JP2021021159A - Napped artificial leather - Google Patents

Abstract

To provide a napped artificial leather having a deep color and excellent in color migration resistance while maintaining a high-class feeling of a surface appearance and a soft feeling in a napped artificial leather comprising a fiber entangled body obtained by entangling colored ultra fine fibers.SOLUTION: A napped artificial leather comprises a fiber entangled body obtained by entangling colored fibers having an average diameter of 0.7 to 7 μm and (meth) acrylic polymer particles attached to a surface of the fibers and having an average particle diameter of 0.1 to 0.9 μm, and has a napped surface on which a fiber is napped. The fibers include a color pigment in an amount of 1 to 8 mass%. The napped surface has a lightness L*value of 20 or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a napped artificial leather having a napped surface in which fibers are napped, such as suede leather.

Raised artificial leather having a raised surface such as suede is preferably used as a surface material for bags, shoes, clothing, furniture, car seats, miscellaneous goods and the like. The napped artificial leather includes a fiber entangled body such as a non-woven fabric and a polymer elastic body impregnated with the fiber entangled body, and has a napped surface in which fibers are napped on at least one surface.

As a fiber used for producing napped artificial leather, polyester is often used because it can be dyed, has a small change in water absorption, and has excellent durability. However, since polyester has a low refractive index, it has a drawback that it is difficult to color it in a deep color.

The following Patent Documents 1 to 4 disclose a technique for darkening a fabric which is a woven or knitted fabric made of a polyester multifilament.

For example, Patent Document 1 is a cloth containing dyed polyester fibers whose surface is coated with an aqueous resin, and the L value of the cloth is 10.5 or less, and the water fastness is discolored or contaminated. Discloses a dark-colored polyester fabric having a grade 4 or higher, and having a discoloration and fading of washing fastness and a contamination of grade 4 or higher. Then, Patent Document 1 discloses a fluorine-based resin, a silicon-based resin, and a urethane-based resin as the water-based resin that coats the surface of the dyed polyester fiber.

Further, in Patent Document 2, after adhering a cationizing agent to a colored fiber structure, it is treated with a treatment liquid containing a film-forming resin and inorganic fine particles, and a film-forming resin is applied to the surface of the colored fiber structure. And a method for processing a fiber structure by forming a film containing inorganic fine particles. Then, Patent Document 2 discloses a silicone-based resin, a urethane-based resin, and a fluorine-based resin as the film-forming resin.

Further, Patent Document 3 discloses a polyester-based composite fiber structure containing a disperse dye and a polyester fiber containing a mesoporous substance such as mesoporous silica having a size of 0.5 to 10 times the disperse dye size.

Further, in Patent Document 4, in a polyester multifilament having a single yarn fineness of 0.11 to 1.0 decitex, polyester containing inorganic fine particles as a fine pore forming agent is used as a fiber raw material, and fine irregularities are present on the filament surface. Disclosed are dark-colored polyester mixed yarns and woven and knitted fabrics using the same.

Japanese Unexamined Patent Publication No. 2003-3372 Japanese Unexamined Patent Publication No. 2005-2525 Japanese Unexamined Patent Publication No. 2003-27342 Japanese Unexamined Patent Publication No. 2001-164434

The method disclosed in Patent Document 1 is a method of coating the surface of the dyed polyester fiber with a film-forming resin having a low refractive index such as a fluororesin, a silicone resin, or a urethane resin. When an appropriate amount of the film-forming resin is applied, there are problems that the ultrafine fibers are bundled to deteriorate the surface appearance and the texture is hardened. Further, the method disclosed in Patent Document 2 is also a method of coating the ultrafine fibers of the colored fiber structure with a film-forming resin such as a silicone-based resin, a urethane-based resin, or a fluorine-based resin. There is a problem that the formable resin bundles ultrafine fibers to deteriorate the surface appearance and harden the texture.

Further, the method disclosed in Patent Document 3 is a method of forming a fine concave structure on the surface of the polyester fiber and darkening the color by blending the polyester fiber with inorganic fine particles which are mesoporous substances. Further, the method disclosed in Patent Document 4 is also a method of blending inorganic fine particles with fibers to form a fine concave structure on the fiber surface to darken the color. When these methods are applied to ultrafine fibers that are difficult to darken, if an amount of inorganic fine particles is added to sufficiently darken the color, the mechanical properties of the fibers are greatly reduced and friction with other articles causes the fibers to become darker. There is a problem that fluffing is likely to occur and the color transfer resistance is lowered. Therefore, when a method of blending such inorganic fine particles with ultrafine fibers to darken the color is applied to napped artificial leather, it is difficult to maintain high color transfer resistance.

In particular, the techniques disclosed in Patent Documents 1 to 4 relating to the improvement of darkening of woven and knitted fabrics made of multifilaments are applied to ultrafine fibers that are diffusely reflected and tend to appear light in color because the fiber directions are random. When applied to napped artificial leather containing non-woven fabric, it was difficult to obtain a sufficient darkening effect. Further, when the above-mentioned method is applied to napped artificial leather containing ultrafine fibers, it is difficult to obtain a high-quality surface appearance and a soft texture.

According to the present invention, in a napped artificial leather containing a fiber entangled body in which colored ultrafine fibers are entangled, fluff that is dark in color and has excellent color transfer resistance while maintaining a high-quality surface appearance and a soft texture. The purpose is to provide artificial leather.

One aspect of the present invention is a fiber entangled body in which colored fibers having an average diameter of 0.7 to 7 μm are entangled, and (meth) acrylic having an average particle size of 0.1 to 0.9 μm adhering to the surface of the fibers. It contains polymer particles, and has a fluffy surface on which fibers are fluffed, the fiber contains 1 to 8% by mass of a coloring pigment, and the fluffy surface is a color coordinate space (L ^* a ^* b ^* color). It is a napped artificial leather having a lightness L ^* value of 20 or less in space). In such fluffy artificial leather, the fibers are roughened by the (meth) acrylic polymer particles adhering to the surface of the fibers, so that the reflectance on the fiber surface is reduced and the color is darkened. Further, since the (meth) acrylic polymer particles are not blended inside the ultrafine fibers but adhered to the surface of the ultrafine fibers, a large amount of inorganic fine particles are blended for darkening. Compared to ultrafine fibers, it is less likely to cause fluffing due to friction with other articles. Further, since the fiber is colored by containing 1 to 8% by mass of a coloring pigment, it maintains darkening, high fastness and color transfer resistance. Further, since the (meth) acrylic polymer particles do not form a film on the surface of the fiber, the high-quality appearance and soft texture of the surface appearance of the napped surface are not easily impaired. The result is a napped artificial leather that is dark in color and has excellent color transfer resistance while maintaining a high-class appearance and a soft texture.

Further, it is preferable that the (meth) acrylic polymer particles contain a methacrylic polymer containing 50% by mass or more of methacrylic monomer units from the viewpoint that the shape of the particles can be easily maintained without softening even in a high temperature environment.

Further, it is preferable that the (meth) acrylic polymer particles have at least one of a thermal melting temperature of 140 ° C. or higher and a glass transition temperature (Tg) of 70 ° C. or higher from the viewpoint of being particularly excellent in darkening.

Further, it is preferable that the content ratio of the (meth) acrylic polymer particles is 0.05 to 1.5% by mass from the viewpoint of excellent balance between the high-class appearance of the surface, the soft texture and the darkening.

Further, the inclusion of silicone adhering to the surface of the fiber suppresses the formation of (meth) acrylic polymer particles into a film or coarse particles, and the (meth) acrylic particles are in the state of primary particles. It is preferable because the polymer particles are easily attached to the surface of the fiber. In addition, silicone also has the effect of imparting slipperiness to the surface of the fiber and suppressing diffused reflection on the surface of the fiber without deteriorating the mechanical properties of the fiber or bundling the fiber to harden the texture. Further, as the silicone, amino-modified silicone is preferable from the viewpoint of excellent effects of darkening and softening.

Further, it is preferable that the content ratio of silicone is 0.01 to 1% by mass from the viewpoint of excellent effects of darkening and softening.

In addition, the mass ratio of (meth) acrylic polymer particles to silicone ((meth) acrylic polymer particles: silicone) is 95: 5 to 70:30, which gives a deeper color, a high-quality surface, and is soft. It is preferable because it has a particularly excellent texture.

Further, it is preferable that the total content ratio of the (meth) acrylic polymer particles and the silicone is 0.1 to 2% by mass, because it is particularly excellent in darkening, surface quality, and soft texture.

Further, it is preferable that the coloring pigment contains carbon black because it is more excellent in darkening, fastness and color transfer resistance.

Further, it is preferable to further include a polymer elastic body impregnated in the fiber entangled body from the viewpoint of giving a feeling of fullness to the napped artificial leather and improving morphological stability.

According to the present invention, in a napped artificial leather containing a fiber entangled body in which colored ultrafine fibers are entangled, a dark color and excellent color transfer resistance are excellent while maintaining a high-class appearance and a soft texture. A fluffy artificial leather can be obtained.

FIG. 1 is a scanning electron microscope (SEM) photograph of the surface of fibers contained in the napped artificial leather obtained in Example 1. FIG. 2 is an SEM photograph of the surface of the fiber contained in the napped artificial leather obtained in Comparative Example 1.

The napped artificial leather of the present embodiment has a fiber entangled body in which colored fibers having an average diameter of 0.7 to 7 μm are entangled, and a fiber entangled body having an average particle size of 0.1 to 0.9 μm attached to the surface of the fibers (polymer). ) Acrylic polymer particles are contained, and at least one surface thereof has a napped surface on which fibers are napped, the fibers contain 1 to 8% by mass of a coloring pigment, and the napped surface is a color coordinate space (L ^* a ^* b). ^* Color space) is a napped artificial leather with a lightness L ^* value of 20 or less.

FIG. 1 is an SEM photograph of the surface of the fibers forming the fiber entanglement contained in the napped artificial leather obtained in Example 1 described later. Referring to FIG. 1, the fluffy artificial leather of the present embodiment contains (meth) acrylic polymer particles P having an average particle size of 0.1 to 0.9 μm adhering to the surface of the fiber F. In addition, the napped artificial leather contains a polymer elastic body E.

First, a fiber entangled body in which colored fibers having an average diameter of 0.7 to 7 μm are entangled will be described. The fiber entangled body is a fiber structure in which colored fibers having an average diameter of 0.7 to 7 μm are entangled. Examples of the fiber structure include non-woven fabrics, woven fabrics, knitted fabrics, and fiber entanglements in which these are combined. As the fiber entanglement, a non-woven fabric is particularly preferable because the effect of darkening according to the present invention becomes remarkable.

As a method for forming fibers having an average diameter of 0.7 to 7 μm, for example, a sea island in which a resin of a sea component for forming a fiber having an average diameter of 0.7 to 7 μm and a resin of an island component to be removed later are composited. Examples thereof include a method of forming ultrafine fiber generation type fibers such as type composite fibers and peeling split type fibers, and converting the ultrafine fiber generation type fibers into ultrafine fibers to form fiber bundle-like ultrafine fibers. When the fiber entanglement in which colored fibers having an average diameter of 0.7 to 7 μm are entangled is a non-woven fabric, the web, which is an aggregate of ultrafine fiber generation type fibers, is entangled by a needle punch method or a water flow entanglement method. After the treatment, a non-woven fabric is obtained by subjecting the ultrafine fiber generation type fiber to an ultrafine fiber by a known method.

As a method for producing a web of ultrafine fiber generation type fibers, a method of collecting long fiber sea-island type composite fibers spun by a spunbond method or the like on a net without cutting to form a long fiber web, or Examples thereof include a method of cutting melt-spun long fibers into staples to form a web of short fibers. Among these, it is particularly preferable to use a long fiber web from the viewpoint that the entangled state can be easily adjusted and a high sense of fulfillment can be obtained. In addition, the formed web may be subjected to a fusion treatment in order to impart its morphological stability. In addition, in any of the steps from removing the sea component of the sea-island type composite fiber to forming the ultrafine fiber, the sea-island type composite fiber is subjected to fiber shrinkage treatment such as heat shrinkage treatment by steam, hot water or dry heat. It may be densified.

The long fiber means a continuous fiber that is not a short fiber intentionally cut after spinning. Specifically, for example, it means a filament or a continuous fiber that is not a short fiber intentionally cut so that the fiber length is about 3 to 80 mm. The fiber length of the sea-island type composite fiber before being made into ultrafine fibers is preferably 100 mm or more, and unless it is technically manufacturable and inevitably cut in the manufacturing process, it is several meters, several hundred meters, or several. The fiber length may be km or longer.

Specific examples of the resin forming fibers having an average diameter of 0.7 to 7 μm include polyethylene terephthalate (PET), isophthalic acid-modified PET, sulfoisophthalic acid-modified PET having cationic dye dyeability, polybutylene terephthalate, and poly. Aromatic polyesters such as hexamethylene terephthalate; aliphatic polyesters such as polylactic acid, polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvariate copolymer; nylon 6, nylon 66 , Nylon 10, Nylon 11, Nylon 12, Nylon 6-12, etc .; Polyester, Polyethylene, Polybutene, Polymethylpentene, Chlorine-based polyolefin, etc. Polyester; Modified polyvinyl alcohol containing 25 to 70 mol% of ethylene unit, etc. Modified polyvinyl alcohol; and thermoplastic resins such as polyurethane-based elastoma, polyamide elastoma, and elastoma such as polyester elastoma. These may be used alone or in combination of two or more. Among these, polyester is preferable because the effect of darkening tends to be remarkable.

Further, as the resin used as the sea component of the sea-island type composite fiber, a polymer having higher solubility in a solvent or higher decomposability by a decomposing agent than the resin of the island component is selected. Specific examples of such sea component resins include water-soluble polyvinyl alcohol-based resins (water-soluble PVA), polyethylene, polypropylene, polystyrene, ethylene-propylene-based copolymers, ethylene-vinyl acetate-based copolymers, and the like. Examples thereof include a styrene-ethylene copolymer and a styrene-acrylic copolymer. Among these, water-soluble PVA is preferable because it can be dissolved and removed by an aqueous medium without using an organic solvent, and therefore has a low environmental load.

Fibers having an average diameter of 0.7 to 7 μm are colored fibers containing 1 to 8% by mass of a coloring pigment. Here, the coloring pigment is a pigment that darkens the fiber by being blended with the fiber. By blending a coloring pigment in the fiber and coloring it, the fastness of the obtained napped artificial leather can be enhanced. In the coloring of napped artificial leather, the method of coloring the resin forming the fiber with a coloring pigment may be combined with the coloring with a dye.

The type of coloring pigment is not particularly limited. Specific examples thereof include carbon black, phthalocyanine pigments, quinone pigments and the like. Among these, carbon black is preferable because it easily darkens the fibers and is excellent in fastness.

The proportion of the coloring pigment blended in the fiber is 1 to 8% by mass, preferably 2 to 7% by mass. When the proportion of the coloring pigment blended in the fiber exceeds 8% by mass, the mechanical properties of the fiber are deteriorated, and friction with other articles tends to cause fluffing. Further, when the proportion of the coloring pigment blended in the fiber is less than 1% by mass, a large amount of dye is absorbed in order to form a dark fluffy surface having a lightness L ^* value of 20 or less. In that case, the fastness is lowered and the color transfer resistance is lowered.

In addition to coloring pigments, fibers having an average diameter of 0.7 to 7 μm may be provided with antioxidants, ultraviolet absorbers, fluorescent agents, heat stabilizers, etc., as necessary, as long as the effects of the present invention are not impaired. Various stabilizers, deodorants, fungicides, lubricants, water repellents, oil repellents, bulking agents, inorganic fine particles, conductive agents and the like may be contained.

Fibers with an average diameter of 0.7-7 μm have an average diameter of 0.7-7 μm, preferably 0.8-6 μm, more preferably 1-5 μm. When the average diameter of the fibers exceeds 7 μm, it becomes difficult to obtain a high-quality surface appearance having a graceful fluffy feeling due to the napped fibers. On the other hand, when the average diameter of the fiber is less than 0.7 μm, the color development property is lowered, so that it is difficult to obtain a dark color having a lightness L ^* value of 20 or less, and the mechanical properties of the fiber are lowered. As a result, fluffing is likely to occur due to friction with other articles, and color transfer resistance is also reduced.

The average diameter of the fibers was taken as the average value of the 15 fiber diameters selected evenly by taking a 3000-fold magnification photograph of a cross section parallel to the thickness direction of the fluffy artificial leather with a scanning electron microscope (SEM). Desired.

Further, the napped artificial leather may contain a polymer elastic body impregnated with the fiber entanglement. The polymer elastic body improves the fullness and morphological stability of the napped artificial leather.

Specific examples of the polymer elastic body include polyurethane, acrylonitrile elastomer, olefin elastomer, polyester elastomer, polyamide elastomer, and acrylic elastomer. Of these, polyurethane is preferred.

Since the polymer elastic body has elasticity, the glass transition temperature (Tg) is low, and the polymer elastic body forms a film in the drying step, so that it does not adhere to the fibers as fine particles. In that respect, the polymer elastic material is distinguished from (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm.

In addition, the polymer elastic body may also be colored in order to produce colored napped artificial leather. The method for coloring the polymer elastic body is not particularly limited, and examples thereof include a method in which the polymer elastic body contains a coloring pigment.

The content ratio of the polymer elastic body is preferably 5 to 45% by mass, more preferably 8 to 40% by mass, and particularly preferably 8 to 35% by mass with respect to the mass of the napped artificial leather. When the content ratio of the polymer elastic body is in such a range, the effect of imparting the polymer elastic body can be obtained, and a dark-colored napped artificial leather having a lightness L ^* value of 20 or less can be obtained. It is preferable because it is easy.

The napped artificial leather of the present embodiment has a napped surface in which the fibers of the fiber entanglement are napped, at least on one surface thereof. Such a napped surface is formed by buffing the surface of the fiber entangled body with a contact buff, an emery buff, or the like. The buffing is preferably performed using, for example, sandpaper or emery paper having a count of 120 to 600.

Further, on the napped surface of the napped artificial leather, the napped fibers are made of napped fibers for the purpose of improving the appearance quality by suppressing the fluffy fibers from coming off and making the fibers less likely to be caused by friction. A polymer elastic body that locally fixes the vicinity of the root may be further provided. Specifically, for example, a solution or emulsion containing a polymer elastic body is applied to a fluff surface and then dried to solidify the polymer elastic body. By imparting a polymer elastic body that locally fixes the vicinity of the roots of the napped fibers existing on the nap surface, the vicinity of the roots of the fibers existing on the nap surface is restrained by the polymer elastic body, and the fibers are elementary. It becomes difficult to pull out.

In addition, for napped artificial leather, if necessary, kneading softening treatment, reverse seal brushing treatment, antifouling treatment, hydrophilic treatment, lubricant treatment, antioxidant treatment, ultraviolet absorber treatment, fluorescent agent treatment, flame retardant Finishing treatment such as treatment may be performed.

As described above, the napped artificial leather may be colored by dyeing in combination with coloring by a coloring pigment. The type of dye used for dyeing is not particularly limited, and specific examples thereof include disperse dyes, acid dyes, cationic dyes, sulfur dyes, gold-containing dyes, and slene dyes. The dyeing method used for dyeing is appropriately selected according to the type of fiber and the type of dye, and specific examples thereof include high-pressure liquid flow dyeing method, jigger dyeing method, thermosol continuous dyeing method, and wins. Examples include a dyeing method.

The fluffy artificial leather of the present embodiment contains (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm adhering to the surface of the fiber. Such (meth) acrylic polymer particles impart a large number of fine protrusions to the surface of the fiber to roughen the surface of the fiber, reduce the surface reflectance, and darken the color. The (meth) acrylic polymer means an acrylic polymer containing 50% by mass or more of an acrylic monomer unit, or a methacrylic polymer containing 50% by mass or more of a methacrylic monomer unit. Such a (meth) acrylic polymer is obtained by polymerizing, for example, a composition of an ethylenically unsaturated monomer containing 50% by mass or more of an acrylic monomer or a methacrylic monomer by a polymerization method such as emulsion polymerization or suspension polymerization. And get it.

The (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm adhering to the surface of the fiber have, for example, that the average particle size of the (meth) acrylic polymer particles contained in the emulsion or dispersion is 0. It is derived from the fact that it is 1 to 0.9 μm. The average particle size of the (meth) acrylic polymer particles contained in the emulsion or dispersion means a median diameter D ₅₀ measured using a laser diffraction type particle size distribution measuring device. The average particle size of the (meth) acrylic polymer particles adhering to the surface of the fiber maintains the average particle size of the (meth) acrylic polymer particles adjusted as an emulsion or a dispersion. Therefore, the average particle size of the (meth) acrylic polymer particles attached to the fiber surface of the napped artificial leather can be directly measured with a scanning electron microscope (SEM).

Examples of the method for directly measuring the average particle size of the (meth) acrylic polymer particles adhering to the fiber surface of the napped artificial leather include the following methods. The surface layer cross section parallel to the thickness direction of the fluffy artificial leather is magnified 3000 times with a scanning electron microscope (SEM), and 15 points are uniformly obtained as the average value of all particle sizes contained in the selected image. it can.

The average particle size of such (meth) acrylic polymer particles is 0.1 to 0.9 μm, preferably 0.15 to 0.7 μm. When the average particle size is less than 0.1 μm, the effect of darkening the fluffy artificial leather is reduced, or the primary particles are likely to aggregate and the distribution of the particle size of the particles adhering to the fibers becomes wide and dense. Spots are likely to occur in the colorization effect. Further, when the average particle size exceeds 0.9 μm, diffused reflection is likely to occur on the surface of the fiber, thereby reducing the effect of darkening the napped artificial leather.

When the (meth) acrylic polymer particles have a glass transition temperature (Tg) of 80 ° C. or higher and further 100 ° C. or higher, a large number of fine protrusions are formed on the surface of the fiber to roughen the surface of the fiber. It is preferable because it is easy and it is difficult to cause color transfer due to adhesion. The upper limit of the glass transition temperature (Tg) is not particularly limited, but is preferably about 200 ° C. from the viewpoint of availability. When the Tg of the (meth) acrylic polymer particles is too low, the adhesiveness tends to be high and the plurality of (meth) acrylic polymer particles tend to be fused to make the protrusions larger.

Further, it is preferable that the (meth) acrylic polymer particles have a heat melting temperature of 140 ° C. or higher because a large number of fine protrusions are formed on the surface of the fiber and the surface of the fiber is easily roughened. The upper limit of the heat melting temperature is not particularly limited, but is preferably about 250 ° C. from the viewpoint of availability. If the heat melting temperature of the (meth) acrylic polymer particles is too low, the heat of the drying process during manufacturing makes it easier to melt, increasing the adhesiveness and fusing a plurality of (meth) acrylic polymer particles. By doing so, there is a tendency to make the protrusions larger.

The (meth) acrylic polymer forming the (meth) acrylic polymer particles is obtained by, for example, polymerizing a monomer composition in which the following ethylenically unsaturated monomers are combined by emulsion polymerization, suspension polymerization or the like. Polymer particles can be mentioned.

Specific examples of the ethylenically unsaturated monomer include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl (meth) acrylate, n-butyl acrylate, and isobutyl acrylate. Cyclohexyl acrylate, benzyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, diacetone acrylamide, isobutyl methacrylate, isopropyl methacrylate , Acrylic acid, methacrylic acid, acrylamide, acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, (meth) acrylamide, diacetone (meth) acrylamide, methyl methacrylate, maleic acid, itaconic acid, fumaric acid, methacrylic acid Cyclohexyl, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinylamide, ethylene, propylene, vinylpyrrolidone, isopropylacrylic acid, n-hexyl methacrylate, n-hexyl acrylate, methyl acrylate , N-butyl methacrylate, hydroxypropyl methacrylate, vinyl acetate, methyl acrylate, n-butyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like.

Further, in the monomer composition in which the ethylenically unsaturated monomer is combined, a crosslinkable monomer for forming a crosslinked structure in the polymer by having polyfunctionality may be used in combination. By forming the crosslinked structure, the heat melting temperature of the (meth) acrylic polymer particles is raised, and it is suppressed that a plurality of (meth) acrylic polymer particles are fused to enlarge the protrusions, and the surface of the fiber is formed. A large number of fine protrusions are formed to facilitate roughening the surface of the fiber. Specific examples of such crosslinkable monomers include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. , 1,6-Hexanediol di (meth) acrylate and other polyfunctional ethylenically unsaturated monomers; various monomers having hydroxyl groups such as (meth) acrylate 2-hydroxyethyl and (meth) acrylate 2-hydroxypropyl; Examples thereof include polyfunctional ethylenically unsaturated monomers having a reactive group forming a crosslinked structure, such as a (meth) acrylic acid derivative having an epoxy group such as glycidyl (meth) acrylate.

The (meth) acrylic polymer particles include silicone-modified (meth) acrylic polymer particles obtained by copolymerizing silicone, ether-modified (meth) acrylic polymer particles, fluorine-modified (meth) acrylic polymer particles, and urethane-modified (meth) acrylic polymer particles. Various modified (meth) acrylic polymer particles such as meta) acrylic polymer particles may be included.

The ethylenically unsaturated monomer, the crosslinkable monomer, or various modified (meth) acrylic polymer particles may be used alone or in combination of two or more.

As the (meth) acrylic polymer, methacrylic is used because a plurality of (meth) acrylic polymer particles are difficult to fuse due to the heat of the drying process during production and easily form a large number of fine protrusions on the surface of the fiber. A methacrylic polymer containing 50% by mass or more, more preferably 60% by mass or more of the system monomer unit is particularly preferable.

Further, it is preferable that the napped artificial leather of the present embodiment further contains silicone adhering to the surface of the fiber. Silicone makes it difficult for (meth) acrylic polymer particles to aggregate and facilitates the formation of fine protrusions on the surface of the fiber.

As the silicone, various silicones can be used. Specific examples of the types of silicone include alkyl silicone, phenyl silicone, amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, ether-modified silicone, mercapto-modified silicone, fluorine-modified silicone, hydrogen group-containing silicone, and hydroxyl group-containing silicone. Examples thereof include alkoxysilicone. These may be used alone or in combination of two or more. Further, the silicone may be a non-reactive silicone or a reactive silicone. Among these, amino-modified silicone, epoxy-modified silicone, and ether-modified silicone, particularly amino-modified silicone, are preferable because they tend to form fine protrusions on the surface of the fiber. Further, the properties of the silicone may be a liquid such as oil, a viscous body, a solid such as granules, or a film-forming one. Further, in the production of napped artificial leather, it is preferable that the leather is adjusted to an emulsion or suspension from the viewpoint of excellent handleability.

When the silicone is solid, it is preferable that the thermal melting temperature of the silicone is 140 ° C. or higher because a large number of fine protrusions are formed on the surface of the fiber and the surface of the fiber is easily roughened. Even if the heat melting temperature of the silicone is too low, the heat of the drying process during manufacturing makes it easier to melt, increasing the adhesiveness and fusing multiple (meth) acrylic polymer particles to create protrusions. It tends to be easier to make larger.

The content ratio of the (meth) acrylic polymer particles contained in the fluffy artificial leather is 0.05 to 1.5% by mass, and further 0.1 to 0.5% by mass, which is fine on the surface of the fiber. It is preferable from the viewpoint that various protrusions are easily formed. When the content ratio of the (meth) acrylic polymer particles is too low, it tends to be difficult for fine protrusions to be sufficiently formed on the surface of the fiber. Further, when the content ratio of the (meth) acrylic polymer particles is too high, the color transfer resistance tends to be lowered and the touch feeling of the surface tends to be lowered.

Further, the content ratio of silicone contained in the fluffy artificial leather is preferably 0 to 2% by mass, more preferably 0.01 to 1% by mass, from the viewpoint of facilitating the formation of fine protrusions on the fiber surface. .. If the silicone content is too low, the effect of facilitating the formation of fine protrusions on the surface of the fiber tends to be insufficient. Further, when the content ratio of silicone is too high, the color transfer resistance tends to be lowered and the touch feeling of the surface tends to be lowered.

Further, the total content ratio of the (meth) acrylic polymer particles and the silicone contained in the napped artificial leather is 0.1 to 2% by mass, and further, 0.2 to 1% by mass is darkened. It is preferable from the viewpoint that the effect of improving the above is sufficiently exhibited. If the total content of the (meth) acrylic polymer particles and the silicone is too high, the color transfer resistance tends to decrease and the touch feeling on the surface tends to decrease.

The mass ratio of (meth) acrylic polymer particles to silicone ((meth) acrylic polymer particles: silicone) is 100: 0 to 70:30, and moreover, 95: 5 to 70:30. It is preferable because fine protrusions are easily formed on the surface of the fiber, the surface appearance and soft texture are good, and the color transfer resistance is also excellent.

The napped artificial leather of the present embodiment has a fiber entangled body in which colored fibers having an average diameter of 0.7 to 7 μm are entangled, and a fiber entangled body having an average particle size of 0.1 to 0.9 μm attached to the surface of the fibers (polymer). ) Acrylic polymer particles, preferably silicone attached to the surface of the fiber. Then, (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm adhering to the surface of the fiber, or (meth) acrylic polymer particles and silicone when silicone is contained, are attached to the surface of the fiber. Form fine protrusions.

In the production of the fluffy artificial leather of the present embodiment, as a method of adhering (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm and, if necessary, silicone to the surface of the fibers, the fluffy artificial leather is used. In the step after the coloring is completed, after impregnating the napped artificial leather with a dispersion liquid or an emulsion containing (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm and, if necessary, silicone. , The method of pulling up and drying the dispersion medium can be mentioned. The drying conditions for the dispersion medium are that the (meth) acrylic polymer particles and silicone are dried at a temperature at which they are difficult to melt or soften, specifically, at a temperature below the thermal melting temperature or below the glass transition temperature. preferable.

In this way, the napped artificial leather of the present embodiment is obtained. The napped artificial leather of the present embodiment has a fiber entangled body in which colored fibers having an average diameter of 0.7 to 7 μm are entangled, and a fiber entangled body having an average particle size of 0.1 to 0.9 μm attached to the surface of the fibers (polymer). ) Acrylic polymer particles are contained, and at least one surface thereof has a napped surface on which fibers are napped, the fibers contain 1 to 8% by mass of a coloring pigment, and the napped surface is a color coordinate space (L ^* a ^* b). ^* Color space) is a napped artificial leather with a lightness L ^* value of 20 or less. The napped artificial leather of the present embodiment is colored so that the brightness L ^* value of the napped surface is 20 or less, preferably 18 or less. By being colored in such a dark color, the darkening effect due to the formation of fine protrusions on the surface of the fiber becomes remarkable.

Further, the clocking friction fastness is preferably grade 3 or higher when dry and grade 2 or higher when wet.

Hereinafter, the present invention will be described in more detail with reference to Examples. The scope of the present invention is not limited to these examples.

[Example 1]
Isophthalic acid-modified polyethylene terephthalate (IPA-modified PET) having a degree of modification of 6 mol% containing 5% by mass of water-soluble thermoplastic polyvinyl alcohol (PVA) as a sea component and carbon black (CB) as an island component was prepared. Then, the sea component and the island component are set to a base temperature of 260 ° C., and the nozzle holes forming a cross section in which 12 island components having a uniform cross-sectional area are distributed in the sea component resin are arranged in parallel. It was supplied to the mouthpiece and the molten strand was discharged from the nozzle hole. At this time, the pressure was adjusted so that the mass ratio of the sea component and the island component was 25/75 of the sea component / island component.

Then, the molten strand was drawn by suction with a suction device so that the average spinning speed was 3700 m / min, thereby spinning a sea-island type composite fiber having a fineness of 3.3 dtex. The sea-island type composite fibers were continuously deposited on a movable net and lightly pressed with a metal roll at 42 ° C. to reduce surface fluffing. Then, the sea-island type composite fiber was peeled off from the net and passed between the metal roll of the lattice pattern and the back roll at a surface temperature of 55 ° C. and a linear pressure of 200 N / mm. In this way, a web having a basis weight of 32 g / m ² was produced.

Next, a stacked web was prepared by stacking the web in 12 layers so as to have a total basis weight of 380 g / m ² with a cross wrapper device, and a needle breakage prevention oil was sprayed. Then, by using a 6-barb needle having a distance of 3.2 mm from the tip of the needle to the first barb, the stacked web is alternately needle-punched from both sides at a needle depth of 8.3 mm at 3300 punches / cm ² . An entangled web of sea-island type composite fibers with a basis weight of 500 g / m ² was produced. Then, the entangled web was subjected to moist heat shrinkage treatment under the conditions of a winding line speed of 10 m / min, 70 ° C., a humidity of 50% RH, and 30 seconds.

Then, a polyurethane emulsion containing 15% by mass of a self-emulsifying amorphous polycarbonate urethane having a 100% modulus of 3.0 MPa and 2.5% by mass of ammonium sulfate as a heat-sensitive gelling agent was prepared. Then, a polyurethane emulsion was impregnated into the moist heat-shrinked entangled web, and then dried at 150 ° C. to solidify the polyurethane. This polyurethane was fixed as a continuous film on the surface of the sea-island type composite fiber.

Then, the entangled web to which polyurethane was applied was repeatedly subjected to a dip / nip treatment in hot water at 95 ° C. to dissolve and remove PVA, which is a sea component, and then dried. In this way, an artificial leather raw machine containing a non-woven fabric in which fiber bundles containing 12 ultrafine fibers of isophthalic acid-modified polyethylene terephthalate having an average diameter of 4.8 μm were three-dimensionally entangled was prepared. The proportion of polyurethane contained in the artificial leather raw machine was 9.5% by mass.

Then, the artificial leather raw machine was sliced and cut in half, and one side thereof was buffed to adjust the thickness to 0.6 mm to obtain a napped artificial leather base material.

Then, a solution containing 0.7% by mass of polycarbonate-based polyurethane was gravure-coated on the surface of the napped artificial leather base material, and then dried at 135 ° C. Then, the napped artificial leather base material was treated with a liquid flow dyeing machine at a temperature of 120 ° C. for 10 minutes to perform a softening treatment.

Then, methacrylic polymer particles having an average particle size (median diameter D ₅₀ ) of 0.2 μm measured using a laser diffraction type particle size distribution measuring device and liquid amino-modified silicone are mixed at a mass ratio of 90:10. An aqueous dispersion A containing a total of 0.6% by mass of the above-mentioned formulations was prepared. Then, the water dispersion liquid A was impregnated into the softened artificial leather base material so that the total content after drying was 0.3% by mass, and then dried at 110 ° C. In this way, a black-colored napped artificial leather having a napped surface on which ultrafine fibers were napped was obtained.

The methacrylic polymer particles had a glass transition temperature of 115 ° C. and a thermal melting temperature of 140 ° C. or higher. Further, the thermal melting temperature of the mixture of the methacrylic polymer particles having an average particle size of 0.2 μm and the amino-modified silicone which is liquid even after drying was 140 ° C. or higher. To evaluate the thermal melting temperature, the aqueous dispersion was treated at 100 ° C. for 1 hour to remove water, and the remaining residue was treated at different temperatures every 10 ° C for 30 minutes, and the molten state at that time was visually observed. Observed at. A thermal melting temperature of 140 ° C. or higher means that it did not melt at 140 ° C.

Then, the obtained artificial napped leather was evaluated as follows.

(Evaluation of (meth) acrylic polymer particles adhering to the surface of fibers)
The surface layer cross section parallel to the thickness direction of the fluffy artificial leather was magnified 3000 times with a scanning electron microscope (SEM), and the formation of fine protrusions was observed. Then, it was confirmed whether the methacrylic polymer particles adhered to the surface of the fiber while maintaining the state of the particles. In addition, the average value of all particle diameters contained in the images in which 15 locations were selected evenly was obtained. In addition, the measurement was performed excluding the apparently extremely large particles that are not considered to be methacrylic polymer particles. FIG. 1 shows an example of an SEM photograph of the surface of the fiber forming the non-woven fabric contained in the napped artificial leather obtained in Example 1.

(Measurement of brightness L ^* value)
Using a spectrophotometer (manufactured by Minolta Co., Ltd .: CM-3700), the brightness L ^* value was obtained from the coordinate values of the L ^* a ^* b ^* color space on the surface of the napped artificial leather in accordance with JISZ 8729. The brightness L ^* value is the average value of three points measured by selecting the average position evenly from the test piece.

(Color resistance: clocking friction fastness)
A clock meter (atlas electronic clock meter (manufactured by ATLAS ELECTRIC DEVICES CO)) conforming to the AATCC Method 8 method, a cotton white cloth, and a test piece of napped artificial leather were prepared. Then, according to AATCC Method 8, the friction fastness during drying and wet was measured using a clock meter.

Specifically, the frictional fastness during drying was evaluated as follows. A dry cotton white cloth was attached to a glass friction element, and the cotton white cloth attached to the friction element was brought into contact with the napped surface of a piece of napped artificial leather under a load of 900 g and reciprocated 10 times. Then, the cotton white cloth was removed, cellophane tape (registered trademark) was attached onto the contaminated part, a 1.5-pound cylindrical load was rolled once, and then the cellophane tape was peeled off from the cotton white cloth. On the other hand, the frictional fastness when wet was evaluated as follows. After soaking in distilled water, a moistened cotton white cloth from which excess water has been removed is attached to a glass friction element, and the cotton white cloth attached to the friction element is brought into contact with the fluffy surface of a piece of napped artificial leather with a load of 900 g. I made 10 round trips. Then, after removing the cotton white cloth and drying it at 60 ° C. or lower, a cellophane tape was attached on the contaminated portion, a 1.5-pound cylindrical load was rolled once, and then the cellophane tape was peeled off from the cotton white cloth.

Then, the change in color transfer to the cotton-white cloth during drying and wetting was determined by a gray scale for contamination (5th grade to 1st grade).

(Surface texture and surface appearance)
A 20 cm × 20 cm test piece was cut out from the napped artificial leather. Then, the surface feel and surface appearance of the napped surface of the test piece were judged according to the following criteria.
A: It had a smooth feel and a luxurious and elegant appearance.
B: The ultrafine fibers were focused and had a rough texture, or the appearance was uneven.

(Texture)
A 20 cm × 20 cm test piece was cut out from the napped artificial leather. Then, the texture of the test piece was judged according to the following criteria.
A: It had a soft texture. B: It had a hard texture or paper-like creases.

The above results are shown in Table 1 below.

[Example 2]
Instead of producing a non-woven fabric containing ultrafine fibers of isophthalate-modified polyethylene terephthalate, which is a long fiber having an average diameter of 4.8 μm containing 5% by mass of carbon black, a long fiber having an average diameter of 6.7 μm containing 3% by mass of carbon black. A non-woven fabric containing ultrafine fibers of isophthalic acid-modified polyethylene terephthalate is produced, dyed at 120 ° C. with a disperse dye instead of being softened using a liquid flow dyeing machine, and then alkaline reduction cleaning treatment and neutralization. A napped artificial leather was produced in the same manner as in Example 1 except that the treatment was performed. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
Instead of producing a non-woven fabric containing ultrafine fibers of isophthalic acid-modified polyethylene terephthalate of long fibers having an average diameter of 4.8 μm containing 5% by mass of carbon black, isophthal of long fibers having an average diameter of 1 μm containing 7% by mass of carbon black. A non-woven fabric containing ultrafine fibers of acid-modified polyethylene terephthalate is produced, and instead of being softened using a liquid flow dyeing machine, it is dyed at 120 ° C. with a disperse dye, followed by alkali reduction treatment and neutralization. A napped artificial leather was produced in the same manner as in Example 1 except that the treatment was performed. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
Prepare an aqueous dispersion B containing a total of 0.6% by mass of a mixture of methacrylic polymer particles having an average particle size of 0.7 μm and amino-modified silicone which is liquid even after drying at a mass ratio of 70:30. did. The methacrylic polymer particles having an average particle size of 0.7 μm had a glass transition temperature of 80 ° C. and a thermal melting temperature of 140 ° C. or higher.

The same as in Example 1 except that the water-splitting liquid B instead of the water dispersion A was changed so that the total content after drying was 0.1% by mass instead of 0.3% by mass. Manufactured fluffy artificial leather. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]
0.6 mass of a mixture of methacrylic polymer particles with an average particle size of 0.1 μm and amino-modified silicone that is liquid before curing and hardens after drying to solidify into particles in a mass ratio of 95: 5. An aqueous dispersion C containing% was prepared. The methacrylic polymer particles having an average particle size of 0.1 μm had a glass transition temperature of 115 ° C. and a thermal melting temperature of 140 ° C. or higher.

The same as in Example 1 except that the aqueous dispersion C was used instead of the aqueous dispersion A and the total content after drying was changed to 1.5% by mass instead of 0.3% by mass. Manufactured artificial fluffy leather. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
A fluffy artificial leather was produced and evaluated in the same manner as in Example 1 except that the step of impregnating the aqueous dispersion A and the step of drying were omitted. The results are shown in Table 1. Further, FIG. 2 shows an example of an SEM photograph of the surface of the fiber forming the non-woven fabric contained in the napped artificial leather obtained in Comparative Example 1.

[Comparative Example 2]
In Example 2, instead of adding 3% by mass of carbon black to the ultrafine fibers, 0.8% by mass of carbon black was added, and the dye concentration was doubled to perform the dyeing treatment in the same manner. A fluffy artificial leather was manufactured and evaluated. The results are shown in Table 1.

[Comparative Example 3]
In Example 1, napped artificial leather was produced and evaluated in the same manner except that carbon black was added in an amount of 9% by mass instead of adding 5% by mass of carbon black to the ultrafine fibers. The results are shown in Table 1.

[Comparative Example 4]
An aqueous dispersion D containing 0.6% by mass of acrylic polymer particles having an average particle size of 0.4 μm was prepared. The acrylic polymer particles having an average particle size of 0.4 μm were polymer elastic bodies having a glass transition temperature of −17 ° C. and a thermal melting temperature of 140 ° C. or higher.

A napped artificial leather was produced in the same manner as in Example 1 except that the aqueous dispersion D was used instead of the aqueous dispersion A. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1. Acrylic polymer particles do not maintain their shape after drying. The fiber surface was covered in a film shape without forming many fine protrusions on the fiber surface.

[Comparative Example 5]
In Example 1, a fluffy artificial leather was produced in the same manner except that the aqueous dispersion E containing only the liquid amino-modified silicone obtained by removing the methacrylic polymer particles from the aqueous dispersion A was used instead of the aqueous dispersion A. ,evaluated. The results are shown in Table 1.

[Comparative Example 6]
An aqueous dispersion F containing a total of 0.6% by mass of a mixture of methacrylic polymer particles having an average particle size of 2 μm and amino-modified silicone which is liquid even after drying at a mass ratio of 50:50 was prepared. The methacrylic polymer particles having an average particle size of 2 μm had a glass transition temperature of 115 ° C. and a thermal melting temperature of 140 ° C. or higher.

A napped artificial leather was produced in the same manner as in Example 1 except that the aqueous dispersion E was used instead of the aqueous dispersion A. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 7]
Prepare an aqueous dispersion G containing a total of 0.6% by mass of a mixture of methacrylic polymer particles having an average particle size of 0.05 μm and amino-modified silicone which is liquid even after drying at a mass ratio of 90:10. did. The methacrylic polymer particles having an average particle size of 0.05 μm had a glass transition temperature of 80 ° C. and a thermal melting temperature of 120 ° C.

A napped artificial leather was produced in the same manner as in Example 1 except that the aqueous dispersion G was used instead of the aqueous dispersion A. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 8]
An aqueous dispersion H containing a total of 0.6% by mass of a mixture of polyurethane particles having an average particle size of 0.3 μm and amino-modified silicone which is liquid even after drying at a mass ratio of 90:10 was prepared. The polyurethane particles having an average particle size of 0.3 μm had a hot melting temperature of 140 ° C. or higher.

A napped artificial leather was produced in the same manner as in Example 1 except that the aqueous dispersion H was used instead of the aqueous dispersion A. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 9]
An aqueous dispersion I containing a total of 0.6% by mass of a mixture of colloidal silica having an average particle size of 0.1 μm and amino-modified silicone which is liquid even after drying at a mass ratio of 80:20 was prepared. The polyurethane particles having an average particle size of 0.1 μm had a hot melting temperature of 140 ° C. or higher.

A napped artificial leather was produced in the same manner as in Example 1 except that the aqueous dispersion I was used instead of the aqueous dispersion A. Then, the obtained napped artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

With reference to the results in Table 1, the following can be seen. It contains a fiber entangled body in which colored fibers having an average diameter of 0.7 to 7 μm are entangled, and (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm adhering to the surface of the fibers. The fluffy artificial leather of Example 1 is similar to the fluffy artificial leather of Comparative Example 1 except that (meth) acrylic polymer particles are not attached, and has a high-quality surface appearance, a soft texture, and color transfer resistance. The brightness L ^* value was low and the color was darkened while maintaining the above. It contains a fiber entangled body in which colored fibers having an average diameter of 0.7 to 7 μm are entangled, and (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm adhering to the surface of the fibers. Similarly, the fluffy artificial leathers of Examples 2 to 5 were dark in color while maintaining a high-class surface appearance, a soft texture, and color transfer resistance.

On the other hand, the napped artificial leather of Comparative Example 2 in which the fiber contains only 0.8% by mass of the coloring pigment has a sufficient lightness L ^* value even if the dye concentration of the disperse dye is changed to twice the amount and dyed. It was not low, and the color transfer resistance was also low. On the other hand, the napped artificial leather of Comparative Example 3 in which the fibers contained 9% by mass of a coloring pigment could have a sufficiently low lightness L ^* value, but the strength of the fibers decreased and the fibers were cut and colored due to friction. Due to the color transfer of the fibers, the color transfer resistance was lowered. Further, the napped artificial leather of Comparative Example 4 obtained by adhering acrylic polymer particles having a low glass transition temperature has a soft surface feel due to the acrylic polymer particles forming a film and coating the fibers after drying. The texture has deteriorated. In addition, the napped artificial leather of Comparative Example 6 containing (meth) acrylic polymer particles having an average particle size of 2 μm did not darken, and the surface texture was rough. Further, in the napped artificial leather of Comparative Example 7 containing (meth) acrylic polymer particles having an average particle size of 0.05 μm, aggregation was observed in the particles, the protrusions on the surface became large, and the color did not darken. Further, in the napped artificial leather of Comparative Example 8 in which polyurethane particles were used instead of the (meth) acrylic polymer particles, the polyurethane formed a film in the drying step and adhered to the fibers in a film form, so that the fibers converged. It became a rough texture and the texture became hard. The napped artificial leather of Comparative Example 9 to which colloidal silica, which is an inorganic fine particle, was attached also had a rough surface texture and a hard texture.

F fiber P (meth) acrylic polymer particles

Claims (11)

It contains a fiber entangled body in which colored fibers having an average diameter of 0.7 to 7 μm are entangled, and (meth) acrylic polymer particles having an average particle size of 0.1 to 0.9 μm adhering to the surface of the fibers. , At least one surface thereof has a napped surface on which the fibers are napped.
The fiber contains 1 to 8% by mass of a coloring pigment.
The fluffy surface is a fluffy artificial leather having a lightness L ^* value of 20 or less in a color coordinate space (L ^* a ^* b ^* color space). The napped artificial leather according to claim 1, wherein the (meth) acrylic polymer particles contain a methacrylic polymer containing 50% by mass or more of a methacrylic monomer unit. The fluffy artificial leather according to claim 1 or 2, wherein the (meth) acrylic polymer particles have at least one of a heat melting temperature of 140 ° C. or higher and a glass transition temperature (Tg) of 70 ° C. or higher. The napped artificial leather according to any one of claims 1 to 3, wherein the content ratio of the (meth) acrylic polymer particles is 0.05 to 1.5% by mass. The napped artificial leather according to any one of claims 1 to 4, further comprising silicone adhering to the surface of the fiber. The napped artificial leather according to claim 5, wherein the silicone is an amino-modified silicone. The napped artificial leather according to claim 5 or 6, wherein the content ratio of the silicone is 0.01 to 1% by mass. The fluff according to any one of claims 5 to 7, wherein the mass ratio of the (meth) acrylic polymer particles to the silicone ((meth) acrylic polymer particles: silicone) is 95: 5 to 70:30. Artificial leather. The fluffy artificial leather according to any one of claims 5 to 8, wherein the total content ratio of the (meth) acrylic polymer particles and the silicone is 0.1 to 2% by mass. The napped artificial leather according to any one of claims 1 to 9, wherein the coloring pigment contains carbon black. The napped artificial leather according to any one of claims 1 to 10, further comprising a polymer elastic body impregnated and imparted to the fiber entangled body.