Composite artificial leather and method for manufacturing the same

Abstract

To provide a composite artificial leather that is obtained by laminating an artificial leather and a foam resin layer and has excellent quality, clear convexoconcave, excellent durability in addition to soft feeling specific to the artificial leather.SOLUTION: A composite artificial leather is formed by disposing a foam resin layer on one surface of an artificial leather consisting of a fiber-entangled form including nonwoven fabric formed of ultra fine fiber with average single fiber diameter of 1.0 μm or more and 10.0 μm or less as component and elastomer. The composite artificial leather has a convex part and a concave part. Cross-sectional porosity of the artificial leather is 20% or more and 50% or less at the convex part. Compression modulus RA (%) at the convex part of the composite artificial leather is 60% or more and 100% or less.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] This invention relates to a composite artificial leather having an uneven surface pattern, and more specifically, to a composite artificial leather that combines the soft texture and good quality characteristic of artificial leather with aesthetic appeal. [Background technology]

[0002] Suede-like artificial leather, composed primarily of nonwoven fabric made of ultrafine fibers and a polymeric elastic material, possesses high durability and a soft texture, and is used in a wide range of applications including automotive interiors, furniture, general merchandise, and clothing. In particular, artificial leather used for automotive interiors and furniture may require post-processing such as embossing or molding depending on the application. Embossing is generally done by laminating a sheet of a different material on the back of the surface material and compressing the surface material with a heat press to create a raised and recessed pattern on the surface. However, a problem with this method is that the raised parts of the composite material molded in this way lose the soft texture characteristic of the surface material.

[0003] This problem is particularly pronounced when the surface material is artificial leather. In order to maintain the embossed pattern even after long-term use, increasing the heat pressing time and pressure during embossing causes the raised areas to harden, compromising the soft texture characteristic of artificial leather. On the other hand, if the heat pressing time and pressure during embossing are reduced to maintain the soft texture, the shape retention of the embossed pattern decreases, making it impossible to maintain the design over the long term. Therefore, there has long been a need for a means to achieve both the soft texture characteristic of artificial leather and the design appeal of embossing in embossed composite artificial leather.

[0004] As an example of such technology, the technology disclosed in Patent Document 1 proposes a method for maintaining the soft texture characteristic of artificial leather by keeping a certain amount of voids in the thickness direction of the artificial leather. Furthermore, the technologies disclosed in Patent Documents 2 to 4 propose an embossed composite material with clearly defined uneven surfaces and excellent cushioning performance, in which a soft polyurethane foam sheet having a specific compression ratio and compression residual strain is laminated on the back surface of the surface material. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2017 / 043322 [Patent Document 2] International Publication No. 2017 / 056465 [Patent Document 3] International Publication No. 2017 / 006556 [Patent Document 4] Japanese Patent Publication No. 2014-184580 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Artificial leather obtained by the method disclosed in Patent Document 1 achieves the soft texture characteristic of artificial leather by maintaining a certain amount of voids in the thickness direction. However, if this artificial leather itself is embossed, the voids are compressed, and the texture is impaired.

[0007] The composite materials obtained by the methods disclosed in Patent Documents 2 to 4 involve laminating a specific soft polyurethane foam sheet to the back of the surface material. This method results in a composite material with a certain degree of clarity in the shape of the raised and recessed areas after embossing, and the shape remains relatively clear even after prolonged use, while also providing a certain level of cushioning performance. However, when artificial leather is used as the surface material, the pressure applied in the thickness direction of the surface material cannot be suppressed during embossing, causing the raised areas to be compressed. This prevents the maintenance of the voids within the artificial leather, and the texture is ultimately compromised.

[0008] Therefore, the present invention has been made in view of the above circumstances, and its object is to provide a composite artificial leather in which artificial leather and a foamed resin layer are laminated, which has the soft texture characteristic of artificial leather, while having excellent quality, a clearly defined shape of the uneven parts, and a highly durable uneven surface shape. [Means for solving the problem]

[0009] As a result of repeated studies by the inventors in order to achieve the above objectives, they have found that in a composite artificial leather having an uneven pattern and a foamed resin layer laminated on one surface, by setting the cross-sectional void ratio and compressive modulus of the artificial leather in the raised parts of the composite artificial leather to a specific range, it is possible to maintain the soft texture characteristic of artificial leather and achieve good cushioning and touch feel.

[0010] This invention was completed based on these findings, and according to this invention, the following inventions are provided.

[0011] [1] A composite artificial leather comprising a fiber entanglement body containing a nonwoven fabric made of ultrafine fibers with an average single fiber diameter of 1.0 μm or more and 10.0 μm or less as constituent elements, and a polymer elastic body, wherein a foamed resin layer is provided on one surface of the artificial leather, the composite artificial leather having convex portions and concave portions, the cross-sectional void ratio of the artificial leather in the convex portions being 20% ​​or more and 50% or less, and furthermore, the compressive modulus of elasticity of the composite artificial leather in the convex portions R AA composite artificial leather in which the percentage is between 60% and 100%.

[0012] [2] Compression modulus R of the composite artificial leather in the convex portion A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The composite artificial leather described in [1] above, wherein the ratio is 1.2 or more and 2.5 or less.

[0013] [3] The composite artificial leather according to [1] or [2], wherein the fiber entanglement further comprises a woven or knitted fabric (a), the woven or knitted fabric (a) being entangled and integrated with the nonwoven fabric.

[0014] [4] The composite artificial leather according to any one of [1] to [3], wherein a woven or knitted fabric (b) is further provided on the surface of the composite artificial leather that has a foamed resin layer.

[0015] [5] The composite artificial leather according to any one of [1] to [4], wherein the thickness of the artificial leather in the recess is 25% or more and 75% or less of the thickness of the composite artificial leather in the recess.

[0016] [6] The composite artificial leather according to any one of [1] to [5], wherein the depth of the recess is 1.0 mm or more and 20.0 mm or less.

[0017] [7] A method for manufacturing a composite artificial leather according to any one of [1] to [6], comprising: laminating a foamed resin layer on one surface of an artificial leather made of a fiber entanglement body including a nonwoven fabric made of ultrafine fibers having an average single fiber diameter of 1.0 μm or more and 10.0 μm or less as a component, and a polymer elastic body; setting the temperature of the upper die surface and the lower die surface of an embossing mold to 60°C or more and 240°C or less; placing the laminate made of the artificial leather and the foamed resin layer on the embossing mold; closing the embossing mold and holding it for 5 seconds or more and 150 seconds or less.

[0018] [8] A method for manufacturing a composite artificial leather according to any one of [1] to [6], comprising laminating a foam resin layer on one surface of an artificial leather composed of a fiber complex containing a non-woven fabric made of ultra-fine fibers having an average single fiber diameter of 1.0 μm or more and 10.0 μm or less and a polymer elastomer, setting the surface temperature of an embossing roll to 60°C or more and 240°C or less, passing a laminate composed of the artificial leather and the foam resin layer between the embossing rolls, and bringing the laminate into contact with the embossing rolls for 0.05 seconds or more and 30 seconds or less.

[0019] <> [9] The thickness t of the artificial leather before the lamination A (mm) and the thickness t of the foam resin layer B (mm), the ratio (t A / t B ) is in the range of 0.15 or more and 0.40 or less, the method for manufacturing a composite artificial leather according to [7] or [8].

[0020] [[]END]]

[10] When laminating or after laminating, a woven or knitted fabric (b) having a constant load elongation rate of 130% or more and 300% or less is laminated on the surface of the foam resin layer opposite to the surface on the artificial leather side, the method for manufacturing a composite artificial leather according to any one of [7] to [9].

[0021]

[11] The thickness t of the woven or knitted fabric (b) before the lamination C (mm) and the foam resin layer t B (mm), the ratio (t C / t B ) is in the range of 0.10 or more and 0.15 or less, the method for manufacturing a composite artificial leather according to

[10] . [Advantages of the Invention]

[0022] According to the present invention, in a composite artificial leather having a concavo-convex pattern and having a foam resin layer laminated on one surface, it is possible to maintain a soft texture peculiar to artificial leather, and it is possible to obtain a composite artificial leather having good cushioning properties and touch feeling. [Brief Description of the Drawings]

[0023] [Figure 1] Figure 1 is a perspective view illustrating and explaining a case in which the composite artificial leather according to the present invention has a texture-like pattern in the logo-shaped recess. [Figure 2] Figure 2 is a cross-sectional conceptual diagram illustrating and explaining a recess in one embodiment of the composite artificial leather according to the present invention. [Figure 3] Figure 3 is a cross-sectional conceptual diagram illustrating and explaining a convex portion in another embodiment of the composite artificial leather according to the present invention. [Figure 4] Figure 4 is a cross-sectional conceptual diagram illustrating and illustrating a recess in yet another embodiment of the composite artificial leather according to the present invention. [Figure 5] Figure 5 is a perspective view illustrating and explaining a case in which the composite artificial leather according to the present invention combines the shapes exemplified in Figures 2 to 4. [Modes for carrying out the invention]

[0024] The composite artificial leather of the present invention is a composite artificial leather comprising a fiber entanglement body containing a nonwoven fabric made of ultrafine fibers with an average single fiber diameter of 1.0 μm or more and 10.0 μm or less as constituent elements, and a polymer elastic body, wherein a foamed resin layer is provided on one surface of the artificial leather, and the composite artificial leather has convex portions and concave portions, the cross-sectional void ratio of the artificial leather in the convex portions is 20% or more and 50% or less, and furthermore, the compressive modulus of the composite artificial leather in the convex portions is 60% or more and 100% or less.

[0025] These components will be described in detail below, but the present invention is not limited in any way to the scope described below, as long as it does not exceed the gist of the invention.

[0026] [Fiber entanglement] The ultrafine fibers constituting the fibrous entanglement used in the present invention are preferably made of polyester resin, from the viewpoint of durability, particularly mechanical strength and heat resistance.

[0027] Examples of the aforementioned polyester resins include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylenedimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate. Among these, polyethylene terephthalate, which is the most commonly used, or polyester copolymers mainly containing ethylene terephthalate units are preferably used.

[0028] Furthermore, as the polyester resin, a single polyester may be used, or two or more different polyesters may be used. However, when two or more different polyesters are used, from the viewpoint of compatibility between the two or more components, the difference in the intrinsic viscosity (IV value) of the polyesters used is preferably 0.50 or less, and more preferably 0.30 or less.

[0029] In this invention, the intrinsic viscosity is calculated by the following method. (1) Dissolve 0.8 g of the sample polymer in 10 mL of orthochlorophenol. (2) Relative viscosity η measured at a temperature of 25°C using an Ostwald viscometer r Calculate it using the following formula and round it to the third decimal place. η r =η / η0=(t×d) / (t0×d0) Intrinsic viscosity (IV value) = 0.0242η r +0.2634 (Here, η is the viscosity of the polymer solution, η0 is the viscosity of orthochlorophenol, t is the fall time of the solution (seconds), and d is the density of the solution (g / cm³) 3 ), t0 is the fall time of orthochlorophenol (seconds), and d0 is the density of orthochlorophenol (g / cm³). 3 ) represents each of these.

[0030] While a round cross-section is preferable for the cross-sectional shape of ultrafine fibers from the viewpoint of ease of processing and operation, other irregular cross-sectional shapes such as elliptical, flat, triangular, sector-shaped, cross-shaped, hollow, Y-shaped, T-shaped, and U-shaped can also be adopted.

[0031] The average single fiber diameter of the ultrafine fibers is 1.0 μm or more and 10.0 μm or less. An average single fiber diameter of 1.0 μm or more, preferably 1.5 μm or more, provides excellent color development after dyeing, lightfastness, friction fastness, and spinning stability. On the other hand, an average single fiber diameter of 10.0 μm or less, preferably 6.0 μm or less, more preferably 4.5 μm or less, yields a dense, flexible, and high-quality artificial leather.

[0032] In this invention, the average single fiber diameter of ultrafine fibers is calculated by taking a scanning electron microscope (SEM) photograph of the cross-section of artificial leather, randomly selecting 10 ultrafine fibers that are circular or nearly circular in shape, measuring the single fiber diameter, calculating the arithmetic mean of the 10 fibers, and rounding to the second decimal place. However, if ultrafine fibers with an irregular cross-section are used, the single fiber diameter is determined by first measuring the cross-sectional area of ​​the single fiber and calculating the diameter (equivalent diameter of a circle) when the cross-section is considered to be circular.

[0033] In the present invention, the ultrafine fibers may further contain carbon black. Carbon black readily yields black pigments with fine particle sizes and exhibits excellent dispersibility in polymers. Therefore, by further containing carbon black in the ultrafine fibers, it is possible to achieve excellent colorfastness, abrasion resistance, and strength while maintaining excellent deep and uniform color development.

[0034] In addition to carbon black, the polyester resin forming the ultrafine fibers may contain, depending on the purpose, inorganic particles such as titanium dioxide particles, lubricants, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, and antibacterial agents, to the extent that they do not hinder the objectives of the present invention.

[0035] In the artificial leather of the present invention, one of the constituent elements is a fiber entanglement composite that includes a nonwoven fabric composed of ultrafine fibers made of the aforementioned polyester resin.

[0036] In the present invention, "a fiber entanglement body containing a nonwoven fabric as a component" refers to embodiments in which the fiber entanglement body is a nonwoven fabric, or embodiments in which the fiber entanglement body is formed by the entanglement and integration of a nonwoven fabric and a woven or knitted fabric (a), as described later.

[0037] By creating a fiber entanglement composite that includes nonwoven fabric as a component, a uniform and elegant appearance and texture can be obtained when the surface is napped.

[0038] Nonwoven fabrics can take two forms: long-fiber nonwoven fabrics, which are mainly composed of filaments, and short-fiber nonwoven fabrics, which are mainly composed of fibers with a fiber length of 100 mm or less. When long-fiber nonwoven fabric is used as the fibrous base material, it is preferable because it is possible to obtain artificial leather with excellent strength. On the other hand, when short-fiber nonwoven fabric is used, it is possible to have more fibers oriented in the thickness direction of the artificial leather compared to the case of long-fiber nonwoven fabric, and it is possible to give the surface of the artificial leather a high density when it is napped.

[0039] When using short-fiber nonwoven fabric, the average fiber length of the ultrafine fibers is preferably 25 mm to 90 mm. By setting the fiber length to 90 mm or less, more preferably 80 mm or less, and even more preferably 70 mm or less, good quality and a soft texture can be obtained. On the other hand, by setting the fiber length to 25 mm or more, more preferably 35 mm or more, and even more preferably 40 mm or more, an artificial leather with excellent abrasion resistance can be obtained.

[0040] The basis weight of the nonwoven fabric constituting the artificial leather according to the present invention was measured according to "6.2 Mass per unit area (ISO method)" of JIS L1913:2010 "General nonwoven fabric test methods", and was 50 g / m². 2 More than 600g / m 2 The following range is preferable: The basis weight of the nonwoven fabric is 50 g / m². 2 More preferably 80 g / m²2 By doing so, it is possible to produce artificial leather with a substantial feel and excellent texture. On the other hand, the basis weight of the nonwoven fabric is 600g / m². 2 More preferably 500g / m 2 By doing the following, it is possible to create a flexible artificial leather with excellent shapeability and design properties.

[0041] In the artificial leather of the present invention, the fiber entanglement further includes a woven or knitted fabric (a), and it is preferable that the woven or knitted fabric (a) is entangled and integrated with the nonwoven fabric. This improves the strength and dimensional stability of the artificial leather. Examples of "further including a woven or knitted fabric (a)" include those laminated in the order of nonwoven fabric / woven or knitted fabric (a), those laminated in the order of woven or knitted fabric (a) / nonwoven fabric, those laminated in the order of nonwoven fabric / woven or knitted fabric (a) / nonwoven fabric, those laminated in the order of woven or knitted fabric (a) / nonwoven fabric / nonwoven fabric / woven or knitted fabric (a), and those laminated in the order of nonwoven fabric / woven or knitted fabric (a) / woven or knitted fabric (a) / nonwoven fabric. Among these, those laminated in the order of nonwoven fabric / woven or knitted fabric (a) are more preferable in terms of surface quality and strength of the artificial leather.

[0042] The aforementioned woven or knitted fabric (a) can be a woven fabric or a knitted fabric. When the woven or knitted fabric (a) is a woven fabric, the weave structure can be a plain weave, twill weave, satin weave, etc. When the woven or knitted fabric (a) is a knitted fabric, the knit structure can be a weft knit such as a plain knit, rib knit, or pearl knit, or a warp knit such as a single denby knit, single atlas knit, single cord knit, double denby knit, double atlas knit, double cord knit, or half tricot knit. In particular, when the woven fabric has a plain weave structure, it can be made into an artificial leather with excellent strength, which is especially preferable.

[0043] The types of fibers constituting the woven or knitted fabric (a) described above are preferably filament yarn, spun yarn, or a composite yarn made of filament yarn and spun yarn, and it is more preferable to use multifilaments made of polyester resin or polyamide resin from the viewpoint of durability, and especially mechanical strength.

[0044] By setting the average single fiber diameter of the fibers constituting the woven fabric (a) to preferably 50.0 μm or less, more preferably 15.0 μm or less, and even more preferably 13.0 μm or less, not only is it possible to obtain artificial leather with excellent flexibility, but even when the fibers of the woven fabric (a) are exposed on the surface of the artificial leather, the difference in hue between them and the ultrafine fibers containing pigment after dyeing is reduced, thus not impairing the uniformity of the hue on the surface. On the other hand, by setting the average single fiber diameter to preferably 1.0 μm or more, more preferably 8.0 μm or more, and even more preferably 9.0 μm or more, the morphological stability of the product as artificial leather is improved.

[0045] In this invention, the average single fiber diameter of the fibers constituting the woven or knitted fabric (a) is calculated by taking a scanning electron microscope (SEM) photograph of the cross-section of the artificial leather, randomly selecting 10 fibers constituting the woven or knitted fabric (a), measuring the single fiber diameter of those fibers, calculating the arithmetic mean of the 10 fibers, and rounding to the second decimal place.

[0046] If the fibers constituting the woven or knitted fabric (a) are multifilaments, the total fineness of the multifilaments is measured by "8.3 Fineness" of "8.3.1 True Fineness b) Method B (Simplified Method)" in JIS L1013:2010 "Test Methods for Chemical Fiber Filament Yarns," and is preferably between 30 dtex and 170 dtex.

[0047] By setting the total fineness of the yarns constituting the woven or knitted fabric (a) to 170 dtex or less, a highly flexible artificial leather can be obtained. On the other hand, setting the total fineness to 30 dtex or more is preferable not only because it improves the morphological stability of the artificial leather product, but also because when the nonwoven fabric and the woven or knitted fabric (a) are interwoven and integrated by needle punching or the like, the fibers constituting the woven or knitted fabric (a) are less likely to be exposed on the surface of the artificial leather. In this case, it is preferable that the total fineness of the warp and weft multifilaments be the same.

[0048] Furthermore, it is preferable that the twist count of the yarn constituting the woven or knitted fabric (a) be between 1000 T / m and 4000 T / m. By setting the twist count to 4000 T / m or less, more preferably 3500 T / m or less, and even more preferably 3000 T / m or less, an artificial leather with excellent flexibility can be obtained. By setting the twist count to 1000 T / m or more, more preferably 1500 T / m or more, and even more preferably 2000 T / m or more, it is possible to prevent damage to the fibers constituting the woven or knitted fabric (a) when the nonwoven fabric and the woven or knitted fabric (a) are intertwined and integrated by needle punching or the like, resulting in an artificial leather with excellent mechanical strength, which is preferable.

[0049] [Polymer elastic material] Since the polymeric elastic material constituting the artificial leather of the present invention is a binder that grips the ultrafine fibers constituting the artificial leather, polyurethane is preferred as the polymeric elastic material used, considering the flexible texture of the artificial leather of the present invention.

[0050] In the present invention, the polyurethane preferably used as the polymeric elastic material can be either an organic solvent-based polyurethane used in a dissolved state in an organic solvent, or a water-dispersible polyurethane used in a dispersed state in water. Furthermore, a polyurethane preferably used in the present invention is a polyurethane obtained by the reaction of a polymer diol, an organic diisocyanate, and a chain extender.

[0051] Examples of the polymer diols used include polycarbonate-based diols, polyester-based diols, polyether-based diols, silicone-based diols, and fluorine-based diols, and copolymers combining these can also be used. Among these, polycarbonate-based diols are more preferable from the viewpoint of hydrolysis resistance and abrasion resistance.

[0052] The above polycarbonate diols can be produced by transesterification of alkylene glycol and carbonate ester, or by reaction of phosgene or chlorformate ester with alkylene glycol.

[0053] Examples of alkylene glycols include linear alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol; branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 2-methyl-1,8-octanediol; alicyclic diols such as 1,4-cyclohexanediol; aromatic diols such as bisphenol A; glycerin; trimethylolpropane; and pentaerythritol. In the present invention, either polycarbonate diols obtained from individual alkylene glycols or copolymerized polycarbonate diols obtained from two or more alkylene glycols can be used.

[0054] Furthermore, examples of polyester diols include polyester diols obtained by condensing various low molecular weight polyols with polybasic acids.

[0055] As low molecular weight polyols, for example, one or more selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, and cyclohexane-1,4-dimethanol can be used.

[0056] In addition, adducts obtained by adding various alkylene oxides to bisphenol A can also be used.

[0057] Examples of polybasic acids include one or more selected from the group consisting of succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydroisophthalic acid.

[0058] Examples of polyether-based diols used in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymer diols combining these.

[0059] The number-average molecular weight of the polymer diol is preferably in the range of 500 to 4000 when the molecular weight of the polyurethane elastomer is constant. By setting the number-average molecular weight to preferably 500 or more, and more preferably 1500 or more, it is possible to prevent the artificial leather from becoming hard. Furthermore, by setting the number-average molecular weight to preferably 4000 or less, and more preferably 3000 or less, it is possible to maintain the strength of the polyurethane.

[0060] Examples of organic diisocyanates preferably used in the present invention include aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, as well as aromatic diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate, and these can also be used in combination.

[0061] Preferably, amine-based chain extenders such as ethylenediamine and methylenebisaniline, and diol-based chain extenders such as ethylene glycol can be used. Alternatively, polyamines obtained by reacting polyisocyanate with water can also be used as chain extenders.

[0062] In the present invention, polyurethane, which is preferably used as a polymeric elastic material, can be used in combination with a crosslinking agent for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance, etc. The crosslinking agent may be an external crosslinking agent added to the polyurethane as a third component, or an internal crosslinking agent that introduces reaction sites that form a crosslinked structure into the polyurethane molecular structure in advance can be used. From the viewpoint of forming crosslinking points more uniformly within the polyurethane molecular structure and reducing the decrease in flexibility, it is preferable to use an internal crosslinking agent.

[0063] Compounds containing isocyanate groups, oxazoline groups, carbodiimide groups, epoxy groups, melamine resins, and silanol groups can be used as crosslinking agents.

[0064] Furthermore, polymeric elastic materials may contain various additives depending on the purpose, such as flame retardants (e.g., phosphorus-based, halogen-based, and inorganic types), antioxidants (e.g., phenol-based, sulfur-based, and phosphorus-based types), ultraviolet absorbers (e.g., benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, and oxalic acid anilide-based types), light stabilizers (e.g., hindered amine-based and benzoate-based types), hydrolysis-resistant stabilizers (e.g., polycarbodiimide), plasticizers, antistatic agents, surfactants, coagulation modifiers, carbon black, and dyes.

[0065] Generally, the content of polymeric elastic material in artificial leather can be adjusted as appropriate, taking into account the type of polymeric elastic material used, the manufacturing method of the polymeric elastic material, and the texture and physical properties. However, in the present invention, it is preferable that the content of polymeric elastic material be 10% by mass or more and 60% by mass or less relative to the mass of the fiber entanglement. By setting the content of polymeric elastic material to 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, the bonding between fibers by the polymeric elastic material can be strengthened, and the durability of the artificial leather can be improved. On the other hand, by setting the content of polymeric elastic material to 60% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, the artificial leather can be made more flexible and have a softer texture.

[0066] [Artificial leather] In the artificial leather of the present invention, it is preferable to have a nap on the surface. It is preferable that the nap be present on at least one surface of the artificial leather, and from the viewpoint of design effect, it is preferable that the nap has a length and directional flexibility such that when the nap is traced with a finger, the direction of the nap changes, leaving a mark, so-called finger marks.

[0067] More specifically, the pile length on the surface is preferably 200 μm to 500 μm, and more preferably 250 μm to 450 μm. By setting the pile length to 200 μm or more, the surface pile covers the polymer elastic material, suppressing the exposure of the polymer elastic material to the surface of the artificial leather, thereby obtaining artificial leather with excellent quality and density. Furthermore, when a woven fabric is intertwined and integrated with the nonwoven fabric constituting the artificial leather, it is preferable to set the surface pile length within the above range so that the fibers of the woven fabric near the surface of the artificial leather can be sufficiently covered. On the other hand, by setting the pile length to 500 μm or less, it is possible to obtain artificial leather with excellent shapeability and abrasion resistance.

[0068] In this invention, the pile length of the artificial leather is calculated by the following method. (1) Using a lint brush or the like, raise the nap of the artificial leather and prepare a 1 mm thick section in the cross-sectional direction of a surface perpendicular to the longitudinal direction of the artificial leather. (2) Observe the cross-section of the artificial leather at 90x magnification using a scanning electron microscope (SEM). (3) In the captured SEM image, the height of the pile (layer consisting only of ultrafine fibers) is measured at 10 points at 200 μm intervals in the width direction of the cross-section of the artificial leather. (4) Calculate the average value (arithmetic mean) of the heights of the 10 measured pile sections (layers consisting only of ultrafine fibers).

[0069] In the artificial leather of the present invention, it is preferable that the proportion of the artificial leather's pile covering the pile surface (pile coverage rate) is 50% or more and 100% or less. By setting the pile coverage rate to 50% or more, the exposure of the polymer elastic material on the surface of the artificial leather can be suppressed, thereby obtaining artificial leather with excellent quality and a dense feel.

[0070] The coverage rate of the pilous surface was determined by magnifying the surface with an SEM to 30x to 90x to make the presence of pilous hairs visible, and then analyzing the total area of ​​9 mm² using image analysis software. 2 This refers to the value calculated as the ratio of the total area of ​​the standing pile portion per unit area. The ratio of the total area can be calculated by binarizing the captured SEM image using image analysis software such as "ImageJ," developed by the National Institutes of Health (NIH) in the United States, with the threshold for standing pile portions and non-standing pile portions set to 100. In addition, when calculating the standing pile coverage rate, if non-standing pile material is calculated as standing pile and significantly affects the standing pile coverage rate, the image is manually edited and that part is calculated as a non-standing pile portion.

[0071] While the aforementioned image analysis software "ImageJ" is an example of an image analysis system, an image analysis system is not limited to "ImageJ" as long as it consists of image processing software that has the function of calculating the area ratio of specified pixels. "ImageJ" is a general-purpose software developed by the National Institutes of Health in the United States. This "ImageJ" software has the function of identifying necessary regions in an acquired image and performing pixel analysis.

[0072] The artificial leather of the present invention preferably has a thickness measured by "6.1.1 Method A" of "6.1 Thickness (ISO Method)" in "General Nonwoven Fabric Test Methods" of JIS L1913:2010, which is in the range of 0.2 mm to 1.2 mm. By setting the thickness of the artificial leather to 0.2 mm or more, more preferably 0.3 mm or more, and even more preferably 0.4 mm or more, it not only becomes easy to process during manufacturing but also has a substantial feel and excellent texture. On the other hand, by setting the thickness to 1.2 mm or less, more preferably 1.1 mm or less, and even more preferably 1.0 mm or less, it becomes easier to apply a design to a sheet-like material in which a foamed resin layer is provided on one surface of the artificial leather, and the design becomes clearer, it becomes more durable against friction, and it is possible to make an artificial leather with a flexible texture.

[0073] [Foam resin layer] The composite artificial leather of the present invention has a foamed resin layer provided on one surface of the artificial leather. In the present invention, this foamed resin layer means a layer composed of a resin having a porous structure. This foamed resin layer includes, for example, a layer having a foamed structure formed by a foaming agent, and a layer having a porous structure formed by wet solidification of a polyurethane solution dissolved in an organic solvent, where the organic solvent is replaced by water, but is not particularly limited as long as it is a layer having a porous structure. Among these, a polyurethane-based foamed resin layer is preferred from the viewpoint of manufacturing cost if it is foamed while mixing a foaming agent and the like with a polyol and polyisocyanate as the main components and resinifying.

[0074] The aforementioned foamed resin layer is, for example, a layer made of a resin obtained by foaming a general polyurethane-based or olefin-based resin to achieve desired properties. Among these, a sheet made of foamed soft polyurethane (soft polyurethane foam), which has high flexibility and cushioning properties, is preferably used.

[0075] The aforementioned "polyurethane-based, olefin-based, and other resins" preferably have a molecular weight of 500 to 20,000. A molecular weight of 500 or more allows for clear unevenness and enables the creation of complex patterns. A molecular weight of 20,000 or less maintains heat resistance, minimizes heat damage during embossing, and provides good cushioning and tactile feel.

[0076] The aforementioned foamed resin layer has an apparent density of 15 kg / m³. 3 More than 50kg / m 3 Preferably, the apparent density is 15 kg / m³. 3 As a result, the strength of the composite artificial leather is maintained, and the clear design can be preserved for a long period of time. The apparent density is 50 kg / m³. 3 The following conditions allow for the creation of complex textured surfaces using composite artificial leather.

[0077] In this invention, the apparent density of the foamed resin layer refers to the density measured and calculated in accordance with JIS K7222 "Foamed plastics and rubber - Method for determining apparent density".

[0078] Preferably, the foamed resin layer has a compression set of 3% or more and 10% or less. A compression set of 3% or more improves the durability of the uneven surface. A compression set of 10% or less improves the shapeability of the uneven surface and maintains cushioning properties.

[0079] In this invention, the compressive residual strain (%) refers to the value measured and calculated according to "4.5.2 Method A (compression at 70°C)" described in "4. Compressive Residual Strain Test" of "4. Compressive Residual Strain Test" in JIS K6400-4:2004 "Flexible foamed materials - Method for determining physical properties - Part 4: Compressive residual strain and repeated compressive residual strain".

[0080] Preferably, the foamed resin layer has a rebound elasticity of 40% to 100%. A rebound elasticity of 40% or more allows the soft texture and cushioning properties of the composite artificial leather to be maintained. On the other hand, a rebound elasticity of 100% or less improves the shapeability during embossing, allowing a clear embossed design to be maintained over the long term.

[0081] In this invention, the rebound elasticity (%) refers to the value measured and calculated in accordance with JIS K6400-3:2011 "Flexible foamed materials - Method for determining physical properties - Part 3: Method for determining rebound elasticity".

[0082] [Composite artificial leather] The composite artificial leather of the present invention is a composite artificial leather in which the foamed resin layer is provided on one surface of the artificial leather, wherein the composite artificial leather has convex portions and concave portions, the cross-sectional void ratio of the artificial leather in the convex portions is 20% to 50%, and furthermore, the compressive modulus of the composite artificial leather in the convex portions is 60% to 100%. A composite artificial leather having such an uneven pattern can be obtained that has excellent design durability and the soft texture characteristic of artificial leather.

[0083] The composite artificial leather of the present invention has convex and concave portions. The presence of these convex and concave portions makes it possible to form a continuous embossed pattern or a logo-like mark. Furthermore, as illustrated in Figure 1, the concave portions (15) arranged in a logo-like manner on the composite artificial leather (11) can also have patterns such as grid patterns or stripe patterns, which are textures. The convex and concave portions of the composite artificial leather in the present invention will be described below.

[0084] First, the composite artificial leather (21) shown in Figure 2 is formed by creating a desired design in a convex shape on the surface of either the upper or lower die of an embossing mold or on the surface of one of the rolls of an embossing roll, and then adding a corresponding concave shape using a method described later. In this case, the concave part of the composite artificial leather (21) is the thickness (T) of the composite artificial leather, as measured by a method described later. A This refers to the portion that is 95% or less of the (25) portion in the figure, and the remaining portion is the convex part.

[0085] Furthermore, the composite artificial leather (31) shown in Figure 3 is obtained by, for example, forming a desired design in a concave shape on the surface of either the upper or lower die of an embossing mold or on the surface of one of the rolls of an embossing roll, and then adding a convex shape corresponding to the concave shape using a method described later. In this case, the convex part of the composite artificial leather is the thickness (T) of the composite artificial leather as measured by a method described later. B This refers to the portion that is 105% or more of the original value (part (36) in the diagram), and the remaining portion is the concave part.

[0086] Furthermore, the composite artificial leather (41) shown in Figure 4 is formed by creating a desired design in a convex shape on the surfaces of both the upper and lower embossing molds or on the surfaces of the rolls on both sides of the embossing roll, and then adding a corresponding concave shape using a method described later. Unlike the composite artificial leather shown in Figures 1 and 2, the thinnest part is formed in the center of the thickness direction of the composite artificial leather. In this case, the concave part of the composite artificial leather is the thickness (T) of the composite artificial leather as measured by a method described later. A This refers to the portion that is 95% or less of the curve (the part labeled (45) in the diagram), and the remaining portion is the convex part.

[0087] Furthermore, for artificial leathers that combine the elements shown in Figures 2 to 4, the convex and concave portions are determined according to the method described above. For example, in the composite artificial leather (51) shown in Figure 5, the portion indicated by (55) in the figure can be formed by the method shown in the example in Figure 2, and the portion indicated by (56) in the figure can be formed by the method shown in the example in Figure 3. In this case, the convex portion (56) of the composite artificial leather (51) is the thickness (T) of the composite artificial leather (51) measured by the method described later. T This refers to the portion that is 105% or more of the composite artificial leather (51), and the recess (55) of the composite artificial leather (51) is the thickness (T) of the composite artificial leather (51) as measured by the method described below. T This refers to the portion that is 95% or less of the total.

[0088] In this invention, the thickness of the composite artificial leather shall be measured and calculated by the following method. (1) Take a scanning electron microscope (SEM) image of the cross-section of the composite artificial leather. (2) Based on the above, it is determined whether the cross-sectional shape of the composite artificial leather is one of those shown in Figures 2 to 4, or a combination of cross-sectional shapes as shown in Figure 5. (2-1) When the cross-sectional shape is as shown in Figures 2 and 4, the thickness of the composite artificial leather is as described above (T A Therefore, the thickness of the protrusions of the composite artificial leather is measured at 10 locations in the SEM image, and the arithmetic mean of the measured values ​​is rounded to two decimal places to obtain the thickness of the composite artificial leather. (2-2) When the cross-sectional shape is as shown in Figure 3, the thickness of the composite artificial leather is as described above (T B Therefore, the thickness of the recessed areas of the composite artificial leather was measured at 10 locations in the SEM image, and the arithmetic mean of the measured values ​​was rounded to two decimal places to obtain the thickness of the composite artificial leather. (2-3) When the cross-sectional shape is as shown in Figure 5, the thickness of the composite artificial leather is as described above (T T Therefore, the thickness of the composite artificial leather is measured at 10 locations in the SEM image where there are neither concave nor convex parts, and the arithmetic mean of the measured values ​​is rounded to two decimal places to obtain the thickness of the composite artificial leather.

[0089] The composite artificial leather of the present invention has a cross-sectional void ratio of 20% or more and 50% or less in the raised portion of the artificial leather. By setting the cross-sectional void ratio of the artificial leather in the raised portion to 20% or more, preferably 22% or more, the soft texture characteristic of artificial leather can be retained in the raised portion even after embossing. On the other hand, by setting the cross-sectional void ratio of the artificial leather in the raised portion to 50% or less, preferably 40% or less, and more preferably 30% or less, a composite artificial leather with a dense feel and high shaping design properties can be obtained through embossing.

[0090] In this invention, the porosity of the cross-sectional area of ​​the artificial leather at the convex portion of the composite artificial leather is calculated by taking a scanning electron microscope (SEM) image of the cross-section of the composite artificial leather at 500x magnification, capturing only the artificial leather portion within 1000 μm from the boundary between the concave and convex portions, and using image analysis software to determine the total area of ​​0.35 mm². 2 This refers to the value obtained by calculating the ratio of the total area of ​​the cross-sectional voids per unit area. The ratio of the total area can be calculated by binarizing the captured SEM image using image analysis software such as "ImageJ," developed by the National Institutes of Health (NIH) in the United States, with a threshold of 40 set for the void areas and the areas filled with ultrafine fibers or polymeric elastic materials. Furthermore, in the calculation of the cross-sectional void ratio, if the voids are calculated as areas filled with ultrafine fibers or polymeric elastic materials and significantly affect the cross-sectional void ratio, the image is manually edited to calculate those areas as voids.

[0091] While the aforementioned image analysis software "ImageJ" is an example of an image analysis system, an image analysis system is not limited to "ImageJ" as long as it consists of image processing software that has the function of calculating the area ratio of specified pixels. It should be noted that "ImageJ" is a general-purpose software developed by the National Institutes of Health in the United States. This "ImageJ" software has the function of identifying necessary regions in an acquired image and performing pixel analysis.

[0092] The composite artificial leather of the present invention has a compression modulus of 60% or more and 100% or less at the protruding portion. By setting the compression modulus of the composite artificial leather at the protruding portion to 60% or more, preferably 65% ​​or more, the protruding portion of the composite artificial leather can have good cushioning and tactile feel.

[0093] The composite artificial leather of the present invention has a compression modulus R of the composite artificial leather at the aforementioned protrusion. A (%) Compression ratio R of the composite artificial leather at the aforementioned protrusion B (Ratio to %) A / R B It is preferable that the compression modulus R of the composite artificial leather in the convex portion is between 1.2 and 2.5. A (%) Compression ratio R of the composite artificial leather at the aforementioned protrusion B (Ratio to %) A / R B By setting the compression modulus R of the composite artificial leather in the raised portion to 1.2 or higher, preferably 1.4 or higher, high cushioning is maintained in the embossed raised portion, and a soft touch can be obtained. A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B By setting the ratio to 2.5 or less, compression on the embossed raised areas during use can be reduced, thereby achieving excellent design durability.

[0094] In the present invention, the compression modulus R of composite artificial leather A (%), Compression ratio R B (%) represents the value measured in accordance with JIS L1913:2010 "General Nonwoven Fabric Testing Methods" as follows: (1) The thickness of the protruding portion of the composite artificial leather is measured using a compression elasticity tester with an initial load of 0.5 kPa (thickness T0). (2) Next, apply a load of 30 kPa for 1 minute, and then measure the thickness while the load is applied (thickness T1). (3) Remove the load, leave it for 1 minute, and then measure the thickness again with an initial load of 0.5 kPa (thickness T0'). (4) The above measurements are performed a total of five times, and the compressive modulus (%) and compressibility (%) are calculated using the following formula, and the average value is determined. Compression modulus R A =(T0'-T1) / (T0-T1)×100 Compression ratio R B = (T0 - T1) / T0 × 100.

[0095] In the composite artificial leather of the present invention, it is preferable that a woven or knitted fabric (b) is further provided on the surface of the composite artificial leather on the side where the foamed resin layer is provided. As for the woven or knitted fabric (b), in order to suppress wrinkle formation when forming an uneven pattern and maintain the soft texture of the artificial leather, a woven or knitted fabric that can easily follow the deformation of the artificial leather and the foamed resin layer during embossing is preferred, and a circular knitted fabric is particularly preferred. By providing the woven or knitted fabric (b), excellent strength, embossable design and quality of the composite artificial leather can be obtained.

[0096] The woven or knitted fabric (b) described above preferably has an average fiber diameter of 10 μm or more and 150 μm or less. By setting the average fiber diameter of the woven or knitted fabric (b) to 10 μm or more, preferably 20 μm or more, the strength and shape retention of the composite artificial leather can be improved by laminating the woven or knitted fabric (b). By setting the average fiber diameter of the woven or knitted fabric (b) to 150 μm or less, preferably 100 μm or less, appropriate elasticity can be obtained, and the soft texture of the composite artificial leather can be maintained.

[0097] In this invention, the average fiber diameter of the fibers constituting the woven fabric (b) is calculated by taking a scanning electron microscope (SEM) image of the cross-section of the composite artificial leather, randomly selecting 10 fibers constituting the woven fabric (b), measuring the diameter of those fibers (if they are multifilaments, taking a scanning electron microscope (SEM) image of the cross-section of the composite artificial leather, randomly selecting 10 fiber bundles constituting the woven fabric (b), measuring the diameter of those fiber bundles), calculating the arithmetic mean of the 10 fibers, and rounding to the first decimal place. Therefore, the average fiber diameter of the woven fabric (b) is the average diameter of the multifilaments if the fibers constituting the woven fabric (b) are multifilaments, and the average diameter of the monofilaments if they are monofilaments.

[0098] The woven or knitted fabric (b) described above preferably has a constant load elongation rate of 130% or more and 300% or less. By setting the constant load elongation rate to 130% or more, preferably 140% or more, it is possible to easily follow the deformation of the artificial leather and foamed resin layer during embossing, making the pattern in the uneven areas clearer and preventing wrinkles. By setting the constant load elongation rate to 300% or less, preferably 250% or less, it is possible to limit the overall elongation of the composite artificial leather due to embossing, suppressing wrinkles caused by excessive stretching and maintaining the shape of the uneven areas and the composite artificial leather itself.

[0099] In the present invention, the constant load elongation rate of the woven or knitted fabric (b) is a value measured by the following method. (1) Take a test specimen measuring 80 mm in width and 250 mm in length from both the longitudinal and transverse directions, and mark a gauge line 100 mm apart in the center (gauge line distance: L0 (mm)). (2) Next, a Martens fatigue tester is used, with a gripping distance of 150 mm and a load of 1 kg applied. (3) Measure the distance between the gauge marks (L1 (mm)) after 1 minute has elapsed. (4) The above measurements are performed a total of three times, and the constant load elongation rate is calculated using the following formula to determine the average value. Constant load elongation rate L(%) = (L1 - L0) / L0 × 100 In the composite artificial leather of the present invention, it is preferable that the thickness of the artificial leather in the recess is 25% to 75% of the thickness of the composite artificial leather in the recess (the ratio of the thickness of the artificial leather is 25% to 75% (hereinafter sometimes simply referred to as the ratio of the thickness of the artificial leather)). By setting the thickness of the artificial leather in the recess to 25% or more, preferably 40% or more, and more preferably 50% or more, of the thickness of the composite artificial leather in the recess, the compression of the artificial leather in the recess due to embossing can be reduced, and the soft texture of the artificial leather in the convex parts can be maintained. By setting the thickness of the artificial leather in the recess to 75% or less, preferably 65% ​​or less, of the thickness of the composite artificial leather in the recess, the rebound of the artificial leather in the recess due to embossing can be suppressed, and a clear and highly durable uneven surface can be obtained.

[0100] In the present invention, the ratio of the thicknesses of the artificial leather shall be measured and calculated by the following method. (1) Take a scanning electron microscope (SEM) image of the cross-section of the composite artificial leather. (2) Based on the above, it is determined whether the cross-sectional shape of the composite artificial leather is one of those shown in Figures 2 to 4, or a combination of cross-sectional shapes as shown in Figure 5. (2-1) When the cross-sectional shape is as shown in Figures 2 and 4, the thickness of the composite artificial leather in the recess is the same as (T B ) is. Also, the thickness of the artificial leather in the recess is the same as the above (T B Therefore, the thickness of the composite artificial leather and the recessed areas of the artificial leather were measured at 10 locations in the SEM image, the ratio of the artificial leather thickness at each location was calculated, and the arithmetic mean was rounded to two decimal places to obtain the ratio of the artificial leather thickness. (2-2) When the cross-sectional shape is as shown in Figure 3, the thickness of the composite artificial leather in the recess is the same as (T B ) is. Also, the thickness of the artificial leather in the recess is the same as the above (T BTherefore, the thickness of the composite artificial leather and the recessed areas of the artificial leather were measured at 10 locations in the SEM image, the ratio of the artificial leather thickness at each location was calculated, and the arithmetic mean was rounded to two decimal places to obtain the ratio of the artificial leather thickness. (2-3) When the cross-sectional shape is as shown in Figure 5, the thickness of the composite artificial leather in the recess is the same as (T T ) is the case. Furthermore, the thickness of the artificial leather in the recess is the thickness of the artificial leather in the recess (55) mentioned above.Therefore, the thickness of the composite artificial leather and the recess of the artificial leather is measured at 10 locations in the SEM image, the ratio of the thickness of the artificial leather at each location is calculated, and the arithmetic mean is rounded to the second decimal place to obtain the ratio of the thickness of the artificial leather.

[0101] In the composite artificial leather of the present invention, the depth of the recess is preferably 1.0 mm or more and 4.0 mm or less. By setting the depth of the recess to 1.0 mm or more, preferably 2.0 mm or more, the design features created by embossing can be clearly defined. By setting the depth of the recess to 4.0 mm or less, preferably 3.0 mm or less, compression of the artificial leather can be suppressed, and the soft texture of the raised areas can be maintained.

[0102] In the present invention, the depth of the recess in the composite artificial leather shall be measured and calculated by the following method. (1) Take a scanning electron microscope (SEM) image of the cross-section of the composite artificial leather. (2) Based on the above, it is determined whether the cross-sectional shape of the composite artificial leather is one of those shown in Figures 2 to 4, or a combination of cross-sectional shapes as shown in Figure 5. (2-1) When the cross-sectional shape is as shown in Figures 2 and 4, the thickness of the composite artificial leather in the recess is the same as (T B ) is. Also, the thickness of the composite artificial leather in the convex portion is the same as the above (T A Therefore, the thickness of the composite artificial leather in the recessed and convex parts was measured at 10 locations in the SEM image, and the depth of the recessed part of the composite artificial leather at each location (T A -T BThe arithmetic mean is calculated and rounded to two decimal places to obtain the depth of the recess in the composite artificial leather. (2-2) When the cross-sectional shape is as shown in Figure 3, the thickness of the composite artificial leather in the recess is the same as (T B ) is. Also, the thickness of the composite artificial leather in the convex portion is the same as the above (T A Therefore, the thickness of the composite artificial leather in the recessed and convex parts was measured at 10 locations in the SEM image, and the depth of the recessed part of the composite artificial leather at each location (T A -T B The arithmetic mean is calculated and rounded to two decimal places to obtain the depth of the recess in the composite artificial leather. (2-3) When the cross-sectional shape is as shown in Figure 5, the thickness of the composite artificial leather in the recess is the thickness of the composite artificial leather in the recess (55) mentioned above. Also, the thickness of the composite artificial leather is the (T) mentioned above. T Therefore, the thickness of the composite artificial leather in the recessed and convex parts was measured at 10 locations in the SEM image, the depth of the recessed part of the composite artificial leather at each location was calculated, and the arithmetic mean was rounded to two decimal places to obtain the depth of the recessed part of the composite artificial leather.

[0103] [Method for manufacturing composite artificial leather] The method for manufacturing artificial leather according to the present invention will be described in detail for each step.

[0104] <Process for forming a fiber entanglement compound that includes a nonwoven fabric made of ultrafine fibers as a component> First, a fiber entanglement composite is formed and prepared, which includes a nonwoven fabric as a component, consisting of ultrafine fibers with an average single fiber diameter of 1.0 μm or more and 10.0 μm or less.

[0105] To form a nonwoven fabric consisting of ultrafine fibers with an average single fiber diameter of 1.0 μm or more and 10.0 μm or less, methods include forming a nonwoven fabric from ultrafine fibers with the above-mentioned average single fiber diameter, and forming a nonwoven fabric from ultrafine fiber-generating fibers and then generating ultrafine fibers later. Among these, forming a nonwoven fabric using ultrafine fiber-generating fibers is preferable from the viewpoint of being highly operable and being able to obtain uniform ultrafine fibers.

[0106] As a type of ultrafine fiber generating fiber, a sea-island type composite fiber is used, in which thermoplastic resins with different solvent solubility are used as a sea component (easily soluble polymer) and an island component (poorly soluble polymer), and the sea component is dissolved and removed using a solvent or the like to form ultrafine fibers from the island component. By using a sea-island type composite fiber, it is possible to create appropriate voids between the island components, i.e., between the ultrafine fibers inside the fiber bundle, when removing the sea component, which is preferable from the viewpoint of the flexible texture and surface quality of artificial leather.

[0107] As a method for spinning ultrafine fibers having a sea-island type composite structure, a method using a polymer interconnected array that is spun by using a spinneret for sea-island type composite fibers and interconnecting the sea component and island component is preferred from the viewpoint of obtaining ultrafine fibers with uniform single fiber fineness.

[0108] As the marine component of sea-island type composite fibers, polyethylene, polypropylene, polystyrene, copolymerized polyester obtained by copolymerizing sodium sulfoisophthalic acid or polyethylene glycol, and polylactic acid can be used, but from the viewpoint of spinnability and ease of elution, polystyrene and copolymerized polyester are preferably used.

[0109] In the method for manufacturing artificial leather of the present invention, it is preferable to use sea-island type composite fibers in which the strength of the island components is 2.0 cN / dtex or more. By having island component strengths of 2.0 cN / dtex or more, more preferably 2.3 cN / dtex or more, and even more preferably 2.8 cN / dtex or more, the abrasion resistance of the artificial leather can be improved and the decrease in friction fastness due to fiber shedding can be suppressed.

[0110] In the present invention, the strength of the island component of the sea-island type composite fiber is calculated by the following method. (1) Bundle together 10 pieces of sea-island type composite fiber, each 20 cm long. (2) After dissolving and removing marine components from the sample in (1), air dry it. (3) The test is performed 10 times (N=10) in accordance with "8.5 Tensile strength and elongation" of "8.5 Standard time test" in JIS L1013:2010 "Test method for chemical fiber filament yarn", under the conditions of grip length 5 cm, tensile speed 5 cm / min, and load 2 N. (4) The arithmetic mean (cN / dtex) of the test results obtained in (3) is rounded to two decimal places and the resulting value is taken as the strength of the island component of the sea-island composite fiber.

[0111] Next, the spun ultrafine fiber-generating fibers are opened and then formed into a fiber web using a cross wrapper or the like, and then entangled to obtain a fiber entanglement body containing nonwoven fabric as a component. As a method for entangling the fiber web to obtain a fiber entanglement body containing nonwoven fabric as a component, needle punching or water jet punching can be used.

[0112] As mentioned above, both short-fiber and long-fiber nonwoven fabrics can be used as the form of the nonwoven fabric. However, with short-fiber nonwoven fabrics, there are more fibers oriented in the thickness direction of the artificial leather compared to long-fiber nonwoven fabrics, resulting in a highly dense and flexible texture on the surface of the artificial leather when it is napped.

[0113] When a short-fiber nonwoven fabric is to be produced, the sea-island type composite fibers obtained in the process of forming the sea-island type composite fibers are preferably crimped and cut to a predetermined length to obtain raw fibers, which are then opened, laminated, and interwoven to obtain a short-fiber nonwoven fabric. Known methods can be used for the crimping and cutting processes.

[0114] Furthermore, if the fiber entanglement includes a woven or knitted fabric (a), the nonwoven fabric obtained by the above method and the woven or knitted fabric (a) are laminated and then entangled and integrated. To entangle and integrate the nonwoven fabric and the woven or knitted fabric (a), the woven or knitted fabric (a) can be laminated on one or both sides of the nonwoven fabric, or the woven or knitted fabric (a) can be sandwiched between multiple nonwoven fabric webs, and then the fibers of the nonwoven fabric and the woven or knitted fabric (a) can be entangled by needle punching, water jet punching, or the like.

[0115] The apparent density of a nonwoven fabric made of sea-island type composite fibers after needle punching or water jet punching is 0.15 g / cm³. 3 More than 0.45g / cm 3 Preferably, the apparent density is 0.15 g / cm³. 3 By doing so, the artificial leather can be made to have sufficient morphological and dimensional stability. On the other hand, the apparent density is preferably 0.45 g / cm³. 3 By doing the following, it is possible to maintain sufficient space for imparting polymeric elasticity and preserve the voids in the cross-section, thereby achieving a flexible texture.

[0116] In order to improve the density of the fibers, it is also preferable to subject the aforementioned fiber entanglement to a heat shrinkage treatment using hot water or steam.

[0117] Next, the aforementioned fiber entanglement can be impregnated with an aqueous solution of a water-soluble resin and dried to impregnate it with the water-soluble resin. By impregnating the fiber entanglement with the water-soluble resin, the fibers are fixed and dimensional stability is improved.

[0118] Next, the obtained fibrous substrate is treated with a solvent or solution to form ultrafine fibers with an average single fiber diameter of 1.0 μm or more and 10.0 μm or less.

[0119] The formation of ultrafine fibers can be achieved by immersing the aforementioned fiber entanglement in a solvent or solution to dissolve and remove the marine component of the sea-island type composite fiber.

[0120] For dissolving and removing marine components, organic solvents such as toluene or trichloroethylene can be used if the marine components are polyethylene, polypropylene, or polystyrene. If the marine components are copolymerized polyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide can be used. Furthermore, if the marine components are water-soluble thermoplastic polyvinyl alcohol-based resins, hot water can be used.

[0121] <Process for imparting polymeric elasticity> In this process, a polymer elastomer is impregnated into a fiber entanglement mainly composed of ultrafine fibers or sea-island composite fibers by impregnating it with a polymer elastomer solution and then solidifying the polymer elastomer. Methods for solidifying the polymer elastomer include wet solidification or dry solidification after impregnating the fiber entanglement with the polymer elastomer solution; these methods can be appropriately selected depending on the type of polymer elastomer used.

[0122] When polyurethane is selected as the polymeric elastic material, N,N'-dimethylformamide and dimethyl sulfoxide are preferred solvents. Alternatively, a water-dispersible polyurethane solution, in which polyurethane is dispersed as an emulsion in water, may be used.

[0123] Furthermore, the addition of the polymeric elastic material to the fiber entanglement may be done before generating ultrafine fibers from the sea-island type composite fiber, or it may be done after generating ultrafine fibers from the sea-island type composite fiber.

[0124] <The process of cutting artificial leather in half and grinding it> After completing the above-mentioned process, the artificial leather to which the polymeric elastic material has been applied can, from the viewpoint of manufacturing efficiency, be cut in half in the thickness direction to form two pieces of artificial leather, which is also a preferred embodiment.

[0125] Furthermore, the surface of the artificial leather to which the polymeric elastic material has been applied, or the surface of the half-cut artificial leather, is subjected to a napping treatment. The napping treatment can be performed by grinding using sandpaper or a roll sander. The napping treatment can be applied to at least one surface of the artificial leather.

[0126] When applying a napped finish, a lubricant such as a silicone emulsion can be applied to the surface of the artificial leather before the napping process. Additionally, applying an antistatic agent before the napping process reduces the accumulation of grinding dust on the sandpaper. In this way, the artificial leather is formed.

[0127] <Process of dyeing artificial leather> For dyeing, various methods can be used, such as immersion dyeing using a jigger dyeing machine or a jet dyeing machine, thermosol dyeing using a continuous dyeing machine, or printing on the pile surface using roller printing, screen printing, inkjet printing, sublimation printing, and vacuum sublimation printing. Among these, using a jet dyeing machine is preferable in terms of quality and finish because it provides a flexible texture. Furthermore, various resin finishing processes can be applied after dyeing as needed.

[0128] The artificial leather of the present invention, obtained by the manufacturing method exemplified above, possesses a soft, natural leather-like feel, excellent strength, quality, and density, and can be used in a wide range of applications, from furniture, chairs, and vehicle interior materials to clothing. However, due to its excellent strength, it is particularly suitable for use in vehicle interior materials.

[0129] <Process of laminating a foamed resin layer onto artificial leather> Then, a foamed resin layer is laminated onto one surface of the aforementioned artificial leather.

[0130] It is preferable to integrate the artificial leather and the foamed resin layer after lamination. The method of integration is not particularly limited, and known methods such as using an adhesive or frame lamination can be used. The frame lamination method is particularly preferred from the viewpoint of easy lamination and integration, and from the viewpoint of the strength of the composite artificial leather.

[0131] In this process, the thickness t of the artificial leather before lamination A (mm) Thickness t of the foamed resin layer B (mm) Ratio (t A / t B ) is preferably in the range of 0.15 to 0.40. A / t B However, by making it 0.15 or greater, preferably greater than 0.20, a composite artificial leather with high strength and shapeability can be obtained. A / t BHowever, by setting the value to 0.40 or less, preferably less than 0.30, the pressure during embossing can be dispersed across the foamed resin layer, maintaining the soft texture of the artificial leather in the raised areas.

[0132] Furthermore, when laminating the foamed resin layer onto one surface of the artificial leather, or after laminating the foamed resin layer onto one surface of the artificial leather, a woven or knitted fabric (b) with a constant load elongation rate of 130% to 300% can also be laminated onto the side of the foamed resin layer opposite to the side facing the artificial leather. In other words, the layers can also be laminated in the order of artificial leather / foamed resin layer / woven or knitted fabric (b).

[0133] When laminating woven or knitted fabrics (b) in this manner, the thickness t of the woven or knitted fabric (b) before lamination is C (mm) of the foamed resin layer t B (mm) Ratio (t C / t B ) is preferably in the range of 0.10 or more and 0.15 or less. C / t B By setting this to 0.10 or higher, preferably 0.11 or higher, wrinkle formation during embossing can be suppressed, and clear uneven surfaces can be obtained. C / t B By setting the ratio to 0.15 or less, preferably 0.14 or less, the soft texture of the composite artificial leather can be maintained.

[0134] When laminating the aforementioned woven or knitted fabric (b), or after lamination, the method for integrating the artificial leather, the foamed resin layer, and the woven or knitted fabric (b) is not particularly limited, as is the case when integrating the artificial leather and the foamed resin layer. For example, known integration methods such as using an adhesive or using frame lamination can be used. The frame lamination method is particularly preferred from the viewpoint of easy lamination and integration, and from the viewpoint of the strength of the composite artificial leather. As for the order of integration, as described above, the artificial leather, the foamed resin layer, and the woven or knitted fabric (b) may be integrated simultaneously, or the artificial leather may be integrated with the woven or knitted fabric (b) after integrating the artificial leather with the foamed resin layer, or the foamed resin layer and the woven or knitted fabric (b) may be integrated first, and then the artificial leather may be integrated with it.

[0135] Next, the temperature of the upper and lower surfaces of the embossing die is set to 60°C to 240°C, the laminate consisting of the artificial leather and the foamed resin layer is placed on the embossing die, and the embossing die is closed and held for 5 to 80 seconds to produce the composite artificial leather. Alternatively, the surface temperature of the embossing roll is set to 60°C to 240°C, the laminate consisting of the artificial leather and the foamed resin layer is passed between the embossing rolls, and the laminate is brought into contact with the embossing rolls for 0.05 to 30 seconds to obtain the composite artificial leather. By these methods, the composite artificial leather having convex and concave portions can be obtained.

[0136] Designs formed on composite artificial leather by convex and concave areas include logo-like patterns, intermittently continuing patterns, and combinations thereof. Examples of intermittently continuing patterns include grain patterns, woven textures, and geometric patterns formed by combining random dots, lines, circles, figures, etc., either individually or in combination of two or more types. When forming logo-like patterns, a flat embossing die is commonly used, and when forming intermittently continuing patterns, an embossing roll is commonly used, but the design is not limited to these.

[0137] Furthermore, in the composite artificial leather (21) as shown in FIG. 2 above, for example, when a concave portion is formed by melting or compressing at least a part of the raised hairs of the artificial leather by a convex shape provided on the surface of either the upper die or the lower die of the embossing die or on the surface of one side of the embossing roll, the concave portion becomes a smooth surface. In this case, a gloss can be imparted to the concave portion compared to the surrounding convex portions. Also, by adjusting the surface temperature, holding time, and pressure described later, the gloss of this concave portion can be enhanced or weakened. And by this strength or weakness, the difference in appearance between the concave portion and the convex portion can be increased, and the design formed by the concave portion and the convex portion can be made clearer.

[0138] The composite artificial leather of the present invention has a color difference ΔE between the concave portion and the convex portion * ab and a color hue difference ΔH * which preferably satisfy the following equations respectively 7.5≦ΔE * ab ≦9.0 0.1≦ΔH * ≦1.0.

[0139] ​​​​​​​​​​​​​​​By setting this value preferably to 1.0 or less, and more preferably to 0.9 or less, a composite artificial leather can be obtained that does not discolor due to embossing and in which the pattern of the recessed areas blends in with the raised areas.

[0141] In the present invention, the color difference ΔE of the artificial leather * ab and hue difference ΔH * It shall be measured and calculated by the following method. (1) Using a spectrophotometer (for example, Konica Minolta Japan's "CM-2600d"), five locations are randomly selected on the raised parts of the composite artificial leather, and the lightness L of the raised parts is measured. * , hue a * , b * The measurement is taken. However, if the size of the protrusions on the composite artificial leather is small compared to the measurement diameter of the spectrophotometer, specifically if the diameter is less than 30 mm, the measurement can be taken in the same manner as above by cutting out multiple protrusions and arranging them without gaps. (2) Similarly, five recesses in the composite artificial leather are randomly selected, and the brightness L of the recesses is determined. * , hue a * , b * The following measurement is taken. However, if the size of the recess in the composite artificial leather is small compared to the measurement diameter of the spectrophotometer, specifically if the diameter is less than 30 mm, the measurement can be taken in the same manner as above by cutting out multiple recesses and arranging them without gaps. (3) The obtained brightness L * , hue a * , b * Therefore, the color difference ΔE between the convex and concave parts can be calculated using the following formula. * ab and hue difference ΔH * Calculate the arithmetic mean of the five values ​​and round it to two decimal places. ΔL * =(Brightness L of the recessed area) * )-(Brightness L of the convex part * ) Δa * =(Hue a of the recessed area) * )-(hue a of the convex part * ) Δb*=(hue b of the concave area) * )-(hue b of the convex part) * ) ΔE * ab ={(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2} 1 / 2 ΔC * ={( Δa * ) 2 +(Δb * ) 2} 1 / 2 ΔH * ={( Δa * ) 2 +(Δb * ) 2 -(ΔC * ) 2} 1 / 2 .

[0142] When using an embossing die, it is preferable to set the temperature of the upper die surface and the lower die surface to 60°C or higher and 240°C or lower. Setting the surface temperature to 60°C or higher, preferably 80°C or higher, can improve clarity and durability in the raised and recessed areas. Setting the surface temperature to 240°C or lower, preferably 200°C or lower, allows for embossing while maintaining the nap and quality of the artificial leather in the raised areas, resulting in a composite artificial leather in which the physical properties of the artificial leather are not impaired by high heat.

[0143] After placing the laminate on the heated embossing die, it is preferable that the embossing die is closed and held for 5 seconds to 150 seconds. By holding it for 5 seconds or more, preferably 20 seconds or more, a composite artificial leather can be obtained that combines high embossing design and design durability. By holding it for 150 seconds or less, preferably 140 seconds or less, a composite artificial leather can be obtained that does not impair the nap and quality of the artificial leather in the raised areas, and does not impair the physical properties of the artificial leather, such as friction fastness which decreases with heat.

[0144] When performing this retention, it is preferable that the pressure by the embossing mold is 0.1 kPa or more and 10 kPa or less. By setting it to 0.1 kPa or more, a clear and durable uneven pattern can be applied. On the other hand, by setting it to 10 kPa or less, processing can be performed without impairing the texture of the artificial leather at the convex portions in the composite artificial leather.

[0145] When using an embossing roll, it is preferable that the surface temperature of the embossing roll is 60°C or more and 240°C or less. By setting the surface temperature to 60°C or more, preferably 80°C or more, clear uneven portions can be obtained. By setting the surface temperature to 240°C or less, preferably 200°C or less, embossing can be performed while maintaining the hairiness, quality, and physical properties of the artificial leather at the convex portions.

[0146] Pass the above-mentioned laminate through between heated embossing rolls, and the contact time with the above-mentioned embossing roll is preferably 0.05 seconds or more and 30 seconds or less. By setting the pressing time to 0.05 seconds or more, preferably 0.1 seconds or more, a composite artificial leather having both high shaping designability and durability of the embossed portion can be obtained. By setting the pressing time to 30 seconds or less, preferably 20 seconds or less, excellent friction fastness can be obtained without impairing the hairiness and quality of the artificial leather at the convex portions.

[0147] The processing speed on the heated embossing roll is preferably 0.5 m / min or more and 10 m / min or less. By setting the processing speed on the embossing roll to 0.5 m / min or more, preferably 1.0 m / min or more, the soft texture peculiar to artificial leather can be maintained without impairing the hairiness and quality of the artificial leather at the convex portions. By setting the processing speed on the embossing roll to 10 m / min or less, preferably 8 m / min or less, a composite artificial leather having both high shaping designability and durability of the embossed portion can be obtained.

[0148] When making this contact, it is preferable that the pressure by the embossing roll be 1.0 MPa or more and 10 MPa or less. By setting it to 1.0 MPa or more, a clear and durable uneven pattern can be applied. On the other hand, by setting it to 10 MPa or less, processing can be performed without impairing the texture of the artificial leather at the convex portions in the composite artificial leather.

[0149] The composite artificial leather of the present invention obtained by the manufacturing method exemplified above maintains a soft texture even at the convex portions of the embossed portion, and has excellent shaping designability, touch, quality, and denseness, and can be widely used for furniture, chairs, vehicle interior materials, etc. In particular, due to its excellent texture and shaping designability, it is preferably used for vehicle interior materials.

Example

[0150] Next, the composite artificial leather of the present invention will be described more specifically using examples, but the present invention is not limited only to these examples. Next, the evaluation method and its measurement conditions used in the examples will be described. However, in the measurement of each physical property, those without special description were measured based on the above method.

[0151] (1) Average single fiber diameter (μm) of ultra-fine fibers: In the measurement of the average single fiber diameter of ultra-fine fibers, ultra-fine fibers were observed using a "VHX-D500 / D510 type" scanning electron microscope manufactured by Keyence Corporation, and the average single fiber diameter was calculated.

[0152] (2) Cross-sectional porosity (%) of artificial leather at convex portions: In the measurement of the cross-sectional porosity of artificial leather at convex portions, only the artificial leather portion of the composite artificial leather cross-section was observed using a "VHX-D500 / D510 type" scanning electron microscope manufactured by Keyence Corporation, and the ratio of the total area of cross-sectional voids was calculated using image analysis software.

[0153] (3) Compression elastic modulus, compression ratio (%) of composite artificial leather: In measuring the compression modulus and compressibility of composite artificial leather, the SE-15 compression elasticity tester manufactured by Intec Co., Ltd. was used to measure the thickness at 0.5 kPa and 30 kPa, as described above, and the compression modulus and compressibility were calculated.

[0154] (4) Constant load elongation rate (%) of woven or knitted fabric (b): In measuring the constant-load elongation rate of woven / knitted fabrics (b), a constant-load elongation test device (Martens type) manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd., "FLM-6M," was used to apply a load of 1 kg and measure the distance between gauge marks, thereby calculating the constant-load elongation rate.

[0155] (5) Thickness of artificial leather and composite artificial leather in the recess (μm): In measuring the thickness of artificial leather and composite artificial leather in recessed areas, a Keyence VHX-D500 / D510 scanning electron microscope was used to observe the cross-section of the recessed areas of the composite artificial leather, and the thickness of the artificial leather and composite artificial leather in the recessed areas was measured.

[0156] (6) Depth of the recess in the composite artificial leather (mm): In measuring the depth of the recesses in the composite artificial leather, a Keyence VHX-D500 / D510 scanning electron microscope was used to measure the cross-section of the uneven surface of the composite artificial leather, thereby determining the depth of the recesses.

[0157] (7) Pile length of artificial leather (μm): For measuring the pile length of artificial leather, a scanning electron microscope, the "VHX-D500 / D510" model manufactured by Keyence Corporation, was used.

[0158] (8) Texture and uniformity of composite artificial leather: The texture and uniformity of the composite artificial leather were evaluated by measuring the depth of the recesses and then visually assessing the following criteria using 10 healthy adult men and 10 healthy adult women (20 people in total). The most frequent rating was used to determine the texture and design of the composite artificial leather. In the event of a tie in ratings, the higher rating was used to determine the appearance quality of the composite artificial leather. A: The textured design is very clear (the boundary between the recessed and raised parts is clearly visible) and uniform (there is no distortion or variation at the boundary between the recessed and raised parts). B: The uneven design is clear (the boundary between the recessed and raised parts is visible) and uniform. • C: The uneven design is not clear (the boundary between the recessed and raised parts is difficult to see, but the presence of unevenness is discernible), and it is not uniform (there is distortion or variation at the boundary between the recessed and raised parts). • D: The textured design is very unclear (the boundary between the recessed and raised parts is not visible, and it is not apparent that there are any irregularities), and it is uneven.

[0159] (9) Visibility of the texture of composite artificial leather, glossiness of recessed areas: For the glossiness and visibility of the texture of the recessed areas of the composite artificial leather, a Konica Minolta Japan "CM-2600d" spectrophotometer was used, and the color difference ΔE was measured according to the method described above. * ab and hue difference ΔH * The following parameters were measured and calculated, and an evaluation was conducted on 20 participants (10 healthy adult men and 10 healthy adult women) based on the following criteria. A: 7.5 ≤ ΔE * ab ≤9.0 and 0.1 ≤ΔH * It satisfies the requirement of ≤1.0. Visibility is very good, no pile is observed in recessed areas, and it has sufficient gloss. · B: 7.5 ≤ ΔE * ab ≤9.0 and 0.1 ≤ΔH * It satisfies the ≤1.0 requirement. Visibility is good, and although some fuzzy texture is visible in the recessed areas, a glossy finish is present. ·C:0.1≦ΔH * The condition ≤1.0 is met. Visibility is insufficient due to whitening or darkening in the recesses, and the gloss is somewhat low due to the presence of raised fibers in the recesses. · D: 7.5 ≤ ΔE * ab The condition ≤ 9.0 is not satisfied, and 0.1 ≤ ΔH * It does not even meet the ≤1.0 standard. Visibility is low due to discoloration in recessed areas, and gloss is low due to a lot of lint remaining in recessed areas.

[0160] (10) Appearance quality of the composite artificial leather: Using 10 healthy adult males and 10 healthy adult females, a total of 20 people as evaluators, the following evaluations were discriminated visually and tactilely, and the most common evaluation was taken as the appearance quality of the composite artificial leather. When the number of evaluations was the same, the higher evaluation was taken as the appearance quality of the composite artificial leather. ·A: There is no variation in the piloerection on the convex part, it is smooth, and it has a very uniform appearance quality. ·B: There is no variation in the piloerection on the convex part, and it has a uniform appearance quality. ·C: The piloerection on the convex part is not smooth, and it has a somewhat variable appearance quality. ·D: The piloerection on the convex part is rough, and it has a large variation in appearance quality.

[0161] (11) Texture of the composite artificial leather: Using 10 healthy adult males and 10 healthy adult females, a total of 20 people as evaluators, the following evaluations were discriminated tactilely, and the most common evaluation was taken as the texture of the composite artificial leather. When the number of evaluations was the same, the higher evaluation was taken as the texture of the composite artificial leather. ·A: A very soft texture peculiar to artificial leather is felt. ·B: A soft texture peculiar to artificial leather is felt. ·C: The soft texture peculiar to artificial leather is not sufficient, and it has a somewhat hard texture. ·D: There is no soft texture peculiar to artificial leather, and it has a hard texture.

[0162] (12) Durability of the concave-convex design: For the durability of the concave-convex design of the composite artificial leather, the degree of pattern recovery in the composite artificial leather after the abrasion resistance evaluation (200 g × 14,000 times) was discriminated visually and tactilely using 10 healthy adult males and 10 healthy adult females, a total of 20 people as evaluators, and the most common evaluation was taken as the durability of the concave-convex design of the composite artificial leather. When the number of evaluations was the same, the higher evaluation was taken as the durability of the concave-convex design of the composite artificial leather. ·A: There is no pattern recovery or abrasion, and it has a very uniform appearance quality. • B: No pattern deformation or wear, and uniform appearance quality. • C: The pattern has reverted or worn, and the appearance quality is not uniform. • D: The appearance quality is inconsistent, with some wear and tear on the handle.

[0163] [Example 1] <Process for forming sea-island type composite fibers> A sea-island type composite fiber having a sea-island type composite structure consisting of island components and sea components was melt-spun under the following conditions. • Island component: Polyethylene terephthalate A with an intrinsic viscosity (IV value) of 0.73 • Marine components: Polystyrene with MFR (Melt Flow Rate, measured according to the test method specified in ISO 1133:1997) of 65 g / 10 min • Clamp: Clamp for sea-island type composite fiber with 16 islands / hole Spinning temperature: 285℃ ·Island component / sea component mass ratio: 80 / 20 • Discharge rate: 1.2g / (min / hole) Spinning speed: 1100 m / min Next, the sea-island type composite fiber was stretched 2.7 times in a steam box heated to 150°C.

[0164] <Process for forming fiber entanglements> First, the sea-island composite fibers obtained above were crimped using a press-type crimping machine, then cut to a length of 51 mm to form a sea-island composite fiber web with a single fiber fineness of 4.2 dtex. The average single fiber diameter of the ultrafine fibers obtained from this sea-island composite fiber was 4.4 μm.

[0165] Then, using the sea-island type composite fiber web obtained as described above, a laminated web (nonwoven fabric) was formed through carding and cross-wrapping processes. Finally, a plain weave fabric (weight 75g / m²) was created using twisted yarn made from polyethylene terephthalate multifilaments with an intrinsic viscosity (IV value) of 0.65 (average single fiber diameter: 11.0 μm, total fineness: 84 dtex, 72 filaments) twisted at 2500 T / m, with a weave density of 95 threads / 2.54 cm in the warp and 76 threads / 2.54 cm in the weft, using this yarn for both the warp and weft. 2 (Woven fabric (a)) was laminated above and below the laminated web (nonwoven fabric). Then, 2500 threads / cm 2 The needle punching process is performed with this number of punches, resulting in a basis weight of 700g / m². 2 Then, a fiber entanglement composite with a thickness of 3.0 mm was obtained.

[0166] <Process for forming ultrafine fibers> The nonwoven fabric obtained as described above was subjected to shrinkage treatment with hot water at 96°C. Subsequently, an aqueous solution of polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) with a concentration of 5% by mass and a degree of saponification of 88% was impregnated into the fiber entanglement that had been shrunk with hot water. Furthermore, this was squeezed with a roll and dried for 10 minutes with hot air at a temperature of 125°C while migrating the PVA, thereby obtaining a PVA-coated sheet in which the mass of PVA relative to the mass of the sheet was 45% by mass. The PVA-coated sheet thus obtained was immersed in trichloroethylene, and the process of mangle extraction and compression was performed 10 times. This dissolved and removed marine components (demarinization) and compressed the PVA-coated sheet, obtaining a PVA-coated sheet in which ultrafine fiber bundles were entangled.

[0167] <Process for imparting polymeric elasticity> The PVA-coated sheet obtained as described above was immersed in a polyurethane dimethylformamide (hereinafter sometimes abbreviated as DMF) solution, which was prepared so that the concentration of the solid content, mainly polyurethane, was 11.3% by mass. Then, the PVA-coated sheet immersed in the polyurethane DMF solution was squeezed with a roll. Next, this sheet was immersed in a 30% by mass DMF aqueous solution to solidify the polyurethane. After that, the PVA and DMF were removed with hot water, and a silicone oil emulsion solution adjusted to a concentration of 1% by mass was impregnated into the sheet. A silicone lubricant was applied in an amount of 0.5% by mass relative to the total mass of the fiber entanglement and the polyurethane, and the sheet was dried with hot air at a temperature of 120°C for 10 minutes. As a result, a polyurethane-coated sheet with a thickness of 2.1 mm and a polyurethane mass of 28% by mass relative to the mass of the fiber entanglement was obtained.

[0168] <Half-cutting and napping process> The polyurethane-coated sheets obtained as described above were cut in half so that each half had half its original thickness. Next, the surface layer of the cut surfaces was sanded to a thickness of 0.15 mm using 240-grit endless sandpaper to create a napped surface, resulting in a 0.9 mm thick napped sheet.

[0169] <Dyeing process> The pile sheets obtained as described above were stained using a liquid jet staining machine. Afterward, they were dried at 100°C for 7 minutes, resulting in an average single fiber diameter of 4.4 μm and a basis weight of 375 g / m². 2 We obtained artificial leather with a thickness of 1.1 mm and a pile length of 330 μm.

[0170] <Process of laminating foamed resin layers> The artificial leather obtained as described above is then covered with a foamed resin layer made of polyurethane resin (apparent density: 20 kg / m³). 3The foamed resin layer was laminated, and on the side where the artificial leather layer was not laminated, a circular knitted fabric (with constant load elongation of 225% (vertical)) (woven fabric (b)-(1)) was further laminated as a woven fabric (b), using filaments made of polyethylene terephthalate with an intrinsic viscosity (IV value) of 0.65 (average single fiber diameter: 88 μm), and then frame-laminated and bonded to obtain a composite artificial leather. Note that the thickness of the artificial leather before lamination of the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.31, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.11.

[0171] <The process of applying embossing> The composite artificial leather obtained as described above was placed on an embossing mold with a mold temperature of 180°C, and the embossing mold was closed and held for 40 seconds to obtain embossed composite artificial leather. The resulting composite artificial leather had a cross-sectional void ratio of 25.3% in the raised areas and a compressive modulus of elasticity (R) in the raised areas. A ) is 97%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 2.4. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 61.1%, and the depth of the recess was 2.9 mm. The obtained composite artificial leather had excellent gloss, textured design and durability, and a very soft texture in the raised areas. The results are shown in Table 1.

[0172] [Example 2] In the <process of forming a fiber entanglement> of Example 1, the woven or knitted fabric (a) was not laminated above or below the laminated web, and the basis weight was 525 g / m². 2Then, a composite artificial leather was obtained in the same manner as in Example 1, except that a fiber entanglement composite with a thickness of 2.3 mm was obtained. The basis weight of the artificial leather at this time was 230 g / m². 2 The thickness is 0.7 mm, the pile length is 325 μm, and the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.20, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.11. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 33.6%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 95%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 2.2. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 58.6%, and the depth of the recess was 2.7 mm. The obtained composite artificial leather had excellent gloss, textured design and high durability, and a very soft texture in the raised areas. The results are shown in Table 1.

[0173] [Example 3] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the thickness of the foamed resin layer was increased in the <step of laminating the foamed resin layer> and the embossing process was changed from holding the embossing mold closed for 40 seconds to holding it for 60 seconds. At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.29, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t BThe value was 0.11. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 23.2%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 64%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 1.1. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 45.8%, and the depth of the recess was 4.2 mm. The obtained composite artificial leather had excellent gloss, textured design and durability, and a soft texture in the raised areas. The results are shown in Table 1.

[0174] [Example 4] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the thickness of the foamed resin layer was reduced in the <process of laminating the foamed resin layer> and the mold temperature was changed from 180°C to 140°C in the <process of applying embossing>. At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.39, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The ratio was 0.14. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 36.3%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 91%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R BThe ratio was 3.0. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 67.8%, and the depth of the recess was 2.0 mm. The obtained composite artificial leather had good visibility, a clear embossed design, high durability, and a very soft texture in the raised areas. The results are shown in Table 1.

[0175] [Example 5] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the thickness of the foamed resin layer was increased in the <step of laminating the foamed resin layer> and the holding time of the embossing die was changed from 40 seconds to 80 seconds in the <step of applying embossing>. At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.12, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The ratio was 0.04. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 35.2%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 75%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 1.6. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 20.5%, and the depth of the recess was 15.6 mm. The obtained composite artificial leather had good visibility, a clear embossed design, and durability, and the raised parts had a very soft texture. The results are shown in Table 1.

[0176] [Example 6] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the thickness of the foamed resin layer was reduced in the <step of laminating the foamed resin layer>. The thickness of the artificial leather before laminating the foamed resin layer was (t A) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.44, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.16. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 20.9%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 85%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 2.3. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 77.2%, and the depth of the recess was 1.5 mm. The obtained composite artificial leather had excellent gloss, durability against unevenness, and a soft texture in the raised areas. The results are shown in Table 1.

[0177] [Example 7] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the foamed resin layer was made thinner in the <process of laminating the foamed resin layer>, and in the <process of applying embossing>, the mold temperature was changed from 180°C to 100°C, and the embossing mold was closed and held for 40 seconds to 20 seconds. The thickness of the artificial leather before laminating the foamed resin layer was (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.39, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The ratio was 0.14. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 45.2%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 96%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R ACompression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 1.9. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 73.1%, and the depth of the recess was 0.8 mm. The obtained composite artificial leather had good visibility of the unevenness and a very soft texture in the raised areas. The results are shown in Table 2.

[0178] [Example 8] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the foamed resin layer was made thicker in the <process of laminating the foamed resin layer>, and in the <process of applying embossing>, the mold temperature was changed from 180°C to 200°C, and the embossing mold was closed and held for 40 seconds to 100 seconds. At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.29, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.11. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 20.2%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 62%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 1.6. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 48.2%, and the depth of the recess was 20.5 mm. The obtained composite artificial leather had good visibility, excellent textured design and durability. The results are shown in Table 2.

[0179] [Example 9] In the <Laminating foamed resin layer process> of Example 1, woven / knitted fabric (b)-(1) was used, but in this case, a composite artificial leather was obtained in the same manner as in Example 1, except that a half-tricot knitted fabric (constant load elongation rate of 125% (warp)) (woven / knitted fabric (b)-(2)) was used, which was made of nylon filaments (average single fiber diameter: 4 μm) with a sulfuric acid relative viscosity (ηr) of 2.68. At this time, the thickness of the artificial leather before laminating the foamed resin layer was (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.31, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.13. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 22.7%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 82%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 2.1. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 55.8%, and the depth of the recess was 2.4 mm. The obtained composite artificial leather had good visibility, a clear embossed design, excellent durability, and a soft texture in the raised areas. The results are shown in Table 2.

[0180] [Example 10] In the <step of laminating the foamed resin layer> of Example 1, woven fabric (b)-(1) was used, but in this case, a composite artificial leather was obtained in the same manner as in Example 1, except that a woven fabric (constant load elongation rate of 315% (warp)) (woven fabric (b)-(3)) was used, which consisted of a filament made of polyethylene terephthalate with an intrinsic viscosity (IV value) of 0.65 (average single fiber diameter: 88 μm). At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B0.31, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.08. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 37.8%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 90%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 1.5. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 65.3%, and the depth of the recess was 2.9 mm. The obtained composite artificial leather had good visibility, a clear embossed design, and durability, and the raised parts had a soft texture. The results are shown in Table 2.

[0181] [Example 11] In the <step of laminating the foamed resin layer> of Example 1, the foamed resin layer made of polyurethane resin (apparent density: 20 kg / m³) 3 ) was used, but a foamed resin layer made of olefin resin (apparent density: 70 kg / m³) 3 A composite artificial leather was obtained in the same manner as in Example 1, except that ) was used. The thickness of the artificial leather before laminating the foamed resin layer was (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.37, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.13. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 20.2%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 65%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %)A / R B The ratio was 2.2. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 72.3%, and the depth of the recess was 2.1 mm. The obtained composite artificial leather had good visibility, a clear embossed design, and high durability. The results are shown in Table 2.

[0182] [Table 1]

[0183] [Table 2]

[0184] [Comparative Example 1] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the foamed resin layer was made thinner in the <process of laminating the foamed resin layer>, and in the <process of applying embossing>, the mold temperature was changed from 180°C to 250°C, and the embossing mold was closed and held for 40 seconds to 100 seconds. At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.55, the thickness (t) of the woven or knitted fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.20. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 15.7%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 82%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R BThe ratio was 1.1. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 82.5%, and the depth of the recess was 3.0 mm. The obtained composite artificial leather had excellent high durability against unevenness, but discoloration was observed, the texture in the raised areas was hard, and it was a composite artificial leather that lacked the touch and flexibility characteristic of artificial leather. The results are shown in Table 3.

[0185] [Comparative Example 2] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the foamed resin layer was made thicker in the <process of laminating the foamed resin layer>, and in the <process of applying embossing>, the mold temperature was changed from 180°C to 55°C, and the embossing mold was closed and held for 40 seconds to 3 seconds. At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.09, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The ratio was 0.03. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 62.8%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 75%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 1.6. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recessed areas was 47.1%, and the depth of the recessed areas was 0.5 mm. The obtained composite artificial leather had a soft texture in the raised areas, but some fuzz remained, and it was a composite artificial leather with poor durability of the uneven surface. The results are shown in Table 3.

[0186] [Comparative Example 3] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the foamed resin layer was made thinner in the <process of laminating the foamed resin layer>, and in the <process of applying embossing>, the mold temperature was changed from 180°C to 250°C, and the embossing mold was closed and held for 40 seconds to 160 seconds. At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t B 0.39, the thickness (t) of the woven fabric (b) before laminating the foamed resin layer. C ) and the thickness of the foamed resin layer (t B ) ratio t C / t B The value was 0.14. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 10.8%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 52%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 1.2. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 78.5%, and the depth of the recess was 4.2 mm. The obtained composite artificial leather had a clear textured design, but discoloration was observed, the texture in the raised areas was hard, and it was a composite artificial leather that lacked the touch and flexibility characteristic of artificial leather. The results are shown in Table 3.

[0187] [Comparative Example 4] In Example 1, a composite artificial leather was obtained in the same manner as in Example 1, except that the woven or knitted fabric (b)-(1) was not used in the <process of laminating the foamed resin layer>, and in the <process of applying embossing>, the mold temperature was changed from 180°C to 250°C, and the embossing mold was closed and held for 40 seconds to 150 seconds. At this time, the thickness of the artificial leather before laminating the foamed resin layer (t A ) and the thickness of the foamed resin layer (t B ) ratio t A / t BThe value was 0.31. Furthermore, the porosity of the cross-sectional area of ​​the artificial leather in the convex portion of the obtained composite artificial leather was 12.5%, and the compressive modulus of the composite artificial leather in the convex portion was (R A ) is 58%, and the compression modulus of elasticity of the composite artificial leather in the convex portion is R A Compression ratio R of composite artificial leather at the convex portion (%) B (Ratio to %) A / R B The ratio was 1.2. In addition, the ratio of the thickness of the artificial leather to the thickness of the composite artificial leather in the recess was 80.5%, and the depth of the recess was 2.8 mm. The obtained composite artificial leather had a clear textured design, but discoloration was observed, the texture in the raised areas was hard, and it was a composite artificial leather that lacked the touch and flexibility characteristic of artificial leather. The results are shown in Table 3.

[0188] [Table 3]

[0189] As shown in Tables 1 and 2, the composite artificial leathers of Examples 1 to 11 achieved a clear textured design by setting the cross-sectional porosity of the artificial leather at the convex portions constituting the composite artificial leather and the compressive modulus of the composite artificial leather within a specific range. Furthermore, they were able to achieve the soft texture characteristic of artificial leather even after embossing.

[0190] On the other hand, as shown in Table 3, if the porosity of the cross-sectional area of ​​the artificial leather and / or the compressive modulus of the composite artificial leather at the raised areas are not met, as in the composite artificial leathers of Comparative Examples 1 to 4, the embossed design, durability, and the unique texture of the artificial leather are impaired, resulting in a composite artificial leather with inferior touch and appearance quality. [Explanation of Symbols]

[0191] 11, 21, 31, 41, 51: Composite artificial leather 12, 22, 32, 42, 55: Artificial leather 13, 23, 33, 43, 53: Foamed resin layer 14, 24, 34, 44, 54: Woven or knitted fabrics (b) 15, 25, 45, 55: recessed 36, 56: Convex part

Claims

1. A composite artificial leather comprising a fiber entanglement body containing a nonwoven fabric made of ultrafine fibers with an average single fiber diameter of 1.0 μm to 10.0 μm as a constituent element, and a polymer elastic body, wherein a foamed resin layer is provided on one surface of the composite artificial leather, the composite artificial leather having convex portions and concave portions, the cross-sectional void ratio of the artificial leather in the convex portions being 20% ​​to 50%, and furthermore, the compressive modulus of elasticity R of the composite artificial leather in the convex portions Ａ A composite artificial leather in which the percentage is between 60% and 100%.

2. Compression modulus R of the composite artificial leather in the aforementioned protrusion Ａ Compression ratio R of composite artificial leather at the convex portion (%) Ｂ (Ratio to %) Ａ / R Ｂ The composite artificial leather according to claim 1, wherein the ratio is 1.2 or more and 2.5 or less.

3. The composite artificial leather according to claim 1 or 2, wherein the fiber entanglement further comprises a woven or knitted fabric (a), and the woven or knitted fabric (a) is entangled and integrated with the nonwoven fabric.

4. The composite artificial leather according to claim 1 or 2, wherein a woven or knitted fabric (b) is further provided on the surface of the composite artificial leather on the side where the foamed resin layer is provided.

5. The composite artificial leather according to claim 1 or 2, wherein the thickness of the artificial leather in the recess is 25% or more and 75% or less of the thickness of the composite artificial leather in the recess.

6. The composite artificial leather according to claim 1 or 2, wherein the depth of the recess is 1.0 mm or more and 20.0 mm or less.

7. A method for manufacturing a composite artificial leather according to claim 1, comprising: laminating a foamed resin layer onto one surface of an artificial leather made of a fiber entanglement body containing a nonwoven fabric made of ultrafine fibers with an average single fiber diameter of 1.0 μm or more and 10.0 μm or less as a component, and a polymer elastic body; setting the temperature of the upper die surface and the lower die surface of an embossing mold to 60°C or more and 240°C or less; placing the laminate made of the artificial leather and the foamed resin layer on the embossing mold; and closing the embossing mold and holding it for 5 seconds or more and 150 seconds or less.

8. A method for manufacturing a composite artificial leather according to claim 1, comprising: laminating a foamed resin layer onto one surface of an artificial leather made of a fiber entanglement body containing a nonwoven fabric made of ultrafine fibers having an average single fiber diameter of 1.0 μm or more and 10.0 μm or less as a component, and a polymer elastic body; setting the surface temperature of an embossing roll to 60°C or more and 240°C or less; passing the laminate made of the artificial leather and the foamed resin layer between the embossing rolls and bringing it into contact with the embossing rolls for 0.05 seconds or more and 30 seconds or less.

9. The thickness t of the artificial leather before laminating Ａ The thickness t of the foamed resin layer Ｂ (mm), the ratio (t Ａ / t Ｂ ) is in the range of 0.15 or more and 0.40 or less. The method for manufacturing a composite artificial leather according to claim 7 or 8

10. A method for manufacturing a composite artificial leather according to claim 7 or 8, wherein, when laminating the aforementioned material, or after laminating the aforementioned material, a woven or knitted fabric (b) having a constant load elongation rate of 130% or more and 300% or less is laminated on the side of the foamed resin layer opposite to the side facing the artificial leather.

11. The thickness t of the woven fabric (b) before lamination. Ｃ (mm) of the foamed resin layer t Ｂ (mm) Ratio (t Ｃ / t Ｂ A method for producing composite artificial leather according to claim 10, wherein the coefficient of

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