JP2022044227A - Artificial leather - Google Patents

Abstract

To obtain an artificial leather composed of a fiber-entangled body obtained by entangling a cloth to unify to a nonwoven fabric composed of an ultrafine fiber, and a polymer elastomer, and little in fiber exfoliation by friction and kneading particularly little in appearance and physical characteristic reduction even when water-washing by a washing machine is performed.SOLUTION: An artificial leather includes: a fiber-entangled body obtained by entangling to unify a cloth to a nonwoven fabric composed of an ultrafine fiber having an average single filament diameter of 1 μm or more and 10 μm or less; and a polymer elastomer, where following requirements (1)-(3) are satisfied. (1) Both surfaces of the artificial leather are surfaces having piloerection. (2) An average piloerection length of a surface having piloerection near to the cloth of surfaces having piloerection is 50 μm or longer and 150 μm or shorter, and a CV value of piloerection length is 30% or less. (3) A resin layer is formed on an opposite side surface of a surface having piloerection near to the cloth of surfaces having piloerection, and a percentage of an area occupied by a resin part on the surface is 10% or more and 90% or less.SELECTED DRAWING: None

Description

The present invention relates to an artificial leather which is composed of a fiber entangled body in which a woven fabric is entangled and integrated with a non-woven fabric made of ultrafine fibers and a polymer elastic body, and the fiber is less likely to fall off due to rubbing or rubbing.

Natural leather-like artificial leather, which is mainly composed of a non-woven fabric mainly made of ultrafine fibers and a polymer elastic body, has excellent characteristics in comparison with natural leather such as high durability and uniformity of quality. Therefore, it is used in various fields such as clothing materials, vehicle interior materials, interiors, shoes and clothing. In particular, it is often used as a material for clothing from the viewpoint of ease of maintenance (easy care) compared to natural leather, the ability to impart functionality such as stretchability, and the flexible texture. Therefore, a method for obtaining artificial leather suitable for clothing has been proposed (see Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 2008-261082 International release 2017/033702 Japanese Unexamined Patent Publication No. 2020-090752

In the technique disclosed in Patent Document 1, the artificial leather has elasticity, and it is possible to obtain an artificial leather preferably used for a jacket or the like. Further, in the technique disclosed in Patent Document 2, it is possible to obtain clothing having artificial leather on the sleeve portion having excellent wiping performance. When artificial leather is used as clothing, from the viewpoint of easy care, when stains adhere to the artificial leather, the stains can be removed by dry cleaning or the like. However, when general artificial leather is washed with water with a washing machine for the purpose of more convenient stain removal, the appearance and physical characteristics are deteriorated because the fibers are removed due to rubbing and rubbing and the deterioration of the polymer elastic body is promoted. It is still difficult to maintain compared to other clothing materials.

Further, in the technique disclosed in Patent Document 3, by unevenly distributing polyurethane on the fluffy surface of artificial leather, the wear resistance of artificial leather can be improved to some extent, and artificial leather suitable for clothing and the like can be obtained. can. However, among the surfaces of artificial leather, the surface on which polyurethane is not unevenly distributed still has low wear resistance, and fibers often fall off due to friction or rubbing.

Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to form a fiber entangled body in which a woven fabric is entangled and integrated with a non-woven fabric made of ultrafine fibers, and a polymer elastic body, and friction or It is possible to obtain artificial leather with less fiber shedding due to kneading, and particularly less deterioration in appearance and physical properties even when washed with water using a washing machine.

As a result of repeated studies by the present inventors to achieve the above object, in the artificial leather containing a woven fabric as a constituent component, among the surfaces of the artificial leather, the ultrafine fibers on the surface side close to the woven fabric are on the surface side far from the woven fabric. It was found that the entanglement between the ultrafine fibers is weaker than that of the ultrafine fibers, and that the fibers fall off more when rubbing or kneading is applied. In addition, especially when the surface on the surface side close to the woven fabric has fluff made of ultrafine fibers, if the fluff length is too long or the fluff length varies too much, the fibers may fall off when friction or kneading is applied. I found that it would increase.

The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.

That is, the artificial leather of the present invention is an artificial leather composed of a fiber entangled body in which a woven fabric is entangled and integrated with a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 1 μm or more and 10 μm or less, and a polymer elastic body. Therefore, the following requirements (1) to (3) are satisfied.
(1) Both surfaces of the artificial leather are surfaces having fluff. (2) Of the surfaces having fluff, the average fluff length of the surface having fluff on the side closer to the woven fabric is 50 μm or more and 150 μm or less. In addition, the CV value of the fluff length is 30% or less. The ratio (area) to the surface is 10% or more and 90% or less.

According to a preferred embodiment of the artificial leather of the present invention, the polymer elastic body is a polycarbonate-based polyurethane.

According to a preferred embodiment of the artificial leather of the present invention, the resin constituting the resin layer is a polycarbonate-based polyurethane.

According to a preferred embodiment of the artificial leather of the present invention, the nonwoven fabric is made of a polyester resin, and the polyester resin contains 1 ppm or more and 500 ppm or less of a component derived from 1,2-propanediol.

According to a preferred embodiment of the artificial leather of the present invention, the biomass plastic degree defined by ISO16620 (2015) is 10% or more and 100% or less.

According to the artificial leather of the present invention, it is possible to obtain an artificial leather that has less fiber shedding due to rubbing and rubbing, and particularly has less deterioration in appearance and physical properties even when washed with water using a washing machine. Further, the artificial leather of the present invention has a graceful appearance and a flexible touch like natural leather, and can be widely used from furniture, chairs and vehicle interior materials to clothing applications, but it is particularly easy to care for. From this point of view, it is suitably used for clothing applications.

The artificial leather of the present invention is an artificial leather composed of a fiber entangled body in which a woven fabric is entangled and integrated with a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 1 μm or more and 10 μm or less, and a polymer elastic body. The following requirements (1) to (3) are satisfied.
(1) Both surfaces of the artificial leather are surfaces having fluff. (2) Of the surfaces having fluff, the average fluff length of the surface having fluff on the side closer to the woven fabric is 50 μm or more and 150 μm or less and the fluff length. (3) Of the surfaces having fluff, a resin layer is formed on the surface opposite to the surface having fluff on the side close to the woven fabric, and the ratio of the resin layer to the surface of the resin portion. (Area) is 10 to 90%. The components thereof will be described in detail below, but the present invention is not limited to the scope described below as long as the gist of the present invention is not exceeded.

[Non-woven fabric]
The nonwoven fabric according to the artificial leather of the present invention is made of ultrafine fibers having an average single fiber diameter of 1 μm or more and 10 μm or less. As a component constituting the ultrafine fiber, a polyester resin or a polyamide resin is preferably used from the viewpoint of durability, particularly mechanical strength, and it is more preferable to use a polyester resin having excellent heat resistance.

Examples of the polyester resin include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylenemethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and polyethylene-1,2-. Examples thereof include bis (2-chlorophenoxy) ethane-4,4'-dicarboxylate and the like. Among them, polyethylene terephthalate, which is the most commonly used, or a polyester copolymer containing mainly ethylene terephthalate units is preferably used.

When a polyester resin is used as a component of the ultrafine fibers, 1,2- It is preferable to contain a component derived from propanediol at 1 ppm or more and 500 ppm or less.

The concentration of the 1,2-propanediol-derived component referred to here is determined by the total amount of 1,2-propanediol detected when the polyester is decomposed and analyzed by the method described in the section of Examples. Therefore, it is considered that the structure derived from 1,2-propanediol copolymerized in the polymer chain and the total amount of 1,2-propanediol mixed between the polymers. That is, the 1,2-propanediol may be partially copolymerized in the polyester main chain, and it is permissible that the 1,2-propanediol is contained as a simple substance without being copolymerized. When the fiber contains a polymer other than polyester, polyester is selectively selected by using a solvent such as 1,1,1,3,3,3-hexafluoro-2-propanol or orthochlorophenol. After extraction and distilling off the solvent, the concentration is determined by the method described in the section of Examples.

The components constituting the ultrafine fibers include inorganic particles such as titanium oxide, lubricants, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents and antibacterial agents according to various purposes and within a range that does not impair the object of the present invention. Agents and the like can be added.

The cross-sectional shape of the ultrafine fiber is preferably a round cross section from the viewpoint of processing operability, but polygonal shapes such as ellipse, flat and triangular, fan-shaped and cross-shaped, hollow type, Y-shaped, T-shaped, and U-shaped. It is also possible to adopt a cross-sectional shape of a deformed cross section such as a mold.

The average single fiber diameter of the ultrafine fibers according to the present invention is 1 μm or more and 10 μm or less. By setting the average single fiber diameter of the ultrafine fibers to 1.0 μm or more, preferably 1.5 μm or more, more preferably 2.0 μm or more, the color development property after dyeing, light resistance, friction fastness, and stability during spinning are improved. It has an excellent effect. On the other hand, by setting the thickness to 10.0 μm or less, preferably 6.0 μm or less, more preferably 5.0 μm or less, artificial leather having a fine and soft touch and excellent surface quality can be obtained.

In the present invention, the average single fiber diameter of ultrafine fibers is defined as the single fiber diameter (single fiber diameter) by taking a scanning electron microscope (SEM) photograph of an artificial leather cross section and randomly selecting 10 circular or near-circular elliptical ultrafine fibers. It shall be calculated by measuring μm), calculating the arithmetic mean value of 10 lines, and rounding to the second digit after the decimal point. However, when an ultrafine fiber with a modified cross section is used, the cross-sectional area (μm ² ) of the single fiber is first measured, and the diameter when the cross section is regarded as a circle, that is, the equivalent circle diameter is calculated. It is assumed that the diameter (μm) of the fiber is obtained.

Further, the artificial leather of the present invention has the non-woven fabric made of the above-mentioned ultrafine fibers as a constituent element, that is, in the artificial leather, an aggregate of the ultrafine fibers forms a non-woven fabric. By using a non-woven fabric, not only can a uniform and graceful appearance be obtained when the surface is raised, but also artificial leather having a soft texture can be obtained.

As the form of the non-woven fabric, either a long-fiber non-woven fabric such as a spunbond non-woven fabric or a melt-blow non-woven fabric, or a short-fiber non-woven fabric composed of fibers of a certain length can be adopted. Since it is easy, a short fiber non-woven fabric is a preferable embodiment.

The fiber length of the ultrafine fibers when made into a short fiber non-woven fabric is preferably 25 to 90 mm. By setting the fiber length to 90 mm or less, more preferably 80 mm or less, still more preferably 70 mm or less, the obtained artificial leather has good quality and texture. On the other hand, by setting the fiber length to 25 mm or more, more preferably 35 mm or more, still more preferably 40 mm or more, artificial leather having excellent wear resistance can be obtained.

[fabric]
As the type of fiber constituting the woven fabric according to the artificial leather of the present invention, it is preferable to use a filament yarn, a spun yarn, a mixed composite yarn of a filament yarn and a spun yarn, and the like, from the viewpoint of durability, particularly mechanical strength and the like. Therefore, it is more preferable to use a multifilament made of a polyester resin or a polyamide resin.

The average single fiber diameter of the fibers constituting the woven fabric is preferably 1 μm or more and 50 μm or less. By setting the average single fiber diameter of the fibers constituting the woven fabric to 50.0 μm or less, more preferably 15.0 μm or less, still more preferably 13.0 μm or less, artificial leather having excellent flexibility can be obtained. On the other hand, when the average single fiber diameter is 1.0 μm or more, more preferably 8.0 μm or more, still more preferably 9.0 μm or more, the morphological stability of the product as artificial leather is improved.

In the present invention, the average single fiber diameter of the fibers constituting the woven fabric is determined by taking a scanning electron microscope (SEM) photograph of an artificial leather cross section, randomly selecting 10 fibers constituting the woven fabric, and determining the single fiber diameter of the fibers. It shall be calculated by measuring and calculating the arithmetic average value of 10 fibers and rounding to the second digit after the decimal point. However, when a fiber with a modified cross section is used, the cross-sectional area (μm ² ) of the fiber is first measured and the cross section is measured in the same manner as in the case of measuring and calculating the average single fiber diameter of the ultrafine fibers constituting the non-woven fabric. It is assumed that the diameter (μm) of the fiber is obtained by calculating the diameter when it is regarded as a circle, that is, the diameter equivalent to a circle.

When the fibers constituting the woven fabric are multifilaments, the total fineness of the multifilaments is "8.3.1 Fineness" of "8.3 Fineness" of JIS L1013: 2010 "Chemical Fiber Filament Thread Test Method" b. ) B method (simple method) ”, and it is preferably 30 dtex or more and 170 dtex or less.

By setting the total fineness of the multifilament constituting the woven fabric to 170 dtex or less, more preferably 150 dtex or less, artificial leather having excellent flexibility can be obtained. On the other hand, by setting the total fineness to 30 dtex or more, not only the morphological stability of the product as artificial leather is improved, but also when the nonwoven fabric and the woven fabric are entangled and integrated by a needle punch or the like, the fibers constituting the woven fabric are formed. It is preferable because it is less likely to be exposed on the surface of artificial leather. At this time, the total fineness of the multifilaments of the warp and weft may be the same or different.

Further, in the case of the multifilament constituting the woven fabric, the twist number is preferably 1000 to 4000 T / m. By setting the twist number to 4000 T / m or less, more preferably 3500 T / m or less, still more preferably 3000 T / m or less, artificial leather having excellent flexibility can be obtained, and the twist number is 1000 T / m or more, more preferably 3000 T / m or less. By setting the value to 1500 T / m or more, more preferably 2000 T / m or more, it is possible to prevent damage to the fibers constituting the woven fabric when the non-woven fabric and the woven fabric are entangled and integrated by a needle punch or the like, and the machine of artificial leather. It is preferable because it has excellent target strength.

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

The weaving density of the woven fabric is preferably adjusted so that both the warp and weft are 40 threads / 2.54 cm to 200 threads / 2.54 cm in the artificial leather. By setting the weaving density of the woven fabric constituting the artificial leather to 40 pieces / 2.54 cm or more, more preferably 60 pieces / 2.54 cm or less, artificial leather having excellent morphological stability can be obtained. On the other hand, by setting the weaving density of the woven fabric constituting the artificial leather to 200 / 2.54 cm or less, more preferably 150 / 2.54 cm or less, not only the texture of the artificial leather can be made flexible, but also the non-woven fabric can be made flexible. When the woven fabric and the woven fabric are entangled and integrated, the entanglement of the fibers of the non-woven fabric is not hindered, and as a result, the fiber dropout of the artificial leather can be suppressed.

[Polymer elastic body]
The polymer elastic body constituting the artificial leather of the present invention serves as a binder for gripping the ultrafine fibers in the artificial leather. Therefore, it is preferable to use polyurethane, polyurethane, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), acrylic resin or the like as the polymer elastic body so that the artificial leather has a more flexible texture. Above all, it is more preferable to use polyurethane as a main component. By using polyurethane, it is possible to obtain artificial leather having a full feel, a leather-like appearance, and physical characteristics that can withstand actual use. The term "main component" as used in the present invention means that the mass of polyurethane is more than 50% by mass with respect to the mass of the entire polymer elastic body.

When polyurethane is used in the present invention, both an organic solvent-based polyurethane used in a state of being dissolved in an organic solvent and a water-dispersible polyurethane used in a state of being dispersed in water can be adopted. Further, as the polyurethane, a polyurethane obtained by reacting a polymer diol with an organic diisocyanate and a chain extender is preferably used.

When polyurethane is used in the present invention, the polymer diol used is at least one selected from a polyester diol having an average molecular weight of 500 or more and 3000 or less, a polyether diol, a polycarbonate diol, or a polymer diol such as a polyester polyether diol. Although various types of polymer diols can be used, it is preferable that polyurethane contains a polycarbonate diol having excellent hydrolysis resistance, which does not easily impair the function as a binder against repeated washing.

Further, for the polymer elastic body, various additives such as pigments such as carbon black, flame retardants such as "phosphorus-based, halogen-based and inorganic-based", and "phenol-based, sulfur-based and phosphorus-based" are used depending on the purpose. Antioxidants such as "benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based and oxalic acid anilide-based" UV absorbers, light stabilizers such as "hindered amine-based and benzoate-based", polycarbodiimide Hydrolysis-resistant stabilizers such as, plasticizers, antistatic agents, surfactants, coagulation modifiers, dyes and the like can be contained.

Generally, the content of the polymer elastic body in the artificial leather can be appropriately adjusted in consideration of the type of the polymer elastic body to be used, the method for producing the polymer elastic body, the texture and the physical properties, but in the present invention. The content of the polymer elastic body is preferably 20% by mass or more and 50% by mass or less with respect to the mass of the non-woven fabric. By setting the content of the polymer elastic body to 20% by mass or more, more preferably 25% by mass or more, the wear resistance of the artificial leather can be improved. On the other hand, by setting the content of the polymer elastic body to 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, the artificial leather can be made more flexible. can.

[Resin layer]
The resin used in the resin layer in the present invention is a polymer compound having rubber elasticity that expands and contracts, and for example, polyurethane, SBR, NBR, acrylic resin and the like are preferably used. Above all, it is more preferable to use polyurethane as a main component. By using polyurethane, it is possible to obtain artificial leather having a full feel, a leather-like appearance, and physical characteristics that can withstand actual use.

When polyurethane is used in the present invention, both an organic solvent-based polyurethane used in a state of being dissolved in an organic solvent and a water-dispersible polyurethane used in a state of being dispersed in water can be adopted. Further, as the polyurethane, a polyurethane obtained by reacting a polymer diol with an organic diisocyanate and a chain extender is preferably used.

As the polyol, for example, a polycarbonate-based diol, a polyester-based diol, a polyether-based diol, a silicone-based diol, a fluorine-based diol, or a copolymer obtained by combining these can be used. Above all, it is preferable to use a polycarbonate-based diol from the viewpoint of light resistance and hydrolysis resistance.

The polycarbonate-based diol can be produced by a transesterification reaction between an alkylene glycol and a carbonic acid ester, a reaction between a phosgen or a chloraterate and an alkylene glycol, or the like.

Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol. Linear alkylene glycol, branched alkylene glycol such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1 , Alicyclic diols such as 4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, pentaerythritol and the like.

In the present invention, either a polycarbonate diol obtained from a single alkylene glycol or a copolymerized polycarbonate diol obtained from two or more types of alkylene glycol can be used.

Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and xylylene diisocyanate, and aromatic polyisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. Can be used in combination. Among them, aromatic polyisocyanates such as diphenylmethane diisocyanate are preferable when durability and heat resistance are important, and aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferable when light resistance is important. A polyisocyanate system is preferably used.

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

The resin used in the resin layer in the present invention may contain elastomer resins such as polyester, polyamide and polyolefin, acrylic resins and ethylene-vinyl acetate resins as long as the wear resistance and texture are not impaired. .. In addition, these resins include various additives such as pigments such as carbon black, flame retardants such as phosphorus-based, halogen-based and inorganic-based, antioxidants such as phenol-based, sulfur-based and phosphorus-based, and benzotriazoles. Ultraviolet absorbers such as systems, benzophenone-based, salicylate-based, cyanoacrylate-based and oxalic acid-anilide-based, light stabilizers such as hindered amine-based and benzoate-based, hydrolysis-resistant stabilizers such as polycarbodiimide, plasticizers, and anti-electricity resistance. Agents, surfactants, coagulation modifiers, dyes and the like can be contained.

In the present invention, the proportion (area) of the resin portion on the surface is 10 to 90%. By setting the proportion (area) of the resin portion on the surface of the resin portion to 10% or more, more preferably 20% or more, still more preferably 30% or more, the artificial leather on the side opposite to the surface having fluff on the side close to the woven fabric. It is possible to prevent the fibers from falling off from the surface. On the other hand, when the proportion (area) of the resin portion on the surface is 90% or less, more preferably 85% or less, still more preferably 80% or less, the tactile sensation of the artificial leather becomes excellent.

In the present invention, the ratio (area) to the surface of the resin portion is the ratio of the area of the resin portion to the area of the artificial leather by taking a scanning electron microscope (SEM) photograph of the surface of the surface having the resin layer of the artificial leather. Obtained by calculation.

[Artificial leather]
The artificial leather of the present invention is composed of the above-mentioned fiber entangled body and a polymer elastic body, and both surfaces of the artificial leather are surfaces having fluff. First, among the surfaces having fluff, the surface having fluff on the side closer to the woven fabric will be described. In the present invention, the surface having fluff refers to a surface having a raised layer of ultrafine fibers having a length and directional flexibility to the extent that a so-called finger mark is expressed by tracing the surface with a finger. The side closer to the woven fabric is the side where the distance from the center of the woven fabric to the surface with fluff, which is the center point of the highest point and the lowest point in the thickness direction of the woven fabric, is short when a cross-sectional photograph of the artificial leather is taken. Refers to the face of.

The average fluff length of the surface having fluff on the side close to the woven fabric is 50 μm or more and 150 μm or less. When the average fluff length is 50 μm or more, preferably 60 μm or more, more preferably 80 μm or more, the friction of the surface having the fluff on the side close to the woven fabric can be reduced, and the ultrafineness generated when the artificial leather is kneaded can be reduced. It is possible to prevent the fibers from falling off. On the other hand, by setting the average nap length to 150 μm or less, preferably 130 μm or less, more preferably 120 μm or less, it is possible to suppress the entanglement of the fluffed ultrafine fibers when the artificial leather is kneaded, resulting in lumps and falling off of the fibers. It can be suppressed from being lost.

Further, the CV value (Coefficient of Variation) of the fluff length of the surface having fluff on the side close to the woven fabric is 30% or less. When the CV value of the nap length is 30% or less, preferably 25% or less, more preferably 20% or less, the fibers having a long nap length and the short fibers are mixed, and only the long fibers are entangled, resulting in ultrafine fibers. It is possible to prevent the fibers from falling off. The lower limit of the CV value of the nap length is not particularly limited, but is preferably 5% or more from the viewpoint of process stability and productivity.

Next, the opposite side of the side having fluff on the side close to the fabric will be described. The fluff on the opposite side of the surface having the fluff on the side close to the fabric preferably has an average fluff length of 100 μm or more, more preferably 150 μm or more, and 200 μm or more so as to obtain an elegant appearance. It is more preferable to have. On the other hand, in order to suppress fiber dropout during friction, it is preferably 400 μm or less, and more preferably 350 μm or less.

In the present invention, the average fluff length and the CV value of the fluff length are obtained by photographing the cross section of the artificial leather with a scanning electron microscope (SEM) at a magnification of 50 times with the fluff of the artificial leather turned upside down using a lint brush or the like. The height of the napped portion (layer consisting only of ultrafine fibers) is measured at 10 points, and the average value and the CV value are calculated.

Further, the artificial leather of the present invention preferably satisfies the following formula (i) in the cross section of the artificial leather in the thickness direction.

B> A / 2 ... (i)
Here, A is the thickness (μm) of the woven fabric, and B is the distance (μm) between the woven fabric and the surface having fluff on the side close to the woven fabric. When A and B satisfy the formula (i), it means that the layer of the non-woven fabric covering the woven fabric is thin, and the layer of the woven fabric is damaged when forming the fluff on the side close to the woven fabric during manufacturing. Since it becomes difficult, artificial leather having high mechanical strength can be used. Furthermore, even if the fibers on the surface fall off, the woven fabric can be less likely to be exposed on the surface, so that artificial leather can be obtained that does not impair the appearance quality even during long-term use. Become.

The above formula (i) preferably satisfies the following formula (i').

A> B ... (i')
In the present invention, the thickness A (μm) of the woven fabric is obtained by photographing the cross section of the artificial leather with a scanning electron microscope (SEM, for example, “VE-7800” manufactured by KEYENCE CORPORATION) at a magnification of 50 to 200 times. The height is measured at 10 points and the average value is calculated. Also, the distance B (μm) between the woven fabric and the surface with fluff on the side close to the woven fabric is also the distance between the woven fabric and the surface with fluff on the side close to the woven fabric (using the image used in the calculation of A). (Including the napped part) is measured at 10 points and the average value is calculated.

In the artificial leather of the present invention, the thickness of the artificial leather measured by "6.1.1 A method" of "6.1 thickness (ISO method)" of JIS L1913: 2010 "general nonwoven fabric test method" is 0. It is preferably in the range of .2 mm or more and 1.0 mm or less. By setting the thickness of the artificial leather to 0.2 mm or more, more preferably 0.3 mm or more, still more preferably 0.4 mm or more, not only the workability at the time of manufacturing is excellent, but also the texture is excellent. It will be. On the other hand, by setting the thickness to 1.0 mm or less, more preferably 0.9 mm or less, still more preferably 0.8 mm or less, a flexible artificial leather having excellent moldability can be obtained.

Further, the artificial leather of the present invention preferably has a biomass plastic degree of 10% or more as defined by ISO16620 (2015) from the viewpoint of carbon neutrality. From the viewpoint of reducing the environmental load, the biomass plastic degree is more preferably 15% or more, and further preferably 20% or more.

Further, the artificial leather of the present invention is subjected to the washing test of one piece of the artificial leather at the time of the washing test according to the ISO6330 (2012) C4N method, and the fiber debris adhering to the collection bag attached to the drain hose after the test is removed. , The amount of fiber waste when collected using a membrane filter is preferably 10.0 (mg / artificial leather 100 cm ² ) or less. Above all, by 8.0 (mg / artificial leather 100 cm ² ) or less, more preferably 6.0 (mg / artificial leather 100 cm ² ) or less, still more preferably 5.0 (mg / artificial leather 100 cm ² ) or less. , Artificial leather has less fiber dropout during washing and has less environmental load.

In the present invention, during the washing test according to the ISO6330 (2012) C4N method, the washing test of the artificial leather is carried out, and after the test, the fiber debris adhering to the collection bag attached to the drain hose is removed by using a membrane filter. The amount of fiber waste when collected using is a value calculated by measuring in the following procedure.
(1) Collect a test piece 100 cm ² from artificial leather.
(2) Wash the washing machine according to the ISO6330 (2012) C4N method without putting the object to be washed and detergent in the washing machine.
(3) Test piece 1 to be evaluated with a collection bag manufactured using a "nylon screen"("NY10-HC" (manufactured by Freon Industries, Ltd.)) with a 10 μm opening attached to the drain hose of the washing machine. The sheets are placed in a washing machine and washed according to the ISO6330 (2012) C4N method. However, detergent and load cloth shall not be used.
(4) After washing, the fiber debris adhering to the "nylon screen" is suction-filtered using a polycarbonate membrane ("K040A047A" (manufactured by Advantech Toyo Co., Ltd.)) whose mass has been measured in advance.
(5) The polycarbonate membrane after filtration and the fiber debris are dried at 105 ° C. for 1 hour, the mass of the residue is measured, and the difference from the mass before filtration is taken as the amount of fiber debris at the time of washing.

Further, the artificial leather of the present invention is prepared by JIS L1096: 2010 "8.19.5 E method (Martindale method)" of "8.19 Abrasion strength and frictional discoloration" of "Fabric test method of woven fabric and knitted fabric". In the wear resistance test to be measured, the pressing load is 12.0 kPa, and the mass reduction of the artificial leather after being worn 20000 times is preferably 10 mg or less, preferably 8 mg or less on both sides of the artificial leather. Is more preferable, and 6 mg or less is further preferable. When the mass reduction on both sides of the artificial leather is 10 mg or less, it is possible to prevent contamination due to fluffing during actual use and fiber loss during washing.

[Manufacturing method of artificial leather]
The method for producing artificial leather of the present invention is a sheet-like material composed of a fiber entangled body in which a woven fabric is entangled and integrated with a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 1 μm or more and 10 μm or less, and a polymer elastic body. A method for producing artificial leather that forms fluff on both surfaces, the average fluff length of the surface on the side close to the woven fabric is 50 μm or more and 150 μm or less, and the CV value of fluff tone is 30% or less. It is manufactured. Hereinafter, the method for producing the artificial leather of the present invention will be further described in detail.

The fiber entangled body used in the method for producing artificial leather of the present invention is obtained by entwining and integrating a woven fabric with a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 1 μm or more and 10 μm or less. Even if ultrafine fibers having an average single fiber diameter of 1 μm or more and 10 μm or less are used as the fibers constituting the non-woven fabric before being entangled and integrated with the woven fabric, the average single fiber diameter is 1 due to the ultrafine fibers being made into ultrafine fibers in a later step. Although ultrafine fiber-expressing fibers capable of expressing ultrafine fibers of 0.0 μm or more and 10.0 μm or less may be used, preferably, by using ultrafine fiber-expressing fibers, when the non-woven fabrics are entangled with each other, or It is possible to prevent damage to the ultrafine fibers when the non-woven fabric and the woven fabric are entangled with each other.

When ultrafine fiber-expressing fibers are used, two components of thermoplastic resins having different solvent solubility are used as a sea component and an island component, and the above sea component is dissolved and removed using a solvent or the like to make the island component ultrafine. Kaishima-type composite fibers used as fibers, and peel-type composite fibers in which two-component thermoplastic resins are alternately arranged in a radial or multi-layered manner and each component is separated and divided into ultrafine fibers. Can be adopted.

Above all, the sea-island type composite fiber can provide an appropriate void between the island components, that is, between the ultrafine fibers inside the fiber bundle by removing the sea component, and therefore, from the viewpoint of the texture and surface quality of the artificial leather. Is also preferably used.

For the sea-island type composite fiber, a method using a sea-island type composite base and a polymer mutual arrangement in which two components of the sea component and the island component are mutually arranged and spun, and a method of mixing the two components of the sea component and the island component are mixed. A mixed spinning method or the like can be used, but from the viewpoint of obtaining ultrafine fibers having a uniform single fiber fineness, a sea-island type composite fiber by a method using a polymer mutual arrangement is preferably used.

As the sea component of the sea-island type composite fiber, polyethylene, polypropylene, polystyrene, a copolymerized polyester obtained by copolymerizing sodium sulfoisophthalic acid, polyethylene glycol, or the like, polylactic acid, or the like can be used. Among them, polystyrene and copolymerized polyester are preferably used from the viewpoint of silk-reeling property and easy elution property.

When the above-mentioned sea-island type composite fiber is used, it is preferable to use the sea-island type composite fiber in which the strength of the island component fiber is 0.3 cN or more. When the strength of the island component fiber is 0.3 cN or more, more preferably 0.35 cN or more, still more preferably 0.4 cN or more, the wear resistance of the artificial leather can be improved.

In the present invention, the strength of the island component fiber of the sea-island type composite fiber shall be calculated by the following method.
(1) Bundle 10 sea-island type composite fibers with a length of 20 cm.
(2) After dissolving and removing the sea component from the sample of (1), it is air-dried.
(3) Grasp length 5 cm, tensile speed 5 cm / min in "8.5.1 Standard time test" of "8.5 Tensile strength and elongation" of JIS L1013: 2010 "Chemical fiber filament yarn test method". , Test 10 times under the condition of load 2N (N = 10).
(4) The value obtained by rounding off the arithmetic mean value (cN) of the test results obtained in (3) to the third decimal place is taken as the strength of the island component fiber of the sea-island type composite fiber.

Next, the obtained ultrafine fiber-expressing fiber is formed into a fiber web by a cloth wrapper or the like, and entangled to obtain a nonwoven fabric. As a method of entwining the fiber webs to obtain a nonwoven fabric, a needle punch, a water jet punch, or the like can be used.

As the form of the non-woven fabric, either the short-fiber non-woven fabric or the long-fiber non-woven fabric can be used as described above, but the short-fiber non-woven fabric has more ultrafine fibers facing the thickness direction of the artificial leather than the long-fiber non-woven fabric. , It is preferable because a high degree of fineness can be obtained on the surface of the artificial leather when it is raised.

In the case of a short fiber non-woven fabric, the obtained ultrafine fiber-expressing fiber is preferably subjected to a crimping process, cut to a predetermined length, and then made into a non-woven fabric. At this time, a known method can be used for the crimping process and the cutting process.

To entangle and integrate the woven fabric into the non-woven fabric, the woven fabric is laminated on one or both sides of the non-woven fabric, or the non-woven fabric is sandwiched between a plurality of non-woven fabric webs and then subjected to needle punching or water jet punching. And the method of entwining the fibers of the woven fabric can be adopted.

When the needle punching process is used, the barb direction of the needle of the needle punch is set to 90 ± 25 °, which is preferably orthogonal to the traveling direction of the non-woven fabric and the woven fabric, so that the weft of the fragile woven fabric is hooked. It becomes difficult.

Further, when the water jet punching treatment is used, it is preferable that the water in the water jet punching treatment is performed in a columnar flow state. Specifically, it is a preferred embodiment to eject water from a nozzle having a diameter of 0.05 to 1.0 mm at a pressure of 1 to 60 MPa.

The apparent density of the fiber entangled body after the needle punching treatment or the water jet punching treatment is preferably 0.15 g / cm3 or more and 0.45 g / cm3 or less. By setting the apparent density to preferably 0.15 g / cm3 or more, artificial leather having excellent morphological stability and dimensional stability can be obtained. On the other hand, by setting the apparent density to preferably 0.45 g / cm3 or less, a sufficient space for imparting a polymer elastic body can be formed.

When the woven fabric is laminated on one side or both sides of the non-woven fabric, it is preferable to entangle and integrate the woven fabric so that the fibers constituting the non-woven fabric completely cover the woven fabric. More specifically, in a fiber entangled fabric in which a woven fabric is entangled and integrated with a non-woven fabric, it is preferable that the woven fabric is not exposed on the surface of the fiber entangled fabric.

It is also a preferable embodiment that the fiber entangled body is subjected to a heat shrinkage treatment with warm water or steam in order to improve the denseness of the fibers.

Further, the water-soluble resin can be imparted by impregnating the fiber entanglement with an aqueous solution of a water-soluble resin and drying the fiber entangled body. By applying the water-soluble resin to the fiber entanglement, the fibers are fixed and the dimensional stability is improved. The water-soluble resin referred to here is a resin having a hydrophilic group and having a property that the solution becomes a viscous liquid when dissolved in water, and specifically, polyvinyl alcohol (specifically, polyvinyl alcohol (). Hereinafter, PVA may be abbreviated) and polyvinylpyrrolidone (hereinafter, may be abbreviated as PVP).

When ultrafine fiber-expressing fibers are used as the fibers constituting the non-woven fabric, the obtained fiber entanglement is treated with a solvent, and the average single fiber diameter from the ultrafine fiber-expressing fibers is 1 μm or more and 10 μm or less. Expresses ultrafine fibers. The expression treatment of the ultrafine fibers can also be performed after the application of the polymer elastic body described later.

When the ultrafine fiber-expressing fiber is a sea-island type composite fiber, an organic solvent such as toluene or trichlorethylene can be used as the solvent for dissolving and removing the sea component when the sea component is polyethylene, polypropylene or polystyrene. When the sea component is a copolymerized polyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide can be used. Further, when the sea component is a water-soluble thermoplastic polyvinyl alcohol-based resin, hot water can be used.

Then, the fiber entangled body in which the woven fabric is entangled and integrated with the non-woven fabric is impregnated with the solution of the polymer elastic body and solidified to impart the polymer elastic body. In this case, as a method of fixing the polymer elastic body to the non-woven fabric, a wet coagulation method in which a solution of the polymer elastic body is impregnated into a fiber entangled body and then immersed in a coagulating liquid such as water to coagulate, or There is a dry coagulation method in which the solvent in the solution of the polymer elastic body is removed by heating to perform coagulation, and these methods can be appropriately selected depending on the type of the polymer elastic body to be used.

As the solvent used for imparting polyurethane as a polymer elastic body, N, N'-dimethylformamide, dimethyl sulfoxide and the like are preferably used. Further, an aqueous dispersion type polyurethane liquid in which polyurethane is dispersed as an emulsion in water may be used.

When a fiber entangled body in which a woven fabric is laminated on both sides of the non-woven fabric is used, it is a preferable embodiment to cut the obtained sheet in half in the thickness direction.

Further, a sheet-like material (including a half-cut material) composed of the fiber entangled body and the polymer elastic body is subjected to a raising treatment to form fluff, and a fluff sheet is obtained. This raising treatment can be performed by a method such as grinding using sandpaper or the like. It is also a preferred embodiment to apply a lubricant such as a silicone emulsion or an antistatic agent before the raising treatment.

When the raising treatment is performed using sandpaper, in the raising treatment of the surface on the side close to the woven fabric, the roughness of the sandpaper, the grinding resistance, etc. It is preferable to adjust by.

Further, it is preferable that the fluffy sheet is shirred at least on the surface close to the woven fabric. By applying the shirring process, the fluff length on the surface close to the woven fabric can be made more uniform, and the CV value of the fluff length of the obtained artificial leather can be easily set to 30% or less.

The above-mentioned fluff sheet can be dyed if necessary. The dyeing process includes, for example, a liquid flow dyeing process using a jigger dyeing machine or a liquid flow dyeing machine, a dip dyeing process such as a thermosol dyeing process using a continuous dyeing machine, or roller printing, screen printing, inkjet printing, and sublimation. It is possible to use a printing treatment on a napped surface by printing, vacuum sublimation printing, or the like. Above all, it is preferable to use a liquid flow dyeing machine in terms of quality and quality because a flexible texture can be obtained.

Further, a resin layer is formed on the surface of the above-mentioned fluff sheet on the side opposite to the surface having fluff on the side close to the woven fabric to obtain artificial leather.

Examples of the method for forming the resin layer in the present invention include a method of forming a resin layer by drying after coating by a screen method such as a flat screen or a rotary screen or a gravure coating method, or on a supporting base material such as a release paper. A method of forming a resin layer by applying an adhesive to the surface of the resin film after forming a discontinuous resin film, adhering the resin film to the surface of the base material, and peeling off the release paper. Can be mentioned.

The surface of the artificial leather can be designed as needed. For example, post-processing such as perforation and other drilling, embossing, laser processing, pinsonic processing, and printing can be performed.

Next, the artificial leather of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Next, the evaluation method used in the examples and the measurement conditions thereof will be described. However, in the measurement of each physical property, if there is no particular description, the measurement is performed based on the above method.

[Measurement method and processing method for evaluation]
(1) Amount of fiber waste during washing A test piece of 10 cm × 10 cm (100 cm ² ) was cut out from artificial leather, and a washing test was carried out by the above method to calculate the amount of fiber waste. The measurement was performed twice, and the average value was taken as the amount of fiber waste at the time of washing.

(2) Percentage (area) of the resin part on the surface
The surface of the artificial leather (the surface having the resin layer) was observed at a magnification of 100 times using a scanning electron microscope (SEM, manufactured by Keyence Corporation, "VE-7800"). A range of 3 cm × 3 cm was cut out from the obtained observation image, and the ratio of the total area of the resin portion was calculated. The measurement was performed three times, and the average value was taken as the ratio of the resin portion to the surface.

(3) Content of component derived from 1,2-propanediol in polyester First, a 1000 μg / ml aqueous solution of 1,2-butanediol was prepared, and this was used as an internal standard solution A. Weigh 0.1 g of the sample into a vial, add 0.015 ml of internal standard solution A and 1 ml of ammonia water to the vial, seal tightly, heat at a temperature of 150 ° C. for 3 hours, and then allow to cool to room temperature (25 ° C.). did. Subsequently, 2 ml of methanol and 2.0 g of terephthalic acid were added, and the mixture was shaken for 15 minutes and centrifuged at 4000 G for 3 minutes. Take out the supernatant, measure it with a gas chromatograph (5890 series II manufactured by Hewlett-Packard, injection port: split / splitless injection port, detector: hydrogen flame ionization detector) under the following setting conditions, and use the calibration curve described later. The content was determined.
・ Injector temperature: 220 ℃
-Column head pressure: 20 psi
-Carrier gas: Helium-Sample introduction method: Division (Linear flow velocity 25 ml / min)
・ Septum purge: helium 3.0 ml / min ・ Sample introduction amount: 1.0 μl
・ Detector temperature: 220 ℃
・ Gas flow rate: hydrogen 40 ml / min, air 400 ml / min, nitrogen 40 ml / min ・ oven temperature rise start temperature: 60 ° C (holding time 2 minutes)
・ Oven temperature rise stop temperature: 220 ° C (holding time 2 minutes)
-Oven heating rate: 20 ° C / min (straight slope).

The calibration curve of 1,2-propanediol was prepared by the following procedure. After preparing a 1000 μg / ml aqueous solution of 1,2-propanediol to prepare a standard mother liquor B, add 0.003 to 0.08 ml of the standard mother liquor B and 0.025 ml of the internal standard solution A in a 5 ml volumetric flask and mix them. Seven kinds of standard solution C prepared with a solvent (methanol: purified water = 2: 1, containing 1.1% ethylene glycol) were prepared by changing the amount of standard mother liquor B. The amount of the standard mother liquor B to be added is selected so as to have a concentration of 1,2-propanediol sufficient for measuring the sample. The prepared standard solution C was measured by gas chromatography under the above conditions, and then the peak area ratio of the obtained 1,2-propanediol and the internal standard substance and the 1,2-propanediol in the standard solution C were used. A calibration curve of 1,2-propanediol was prepared by plotting the concentration ratio of the internal standard substance on the graph.

(4) Thickness of the woven fabric (A) and the distance between the woven fabric and the surface having fluff on the side close to the woven fabric (B).
The cross section of the artificial leather was observed at a magnification of 100 times using a scanning electron microscope (SEM, manufactured by KEYENCE Co., Ltd., "VE-7800"), and the thickness (A) of the woven fabric and the woven fabric and the woven fabric were obtained by the above method. The distance (B) between the surface having the fluff on the near side was calculated. The measurement was performed three times, and the average value was taken as the ratio of the resin portion to the surface.

[Example 1]
<Process for manufacturing fiber entanglement>
Polyethylene terephthalate (PET A) having an intrinsic viscosity (IV value) of 0.73 as an island component, using ethylene glycol derived from a biomass resource as a polymerization component and containing 15 ppm of a component derived from 1,2-propanediol is used, and a sea component. Using polystyrene with an MFR of 65 and a sea-island type composite base with 16 islands / hole, the spinning temperature is 285 ° C, the island / sea mass ratio is 80/20, and the discharge rate is 1.2 g / min. -Melting spinning was performed under the conditions of holes and spinning speed of 1100 m / min. Then, it was stretched 2.7 times in an oil bath for spinning at a temperature of 90 ° C., crimped using a push-in crimping machine, and then cut to a length of 51 mm to form a sea-island type composite. The raw cotton of the fiber was obtained.

Next, using the raw cotton of the above-mentioned sea-island type composite fiber, a laminated web is formed through a curd and cross wrapper steps, and an ethylene glycol derived from a biomass resource having an intrinsic viscosity (IV value) of 0.65 is polymerized. A multifilament made from polyethylene terephthalate (average single fiber diameter: 11 μm, total fineness: 84 dtex) twisted at 2500 T / m was used for both weft and warp, and the weaving density was 95. A plain woven fabric (with a grain of 75 g / m ² ) having a / 2.54 cm and a weft of 76 lines / 2.54 cm is laminated on the upper and lower sides of the laminated web, and needle punched with a punch number of 2500 lines / cm ² to obtain a grain. A fiber entangled body having a thickness of 3.0 mm was obtained at 700 g / m ² .

The fiber entanglement obtained as described above is shrink-treated with hot water at a temperature of 96 ° C., impregnated with a PVA aqueous solution having a saponification degree of 88% and a 5% by mass, and then squeezed with a roll to obtain a temperature. The PVA was dried while migrating with hot air at 120 ° C. for 10 minutes to obtain a sheet with PVA having a PVA mass of 7.5% by mass based on the mass of the fiber entanglement.

By immersing the sheet with PVA obtained as described above in trichloroethylene and squeezing and compressing it with a mangle 10 times, the sea components are dissolved and removed and the sheet with PVA is compressed to obtain an ultrafine fibrous nonwoven fabric. A sheet with desea PVA made of PVA was obtained.

<Step of applying polymer elastic body>
The sheet with desea PVA obtained as described above is put into a dimethylformamide (hereinafter, abbreviated as DMF) solution of polyurethane (PU A, polycarbonate type) adjusted to a solid content concentration of 11.3%. After soaking, it was squeezed with a roll, and then the polyurethane was solidified in an aqueous solution having a DMF concentration of 30%. Then, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet with polyurethane having a thickness of 2.4 mm and a polyurethane mass of 27 mass% with respect to the mass of the fiber entanglement. Obtained.

The polyurethane-attached sheet obtained as described above was cut in half vertically in the thickness direction to obtain a half-cut sheet having a thickness of 1.2 mm.

<Step of forming fluff on both surfaces of sheet-like material>
The surface of the half-cut sheet obtained as described above on the side close to the woven fabric is ground with sandpaper count 320 endless sandpaper, and the surface on the opposite side close to the woven fabric is sandpaper count 180 endless sandpaper. A brushed sheet having a thickness of 0.9 mm was obtained by grinding with paper to form a raised surface.

The raised sheet obtained as described above is dyed black with a disperse dye under a temperature condition of 120 ° C. using a liquid flow dyeing machine, dried and set in width, and the dyed nap sheet is obtained. Obtained.

<Step of applying the resin layer>
Polycarbonate polyurethane was applied discontinuously to the surface of the dyed fluff sheet obtained as described above on the opposite side of the surface on the side close to the woven fabric using a rotary coating method, and further close to the woven fabric. The surface on the side was shirred to obtain artificial leather. The results are shown in Table 1. The obtained artificial leather has an average short fiber diameter of 4.2 μm, a thickness of 1.0 mm, and a grain size of 300 g / m ² , and the average nap length of the surface having fluff on the side close to the woven fabric is 95 μm. The value was 14%, the thickness of the woven fabric was 290 μm, and the distance between the woven fabric and the surface having naps on the side closer to the woven fabric was 170 μm. The ratio of the resin portion of the artificial leather to the surface was 80%, and the amount of fiber waste during washing was 1.5 (mg / artificial leather 100 cm ² ), and the fiber loss during washing was extremely small.

[Example 2]
<Process for manufacturing fiber entanglement>
Implemented except that polyethylene terephthalate (PET B), which has an intrinsic viscosity (IV value) of 0.73 as an island component, uses ethylene glycol derived from petroleum resources as a polymerization component, and does not contain a component derived from 1,2-propanediol. In the same manner as in Example 1, raw cotton of sea-island type composite fiber was obtained.

Next, using the raw cotton of the above-mentioned sea-island type composite fiber, a laminated web is formed through a curd and cross wrapper steps, and further, an intrinsic viscosity (IV value) of 0.65 and ethylene glycol derived from petroleum resources are polymerized. A multifilament made from polyethylene terephthalate (average single fiber diameter: 11 μm, total fineness: 84 dtex) twisted at 2500 T / m was used for both weft and warp, and the weaving density was 95. A plain woven fabric (75 g / m 2 with a grain of 75 g / m ² ) having a / 2.54 cm and a weft of 76 / 2.54 cm is laminated on the upper and lower sides of the laminated web, and needle punched with a punch number of 2500 / cm ² to obtain a grain. A fiber entangled body having a thickness of 3.0 mm was obtained at 700 g / m2.

A sheet with desea PVA was obtained in the same manner as in Example 1 except that the fiber entanglement obtained as described above was used.

<Step of applying a polymer elastic body-Step of applying a resin layer>
An artificial leather was obtained in the same manner as in Example 1 except that the sheet half-cut sheet with desea PVA obtained as described above was used. The results are shown in Table 1. The obtained artificial leather has an average short fiber diameter of 4.2 μm, a thickness of 1.0 mm, and a grain size of 300 g / m ² , and the average nap length of the surface having fluff on the side close to the woven fabric is 94 μm. The value was 16%, the thickness of the woven fabric was 294 μm, and the distance between the woven fabric and the fluffy surface on the side closer to the woven fabric was 166 μm. The ratio of the resin portion of the artificial leather to the surface was 80%, and the amount of fiber waste during washing was 2.1 (mg / artificial leather 100 cm ² ), so that the fiber was less likely to fall off during washing.

[Example 3]
<Process of manufacturing fiber entangled body-process of applying polymer elastic body>
A half-cut sheet having a thickness of 1.2 mm was obtained in the same manner as in Example 1.

<Step of forming fluff on both surfaces of sheet-like material-step of applying resin layer>
The half-cut sheet obtained as described above was obtained in the same manner as in Example 1 except that the surface on the side close to the woven fabric was not shirred to obtain artificial leather. The results are shown in Table 1. The obtained artificial leather has an average short fiber diameter of 4.2 μm, a thickness of 1.0 mm, and a grain size of 300 g / m ² , and the average nap length of the surface having fluff on the side close to the woven fabric is 133 μm. The value was 24%, the thickness of the woven fabric was 290 μm, and the distance between the woven fabric and the fluffy surface on the side closer to the woven fabric was 170 μm. The ratio of the resin portion of the artificial leather to the surface was 80%, and the amount of fiber waste during washing was 3.2 (mg / artificial leather 100 cm ² ), so that the fiber was less likely to fall off during washing.

[Comparative Example 1]
<Process of manufacturing fiber entangled body-process of applying polymer elastic body>
A half-cut sheet having a thickness of 1.2 mm was obtained in the same manner as in Example 1.

<Step of forming fluff on both surfaces of sheet-like material-step of applying resin layer>
Examples of the half-cut sheet obtained as described above, except that the surface on the side close to the woven fabric was ground with sandpaper count 180 endless sandpaper and the surface on the side close to the woven fabric was not shirred. Artificial leather was obtained in the same manner as in 1. The results are shown in Table 1. The obtained artificial leather has an average short fiber diameter of 4.2 μm, a thickness of 1.0 mm, and a grain size of 300 g / m ² , and the average nap length of the surface having fluff on the side close to the woven fabric is 172 μm. The value was 35%, the thickness of the woven fabric was 287 μm, and the distance between the woven fabric and the surface having naps on the side closer to the woven fabric was 191 μm. In this artificial leather, the amount of fiber waste during washing was 8.8 (mg / artificial leather 100 cm ² ), and the amount of fiber dropped during washing was large.

Claims (5)

An artificial leather composed of a fiber entangled body in which a woven fabric is entangled and integrated with a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 1 μm or more and 10 μm or less, and a polymer elastic body, and the following requirements (1) to Artificial leather that satisfies (3).
(1) Both surfaces of the artificial leather are surfaces having fluff. (2) Of the surfaces having fluff, the average fluff length of the surface having fluff on the side closer to the woven fabric is 50 μm or more and 150 μm or less and the fluff length. (3) Of the surfaces having fluff, a resin layer is formed on the surface opposite to the surface having fluff on the side close to the woven fabric, and the ratio of the resin layer to the surface of the resin portion. (Area) is 10% or more and 90% or less. The artificial leather according to claim 1, wherein the polymer elastic body is a polycarbonate-based polyurethane. The artificial leather according to claim 1 or 2, wherein the resin constituting the resin layer is a polycarbonate-based polyurethane. The artificial leather according to any one of claims 1 to 3, wherein the nonwoven fabric is made of a polyester resin and contains 1 ppm or more and 500 ppm or less of a component derived from 1,2-propanediol in the polyester resin. The artificial leather according to any one of claims 1 to 4, wherein the biomass plastic degree specified in ISO 16620 (2015) is 10% or more and 100% or less.