JP6473412B2 - Artificial leather base material, silver-tone artificial leather, method for manufacturing artificial leather base material, and modifier for artificial leather base material - Google Patents

Description

  The present invention relates to an artificial leather that has both flexibility and a high sense of fulfillment.

  Conventionally, artificial leather including a nonwoven fabric is known. Artificial leather is used as an alternative to natural leather in fields such as shoes, clothing, gloves, bags, balls, interiors, and vehicles.

  Artificial leather is manufactured by applying a surface treatment for imparting a desired appearance to an artificial leather base obtained by impregnating a void inside a nonwoven fabric with a polymer elastic body. The polymer elastic body gives a sense of fulfillment to the nonwoven fabric. As artificial leather, for example, silver-added artificial leather with a silver-like appearance, suede-like or nubuck-like artificial leather with fluffed fibers on the surface of a nonwoven fabric, and the like are known.

  Natural leather has a high level of flexibility and flexibility because it contains dense collagen fibers. The high sense of fullness of natural leather, when bent, forms a fine crease that is rounded and has a high-class feel, and also exhibits excellent drape.

  However, natural leather has been difficult to use in applications that require heat resistance and water resistance, such as automobile interior materials. This is because collagen fibers are inferior in heat resistance and water resistance. There is also a method of forming a thick resin layer on the surface in order to impart heat resistance and water resistance to natural leather. However, when a thick resin layer is formed, the flexibility of natural leather is lost.

  On the other hand, artificial leather is superior in heat resistance, water resistance, quality stability and wear resistance to natural leather, and is easy to care for. However, since artificial leather has voids that are not filled with a polymer elastic body in the nonwoven fabric, it is inferior in density and fullness compared to natural leather. For this reason, when the artificial leather is bent, it is not rounded and bent like natural leather, but bends and bends so as to be called “boiled”. Such bending is not high-class. Further, when the voids are reduced by increasing the content of the polymer elastic body in the nonwoven fabric, the feeling of rebound is increased and a rubber-like rigid texture is obtained.

  In order to resemble the suppleness of natural leather, an artificial leather using a nonwoven fabric formed from ultrafine fibers is also known (for example, Patent Document 1 below). However, in the case of artificial leather using a non-woven fabric formed from ultrafine fibers, it has not been possible to obtain a product that has sufficient flexibility and fullness. Patent Document 2 below discloses a leather sheet-like material including an oily substance having a viscosity of 50 to 10,000 mPa · s at 30 ° C. and a support such as an olefinic elastomer at least inside a fibrous base material. Patent Document 2 discloses that such a leather sheet-like material has both natural leather-like flexibility (flexibility) and a sense of fulfillment, and less oil transfer.

  By the way, although not in the field of artificial leather, for example, the following Patent Document 3 is a wiping sheet in which a drug having a dust absorption performance is held in an acrylic wet nonwoven fabric in an amount of 1 to 30% by weight of the nonwoven fabric, Disclosed is the use of synthetic oils such as liquid paraffin, mineral oil, silicone oil, alkylbenzene oil, and the like as chemicals.

WO2008 / 120702 pamphlet WO2003 / 06212 pamphlet JP-A-9-313418

  The present invention provides an artificial leather that has both flexibility and a high sense of fulfillment.

One aspect of the present invention includes a fiber entangled body, a first filler, a liquid nonvolatile oil, and a first polymer elastic body impregnated in the fiber entangled body, and the first filler. is a metal filler, a metal oxide filler, inorganic filler, flame retardant fillers, and artificial leather substrate comprising at least one selected from a carbon-based filler.

  Another aspect of the present invention is silver-tone artificial leather having a resin layer laminated on the artificial leather substrate.

Another aspect of the present invention is a method for producing an artificial leather base material, the fiber entangled body, the first filler, the liquid non-volatile oil impregnated in the fiber entangled body, and the first wherein the elastic polymer, a first filler, metal filler, metal oxide filler, inorganic filler, artificial leather group containing at least one selected from flame-retardant fillers, and carbon-based filler A step of preparing a raw material fabric, a step of forming a smoothing layer having a thickness of 10 to 100 μm by applying a coating solution for forming a smoothing layer on the surface of an artificial leather base material, and then drying; The coating liquid for forming a smoothing layer contains the second polymer elastic body and the second filler as solid contents, and the number of rotations is 0 using a B-type rotational viscometer at a temperature of 25 ° C. viscosity when measured viscosity eta _0.6 and the rotation number 3 rotation / sec when measured at .6 rotation / sec thixotropic index is the ratio (η _0.6 / η _3.0) with eta _3.0 is 2-4, a process for producing an artificial leather substrate.

Further, another aspect of the present invention, as non-volatile components, and 3 to 90 wt% non-volatile oil liquid, and a first filler and formulation 10-97 wt% of a first elastic polymer , wherein the first filler, metal filler, metal oxide filler, inorganic filler, flame retardant fillers, and artificial leather substrate modifier for containing at least one selected from a carbon-based filler is there.

  ADVANTAGE OF THE INVENTION According to this invention, the artificial leather which has suppleness and a high fullness feeling is obtained.

FIG. 1 is a schematic cross-sectional view of a silver-tone artificial leather 10 according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of a silver-tone artificial leather 20 according to another embodiment of the present invention. FIG. 3 shows a cross section of the fiber entangled body before impregnation with the first filler, the non-volatile oil, and the first polymer elastic body in Example 6 observed with a scanning electron microscope (SEM). It is a cross-sectional photograph. FIG. 4 is a cross-sectional photograph of the cross section of the artificial leather base material obtained by impregnating the first filler, the non-volatile oil, and the first polymer elastic body in Example 6 with an SEM. is there. FIG. 5 is a cross-sectional photograph of a cross-section of a silver-tone artificial leather substrate in Example 6 observed with an SEM. FIG. 6 is an SEM photograph of an oblique cross section before forming the smoothing layer of the artificial leather base material obtained in Example 13. FIG. 7 is an SEM photograph of an oblique section after the smoothing layer of the artificial leather base material obtained in Example 13 is formed. FIG. 8 is an SEM cross-sectional photograph of an oblique cross-section of the silver-tone artificial leather base material obtained in Example 13. FIG. 9 is an SEM photograph of an oblique section after the smoothing layer of the artificial leather base material obtained in Example 22 is formed. FIG. 10 is an SEM cross-sectional photograph of an oblique cross-section of the silver-tone artificial leather base material obtained in Example 22.

FIG. 1 is a schematic cross-sectional view of a silver-tone artificial leather 10 according to an embodiment of the present invention. The silver-added artificial leather 10 includes an artificial leather substrate 1 including a fiber entangled body, and a resin silver surface layer 2 including a polymer elastic body formed on the surface of the artificial leather substrate 1. The artificial leather substrate 1 includes a fiber entangled body 1a, and in the gaps between the fibers of the fiber entangled body 1a, as shown in the enlarged view in FIG. 1, a liquid non-volatile oil 3 and a first filler 4 are provided.及beauty first elastic polymer 5 are impregnated granted. The liquid nonvolatile oil, the first filler, and the first polymer elastic body are collectively referred to as a modifier.

  Hereinafter, the artificial leather of the present embodiment will be described in detail along with an example of a manufacturing method thereof.

  The fiber entangled body is not particularly limited as long as it is a fiber structure such as nonwoven fabric, woven fabric, woven fabric, or knitted fabric. Among these, nonwoven fabrics, particularly nonwoven fabrics of ultrafine fibers are preferable. Since the nonwoven fabric of ultrafine fibers has a dense fiber density, the density unevenness of the fibers is low and the homogeneity is high. For this reason, artificial leather that is particularly excellent in flexibility and high fulfillment can be obtained. In the present embodiment, the case where a non-woven fabric of ultrafine fibers is used as the fiber entanglement will be described in detail as a representative example.

  The nonwoven fabric of ultrafine fibers can be obtained, for example, by entanglement treatment of ultrafine fiber-generating fibers such as sea-island type (matrix-domain type) composite fibers and the ultrafine fiber treatment. In this embodiment, the case where the sea-island type composite fiber is used will be described in detail. However, even if an ultrafine fiber-generating fiber other than the sea-island type composite fiber is used, it is possible to directly Ultra fine fibers may be spun. In addition, as a specific example of the ultrafine fiber generation type fiber other than the sea-island type composite fiber, a plurality of ultrafine fibers are formed by lightly bonding immediately after spinning, and a plurality of ultrafine fibers are formed by unraveling by mechanical operation. Such as a split-divided fiber, or a petal-type fiber in which a plurality of resins are alternately gathered in a petal shape in the melt spinning process, and any fiber that can form ultrafine fibers is used without particular limitation. It is done.

  In the production of the ultrafine fiber nonwoven fabric, the island of the sea-island type composite fiber that is the resin component that forms the sea component (matrix component) of the sea-island type composite fiber that can be selectively removed and the resin component that forms the ultrafine fiber are first introduced. A sea-island type composite fiber is obtained by melt spinning and stretching a thermoplastic resin constituting the component (domain component).

  As the sea component thermoplastic resin, a thermoplastic resin having a different solubility in a solvent or a decomposability in a decomposing agent is selected from the island component resin. Specific examples of the thermoplastic resin constituting the sea component include, for example, a water-soluble polyvinyl alcohol resin, polyethylene, polypropylene, polystyrene, ethylene propylene resin, ethylene vinyl acetate resin, styrene ethylene resin, styrene acrylic resin, and the like. .

  The thermoplastic resin, which is a resin component that forms island components and forms ultrafine fibers, is not particularly limited as long as it is a resin capable of forming sea-island composite fibers and ultrafine fibers. Specifically, for example, polyethylene terephthalate (PET), isophthalic acid modified PET, sulfoisophthalic acid modified PET, polybutylene terephthalate, polyhexamethylene terephthalate and other aromatic polyesters; polylactic acid, polyethylene succinate, polybutylene succinate, Aliphatic polyesters such as polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalerate resin; polyamides such as polyamide 6, polyamide 66, polyamide 10, polyamide 11, polyamide 12, polyamide 6-12; polypropylene, polyethylene, polybutene , Polyolefins such as polymethylpentene and chlorinated polyolefin. These may be used alone or in combination of two or more.

  As a method for producing a nonwoven fabric of ultrafine fibers, for example, a sea-island composite fiber is melt-spun to produce a web, the web is entangled, and then sea components are selectively removed from the sea-island composite fiber. The method of forming is mentioned. As a method for producing a web, a long-fiber sea-island composite fiber spun by a spunbond method or the like is collected on a net without being cut to form a long-fiber web, or a long fiber is cut into staples. And a method of forming a short fiber web. Among these, a long fiber web is particularly preferable because it is excellent in denseness and fullness. In addition, the formed web may be subjected to a fusion treatment in order to impart shape stability.

  In addition, a long fiber means a continuous fiber that is not a short fiber intentionally cut after spinning. More specifically, for example, it means a fiber that is not a short fiber intentionally cut so that the fiber length is about 3 to 80 mm. It is preferable that the fiber length of the sea-island type composite fiber before the ultrafine fiber formation is 100 mm or more, and it can be technically manufactured and unavoidably cut in the manufacturing process. The fiber length may be km or more. In addition, a part of long fiber may be inevitably cut | disconnected and become a short fiber in a manufacturing process by the needle punch at the time of the entanglement mentioned later, or buffing of the surface.

  Sea island type composite fiber is densified by performing fiber shrinkage treatment such as entanglement treatment and heat shrink treatment with water vapor in any process from removing sea components of sea island type composite fiber to forming ultra fine fiber can do. Examples of the entanglement treatment include a method of stacking about 5 to 100 webs and performing needle punching or high-pressure water flow treatment.

  The sea component of the sea-island type composite fiber is removed by dissolution or decomposition at an appropriate stage after the web is formed. By such decomposition removal or dissolution extraction removal, the sea-island type composite fibers are made into ultrafine fibers, and fiber bundle-like ultrafine fibers are formed.

  The fineness of the ultrafine fibers is not particularly limited, but is preferably 0.001 to 0.9 dtex, more preferably 0.01 to 0.6 dtex, and particularly preferably 0.02 to 0.5 dtex. When the fineness is too high, there is a tendency that a non-woven fabric with insufficient density is obtained. Moreover, it is difficult to produce a fiber having a fineness that is too low. Moreover, there exists a tendency for fibers to converge and the rigidity of a nonwoven fabric to become high.

  The ultrafine fiber nonwoven fabric thus obtained is subjected to thickness adjustment and flattening treatment as necessary. Specifically, slice processing and buffing processing are performed. In this way, a non-woven fabric of ultrafine fibers that is a fiber entangled body is obtained.

Although the thickness of a fiber entangled body is not specifically limited, It is preferable that it is about 100-3000 micrometers, Furthermore, about 300-2000 micrometers. The apparent density of the fiber entangled body is not particularly limited, but is 0.25 to 0.70 g / cm ³ , further 0.45 to 0.65 g / cm ³ , particularly 0.55 to 0.60 g / cm ³ . ^3, it is preferable from the viewpoint of artificial leather substrate having both fulfillment and a supple texture is obtained of the order.

  Next, the process of impregnating and applying the first filler and liquid nonvolatile oil to the voids of the fiber entangled body will be described.

  In this step, first, a dispersion containing a non-volatile oil and a first filler is prepared.

  In the dispersion, for example, liquid non-volatile oil and the first filler are homogeneously mixed and dispersed in a dispersion medium such as water or a mixture of water and a polar solvent such as alcohol.

  The liquid non-volatile oil in the present embodiment is a liquid having a boiling point of 150 ° C. or higher and substantially not dissolved in a polar solvent. Specific examples include liquid paraffin, paraffinic or naphthenic process oil, mineral oil, silicone oil, and phthalates. These may be used alone or in combination of two or more. Among these, liquid paraffin is preferable because it is excellent in chemical stability and hardly oxidized.

  Moreover, an inorganic filler and an organic filler are mentioned as a 1st filler in this embodiment.

Is a first filler, for example, an average particle diameter of 0.1-15, more metal having an average particle diameter of 0.5 to 10 [mu] m, the metal oxide, various fillers consisting of inorganic compounds are particularly limited Used without . Specific examples of that, alumina _{(Al 2 O} 3), titanium dioxide _(TiO 2), zinc oxide (ZnO), cerium dioxide _(CeO 2), silica (SiO ₂₎ metal oxides such or metalloid oxide Fillers of inorganic compounds such as talc, clay, aluminum hydroxide, mica, calcium carbonate, caged polysilsesquioxane (POSS); Flammable fillers such as carbon nanotubes (CNT), carbon fibers (CF), carbon black (CB), graphite (GF), and acetylene black (AB). These may be used alone or in combination of two or more. In these, various flame-retardant fillers are especially preferable from the point which can provide a flame retardance simultaneously.

Further, the gap of the fiber-entangled body, in addition to the oils of the first filler and liquid, you further impregnation imparts a first elastic polymer. In this case, a dispersion liquid containing non-volatile oil, a first filler, and a first polymer elastic body is used.

  Specific examples of the first polymer elastic body include, for example, polyurethane, acrylic elastic body, silicone elastic body, diene elastic body, nitrile elastic body, fluorine elastic body, polystyrene elastic body, and polyolefin elastic body. Body, polyamide elastic body, halogen elastic body and the like. These may be used alone or in combination of two or more. Among these, polyurethane is preferable from the viewpoint of excellent wear resistance and mechanical properties.

  The polyurethane is preferably an aqueous polyurethane such as polycarbonate polyurethane, polyester polyurethane, polyether polyurethane, or polycarbonate / ether polyurethane emulsion. These polyurethanes are particularly preferable because the dispersion is easily prepared, a crosslinked structure is easily formed, and a soft texture is easily exhibited by being present in the voids without being too close to the fibers.

  Moreover, you may mix | blend components, such as surfactant, a dispersing agent, and a coloring agent, with a dispersion liquid as needed in the range which does not impair the effect of this invention.

  The concentration of each component in the dispersion is appropriately adjusted in consideration of the target characteristics, the viscosity and stability of the dispersion, and the like. Specifically, the proportion of the non-volatile oil in the dispersion is, for example, preferably 1 to 50% by mass, and more preferably 3 to 30% by mass. The total ratio of the filler and the polymer elastic body in the dispersion is, for example, preferably 5 to 99% by mass, more preferably about 7 to 80% by mass.

  The method for impregnating the fiber entangled body with the dispersion is not particularly limited. Specifically, for example, a method of impregnating the fiber entangled body by dip-niping the dispersion is preferably used. The viscosity of the dispersion is not particularly limited as long as it is a viscosity capable of impregnating the fiber entangled body with a desired amount. Specifically, for example, the solution viscosity is preferably about 10 to 1000 mPa · s (millipascal seconds), more preferably about 50 to 500 mPa · s as a value measured with a rotary viscometer.

Then, the fiber entangled body is impregnated with the dispersion liquid, and then dried to remove volatile components such as the dispersion medium in the dispersion liquid. Thereby, the first filler in the dispersion, the first elastic polymer及 beauty nonvolatile oil or the like remains in the voids between the fibers of the fiber-entangled body. Although drying conditions are not specifically limited, For example, the conditions of making it dry for about 1 to 10 minutes at 70-150 degreeC are mentioned. Thus, a 1st filler, a non-volatile oil, etc. are provided to the space | gap between the fibers of a fiber entanglement body. These exist, for example, in a void in the form of clay or paste.

  The ratio of the non-volatile oil to the fiber entangled body is preferably 0.5 to 10% by mass, more preferably 1 to 10% by mass, and particularly preferably 3 to 8% by mass. When the ratio of the non-volatile oil to the fiber entangled body is less than 0.5% by mass, it is difficult to sufficiently obtain a supple texture. Moreover, when the ratio of the non-volatile oil with respect to a fiber entanglement body is too high, a fiber entanglement body cannot hold | maintain a non-volatile oil and it will become easy to take off.

  Although the ratio of the 1st filler with respect to a fiber entangled body is not specifically limited, It is 1-60 mass%, It is preferable that it is 10-50 mass%, Furthermore, it is 10-40 mass%. When the ratio of the 1st filler with respect to a fiber entanglement body is too low, there exists a tendency for a feeling of fulfillment to fall. Moreover, when the ratio of the 1st filler with respect to a fiber entangled body is too high, there exists a tendency for a supple texture to fall.

The ratio of the first polymer elastic body to the fiber entangled body is preferably 0.5 to 15% by mass, more preferably 1 to 14% by mass, and particularly preferably 1 to 10% by mass. When the ratio of the 1st polymer elastic body with respect to a fiber entanglement body is too high, there exists a tendency for a soft feeling to fall because a rubber feeling becomes strong and resilience becomes high. Although the first polymer elastic body is not an essential component, it can increase the form stability and adjust the elasticity by blending.

  Moreover, the ratio of the non-volatile oil in the modifier that combines the first filler, the non-volatile oil and the first polymer elastic body is not particularly limited, but is 1 to 90% by mass, and more preferably 3 to 70%. It is preferable that the content is 10% by mass, particularly 10 to 50% by mass, and particularly 20 to 35% by mass, because a supple texture and a sense of fulfillment can be obtained. When the proportion of the non-volatile oil in the modifier is too low, the supple texture tends to decrease, and when it is too high, the proportion of the filler becomes relatively low, and the sense of fulfillment tends to decrease. There is.

  Moreover, as a ratio of the 1st filler in a modifier, it is 10-99 mass%, Furthermore, 30-97 mass%, It is preferable that it is 50-90 mass% especially. When the ratio of the first filler is too low, the sense of fulfillment tends to decrease, and when it is too high, the ratio of the non-volatile oil tends to be relatively low, and the supple texture tends to decrease.

The ratio of the first polymer elastic body in the modifier is preferably 1 to 40% by mass, and more preferably 1 to 20% by mass. When the ratio of the first polymer elastic body is too high, it tends to have a rubber-like texture.

  The ratio of the modifier to the fiber entanglement is not particularly limited, but is 1 to 60% by mass, preferably 3 to 45% by mass, particularly 10 to 40% by mass, and more preferably 10 to 30% by mass. . When the ratio of the modifier to the fiber entanglement is too high, it tends to be difficult to sufficiently impregnate the voids.

Thus the first filler in the gap between the fibers of the fiber-entangled body, fixed oils及beauty first modifier artificial leather base material impregnated grant including the elastic polymer is obtained. Such artificial leather base materials are subjected to thickness adjustment and flattening treatment by slicing or buffing treatment as necessary, stagnation softening treatment, blanking softening treatment, reverse seal brushing treatment, antifouling treatment Finishing treatment such as treatment, hydrophilization treatment, lubricant treatment, softener treatment, antioxidant treatment, ultraviolet absorber treatment, fluorescent agent treatment, flame retardant treatment and the like may be performed.

For the purpose of adjusting the fullness and suppleness of the artificial leather base material, flexible first filler, artificial leather base material and the modifying agent is impregnated imparted comprising a first elastic polymer oils及beauty It is preferable to process. The method of softening is not particularly limited, but there is a method in which an artificial leather base material is brought into close contact with an elastic sheet and mechanically contracted in the vertical direction (MD of the production line), and heat-set by heat treatment in the contracted state. preferable. By adopting this method, it is possible to make it flexible while improving the smoothness of the surface.

The thickness of the artificial leather base material thus obtained is not particularly limited, but is preferably about 100 to 3000 μm, more preferably about 300 to 2000 μm. Further, the apparent density of the artificial leather base material is not particularly limited, but it is 0.55 to 0.85 g / cm ³ , and further 0.60 to 0.80 g / cm ³ is a sense of fulfillment and a supple texture. From the viewpoint of excellent balance.

  The artificial leather substrate thus obtained is finished into artificial leather by subjecting it to a treatment for imparting a desired appearance. Artificial leather includes, for example, silver-tone artificial leather in which a surface of the artificial leather base is provided with a silver-tone resin layer, or fluffing by raising the fibers by buffing the surface of the artificial leather base. Examples include raised artificial leather (suede, nubuck, velor, buckskin) that has a raised appearance.

  Silver-tone artificial leather is obtained by forming a silver-tone resin layer on the surface of an artificial leather substrate. The method for forming a silver-tone resin layer on the surface of the artificial leather substrate is not particularly limited, and for example, a dry surface forming method or a direct coating method is used. In the dry surface-forming method, a coating liquid containing a colored resin for forming a silver surface layer is applied on a release sheet, and then a film is formed by drying, and the film is adhered to the surface of the artificial leather substrate. This is a method of peeling the release sheet after pasting together. The direct coating method is a method in which a coating liquid containing a resin is applied directly to the surface of an artificial leather substrate by a roll coater or a spray coater and then dried.

  Conventionally, in general, the silver surface layer is formed by a dry surface forming method in which a pre-formed film is laminated on an artificial leather base material through a semi-cured adhesive layer and bonded by hot pressing. Has been. The silver surface layer formed by the dry-type surface is relatively thick, and the forming process is complicated. On the other hand, the direct coating method has an advantage that the formation process is simple because the silver surface layer can be formed by coating. However, when trying to form a silver layer by the direct coating method, the artificial leather substrate becomes hard because the coating solution penetrates too much from the voids on the surface of the artificial leather substrate, and the supple texture is impaired. There was a problem.

  Since the artificial leather base material of this embodiment is excellent in a sense of fulfillment as described above and has a smooth surface, it can impart extremely high smoothness to the surface by the following method. Thus, by increasing the smoothness of the surface of the artificial leather base material, even if a coating liquid is applied to the surface of the artificial leather base material using the direct coating method, it becomes difficult to penetrate inside. Thereby, since the formed resin layer does not sink deeply into the artificial leather base material, a supple texture can be maintained.

  As the first method, as shown in FIG. 2, the surface layer of the artificial leather substrate 1 includes a second polymer elastic body and a second filler in order to smooth the surface. The method of forming the layer 6 is mentioned. Then, the silver surface layer 12 is formed on the surface of the smoothing layer 6. A method for forming such a smoothing layer will be described below.

  A smoothing layer is formed by applying a coating solution having a thixotropy index of 2 to 4 including the second polymer elastic body and the second filler on the surface of the artificial leather base material, followed by drying. Form. Such a coating liquid has a thixotropy index of 2 to 4, so that it has a low viscosity at the time of coating where the shear is applied, and the viscosity becomes higher after the application where the shear is not applied. According to such a method, since it becomes difficult for a coating liquid to sink inside from the space | gap of the surface of an artificial leather base material, a thin smoothing layer can be easily formed in the surface of an artificial leather base material.

The coating liquid used for the formation of the smoothing layer is not particularly limited as long as it is a coating liquid having a thixotropy index of 2 to 4 including the second polymer elastic body and the second filler. Here, the “thixotropic index” is measured at a viscosity of η _0.6 and a rotational speed of 3 revolutions / second when measured at a rotational speed of 0.6 revolutions / second using a B-type rotational viscometer at a temperature of 25 ° C. It means the ratio (η _0.6 / η _3.0 ) to the viscosity η _3.0 when measured.

  The coating liquid used for forming the smoothing layer contains a second polymer elastic body and a second filler. As a specific example of the coating liquid, for example, a mixed liquid in which a second filler is mixed with a resin liquid such as an emulsion, suspension, or dispersion of the second polymer elastic body is preferably used.

  Specific examples of the second polymer elastic body are the same as the first polymer elastic body described above, for example, polyurethane, acrylic elastic body, silicone elastic body, diene elastic body, nitrile elastic body, Examples thereof include a fluorine-based elastic body, a polystyrene-based elastic body, a polyolefin-based elastic body, a polyamide-based elastic body, and a halogen-based elastic body. The concentration of the second polymer elastic body in the resin liquid is not particularly limited. For example, in the case of an emulsion, it is 10 to 50% by mass, more preferably 20 to 40% by mass, and particularly 25 to 35% by mass. preferable.

  The second filler is a component that imparts thixotropy to the coating liquid and also seals the voids on the surface of the artificial leather substrate. Specific examples of the second filler include solid particles that are the same filler as the first filler described above, and hollow particles such as plastic beads. Among these, clay, aluminum hydroxide, calcium carbonate, hollow particles and the like are particularly preferable from the viewpoint that the thixotropy index can be easily adjusted.

  The particle diameter of the solid particles is preferably 0.5 to 15 μm from the viewpoint of easy adjustment of the thixotropy index. The particle diameter of the hollow particles is preferably 10 to 80 μm from the viewpoint of easy adjustment of the thixotropy index.

  The blending amount of the second filler is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, and particularly preferably 10 to 30% by mass in the solid content of the coating liquid. . In addition, as the blending amount of the second filler in the case of hollow particles, the hollow particles corresponding to the volume of 5 to 70%, more preferably 10 to 50%, are blended with respect to the solid content volume of the coating liquid. It is preferable to do.

  Moreover, the coating liquid used for formation of a smoothing layer may contain the thickener for adjusting a thixotropic index and a viscosity as needed. Specific examples of the thickener include polyacrylic acid ammonium and polyacrylic acid. As a compounding quantity of a thickener, it is preferable that it is 0.5-5 mass parts with respect to 100 mass parts of solid content of a 2nd polymeric elastic body. Further, it may contain a dispersant for improving the stability of the coating liquid, a crosslinking agent for crosslinking the polymer elastic body, and a coloring agent such as a pigment. Specific examples of the dispersant include low molecular weight sodium polycarboxylate and sodium tripolyphosphate. As a compounding quantity of a dispersing agent, it is preferable that it is 0.2-2 mass parts with respect to 100 mass parts of solid content of a 2nd polymeric elastic body.

The coating liquid is prepared by adding the second filler and other additives such as a thickener blended as needed to the resin liquid of the second polymer elastic body, and stirring and mixing. . The viscosity of the coating liquid thus prepared is 100 to 600 Pa as a viscosity η _0.6 measured at a rotation speed of 0.6 rotations / second using a B-type rotational viscometer at a temperature of 25 ° C. S (Pascal second), more preferably 150 to 350 Pa · s. When it is such a viscosity, it is excellent in the coating property of a coating liquid, and it becomes difficult for a coating liquid to sink inside from the space | gap of the surface of an artificial leather base material.

  Further, the ratio of the solid content in the coating liquid is not particularly limited, but is preferably in the range of about 40 to 60% by mass from the viewpoint of excellent thixotropy, moderately thickening after coating, and excellent drying properties. .

  A smoothing layer is formed by applying such a coating liquid on the surface of the artificial leather base material and drying it. As a coating method, various coating methods such as a reverse coater and a doctor knife coater are used without particular limitation. The coating liquid receives a share at the time of coating and lowers the viscosity. After the coating, the viscosity increases, so that the coating liquid hardly sinks into the interior from the voids on the surface of the artificial leather base material.

  And the smoothing layer is formed by drying the applied coating liquid. The average thickness of the smoothing layer thus formed is preferably 10 to 100 μm, more preferably 20 to 70 μm. When the smoothing layer is too thick, the suppleness of the resulting artificial leather tends to decrease, and when it is too thin, the voids on the surface of the artificial leather substrate tend not to be sufficiently filled. Moreover, as a ratio of the 2nd filler in a smoothing layer, it is 1-50 mass%, Furthermore, 5-50 mass%, It is especially preferable that it is 10-30 mass%.

  The artificial leather substrate on which the smoothing layer is formed is preferably smoothed by filling most of the voids on the surface. In such a case, even if a resin liquid for imparting a silver-like appearance is applied to the surface of the smoothing layer, the resin liquid does not easily penetrate into the artificial leather base material. By using an artificial leather base material on which such a smoothing layer is formed, a silver-tone artificial leather that does not lose the flexibility of the artificial leather base material can be produced.

  The surface of the artificial leather substrate on which such a smoothing layer is formed has, for example, a surface water absorption rate of 100 seconds or more, 150 seconds or more, particularly 180 seconds in accordance with the dropping method of JIS L1907-7.1.1. The above is preferable. When the surface water absorption speed is less than 100 seconds, since the voids remain, the resin liquid tends to easily penetrate into the inside.

  Moreover, as a 2nd method for smoothing the surface of the artificial leather base material of this embodiment, the method of densifying the surface by hot-pressing the surface of the artificial leather base material of this embodiment is mentioned. . In this case, in particular, when the modifier is contained so as to be 10% by mass or more with respect to the fiber entanglement, the surface voids are filled with the modifier and the surface voids are reduced. For this reason, even if a resin liquid for imparting a silver-tone appearance is applied to the surface of the heat-pressed artificial leather base material, the resin liquid is suppressed from sinking inside the artificial leather base material. Therefore, by using an artificial leather substrate having a hot-pressed surface, it is possible to produce a silver-tone artificial leather without losing flexibility.

  And the coating liquid for forming a resin layer is apply | coated to the surface of the formed smoothing layer, Then, the resin layer of a silver surface tone is formed by the direct coat method which dries. The coating liquid for forming the resin layer is applied to the surface of the smoothing layer by a method such as spray coating or reverse coating. Among these, spray coating is preferable because a small amount of resin can be uniformly applied.

  Examples of the resin component for forming a silver-tone resin layer by the direct coating method include polyurethane, acrylic elastic body, silicone elastic body, diene elastic body, nitrile elastic body, fluorine elastic body, and polystyrene. Examples thereof include resin emulsions such as emulsions, suspensions, dispersions, and solutions of elastomers such as elastomers, polyolefins, polyamides, and halogens. These may be used alone or in combination of two or more. Of these, polyurethane emulsions are preferred because of their excellent wear resistance and mechanical properties. Further, the resin component for forming the silver layer may contain a colorant, an ultraviolet absorber, a surfactant, a flame retardant, an antioxidant, and the like, if necessary.

  The thickness of the silver-tone resin layer is preferably 10 to 1000 μm, more preferably 50 to 300 μm. The resin layer may have a laminated structure in which a plurality of layers such as a base coat layer, a colored layer, and a top clear layer are appropriately laminated. Moreover, it is preferable from the point of the designability that the resin layer has a wrinkle pattern formed by embossing or the like. The embossing includes a method of completely curing the silver surface layer after transferring the texture pattern in a state where the silver surface layer is uncured.

The silver-tone artificial leather according to the present embodiment has both flexibility as natural leather and high sense of fulfillment. Specifically, for example, it is preferable that the softness measured by a softness tester is 1.5 mm or more, preferably 1.8 to 2.5 mm. The apparent density is preferably 0.55 to 0.85 g / cm ³ , more preferably 0.60 to 0.80 g / cm ³ .

  Further, the raised artificial leather (suede, nubuck, velor, buckskin) can be obtained by buffing the surface layer of the artificial leather base material with sandpaper or the like and raising or raising the surface.

  In addition, it is possible to soften stagnation, soften by punching, brushing reverse seal, antifouling, hydrophilization, lubricant, softener, antioxidant, UV absorber, fluorescent agent, flame retardant. A finishing process such as a process may be performed.

  The present invention will be described more specifically with reference to examples. The scope of the present invention is not limited by the examples.

[Example 1]
<Manufacture of non-woven fabric>
Water-soluble thermoplastic polyvinyl alcohol (PVA) as the sea component, isophthalic acid-modified polyethylene terephthalate having a modification degree of 6 mol% as the island component, and a uniform cross-sectional area in the sea component set at a base temperature of 260 ° C. Molten resin was supplied to a plurality of spinning nozzles in which nozzle holes forming a cross section in which 25 island components were distributed were arranged in parallel, and were discharged from the nozzle holes. At this time, it supplied, adjusting pressure so that the mass ratio of a sea component and an island component might become sea component / island component = 25/75.

Then, the discharged melted fiber was drawn by a suction device so that the average spinning speed was 3700 m / min, and a long fiber of a sea-island type composite fiber having a fineness of 2.1 dtex was spun. The spun long islands of sea-island type composite fibers were continuously deposited on a movable net, and lightly pressed with a metal roll at 42 ° C. to suppress surface fuzz. And the long fiber of the sea-island type composite fiber was peeled off from the net, and passed between a lattice-shaped metal roll having a surface temperature of 55 ° C. and a back roll. In this way, a long fiber web having a basis weight of 31 g / m ² was obtained by hot pressing at a linear pressure of 200 N / mm.

Next, the web was overlapped on 8 layers by using a cross wrapping apparatus so that the total basis weight was 250 g / m ² , a superposed web was prepared, and a needle breakage preventing oil was further sprayed. Next, using a 6 barb needle with a distance of 3.2 mm from the tip of the needle to the first barb, needle punching was alternately performed at 3300 punch / cm ² from both sides at a needle depth of 8.3 mm. The area shrinkage rate by the needle punching process was 68%, and the basis weight of the entangled web after the needle punching was 550 g / m ² .

The entangled web was immersed in hot water at 70 ° C. for 14 seconds at a winding line speed of 10 m / min to cause area shrinkage. Next, by repeatedly performing dip nip treatment in hot water at 95 ° C. to dissolve and remove PVA, a fiber bundle having a fineness of 2.5 dtex containing 25 ultrafine fibers having a fineness of 0.1 dtex was entangled three-dimensionally. A nonwoven fabric was prepared. The area shrinkage percentage measured after drying was 52%. The nonwoven fabric was sliced and buffed to adjust the thickness to 1.05 mm. The nonwoven fabric of ultrafine fibers, which is the fiber entangled body thus obtained, had a basis weight of 576 g / m ² and an apparent density of 0.565 g / cm ³ .

<Impregnation with modifier>
A modifier was prepared by dispersing the components of a modifier composed of a flame retardant filler 38% owf, liquid paraffin 3.75% owf, and aqueous polyurethane 5% owf in water. Then, after impregnating the dispersion into the non-woven fabric of ultrafine fibers at a pickup rate of 80%, the modifier was homogeneously impregnated by drying the moisture. Then, using a shrink processing device (manufactured by Komatsubara Iron Works Co., Ltd., Sun Forging Machine), a nonwoven fabric made of impregnated ultrafine fibers impregnated with a modifier is used. The artificial leather base material was obtained by shrinking by 5.5% in the vertical direction (length direction) by treating at 10 ° C. and a conveyance speed of 10 m / min. The obtained artificial leather base material had a basis weight of 676 g / m ² and an apparent density of 0.633 g / cm ³ .

  As the flame retardant filler, a dispersion of aluminum dialkylphosphinate having an average particle diameter of 5 μm (solid content: 40%) was blended. Further, as the water-based polyurethane, the soft segment is a 70:30 mixture of polyhexylene carbonate diol and polymethylpentanediol, and the hard segment is a crosslinked type polyurethane mainly composed of hydrogenated methylene diisocyanate (solid content 30% by mass, An emulsion having a melting point of 180 to 190 ° C., a loss elastic modulus peak temperature of −15 ° C., and a hot water swelling ratio at 130 ° C. of 35% was used.

<Formation of silver layer>
A base coat layer having a thickness of 28 μm was formed on the surface of the artificial leather base material by roll-coating the base coat solution at a coating amount of 140 g / m ² using STARPLUS manufactured by Gemata. In addition, as the base coat solution, a polyurethane emulsion (DIC Co., Ltd., LCC binder UB1770 solid content 30% by mass) adjusted with a thickener so that the viscosity of Ford Cup No. 4 55S was 195 mPa · s was used. . Then, a color coat layer having a film thickness of 14 μm was formed by spray coating the surface of the formed base coat layer with a color coat solution at a coating amount of 70 g / m ² using STARPLUS manufactured by Gemata. As the color coating solution, a polyurethane emulsion (DIC Co., Ltd., LCC binder UB1770 solid content 30%) adjusted with an Iwata cup (IWATA NK-2 12s) to 30 mPa · s was used. Further, the blanking process was performed at 40 to 50 ° C. for 2 to 4 hours. Then, the surface layer was embossed using an embossing roll at 125 ° C. and 50 kg / cm ² at a line speed of 7.0 m / min. Then, a top coat paint (clear paint made by Tope Co., Ltd.) adjusted to 30 mPa · s with an Iwata cup (IWATA NK-2 12s) was applied to the surface to form a top coat with a film thickness of 13.5 μm. Thus, a silver-tone artificial leather having a basis weight of 777 g / m ² and an apparent density of 0.762 g / cm ³ was obtained.

<Evaluation of artificial leather with silver tone>
The obtained silver-tone artificial leather was evaluated according to the following evaluation methods.

(Flexibility)
Bending softness was measured using a softness tester (leather softness measuring device ST300: manufactured by MSA Engineering System, UK). Specifically, a predetermined ring having a diameter of 25 mm was set in the lower holder of the apparatus, and then a silver-tone artificial leather was set in the lower holder. And the metal pin (diameter 5 mm) fixed to the upper lever was pushed down toward the silver-finished artificial leather. And the numerical value when the upper lever was pushed down and the upper lever was locked was read. The numerical value represents the penetration depth, and the larger the numerical value, the more flexible.

(Texture)
A sample was prepared by cutting out the artificial leather with silver into 20 × 20 cm. Then, the appearance when bent inward from the center and the appearance when gripped were determined according to the following criteria.
A: When it was bent, it was bent like a round, and fine and fine creases were generated. It was also excellent in drape.
B: When bent, it bent and bent, and rough wrinkles and deep wrinkles were generated. Moreover, it was inferior to the drape property.
C: The texture was remarkably low.

(Silver surface coating)
A: A smooth and smooth surface was formed with little sinking of the silver layer.
B: There was a slight sinking of the silver layer, and a slight roughness of the surface fibers was felt.
C: The silver layer was almost submerged, and the surface was exposed with fibers and was fuzzy.

(Apparent density)
The thickness (mm) and the basis weight (g / cm ² ) were measured according to JIS L1913, and the apparent density (g / cm ³ ) was calculated from these values.

  The above evaluation results are shown in Table 1 below.

[Examples 2 to 11]
Except for impregnating and imparting the modifier prepared by changing the composition of the dispersion for the modifier prepared in Example 1 to the composition and amount as shown in Table 1, the nonwoven fabric of ultrafine fibers, In the same manner as in Example 1, a silver-tone artificial leather was obtained and evaluated. The results are shown in Table 1 . Example 4 is a reference example. Also, the cross-sectional photograph of when observed in nonwoven scanning electron microscope of the ultrafine fiber obtained in Example 6 in FIG. 3 (SEM), artificial leather obtained by impregnating imparting modifier 4 The cross-sectional photograph of SEM of a base material is shown. Moreover, the cross-sectional photograph of SEM of the silver-tone artificial leather base material obtained in Example 6 is shown in FIG.

[Example 12]
In the composition of the dispersion for the modifier prepared in Example 6, the same procedure as in Example 1 was conducted except that alumina (Al ₂ O ₃ ) particles were blended instead of blending aluminum dialkylphosphinate as the particulate filler. A silver-tone artificial leather was obtained and evaluated. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, instead of impregnating the fine fiber non-woven fabric with the modifier dispersion, it was used in Example 1 so that the solid content was 12.5% by mass with respect to the ultra-fine fiber non-woven fabric. A silver-tone artificial leather was obtained and evaluated in the same manner except that it was impregnated with the same aqueous polyurethane dispersion and dried at 120 ° C. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, a silver-finished artificial leather was obtained and evaluated in the same manner as in Example 1 except that the step of impregnating with the modifier was omitted. The results are shown in Table 1.

[Comparative Examples 3 to 6]
Except for adjusting the composition of the dispersion for the modifier prepared in Example 1 and impregnating the artificial leather base material with the composition and amount of the modifier as shown in Table 1, Example 1 and In the same manner, a silver-tone artificial leather was obtained and evaluated. The results are shown in Table 1.

The artificial leather substrates obtained in Examples 1 to 12 according to the present invention all have an apparent density of 0.6 g / cm ³ or more, and the softness of the silver-tone artificial leather is 1.8 mm or more. Thus, an artificial leather having a sense of fullness and flexibility was obtained. On the other hand, the artificial leather obtained in Comparative Example 1, which is a conventional representative artificial leather, imparting a sense of fulfillment to the nonwoven fabric by applying a polymer elastic body, has an apparent density of 0.6 g / cm ³ or more. Although there was a sense of fulfillment, the bending resistance was 0.89 mm and the flexibility was low. Further, in the production of the artificial leather of Comparative Example 1, it was easy to soak into the artificial leather base material when the resin liquid for the silver surface layer was coated. This is because many voids remained on the surface. Moreover, the artificial leather of Comparative Example 6 containing no filler had a low apparent density and a low sense of fulfillment.

  In addition, although the artificial leather of Example 8 had a slightly low sense of fulfillment due to the relatively low proportion of the modifier, it showed very high flexibility. However, since the artificial leather of Example 8 had voids on the surface, the coated resin liquid was likely to penetrate.

  From the above examples, according to the present invention, an artificial leather having a supple texture and a sense of fulfillment can be obtained by impregnating and imparting the above modifier to the gaps between the fibers of the fiber entangled body. I understand that.

[Example 13]
Instead of forming a base coat having a film thickness of 28 μm on the surface of the artificial leather substrate obtained in Example 6, a smoothing layer was formed as follows. Specifically, 42.9 parts by mass of filler (calcium carbonate having an average particle diameter of 5 μm) is blended with 100 parts by mass of the solid content of polyurethane emulsion (DIC Co., Ltd., LCC binder UB1770 solid content 30% by mass). Then, a smoothing layer coating solution was prepared by adding a thickener and stirring and mixing. The obtained smoothing layer coating liquid had a viscosity η _0.6 of 240 Pa · s when measured at a rotation speed of 0.6 revolutions / second using a B-type rotational viscometer at a temperature of 25 ° C. The viscosity η _3.0 when measured at a rotational speed of 3 revolutions / second was 75 Pa · s, and η _0.6 / η _3.0 was 3.2. In the case of only the polyurethane emulsion, the viscosity η _0.6 was 4.2 Pa · s, the viscosity η _3.0 was _3.0 Pa · s, and η _0.6 / η _3.0 was 1.4.

A smoothing layer having a thickness of 45 μm was formed by applying 140 g / m ² of a smoothing layer coating solution on the surface of the artificial leather substrate obtained in Example 6 using a reverse coater and drying. The surface water absorption rate of the smoothing layer thus formed was measured by the following method. As a result, the surface water absorption speed was 180 seconds or more. The results are shown in Table 2.

(Surface water absorption speed)
It measured according to the dropping method of JIS L1907-7.1.1. Specifically, the artificial leather base material was cut into a size of about 200 mm × 200 mm to prepare a test piece. The prepared test piece was attached to the test piece holding frame, placed between the light source and the observer, and adjusted so that the height from the surface on the smoothing layer side of the test piece to the tip of the buret was 10 mm. Then, one drop of water is dropped from the burette on the surface of the smoothing layer side of the test piece, and when the water drop reaches the surface of the test piece, the specular reflection disappears as the test piece absorbs the water drop, and only wetness remains. The time to the state was measured with a stopwatch. The results are shown in Table 2.

Then, a color coat layer having a film thickness of 14 μm was formed on the surface of the smoothing layer of the artificial leather substrate in the same manner as in Example 1. Further, the blanking process was performed at 40 to 50 ° C. for 2 to 4 hours. Then, in the same manner as in Example 1, the surface layer was embossed using an embossing roll at 125 ° C. and 50 kg / cm ² at a line speed of 7.0 m / min. In the same manner as in Example 1, a top coat having a thickness of 13.5 μm was formed. Thus, a silver-tone artificial leather having a basis weight of 665 g / m ² and an apparent density of 0.629 g / cm ³ was obtained. FIG. 6 shows an SEM photograph of the oblique section before the formation of the smoothing layer of the artificial leather substrate obtained in Example 13, and FIG. 7 shows an SEM photograph of the oblique section after the formation of the smoothing layer. Moreover, the cross-sectional photograph of SEM of the silver-tone artificial leather base material obtained in Example 13 is shown in FIG. Further, the amount of sinking (g / m ² ) was calculated from the difference between the coating amount when forming the smoothing layer and the thickness of the actually formed film. However, it was set to 0 when it became a value smaller than 0. Table 2 shows the results of bending resistance and texture.

[Examples 14 to 18]
As shown in Table 2, the smoothing layer was the same as Example 13 except that 5% by mass, 10% by mass, 20% by mass, 40% by mass, and 50% by mass of the filler (calcium carbonate) were blended. The coating liquid was blended. A silver-tone artificial leather was obtained in the same manner as in Example 13 except that the adjusted smoothing layer coating solution was used. The results are shown in Table 2.

[Examples 19 to 21]
As shown in Table 2, silver-tone artificial leather was obtained in the same manner as in Example 13 except that the thickness of the smoothing layer was changed to 20 μm, 31 μm, and 54 μm, respectively. The results are shown in Table 2.

[Example 22]
As shown in Table 2, instead of blending 30% by mass of the filler (calcium carbonate), the filler (vinylidene chloride / nitrile plastic balloon having an average particle size of 30 μm) is added to 100 parts by mass of the solid content of the polyurethane emulsion. 1.5 parts by weight, except that 50% by volume was blended, the smoothing layer coating solution was blended in the same manner as in Example 13, and the adjusted smoothing layer coating solution was used. In the same manner as in Example 13, a silver-tone artificial leather was obtained. The results are shown in Table 2. 9 shows an SEM photograph of the oblique section after the formation of the smoothing layer of the artificial leather base material obtained in Example 22, and FIG. 10 shows the SEM of the silver-tone artificial leather base material obtained in Example 22 in FIG. A cross-sectional photograph is shown.

In any of the artificial leather base materials obtained in Examples 13 to 22, the smoothing layer and the silver surface layer were subducted, and the surface water absorption rate of the artificial leather base material was low. Therefore, it can be seen that the provision of the smoothing layer can suppress the sinking of the silver-tone resin layer on the surface of the artificial leather substrate. By suppressing the sinking of the resin layer having a silver surface tone, a silver-tone artificial leather having an extremely supple texture can be obtained. On the other hand, as shown in Example 6, when a polyurethane emulsion having a η _0.6 / η _3.0 of 1.4, in which no filler was added, was used, it was found that a slight sink was observed.

  The artificial leather of the present invention is used as a leather-like material for shoes, clothing, gloves, bags, balls, interiors, vehicle interiors, and the like.

Claims (19)

Wherein the fiber-entangled body, the fiber-entangled body impregnated granted, fixed oils of the first filler and the liquid and the first elastic polymer, and
The first filler, metal filler, metal oxide filler, inorganic filler, flame retardant fillers, and artificial leather substrate comprising at least one selected from a carbon-based filler.   The artificial leather base material according to claim 1, wherein the non-volatile oil contains at least one selected from liquid paraffin, silicone oil, mineral oil, and phthalates.   The artificial leather substrate according to claim 1 or 2, wherein the fiber entangled body is a non-woven fabric of ultrafine fibers having a fineness of 0.9 dtex or less.   The artificial leather base material of any one of Claims 1-3 which contain 1-60 mass% of said 1st fillers with respect to the said fiber entanglement body.   The artificial leather base material according to any one of claims 1 to 4, comprising 0.5 to 10% by mass of the non-volatile oil with respect to the fiber entangled body.   The artificial leather base material according to any one of claims 1 to 5, comprising 0.5 to 15% by mass of the first polymer elastic body with respect to the fiber entangled body.   In any one of Claims 1-6 which contains 10-30 mass% of said 1st filler, the said non-volatile oil, and said 1st polymeric elastic body in total with respect to the said fiber entanglement body. The artificial leather substrate as described.   The non-volatile oil according to any one of claims 1 to 7, comprising 3 to 70% by mass of the non-volatile oil in a total amount of the first filler, the non-volatile oil, and the first polymer elastic body. Artificial leather base material.   In any one of Claims 1-8 which contain 30-97 mass% of said 1st fillers in the total amount of a said 1st filler, the said non-volatile oil, and a said 1st polymer elastic body. The artificial leather substrate as described.   10. The composition according to claim 1, wherein 1 to 20 mass% of the first polymer elastic body is contained in the total amount of the first filler, the non-volatile oil, and the first polymer elastic body. The artificial leather substrate according to Item. The artificial leather base material according to any one of claims 1 to 10, which has an apparent density of 0.60 g / cm ³ or more. A smoothing layer for smoothing the surface;
The smoothing layer includes a second elastic polymer, metal filler, metal oxide filler, inorganic filler, flame retardant fillers, and also one of the second filling and less selected carbon-based filler or al The artificial leather base material according to any one of claims 1 to 11, which is a layer having a thickness of 10 to 100 µm containing an agent.   The artificial leather substrate according to claim 12, wherein the smoothing layer contains 1 to 50% by mass of the second filler.   The artificial leather substrate according to claim 12 or 13, wherein a surface water absorption rate of the smoothing layer based on a dropping method of JIS L1907-7.1.1 is 100 seconds or more.   A silver-tone artificial leather formed by further laminating a resin layer on the smoothing layer of the artificial leather base material according to any one of claims 12 to 14.   The silver-finished artificial leather according to claim 15, wherein the bending resistance measured by a soft tester is 1.8 to 2.5 mm. It is a manufacturing method of the artificial leather base material of Claim 12, Comprising: The process of preparing the raw material of the artificial leather base material in any one of Claims 1-11,
Forming a smoothing layer having a thickness of 10 to 100 μm by applying a smoothing layer-forming coating liquid on the surface of the original fabric and then drying the coating solution;
The smoothing layer forming coating liquid is:
Including the second polymer elastic body and the second filler as a solid content,
Ratio of viscosity η _0.6 when measured at a rotational speed of 0.6 revolutions / second using a B-type rotational viscometer at a temperature of 25 ° C. and viscosity η _3.0 when measured at a rotational speed of 3 revolutions / second ( thixotropic index is η _0.6 / η _3.0) is 2-4, process for producing an artificial leather substrate.   The method for producing an artificial leather base material according to claim 17, wherein the smoothing layer forming coating solution contains 1 to 50 mass% of the second filler in a solid content. As non-volatile components, it includes a 3 to 90 wt% non-volatile oil liquid, the first filler and the blend 10-97% by weight of the first elastic polymer, and
The first filler, metal filler, metal oxide filler, inorganic filler, flame retardant fillers, and artificial leather substrate modifier for containing at least one selected from a carbon-based filler.