JP2002030580A - Leather like sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a leather like sheet having a grain tone as an original natural leather, generating a pattern as peculiar to the natural leather caused by flaws, also having a peculiar textured feeling resembling to the natural leather and soft touch feeling, and useful for shoes, etc. SOLUTION: This leather like sheet material constituted by an interlaced non-woven fabric consisting of bundles of <=0.1 decitex very fine fiber and an elastic polymer, of which at least one side surface is napped and colored, is characterized by covering the napped very fine fibers with a polymer being a solid at a normal temperature and having <=60 deg.C melting point and <=10% breaking elongation, and co-residing a part looking whitish caused by separations of the boundary of the polymer and very fine fibers or cracks of the polymer with a part looking dark color caused by the small amount of the separations of boundary of the polymer and the very fine fibers or the cracks of the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a natural leather with a silvery tone, a unique pattern of natural leather due to scratches, a unique texture similar to natural leather and a soft touch, and is applied to shoes and the like. The present invention relates to a useful leather-like sheet and a method for producing the same, a method for producing shoes using the leather-like sheet produced by the production method, and shoes obtained by the method.

[0002]

2. Description of the Related Art In recent years, the tendency toward naturalism and outdoor orientation has become one trend, and this trend is reflected in the field of shoes and the like, and outdoor and trekking shoes using natural leather and artificial leather materials. Naturalist oriented shoes are increasing. In particular, the texture and texture of the embedded surface of natural leather is unique, and in order to express such appearance and touch using artificial leather or synthetic leather, the structure and surface finish etc. have been devised conventionally, It has not yet satisfied its reputation in the market.

[0003] Conventionally, regarding artificial leather and synthetic leather,
Various types of surface finish coating agents have been proposed. For example, Japanese Patent Application Laid-Open No. 61-285268 discloses a method of using a surface coating agent obtained by blending polybutylene and silica in a resin containing polyurethane as a main component, and Japanese Patent Application Laid-Open No. 1-139877 discloses an oil-soluble resin. Have been proposed, respectively. However, although these methods improve the touch on the surface, they do not reproduce the appearance of natural leather with a silvery tone and a pattern with scratches. Also, a method of applying wax or the like to artificial leather is described in Japanese Patent Publication No. 3-25551, and the purpose of the invention described in the publication is to improve the color fastness of suede-like artificial leather. It is not an object of the present invention to have a unique grain pattern similar to natural leather, and to obtain what can be used for shoes with a silvery tone and a pattern with scratches, and more specifically, The invention described in JP-B-3-25551 also applies a wax to the nap surface made of ultrafine fibers, and then heat-treats the nap fibers that have been laid down by the wax. This is a method of raising the nap by raising and further brushing, which is completely different from the present invention for obtaining a silvery tone.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by adopting the following structure, the leather similar to natural leather which can be used for shoes is used. The present inventors have found that the appearance is unique, and have reached the present invention. That is, the present invention relates to a leather-like sheet in which at least one side of a sheet composed of an entangled nonwoven fabric and an elastic polymer, which is made of a bundle of ultrafine fibers of 0.1 decitex or less, is brushed and colored, Is covered with a polymer that is solid at room temperature and has a melting point of 60 ° C. or more and an elongation at break of 10% or less, and a portion where the interface between the polymer and the fine fibers looks whitish due to separation or cracking of the polymer and the polymer and the fine The leather-like sheet is characterized in that the separation of the interface of the fibers or the cracks of the polymer are mixed together with a portion that looks dark.

[0005] Preferably, the leather-like sheet is such that the polymer is at least one selected from the group consisting of petroleum wax, synthetic wax, polyethylene wax, paraffin wax, natural wax, and microcrystalline wax. Then, after the present invention raises and colors at least one surface of the fibrous substrate made of an entangled nonwoven fabric and an elastic polymer of an ultrafine fiber bundle of 0.1 decitex or less, it is a solid at normal temperature and has a melting point of 60 ° C. or more and breaks. This is a method for producing a leather-like sheet, which comprises applying a polymer having an elongation of 10% or less, followed by kneading. Further, in the present invention, in making a shoe using the above-mentioned leather-like sheet as an upper material, a portion of the leather-like sheet where the polymer is present in a portion to be bonded to the shoe sole material is ground and bonded to the shoe sole material. This is a method for producing artificial leather shoes. Further, the present invention is an artificial leather shoe obtained by such a method.

Hereinafter, the present invention will be described in detail. First, the structure of the leather-like sheet to which the polymer is applied in the present invention will be described. The leather-like sheet used in the present invention is composed of a nonwoven fabric obtained by entanglement of ultrafine fibers of 0.1 decitex or less, and an elastic polymer contained therein. The fineness of the fibers constituting the leather-like sheet is 0.1
It is necessary to be less than decitex, preferably,
It is in the range of 0.1 to 0.0001 decitex. 0.
If it exceeds 1 decitex, the polymer to be applied and the ultrafine fibers are separated or cracks in the polymer cause the contrast between the whitish portion and the dark portion to be lost, which is not preferable because it cannot be discriminated as a grain pattern. On the other hand, if the fineness is less than 0.0001 decitex, the breaking strength of the fiber decreases, and the peel strength and breaking strength of the layer decrease, which is not preferable. The fineness of the fiber is determined by selecting any 50 fibers from a cross-sectional photograph of the fiber taken with an electron microscope, obtaining the cross-sectional area, and obtaining the fineness from the average value.

As a method for producing ultrafine fibers, a mixed spinning method, a sea-island type composite spinning method, a split type composite spinning method using two or more kinds of polymers which are not compatible and have different solubility or degradability are used. A method of extracting or decomposing and removing a part (for example, a sea component) of the ultrafine fiber-generating fibers obtained by a spinning method such as a method to form ultrafine fibers, or forming a sheet having naps made of the ultrafine fiber-generating fibers A method of decomposing and removing at least a part (for example, a sea component) of the fiber in the nap portion to form an ultrafine fiber later, or a method of blowing a high-speed gas immediately after discharging a fiber-forming polymer from a melt spinning nozzle to make the fiber thinner, A known method for producing ultrafine fibers such as a melt-blowing method can be used.However, from the viewpoint of controlling the fiber thickness and the stability of the ultrafine fibers, it is preferable that It is.

[0008] The resin constituting the ultrafine fiber (in the case where the ultrafine fiber is formed from ultrafine fiber-generating fibers, means an island component resin) is not particularly limited, but polyethylene terephthalate. , Polybutylene terephthalate, polyethylene naphthalate, and aromatic polyesters such as copolymerized polyesters based on these, polyamides such as nylon-6, nylon-66, nylon-610, and polyolefins such as polyethylene and polypropylene. And polymers selected from known resins. Among them, the aromatic polyesters and polyamides are preferable in that natural leather-like artificial leather can be obtained and dyeability is excellent. Further, a coloring agent such as carbon black may be added to these resins as long as the stability during spinning is not impaired.

Examples of the resin component (ie, sea component) which is extracted and decomposed and removed from the microfine fiber-generating fiber are polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, At least one polymer selected from polymers such as polystyrene, styrene-acrylic monomer copolymer, and styrene-ethylene copolymer is exemplified. Among them, polyethylene, polystyrene, copolymers mainly composed of these, and the like are preferable in terms of ease of extraction.

Next, a method for forming a base of artificial leather using the ultrafine fiber-generating fibers will be described. As a method of forming the substrate, a known method, for example, a step of producing an entangled nonwoven fabric made of ultrafine fiber-generating fibers, a step of impregnating and coagulating the entangled nonwoven fabric with an elastic polymer solution, This can be achieved by sequentially performing the step of modifying into ultrafine fibers. Needless to say, the step of modifying into ultrafine fibers and the step of impregnating and coagulating an elastic polymer may be reversed.

As a method for producing an entangled nonwoven fabric using the ultrafine fiber generating fiber, the ultrafine fiber generating fiber is subjected to spinning, drawing, heat setting, crimping, cutting, and the like by a conventionally known method. Then, a raw cotton of the same fiber is produced, and the raw cotton is defibrated with a card and formed into a random web or a cross-wrap web with a weber. The resulting web is laminated as needed to the desired weight. The weight of the web is appropriately selected depending on the intended final use field, and generally is preferably in the range of 100 to 3000 g / m ² . For the purpose of cost reduction, etc., an entangled non-woven fabric of about twice the required weight is impregnated with an elastic polymer solution and then divided in the thickness direction with a band knife or the like, so that the woven fabric can be efficiently treated at a time. One piece of substrate can also be manufactured. Next to the lamination of the web, an entangled nonwoven fabric is formed by performing an entanglement treatment using a known means, for example, a needle punching method or a high-pressure water jet method. The number of needle punchings and the conditions of needle punching vary depending on the shape of the needle used and the thickness of the web, but are generally preferably set in the range of 200 to 2500 punches / cm ² .

Prior to the process of containing the elastic polymer, the surface of the entangled nonwoven fabric may be subjected to a smoothing treatment by a known method such as hot pressing, if necessary. When the fibers constituting the entangled nonwoven fabric are, for example, multi-component fibers having polyethylene as a sea component and polyester or polyamide as a very fine island component, the surface component can be extremely fused by fusing the sea component polyethylene with a hot press. It is particularly preferable because an entangled nonwoven fabric having excellent smoothness can be obtained. In addition, when the fibers constituting the entangled nonwoven fabric are not multicomponent fibers that can be dissolved and removed as one component to be modified into ultrafine fibers, the elastic polymer contained therein is prevented from sticking to the fibers and hardening the hand. In order to do so, before the impregnation process, cover the fiber surface with a temporary filling material such as polyvinyl alcohol,
It is preferable to remove the temporary filling material after applying the elastic polymer. Also, in the case of a multicomponent fiber which can be made into an ultrafine fiber by dissolving and removing one component, a more flexible sheet can be obtained by providing the temporary filling substance at the stage of the entangled nonwoven fabric.

As the elastic polymer to be contained in the entangled nonwoven fabric, known ones can be used, but it is preferable to use a polyurethane resin from the viewpoint of feeling. Preferred polyurethane resins are selected from the group consisting of polyester-based diols, polylactone-based diols, polycarbonate-based diols, and polyether-based diols obtained by reacting a diol with a dicarboxylic acid or an ester-forming derivative thereof as a soft segment. A so-called segmented polyurethane obtained by using at least one kind of polymer diol having a number average molecular weight of 500 to 5,000 and reacting this with a diisocyanate compound and a low molecular chain extender is used.

The diol compound constituting the soft segment is preferably a compound having 6 to 10 carbon atoms in terms of durability or leather-like texture.
Examples thereof include 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol. Representative examples of dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.

The number average molecular weight of the polymer diol is 500
If it is less than 10%, it is not preferable because it lacks flexibility and a natural leather-like texture cannot be obtained. When the number average molecular weight of the polymer diol exceeds 5,000, the urethane group concentration decreases, so that it is difficult to obtain a base sheet having a balance in flexibility, durability, heat resistance, and hydrolysis resistance.

As the diisocyanate compound, diphenylmethane-4,4'-diisocyanate, tolylenediisocyanate, dicyclohexylmethane-4,4'-
Aromatic, aliphatic such as diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate,
An alicyclic diisocyanate compound is exemplified. If necessary, a small amount of a polyisocyanate compound having three or more isocyanate groups such as triisocyanate may be added.

Examples of the low molecular chain extender include low molecular compounds having two active hydrogen atoms having a molecular weight of 300 or less, such as ethylene glycol, propylene glycol, butanediol, hexanediol, N-methyldiethanolamine and ethylenediamine. Can be If necessary, a coagulation regulator, a stabilizer and the like may be added to the elastic polymer, and two or more polymers may be used in combination. Further, a coloring agent such as carbon black may be added.

The method of incorporating the elastic polymer into the entangled nonwoven fabric is not particularly limited, but from the viewpoint of the balance of the texture, a method of directly impregnating the entangled nonwoven fabric with the elastic polymer solution and, if necessary, squeezing with a mangle. Also, a method of impregnating an elastic polymer solution while coating it with a coater is preferable. From the viewpoint of natural leather-like soft texture, the weight ratio of the fibers constituting the sheet to the elastic polymer is preferably in the range of 30/70 to 90/10, and more preferably 40/60 to 80/20. Within range. If the ratio of the fibers is too low, the leather-like sheet has a rubber-like texture, which is not preferable. If the ratio of the fibers is too high, the texture becomes a paper-like texture, and the target natural leather-like texture cannot be obtained.

After the impregnation with the elastic polymer solution, a liquid which is not compatible with the elastic polymer and the resin constituting the fiber but is compatible with the solvent of the elastic polymer solution, A method of immersing the elastic polymer solution-impregnated sheet to solidify the elastic polymer, that is, a so-called wet solidification method, is preferable from the viewpoint of obtaining a natural leather-like flexibility and texture. For example, when the polyurethane solution is a dimethylformamide solution of polyurethane, a method of coagulating the polyurethane by immersing the polyurethane solution-impregnated nonwoven fabric in water is used. When the elastic polymer is an emulsion, a method of dry coagulation may be used instead of the above wet coagulation method.

After the elastic polymer is contained in the entangled nonwoven fabric, a liquid which acts as a non-solvent for the island component of the elastic polymer and the microfiber-generating fiber and acts as a solvent or decomposer for the sea component. To convert the ultrafine fiber-generating fibers into an ultrafine fiber bundle, thereby obtaining a sheet comprising an ultrafine fiber entangled nonwoven fabric and an elastic polymer. Needless to say, the sheet may be formed by using a method of transforming the ultrafine fiber-generating fibers into an ultrafine fiber bundle prior to containing the elastic polymer.

The leather-like sheet substrate thus obtained may have the following structure in order to make the wrinkles and hand feel closer to natural leather. That is,
In the step of producing the sheet substrate, a sheet substrate obtained by laminating two or more nonwoven fabrics made of fibers having different finenesses and then impregnating with an elastic polymer, or a structure having a different fineness between the back and front of the sheet substrate. And a sheet base having a multilayer structure in which a sheet base made of fine fibers and a sheet base made of fine fibers are bonded with an adhesive. In the case of having a multilayer structure, it is better that the adhesive layer is present as a discontinuous layer (for example, dot-shaped points) than on the entire interface between the two sheets. It is preferable in terms of air permeability. Also,
For the purpose of providing a waterproof function, the sheet base may have a structure in which a gas permeable film is inserted or laminated on the intermediate portion or the back surface side.

In the present invention, the raised surface of the sheet comprising the obtained entangled nonwoven fabric of ultrafine fibers and the elastic polymer needs to be colored. In the case where the coloring treatment is not performed, the contrast between the portion that looks whitish and the portion that looks dark due to separation of the polymer and the microfibers or cracks in the polymer is lost, which is not preferable because it cannot be discriminated as a grain pattern. The colorant is not particularly limited, but various dyes and pigments can be selected and used depending on the selected material.

In the present invention, the polymer applied to the surface of the leather-like sheet must be solid at room temperature and have a melting point of 60 ° C. or higher. When a polymer having a melting point of less than 60 ° C. is used, the polymer and the ultrafine fibers are not suitable because it hardly separates or a whitish portion appears due to cracks in the polymer. In many cases, the finished leather-like sheet is heated in post-processing, and the polymer covered at this time sinks into the tissue due to the heating, which is inappropriate. Preferably, it is a polymer having a melting point of 70 to 130 ° C.

The elongation at break of the polymer must be 10% or less. When a polymer having an elongation at break exceeding 10% is used, the coating film covered by the fir treatment performed after coating does not easily separate or crack, and therefore the object of the present invention is to remove the whitish portion. There is no mixing of dark-colored parts. A more preferred range is 5% or less.

The polymer applied in the present invention is preferably selected from at least one of petroleum wax, synthetic wax, polyethylene wax, paraffin wax, natural wax, and microcrystalline wax. Of course, among these waxes and waxes, there are various types such as those having a melting point of 60 ° C. or more and those having a melting point of 10% or less and those having a melting point of more than 10%. It is necessary to use one that satisfies the conditions and the elongation at break. Of course, these waxes may be used by selecting a plurality of waxes within the scope of the present invention. A part of the waxes may be modified with an amide group or a fluorine atom. Further, within a range that does not impair the effects of the present invention, for example, a paraffin-based, naphthene-based process oil, white oil, mineral oil, liquid paraffin, silicone oil, surfactants such as metal soaps, colorants and the like are added. Can be done. The preferred compounding weight ratio is preferably 20% or less. 2
If it exceeds 0%, the effect of the additive becomes remarkable and the effect of the present invention is impaired, which is not preferable.

In the present invention, by changing the melting point and the application amount of the wax to be used, it is possible to reproduce any of a rough and waxy type touch from a smooth and oily appearance. is there.
In any case, as the amount of polymer coating 1 to 100 g / m ² by solid content, particularly 5 to 50 g / m ² preferably.

In the present invention, the polymer needs to be applied so as to be present on at least the raised surface of the sheet substrate. When a polymer is applied to the surface with a so-called silver finish, the polymer does not penetrate into the inside, and the polymer is present in a floating state on the surface, and is peeled off by a slight external force, which is not appropriate. .

In order to make the surface of the sheet substrate of the present invention a raised surface, it can be carried out by a known method such as buffing or styling. Since the fluff length to be raised affects the appearance after coating or impregnating the polymer, it is adjusted by selecting the conditions of buffing and hair trimming, for example, the number of sandpaper used for buffing, the cutting speed, the pressing pressure, and the like. .

When the polymer is applied, a known method can be used. For example, the polymer is heated to a melting point or higher to make it liquid or dissolved in a solvent, and then knife-coated or Use of a method of gravure transfer, a method of dispersing the polymer in water using a surfactant or the like, and applying it as a water emulsion by spraying, a method of applying it on a sheet-like material with a gravure roll, a comma coater, or the like. Can be done. The polymer applied in the present invention needs to be present as a layer on the surface of the leather-like sheet integrally with the raised fluff. For example, when the applied polymer does not exist as a layer on the surface but merely exists so as to cover the surface of each raised fiber independently, or most of the polymer penetrates into the sheet base. If the napping surface hardly exists, the object of the present invention cannot be achieved.

In the present invention, it is necessary to perform a fir treatment in order to develop a light and shaded grain pattern after the application of the polymer.
As the fir treatment, a so-called dry fir method, in which both ends in the width direction of the leather-like sheet are gripped and processed, is preferably used. The leather-like sheet obtained by such a method has a silvery tone, a unique pattern of natural leather due to scratches, and has a unique texture and soft touch similar to natural leather.

Next, a method for making shoes using the leather-like sheet of the present invention will be described. In the present invention, when making a shoe using the above-mentioned leather-like sheet as an upper material having the polymer-coated surface as a front side, a portion of the leather-like sheet where the polymer is present in a portion to be bonded to a sole material is ground. And directly bonding and integrating the sole material and the portion substantially free of the polymer. As a method of manufacturing shoes, it is common to bond a so-called upper part and a sole part with an adhesive or the like to integrate them, but in the present invention, when a shoe is manufactured with such a configuration, In some cases, the polymer present on the surface to which the upper is adhered may not be sufficiently bonded, and a problem may occur in which the upper and the sole are separated when the shoe is used. In order to prevent such troubles, in the present invention, the portion where the polymer is adhered is ground and adhered.

The grinding amount is preferably completely removed by grinding, but a part of the polymer may remain. Examples of the grinding method include a method using a sandpaper, a wire brush, a grindstone, or the like. As the sole material,
Vulcanized rubber, EVA sponge, polyurethane, polyvinyl chloride, nylon and the like are used. Polyurethane, chloroprene, natural rubber and the like are used as an adhesive used for bonding the shoe sole and the upper, and among them, polyurethane is preferable in view of workability and the like. Examples of the method of applying the adhesive include hand coating and an automatic coater.

A shoe made of artificial leather obtained by the above-described manufacturing method has a characteristic grain pattern similar to natural leather, has a silvery tone, and remains after being scratched with a hard material. It has such a weak pattern, has a soft touch feeling, is useful as a shoe, and is suitable for trekking shoes, climbing shoes, safety shoes, general shoes, and the like.

[0034]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The parts in the examples relate to weight unless otherwise specified. In the examples, appearance and peel strength were evaluated by the following methods. The elongation at break and the melting point of the polymer applied to the surface are measured by the following methods.

[Evaluation of Appearance] The leather-like sheet having the excellent appearance with a large contrast between the part that looks dark and the part that does not, according to the visual and tactile sensations is best (◎).
Inferior ones with almost no contrast were poor (x), and the interval was divided into two types, which were classified as good (o) and normal (△).

[Peeling strength of adhesive part] width 25 mm, length 5
0mm, a 5mm thick polyurethane rubber plate and a sample of the same width are bonded with a two-component polyurethane adhesive,
After curing at 25 ° C. for 24 hours, both ends of the rubber plate and the sample were pulled at a speed of 100 mm / min using a Shimadzu Autograph Tensile Tester, and the stress was measured. The average value of the portion of the SS curve where the stress reached parallel was determined and defined as the peel strength.

[Elongation at break of polymer] The polymer was melted and formed into a dumbbell type having a width of 10 mm, and both ends were pulled by a Shimadzu autograph tensile tester to measure the elongation at break. [Polymer melting point] Measured according to the method of JIS K 2235.

Production Example 1 Nylon-6 and polyethylene were mixed in a chip form at a ratio of 50: 5.
The mixture is melt-spun by an extruder, and polyethylene is spun into a sea-island mixed spun fiber having a sea component, stretched, crimped, and cut to form a 4 dtex, 51 mm long short fiber (ultrafine fiber forming). Fiber). The fibers were cross-wrapped with a weber and needle punched at 700 punches / cm ² using a needle punching machine to obtain an entangled nonwoven fabric. Poly 3
After impregnating with a dimethylformamide solution of a methylpentane adipate diol / polyethylene glycol copolymer-based polyurethane resin and performing wet coagulation, polyethylene, which is a sea component of the fiber, was extracted with toluene at 80 ° C.
A substrate having 0 g / m ² , a thickness of 1.3 mm, and a weight ratio of polyurethane resin to fiber of 50/50 was obtained. The fineness of the resulting nylon microfine fibers of the substrate was 0.001 dtex. One side of the obtained substrate was buffed with sandpaper and dyed brown to obtain a sheet substrate whose surface was covered with nap fibers made of ultrafine nylon fibers.

Production Example 2 The same manufacturing method as in Production Example 1 was carried out except that some of the spinning raw materials and conditions were changed, and the basis weight was 650 g / m ² and the thickness was 1.5 m.
m, a sheet substrate having a polyurethane resin to fiber ratio of 40/60 was obtained. The fineness of the resulting nylon ultrafine fibers of the substrate was 0.003 dtex. One side of the obtained substrate was buffed with sandpaper and dyed brown to obtain a sheet substrate whose surface was covered with nap fibers made of ultrafine nylon fibers.

Production Example 3 Using a multi-component fiber production apparatus for forming a mixed stream by a static mixing method in which a molten polymer stream is merged at a spinning head and divided and integrated repeatedly by two extruders, and melt-spun. Then, composite spinning was performed using nylon-6 as an island component and polyethylene as a sea component, and stretched, crimped, and cut to prepare short fibers (fine fiber-forming fibers) having a length of 4 dtex and 51 mm in length. Next, a cross wrap was formed with a weber using the fibers, and needle punching at 700 punches / cm ² was performed using a needle punching machine to obtain an entangled nonwoven fabric. The entangled nonwoven fabric is impregnated with a dimethylformamide solution of a poly (3-methylpentane adipate diol / polyethylene glycol copolymer polyurethane resin) and wet-coagulated, and then polyethylene, which is a sea component of the fiber, is extracted with toluene at 80 ° C. 450g
/ M ² , a thickness of 1.3 mm, and a weight ratio of polyurethane resin to fiber of 40/60 were obtained. The fineness of the resulting nylon ultrafine fibers of the substrate was 0.07 dtex. One side of the obtained substrate was buffed with sandpaper and dyed brown to obtain a sheet substrate whose surface was covered with nap fibers made of ultrafine nylon fibers.

Production Example 4 The same production method as in Production Example 3 was carried out except that some of the spinning raw materials and the conditions were changed to a basis weight of 450 g / m ² and a thickness of 1.3 m.
m, a substrate having a polyurethane resin to fiber ratio of 40/60 was obtained. The fineness of the nylon fiber of the obtained substrate is 0.5
It was decitex. One side of the obtained substrate was buffed with sandpaper and dyed brown to obtain a sheet substrate having a raised surface made of nylon fibers.

Example 1 The sheet substrate prepared in Production Example 1 had a melting point of 1
A synthetic wax (FT-10) having a breaking elongation of 0.1% at 06 ° C.
0: Ciel MDS) into a warmable bath, 130
After applying 30 g / m ² with a gravure roll heated to 200 ° C. and heated to the same temperature of 200 mesh, fir treatment was performed using a dry-type fir treatment machine. The obtained leather-like sheet had a very high contrast between the part which appeared dark by the fir treatment and the part which did not, and exhibited a very excellent appearance.

Example 2 The sheet substrate prepared in Production Example 2 was melted at 103 ° C.
An emulsified synthetic wax having an elongation at break of 0.5% (Brian TW-86, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) was applied at 10 g / m ² by spraying, and then subjected to rubbing treatment using a dry-type rubbing machine. The resulting leather-like sheet had a large and excellent appearance in which the contrast between the portion that appeared dark and the portion that did not appear due to the fir treatment was large.

Example 3 The sheet substrate prepared in Production Example 3 was melted at 103 ° C.
An emulsified product of a synthetic wax having a breaking elongation of 0.5% (Brian TW-86, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) was applied at a rate of 20 g / m ² with a gravure roll, and then subjected to a buffing treatment using a dry-type buffing machine. The obtained leather-like sheet had a good appearance with a contrast between a portion that appeared dark by the fir treatment and a portion that was not.

Comparative Example 1 A leather-like sheet was obtained in the same manner as in Example 1 except that paraffin wax having a melting point of 53 ° C. and an elongation at break of 1.0% (paraffin wax 125, manufactured by Nippon Seiro Co., Ltd.) was used. . The obtained leather-like sheet had an appearance in which the contrast between the portion that appeared dark by the fir treatment and the portion that did not appear was small.

Comparative Example 2 A leather-like sheet was obtained in the same manner as in Example 1 except that polyethylene having a melting point (softening point) of 78 ° C. and elongation at break of 250% was used. The hue of the obtained leather-like sheet did not change before and after the rubbing treatment.

Comparative Example 3 In Example 2, a polyurethane solution was applied to the sheet base before the napping obtained in Production Example 2 to finish it with silver, and the same polymer as in Example 1 was applied to the surface. Although applied, the polymer was peeled off by the fir treatment, and the appearance was poor.

Comparative Example 4 In Example 1, a leather-like sheet was obtained by performing the same treatment as in Example 1 on the substrate composed of 0.5 decitex nylon-6 of Production Example 4. There was almost no contrast between the dark portion and the light portion before and after the fir treatment.

Example 4 A portion of the leather-like sheet obtained in Example 1 where the surface-applied polymer was present was ground and the adhesive strength was measured. The adhesive strength was 7.0 kg / 25 mm, which was sufficient for practical use as a shoe. It was something with.

Comparative Example 5 The adhesive strength of the leather-like sheet obtained in Example 1 was measured without grinding the portion where the polymer was present.
It was 4.0 kg / 25 mm, a low level unusable as a shoe.

Example 5 A portion of the leather-like sheet obtained in Example 1 where a surface-applied polymer is present at a portion to be bonded was ground and bonded to a sole material to produce a trekking shoe. did. The resulting shoes formed a grain pattern having a large contrast between the dark and light colors, and exhibited an excellent appearance.

Comparative Example 6 When the leather-like sheet obtained in Comparative Example 1 was made in the same manner as in Example 5, the resulting shoe faded during shoe making. Tables 1 and 2 show the performance and the like of the leather-like sheets obtained in the above Examples and Comparative Examples.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

The leather-like sheet obtained according to the present invention and the shoes produced therefrom have a unique grained pattern similar to natural leather, a weak scratch pattern, a so-called silver-like appearance with a writing effect, and a flexible appearance. It has a touch feeling and physical properties as shoes.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06M 11/00 D06M 11/00 4L047 13/02 13/02 15/564 15/564 // D06M 101: 34 101: 34 3/38 F term (reference) 3B154 AA07 AA08 AA09 AA17 AB22 BA14 BA23 BA25 BA39 BB58 BB59 BD18 BF01 BF07 BF18 DA09 DA13 DA30 4F050 CA08 HA05 KA06 4F055 AA03 AA27 BA12 DA07 DA17 EA05 HA03 FA03 EA12 HA03 FA03 AA14 AA20 AB34 BA32 CA15 4L033 AA08 AB07 BA00 CA50 4L047 AA14 AA21 AA23 AB08 BA03 BA04 CA06 CA08 CA12

Claims (5)

[Claims] 1. A leather-like sheet in which at least one surface of a sheet made of an entangled nonwoven fabric comprising a bundle of ultrafine fibers of 0.1 decitex or less and an elastic polymer is brushed and colored, Is covered with a polymer that is solid at room temperature and has a melting point of 60 ° C. or more and an elongation at break of 10% or less, and a portion where the interface between the polymer and the fine fibers looks whitish due to separation or cracking of the polymer and the polymer and the fine A leather-like sheet characterized by being mixed with a portion which is separated at a fiber interface or a portion of the polymer which has a small number of cracks and looks dark. 2. The leather-like sheet according to claim 1, wherein the polymer is at least one selected from the group consisting of petroleum wax, synthetic wax, polyethylene wax, paraffin wax, natural wax, and microcrystalline wax. 3. After raising and coloring at least one side of a fibrous substrate comprising an entangled nonwoven fabric of an ultrafine fiber bundle of 0.1 decitex or less and an elastic polymer, the solid is at room temperature and has a melting point of 60 ° C.
A method for producing a leather-like sheet, comprising applying a polymer having the elongation at break of not more than 10% and then subjecting the polymer to kneading. 4. A shoe made by using the leather-like sheet according to claim 1 as an upper material, wherein a portion of the leather-like sheet to be bonded to a sole material is solid at room temperature, has a melting point of 60 ° C. or more, and has an elongation at break. A method for producing artificial leather shoes, in which a portion having a polymer of 10% or less is ground and bonded and integrated with a sole material. 5. An artificial leather shoe according to claim 4.