. It was confirmed that no crimp was developed in the ultrafine fibers. Moreover, it was confirmed by SEM observation (500 times) of the cross section that the polyurethane was porous, but the stretchability of the sheet was poor. The results are shown in Table 1.

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

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm ² , and then needle punched at a punch number of 3000 / cm ^2. Thus, a sheet-like material having a basis weight of 340 g / m ² and a thickness of 1.80 mm was obtained.

(Sheet)
After shrinking the nonwoven fabric with hot water at a temperature of 98 ° C., the nonwoven fabric was impregnated with an aqueous solution of PVA (polyvinyl alcohol) having a concentration of 12% and dried with hot air at a temperature of 120 ° C. for 10 minutes. A nonwoven fabric having a PVA mass of 33 mass% relative to the mass was obtained. The nonwoven fabric obtained in this way was immersed in trichlorethylene to dissolve and remove sea components, and a nonwoven fabric (sea removal sheet) made of ultrafine hollow fibers was obtained. The nonwoven fabric (sea removal sheet) made of ultrafine fibers thus obtained is immersed in a DMF (dimethylformamide) solution of polycarbonate polyurethane having a solid content adjusted to 12%, and then in an aqueous solution having a DMF concentration of 30%. To solidify the polyurethane. Thereafter, 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 material having a polyurethane mass of 38% by mass with respect to the mass of the ultrafine fibers comprising the island components. .
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

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

[Comparative Example 4]
(raw cotton)
A 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 20/80.

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

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

(Nonwoven fabric composed of ultrafine fibers)
Using this sea-island type composite fiber raw material, a laminated fiber web is formed through a card and cross wrapping process, needle punched at a punch number of 600 / cm ² , and then needle punched at a punch number of 3000 / cm ^2. As a result, a sheet-like material having a basis weight of 340 g / m ² and a thickness of 1.83 mm was obtained.

(Sheet)
The nonwoven fabric was shrunk with hot water at a temperature of 98 ° C. and then hot-air dried at a drying temperature of 100 ° C. for 5 minutes. Then, the polyurethane mass with respect to the mass of the ultrafine fibers composed of island components is impregnated with a water-dispersed 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. Of 45% by mass was obtained.

Next, the sheet-like material thus obtained is immersed in a 15 g / L sodium hydroxide aqueous solution heated to a temperature of 80 ° C. and treated for 30 minutes to remove sea components of the sea-island type composite fiber. Thus, a sheet-like material made of ultrafine fibers and water-dispersed polyurethane was obtained.
Thereafter, the sheet-like material is cut in the thickness direction, and the surface opposite to the half-cut surface is made of 240 mesh sand paper, the bafrol speed is 500 m / min, the sheet conveyance speed is 1.0 m / min, and the bafrol and the sheet are in contact with each other. Buffing was performed at a sheet contact angle of 50 ° to form a raised surface.

The obtained sheet-like material has a sheet thickness of 0.75 mm, an average single fiber diameter of 4.4 μm, and as a result of observing the napped layer portion, it is confirmed that crimps are expressed in the ultrafine fibers constituting the napped layer. As confirmed, the radius average value of crimps was 60 μm. Moreover, the SEM observation (500 times) of the cross section revealed that the polyurethane was nonporous, and the stretchability of the sheet was poor. The results are shown in Table 1.

[Comparative Example 6]
(raw cotton)
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. When the base was discharged, the yarn was bent significantly, and the yarn was broken frequently and could not be manufactured stably.

[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 in Example 1.

The leather-like sheet-like material thus obtained had a napped layer thickness of 210 μm, no napped surface, and the napped direction was 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-described measurement method, ΔE * ab between each point was obtained, and ΔE * ab average of the three points was obtained. The value was 2.51, and there was a difference in hue depending on the viewing angle, and when it was molded into a sheet, a feeling of patching or blur occurred. The results are shown in Table 2.

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

In the leather-like sheet thus obtained, the napped layer has a thickness of 195 μm, and the napped surface is weakly crimped, and the crimps developed before the napping treatment are stretched by the napping treatment. It became. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-described measurement method, ΔE * ab between each point was obtained, and ΔE * ab average of the three points was obtained. The value was 2.31, and there was a difference in hue depending on the viewing angle, and when the sheet was molded, a feeling of patching or blurring occurred. 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 were used as island components, and the draw ratio was 3.9 times, boiling water shrinkage. A leather-like sheet was obtained by processing under the same conditions as in Example 3 except that a raw cotton having a rate of 25.2% was obtained.

The leather-like sheet thus obtained has a raised layer thickness of 170 μm, and the raised surface of the surface is weakly crimped, and the crimp developed in the heat shrinking process before the raising treatment is raised. It became a shape stretched by. With respect to the surface of the obtained sheet, L *, a *, and b * were measured from three directions by the above-described measurement method, ΔE * ab between each point was obtained, and ΔE * ab average of the three points was obtained. The value was 1.98, and there was a difference in hue depending on the viewing angle. When molded into a sheet, a feeling of patching or blurring occurred. The results are shown in Table 2.

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

It was confirmed that the leather-like sheet-like material thus obtained had a nap layer thickness of 40 μm, the nap on the surface was crimped, and the napping direction was random. With respect to the surface of the obtained sheet, L *, a *, and b * are measured from three directions by the above-described measurement method, ΔE * ab between each point is obtained, and ΔE * ab average value of the three points Was 0.17, and there was no hue difference depending on the viewing angle, but the change in facial expression was poor and the sense 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: Napped forward direction

Claims

A sheet-like material composed of an ultrafine fiber and a porous elastic polymer, the sheet-like material comprising a base material layer and a raised layer, and the ultrafine fiber has a coiled crimp and has an average size It includes fibers having a fiber diameter of 0.1 to 10 μm and a fiber length of 8 to 90 mm, and the sheet material has an elongation rate of 10% or more and an elongation recovery rate of 80% or more. Sheet material.
2. The sheet-like material according to claim 1, wherein the ultrafine fibers constituting the sheet-like material contain fibers having a fiber length of 25 to 90 mm.
The sheet-like material according to claim 1 or 2, wherein the coiled crimp radius of the ultrafine fibers constituting the napped layer is an arc shape of 5 to 100 µm.
4. The ultrafine fiber according to any one of claims 1 to 3, wherein two different types of polymers (A) and polymers (B) are bonded side by side along the fiber length direction. Sheet material.
The sheet-like material according to claim 4, wherein the polymer (A) and the polymer (B) are polyester polymers and have a difference in intrinsic viscosity (IV) of 0.002 to 1.5. .
6. The sheet-like material according to claim 4 or 5, wherein at least one of the polymer (A) and the polymer (B) is a polybutylene terephthalate polymer.
A method for producing a sheet-like material according to any one of claims 1 to 6, characterized in that the ultrafine fibers are expressed from the sheet-like material comprising the ultrafine fiber-expressing fibers.
The method for producing a sheet-like material according to claim 7, wherein the ultrafine fiber-expressing fiber is a sea-island type composite fiber, and the island component is a side-by-side type.
Two or more types of polyethylene terephthalate polymers with different intrinsic viscosities are bonded side by side along the fiber length direction, or the average single fiber diameter forming an eccentric core-sheath structure is 0.3 μm A leather-like sheet-like material having a nonwoven fabric composed of a composite fiber of 7 μm or less and a polymer elastic body inside thereof and having a raised layer on the surface thereof, with respect to the measurement target point on the surface of the leather-like sheet , The viewpoint from the upper 45 ° oblique direction of the vertical napping direction of the leather-like sheet, the viewpoint 1 from the upper oblique direction 45 ° of the vertical napping direction of the vertical direction, the viewpoint 2 from any one of the horizontal direction The viewpoint from obliquely upward 45 ° is set as viewpoint 3, the color difference between viewpoint 1 and viewpoint 2 is ΔE * ab 12 , the color difference between viewpoint 2 and viewpoint 3 is ΔE * ab 23 , and the color difference between viewpoint 3 and viewpoint 1 is when was the △ E * ab 31, the following Leather-like sheet material and satisfies the.
0.2 ≦ (ΔE * ab 12 + ΔE * ab 23 + ΔE * ab 31 ) /3≦1.5