KR102128640B1 - Artificial leather substrate, grain-finished artificial leather, artificial leather substrate manufacturing method, and artificial leather substrate modifying agent - Google Patents

Abstract

As an artificial leather base material containing a fiber entangled body, a filler and a liquid non-volatile oil impregnated with the fiber entangled body, preferably a polymer elastic body, preferably non-volatile oil is 0.5 to 0.5 to the fiber entangled body. Artificial leather base containing 10% by mass. More preferably, the artificial leather substrate further comprises a smoothing layer for smoothing the surface, and the smoothing layer is a layer having a thickness of 10 to 100 µm containing a second polymer elastic body and a second filler.

Description

ARTIFICIAL LEATHER SUBSTRATE, GRAIN-FINISHED ARTIFICIAL LEATHER, ARTIFICIAL LEATHER SUBSTRATE MANUFACTURING METHOD, AND ARTIFICIAL LEATHER SUBSTRATE MODIFYING AGENT

The present invention relates to an artificial leather having both elasticity and high fidelity.

Conventionally, artificial leathers including nonwoven fabrics are known. Artificial leather is a substitute for natural leather and is used in fields such as shoes, medical care, gloves, bags, balls, interiors, and vehicle applications.

The artificial leather is produced by subjecting an artificial leather substrate obtained by impregnating a void in the nonwoven fabric with a polymer elastic body to a desired appearance. The polymer elastic body imparts fidelity to the nonwoven fabric. As artificial leathers, for example, silver relief artificial leathers having a silver-faced appearance, suede-like or nubuck-like artificial leathers having fibers on the surface of a non-woven fabric are known.

Since natural leather contains dense collagen fibers, it has both elasticity and high fidelity. The high fidelity of the natural leather, when bent, has a round shape and forms fine, high-quality bending wrinkles, and also exhibits excellent drape properties.

However, it has been difficult to use natural leather for applications requiring heat resistance and water resistance, such as interior materials for automobiles, for example. This is because collagen fibers are inferior in heat resistance and water resistance. In order to provide heat resistance and water resistance to natural leather, there is also a method of forming a thick resin layer on the surface. However, when a thick resin layer is formed, the elasticity of natural leather is lost.

On the other hand, artificial leather is superior to natural leather in heat resistance, water resistance, quality stability, abrasion resistance, and is easy to care for. However, in artificial leather, voids that are not filled with a polymer elastic body exist in the non-woven fabric, so that the feeling of closeness and fidelity are inferior to that of natural leather. Therefore, the artificial leather, when bent, has a round shape like a natural leather, does not bend, and is bent and bent as it is also called a straightening. This bending method has no sense of quality. In addition, when the pores are reduced by increasing the content of the polymer elastic body in the nonwoven fabric, the repellency increases, resulting in a rigid texture similar to that of rubber.

In order to more closely resemble the elasticity of natural leather, artificial leather using a nonwoven fabric formed of ultrafine fibers is also known (for example, Patent Document 1 below). However, in the case of artificial leather using a non-woven fabric formed of ultrafine fibers, a sufficient combination of elasticity and fidelity was not obtained. In addition, Patent Document 2 below discloses a leather sheet-like article containing an oily substance having a viscosity at 30° C. of 50 to 10000 mPa·s inside at least inside the fibrous substrate and a holding body such as an olefin-based elastomer. Patent Document 2 discloses that such a leather sheet-like article has flexibility (elasticity) and fidelity of a natural leather wind, and has little oil migration.

By the way, although it is not in the field of artificial leather, for example, Patent Document 3 below is a wiping sheet made of an acrylic wet nonwoven fabric having a dust-absorbing performance maintained at 1 to 30% by weight of the nonwoven fabric. Disclosed is the use of synthetic oils such as liquid paraffin, mineral oil, silicone oil, and alkylbenzene oil.

Pamphlet of International Publication WO2008/120702 Pamphlet of International Publication WO2003/06212 Japanese Patent Application Publication No. Hei 9-313418

The present invention provides an artificial leather having both elasticity and high fidelity.

One aspect of the present invention is an artificial leather substrate containing a fiber entangled body, a first filler impregnated with the fiber entangled body, and a liquid nonvolatile oil.

In addition, another aspect of the present invention is a silver relief artificial leather having a resin layer laminated on the artificial leather substrate.

In addition, another aspect of the present invention, as a method for manufacturing an artificial leather base material, an artificial leather base fabric containing a fiber entangled body, a first filler impregnated into the fiber entangled body, and a liquid nonvolatile oil. ) And 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 the artificial leather base fabric and drying the coating solution for forming a smoothing layer. , Containing a second polymer elastic body and a second filler as a solid content, and measured at a viscosity of η _0.6 and a revolution of 3 revolutions/sec when measured at a rotation speed of 0.6 revolutions/sec using a B-type rotational viscometer at a temperature of 25°C. It is a manufacturing method of an artificial leather base material having a thixotropy index of 2 to 4, which is a ratio (η _0.6 /η _3.0 ) of the viscosity η _{3.0 at} the time.

In addition, another aspect of the present invention contains, as a non-volatile component, 3 to 90 mass% of a liquid non-volatile oil and 10 to 97 mass% of at least one first filler selected from inorganic fillers and organic fillers. It is a modifier for artificial leather substrates.

According to the present invention, an artificial leather having both elasticity and high fidelity is obtained.

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

1 is a schematic cross-sectional view of a silver relief artificial leather 10 according to an embodiment of the present invention. The silver relief artificial leather 10 includes an artificial leather base 1 containing a fiber entangled body, and a resin silver surface layer 2 containing a polymer elastic body formed on the surface of the artificial leather base 1. The artificial leather substrate 1 contains the fiber entangled body 1a, and the voids between the fibers of the fiber entangled body 1a are liquid nonvolatile oils 3 and 1, as shown in the enlarged view in FIG. The filler 4 and the first polymer elastic body 5 contained as necessary are impregnated. The liquid nonvolatile oil, the first filler, and the first polymer elastic body are also called modifiers.

Hereinafter, the artificial leather of this embodiment is demonstrated in detail along an example of the manufacturing method.

The fiber entangled body is not particularly limited as long as it is a fibrous structure such as a nonwoven fabric, woven fabric, fabric, or knitted fabric. Among them, non-woven fabrics, particularly micro-fiber non-woven fabrics, are preferred. Since the non-woven fabric of the ultrafine fiber has a dense fiber density, the dense nonuniformity of the fiber is low and the homogeneity is high. As a result, artificial leather having excellent elasticity and high fidelity is obtained. In this embodiment, a case where a nonwoven fabric of ultrafine fibers is used as the fiber entangled body will be described in detail as a representative example.

The nonwoven fabric of the ultrafine fibers is obtained, for example, by subjecting ultrafine fiber-generating fibers such as island-in-the-sea (matrix-domain) composite fibers to entanglement and ultrafine fiberization treatment. In addition, in this embodiment, although the case of using island-in-the-sea composite fibers is explained in detail, even if ultrafine fiber-generating fibers other than the island-in-the-sea composite fibers are used, or directly using ultrafine fiber-generating fibers without using ultrafine fibers The fibers may be spun. Further, as a specific example of ultrafine fiber-generating fibers other than island-in-the-sea composite fibers, a plurality of ultrafine fibers are formed by lightly adhering immediately after spinning, and peeled split fibers in which a plurality of ultrafine fibers are formed by loosening by mechanical manipulation. B. In the melt spinning step, petal-shaped fibers or the like formed by alternately gathering a plurality of resins in the form of petals are mentioned, and any fibers that can form ultrafine fibers are not particularly limited and used.

In the manufacture of a non-woven fabric of ultrafine fibers, first, the thermoplastic resin constituting the sea component (matrix component) of the island-in-the-sea composite fibers that can be selectively removed, and the island-in-the-sea composite fibers that are resin components that form the ultrafine fibers The island-in-the-sea composite fiber is obtained by melt spinning and spinning a thermoplastic resin constituting the island component (domain component).

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

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

As a method for producing a non-woven fabric of ultrafine fibers, for example, a sea-island composite fiber is melt spun to produce a web, and after the web is subjected to fusion treatment, sea components are selectively removed from the sea-island composite fibers to form ultrafine fibers. And how to do it. As a method of manufacturing the web, a method of forming a long fiber web by collecting on the net without cutting the island-in-the-sea composite fibers of long fibers spun by a spunbond method or the like, or a short fiber web by cutting long fibers with staples And a method of forming the same. Among these, long-fiber webs are particularly preferred from the viewpoint of excellent compactness and fidelity. In addition, a fusion treatment may be performed on the formed web to impart shape stability.

In addition, a long fiber means a continuous fiber, 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. The fiber length of the island-in-the-sea composite fiber before ultrafine fiberization is preferably 100 mm or more, and can be manufactured technically, and may be several m, hundreds of m, several mm or more, unless it is inevitably cut in the manufacturing process. It may be a length. In addition, some of the long fibers are inevitably cut into short fibers in the manufacturing process due to needle punching during fusion described later or buffing of the surface.

In any process until the sea component of the island-in-the-sea composite fiber is removed to form ultrafine fibers, the island-in-the-sea composite fiber can be densified by performing fiber shrinkage treatment such as entanglement treatment and heat shrink treatment by water vapor. As the fusion treatment, for example, a method of superimposing about 5 to 100 sheets of the web and performing a needle punch or high-pressure water flow treatment is exemplified.

The sea component of the island-in-the-sea composite fibers is removed by dissolving or decomposing at an appropriate step after forming the web. The island-in-the-sea composite fibers are made into ultrafine fibers by such decomposition removal or dissolution extraction and removal to form ultrafine fibers on the fiber bundle.

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 to obtain a nonwoven fabric with insufficient density. Moreover, it is difficult to manufacture a fiber with too low a fineness. In addition, the fibers tend to be bundled, and the non-woven fabric tends to have high rigidity.

The nonwoven fabric of the ultrafine fibers thus obtained is subjected to thickness adjustment and flattening treatment as necessary. Specifically, a slice process or a buffing process is performed. In this way, a nonwoven fabric of ultrafine fibers that are fiber entanglements is obtained.

The thickness of the fiber entangled body is not particularly limited, but is preferably about 100 to 3000 μm, and more preferably about 300 to 2000 μm. In addition, the apparent density of the fiber entangled body is not particularly limited, but it is 0.25 to 0.70 g/cm 3, furthermore, about 0.45 to 0.65 g/cm 3, particularly 0.55 to 0.60 g/cm 3, which combines a sense of fidelity and elastic texture. It is preferable in that an artificial leather substrate is obtained.

Next, a step of impregnating the voids of the fiber entangled body with the first filler and the liquid nonvolatile oil will be described.

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

The dispersion liquid is, for example, homogeneously mixed and dispersed with a liquid nonvolatile oil and a first filler in a dispersion medium such as water or a mixture of a polar solvent such as water and alcohol.

The liquid non-volatile oil in the present embodiment is a liquid having a boiling point of 150°C or higher and substantially insoluble in a polar solvent. Specifically, for example, liquid paraffin, paraffin-based or naphthenic-based process oil, mineral oil, silicone (silicone) oil, phthalic acid esters and the like can be mentioned. These may be used alone or in combination of two or more. Among these, liquid paraffin is preferred because of its excellent chemical stability and poor oxidation.

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

As the inorganic filler and the organic filler, for example, various fillers made of metal, metal oxide, inorganic compound, organic compound, or the like having an average particle diameter of 0.1 to 15 µm, and more preferably about 0.5 to 10 µm, are used without particular limitation. . Specific examples thereof include fillers of metal oxides or semimetal oxides such as alumina (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), cerium dioxide (CeO ₂ ), and silica (SiO ₂ ); Fillers of inorganic compounds such as talc, clay, aluminum hydroxide, mica, calcium carbonate, and basket-shaped polysilsesquioxane (POSS); Flame retardant fillers such as ammonium polyphosphate, aluminum dialkylphosphinate, and melamine polyphosphate; And carbon-based fillers with 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. Among these, various flame-retardant fillers are particularly preferable from the viewpoint of providing flame retardancy at the same time.

Moreover, it is preferable to impregnate the voids of the fiber entangled body with the first filler and the liquid nonvolatile oil, and further impregnate the first polymer elastic body. In this case, a dispersion liquid containing a 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 elastomer, silicone elastomer, diene elastomer, nitrile elastomer, fluorine elastomer, polystyrene elastomer, polyolefin elastomer, polyamide elastomer, halogen elastomer And the like. These may be used alone or in combination of two or more. Among them, polyurethane is preferred from the viewpoint of excellent wear resistance and mechanical properties.

As the polyurethane, water-based polyurethanes such as emulsions of polycarbonate-based polyurethanes, polyester-based polyurethanes, polyether-based polyurethanes, and polycarbonate/ether-based polyurethanes are preferred. These polyurethanes are particularly preferable in that the dispersion is easily prepared, it is easy to form a crosslinked structure, and it is easy to express a soft texture by being present in pores without being too close to the fibers.

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

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

The method for impregnating the fiber entangled body with a dispersion is not particularly limited. Specifically, for example, a method of impregnating a fiber entangled body by dipping a dispersion solution 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 10 to 1000 mPa·s (milliPascal seconds), more preferably 50 to 500 mPa·s, as measured by a rotary viscometer.

Then, after impregnating the dispersion with the fiber entangled body and drying it, volatile components such as a dispersion medium in the dispersion are dried and removed. Thereby, the first filler in the dispersion, non-volatile oil, and the like remain in the voids between the fibers of the fiber entangled body. Although the drying conditions are not particularly limited, for example, conditions for drying at 70 to 150°C for about 1 to 10 minutes are mentioned. In this way, a first filler, a non-volatile oil, and the like are imparted to the voids between the fibers of the fiber entangled body. These are present in the pores, for example, in the form of clay or paste.

The ratio of the nonvolatile oil to the fiber entangled body is preferably 0.5 to 10% by mass, more preferably 1 to 10% by mass, particularly 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 an elastic texture. Moreover, when the ratio of the non-volatile oil to the fiber entangled body is too high, the fiber entangled body cannot hold the non-volatile oil, and it becomes easy to escape.

The ratio of the first filler to the fiber entangled body is not particularly limited, but is preferably 1 to 60 mass%, preferably 10 to 50 mass%, and further preferably 10 to 40 mass%. When the ratio of the first filler to the fiber entangled body is too low, the fidelity tends to decrease. Moreover, when the ratio of the first filler to the fiber entangled body is too high, the elastic texture tends to decrease.

Moreover, it is preferable that the ratio of the 1st polymer elastic body with respect to a fiber entangled body is 0-15 mass %, furthermore 1-14 mass %, especially 1-10 mass %. When the ratio of the first polymer elastic body to the fiber entangled body is too high, the rubber feeling becomes strong and the repellency increases, so that the elastic texture tends to decrease. In addition, although the first polymer elastic body is not an essential component, it is possible to increase shape stability or adjust elasticity by blending.

In addition, the proportion of the non-volatile oil in the modifier in which the first filler, the non-volatile oil and the first polymer elastic body are combined is not particularly limited, but is 1 to 90% by mass, furthermore, 3 to 70% by mass, particularly 10 to 50% by mass , Especially, it is preferable that it is 20-35 mass% from the point which elastic texture and fidelity are obtained. When the proportion of the non-volatile oil in the modifier is too low, the elastic texture tends to deteriorate, and when it is too high, the proportion of the filler decreases relatively, so that the fidelity tends to decrease.

Moreover, it is preferable that it is 10-99 mass %, furthermore, it is 30-97 mass %, especially 50-90 mass% as ratio of the 1st filler in a modifier. When the proportion of the first filler is too low, the feeling of fidelity tends to decrease, and when the proportion of the first filler is too high, the elastic texture tends to decrease due to a relatively low proportion of non-volatile oil.

The proportion of the first polymer elastic body in the modifier is preferably 0 to 40% by mass, more preferably 1 to 20% by mass. When the proportion of the first polymer elastic body is too high, it tends to have a texture similar to that of rubber.

The ratio of the modifier to the fiber entangled body is not particularly limited, but is preferably 1 to 60% by mass, preferably 3 to 45% by mass, particularly 10 to 40% by mass, particularly 10 to 30% by mass. When the ratio of the modifier to the fiber entangled body is too high, it is likely that it is difficult to sufficiently impregnate the voids.

Thus, an artificial leather substrate obtained by impregnating voids between fibers of a fiber entangled body with a first filler, a non-volatile oil and a modifier containing a first polymer elastic body as required is obtained. Such artificial leather substrates may be subjected to a thickness adjustment and flattening treatment by slicing or buffing treatment as necessary, or rubbing softening treatment, air shot softening treatment, reverse seal brushing treatment, antifouling treatment, hydrophilization treatment, lubricant treatment , Finishing treatment such as softener treatment, antioxidant treatment, ultraviolet absorber treatment, fluorescent agent treatment, flame retardant treatment may be performed.

For the purpose of adjusting the fidelity and elasticity of the artificial leather base material, it is preferable to perform flexible processing on the artificial leather base material impregnated with a modifier containing a first filler, a non-volatile oil and, if necessary, a first polymer elastic body. The method of casting is not particularly limited, but a method in which the artificial leather substrate is brought into close contact with the elastic sheet, mechanically contracted in the longitudinal direction (MD of the manufacturing line), and heat-set by heat treatment in the contracted state is preferable. By employing this method, it is possible to soften 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, and more preferably about 300 to 2000 μm. The apparent density of the artificial leather substrate is not particularly limited, but is preferably 0.55 to 0.85 g/cm 3, furthermore 0.60 to 0.80 g/cm 3, from the viewpoint of excellent balance between fidelity and elastic texture.

The artificial leather base material thus obtained is subjected to a treatment for imparting a desired appearance, thereby finishing the artificial leather. As artificial leather, for example, a silver relief artificial leather having a silver-like resin layer on the surface of an artificial leather substrate, or a buffing treatment on the surface of an artificial leather substrate to make the fibers fluff or hair to fluff them. And artificial leather (suede, nubuck, velor, and buckskin) with a raised appearance that gives a raised appearance.

The silver relief artificial leather is obtained by forming a silver-like resin layer on the surface of the artificial leather substrate. The method of forming a silver-like resin layer on the surface of the artificial leather substrate is not particularly limited, and for example, a dry roughing method or a direct coat method is used. In the dry roughing method, a coating liquid containing a colored resin for forming a silver surface layer is coated on a release sheet, followed by drying to form a coating, and the coating is adhered to the surface of the artificial leather substrate via an adhesive layer. ), and then peeling the release sheet. Moreover, the direct coat method is a method of forming a coating liquid containing a resin directly on the surface of an artificial leather substrate by applying a roll coater or a spray coater and then drying it.

Conventionally, in general, the silver surface layer is formed by a method using a dry rough surface that is laminated on an artificial leather substrate via an adhesive layer semi-cured of a pre-formed film, and heat-pressed to adhere. The silver surface layer formed by the dry rough surface becomes relatively thick, and the formation process is complicated. On the other hand, according to the direct coat method, since the silver surface layer can be formed by application, it has an advantage that the forming process is simple. However, in the case of attempting to form the silver surface layer by the direct coat method, there is a problem that the artificial leather substrate becomes hard and the elastic texture is inhibited because the coating liquid penetrates excessively from the pores of the surface of the artificial leather substrate into the interior.

Since the artificial leather substrate of the present embodiment is a substrate having excellent fidelity and a smooth surface as described above, it is possible to impart very high smoothness to the surface by the following method. By increasing the smoothness of the surface of the artificial leather substrate in this way, even if the coating solution is applied to the surface of the artificial leather substrate using the direct coat method, it does not penetrate well inside. Thereby, since the formed resin layer does not sink deeply into the artificial leather substrate, it is possible to maintain an elastic texture.

As a first method, as shown in Fig. 2, a method of forming a smoothing layer 6 containing a second polymer elastic body and a second filler in order to smooth the surface on the surface layer of the artificial leather substrate 1 Can be lifted. Then, the silver surface layer 12 is formed on the surface of the smoothing layer 6. The method of forming such a smoothing layer is demonstrated below.

On the surface of the artificial leather base fabric, a coating solution having a thixotropy index of 2 to 4 containing a second polymer elastic body and a second filler is applied, followed by drying to form a smoothing layer. Since such a coating liquid has a thixotropy index of 2-4, it becomes low viscosity at the time of application|coating to which a share is applied, and viscosity increases after application|coating to which a share is not applied. According to such a method, since it is difficult for the coating liquid to sink into the interior from the pores of the surface of the artificial leather substrate, a thin smoothing layer can be easily formed on the surface of the artificial leather substrate.

The coating liquid used for forming the smoothing layer is not particularly limited as long as it is a coating liquid having a thixotropy index of 2 to 4 containing the second polymer elastic body and the second filler. Here, the term "thixotropy index" refers to a viscosity η _0.6 when measured at a rotation speed of 0.6 rotations/second using a B-type rotational viscometer at a temperature of 25°C, and a viscosity η _3.0 when measured at a rotation speed of 3 rotations/second. Ratio (η _0.6 /η _3.0 ).

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.

As a specific example of a 2nd polymer elastic body, it is the same as the 1st polymer elastic body mentioned above, For example, a polyurethane, an acrylic elastic body, a silicone elastic body, a diene elastic body, a nitrile elastic body, a fluorine elastic body, a polystyrene elastic body, and a polyolefin system And an elastic body, a polyamide-based elastic body, and a halogen-based elastic body. Although the concentration of the second polymer elastic body in the resin solution is not particularly limited, for example, in the case of an emulsion, it is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, particularly 25 to 35% by mass.

The second filler is a component that imparts thixotropy to the coating liquid and also glances at the voids on the surface of the artificial leather substrate. As a specific example of a 2nd filler, besides the solid particle which is the same filler as the 1st filler mentioned above, hollow particle|grains, such as plastic beads, are mentioned. Among these, clay, aluminum hydroxide, calcium carbonate, hollow particles, and the like are particularly preferred from the viewpoint of easy adjustment of the thixotropy index.

The particle size of the solid particles is preferably 0.5 to 15 µm, because it is easy to adjust the thixotropic index. Moreover, it is preferable that it is 10-80 micrometers as a particle size of a hollow particle from a point which is easy to adjust a thixotropy index.

It is preferable to mix|blend so that it may become 1-50 mass% in the solid content of a coating liquid, and also 5-50 mass %, especially 10-30 mass% as a compounding quantity of a 2nd filler. Moreover, as a compounding quantity of a 2nd filler in the case of a hollow particle, it is preferable to mix|blend hollow particle|grains corresponding to the volume of 5 to 70%, furthermore, 10 to 50% with respect to the volume of the solid content of a coating liquid.

Moreover, the coating liquid used for formation of a smoothing layer may contain the thickener for adjusting a thixotropy index and viscosity as needed. As a specific example of a thickener, ammonium polyacrylate, polyacrylic acid, etc. are mentioned, for example. It is preferable that it is 0.5-5 mass parts with respect to 100 mass parts of solid content of a 2nd polymer elastic body as a compounding quantity of a thickener. Moreover, you may contain the dispersing agent which improves stability of a coating liquid, the crosslinking agent for bridge|crosslinking a polymer elastic body, and coloring agents, such as a pigment. As a specific example of a dispersing agent, low molecular weight polycarboxylic acid sodium, tripolyphosphate sodium, etc. are mentioned, for example. 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 polymer elastic body.

The coating liquid is prepared by adding an additive such as a second filler and a thickener to be blended as necessary to the resin liquid of the second polymer elastic body, and stirring and mixing. The viscosity of the coating liquid prepared in this way is 100 to 600 Pa·s (Pascal seconds) with a viscosity of η _0.6 when measured at a rotation speed of 0.6 rotations/second using a B-type rotational viscometer at a temperature of 25°C. , Furthermore, it is preferably 150 to 350 Pa·s. In the case of such a viscosity, while the coating property of the coating liquid is excellent, it is difficult for the coating liquid to settle inside from the pores on the surface of the artificial leather substrate.

Moreover, although the ratio of solid content in a coating liquid is not specifically limited, It is preferable from the point which is excellent in thixotropy property, moderate thickening after application, and excellent drying property in the range of about 40-60 mass %.

A smoothing layer is formed by applying such a coating liquid to the surface of the artificial leather base fabric, followed by drying. As the coating method, various coating methods such as reverse coater and doctor knife coater are used without particular limitation. The coating liquid is lowered in viscosity upon application, and the viscosity increases after application, making it difficult for the coating liquid to settle inside from the pores on the surface of the artificial leather substrate.

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

It is preferable that the artificial leather substrate on which the smoothing layer is formed is filled with most of the pores on the surface and smoothed. In such a case, even if a resin solution for imparting a silver-like appearance to the surface of the smoothing layer is applied, it is difficult for the resin solution to settle inside the artificial leather substrate. By using such an artificial leather base on which the smoothing layer is formed, it is possible to manufacture a silver relief artificial leather that does not lose the elasticity of the artificial leather base.

The surface of the artificial leather substrate on which such a smoothing layer is formed has, for example, a surface absorption rate in accordance with JIS L 1907-7.1.1 dripping method of 100 seconds or more, 150 seconds or more, particularly 180 seconds or more. It is preferred. When the surface absorption rate is less than 100 seconds, since the voids remain, the resin liquid tends to settle inside.

Moreover, as a 2nd method for smoothing the surface of the artificial leather base material of this embodiment, the method of densifying a surface by heat-pressing the surface of the artificial leather base material of this embodiment is mentioned. In this case, particularly when the modifier is contained in a proportion of 10% by mass or more with respect to the fiber entangled body, the pores on the surface are filled with the modifier and the pores on the surface are reduced. Therefore, even if the resin liquid for giving the appearance of a silver-like wind is applied to the surface of the heat-pressed artificial leather substrate, it is suppressed that the resin liquid sinks inside the artificial leather substrate. Therefore, even by using an artificial leather substrate having a heat-pressed surface, a silver relief artificial leather can be produced without losing elasticity.

Then, after the coating liquid for forming the resin layer is applied to the surface of the formed smoothing layer, a silver-like resin layer is formed by a direct coat method for drying. 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, a spray coat is preferable in that a small amount of resin can be uniformly applied.

As a resin component for forming a silver-like resin layer by the direct coat method, for example, polyurethane, acrylic elastomer, silicone elastomer, diene elastomer, nitrile elastomer, fluorine elastomer, polystyrene elastomer, polyolefin elastomer, And resin solutions such as emulsions, suspensions, dispersions, or solutions of elastomers such as polyamide-based elastomers and halogen-based elastomers. These may be used alone or in combination of two or more. Among them, an emulsion of polyurethane is preferable because of its excellent wear resistance and mechanical properties. Further, the resin component for forming the silver surface 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-faced resin layer is preferably 10 to 1000 μm, and furthermore, 50 to 300 μm. Moreover, 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 viewpoint of designability that the resin layer has a fine wrinkle shape formed by embossing or the like. The embossing may include a method of completely curing the silver surface layer after transferring the fine wrinkles while the silver surface layer is uncured.

The silver relief artificial leather of this embodiment has the same elasticity and high fidelity as natural leather. Specifically, it is preferable, for example, that the ductility measured by the softness tester is 1.5 mm or more, and preferably exhibits a feeling of elasticity such as 1.8 to 2.5 mm. Moreover, it is preferable to have a fidelity of 0.55 to 0.85 g/cm 3 and apparently 0.60 to 0.80 g/cm 3 of apparent density.

Moreover, the raised-like artificial leather (suede, nubuck, velor, and buckskin) is obtained by buffing the surface layer of the artificial leather substrate using sandpaper or the like to perform a brushing treatment or a hair treatment.

In addition, finish processing such as rubbing softening treatment, air shot softening treatment, brushing treatment of anti-foil, antifouling treatment, hydrophilization treatment, lubricant treatment, softener treatment, antioxidant treatment, ultraviolet absorber treatment, fluorescent agent treatment, flame retardant treatment, etc. You may work.

Example

The present invention will be described more specifically by examples. In addition, the scope of the present invention is not limited at all by Examples.

[Example 1]

<Production of nonwoven fabric>

Water-soluble thermoplastic polyvinyl alcohol (PVA) as a sea component, and an isophthalic acid-modified polyethylene terephthalate having a degree of modification of 6 mol% as a sea component was set at a detention temperature of 260°C, and 25 sea components of uniform cross-sectional area were distributed among the sea components. The molten resin was supplied to the spinnerets for multiple spinnings in which nozzle holes forming a cross section were arranged in parallel, and discharged from the nozzle holes. At this time, it was supplied while adjusting the pressure so that the mass ratio of the sea component and the island component was the sea component/island component = 25/75.

Then, the discharged molten fibers were drawn by suction with a suction device so that the average spinning speed was 3700 m/min, and long fibers of island-in-the-sea composite fibers having a fineness of 2.1 dtex were spun. The long fibers of the spun island-in-the-sea composite fibers were continuously deposited on a movable net, and lightly pressed with a metal roll at 42°C to suppress the fluffing of the surface. Then, the long fibers of the island-in-the-sea composite fibers were peeled from the net and passed between a grid-shaped metal roll and a back roll having a surface temperature of 55°C. Thus, a long-fiber web having an apparent weight of 31 g/m 2 was obtained by heat pressing at a line pressure of 200 N/mm.

Next, the webs were superimposed in eight layers using a cross wrapper device so that the total apparent weight was 250 g/m 2, and an anti-bent emulsion was further sprayed. Subsequently, a needle was punched at 3300 punches/cm 2 alternately from both sides with a needle depth of 8.3 mm using a 6 bar needle with a distance of 3.2 mm from the tip of the needle to the first barb. The area shrinkage by this needle punching treatment was 68%, and the apparent weight of the entangled web after 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 generate area shrinkage. Subsequently, dip-nip treatment was repeatedly performed in hot water at 95°C to dissolve and remove PVA, thereby producing a nonwoven fabric in which three-dimensional fiber bundles of 25 fine fibers having 25 fine fibers having a fineness of 0.1 dtex were interwoven in three dimensions. The area shrinkage measured after drying was 52%. Then, the nonwoven fabric was sliced and buffed to adjust the thickness to 1.05 mm. The nonwoven fabric of the ultrafine fibers, which are the fiber entanglements thus obtained, had an apparent weight of 576 g/m 2 and an apparent density of 0.565 g/cm 3.

<Improving modifier impregnation>

A dispersion liquid was prepared by dispersing a modifier composed of a flame retardant filler 38%owf, a liquid paraffin 3.75%owf, and an aqueous polyurethane 5%owf in water. Then, after impregnating the dispersion with an 80% pick-up ratio to the nonwoven fabric of the ultrafine fibers, the modifier was impregnated homogeneously by drying the moisture. Then, the nonwoven fabric of the ultrafine fibers impregnated with the modifier was contracted using a shrink processing apparatus (Komatsubara Iron Works Co., Ltd., a sanitizing machine), the drum temperature of the shrinking portion was 120°C, the drum temperature was 120°C, and the conveying speed was 10. The treatment was performed at m/min and contracted by 5.5% in the longitudinal direction (longitudinal direction) to obtain an artificial leather substrate. The obtained artificial leather base material had an apparent weight of 676 g/m 2 and an apparent density of 0.633 g/cm 3.

As the flame-retardant filler, a dispersion liquid of aluminum dialkylphosphinate having an average particle size of 5 µm (solid content 40%) was blended. Moreover, as an aqueous polyurethane, the soft segment consists of a mixture of polyhexylene carbonate diol and polymethylpentanediol 70:30, and the hard segment is a crosslinking type polyurethane mainly composed of hydrogenated methylene diisocyanate (solid content 30 Emulsions having a mass%, a melting point of 180 to 190°C, a peak temperature of -15°C of loss elastic modulus and a swelling rate of hot water at 130°C of 35%) were used.

<Formation of silver cotton layer>

A base coat layer having a thickness of 28 µm was formed by rolling coat the base coat solution on the surface of the artificial leather substrate at a coating amount of 140 g/m 2 using STARPLUS manufactured by Gemata. Moreover, as a base coat liquid, the thing which adjusted the polyurethane emulsion (30 mass% of LCC binder UB1770 solid content by DIC Corporation) as a thickener so that the viscosity of Ford Cup No. 4 55s is 195 mPa*s was used. Then, a color coat layer having a film thickness of 14 µm was formed by spray-coating a color coat solution on the surface of the formed base coat layer with a coating amount of 70 g/m 2 using STARPLUS manufactured by Gemata. Moreover, as a color coat liquid, what adjusted the polyurethane emulsion (30% of LCC binder UB1770 solid content by DIC Corporation) to 30 mPa*s with Iwata Cup (IWATA NK-2 12s) was used. And the air shot process was further performed at 40-50 degreeC for 2-4 hours. Then, the embossing was performed on the surface layer at a line speed of 7.0 m/min using an embossing roll at 125°C and 50 kg/cm 2. Then, a top coat coating (clear coating manufactured 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 having a film thickness of 13.5 μm. Thus, a silver relief artificial leather having an apparent weight of 777 g/m 2 and an apparent density of 0.762 g/cm 3 was obtained.

<Evaluation of silver relief artificial leather>

The obtained silver relief artificial leather was evaluated in accordance with the following evaluation methods.

(Lecture year)

The softness was measured using a softness tester (leather softness measuring device ST300: manufactured by MSA Engineering Systems, UK). Specifically, a predetermined ring having a diameter of 25 mm was set in the lower holder of the apparatus, and then silver relief artificial leather was set in the lower holder. Then, a metal pin (diameter 5 mm) fixed to the upper lever was pressed down toward the silver relief artificial leather. Then, the value when the upper lever was locked was read by pushing the upper lever down. In addition, the numerical value indicates the depth of penetration, and the larger the numerical value, the more elastic.

(Texture)

A sample in which silver relief artificial leather was cut into 20×20 cm was prepared. And the outer appearance when it bent inward with respect to the center part and the outer appearance when it grasped was judged with the following criteria.

A: When bent, it bends as if it has a round shape, and a fine and fine bending fine wrinkles are generated. Moreover, the drape property was also excellent.

B: When bent, it was bent and bent, and fine fine lines and deep wrinkles occurred. Moreover, the drape property was also inferior.

C: The texture was remarkably low in fidelity.

(Coating property of silver cotton layer)

A: There was little sinking of the silver surface layer, and a smooth and smooth surface was formed.

B: There was some subsidence of the silver cotton layer, and the roughness of the fibers on the surface was felt a little.

C: The silver cotton layer almost subsided, and the surface was exposed from the fibers, causing fluff.

(Apparent density)

In accordance with JIS L 1913, thickness (mm) and apparent weight (g/cm 2) were measured, and apparent density (g/cm 3) was calculated from these values.

Table 1 below shows the evaluation results.

[Examples 2 to 11]

The composition of the dispersion liquid for a modifier prepared in Example 1 was changed to the composition and amount as shown in Table 1, and the silver relief artificial leather was prepared in the same manner as in Example 1, except that the prepared modifier was impregnated into the nonwoven fabric of ultrafine fibers. And evaluated. Table 1 shows the results. In addition, a cross-sectional photograph of the nonwoven fabric of the ultrafine fiber obtained in Example 6 in FIG. 3 observed by a scanning electron microscope (SEM), and a cross-sectional SEM image of the artificial leather substrate obtained by impregnating the modifier in FIG. 4 Shows. Fig. 5 shows a cross-sectional photograph of the SEM of the silver relief artificial leather substrate obtained in Example 6.

[Example 12]

In the composition of the dispersion for the modifier prepared in Example 6, silver relief was carried out in the same manner as in Example 1 except that alumina (Al ₂ O ₃ ) particles were blended instead of blending aluminum dialkylphosphinate as a particulate filler. Artificial leather was obtained and evaluated. Table 1 shows the results.

[Comparative Example 1]

In Example 1, instead of impregnating the non-woven fabric of the ultrafine fiber with an impregnating agent dispersion, the same aqueous polyurethane dispersion as that used in Example 1 was impregnated so that the solid content of the ultrafine fiber was 12.5% by mass, 120 A silver relief artificial leather was obtained and evaluated in the same manner except that it was dried at ℃. Table 1 shows the results.

[Comparative Example 2]

In Example 1, a silver relief artificial leather was obtained and evaluated in the same manner as in Example 1, except that the step of impregnating the modifier was omitted. Table 1 shows the results.

[Comparative Examples 3 to 6]

A silver relief artificial leather was obtained in the same manner as in Example 1, except that the composition of the dispersion for the modifier prepared in Example 1 was adjusted and impregnated with the artificial leather substrate with the composition and amount of the modifier as shown in Table 1, Was evaluated. Table 1 shows the results.

All of the artificial leather substrates obtained in Examples 1 to 12 according to the present invention have an apparent density of 0.6 g/cm 3 or more, and a silver artificial artificial leather has an elasticity of 1.8 mm or more, and an artificial leather having both a sense of fidelity and elasticity. Was obtained. On the other hand, the artificial leather obtained in Comparative Example 1, which gave the non-woven fabric a sense of fidelity by applying a polymer elastic body, which is a typical artificial leather, had a fidelity of 0.6 g/cm 3 or more, but the strength was 0.89 mm. , Elasticity was low. Moreover, in the manufacture of the artificial leather of Comparative Example 1, when the resin solution for the silver surface layer was coated, it was easy to sink inside the artificial leather substrate. This is because there were many voids remaining on the surface. Moreover, the artificial leather of Comparative Example 6 containing no filler had a low apparent density and a low fidelity.

In addition, the artificial leather of Example 8 exhibited a very high elasticity, although the fidelity was slightly low because the proportion of the modifier was relatively low. However, in the artificial leather of Example 8, since pores remained on the surface, the coated resin solution was likely to sink.

From the above examples, it can be seen that according to the present invention, by artificially impregnating the voids between the fibers of the fiber entangled body with the modifier as described above, an artificial leather having both elastic texture and fidelity is obtained.

[Example 13]

Instead of forming a base coat having a film thickness of 28 µm as a silver surface layer on the surface of the artificial leather substrate obtained in Example 6, a smoothing layer was formed as follows. Specifically, 42.9 parts by weight of a filler (calcium carbonate with an average particle diameter of 5 µm) was blended with 100 parts by weight of the solid content of a polyurethane emulsion (30 mass% of LCC binder UB1770 manufactured by DIC Corporation), and a thickener was added and stirred. The coating liquid for a smoothing layer was prepared by mixing. In addition, the obtained coating liquid for the smoothing layer had a viscosity of η _0.6 of 240 Pa·s when measured using a B-type rotary viscometer at a temperature of 25° C. and measured at 0.6 revolutions/second, and measured at 3 revolutions/second. The viscosity η _{3.0 at} this time was 75 Pa·s, and η _0.6 /η _3.0 was 3.2. Further, 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 the η _0.6 /η _3.0 was 1.4.

The surface of the artificial leather substrate obtained in Example 6 was applied with a reverse coater for 140 g/m 2 of the coating solution for smoothing layer, and dried to form a smoothing layer having a thickness of 45 μm. The surface absorption rate of the smoothing layer thus formed was measured by the following method. As a result, the surface absorption rate was 180 seconds or more. Table 2 shows the results.

(Surface absorption rate)

It measured according to the dropping method of JIS L 1907-7.1.1. Specifically, the artificial leather substrate was cut to 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 to a height of 10 mm from the surface of the smoothing layer side of the test piece to the tip of the burette. Then, 1 drop of water is dropped from the burette onto the surface of the smoothing layer side of the test piece, and the specular reflection disappears as the test piece absorbs the water drop from the time when the water drop reaches the surface of the test piece, and the time until the wet state remains. Measured with a stop watch. Table 2 shows the results.

Then, a color coat layer having a film thickness of 14 µm was formed in the same manner as in Example 1 on the surface of the smoothing layer of the artificial leather substrate. And the air shot process was further performed at 40-50 degreeC for 2-4 hours. Then, in the same manner as in Example 1, an embossing treatment was performed on the surface layer at a line speed of 7.0 m/min using an embossing roll at 125°C and 50 kg/cm 2. And in the same manner as in Example 1, a top coat having a film thickness of 13.5 mu m was formed. Thus, a silver relief artificial leather having an apparent 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 cross section before formation of the smoothing layer of the artificial leather base obtained in Example 13, and Fig. 7 shows an SEM photograph of the cross section after formation of the smoothing layer. Fig. 8 shows a cross-sectional photograph of the SEM of the silver relief artificial leather substrate obtained in Example 13. In addition, the sinking amount (g/m 2) was calculated from the difference between the coating amount at the time of forming the smoothing layer and the thickness of the actually formed film. However, when the value was less than 0, it was set to 0. In addition, the results of the strength and texture are shown in Table 2.

[Examples 14 to 18]

As shown in Table 2, the coating liquid for the smoothing layer was prepared in the same manner as in Example 13 except that the fillers (calcium carbonate) were blended with 5% by mass, 10% by mass, 20% by mass, 40% by mass, and 50% by mass, respectively. It was compounded. A silver relief artificial leather was obtained in the same manner as in Example 13, except that the adjusted coating solution for the smoothing layer was used. Table 2 shows the results.

[Examples 19 to 21]

As shown in Table 2, silver relief 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. Table 2 shows the results.

[Example 22]

As shown in Table 2, instead of blending the filler (calcium carbonate) by 30 mass%, the filler (vinylidene chloride/nitrile-based plastic balloon having an average particle diameter of 30 µm) is 1.5 mass by mass based on 100 parts by mass of the solid content of the polyurethane emulsion. As a part, a silver relief artificial leather was obtained in the same manner as in Example 13 except that the coating solution for the smoothing layer was blended in the same manner as in Example 13 except that 50% was blended in a volume ratio. . Table 2 shows the results. In addition, FIG. 9 shows an SEM photograph of a cross section after formation of the smoothing layer of the artificial leather base obtained in Example 22, and FIG. 10 shows a cross-sectional photograph of an SEM of the silver relief artificial leather base obtained in Example 22.

All of the artificial leather substrates obtained in Examples 13 to 22 had a small settling of the smoothing layer and a silver surface layer, and also had a small surface absorption rate of the artificial leather substrate. Therefore, it turns out that sinking of the silver-like resin layer of the surface of an artificial leather base material can be suppressed by forming a smoothing layer. By suppressing the sinking of the silver-faced resin layer, a silver relief artificial leather that maintains a very elastic texture is obtained. On the other hand, as in Example 6, when using a polyurethane emulsion with a η _0.6 /η _3.0 of 1.4 with no filler, it can be seen that some subsidence was seen.

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

Claims (20)

It contains a fiber entangled body, a first filler impregnated with the fiber entangled body, a liquid non-volatile oil, and a first polymer elastic body,
The first filler is an artificial leather substrate containing at least one selected from metal fillers, metal oxide fillers, inorganic compound fillers, flame retardant fillers, and carbon-based fillers. According to claim 1,
Artificial leather base material containing at least one selected from the non-volatile oil value, liquid paraffin, silicone oil, mineral oil and phthalic acid esters. According to claim 1,
The artificial leather base material wherein the fiber entangled body is a nonwoven fabric of ultrafine fibers having a fineness of 0.9 dtex or less. According to claim 1,
Artificial leather base material containing 1-60 mass% of said 1st filler with respect to the said fiber entanglement body. According to claim 1,
Artificial leather base material containing 0.5-10 mass% of said nonvolatile oil with respect to the said fiber entanglement body. According to claim 1,
Artificial leather base material impregnated with 0.5-15 mass% of 1st polymer elastic body with respect to the said fiber entangled body. The method of claim 6,
Artificial leather base material containing 10-30 mass% of the said 1st filler, the said nonvolatile oil, and the said 1st polymer elastic body with respect to the said fiber entangled body in total. The method of claim 6,
Artificial leather base material containing 1 to 70 mass% of the nonvolatile oil among the total amount of the first filler, the nonvolatile oil, and the first polymer elastic body. The method of claim 8,
Artificial leather base material containing 10 to 97 mass% of the first filler among the total amount of the first filler, the nonvolatile oil, and the first polymer elastic body. The method of claim 9,
Artificial leather base material containing 1 to 20% by mass of the first polymer elastic body among the total amount of the first filler, the non-volatile oil, and the first polymer elastic body. According to claim 1,
Artificial leather substrate with an apparent density of at least 0.60 g/cm 3. According to claim 1,
Further provided with a smoothing layer for smoothing the surface,
The smoothing layer is an artificial leather substrate having a thickness of 10 to 100 µm, which contains a second polymer elastic body and a second filler. The method of claim 12,
The smoothing layer contains an artificial leather base material containing 1 to 50 mass% of the second filler. The method of claim 12,
Artificial leather substrate having a surface absorption rate of 100 seconds or more in the smoothing layer in accordance with the dripping method of JIS L 1907-7.1.1. A silver relief artificial leather formed by further laminating a resin layer on the smoothing layer of the artificial leather substrate according to claim 12. The method of claim 15,
Silver relief artificial leather with a strength of 1.8 to 2.5 mm measured by a softness tester. A method for manufacturing the artificial leather substrate according to claim 12,
A process for preparing the artificial leather base fabric according to claim 1,
After applying the coating liquid for forming a smoothing layer on the surface of the fabric, and then drying it comprises a step of forming the smoothing layer having a thickness of 10 ~ 100 ㎛,
The coating solution for forming the smoothing layer,
The solid contains the second polymer elastic body and the second filler,
At a temperature of 25° C., the ratio of the viscosity η _0.6 when measured at 0.6 revolutions per second using a B-type rotational viscometer and the viscosity η _3.0 when measured at 3 revolutions per second (η _0.6 /η _3.0 ) The manufacturing method of an artificial leather base material whose thixotropy index is 2-4. The method of claim 17,
The said coating liquid for smoothing layer formation contains 1-50 mass% of the said 2nd filler in solid content, The manufacturing method of the artificial leather base material. As a non-volatile component, it contains 3 to 90 mass% of a liquid non-volatile oil and 10 to 97 mass% of a blend of the first filler and the first polymer elastic body,
The first filler is a modifier for artificial leather substrates containing at least one selected from metal fillers, metal oxide fillers, inorganic compound fillers, flame retardant fillers and carbon-based fillers. delete

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