JP6163422B2 - Leather-like sheet and manufacturing method thereof - Google Patents

Description

  The present invention relates to a leather-like sheet having a transparent and deep surface layer such as aniline leather.

  2. Description of the Related Art Conventionally, a leather-like sheet such as artificial leather having a colored surface layer formed on the surface of a fiber entangled body that resembles natural leather is known. Such leather-like sheets are widely used in the fields of shoes, clothing, gloves, bags, balls, interiors, vehicles, and the like as substitutes for natural leather.

  Usually, as a coloring method of natural leather containing collagen fibers, aniline finishing using a dye and pigment finishing using a pigment are known. Specifically, the aniline finish is tanned and tanned on high-quality natural leather with no scratches, and then dyed with an aniline dye that produces a vivid and transparent color. This is a method of finishing leather by forming a thin coating film using a paint containing a dye. Pigment finish, on the other hand, forms a relatively thick, uniform coating film that hides scratches and color unevenness using a paint containing a pigment and a synthetic resin binder on the surface of non-high-grade natural leather that has scratches. This is a method of finishing leather.

  The aniline leather obtained by aniline finish is finished by forming a transparent thin film containing dye, so the silver surface of the dyed natural leather appears on the appearance and the natural texture of the leather itself The remaining high-quality finish and the soft feel can be maintained. On the other hand, the leather obtained by the pigment finish forms a thick film having a concealing property on the surface, so that the original silver surface of the leather does not appear in the appearance, and the finish is inferior in luxury.

  By the way, in applications where natural leather has been widely used, for example, for car skins of automobile seats, further improvements in dye fastness, light resistance and the like are required. For example, car seats equipped with seat heaters for warming seats are becoming popular. When natural leather dyed with a dye is used as the skin material of a car seat equipped with such a seat heater, the dye may sublimate due to the heat of the heater, or the dye may be altered and discolored. . Furthermore, for example, when aniline leather is to be applied to the skin material of a car seat, the aniline leather coating film has low durability and may be disadvantageous in that it easily causes discoloration and water spots. It was difficult.

  From such a point, a leather-like material having a high-grade appearance like aniline leather and excellent colorant fastness has been demanded.

  For example, in Patent Document 1 below, a coating layer made of a mixture of a pigment and a resin is formed on an artificial leather fiber as an artificial leather having an unprecedented excellent appearance by arbitrarily controlling the gloss difference of the surface. In the colored leather sheet, a granular pigment having a particle size of 0.5 to 1.0 μm is disposed as a pigment, and at least a part of the pigment is locally smooth-deformed on the surface of the sheet. A glossy leather sheet in which a gloss difference is induced between the smooth deformation portion and the smooth deformation portion is disclosed.

Japanese Patent Laid-Open No. 8-31778

  An object of the present invention is to provide a leather-like sheet having a transparent and deep color surface, such as aniline leather, and having excellent colorant fastness.

  The leather-like sheet of the present invention includes a base material including a fiber entangled body colored with a first pigment and a skin layer laminated on the base material, and the skin layer has an average particle diameter of less than 500 nm. It is formed from a light-transmitting film colored with the second pigment and having a total light transmittance of 5% or more. According to such a configuration, the coloring of the first pigment of the base material including the fiber entanglement and the second pigment having a particle diameter of less than 500 nm of the light-transmitting film having a total light transmittance of 5% or more. The coloration expresses a translucent and deep color like an aniline leather. Further, compared to dyed aniline leather, since it is colored with a pigment, the colorant has excellent durability such as fastness and light resistance.

  It is preferable that the first pigment contained in the fiber entangled body has an average particle diameter of 500 nm or more because it is easy to fix to the fiber entangled body and is excellent in balance between hiding power and coloring power. When the thickness is less than 500 nm, the concealability with respect to the color of the fiber entangled body tends to be low.

  The base material contains the first pigment in the gaps between the fibers of the fiber entangled body, specifically, it is excellent in fastness of the colorant that is fixed to the fiber with a polymer elastic body serving as a binder. It is preferable from the point. Further, the substrate may be a substrate including a colored resin layer containing the first pigment in the surface layer of the fiber entangled body.

Further, the fiber entangled body has an apparent density of 0.55 g / cm ³ or more, and is an entangled body of ultrafine fibers having a fineness of 0.9 dtex or less. From the viewpoint of excellent balance.

  In addition, the base material is composed of liquid non-volatile oil such as liquid paraffin, silicone oil, mineral oil, phthalates, inorganic filler, organic filler, and polymer elastic body in the gaps between the fibers of the fiber entanglement. A base material impregnated with a modifier containing such a filler, and when the ratio of the non-volatile oil to the fiber entanglement is 0.5% by mass or more, it is soft like aniline leather. It is preferable in that it has both a good feel and a sense of fulfillment. Specifically, the balance between the supple texture and the sense of fulfillment can be adjusted according to the purpose by impregnating and imparting the above-described modifier to the gaps between the fibers of the fiber entangled body. As a result, for example, when bent, it becomes difficult to produce buckled folds, which are also referred to as “boiled” folds, and a rounded and high-quality fold like natural leather can be obtained.

The method for producing a leather-like sheet of the present invention is an entangled body of ultrafine fibers having an apparent density of 0.55 g / cm ³ or more and a fineness of 0.9 dtex or less. A step of preparing a base material containing one pigment, and a coating film is formed by applying a light-transmitting film-forming paint containing a second pigment having an average particle size of less than 500 nm to the surface of the base material And a step of drying the coating film to form a surface film having a total light transmittance of 5% or more. According to such a method, it is possible to easily form a light transmissive film by a coating method for forming a light transmissive film, such as spray coating. Further, by adjusting the color of the light-transmitting film-forming paint, color matching can be performed in the finishing process.

  ADVANTAGE OF THE INVENTION According to this invention, the leather-like sheet | seat excellent in fastness which has a transparent and deep color surface layer like an aniline leather is obtained.

FIG. 1 is a schematic cross-sectional view of a leather-like sheet 10 according to an embodiment of the present invention. FIG. 2 is an explanatory diagram for explaining reflection of light when visible light is applied to the surface of the leather-like sheet 10.

  FIG. 1 is a schematic cross-sectional view of a leather-like sheet 10 according to an embodiment of the present invention. The leather-like sheet 10 includes a fiber base material 1 including a fiber entangled body 1 a and a skin layer 2 formed on the surface of the fiber base material 1. The fiber substrate 1 contains the first pigment 3 whose particle diameter is not limited. The skin layer 2 is made of a light-transmitting film having a total light transmittance of 5% or more, which is colored with the second pigment 4 having an average particle diameter of less than 500 nm. The first pigment 3 in the fiber substrate 1 is preferably fixed to the fiber entangled body 1a with a polymer elastic body 6 serving as a binder. Moreover, the fiber base material 1 may be provided with the base resin layer 5 which becomes the foundation for smoothing the surface as needed and forming the skin layer 2 on the surface layer. In this case, when the base resin layer contains the first pigment, a part of the fiber base material may be formed, and when the base resin layer contains the second pigment 4, a part of the skin layer may be formed.

  FIG. 2 is an explanatory diagram for explaining a state when visible light is applied to the surface of the leather-like sheet 10. When visible light is applied to the leather-like sheet 10, a part of the visible light is reflected by the second pigment 4 contained in the skin layer 2 to visually recognize the colored light hμ due to the pigment 4 to the eyes 20 of the viewer. Let Further, since the second pigment 4 contained in the skin layer 2 is a fine particle having an average particle diameter of less than 500 nm, a part of the visible light passes through the skin layer 2 and the fiber base material 1 layer. Incident up to. Then, the colored light hμ ′ from the pigment 3 is made visible to the eyes 20 of the person who is reflected by the first pigment 3 contained in the fiber substrate 1 and visually recognized. As a result, a person who visually recognizes the surface can visually recognize the color developed by the first pigment 3 and the second pigment 4 to feel a clear and deep color like a dye-finished aniline leather.

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

  The fiber entangled body contained in the fiber substrate is not particularly limited as long as it is a structure in which fibers such as nonwoven fabric, woven fabric, woven fabric, and knitted fabric are entangled three-dimensionally. Among these, when using non-woven fabrics, especially non-woven fabrics of fine fibers, the fiber density is high, and the fiber density is low and the uniformity is high. From the point that a leather-like sheet is obtained. In this embodiment, the case where the fiber entanglement of the ultrafine fiber which is a nonwoven fabric is used is demonstrated in detail as a representative example.

  The fiber entangled body of ultrafine fibers can be obtained, for example, by entanglement processing of ultrafine fiber generating fibers such as sea-island type composite fibers to form a fiber entangled body, and then subject the fibers to ultrafine fiber treatment. In the present 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 directly used without using the ultrafine fiber-generating fiber. 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 entangled body, first, the thermoplastic resin constituting the sea component of the sea-island type composite fiber that can be selectively removed and the island component of the sea-island type composite fiber that is the resin component forming the ultrafine fiber are constituted. A sea-island type composite fiber is obtained by melt spinning and stretching a thermoplastic resin.

  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 that can form 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 fiber entangled body of ultrafine fibers, for example, a sea island type composite fiber is melt spun to produce a web, the web is entangled, and then sea components are selectively removed from the sea island type composite fiber. Examples thereof include a method for forming ultrafine fibers. 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.

  Usually, in any process from removing sea components of the web made of sea-island type composite fibers to forming ultrafine fibers, fiber shrinkage treatment such as entanglement treatment, heat shrinkage treatment with water vapor, etc. It is preferable to apply a crystallization treatment. As the entanglement treatment, for example, a method in which about 5 to 100 obtained webs are stacked and the web is entangled using a known nonwoven fabric manufacturing method such as needle punching or high-pressure water flow treatment is used.

  The sea component of the sea-island composite fiber can be removed by extraction or decomposition at an appropriate stage after the web is formed. By such decomposition removal or extraction removal, the sea-island type composite fibers are made into ultrafine fibers to form fiber bundles of ultrafine fibers.

  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, the feeling of denseness becomes insufficient, and a fiber entangled body with a feeling of coarseness tends to be obtained. Further, fibers with too low fineness are difficult to produce, and the fibers tend to converge without being unraveled, and the resulting fiber entanglement tends to increase in rigidity.

  The fiber entangled body of the ultrafine fibers thus obtained is subjected to thickness adjustment and flattening treatment by slicing or buffing as necessary. In this way, a fiber entanglement of ultrafine fibers 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. Further, 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 is preferable from the viewpoint of obtaining a leather-like sheet excellent in balance between a sense of fulfillment and a supple texture.

  The fiber base material including the fiber entangled body further contains a first pigment whose particle size is not limited. The first pigment is fixed to the fiber entangled body with a polymer elastic body serving as a binder, is kneaded with the fiber itself forming the fiber entangled body, or a colored layer is provided on the surface layer of the fiber entangled body. It is contained in the fiber base material. Among these, the method of fixing the first pigment to the fiber entangled body with a polymer elastic body is preferable from the viewpoint of easy coloring and color matching.

  The kind of 1st pigment is not specifically limited. Specific examples thereof include organic pigments such as diketopyrrolopyrrole pigments, quinacridone pigments, anthraquinone pigments, and inorganic pigments such as iron oxide; Organic pigments such as pigments, quinophthalone pigments, condensed azo pigments and azo complex pigments, inorganic pigments such as bismuth yellow and titanium yellow; copper to phthalocyanine pigments, cobalt blue, bitumen, ultra Inorganic pigments such as marine; examples of the black type include carbon black. Such pigments may be used singly or in combination of two or more in order to adjust the target color.

  The average particle diameter of the first pigment is not particularly limited, but is 500 nm or more, further 1000 nm or more, preferably 200000 nm or less, and more preferably 150,000 nm or less. When the average particle diameter of the first pigment is too small, the colorability tends to be lowered by embedding with the polymer elastic body when the fiber is entangled with the polymer elastic body. In addition, when the average particle diameter of the first pigment is too large, when a fine fiber entangled body of ultrafine fibers is used, it is difficult to enter the void formed by the fiber entangled body and it is difficult to be fixed. Thereby, there exists a tendency for the coloring property of a core part to fall.

  The average particle diameter of the pigment means the average particle diameter of the aggregated pigment formed by fixing the primary particles with a vehicle. The average particle diameter of such a pigment represents the dispersed particle diameter of the pigment particles. When a dispersion is used, the median obtained by measuring the dispersion as a raw material with a dynamic light scattering particle size distribution analyzer. It is substantially the same as the diameter.

  An example of a method for fixing the first pigment to the fiber entangled body with a polymer elastic body will be described. For example, the first pigment is impregnated in the space between the fibers of the fiber entangled body in the state of a dispersion liquid mixed with a dispersion or solution of the polymer elastic body, and the first pigment is removed by removing the dispersion medium. Is fixed to the fiber entangled body with a polymer elastic body.

  Specific examples of the 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, polyolefin elastic body, and polyamide. System elastic body, halogen-based 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.

  Also, as polyurethane, aqueous polyurethane such as polycarbonate polyurethane, polyester polyurethane, polyether polyurethane, polycarbonate / ether polyurethane, etc. prepared in an emulsion is easy to prepare a dispersion, and crosslinking is also possible. By forming the structure, it is particularly preferable from the viewpoint of expressing a softer texture by being present in the voids without being too closely adhered to the fiber.

  When mixing the first pigment and the polymer elastic dispersion, it is preferable to use a pigment dispersion containing the first pigment. For example, when an aqueous polyurethane is used, an aqueous pigment in which the pigment is dispersed in an aqueous medium is preferably used. Such an aqueous pigment can be easily obtained as a commercially available pigment dispersion.

  By mixing the pigment dispersion containing the first pigment and the dispersion of the polymer elastic body, a colored dispersion containing the first pigment and the polymer elastic body is prepared. Then, after impregnating the fiber entangled body with the colored dispersion, the pigment is fixed to the fiber entangled body with a polymer elastic body by removing the dispersion medium.

  The method for impregnating the fiber entangled body with the colored dispersion is not particularly limited. For example, a method of impregnating the fiber entangled body with the colored dispersion by dip-nip is preferably used. Then, after impregnating the fiber entangled body with the colored dispersion, the fiber entangled body that has absorbed the colored dispersion is dried, and the volatile components such as the dispersion medium in the colored dispersion are dried to remove the colored dispersion. The pigment inside and the polymer elastic body are solidified in the gaps 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 pigment and a polymeric elastic body can be provided to the space | gap between the fibers of a fiber entanglement body.

  The ratio of the polymer elastic body to the fiber entangled body is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When the ratio of the polymer elastic body to the fiber entangled body is too high, the rubber feeling becomes strong and the resilience becomes high, so that the supple texture tends to decrease. Further, the ratio of the first pigment to the fiber entangled body is not particularly limited, but the ratio of the pigment attached to the fiber forming the fiber entangled body is, for example, 0.01 to 20% owf (on weight of fiber), Further, it is preferably 0.05 to 10% owf.

  In addition, the fiber entangled body may be further impregnated with a modifier containing a liquid non-volatile oil and a filler that is filled in the gaps of the obtained leather-like sheet. By applying such a modifier to the fiber entangled body, the voids of the fiber entangled body are filled, so when the skin layer is formed by painting on the surface of the fiber substrate containing the fiber entangled body, excessively The penetration of the coating liquid can be suppressed, and flexibility and flexibility are also provided.

  As the modifier dispersion used for imparting the modifier, for example, liquid non-volatile oil and 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. Is used.

  The liquid non-volatile oil is a liquid having a boiling point of 150 ° C. or higher and substantially not dissolved in a polar solvent. Specifically, for example, liquid paraffin, mineral oil, silicone oil, phthalates, etc. Is mentioned. These may be used alone or in combination of two or more. Among these, liquid paraffin is particularly preferable because it has excellent chemical stability and is not easily oxidized.

  The filler in the present embodiment is a component that is solid at room temperature and can be dispersed without substantially dissolving in a polar solvent, and examples thereof include inorganic fillers, organic fillers, and polymer elastic bodies. Further, the inorganic filler and the organic filler may have a function as a pigment.

As the inorganic filler and the organic filler, for example, various fillers composed of metals, metal oxides, inorganic compounds, organic compounds, and the like having an average particle diameter of 100 to 30000 nm and further an average particle diameter of about 500 to 20000 nm are used without particular limitation. . Specific examples thereof include fillers of metal oxides such as alumina (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), cerium dioxide (CeO ₂ ); silica (SiO ₂ ), talc, mica , Fillers of inorganic compounds such as caged polysilsesquioxane (POSS); flame retardant fillers such as ammonium polyphosphate, aluminum dialkylphosphinate, and melamine phosphate; carbon nanotubes (CNT), carbon fibers (CF) Carbon black fillers such as 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.

  The concentration of each component in the modifier dispersion is preferably adjusted as appropriate in consideration of the intended modifier composition, the viscosity and stability of the dispersion, and the like. Specifically, examples of the ratio of the dispersion medium such as water in the dispersion include 1 to 95% by mass, and further about 5 to 90% by mass. Moreover, as a ratio of the non-volatile oil in a modifier dispersion liquid, it is preferable to mix | blend, for example in 1-50 mass%, Furthermore, about 3-30 mass%. Moreover, it is preferable to mix | blend the ratio of the filler in a modifier dispersion liquid, for example in 5 to 99 mass%, Furthermore, about 7 to 80 mass%.

  The fiber entangled body is impregnated with the modifier dispersion, and then dried to remove volatile components such as a dispersion medium by drying, whereby the active ingredient of the modifier is solidified in the gaps 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 pigment and modifier can be provided to the space | gap between the fibers of a fiber entanglement body. The formed modifier is present in the voids, for example, in the form of clay or paste. Therefore, the gap between the fibers of the fiber entangled body is filled, and when the skin layer is formed on the surface of the fiber base material by coating, the coating liquid is prevented from penetrating excessively.

  The amount and composition of the modifier are not particularly limited, but the ratio of the nonvolatile oil to the fiber entangled body is 0.5% by mass or more, further 1 to 10% by mass, particularly 3 to 8% by mass. It is preferable to make it. When the ratio of the non-volatile oil to the fiber entangled body is less than 0.5% by mass, a supple texture tends to be hardly obtained. Moreover, when the ratio of the non-volatile oil with respect to a fiber entanglement body is too high, there exists a tendency for a fiber entanglement body to hold | maintain a non-volatile oil and to drop out.

  Moreover, the ratio of the non-volatile oil in the modifier is not particularly limited, but it is 1 to 90% by mass, more preferably 3 to 90% by mass, and particularly 10 to 70% by mass. From the point of being excellent in balance with. When the proportion of the non-volatile oil contained 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 a sense of fulfillment can be obtained. There is a tendency to decrease.

  Moreover, as a ratio of the filler in a modifier, it is preferable that it is 10-99 mass%, 10-97 mass%, especially 30-90 mass%. When the proportion of the filler contained in the modifier is too low, the sense of fulfillment tends to decrease, and when it is too high, the proportion of the non-volatile oil becomes relatively low, thereby reducing the supple texture. Tend to.

  Moreover, it is preferable that the ratio of the polymeric elastic body in the modifier with respect to a fiber entangled body is 0-10 mass%, 1-5 mass%, especially 1-2 mass%. When the ratio of the polymer elastic body to the fiber entangled body is too high, the rubber feeling becomes strong and the resilience becomes high, so that the supple texture tends to decrease. The polymer elastic body is not an essential component, but the elasticity can be adjusted by blending.

  The ratio of the modifier to the fiber entangled body is not particularly limited, but is 1 to 40% by mass, preferably 3 to 30% by mass, and particularly 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 fiber base material colored with the 1st pigment containing a fiber entanglement body is obtained. Such fiber base material is 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 Further, finishing treatment such as hydrophilization treatment, lubricant treatment, softener treatment, antioxidant treatment, ultraviolet absorber treatment, fluorescent agent treatment, and flame retardant treatment may be performed.

The thickness of the fiber substrate thus obtained is not particularly limited, but is preferably about 100 to 3000 μm, more preferably about 300 to 2000 μm. Moreover, the apparent density of the fiber base material is not particularly limited, but is preferably about 0.55 to 0.85 g / cm ³ from the viewpoint of excellent balance between a sense of fulfillment and a supple texture.

  Formed on the surface of the fiber substrate thus obtained is a skin layer formed from a light-transmitting film having a total light transmittance of 5% or more colored with the second pigment having an average particle diameter of less than 500 nm. By doing so, a leather-like sheet having a transparent and deep surface layer, such as aniline leather colored with a dye, is finished.

  The leather-like sheet is obtained by forming a skin layer formed from a light-transmitting film having a total light transmittance of 5% or more colored with a second pigment having an average particle diameter of less than 500 nm on a fiber substrate. It is done.

  The skin layer is a light-transmitting film having a total light transmittance of 5% or more and colored with a second pigment having an average particle diameter of less than 500 nm, and does not lose transparency with the light-transmitting resin component. A transparent pigment having an average particle size of The transparent pigment can be colored while maintaining the transparency of the skin layer.

  The type of the second pigment is not particularly limited, and specifically, for example, the same pigments as those exemplified for the first pigment are used.

  The average particle diameter of the second pigment is less than 500 nm, preferably 400 nm or less, and more preferably 300 nm or less. When the average particle diameter of the second pigment is 500 nm or more, the light transmittance of the skin layer is lowered. The lower limit of the average particle diameter of the second pigment is not particularly limited, but is preferably about 100 nm from the viewpoint of colorability and productivity. In addition, the dispersion liquid of the pigment with an average particle diameter of less than 500 nm is commercially available from, for example, Nihongo Bix Co., Ltd. Such pigments may be used singly or in combination of two or more in order to adjust the target color.

  The light-transmitting resin component for forming the light-transmitting film of the skin layer is not particularly limited as long as it is a resin component having light transmittance. Specific examples of the resin type include polyurethane, acrylic resin, silicone resin, diene resin, nitrile resin, fluorine resin, polystyrene resin, polyolefin resin, polyamide resin, and halogen resin. Can be mentioned. These may be elastomers. These may be used singly or in combination of two or more as long as the light transmittance is maintained. Among these, polyurethane is preferable from the viewpoint of excellent balance between light transmittance, wear resistance and mechanical properties. Moreover, these resin components may contain a ultraviolet absorber, surfactant, a flame retardant, antioxidant, etc. as needed.

  The method for forming the skin layer on the surface of the fiber substrate is not particularly limited. Specifically, for example, first, a paint for forming a skin layer containing a light-transmitting resin component and a transparent pigment having an average particle diameter of less than 500 nm that does not lose light transmittance is prepared. And the method of applying the prepared coating material on the surface of the fiber substrate to form a coating film, and drying or wet coagulating the coating film to form a surface film having a total light transmittance of 5% or more. Can be mentioned. In addition, the method of apply | coating the coating material for forming a skin layer on a fiber base material is not specifically limited, Means, such as spray coating, roll coating, and knife coating, are used without limitation. Moreover, according to such a method, in the formation process of the skin layer which is a finishing process, since the color can be adjusted by a simple painting process such as spray coating, the production efficiency is also excellent.

  As a method for forming the skin layer, the skin layer is formed on the release paper in advance, and the coating of the formed skin layer is laminated on the surface of the fiber base material through the semi-cured adhesive layer, and the fiber is pressed by heating. A so-called dry surface forming method for bonding to a substrate can also be used. However, according to the dry surface forming method, the skin layer hardly sinks into the surface layer of the fiber base material. Therefore, the skin layer formed by such a method has the disadvantage that the adhesive peel strength is lowered and the process becomes complicated. On the other hand, according to the method of applying the prepared paint to the surface of the fiber base as described above to form a skin layer, the adhesive peel strength is high because the paint penetrates moderately into the fiber base. Since the skin layer can be formed simply by applying the coating to the surface of the fiber substrate, it has an advantage that the process is simple.

  In addition, when coating the surface of the fiber base material to form a skin layer with sufficient thickness at once, the skin layer with sufficient thickness is formed because the paint penetrates too much into the fiber base material. It may be difficult to do. Further, when an attempt is made to form a skin layer having a sufficient thickness, the coating material penetrates too much into the fiber base material and the surface layer becomes hard, and the supple texture may be impaired. In such a case, a base resin layer is formed between the fiber base material and the skin layer to form a base for densifying the surface of the fiber base material so that the skin layer can be easily laminated. The surface layer may be pressed to fuse the surface layer fibers to form a smooth and dense so-called fiber silver surface layer. Such a base resin layer and fiber silver surface layer are coated directly onto the surface of the fiber substrate using a roll coater or spray coater, which contains a resin component for forming a light-transmitting film in the production process. Then, it can be formed by drying or wet coagulation, which is preferable from the viewpoint that the coating liquid is prevented from excessively penetrating into the fiber base material and the film formability is improved. Also, by impregnating the fiber entangled body with the modifier as described above, it is possible to suppress the surface of the fiber entangled body from being filled with the modifier and the coating liquid from penetrating too much.

  The method for forming the base resin layer is not particularly limited. Specifically, for example, a method of forming a base resin layer film by applying a coating liquid containing a resin component for forming a base resin layer on a fiber base material and then drying the coating liquid. In addition, it is more preferable from the point of the designability that the base resin layer is a colored resin layer containing a pigment. For example, when a metallic pigment is blended, a unique appearance can be obtained.

  The thickness of the skin layer is preferably 5 to 300 μm, more preferably 10 to 100 μm. When the skin layer is laminated on the base resin layer as described above, the total thickness of the skin layer and the base resin layer is preferably 10 to 1000 μm, more preferably 30 to 300 μm.

  In addition, the content ratio of the second pigment in the skin layer is not particularly limited as long as sufficient light transmittance is maintained, but is, for example, 0.1 to 10% by mass, and further 0.5 to 5% by mass. Is preferred. When the content ratio of the pigment in the skin layer is too high, the light transmittance tends to decrease, and when it is too low, the colorability tends to decrease.

  The skin layer thus formed has a light transmittance with a total light transmittance of 5% or more. Therefore, when light strikes the leather-like sheet, the color of the fiber base material, in which part of the light passes through the skin layer and is colored with the first pigment, is visually recognized. As a result, a person who visually recognizes the surface can feel the transparency and depth of the color of the dye-finished aniline leather by visually recognizing the coloring by the first pigment and the coloring by the second pigment. Can be made. The skin layer preferably has a total light transmittance of 5% or more, 20% or more, and more preferably 30% or more from the viewpoint of excellent design. The total light transmittance of the skin layer is, for example, a glass plate having a total light transmittance of 98% or more as a control, a film having the same thickness and the same composition as the skin layer is formed on the glass plate, and JIS-K7136 It can be measured by a method based on the prescribed total light transmittance (%) measurement method.

  Further, the leather-like sheet thus obtained is further provided with a clear layer for protecting the surface, if necessary, itching softening treatment, blanking softening treatment, reverse seal brushing treatment, A finishing treatment such as a soil treatment, a hydrophilization treatment, a lubricant treatment, a softener treatment, an antioxidant treatment, an ultraviolet absorber treatment, a fluorescent agent treatment, or a flame retardant treatment may be performed. Further, a texture pattern may be provided on the surface by embossing or the like. In this way, the leather-like sheet of this embodiment is obtained.

  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 entangled nonwoven 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. Then, the long fibers of the sea-island type composite fibers are peeled off from the net and passed between a lattice-patterned metal roll having a surface temperature of 55 ° C. and a back roll, so that they are hot-pressed at a linear pressure of 200 N / mm to have a basis weight of 31 g / mm An m ² long fiber web was obtained.

Next, the web was overlapped on 8 layers using a cross-wrapper apparatus so that the total basis weight was 250 g / m ² , an overlapped web was prepared, and a needle breakage preventing oil was 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, repeated dip nip treatment in 95 ° C. hot water is performed to dissolve and remove PVA, so that a fiber bundle having a fineness of 2.5 dtex containing 25 ultrafine fibers having a fineness of 0.1 dtex is three-dimensionally entangled. An intertwined nonwoven fabric was prepared. An area shrinkage measured after drying was 52%, and a nonwoven fabric having a basis weight of 576 g / m ² and an apparent density of 0.565 g / cm ³ was obtained. Then, the nonwoven fabric was sliced and buffed to adjust the thickness to 1.05 mm, thereby obtaining a fiber entanglement of ultrafine fibers.

  On the other hand, an aqueous pigment dispersion containing a pigment having an average particle size of about 600 nm and an acrylic emulsion were mixed to prepare a pigment impregnation dispersion containing 2% by mass of pigment and 2% by mass of acrylic elastomer as solid content. . In addition, R / W binder 11KS (made by DIC Corporation) was used as an acrylic emulsion. Further, as pigments, R / W Yellow FF3R (manufactured by DIC Corporation) 0.4 mass% and R / W Brown FFR (manufactured by DIC Corporation) 4 mass% R / W Black RC (manufactured by DIC Corporation) ) 1% by mass was blended to prepare a dark brown color.

  On the other hand, 2% owf of water-based polyurethane, 38% owf of flame retardant filler, and 15% owf of liquid paraffin having a solid content of 30% were dispersed in water to prepare a dispersion liquid for impregnation with a modifier. In addition, 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, The melting point was 180 to 190 ° C., the peak temperature of loss elastic modulus was −15 ° C., and the hot water swelling ratio at 130 ° C. was 35%. As the flame retardant filler, a dispersion of aluminum dialkylphosphinate having an average particle diameter of 5000 nm (solid content 40%) was blended.

  Then, the fiber entangled body was impregnated by dipping and niping the prepared dispersion liquid for impregnating the pigment so that the pickup rate was 60%, and dried to fix the pigment to the fiber entangled body. Further, the fiber entangled body to which the pigment is fixed is impregnated by dipping and niping the prepared dispersion for impregnating the modifier so that the pickup rate is 80%, and then the modifier is dried. Homogeneously impregnated.

Then, the fiber entangled body to which the pigment and the modifier are added is contracted by using a shrink processing apparatus (manufactured by Komatsubara Iron Works Co., Ltd., sun forcing machine). The fiber base material was obtained by processing at 120 ° C. and a conveying speed of 10 m / min to shrink 5.5% in the vertical direction (length direction). The obtained fiber base material had a basis weight of 709 g / m ² and an apparent density of 0.645 g / cm ³ .

An aqueous system comprising a mixture of a filler material and an acrylic resin on the surface of the obtained fiber base so that the absorption time when 3 mL of water drops is dropped is 3 minutes or more in order to densify the surface layer of the fiber base. A slurry (RC-13-572 Sthal) 5 g / sqf was applied with a reverse coater (Gemata STARPLUS). Then, a base coat layer having a film thickness of 28 μm was formed by roll-coating the base coat solution onto the surface of the fiber base material having a densified surface layer at a coating amount of 140 g / m ² using a reverse coater. In addition, as the base coat liquid, 400 parts by mass of a polyurethane solution (DIC Co., Ltd., LCC binder UB1770 solid content 30% by mass) and 100 parts by mass of a pigment dispersion liquid (solid content 25%) having an average particle diameter of about 800 nm are added. A liquid prepared by mixing with a viscous agent and adjusted to have a viscosity of 195 cp with Ford Cup No. 4 55S was used.

Then, a 14 μm-thick skin layer was formed by spray-coating a color coating solution for forming a skin layer on the surface of the base coat layer at a coating amount of 70 g / m ² . As the color coating liquid, as a second pigment, a pigment dispersion containing an aqueous transparent pigment and having an average particle diameter of about 98 nm (NSP-WG series manufactured by Nihongo Bix Co., Ltd., solid content: about 20%) 50 mass And 400 parts by mass of polyurethane resin (DIC Co., Ltd., LCC binder UB1770 solid content 30%) and mixed with a thickener so as to be 30 cp with Iwata Cup (IWATA NK-2 12s) Using.

  The content ratio of the pigment in the skin layer thus formed was 2.2% by mass. Further, a glass plate having a total light transmittance of 98% or more is used as a control, a film having the same thickness and the same composition as the skin layer is formed on the glass plate, and a total light transmittance (%) measurement defined in JIS-K7136 is performed. The total light transmittance of the skin layer measured by a method based on the law was 45%.

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 (star clear clear paint) adjusted to 30 cp with Iwata Cup (IWATA NK-2 12s) is applied to the surface to form a top coat with a film thickness of 13.5 μm. ² and artificial leather having an apparent density of 0.762 g / cm ³ was obtained.

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

(Surface color)
A: It was a transparent and deep color like a dye-finished aniline leather.
B: It was a slightly deep color with no transparency, like pigmented leather.
C: It was a color with no transparency and a low-class feeling.

(Light resistance)
The obtained artificial leather was cut into a length of 70 mm and a width of 70 mm to obtain a test piece. The obtained test piece was exposed for 100 hours using a xenon weatherometer equipped with a 7.5 kw xenon long life arc lamp. Then, under the prescribed light source (D65), the sample before and after the test and the attached white cloth were arranged on a determination table at an angle of 45 degrees, and the grade was determined by comparing them with a gray scale for fading. In addition, a grade is judged by 9-step evaluation from 1 to 5 including a half class, and the 1st grade shows the largest light degradation, and the 5th grade shows the least light degradation.

(Flexibility)
The bending resistance was measured using a leather softness measuring device ST300 (manufactured by MSA Engineering System, UK). Specifically, after setting a predetermined ring having a diameter of 25 mm in the lower holder of the apparatus, artificial leather was set in the lower holder, and the numerical value when the upper lever was pushed down and locked was read.

(Sense of fulfillment)
The obtained artificial leather was cut to 20 × 20 cm to prepare a sample. And the external appearance was judged on the following references | standards, such as bending inside by making a center part a boundary.
A: Folding wrinkles with a feeling of solidity such as dense and fine creases and roundness occurred when folded. It was also excellent in drape.
B: Folding wrinkles were rough and deep wrinkles with a large buckling, and a fine feeling of bending wrinkles was not obtained. Moreover, it was inferior to the drape property.
C: The sense of fulfillment was remarkably low.

(Coating properties of the skin layer)
A: The skin layer was hardly submerged, and a smooth and smooth surface was formed.
B: There was a slight sinking of the epidermis layer, and a slight roughness of the surface fibers was felt.
C: The skin layer was almost submerged, and the surface was exposed with fibers and was fuzzy.

  The above evaluation results are shown in Table 1 below.

[Example 2]
In the preparation of the color coating solution of Example 1, a color coating solution was prepared in the same manner except that 25 parts by mass of the same pigment dispersion was blended instead of blending 50 parts by mass of the pigment dispersion having an average particle size of about 98 nm. . Artificial leather was obtained and evaluated through the same steps as in Example 1 except that the above color coat solution was used instead of the color coat solution prepared in Example 1. The content ratio of the pigment in the formed skin layer was 1.2% by mass. The total light transmittance of the skin layer was measured and found to be 65%. The results are shown in Table 1.

[Example 3]
In the preparation of the color coating liquid prepared in Example 1, instead of blending 50 parts by mass of the pigment dispersion having an average particle diameter of about 98 nm, the color coating liquid was similarly prepared except that 100 parts by mass of the same pigment dispersion was blended. Prepared. Artificial leather was obtained and evaluated through the same steps as in Example 1 except that the above color coat solution was used instead of the color coat solution prepared in Example 1. The content ratio of the pigment in the formed skin layer was 4% by mass. The total light transmittance of the skin layer was measured and found to be 30%. The results are shown in Table 1.

[Example 4]
In the preparation of the base coat liquid prepared in Example 1, instead of blending 100 parts by mass of a pigment dispersion liquid (solid content 25%) having an average particle diameter of about 800 nm (manufactured by Nihongo Bix Corporation) (NSP-WG series, solid content of about 20%) A base coat solution was prepared in the same manner except that 100 parts by mass was blended.
Further, in the preparation of the color coating liquid prepared in Example 1, the same color coating was applied except that 50 parts by mass of the pigment dispersion having an average particle diameter of about 98 nm was blended instead of 100 parts by mass of the same pigment dispersion. A liquid was prepared. Artificial leather was obtained and evaluated through the same steps as in Example 1 except that the base coat solution and the color coat solution were used instead of the base coat solution and the color coat solution prepared in Example 1. The content ratio of the pigment in the formed skin layer was 4% by mass. Moreover, the content rate of the pigment contained in a basecoat layer was 5 mass%. Furthermore, the total light transmittance of the skin layer was measured and found to be 30%. The results are shown in Table 1.

[Example 5]
In Example 1, instead of impregnating the fiber entangled body with the dispersion for impregnating the modifier, the same as that used in Example 1 so that the solid content of the fiber entangled body is 12.5% by mass. An artificial leather was obtained and evaluated in the same manner except that it was impregnated with an aqueous polyurethane dispersion and dried at 120 ° C. The results are shown in Table 1.

[Example 6]
In Example 1, 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.

[Example 7]
In Example 1, instead of using a pigment dispersion containing a pigment having an average particle size of about 98 nm as a dispersion of the second pigment blended in the color coating solution, a pigment dispersion containing a pigment having an average particle size of about 480 nm is used. Artificial leather was obtained and evaluated through the same steps as in Example 1 except that they were used. The content ratio of the pigment in the formed skin layer was 2.2% by mass. Moreover, it was 5% when the total light transmittance of the skin layer was measured. The results are shown in Table 1.

[Comparative Example 1]
In the same manner as in Example 1, a fiber entangled body of ultrafine fibers having a thickness adjusted to 1.05 mm was obtained. Then, instead of the pigment impregnation dispersion used in Example 1, the fiber entangled body contains 2% by mass of an acrylic emulsion as a solid content, and the dispersion containing no pigment has a pickup rate of 60%. By impregnation by dipping and niping and drying, a fiber base material in which only an acrylic elastic body was fixed to the fiber entangled body was obtained. Further, dip-nip is performed on the fiber entangled body in which only the acrylic elastic body is fixed, so that the modifier-impregnated dispersion similar to that prepared in Example 1 has a pickup rate of 80%. The modifier was impregnated and impregnated uniformly by drying. Then, the fiber entangled body impregnated with the modifier is passed through hot water at 80 ° C. for 20 minutes to allow the fabric to adjust to the hot water and relax the dough, and then the leveling dye using a high-pressure liquid dyeing machine Was dyed dark brown and dried.

Then, the dyed fiber entangled body is processed in the same manner as in Example 1 by using a shrinkage processing apparatus at a drum temperature of 120 ° C. of the contraction part, a drum temperature of 120 ° C. of the heat setting part, and a conveyance speed of 10 m / min. The fiber base material was obtained by shrinking 5.5% in the vertical direction (length direction). The obtained fiber base material had a basis weight of 709 g / m ² and an apparent density of 0.645 g / cm ³ .

An aqueous system comprising a mixture of a filler material and an acrylic resin on the surface of the obtained fiber base so that the absorption time when 3 mL of water drops is dropped is 3 minutes or more in order to densify the surface layer of the fiber base. A slurry (RC-13-572 Sthal) 5 g / sqf was applied with a reverse coater (Gemata STARPLUS). Then, instead of the base coat solution prepared in Example 1 on the surface of the fiber substrate whose surface layer is densified, the base coat solution colored with a dye instead of being colored with a pigment is rolled with a reverse coater at a coating amount of 140 g / m ² . By coating, a base coat layer having a thickness of 28 μm was formed.

Then, a 14 μm-thick skin layer was formed by spray coating a color coat solution for forming a skin layer on the surface of the formed base coat layer at a coating amount of 70 g / m ² . In addition, as the color coat solution, a solution prepared with the same composition was used except that the color coat solution of Example 1 was colored with a dye instead of being colored with the second pigment.

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 (star clear clear paint) adjusted to 30 cp with Iwata Cup (IWATA NK-2 12s) is applied to the surface to form a top coat with a film thickness of 13.5 μm. ² and artificial leather having an apparent density of 0.762 g / cm ³ was obtained. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
In the same manner as in Example 1, a fiber entangled body of ultrafine fibers having a thickness adjusted to 1.05 mm was obtained. Then, instead of the pigment impregnation dispersion used in Example 1, the fiber entangled body contains 2% by mass of an acrylic emulsion as a solid content, and the dispersion containing no pigment has a pickup rate of 60%. By impregnation by dipping and niping and drying, a fiber base material in which only an acrylic elastic body was fixed to the fiber entangled body was obtained. Further, dip-nip is performed on the fiber entangled body in which only the acrylic elastic body is fixed, so that the modifier-impregnated dispersion similar to that prepared in Example 1 has a pickup rate of 80%. The modifier was impregnated and impregnated uniformly by drying. Then, the fiber entangled body impregnated with the modifier is passed through hot water at 80 ° C. for 20 minutes to allow the fabric to adjust to the hot water and relax the dough, and then the leveling dye using a high-pressure liquid dyeing machine Was dyed dark brown and dried.

Then, in the same manner as in Example 1, the dyed fiber entangled body was processed using a shrinkage processing apparatus at a drum temperature of 120 ° C. of the shrink part, a drum temperature of 120 ° C. of the heat set part, and a conveyance speed of 10 m / min. The fiber base material was obtained by shrinking 5.5% in the vertical direction (length direction). The obtained fiber base material had a basis weight of 709 g / m ² and an apparent density of 0.645 g / cm ³ .

In Example 1, instead of the fiber entangled body to which the pigment and the modifier were applied, the obtained dyed fiber entangled body was used, and thereafter, through the same steps as in Example 1, the basis weight was 777 g. / M ² , an artificial leather having an apparent density of 0.762 g / cm ³ was obtained.

[Comparative Example 3]
In Example 1, instead of forming a skin layer having a thickness of 14 μm by spray-coating the color coating solution at a coating amount of 70 g / m ² , the second pigment was not blended in the color coating solution of Example 1. Except for forming a skin layer having a film thickness of 14 μm by spray coating a clear coat solution prepared with the same composition at a coating amount of 70 g / m ² , an artificial leather was obtained through the same steps as in Example 1, evaluated. The results are shown in Table 1.

[Comparative Example 4]
In Example 1, the same dispersion as that of Example 1 was used except that the dispersion containing the pigment having an average particle diameter of about 800 nm used as the first pigment was used as the dispersion of the second pigment blended in the color coating solution. Through the process, artificial leather was obtained and evaluated. The content ratio of the pigment in the formed skin layer was 2.8% by mass. Moreover, the content rate of the pigment contained in a basecoat layer was 5 mass%. Furthermore, the total light transmittance of the skin layer was measured and found to be 2%. The results are shown in Table 1.

  From the results of Table 1, obtained in Examples 1 to 7 formed from a base material containing a fiber entangled body colored with a pigment and a light-transmitting film colored with a pigment having an average particle size of less than 500 nm All of the leather-like sheets exhibited transparency and deep color as in the dye-finished aniline leather, and were excellent in light resistance. Moreover, since it is colored only with a pigment, it is excellent also in fastness. On the other hand, the leather-like sheet of Comparative Example 1 colored only with a dye exhibits a clear color and a deep color like a dye-finished aniline leather, but is inferior in light resistance due to being dyed, and is also durable. Also inferior. In addition, the leather-like sheet of Comparative Example 2 in which the fiber base is colored with a dye is also dyed, so that the light resistance is inferior and the fastness is also inferior. In addition, the leather-like sheet of Comparative Example 3 in which the fiber base material was colored with a pigment and the skin layer was not colored exhibited a color with a little depth but no transparency, like a pigment-finished leather. Furthermore, the leather-like sheet of Comparative Example 4 in which a pigment layer with a large particle size was blended to form a highly concealed skin layer with a total light transmittance of 2% exhibited a color with no transparency and a high-class feeling. .

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

DESCRIPTION OF SYMBOLS 1 Fiber base material 1a Fiber entanglement body 2 Skin layer 3 First pigment 4 Second pigment 5 Base resin layer 6 Polymer elastic body 10 Leather-like sheet

Claims (9)

A substrate including a fiber entangled body colored with a first pigment, and a skin layer laminated on the substrate;
The leather-like sheet, wherein the skin layer is formed of a light-transmitting film having a total light transmittance of 5% or more colored with a second pigment having an average particle size of less than 500 nm.   The leather-like sheet according to claim 1, wherein the first pigment has an average particle diameter of 500 nm or more.   The leather-like sheet according to claim 1 or 2, wherein the base material is a base material containing the first pigment in a gap between fibers of the fiber entangled body.   The leather-like sheet according to any one of claims 1 to 3, wherein the base material is a base material including a colored resin layer containing the first pigment in a surface layer of the fiber entangled body. The fiber-entangled body, 0.55 g / cm ³ or more apparent with a density, leather-like sheet according to claim 1 which is entangled body of the following ultrafine fiber fineness 0.9 dtex. The base material is a base material impregnated with a modifier containing liquid non-volatile oil and a filler in the gaps between the fibers of the fiber entangled body,
The leather-like sheet according to any one of claims 1 to 5, wherein a ratio of the nonvolatile oil to the fiber entangled body is 0.5 mass% or more.   The leather-like sheet according to claim 6, wherein the non-volatile oil includes at least one selected from liquid paraffin, silicone oil, mineral oil, and phthalates.   The leather-like sheet according to claim 6 or 7, wherein the filler contains at least one selected from an inorganic filler, an organic filler, and a polymer elastic body. A step of preparing a base material having an apparent density of 0.55 g / cm ³ or more and an ultrafine fiber entanglement having a fineness of 0.9 dtex or less and containing a first pigment in a gap between fibers of the fiber entanglement When,
Applying a light-transmitting film-forming coating material containing a second pigment having an average particle size of less than 500 nm to the surface of the substrate to form a coating film;
And a step of drying the coating film to form a surface film having a total light transmittance of 5% or more.

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