Laminates, and interior materials, vehicle parts, and furniture containing the same

Abstract

The present invention addresses the problem of providing a laminate that can maintain the color development and friction fastness of the surface layer even after high-temperature press molding, while also achieving sufficient peel strength. The laminate of the present invention is a laminate formed by laminating a surface layer containing artificial leather and a backing material layer via an adhesive resin, wherein the artificial leather comprises a fiber structure and a polycarbonate-based polyurethane, the fiber structure comprises ultrafine fibers made of a polyester-based resin containing a black pigment and / or a chromatic pigment, the polycarbonate-based polyurethane has a skeleton represented by general formula (1) and a skeleton represented by general formula (2), or has a skeleton represented by general formula (2) and a skeleton represented by general formula (3), and the backing material layer is at least one material selected from the group consisting of woven or knitted fabrics, nonwoven fabrics, and foamed resin sheets. [Formula 1] TIFF0007810316000023.tif116170

Description

[Technical Field]

[0001] The present invention relates to a laminate comprising a surface layer containing artificial leather and a backing layer laminated together via an adhesive resin. [Background technology]

[0002] Artificial leather has superior characteristics compared to natural leather, such as high durability and uniformity of quality, and is used in a variety of fields, including vehicle interior materials, furniture, miscellaneous goods, and clothing. When artificial leather is used as the surface of vehicle interior materials, furniture, miscellaneous goods, etc., a laminate may be formed by laminating a woven or knitted fabric, a nonwoven fabric, a foam resin sheet, or the like as a backing layer to the back surface of the artificial leather, which serves as the surface layer, for the purposes of reinforcing the artificial leather to improve its physical properties, or for the purpose of imparting cushioning properties.

[0003] As such a laminate, for example, Patent Document 1 proposes a flexible decorative laminate that includes a non-porous thermoplastic elastomer layer and a decorative layer containing a fiber structure disposed on the outer surface of the thermoplastic elastomer layer, with the surface layer of the thermoplastic elastomer layer and the surface layer of the fiber structure included in the decorative layer being integrated into a composite layer.The document describes that this laminate can provide a novel sheet material that has an appearance decorated with a decorative layer containing a fiber structure and has elasticity that gives a high sense of resilience when the surface is pressed with a finger.

[0004] Patent Document 2 proposes an embossing composite material in which a flexible polyurethane foam sheet is laminated on one side of a skin material, the flexible polyurethane foam sheet having a specific thickness and a specific range of compressibility within a specific temperature range. It also describes that this composite material can provide an embossed product that has a deep uneven design, is easy to mold, and has excellent cushioning performance and durability. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-61051 [Patent Document 2] International Publication No. 2017 / 056465 Summary of the Invention [Problem to be solved by the invention]

[0006] When these laminates are used for various purposes, they are press-molded at high temperatures (about 200° C. to 250° C.) from a state in which they have a fixed shape such as a sheet, to give them a shape suitable for each purpose.

[0007] However, in the laminate proposed in Patent Document 1, a thermoplastic elastomer is injection molded onto the back surface of a fiber structure at high temperature and high pressure, and while a certain level of peel strength can be achieved by exposing the fiber structure to high temperature conditions, there is a problem in that the color development and friction resistance of the fiber structure are reduced.

[0008] On the other hand, in the laminate proposed in Patent Document 2, the surface material and the flexible polyurethane foam sheet are laminated by frame lamination, and therefore the peel strength depends on the affinity between the backing material and the surface material. As a result, the range of materials that can be selected for the backing material relative to the surface material is narrow, and the peel strength may decrease depending on the material selected.

[0009] In view of the background of the prior art, an object of the present invention is to provide a laminate that can maintain the color development and friction fastness of the surface layer even after high-temperature press molding, and that can also achieve sufficient peel strength, as well as interior materials, vehicle parts, and furniture that include the laminate. [Means for solving the problem]

[0010] As a result of extensive research conducted by the present inventors to achieve the above object, they have found that in a laminate in which a surface layer containing artificial leather and a backing layer are laminated together via an adhesive resin, by making the fiber structure of the artificial leather contain ultrafine fibers made of a polyester-based resin containing a specific pigment, and by using a polycarbonate-based polyurethane having a specific skeleton as the polyurethane contained in the artificial leather, it is possible to obtain a laminate that can maintain the color development and friction fastness of the surface layer even after high-temperature press molding, and that also has sufficient peel strength.

[0011] The present invention has been completed based on these findings, and provides the following inventions.

[0012] [1] A laminate in which a surface layer containing artificial leather and a backing layer are laminated via an adhesive resin, The artificial leather includes a fiber structure and a polycarbonate-based polyurethane, the fiber structure includes ultrafine fibers made of a polyester resin containing a black pigment and / or a chromatic pigment, The polycarbonate-based polyurethane has a skeleton represented by the following general formula (1) and a skeleton represented by the following general formula (2), or It has a skeleton represented by general formula (2) and a skeleton represented by general formula (3), The backing layer is at least one material selected from the group consisting of woven or knitted fabrics, nonwoven fabrics, and foamed resin sheets. Laminate.

[0013] [ka]

[0014] (In the formula, R1 and R2 are aliphatic hydrocarbon groups having 7 to 11 carbon atoms and may be the same or different. Furthermore, n and m are positive integers. When R1 and R2 are different, the copolymer is a block copolymer or a random copolymer.)

[0015] [ka]

[0016] (In the formula, R3 and R4 are aliphatic hydrocarbon groups having 3 to 6 carbon atoms and may be the same or different. Furthermore, x and y are positive integers. When R3 and R4 are different, the copolymer is a block copolymer or a random copolymer.)

[0017] [ka]

[0018] (In the formula, R5 is an aliphatic hydrocarbon group having 3 to 5 carbon atoms, and R6 is an aliphatic hydrocarbon group having 8 to 12 carbon atoms. Furthermore, a and b are positive integers, and R5 and R6 are block copolymers or random copolymers.)

[0019] [2] The laminate according to [1], wherein the adhesive resin is a polyurethane resin.

[0020] [3] The peel strength when the surface layer is peeled from the laminate is 7 N / cm or more and 16 N / cm or less, The failure mode at the time of peeling is cohesive failure of the adhesive resin, a material failure in the backing layer; Interfacial failure or mixed interfacial / cohesive failure between the adhesive resin and the backing layer; The laminate according to [1] or [2] above, wherein the laminate is either of the following:

[0021] [4] The laminate according to any one of [1] to [3], wherein the nap coverage of the surface layer is 70% or more and 100% or less.

[0022] [5] The laminate according to any one of [1] to [4] above, which has a resin layer on at least a part of the surface of the skin layer.

[0023] [6] The laminate according to any one of [1] to [5], wherein the dye content of the surface layer is 3% by mass or less.

[0024] [7] A method for producing the laminate according to any one of [1] to [6], A method for manufacturing a laminate, comprising the steps of applying an adhesive to one surface of sheet A which will become the backing layer, placing sheet B which will become the skin layer on the surface coated with the adhesive, and curing the adhesive to integrate sheets A and B via an adhesive resin which is the cured product of the adhesive.

[0025] [8] The method for producing a laminate according to [7] above, wherein the adhesive is a two-component polyurethane adhesive comprising an isocyanate compound and a polyol compound.

[0026] [9] An interior material comprising the laminate according to any one of [1] to [6].

[0027]

[10] A vehicle part comprising the laminate according to any one of [1] to [6].

[0028]

[11] Furniture comprising the laminate according to any one of [1] to [6]. [Effects of the Invention]

[0029] According to the present invention, it is possible to obtain a laminate that can maintain the color development and friction fastness of the surface layer even after high-temperature press molding, while also achieving sufficient peel strength, as well as interior materials, vehicle parts, and furniture that include the laminate. [Brief explanation of the drawings]

[0030] [Figure 1] FIG. 1 is a cross-sectional conceptual diagram illustrating and explaining a state in which a surface layer and a backing layer are laminated via an adhesive resin in one embodiment of the laminate according to the present invention. [Figure 2] FIG. 2 is a conceptual perspective view illustrating and explaining the method for evaluating the surface quality of a laminate according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0031] The laminate of the present invention is a laminate in which a surface layer containing artificial leather and a backing layer are laminated via an adhesive resin, the artificial leather containing a fiber structure and a polycarbonate-based polyurethane, the fiber structure containing ultrafine fibers made of a polyester-based resin containing a black pigment and / or a chromatic pigment, and the polycarbonate-based polyurethane is It has a skeleton represented by the following general formula (1) and a skeleton represented by the following general formula (2), or It has a skeleton represented by general formula (2) and a skeleton represented by general formula (3), The backing layer is at least one material selected from the group consisting of woven or knitted fabrics, nonwoven fabrics, and foamed resin sheets.

[0032] [ka]

[0033] (In the formula, R1 and R2 are aliphatic hydrocarbon groups having 7 to 11 carbon atoms and may be the same or different. Furthermore, n and m are positive integers. When R1 and R2 are different, the copolymer is a block copolymer or a random copolymer.)

[0034] [ka]

[0035] (In the formula, R3 and R4 are aliphatic hydrocarbon groups having 3 to 6 carbon atoms and may be the same or different. Furthermore, x and y are positive integers. When R3 and R4 are different, the copolymer is a block copolymer or a random copolymer.)

[0036] [ka]

[0037] (In the formula, R5 is an aliphatic hydrocarbon group having 3 to 5 carbon atoms, and R6 is an aliphatic hydrocarbon group having 8 to 12 carbon atoms. Furthermore, a and b are positive integers, and R5 and R6 are block copolymers or random copolymers.) These components will be described in detail below, but the present invention is not limited to the scope of the following description as long as it does not deviate from the gist of the invention.

[0038] [Fiber structures] First, the fiber structure according to one embodiment of the present invention (hereinafter also referred to as "this embodiment") is composed of ultrafine fibers made of polyester resin containing black pigment and / or chromatic pigment.

[0039] (1) Polyester resin First, the ultrafine fibers in this embodiment are made of polyester resin.

[0040] Examples of the polyester resin include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate, polylactic acid, and mixtures and copolymers thereof. Among these, polyethylene terephthalate, which is the most widely used, or a polyester copolymer mainly containing ethylene terephthalate units is preferably used.

[0041] In the present invention, the term "mainly" means that the component that is contained in the largest amount by mass. When the component is composed of equal parts, such as 50:50, both components are considered to be the main components.

[0042] Furthermore, as the polyester-based resin, a single polyester or two or more different polyesters may be used. When two or more different polyesters are used, from the viewpoint of compatibility between the two or more components, the difference in intrinsic viscosity (IV value) of the polyesters used is preferably 0.50 or less, and more preferably 0.30 or less.

[0043] In the present invention, the intrinsic viscosity is calculated by the following method. (i) Dissolve 0.8 g of the sample polymer in 10 mL of orthochlorophenol. (ii) Relative viscosity η measured using an Ostwald viscometer at a temperature of 25°C r Calculate using the formula below and round off to the third decimal place. η r =η / η0=(t×d) / (t0×d0) ···(Formula). Intrinsic viscosity (IV value) = 0.0242η r +0.2634...(expression). (where η is the viscosity of the polymer solution, η0 is the viscosity of orthochlorophenol, t is the solution drop time (seconds), and d is the solution density (g / cm 3 ), t0 is the fall time of orthochlorophenol (seconds), and d0 is the density of orthochlorophenol (g / cm 3 ) respectively.

[0044] Furthermore, the polyester-based resin used in the present embodiment may contain inorganic particles such as titanium oxide particles, a lubricant, a heat stabilizer, an ultraviolet absorber, a conductive agent, a heat storage agent, an antibacterial agent, and the like, as needed, within a range that does not impair the object of the present invention.

[0045] (2) Black pigments, chromatic pigments Next, the polyester resin in this embodiment contains a black pigment and / or a chromatic pigment. Here, in the present invention, the "chromatic pigment" refers to a pigment with a color such as red, blue, green, or yellow, and specifically, a color of CIE1976L determined in accordance with JIS K 5101-2-2. * a * b* In color space, saturation (C * ) is 10 or more. When a polyester resin contains a black pigment and / or a chromatic pigment (hereinafter, black pigment, chromatic pigment, or a mixture of black pigment and chromatic pigment may be collectively referred to as simply "pigment"), the laminate has a surface layer that is resistant to discoloration even when exposed to heat during press molding.

[0046] Preferred examples of black pigments include carbon-based black pigments such as carbon black and graphite, and oxide-based black pigments such as triiron tetroxide and copper-chromium composite oxides. In particular, carbon black is more preferred as the black pigment, from the viewpoints that fine particle diameters can be easily obtained and that it has excellent dispersibility in ultrafine fibers.

[0047] Furthermore, as the chromatic pigment, a pigment close to the target color can be used, and preferred examples thereof include iron oxyhydroxide (e.g., "TM Yellow 8170" manufactured by Dainichiseika Chemicals Co., Ltd.), iron oxide (e.g., "TM Red 8270" manufactured by Dainichiseika Chemicals Co., Ltd.), and cobalt aluminate (e.g., "TM Blue 3490E" manufactured by Dainichiseika Chemicals Co., Ltd.). Here, the above-mentioned white pigments that are not "chromatic," such as zinc oxide and titanium oxide, are not included in the chromatic pigments referred to in the present invention.

[0048] Furthermore, the average particle diameter of the pigment in the ultrafine fibers is preferably 0.05 μm or more and 0.20 μm or less. Here, the average particle diameter of the pigment in this embodiment refers to the particle diameter when present in the ultrafine fibers, and is generally referred to as the secondary particle diameter, measured by the method described below. By setting the lower limit of the average particle diameter of the pigment to preferably 0.05 μm or more, more preferably 0.07 μm or more, the pigment is better held within the ultrafine fibers, further suppressing detachment of the pigment due to heat during press molding, resulting in a laminate having a surface layer that is more resistant to discoloration. On the other hand, by setting the upper limit of the average particle diameter of the pigment to preferably 0.20 μm or less, more preferably 0.18 μm or less, and even more preferably 0.16 μm or less, the ultrafine fibers constituting the artificial leather surface layer have even greater strength, resulting in a laminate that exhibits high abrasion fastness.

[0049] The coefficient of variation (CV) of the particle size of the pigment in the ultrafine fibers is preferably 75% or less. When this coefficient of variation (CV) of particle size is preferably 75% or less, more preferably 50% or less, and even more preferably 35% or less, the particle size distribution becomes narrow, and spinning defects and significant decreases in yarn strength due to small particles falling off the surface or significant aggregation of particles are further suppressed. Note that, although there is no particular lower limit for the coefficient of variation in this embodiment, it is desirable for it to be 0.1% or more from the viewpoint of operability when spinning the ultrafine fibers.

[0050] In the present invention, the average particle size and the coefficient of variation of particle size of the pigment are values ​​measured and calculated by the following methods. (i) Obtain a laminate or a single skin layer before lamination, and randomly select a test piece of 10 mm or larger from the sample. Prepare an ultrathin section 5 μm to 10 μm thick so that the longitudinal cross section of the test piece (if the test piece is a laminate, a cross section that allows the cross sections of the skin layer and backing layer to be observed) can be observed. (ii) The cross section of the laminate in the ultrathin section is observed at 10,000 magnifications using a transmission electron microscope (TEM, for example, Hitachi High-Technologies Corporation's "H7700 Model"). (iii) In the cross section of the test piece, photograph the ultrafine fibers of the artificial leather contained in the skin layer that are circular or elliptical and appear to have a single fiber diameter of 15.0 μm or less. (iv) Using image analysis software (for example, Keyence Corporation's "VW-9000"), measure the circle-equivalent diameter of the pigment particle diameter at 20 points within a 2.3 μm × 2.3 μm field of view of the observed image. If there are fewer than 20 pigment points within the 2.3 μm × 2.3 μm field of view, select another fiber that can measure 20 points and measure it. (v) Calculate the average value (arithmetic mean) and coefficient of variation (CV) for the particle diameters measured at 20 points. Note that in the present invention, the coefficient of variation is calculated using the following formula, and is rounded down to an integer. Coefficient of variation of particle size (%) = (standard deviation of particle size) / (arithmetic mean of particle size) × 100 (formula).

[0051] When measurements are made using a fiber structure containing ultrafine fibers, ultrathin sections with a thickness of 5 μm to 10 μm are prepared from the fiber structure, and the measurements from (ii) onwards are carried out.

[0052] The pigment content in the ultrafine fibers is preferably 0.5% by mass or more and 2.0% by mass or less, based on the mass of the ultrafine fibers. By setting the lower limit of the pigment content to preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and even more preferably 0.9% by mass or more, the amount of dye required to achieve the desired color development during dyeing of the artificial leather surface layer can be further reduced, thereby reducing the amount of dye contained in the artificial leather. This reduces the risk of dye bleeding due to heat during press molding, resulting in a laminate that exhibits high friction fastness. On the other hand, by setting the upper limit of the pigment content to preferably 2.0% by mass or less, more preferably 1.8% by mass or less, and even more preferably 1.6% by mass or less, the physical properties of the artificial leather surface layer, such as strength and elongation, can be further improved, resulting in a laminate that exhibits even higher friction fastness.

[0053] In the present invention, the pigment content is a value measured and calculated by the following method. (i) When measuring from a laminate, carefully peel off the surface layer and remove the backing layer and any layers other than the artificial leather of the surface layer. If you have obtained the surface layer before lamination, remove any layers other than the artificial leather of the surface layer. If you have obtained the artificial leather alone, you can start evaluation from (ii) without performing the above-mentioned removal work. (ii) Immerse artificial leather cut into pieces approximately 8 to 20 cm square in N,N-dimethylformamide (DMF) and boil for at least 2 hours to dissolve only the polyurethane. Collect the remaining ultrafine fibers and measure their mass. This is the mass (g) of the ultrafine fibers before dissolution. (iii) For the collected ultrafine fibers, dissolve the polyester resin using a mixture of phenol and tetrachloroethane, extract the pigment, and filter using a filter with a mesh size of 0.45 μm or equivalent. Measure the mass of the residue remaining on the filter. This is the mass (g) of the residue on the filter. (iv) The residue obtained in (iii) is subjected to elemental analysis, and the ratio of the black pigment to the chromatic pigment is calculated. (v) The proportion (mass%) of pigment contained in ultrafine fibers is calculated using the following formula, and the obtained value is rounded to one decimal place. (Mass of residue on filter (g) × ratio of black pigment to chromatic pigment) / (Mass of ultrafine fibers before dissolution (g)) × 100 (formula).

[0054] If the content can be calculated from the manufacturing process, it can also be calculated using that method.

[0055] (3) Ultrafine fibers The ultrafine fibers in this embodiment are made of the polyester resin containing the pigment. Here, in the present invention, the ultrafine fibers refer to fibers having a single fiber diameter of 15.0 μm or less.

[0056] The average single fiber diameter of the ultrafine fibers is preferably 0.1 μm or more and 10.0 μm or less. By setting the lower limit of the average single fiber diameter of the ultrafine fibers to preferably 0.1 μm or more, more preferably 0.5 μm or more, the ultrafine fibers in the artificial leather of the surface layer have even greater strength, resulting in a laminate with even greater abrasion resistance and a laminate that is free from cracks or tears in the surface layer even when partially stretched by press molding. On the other hand, by setting the upper limit of the average single fiber diameter of the ultrafine fibers to preferably 10.0 μm or less, more preferably 6.0 μm or less, and even more preferably 4.5 μm or less, the artificial leather has even greater surface quality, is denser, and is soft to the touch, and has a flexible surface that can easily conform to the molding die even when partially stretched by press molding.

[0057] In the present invention, the average single fiber diameter of the ultrafine fibers is a value measured and calculated by the following method. (i) Obtain a laminate or a single skin layer before lamination, randomly take test pieces of 10 mm or more square, and prepare ultrathin sections 5 μm to 10 μm thick so that the longitudinal cross section of the test piece (in the case of a laminate, a cross section where the cross sections of the skin layer and backing layer can be observed) can be observed. (ii) A photograph of the cross section of the laminate in the ultrathin slice is taken at 1000x magnification using a scanning electron microscope (SEM, for example, Keyence Corporation's "VHX-D500 / D510 type"). (iii) In the cross section of the test piece in the ultrathin section, fibers in the epidermal layer that are circular or elliptical and appear to have a single fiber diameter of 15.0 μm or less are considered to be ultrafine fibers. Ten such ultrafine fibers are randomly selected, and the single fiber diameter of each is measured. (iv) Calculate the arithmetic mean of the 10 single fiber diameters and round to two decimal places.

[0058] Furthermore, a round cross-sectional shape is preferred for the ultrafine fibers, as this not only facilitates stable formation of the ultrafine fibers during the manufacturing process and results in an artificial leather with an excellent balance of quality, texture, and strength, but also results in a laminate that is flexible enough to conform to the molding die and free of cracks or tears in the skin layer, even when partially stretched during press molding as a laminate. However, cross-sectional shapes such as oval, triangle, and other polygonal (including rounded corners), fan, cross, hollow, Y-, T-, and U-shapes can also be used. In this case, the average single fiber diameter of the ultrafine fibers is determined by first measuring the cross-sectional area of ​​the single fiber and then calculating the diameter when the cross-section is considered to be circular. Furthermore, in the above measurement method, the phrase "circular or elliptical, close to circular" should be read as "having the original cross-sectional shape of the ultrafine fiber being measured or a shape close to circular."

[0059] (4) Fiber structures The fiber structure in this embodiment contains the ultrafine fibers. Examples of the form of the fiber structure include nonwoven fabric, woven / knitted fabric, and those containing both, and these can be used appropriately depending on the properties required for each application and purpose. Among these, it is preferable that the fiber structure is a substrate mainly composed of nonwoven fabric (a fiber sheet in which 60% by mass or more of the fiber structure is nonwoven fabric), and it is more preferable that the fiber structure is nonwoven fabric (100% by mass of the fiber structure is nonwoven fabric). When the fiber structure is a substrate mainly composed of nonwoven fabric, a uniform and elegant appearance and texture can be obtained when the surface is raised. On the other hand, it is also preferable that the fiber structure is a fiber sheet in which a woven / knitted fabric is entangled and integrated with a nonwoven fabric, which results in a laminate with higher strength. In the present invention, woven / knitted fabric is a general term for woven fabrics and knitted fabrics.

[0060] Nonwoven fabrics come in two forms: long-fiber nonwoven fabrics composed mainly of filaments, and short-fiber nonwoven fabrics composed mainly of fibers 100 mm or less. Long-fiber nonwoven fabrics are preferred because they provide a skin layer with excellent strength. On the other hand, short-fiber nonwoven fabrics can provide a larger number of fibers oriented in the thickness direction of the skin layer than long-fiber nonwoven fabrics, and can provide a denser surface for the skin layer when raised.

[0061] When using a short-fiber nonwoven fabric, the average fiber length of the ultrafine fibers is preferably 25 mm or more and 90 mm or less. By setting the average fiber length to 90 mm or less, more preferably 80 mm or less, and even more preferably 70 mm or less, good quality and texture can be achieved. On the other hand, by setting the average fiber length to 25 mm or more, more preferably 35 mm or more, and even more preferably 40 mm or more, a laminate with excellent abrasion resistance can be obtained.

[0062] In the present invention, the average fiber length of the ultrafine fibers is measured and calculated by the following method. When the average fiber length can be determined from the manufacturing process, it can also be calculated by that method. (i) When measuring from a laminate, carefully peel off the surface layer and remove the backing layer and any layers other than the artificial leather of the surface layer. If you have obtained the surface layer before lamination, remove any layers other than the artificial leather of the surface layer. If you have obtained the artificial leather alone, you can start evaluation from (ii) without performing the above-mentioned removal work. (ii) The artificial leather is immersed in N,N-dimethylformamide (DMF) and boiled for more than two hours to dissolve only the polyurethane, and the remaining ultrafine fibers are collected. (iii) Photographs of the collected ultrafine fibers are taken at 20 to 50 magnifications using a scanning electron microscope (SEM, for example, "VHX-D500 / D510" manufactured by Keyence Corporation). (iv) Randomly select 10 ultrafine fibers from the collected ones and measure the fiber length of each. (v) Calculate the arithmetic mean value of the 10 fiber lengths and truncate to an integer.

[0063] [Polycarbonate-based polyurethane] The artificial leather contained in the laminate of this embodiment contains, in addition to the fiber structure, a polycarbonate-based polyurethane having a skeleton represented by the following general formula (1) and a skeleton represented by the following general formula (2), or a skeleton represented by the following general formula (2) and a skeleton represented by the following general formula (3).

[0064] [ka]

[0065] (In the formula, R1 and R2 are aliphatic hydrocarbon groups having 7 to 11 carbon atoms and may be the same or different. Furthermore, n and m are positive integers. When R1 and R2 are different, the copolymer is a block copolymer or a random copolymer.)

[0066] [ka]

[0067] (In the formula, R3 and R4 are aliphatic hydrocarbon groups having 3 to 6 carbon atoms and may be the same or different. Furthermore, x and y are positive integers. When R3 and R4 are different, the copolymer is a block copolymer or a random copolymer.)

[0068] [ka]

[0069] (In the formula, R5 is an aliphatic hydrocarbon group having 3 to 5 carbon atoms, and R6 is an aliphatic hydrocarbon group having 8 to 12 carbon atoms. Furthermore, a and b are positive integers, and R5 and R6 are block copolymers or random copolymers.)

[0070] In other words, by having different structures, such as a polycarbonate skeleton having a long-chain aliphatic hydrocarbon group having 7 to 11 carbon atoms as shown in general formula (1) and a polycarbonate skeleton having a short-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms as shown in general formula (2), or a polycarbonate skeleton having a short-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms as shown in general formula (2) and a polycarbonate skeleton having a short-chain aliphatic hydrocarbon group having 3 to 5 carbon atoms and a long-chain aliphatic hydrocarbon group having 8 to 12 carbon atoms as shown in general formula (3), the polyurethane is more likely to have an amorphous structure, and when bonded to the backing layer with an adhesive resin, it has a higher affinity with the adhesive resin, resulting in high peel strength between the surface layer and the backing layer. Furthermore, when an adhesive for making the adhesive into a polyurethane-based resin is used as the adhesive, the affinity when bonding the surface layer and backing layer is even better, and the crosslinking reaction originating from the adhesive proceeds at the interface with the polycarbonate-based polyurethane, involving the polycarbonate-based polyurethane, thereby achieving even higher peel strength between the surface layer and backing layer.

[0071] Furthermore, R1 and R2 shown in general formula (1) and R3 and R4 shown in general formula (2) may each be the same aliphatic hydrocarbon group, but if they are different aliphatic hydrocarbon groups, as in general formula (3), the polyurethane is more likely to have an amorphous structure, and when bonded to the backing layer with an adhesive resin, the affinity with the adhesive resin is increased, and high peel strength can be obtained between the surface layer and the backing layer, which is preferable.

[0072] In the present invention, when it is unknown whether the polycarbonate-based polyurethane has all of the skeletons represented by the general formulas (1), (2), and (3) and the structure needs to be confirmed, the following method can be used for evaluation. (i) Three test pieces measuring 10 cm x 10 cm are randomly taken from the sample. (ii) If the above sample is a laminate, carefully peel off the surface layer from the test piece, and remove the backing layer and any layers other than the artificial leather of the surface layer, leaving only the artificial leather layer of the surface layer. If it is the surface layer before the sample is laminated, remove any layers other than the artificial leather of the surface layer. If the sample is artificial leather alone, start evaluation from (iii). If it is a fiber structure with polycarbonate-based polyurethane applied before the sample is laminated, start evaluation from (iv). (iii) 30% of the thickness of the above artificial leather layer is removed from both surfaces, excluding the raised portion, by grinding or the like, leaving only the central 40%. (iv) The test piece obtained in (iii) (only the central 40% portion in the thickness direction) was immersed in DMF and boiled for 2 hours or more to dissolve the polyurethane. 1 Measure H-NMR.

[0073] More specifically, the polyurethane is preferably a polyurethane obtained by reacting a polycarbonate diol A having a polycarbonate skeleton represented by the general formula (1) and hydroxyl groups at both ends of the molecular chain, a polycarbonate diol B having a polycarbonate skeleton represented by the general formula (2) and hydroxyl groups at both ends of the molecular chain, an organic diisocyanate, and a chain extender. Alternatively, a polyurethane is preferably obtained by reacting the polycarbonate diol B with a polycarbonate diol C having a polycarbonate skeleton represented by the general formula (3) and hydroxyl groups at both ends of the molecular chain, an organic diisocyanate, and a chain extender. This polycarbonate diol can be produced by the transesterification reaction of an alkylene glycol with a carbonate ester, or by the reaction of phosgene or a chloroformate with an alkylene glycol.

[0074] Here, alkylene glycols that can be used to obtain polycarbonate diol A having a polycarbonate skeleton with a long-chain aliphatic hydrocarbon group having 7 to 11 carbon atoms, as represented by the general formula (1), include linear alkylene glycols such as 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol, and branched alkylene glycols such as 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, and 2,8-dimethyl-1,9-nonanediol. Copolymerized polycarbonate diols obtained from linear alkylene glycols such as those obtained from 1,9-nonanediol and 2-methyl-1,8-octanediol and branched alkylene glycols are particularly preferred, as they have high affinity with adhesive resins when bonded to a backing layer using an adhesive resin, thereby achieving high peel strength between the surface layer and the backing layer. Furthermore, when an adhesive for making the adhesive into a polyurethane-based resin is used as the adhesive, the affinity when bonding the surface layer and backing layer is even better, and the crosslinking reaction originating from the adhesive proceeds at the interface with the polycarbonate-based polyurethane, involving the polycarbonate-based polyurethane, thereby achieving even higher peel strength between the surface layer and backing layer.

[0075] The alkylene glycol used to obtain polycarbonate diol B having a polycarbonate skeleton with a short-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms, as represented by the general formula (2), can be straight-chain alkylene glycols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc., or branched alkylene glycols such as propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc. Copolymerized polycarbonate diols obtained from straight-chain alkylene glycols obtained from 1,6-hexanediol and 3-methyl-1,5-pentanediol, etc., and branched alkylene glycols, are particularly preferred, as they have a high affinity with adhesive resins when bonded to a backing layer using the adhesive resin. Furthermore, when an adhesive for making the adhesive into a polyurethane-based resin is used as the adhesive, the affinity when bonding the surface layer and backing layer is even better, and the crosslinking reaction originating from the adhesive proceeds at the interface with the polycarbonate-based polyurethane, involving the polycarbonate-based polyurethane, thereby achieving even higher peel strength between the surface layer and backing layer.

[0076] On the other hand, as the alkylene glycol for obtaining the polycarbonate diol C having a short-chain aliphatic hydrocarbon group having 3 to 5 carbon atoms and a long-chain aliphatic hydrocarbon group having 8 to 12 carbon atoms represented by the general formula (3), alkylene glycols having 3 to 5 carbon atoms (a1) such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, and 1,3-butanediol can be used. The alkylene glycol (a2) having 8 to 12 carbon atoms can be a linear alkylene glycol such as 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, or 1,12-dodecanediol, or a branched alkylene glycol such as 5-methyl-2,4-heptanediol, 2-methyl-1,7-heptanediol, or 2-methyl-1,8-octanediol. When the alkylene glycol (a1) has 2 or fewer carbon atoms, it may be difficult to handle, and when it has 6 or more carbon atoms, durability and mechanical strength are impaired. When the alkylene glycol (a2) has 7 or fewer carbon atoms, the crystallinity of the copolymerized polycarbonate diol C becomes high, resulting in a hard texture. When the alkylene glycol (a2) has 13 or more carbon atoms, the crystallinity of the copolymerized polycarbonate diol C becomes too low, resulting in impaired durability and abrasion resistance. Among these, copolymerized polycarbonate polyurethanes combining aliphatic hydrocarbon groups with a relatively large difference in carbon number are preferred because they tend to form an amorphous structure, which allows for more active molecular motion and therefore provides high peel strength between the surface layer and the backing layer. Copolymerized polycarbonate diols obtained from 1,4-butanediol and 1,10-decanediol are particularly preferred. These diols are preferred because they have high affinity with adhesive resins when bonded to the backing layer. Furthermore, when an adhesive for forming a polyurethane resin is used as the adhesive, the affinity between the surface layer and the backing layer is even better. Furthermore, the crosslinking reaction of the adhesive proceeds at the interface with the polycarbonate polyurethane, involving the polycarbonate polyurethane, resulting in even higher peel strength between the surface layer and the backing layer.

[0077] Examples of carbonate esters used in the transesterification reaction include diethyl carbonate and diphenyl carbonate.

[0078] The number average molecular weight (Mn) of polycarbonate diols A, B, and C is preferably 500 or more and 3000 or less, more preferably 1500 or more and 2500 or less. When the number average molecular weight is 500 or more, a laminate having a surface layer with a softer feel is obtained. On the other hand, when the number average molecular weight is 3000 or less, a polyurethane with higher strength is obtained, and therefore a laminate having a surface layer with excellent abrasion resistance is obtained.

[0079] The aliphatic hydrocarbon groups of the alkylene glycols in the polycarbonate diols A and B, i.e., R1 and R2, or R3 and R4, may be the same or different, but it is more preferable to use a copolymer of two types of alkylene glycols, which makes the polyurethane more likely to have an amorphous structure, and when bonding to the backing layer with an adhesive, the affinity with the adhesive (adhesive resin) is higher, resulting in high peel strength between the skin layer and the backing layer. Furthermore, when an adhesive for forming a polyurethane-based resin is used as the adhesive, the affinity when bonding the skin layer and the backing layer is even better, and the crosslinking reaction originating from the adhesive proceeds at the interface with the polycarbonate-based polyurethane, involving the polycarbonate-based polyurethane, resulting in even higher peel strength between the skin layer and the backing layer.

[0080] The number average molecular weight of the polycarbonate diol shown here can be determined from the hydroxyl value measured in accordance with the method specified in JIS K 0070-1992 (potentiometric titration method). The composition ratio of alkylene glycols constituting the polycarbonate diol can be determined by gas chromatography (e.g., Shimadzu GC-14B, J&W DB-WAX column) using diethylene glycol diethyl ester as an internal standard and an FID detector.

[0081] Examples of the organic diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and aromatic diisocyanates such as diphenylmethane-4,4'-diisocyanate (MDI) and tolylene diisocyanate, and these can also be used in combination. Among these, it is preferable to use HDI and MDI from the viewpoint of light resistance.

[0082] As the chain extender, an amine-based chain extender such as ethylenediamine or methylenebisaniline, or a diol-based chain extender such as ethylene glycol can be preferably used. Polyamines obtained by reacting polyisocyanate with water can also be used as the chain extender. Among these, ethylene glycol is preferably used from the viewpoint of operability.

[0083] The polycarbonate polyurethane may contain various additives depending on the purpose, such as phosphorus-, halogen-, and inorganic-based flame retardants, phenol-, sulfur-, and phosphorus-based antioxidants, benzotriazole-, triazine-, benzophenone-, salicylate-, cyanoacrylate-, and oxalic acid anilide-based ultraviolet absorbers, hindered amine- and benzoate-based light stabilizers, hydrolysis-resistant stabilizers such as polycarbodiimides, plasticizers, antistatic agents, surfactants, coagulation adjusters, and dyes. The polycarbonate polyurethane may also contain the above-mentioned pigments.

[0084] Generally, the content of polyurethane in an artificial leather is adjusted appropriately taking into consideration the type of polyurethane used, the manufacturing method of the polyurethane, and the texture and physical properties. In this embodiment, however, the content of polycarbonate-based polyurethane in the surface layer is preferably 10% by mass or more and 60% by mass or less. By setting the content of polycarbonate-based polyurethane to preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, the bonding between the ultrafine fibers via the polycarbonate-based polyurethane can be further strengthened, further improving the abrasion resistance of the artificial leather in the surface layer. On the other hand, by setting the content of polycarbonate-based polyurethane to preferably 60% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, not only does the artificial leather have higher flexibility, but also the laminate is flexible enough to easily conform to the molding die even when partially stretched by press molding, and the surface layer is free of cracks or tears.

[0085] In the present invention, the content of polycarbonate-based polyurethane in the artificial leather is measured and calculated by the following method. (i) Three test pieces measuring 10 cm x 10 cm are randomly taken from the sample. (ii) If the above sample is a laminate, carefully peel off the surface layer from the test piece, and remove the backing layer and any layers other than the artificial leather of the surface layer, leaving only the artificial leather layer of the surface layer. If it is the surface layer before the sample is laminated, remove any layers other than the artificial leather of the surface layer. If the sample is artificial leather alone, start evaluation from (iii). If it is a fiber structure with polycarbonate-based polyurethane applied before the sample is laminated, start evaluation from (iv). (iii) 30% of the thickness of the above artificial leather layer is removed from both surfaces, excluding the raised portion, by grinding or the like, leaving only the central 40%. (iv) The test piece obtained in (iii) (only the central 40% of the thickness) is immersed in DMF to dissolve the polyurethane. The test piece remaining after dissolution is dried at 25°C for 24 hours. The mass ratio of the test piece before and after dissolution is calculated using the following formula, and the arithmetic average (%) of the three test pieces is rounded to one decimal place to calculate the polyurethane content. (mass of test piece before dissolution (g) - mass of test piece after dissolution and drying (g)) / (mass of test piece before dissolution (g)) × 100 (formula).

[0086] The number average molecular weight of the polycarbonate polyurethane can be determined by evaluating a 0.125 wt % N,N-dimethylformamide solution using gel permeation chromatography (e.g., HLC-8220GPC manufactured by Tosoh Corporation, using Guardcolumn α and TSKgel α-M columns manufactured by Tosoh Corporation).

[0087] Although it is not possible to obtain an independent value for the composition ratio of the two types of alkylene glycol residues from polycarbonate-based polyurethane, the estimated ratio of the two types of alkylene glycol units can be calculated from the compound structure and number-average molecular weight.

[0088] [Artificial leather] The surface layer of the laminate of this embodiment includes artificial leather containing the fiber-entangled body and the polyurethane.

[0089] In this artificial leather, it is preferable that the surface opposite the backing layer side of the artificial leather, which is not in contact with the adhesive resin, has a napped portion having such length and directional flexibility that when the artificial leather is traced with a finger, the direction of the nap changes, leaving a mark, that is, a so-called finger mark, from the viewpoint of design effect.

[0090] More specifically, the nap length of the napped portion is preferably 200 μm or more and 1000 μm or less, and more preferably 250 μm or more and 800 μm or less. By setting the nap length to 200 μm or more, the surface nap covers the polyurethane, further suppressing exposure of the polyurethane to the surface of the artificial leather, resulting in a laminate with more uniform color development. Furthermore, when the fiber structure constituting the artificial leather is a fiber sheet formed by entanglement and integration of a woven fabric with a nonwoven fabric, setting the nap length of the surface napped portion within the above range is preferred because it can adequately cover the fibers of the woven fabric located near the surface of the artificial leather in the skin layer. On the other hand, setting the nap length to 800 μm or less is preferred because it can provide a laminate with excellent design effects and abrasion resistance.

[0091] In the present invention, the nap length of the napped portion on the surface of the artificial leather is calculated by the following method. (i) When measuring from a laminate, carefully peel off the surface layer and remove the backing layer and any layers other than the artificial leather of the surface layer. If you have obtained the surface layer before lamination, remove any layers other than the artificial leather of the surface layer. If you have obtained the artificial leather alone, you can start evaluation from (ii) without performing the above-mentioned removal work. (ii) With the nap of the surface of the artificial leather of the skin layer raised using a lint brush or the like, a thin slice 1 mm thick is prepared in the cross-sectional direction of a surface perpendicular to the longitudinal direction of the artificial leather using a razor blade or the like. (iii) The cross section of the napped portion on the surface of the artificial leather is observed at 90x magnification using an SEM (for example, Keyence Corporation's "VHX-D500 / D510 model"). (iv) In the SEM image taken, the height of the 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 napped portion on the surface of the artificial leather. (v) The average (arithmetic mean) of the heights of the layers consisting only of ultrafine fibers measured at 10 points is calculated and rounded down to an integer.

[0092] Of course, to further improve adhesion to the backing layer, it is also preferable to have a napped portion on the surface of the backing layer side that comes into contact with the adhesive resin. In this case, it is preferable that the napped coverage rate of the napped portion on the backing layer side is 98% or more.

[0093] [Laminate] The laminate of this embodiment is a laminate formed by laminating a surface layer and a backing layer via an adhesive resin. Here, the "laminate" has a certain area and is not limited to a plate-like, three-dimensional, or other shape, but is preferably a shape that can be press-molded, and a sheet-like shape is particularly preferred. The components of the laminate will be described in order.

[0094] (1) Epidermal layer The surface layer used in the laminate of this embodiment includes the above-mentioned artificial leather.

[0095] The surface layer used in the laminate of this embodiment preferably has a resin layer on at least a part of the surface, in terms of improving the design of the surface.

[0096] In the surface layer used in the laminate of this embodiment, the area covered by the nap (napped coverage) is preferably 70% or more and 100% or less. By setting the napped coverage to 70% or more, exposure of polyurethane to the surface of the surface layer can be further suppressed even when the laminate is stretched during molding processing.

[0097] In the present invention, the nap coverage of the epidermal layer is measured and calculated by the following method. (i) When the artificial leather of the skin layer has a napped portion on its surface, the napped portion on the surface is laid down using a lint brush or the like, and an observation image is taken using an SEM (for example, "VHX-D500 / D510" manufactured by Keyence Corporation) at a magnification of 30 to 90 times to observe the surface of the laminate so that the presence of the nap can be seen. (ii) Using image analysis software (such as "ImageJ" from the National Institutes of Health (NIH)) to calculate the area ratio of a specified pixel, a total actual area of ​​9 mm 2 Total area of ​​the standing hair (mm 2 ) was calculated and used as the nap coverage rate. The percentage of the total area was determined by using image analysis software to correct the captured SEM image so that the pixel value of the brightest part (white part) of the SEM image was 255 and the pixel value of the darkest part (black part) of the SEM image was 0 to obtain a grayscale image, and this 256-level image was then binarized by setting a threshold of 128, and the parts of the grayscale image with pixel values ​​of 128 to 255 (white parts) were considered to be the nap coverage rate. In addition, when calculating the nap coverage rate, if non-napable substances such as exposed polyurethane or attached dirt are calculated as nap coverage and have a significant impact on the nap coverage rate, the image can be manually edited and the color tone of the non-napable substances set to 0, and that part is calculated as the non-napable part.

[0098] The surface layer used in the laminate of this embodiment may be colored by dyeing or the like. The dye is preferably retained in the ultrafine fibers. The dye content of the surface layer after dyeing is preferably 3% by mass or less. The dye used to dye the surface layer may discolor or fade due to the heat generated during press molding, which can cause molecular chain scission and recombination. Therefore, a dye content of 2% by mass or less is more preferable, as this can further suppress the effects of discoloration and fading of the surface layer due to changes in the molecular structure of the dye. In this embodiment, a dye-free embodiment is also preferred. Here, "dye-free" includes an embodiment in which a dye is not used in the design, or an embodiment in which the content measured and calculated by the method described below is below the lower limit of detection. In this specification, "dye-free" refers to a state in which the content measured and calculated by the method described below is equal to or greater than the lower limit of detection, which is the lower limit of the content of the dye. Generally, the lower limit of detection for the content measured and calculated by the method described below is 0.05% by mass.

[0099] The content of the dye in the surface layer used in the laminate of the present invention is calculated by the following method. (i) When measuring from a laminate, carefully peel off the skin layer and remove all layers except the skin layer from the backing layer. If you obtain a single skin layer before lamination, you can evaluate from (ii) without performing the above-mentioned removal work. (ii) 5 g of the surface layer is immersed in 30 mL of dimethylformamide or the like, and refluxed at a heating temperature of 160°C for 30 minutes to obtain a solution in which the polymeric elastomer, dye, and optional resin of the resin layer contained in the surface layer are dissolved. (iii) The solution is reprecipitated in 200 mL of methanol, and separated into methanol solution A in which the dye is dissolved and a coagulated polymeric elastomer. (iv) The coagulated polymeric elastomer is dissolved in 20 mL of dimethylformamide or the like, and reprecipitated with 200 mL of methanol to obtain a methanol solution B in which the dye is dissolved. (v) Methanol solutions A and B are mixed and the solid matter is removed using a filter with a mesh size of 0.45 μm or equivalent. After that, the residue obtained by distilling the methanol under reduced pressure is used as a dye and its mass is measured. (vi) Calculate the dye content in the epidermal layer using the following formula and round off to the first decimal place. Dye content (mass%) = ((dye mass) / (skin layer mass)) × 100 (formula).

[0100] In the laminate of this embodiment, the thickness of the skin layer is preferably 0.3 mm or more and 1.5 mm or less. A skin layer thickness of preferably 0.3 mm or more, more preferably 0.4 mm or more, and even more preferably 0.5 mm or more results in a laminate with better surface quality, in which the adhesive resin is less visible from the surface. On the other hand, a skin layer thickness of preferably 1.5 mm or less, more preferably 1.4 mm or less, and even more preferably 1.3 mm or less results in a flexible skin that easily conforms to the molding die even when partially stretched by press molding, resulting in a laminate with excellent formability.

[0101] The thickness of the skin layer is measured and calculated by the following method. (i) Obtain the laminate or the skin layer alone before lamination. If the sample has raised nap, use a lint brush or similar tool to lay down the raised nap on the surface of the skin layer, and then prepare a thin section 1 mm thick in the cross-sectional direction of a surface perpendicular to the longitudinal direction of the laminate. (ii) The cross section of the surface layer of the laminate is observed at 90x magnification using an SEM (for example, "VHX-D500 / D510" manufactured by Keyence Corporation). (iii) In the SEM image, the length from the adhesive resin to the surface is measured at 10 points at 200 μm intervals across the width of the cross section of the skin layer. Here, the "length from the adhesive resin to the surface" refers to the perpendicular length (not shown) from the boundary (20) between the adhesive resin (14) and the skin layer side shown in FIG. 1 to the outermost layer. (iv) Calculate the average (arithmetic mean) of the lengths (mm) measured at the 10 points and round off to the second decimal place.

[0102] 1 is a cross-sectional conceptual diagram illustrating and explaining a state in which a surface layer and a backing layer are laminated via an adhesive resin in one embodiment of the laminate of the present invention. The laminate (11) is formed by laminating a backing layer (13), a fiber structure including ultrafine fiber bundles (12c) composed of ultrafine fibers (12a), and artificial leather including polycarbonate-based polyurethane (12b) via an adhesive resin (14).

[0103] When a resin layer is present on at least a portion of the surface of the skin layer, the area ratio of the resin portion to the fabric surface is preferably 10% or more. This area ratio is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more, resulting in a laminate with even better abrasion resistance. On the other hand, the upper limit of this area ratio range is 100%, i.e., the entire surface of the skin layer is covered with a resin layer. Therefore, the area ratio of the resin portion to the fabric surface is preferably 10% or more and 100% or less.

[0104] In the present invention, the area ratio of the resin portion of the skin layer is measured and calculated by the following method. (i) When the artificial leather of the skin layer has a napped portion on a part of its surface, lay the nap of the napped portion on the surface flat using a lint brush or the like, and then take an observation image of the laminate surface at a magnification of 30 to 90 times using an SEM (for example, "VHX-D500 / D510" manufactured by Keyence Corporation) so that the presence of the nap can be seen. (ii) Using image analysis software (such as "ImageJ" from the National Institutes of Health (NIH)) to calculate the area ratio of a specified pixel, a total actual area of ​​9 mm 2 Total area of ​​resin portion (mm 2) is calculated and used as the area percentage of the resin portion of the skin layer. The total area percentage can be calculated by using image analysis software to correct the captured SEM image so that the pixel value of the brightest part (white part) of the SEM image is 255 and the pixel value of the darkest part (black part) of the SEM image is 0 to obtain a grayscale image, and then binarizing this 256-level image by setting the threshold value to 128, and considering the parts of the grayscale image with pixel values ​​of 0 to 127 (black parts) to be the resin portion.

[0105] (2) Backing layer The backing layer used in the laminate of this embodiment is at least one material selected from the group consisting of woven or knitted fabrics, nonwoven fabrics, and foamed resin sheets.

[0106] Examples of the woven and knitted fabrics include plain weave, twill weave, satin weave, and various woven fabrics based on these weave structures, weft knitting typified by warp knitting and tricot knitting, lace knitting, and various knitted fabrics based on these knit structures, and the polymers that make up these, i.e., the polymers that are the main components of the fibers that make up the woven and knitted fabrics (polymers that account for 60% by mass or more of the polymers that make up the fibers), include polymers such as polyester, polyamide, polyolefin, various copolymers containing these components, mixtures of these, and polymers that form natural fibers such as cotton and wool. Of these, polyester and polyamide are preferred from the standpoint of durability, particularly mechanical strength, etc.

[0107] Examples of the nonwoven fabric include needle-punched nonwoven fabrics, paper-made nonwoven fabrics, spunbonded nonwoven fabrics, melt-blown nonwoven fabrics, spunlaced nonwoven fabrics, air-through nonwoven fabrics, chemically bonded nonwoven fabrics, flash-spun nonwoven fabrics, and the like, as well as nonwoven fabrics made up of combinations thereof. Polymers constituting the nonwoven fabric, i.e., polymers that are the main components of the fibers constituting the nonwoven fabric (polymers that account for 60% by mass of the polymers constituting the fibers), include polymers such as polyester, polyamide, polyolefin, etc., various copolymers containing these components, mixtures of these, and polymers that form natural fibers such as cotton and wool. Among these, polyester and polyamide are preferred from the viewpoint of durability, particularly mechanical strength, etc.

[0108] Examples of the foamed resin sheet include a resin having bubbles formed therein and molded into a sheet, and a resin sheet containing a foaming agent and foamed. Examples of the resin for the foamed resin sheet include polyolefin resins, polyurethane resins, polyester resins, polyamide resins, polyphenylene sulfide resins, polycarbonate resins, polyether ketone resins, polyether imide resins, and the like, as well as various copolymers containing these components, and mixtures thereof. Among these, polyolefin resins are preferred because of their chemical resistance and resistance to dimensional changes.

[0109] In particular, it is more preferable that the backing layer be a foamed resin sheet, taking into consideration the peel strength with the surface layer, the material strength of the backing layer, the flexibility of the laminate, and the processability described below. In particular, it is preferable that the main component of the foamed resin sheet is a polyolefin-based resin, which allows for a laminate that combines material strength and moldability. Here, the term "main component" refers to the component that is the largest in mass among the components contained. When the components are divided equally, such as 50:50, both components are considered to be the main components.

[0110] The expansion ratio of the foamed resin sheet is preferably 2 to 40 times. An expansion ratio of preferably 2 or more, more preferably 5 or more, results in a flexible laminate. On the other hand, an expansion ratio of preferably 40 or less, more preferably 30 or less, results in a laminate with even higher peel strength and material strength. Here, the expansion ratio can be calculated from the density of the raw material of the foamed resin sheet / the apparent density of the foamed resin sheet.

[0111] The thickness of the backing layer in the laminate of this embodiment is preferably 0.1 mm or more and 5.0 mm or less. A backing layer thickness of preferably 0.1 mm or more, more preferably 0.2 mm or more, and even more preferably 0.3 mm or more results in a laminate with better peel strength and material strength, and excellent shape retention after molding. On the other hand, a backing layer thickness of preferably 5.0 mm or less, more preferably 4.5 mm or less, and even more preferably 4.0 mm or less results in a laminate with better moldability and greater flexibility.

[0112] The thickness of the backing layer is measured and calculated by the following method. (i) A thin section having a thickness of 1 mm is prepared in the cross-sectional direction of a surface perpendicular to the longitudinal direction of the laminate. (ii) The cross section of the backing layer of the laminate is observed at 50x magnification using a scanning electron microscope (SEM, for example, "VHX-D500 / D510" manufactured by Keyence Corporation). (iii) In the SEM image, the length from the adhesive resin to the surface of the backing layer is measured at 10 points at 200 μm intervals across the width of the cross section of the backing layer. Here, "the length from the adhesive resin to the surface of the backing layer" refers to the length of the perpendicular line (18) from the boundary (15) between the backing layer (13) and the adhesive resin (14) to the surface of the backing layer, as illustrated in Figure 1. Note that if the adhesive has penetrated the backing layer, the boundary is considered to be the upper end of the backing layer that is absorbed into the adhesive resin (14). (iv) Calculate the average (arithmetic mean) of the lengths (mm) measured at the 10 points and round off to the second decimal place.

[0113] (3)Adhesive resin The adhesive resin in this embodiment can be appropriately selected from, for example, polyurethane resins, acrylic resins, silicone resins, olefin resins, polyamide resins, epoxy resins, vinyl chloride resins, polyester resins, etc., depending on the material and configuration of the backing layer. Among these, polyurethane resins or acrylic resins are preferred, considering flexibility and adhesive strength at high temperatures. Polyurethane resins, which provide high adhesive strength and flexibility, are particularly preferred. When the adhesive resin is polyurethane, it has a high affinity with the polycarbonate polyurethane of the skin layer, and urethane bonds are easily formed by the crosslinking reaction of the adhesive resin, resulting in high peel strength between the skin layer and the backing layer, which is preferred. Similarly, when the adhesive resin is acrylic resin, it is easily formed with carbonyl bonds, resulting in high peel strength between the skin layer and the backing layer, which is preferred.

[0114] As described below, the polyurethane resin may be a two-component polyurethane adhesive made of an isocyanate compound and a polyol compound.

[0115] In the laminate of this embodiment, the thickness of the adhesive resin is preferably 5 μm or more and 500 μm or less. By having the thickness of the adhesive resin be preferably 5 μm or more, more preferably 75 μm or more, and even more preferably 125 μm or more, the laminate will have high moldability, with wrinkles being further suppressed during molding. Furthermore, by having the thickness of the adhesive resin be preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 300 μm or less, the laminate will be more flexible.

[0116] The thickness of the adhesive resin is measured and calculated by the following method. (i) Take three test pieces, each 3 cm square, at equal intervals of 4 cm from any location on the laminate in the vertical direction. (ii) The collected test piece is cut parallel to the thickness direction. (iii) In the cross section exposed by cutting in the thickness direction, the boundary portion between the skin layer and the backing layer, which contains at least the adhesive resin, etc., is observed at 500x magnification using a scanning electron microscope (SEM, for example, Keyence Corporation's "VHX-D500 / D510 type"). (iv) A 500 μm × 500 μm area containing 500 or more cross-sections of ultrafine fibers is selected at the boundary and photographed. Here, the area containing 500 or more cross-sections of ultrafine fibers refers to an area at the boundary between the skin layer and the backing layer observed in (iii) above, where the number of cut cross-sections is 500 or more. (v) Calculate the average (arithmetic mean) of the thickness (μm) of the adhesive resin present within the above-mentioned region. The thickness of the adhesive resin here refers to the length of the perpendicular line (16) from the boundary (15) between the backing layer and the adhesive resin to the interface of the adhesive resin on the skin layer side (the region with voids of 1 μm or more), as shown in Figure 1. If the adhesive has penetrated the backing layer, the interface of the adhesive resin on the backing layer side (the region with voids of 1 μm or more) is considered to be the boundary (15) between the backing layer and the adhesive resin.

[0117] (4) Laminate The laminate of this embodiment has a peel strength of 7 N / cm or more and 16 N / cm or less when the surface layer is peeled from the laminate, and The failure mode at the time of peeling is cohesive failure of the adhesive resin, a material failure in the backing layer; Interfacial failure or mixed interfacial / cohesive failure between the adhesive resin and the backing layer; It is preferable that either of the above is used.

[0118] A peel strength of preferably 7 N / cm or greater, more preferably 8 N / cm or greater, results in a laminate that is less susceptible to unintended delamination between the skin layer and the backing layer. On the other hand, a peel strength of preferably 16 N / cm or less, more preferably 15 N / cm or less, results in a laminate that is even less susceptible to unintended breakage of the skin layer. This can be achieved by using the preferred skin layer described above to create a high-strength skin layer, or by adjusting the filling depth of the adhesive resin layer.

[0119] The fact that the mode of failure is the above-described mode means that neither the surface layer nor the interface between the surface layer and the adhesive resin layer will be broken until the breaking strength is reached, meaning that at least the surface layer itself or the break caused by the adhesive strength between the surface layer and the adhesive resin will not occur.

[0120] Here, the strength of the skin layer is the value measured in "6.3.1 Tensile strength and elongation (ISO method)" of JIS L1913:2010 "Test methods for general nonwoven fabrics," and a fabric with an average tensile strength of 200 N / 5 cm or more in any two perpendicular directions is considered to be "high strength."

[0121] The peel strength is the peel strength between the surface layer and the backing layer when peeled at an angle of 180°, measured in accordance with JIS K6854-2:1999 "Adhesive - Peel Adhesion Strength Test Method." Specifically, it is measured and calculated using the following method. (i) A test piece measuring 150 mm long x 25 mm wide is cut out from the laminate. (ii) One end of the test piece is immersed in ethanol, immediately removed, and half of the epidermal layer is peeled off. (iii) After thorough drying, the test piece is placed in a tensile testing machine (e.g., Instron Model 3343) with the surface layer side as the "flexible adherend" and the backing layer side as the "rigid adherend," and pulled for 30 mm or more at a gripping speed of 100 mm / min to read the maximum strength. (iv) Determine the type of destruction based on the following criteria: If peeling occurs due to a fracture inside the skin layer: Material fracture in the skin layer If the peeling occurs due to a fracture inside the backing layer: Material fracture in the backing layer When peeling occurs between the adhesive resin and the skin layer: Interfacial fracture between the adhesive resin and the skin layer If there is peeling between the adhesive resin and the backing layer: Interfacial failure between the adhesive resin and the backing layer If the peeling occurs due to a fracture occurring inside the adhesive resin: Cohesive fracture of the adhesive resin If multiple failure modes are observed, it is judged to be a mixed failure. For example, if there are both areas where peeling occurs between the adhesive resin and the backing layer and areas where peeling occurs due to fracture within the adhesive resin, it is considered to be a "mixed interfacial failure / cohesive failure between the adhesive resin and the backing layer."

[0122] In the laminate of this embodiment, the adhesive resin is preferably filled into the skin layer to a depth of 5 μm or more and less than 95 μm. A filling depth of preferably 5 μm or more, more preferably 15 μm or more, and even more preferably 25 μm or more results in a laminate with excellent peel strength between the skin layer and the backing layer. On the other hand, a filling depth of preferably less than 95 μm, more preferably 85 μm or less, and even more preferably 75 μm or less results in a laminate with excellent flexibility. This filling depth shall be measured and calculated by the following method. (i) Take three test pieces, each 3 cm square, at equal intervals of 4 cm from any location on the laminate in the vertical direction. (ii) The collected test piece is cut parallel to the thickness direction. (iii) In the cross section exposed by cutting in the thickness direction, the boundary portion between the skin layer and the backing layer, which contains at least the adhesive resin, etc., is observed at 500x magnification using an SEM (e.g., Keyence Corporation's "VHX-D500 / D510 model"). (iv) A 500 μm × 500 μm region including 500 or more cross-sectional portions of ultrafine fibers is defined in the boundary portion. Here, the region including 500 or more cross-sectional portions of ultrafine fibers refers to a region in the cross section observed in (iii) above where the number of ultrafine fibers whose cut cross sections can be observed is 500 or more. (v) Calculate the average (arithmetic mean) of the filling depth (μm) of the adhesive resin, etc. present in the above-mentioned region. The filling depth here means the distance from the center of the ultrafine fiber (17) closest to the backing layer (13) among the ultrafine fibers whose outer peripheries are entirely covered with the adhesive resin, as illustrated in Figure 1, to the point where there is a gap of 1 μm or more along the direction perpendicular to the surface of the laminate (11) on the skin layer side, i.e., the length of the perpendicular line (19) from the ultrafine fiber closest to the backing layer to the surface on the skin layer side. (vi) The length of the perpendicular line (19) from the microfiber closest to the backing layer to the surface on the skin layer side is measured at 10 points, and the average value (arithmetic mean) is calculated and rounded down to an integer.

[0123] The thickness of the laminate in this embodiment is preferably 0.4 mm or more and 7.0 mm or less. A thickness of preferably 0.4 mm or more, more preferably 0.6 mm or more, of the laminate provides superior material strength, is less likely to break even when partially stretched by molding or deformed into a complex shape, and is more likely to maintain its shape after molding. On the other hand, a thickness of preferably 8.0 mm or less, more preferably 6.5 mm or less, provides a more flexible laminate with superior moldability.

[0124] The thickness of the laminate according to the present invention is measured in accordance with "6.1.1 Method A" of "6.1 Thickness (ISO method)" of JIS L1913:2010 "Testing methods for general nonwoven fabrics," and is measured and calculated as follows. (i) Ten test pieces measuring 5 cm in length and 5 cm in width are randomly taken from the laminate. (ii) The thickness of the test piece of (i) is measured to the nearest 0.01 mm using a thickness measuring device (for example, "Peacock Dial Thickness Gauge H" manufactured by Ozaki Seisakusho Co., Ltd.). (iii) The arithmetic mean value (mm) of the 10 test pieces obtained in (ii) shall be calculated and rounded off to two decimal places.

[0125] The basis weight of the laminate according to this embodiment is 170 g / m 2 More than 1000g / m 2 The weight per unit area is preferably 170 g / m or less. 2 More preferably, 200 g / m 2 By satisfying the above conditions, the laminate has excellent material strength, is less likely to break even when partially stretched by molding or deformed into a complex shape, and is more likely to maintain the shape after molding. 2 Less than 800 g / m 2 When the thickness is equal to or less than 100 μm, a more flexible laminate having excellent moldability can be obtained.

[0126] The basis weight of the laminate according to the present invention is measured in accordance with "6.2 Mass per unit area (ISO method)" of JIS L1913:2010 "Testing methods for general nonwoven fabrics," and is measured and calculated as follows. (i) Three test pieces measuring 30 cm in length and 30 cm in width are randomly taken from the laminate. (ii) Measure the mass of the test piece in (i). (iii) Calculate the mass per unit area of ​​each test piece using the following formula: Mass per unit area (g / m 2 ) = mass of test piece (g) / area of ​​test piece (m 2 )...(expression). (iv) The arithmetic mean value of the mass per unit area obtained in (iii) (g / m 2 ) is rounded down to an integer value.

[0127] The laminate in this embodiment may have an opening. Note that "the laminate has an opening" is not limited to a portion where a hole (through opening) is opened through the laminate in the thickness direction, but also includes, for example, a case where the opening of the surface layer and the opening of the backing layer do not overlap in the surface direction and do not form a through opening. Examples of the latter include a form in which an opening is formed in advance in the surface layer and then laminated on the backing layer, or a form in which an opening is formed in advance in the backing layer and then laminated on the surface layer.

[0128] The openings can be any shape depending on the desired design, including round, oval, polygonal (flat, triangular, etc.), sector, cross, hollow, Y-shaped, T-shaped, U-shaped, and other irregular shapes. The openings may be arranged in a regular or irregular pattern without any particular limitations. However, to ensure uniform strength throughout the laminate, they are preferably arranged regularly at a predetermined interval. The opening diameter is preferably 0.1 mm to 3.0 mm to achieve both breathability and strength for the laminate. The opening ratio is preferably 20% or less to maintain strength, resistance to deformation of the openings, and resistance to fraying around the openings.

[0129] In the present invention, the "opening ratio" refers to the ratio of the area occupied by all openings to the surface area of ​​the laminate.

[0130] [Method of manufacturing laminate] Next, an example of a method for producing a laminate in this embodiment will be given, but various modifications are possible without departing from the gist of the present invention.

[0131] (1) Formation of the epidermal layer The surface layer of this embodiment is the above-mentioned artificial leather, and it is preferable that this artificial leather is formed by including the following steps. Step (1-1): Step of forming ultrafine fiber-forming fibers Step (1-2): Step of forming a fiber structure Step (1-3): Step of forming ultrafine fibers Step (1-4): A step of applying a polycarbonate-based polyurethane.

[0132] Depending on the intended use, it may also be preferable to further include the following steps. Step (1-5): Polishing the sheet-like material Process (1-6): Dyeing the fabric Step (1-7): Other finishing steps Of course, it goes without saying that the sheet-like material obtained may be used as artificial leather not only when it has undergone only steps (1-1) to (1-4), but also when it has undergone steps (1-1) to (1-4) and one or more of steps (1-5), (1-6), and (1-7). Each step will be described in detail below.

[0133] <Step (1-1): Step of forming ultrafine fiber-forming fibers> In this process, ultrafine fiber-forming fibers are formed having an islands-in-sea composite structure consisting of island portions made of a polyester resin containing a black pigment and / or a chromatic pigment and a sea portion made of an easily soluble polymer. The use of islands-in-sea composite fibers is preferred from the viewpoint of texture and surface quality of the skin layer, because it allows appropriate voids to be formed between the island portions, i.e., between the ultrafine fibers within the ultrafine fiber bundle, when the sea portion is removed.

[0134] As a method for spinning ultrafine fiber-forming fibers having an islands-in-sea composite structure, a method using an islands-in-sea composite spinning nozzle and a polymer mutually aligned structure in which sea parts and island parts are mutually aligned and spun is preferred from the viewpoint of obtaining ultrafine fibers with a uniform single fiber fineness.

[0135] The pigment can be incorporated into the island portions by directly kneading the pigment and polyester resin to a predetermined amount, or by mixing a masterbatch with polyester resin chips and spinning them. Among these, the method of mixing the polyester resin chips with a masterbatch is preferred because it allows for the appropriate adjustment of the amount of pigment contained in the ultrafine fibers. The pigment content in the masterbatch is preferably in the range of 10% by mass to 40% by mass. The pigment content in the ultrafine fibers is preferably in the range of 0.1% by mass to 2.0% by mass.

[0136] For the sea portion of the islands-in-sea type composite fiber, polyethylene, polypropylene, polystyrene, copolymer polyesters copolymerized with sodium sulfoisophthalic acid, polyethylene glycol, or the like, and polylactic acid, etc. can be used. From the viewpoints of spinnability and ease of elution, however, polystyrene and copolymer polyesters are preferably used.

[0137] In this step, it is preferable to use islands-in-sea type composite fibers having an island portion strength of 2.5 cN / dtex or more. By making the island portion strength 2.5 cN / dtex or more, more preferably 2.8 cN / dtex or more, and even more preferably 3.0 cN / dtex or more, the abrasion resistance of the laminate can be improved and a decrease in friction fastness due to fiber shedding can be suppressed.

[0138] In the present invention, the strength (cN / dtex) of the island parts of the islands-in-sea type composite fiber is measured and calculated by the following method. (i) Ten islands-in-the-sea composite fibers, each 20 cm long, are bundled together. (ii) After dissolving and removing the sea area from the sample (i), air dry it. (iii) According to JIS L1013:2010 "Testing methods for chemical fiber filament yarns," "8.5 Tensile strength and elongation," "8.5.1 Standard time test," the test shall be carried out 10 times (N=10) under the conditions of a grip length of 5 cm, a pulling speed of 5 cm / min, and a load of 2 N. (iv) Round off the arithmetic mean value (cN / dtex) of the test results obtained in (iii) to one decimal place.

[0139] <Step (1-2): Step of forming a fiber structure> This step is to form a fiber structure containing the ultrafine fiber-developing fibers spun in the above step.

[0140] Methods for forming fiber structures include methods for obtaining direct-bonded fiber webs by spinning, such as the spunbonding method and the meltblown method, and methods for obtaining fiber sheets by dry methods using staple fibers, such as the carding method and the airlaid method, and wet methods, such as the papermaking method. All of these methods are suitable, but fiber sheets produced using staple fibers have small variations in basis weight, excellent uniformity, and are easily able to obtain uniform nap, making them suitable for improving the surface quality of artificial leather. Among methods for producing fiber sheets using staple fibers, a method is particularly preferred in which a fiber structure is formed by carding ultrafine fiber-developing fibers having an islands-in-sea composite structure, and then the sea portion is removed to produce a fiber structure made of ultrafine fibers. The use of islands-in-sea composite fibers allows appropriate voids to be formed between the island portions that form the fiber structure, i.e., between the ultrafine fibers within the ultrafine fiber bundles, when the sea portion is removed, and is therefore preferred from the perspective of the texture and surface quality of the surface layer.

[0141] As a method for entangling the above-mentioned fiber web or fiber sheet to obtain a nonwoven fabric, needle punching, water jet punching, or the like can be used.

[0142] As for the form of this nonwoven fabric, either a short fiber nonwoven fabric or a long fiber nonwoven fabric can be used as described above. However, when using a short fiber nonwoven fabric, the number of fibers oriented in the thickness direction of the laminate is greater than when using a long fiber nonwoven fabric, and a highly dense feel can be obtained on the surface of the skin layer of the laminate when it is raised.

[0143] When this nonwoven fabric is to be a staple fiber nonwoven fabric, the obtained ultrafine fiber-developing fibers are preferably subjected to crimping processing, cut to a predetermined length to obtain raw cotton, and then opened, laminated, and entangled to obtain a staple fiber nonwoven fabric. Known methods can be used for crimping and cutting. When a staple fiber layer is used as the nonwoven fabric, the staple fiber length is preferably 10 mm or more and 90 mm or less, more preferably 20 mm or more and 80 mm or less, and even more preferably 30 mm or more and 60 mm or less.

[0144] Furthermore, when the fiber structure includes a woven or knitted fabric in addition to a nonwoven fabric, the nonwoven fabric and the woven or knitted fabric obtained above are laminated and then entangled together. The entanglement of the nonwoven fabric and the woven or knitted fabric can be achieved by laminating the woven or knitted fabric on one or both sides of the nonwoven fabric, or by sandwiching the woven or knitted fabric between multiple nonwoven fabric webs and then entangling the fibers of the nonwoven fabric and the woven or knitted fabric by needle punching, water jet punching, or the like.

[0145] The apparent density of the fiber structure obtained by needle punching or water jet punching is 0.15 g / cm 3 More than 0.45g / cm 3 The apparent density is preferably 0.15 g / cm or less. 3 By setting the apparent density to 0.45 g / cm or more, a laminate having a surface that can easily follow a complex shape without breaking even when partially stretched by molding can be obtained. 3 By setting the above, it is possible to maintain a sufficient space for applying the polycarbonate-based polyurethane.

[0146] It is also a preferred embodiment that the fiber structure is subjected to a heat shrinking treatment using hot water or steam in order to improve the denseness of the fibers.

[0147] Next, the fiber structure can be impregnated with an aqueous solution of a water-soluble resin such as polyacrylamide (PAA), polyvinyl alcohol (PVA), or carboxymethyl cellulose, followed by drying. By adding a water-soluble resin to the fiber structure before the "step of forming ultrafine fibers" in step (1-3), the fibers are fixed, resulting in a fiber structure that is less susceptible to dimensional changes due to process tension, even after the ultrafine fibers are formed. As a result, the nap density is maintained, resulting in a laminate with a surface that maintains a denser nap appearance. On the other hand, adding a water-soluble resin after the "step of forming ultrafine fibers" in step (1-3) and before the "step of adding polycarbonate-based polyurethane" in step (1-4) prevents the polycarbonate-based polyurethane from firmly adhering to the ultrafine fibers, resulting in a laminate with a flexible surface that can more easily conform to the molding die. In addition, when a water-soluble resin is applied, the water-soluble resin can be removed by immersing the substrate in an organic solvent containing DMF, dimethyl sulfoxide, or the like in step (1-4), the step of applying a polycarbonate-based polyurethane.

[0148] <Step (1-3): Step of forming ultrafine fibers> In this step, the obtained fiber structure is treated with a solvent to produce ultrafine fibers having a single fiber diameter of 15 μm or less, more preferably an average single fiber diameter of 0.1 μm or more and 10.0 μm or less.

[0149] The treatment for developing ultrafine fibers can be carried out by immersing the fiber structure obtained in step (1-2) in a solvent to dissolve and remove the sea portion of the islands-in-sea type composite fibers in the fiber structure.

[0150] As a solvent for dissolving and removing the sea portion, when the sea portion is polyethylene, polypropylene, or polystyrene, an organic solvent such as toluene or trichloroethylene can be used. When the sea portion is a copolymer polyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide can be used. When the sea portion is a water-soluble thermoplastic polyvinyl alcohol resin, hot water can be used.

[0151] <Step (1-4): Step of applying polycarbonate-based polyurethane> In this step, the fiber structure obtained in step (1-2) or the fiber structure that has been subjected to step (1-3) is impregnated with a solution of polycarbonate-based polyurethane to fix the polycarbonate-based polyurethane to the fiber structure, thereby providing the polycarbonate-based polyurethane. The polycarbonate-based polyurethane referred to here is as described above.

[0152] As a solvent used when applying the polycarbonate-based polyurethane, DMF, dimethyl sulfoxide, etc. may be preferably used. Alternatively, an aqueous dispersion in which the polycarbonate-based polyurethane is dispersed in water as an emulsion may be used.

[0153] After impregnating a fiber structure with a polycarbonate-based polyurethane solution, methods for fixing the polycarbonate-based polyurethane to the fiber structure include wet coagulation, in which the solvent is replaced with water if the polyurethane solution is an organic solvent such as DMF or dimethyl sulfoxide, or with an organic solvent such as DMF or dimethyl sulfoxide if the polyurethane solution is water-based, and the polycarbonate-based polyurethane is coagulated by this solvent replacement; and dry coagulation, in which the polyurethane solution is dried with heat and coagulated. These methods can be selected appropriately depending on the type of polycarbonate-based polyurethane used.

[0154] The polyurethane may be applied to the fiber structure material substrate before generating ultrafine fibers from the ultrafine fiber-generating fibers (i.e., immediately after step (1-2)), or after generating ultrafine fibers from the ultrafine fiber-generating fibers (i.e., after step (1-3) and before step (1-5)).

[0155] <Step (1-5): Step of polishing the sheet-like material> In this step, at least one surface of the sheet-like material to which the polycarbonate-based polyurethane has been applied, obtained after the steps (1-1) to (1-4), can be polished. From the viewpoint of production efficiency, it is also a preferred embodiment to cut the sheet-like material in half in the thickness direction to obtain two sheet-like materials prior to this polishing.

[0156] Furthermore, the polishing is preferably performed using sandpaper, a roll sander, or the like. This allows a green cloth to be obtained. As described above, the polishing can be performed on only one surface of the sheet-like material or on both surfaces.

[0157] When polishing, it is also preferable to apply a lubricant such as a silicone emulsion to the surface of the sheet-like material before polishing. Also, by applying an antistatic agent before polishing, grinding powder generated from the sheet-like material during grinding is less likely to accumulate on the sandpaper.

[0158] <Process (1-6): Dyeing the fabric> In this step, the grey fabric is dyed. In this case, a mode in which no dyeing is performed is also preferred. Considering discoloration due to exposure to molding, thermal history, and the like, the most preferred mode is to use no dye or only the small amount required for color matching. When dyeing is performed, examples of dyeing methods that can be used include jet dyeing using a jigger dyeing machine or jet dyeing machine, immersion dyeing such as thermosol dyeing using a continuous dyeing machine, or printing on a napped surface using roller printing, screen printing, inkjet printing, sublimation printing, vacuum sublimation printing, and the like. Of these, jet dyeing machines are preferred because they provide a soft texture and are superior in quality and grade.

[0159] <Steps (1-7): Other finishing steps> If necessary, the obtained sheet material or green fabric may be subjected to various resin finishing processes, such as coating.

[0160] Examples of the method for forming a resin layer on at least a part of the surface layer as described above include a method in which a resin layer is formed by coating using a screen method such as a flat screen or a rotary screen, or a gravure coating method, followed by drying to form a resin layer, and a method in which a discontinuous resin film is formed on a support substrate such as release paper, an adhesive is applied to the surface of the resin film, and the resin film is bonded to the surface of the substrate, and the release paper is removed to form a resin layer.

[0161] The resin layer can also be formed after the skin material and the backing material layer have been laminated together with the adhesive resin interposed therebetween. Even in this case, the laminate still "has a resin layer on at least a portion of the surface of the skin layer."

[0162] Other finishing processes include, for example, finishing processes that add finishing agents such as softeners or antistatic agents after dyeing, finishing processes that add functionality such as antibacterial agents or flame retardants, post-processing such as perforation, embossing, laser processing, pinsonic processing, and printing. Even if these processes are performed, the material is still considered to be a skin material in the present invention.

[0163] <Epidermal layer> Here, more preferred aspects of the properties of the skin layer obtained by the above steps will be described.

[0164] In this embodiment, the skin layer preferably has a bending resistance in the longitudinal direction of 40 mm or more and 300 mm or less. A bending resistance in the longitudinal direction of the skin layer of preferably 40 mm or more, more preferably 50 mm or more, and even more preferably 55 mm or more can provide a laminate with higher strength. On the other hand, by setting the bending resistance in the longitudinal direction of the skin layer to preferably 300 mm or less, more preferably 250 mm or less, and even more preferably 200 mm or less, the occurrence of wrinkles and sagging during the lamination process with the backing layer can be further suppressed, and the operability of the lamination process can be further improved.

[0165] In the present invention, the bending resistance of the skin layer in the longitudinal direction is measured and calculated by the following method. (i) When measuring from a laminate, carefully peel off the skin layer and remove all layers except the skin layer from the backing layer. If you obtain a single skin layer before lamination, you can evaluate from (ii) without performing the above-mentioned removal work. (ii) Five 30 x 2 cm test pieces are taken longitudinally from any location in the epidermal layer. (iii) The surface layer is measured based on Method A (45° cantilever method) described in 8.21 “Bending resistance” of JIS L1096:2010 “Testing methods for woven and knitted fabrics” and 8.21.1, and the average value of five pieces is calculated.

[0166] In the present invention, the longitudinal direction of the skin layer is determined by the following method. When the longitudinal direction can be determined from the appearance of the skin layer, that is, when the winding direction of the skin layer roll can be uniquely determined, this direction is taken as the longitudinal direction. On the other hand, when the longitudinal direction cannot be determined from the appearance, such as when the skin layer is cut and is not in a rolled state, the longitudinal direction is determined by the following procedure. (i) Within the surface of the skin layer, one direction is arbitrarily determined, and the test is conducted along that direction according to "6.3.1 Tensile strength and elongation (ISO method)" of JIS L1913:2010 "General nonwoven fabric test methods." (ii) The same test is conducted in directions rotated 30 degrees, 60 degrees, and 90 degrees from the direction tested in (i). (iii) The maximum strength of each test piece is measured and used as the tensile strength of the skin layer in each direction. (iv) The direction in which the measured value is highest is the longitudinal direction of the skin layer. If there are two or more directions in which the tensile strength is highest, the direction in which the tensile strength is lower in the direction perpendicular to those directions is the longitudinal direction of the skin layer. If there are two or more directions in which the tensile strength is highest and the tensile strengths in the directions perpendicular to those directions are also equal, for example, if the tensile strengths in all four directions are equal, then any of the four directions is the longitudinal direction.

[0167] The weight of the surface layer in this embodiment is 50 g / m 2 More than 400g / m 2 The weight of the surface layer is preferably in the range of 50 g / m 2 More preferably, 80 g / m 2 By setting the weight to 400 g / m or more, it is possible to obtain a surface layer with a rich feel and superior texture. 2 Less than 300 g / m 2 By setting the following, it is possible to obtain a flexible skin layer with excellent formability, and also to make the laminate more flexible.

[0168] The basis weight of the skin layer in the present invention is measured in accordance with "6.2 Mass per unit area (ISO method)" of JIS L1913:2010 "Testing methods for general nonwoven fabrics," and is measured and calculated as follows. (i) Three test pieces measuring 30 cm in length and 30 cm in width are randomly taken from the skin layer to be used for the laminate. (ii) Measure the mass of the test piece in (i). (iii) Calculate the mass per unit area of ​​each test piece using the following formula: Mass per unit area (g / m 2 ) = mass of test piece (g) / area of ​​test piece (m 2 )...(expression). (iv) The arithmetic mean value of the mass per unit area obtained in (iii) (g / m 2 ) is rounded down to an integer value.

[0169] (2) Formation of laminate The laminate of this embodiment can be manufactured by a method including the steps of applying an adhesive to one surface of sheet A, which will serve as the backing layer, placing sheet B, which will serve as the skin layer, on the surface to which the adhesive has been applied, and curing the adhesive to integrate sheets A and B via an adhesive resin, which is the cured product of the adhesive.

[0170] When applying the adhesive, the adhesive can be diluted as needed. The diluent can be selected from toluene, xylene, ethyl acetate, etc., but water is preferable in consideration of the emission of volatile organic compounds (VOCs). By using a water-based adhesive, it is possible to reduce the amount of VOCs emitted when the adhesive is dried, and it is also possible to reduce the amount of VOCs emitted from the resulting laminate.

[0171] As described above, the adhesive used in this step can be appropriately selected depending on the material and form of the backing layer. For example, it can be appropriately selected from adhesives that can be used as adhesive resins, such as polyurethane resins, acrylic resins, silicone resins, olefin resins, polyamide resins, epoxy resins, vinyl chloride resins, and polyester resins. In other words, it can be an embodiment in which the resin is used as a component of the adhesive itself, such as a non-reactive hot melt adhesive, or an embodiment in which the adhesive before coating is composed of unreacted substances that form the resin and reacts to become the resin after coating, and therefore, as described above, it is expressed as an "adhesive that can be used as an adhesive resin."

[0172] Among these, in consideration of flexibility and adhesive strength at high temperatures, an adhesive that can be a polyurethane resin or an acrylic resin is preferable as the adhesive resin, and an adhesive that can be a polyurethane resin that provides high adhesive strength and high flexibility is even more preferable.

[0173] The adhesive used in this process may be a solvent-based adhesive that hardens when the solvent evaporates, a moisture-curing adhesive, a reactive adhesive such as a two-component adhesive, or a hot-melt adhesive such as a reactive hot-melt adhesive or a non-reactive hot-melt adhesive, and among these, a two-component adhesive is preferred.

[0174] Among these, from the viewpoint of operability, it is more preferable to use a two-component polyurethane adhesive composed of an isocyanate compound and a polyol compound as the adhesive. Two-component polyurethane adhesives containing an isocyanate compound and a chain extender are preferred. When this two-component polyurethane adhesive is used, the crosslinking reaction continues even after the surface layer and backing layer are temporarily bonded. Therefore, the crosslinking reaction between the isocyanate compound and the adhesive resin of the polycarbonate polyurethane of Sheet B, which becomes the surface layer, is more likely to proceed, resulting in better peel strength between the surface layer and the backing layer.

[0175] In addition to the isocyanate compound and polyol compound, this two-component polyurethane adhesive may contain additives such as a chain extender, a catalyst, a solvent (e.g., water, an organic solvent such as DMF or toluene), a thickener, and an antistatic agent, as needed.

[0176] The urethane-based resin adhesive is preferably a mixture of 100 parts by weight of the main component polyol compound and 5 to 30 parts by weight of an isocyanate compound. By using 5 parts by weight or more of the isocyanate compound, a crosslinking reaction can be easily induced between the polyol compound in the adhesive and the polycarbonate-based polyurethane contained in Sheet B, resulting in a laminate with higher peel strength between the surface layer and the backing layer. By using 30 parts by weight or less of the isocyanate compound, the pot life of the adhesive can be further extended, improving operability.

[0177] The laminate of this embodiment can be produced by a method including the steps of applying an adhesive to one surface of sheet A, which will serve as the backing layer, placing sheet B, which will serve as the skin layer, on the adhesive-coated surface, and curing the adhesive to integrate sheets A and B via the adhesive resin resulting from the cured adhesive. It is also possible to apply an adhesive to one surface of sheet B, which will serve as the skin layer. However, in this case, the coating method, coating amount, and adhesive type should be adjusted with due consideration given to the possibility that the adhesive resin may seep to the surface of the outermost skin layer, resulting in a hardened surface. Even when woven or knitted fabrics or nonwoven fabrics are used as sheet A, adhesive resin seepage is a concern. However, applying the adhesive to one side of sheet A is preferred because it is on the back side and therefore does not affect the appearance. If seepage is a concern for sheet A, the coating method, coating amount, and adhesive type can be adjusted to achieve the desired properties. When a foam resin sheet is used as sheet A, adhesive resin seepage is less likely to occur. Using a foamed resin sheet as the sheet A is a preferred embodiment from the viewpoint of processability in addition to the above-mentioned advantages.

[0178] Examples of methods for applying the adhesive to one surface of sheet A, which will become the backing layer, include gravure coating, knife coating, screen methods such as flat screens and rotary screens, spray coating, etc., followed by drying to harden the adhesive, and methods for applying the adhesive to a support substrate such as release paper to form an adhesive sheet, then laminating the adhesive sheet to the surface of the backing material, and then removing the release paper to transfer the adhesive. Preferably, the adhesive is transferred to one side of sheet A, which will become the backing layer, using a transfer method using release paper, which suppresses variations in the amount of application due to differences in the surface smoothness and thickness of the backing material, allowing the adhesive to be applied evenly.

[0179] The amount of adhesive applied to the backing layer is 15 g / m2, calculated as the solid content of the adhesive that hardens to become an adhesive resin. 2 More than 500g / m 2 The coating amount is preferably 15 g / m or less. 2More preferably, 20 g / m 2 By setting the coating amount to 500 g / m or more, the peel strength at high temperatures is further improved. 2 Less than 400 g / m 2 By setting the above, the moldability of the laminate will be further improved.

[0180] The basis weight of the sheet A that serves as the backing layer in this embodiment is 120 g / m 2 More than 500g / m 2 The weight of the sheet A is preferably in the range of 120 g / m 2 More preferably, 140 g / m 2 By setting the density to 500 g / m or more, a laminate having superior peel strength and material strength and superior shape retention after molding can be obtained. 2 Less than 400 g / m 2 By setting the following, a more flexible laminate with better moldability can be obtained.

[0181] The basis weight of sheet A, which serves as the backing layer in this embodiment, is measured in accordance with "6.2 Mass per unit area (ISO method)" of JIS L1913:2010 "Test methods for general nonwoven fabrics," and is measured and calculated as follows. (i) Three test pieces measuring 30 cm long x 30 cm wide are taken at random from the backing layer to be used in the laminate before lamination. (ii) Measure the mass of the test piece in (i). (iii) Calculate the mass per unit area of ​​each test piece using the following formula: Mass per unit area (g / m 2 ) = mass of test piece (g) / area of ​​test piece (m 2 )...(expression). (iv) The arithmetic mean value of the mass per unit area obtained in (iii) (g / m 2 ) is rounded down to an integer value.

[0182] The adhesive-coated surface of sheet A, which will serve as the backing layer, is then superimposed on the back surface of sheet B, which will serve as the skin (the surface of the laminate that will not serve as the design surface), and the laminate is obtained by pressing them together. This pressing is preferably performed using a press, dry heat pressing with a calendar roll, or wet heat pressing, which allows for continuous production of the laminate. More preferably, wet heat pressing with a calendar roll is used, which activates the molecular motion of the adhesive between sheet A, which will serve as the backing layer, and sheet B, which will serve as the skin layer, and the polyurethane of sheet B, which will serve as the skin layer, thereby achieving high peel strength between the skin layer and the backing layer. Furthermore, in this embodiment, the polycarbonate-based polyurethanes of the skin layers each contain different aliphatic hydrocarbon groups, which makes the polycarbonate-based polyurethane more likely to have an amorphous structure and further activates molecular motion, resulting in high peel strength between the skin layer and the backing layer.

[0183] When pressing with a press, the temperature of the mold surface is preferably 40°C or higher and 200°C or lower. By setting the temperature at 40°C or higher, more preferably 60°C or higher, the adhesive becomes softer, and the molecular motion of the adhesive between the backing layer and the skin layer and the polyurethane in the skin layer becomes more active, which makes it easier for the crosslinking reaction caused by the adhesive to proceed and results in higher peel strength between the skin layer and the backing layer. On the other hand, by setting the temperature at 200°C or lower, more preferably 140°C or lower, a laminate of good quality can be obtained.

[0184] The pressure of the press is preferably 0.1 MPa or more and 10 MPa or less. By setting the pressure to preferably 0.2 MPa or more, more preferably 0.3 MPa or more, the adhesive can more easily penetrate into the ultrafine fiber bundle, and the peel strength can be further improved. On the other hand, by setting the pressure to preferably 9 MPa or less, more preferably 8 MPa or less, the moldability is more excellent, and a laminate of even better quality can be obtained.

[0185] The temperature of the calender rolls used in dry heat bonding is preferably 40°C or higher and 200°C or lower. A temperature of 40°C or higher, more preferably 60°C or higher, promotes molecular motion in the adhesive between the backing layer and the skin layer, and in the polyurethane of the skin layer, resulting in higher peel strength between the skin layer and the backing layer. A temperature of 200°C or lower, more preferably 140°C or lower, results in a laminate of even higher quality.

[0186] The pressure of the calender roll is preferably 10 N / cm or more and 1000 N / cm or less. By setting the pressure to preferably 20 N / cm or more, more preferably 30 N / cm or more, the adhesive can easily penetrate into the ultrafine fiber bundles, thereby improving the peel strength. On the other hand, by setting the pressure to preferably 900 N / cm or less, more preferably 800 N / cm or less, a laminate with excellent moldability and good quality can be obtained.

[0187] On the other hand, when wet heat pressing is performed using a calendar roll, the steam temperature is preferably 40°C or higher, more preferably 60°C or higher, which softens the adhesive and activates the molecular motion of the adhesive between the backing layer and the skin layer and the polyurethane in the skin layer, thereby achieving high peel strength between the skin layer and the backing layer. On the other hand, the steam temperature is preferably 100°C or lower, more preferably 90°C or lower, which results in a laminate of even better quality.

[0188] The pressure of the calender rolls at this time is the same as that used in dry heat bonding.

[0189] [Interior materials, vehicle parts, furniture] The laminate of the present invention can be formed into any shape by press molding, and since the surface layer has excellent color development and friction fastness even after molding, it is suitable for use in a variety of applications, including interior materials, vehicle parts, and furniture.

[0190] Among these, interior materials containing the laminate are preferred because they can maintain the high quality of the surface layer even after high-temperature press molding and can take advantage of the properties of having sufficient peel strength. Examples of such interior materials include seat covers, ceiling materials, and wall materials for vehicle interiors such as automobiles, trains, and airplanes.

[0191] Alternatively, vehicle parts including the laminate are also preferred because they can take advantage of the property that the high quality of the surface layer can be maintained even after high-temperature press molding. Examples of such vehicle parts include steering wheels, shift levers, handbrakes, control handles, and joysticks for automobiles, trains, and aircraft.

[0192] Furniture containing the laminate is also preferable because it can take advantage of the property that the high quality of the surface layer can be maintained even after high-temperature press molding. Examples of such furniture include chairs, tables, and storage furniture. [Example]

[0193] The present invention will now be described in detail with reference to examples, although the present invention is not limited to these examples.

[0194] [Measurement method] The evaluation methods and measurement conditions used in the examples are explained below. Unless otherwise specified, the measurements of each physical property were carried out according to the above-mentioned methods.

[0195] (1) Physical properties of the epidermis (1-1) Physical properties of fiber structures (1-1-1) Average particle size (μm) of black pigments and chromatic pigments contained in ultrafine fibers, and coefficient of variation of particle size (%) The average particle diameter (μm) of the black pigment and chromatic pigment contained in the ultrafine fibers was measured and calculated using a transmission electron microscope (TEM) "H7700" manufactured by Hitachi High-Technologies Corporation and image analysis software "VW-9000" manufactured by Keyence Corporation, according to the method described above.

[0196] (1-1-2) Pigment content in ultrafine fibers (mass%) The content (mass%) of the pigment in the ultrafine fibers was determined by the method described above. Specifically, the content was calculated from the manufacturing process.

[0197] (1-1-3) Average single fiber diameter of ultrafine fibers (μm) The average single fiber diameter (μm) of the ultrafine fibers was measured and calculated by the above-mentioned method using a scanning electron microscope (SEM) "VHX-D500 / D510" manufactured by Keyence Corporation.

[0198] (1-2) Physical properties of polycarbonate-based polyurethane (1-2-1) Content of polycarbonate-based polyurethane in the skin layer (mass%) The content (mass %) of polycarbonate-based polyurethane in the surface layer was measured and calculated by the method described above.

[0199] (1-3) Physical properties of the epidermis (1-3-1) Artificial leather nap length (μm) The nap length (μm) was measured and calculated by the above-mentioned method using a scanning electron microscope (SEM) "VHX-D500 / D510" manufactured by Keyence Corporation.

[0200] (1-3-2) Dye content (mass%) The content (mass %) of the dye in the skin layer was measured and calculated by the method described above.

[0201] (1-3-3) Pile coverage (%), surface area ratio of resin layer (%) The nap coverage rate (%) and the area ratio (%) of the resin layer on the surface were measured and calculated using the methods described above, using a Keyence Corporation VHX-D500 / D510 SEM and the National Institutes of Health (NIH) ImageJ image analysis software.

[0202] (1-3-4) Bending resistance in the longitudinal direction (mm) The bending resistance (mm) of the skin layer in the longitudinal direction was measured and calculated by the method described above.

[0203] (1-3-5) Thickness (mm) The thickness (mm) of the skin layer was measured and calculated using a Keyence Corporation VHX-D500 / D510 SEM by the method described above.

[0204] (1-3-6) Weight (g / m 2 ) Weight of the surface layer (g / m 2 ) was measured and calculated by the method described above.

[0205] (2) Physical properties of the backing layer (2-1) Thickness (mm) The thickness (mm) of the backing layer was measured and calculated using a SEM "VHX-D500 / D510" manufactured by Keyence Corporation, according to the method described above.

[0206] (2-2) Weight (g / m 2 ) Backing layer weight (g / m 2 ) was measured and calculated by the method described above.

[0207] (3) Physical properties of adhesive resin (3-1) Thickness (mm) The thickness (mm) of the adhesive resin was measured and calculated using a SEM "VHX-D500 / D510 model" manufactured by Keyence Corporation, according to the method described above.

[0208] (3-2) Coating amount (g / m2 ) Amount of adhesive resin applied (g / m 2 ) was carried out by measuring the mass of the backing layer before and after applying the adhesive resin when producing the laminate. Specifically, the following (a) to (c) were carried out. (a) Before applying the adhesive resin, three 10cm x 10cm test pieces were taken from the backing layer at random positions in the longitudinal direction, 10cm from the center, right end, and left end in the width direction, and the basis weight (g / m) of the backing layer before applying the adhesive resin was calculated from the number average of their masses. 2 ) was calculated. (b) Next, after applying the adhesive resin to the backing layer, three 10cm x 10cm test pieces were similarly taken from the backing layer before bonding it to the skin layer at random positions in the longitudinal direction, from the center in the width direction and 10cm from the right and left ends, and the basis weight (g / m2) of the backing layer after applying the adhesive resin was calculated from the number average of their masses. 2 ) was calculated. (c) Finally, the basis weight (g / m) of the backing layer after applying the adhesive resin. 2 ) and the basis weight (g / m2) of the backing layer before applying adhesive resin. 2 ) and the difference (g / m 2 ) and round it off to the first decimal place to obtain the adhesive resin application amount (g / m 2 ) was decided.

[0209] (3-3) Viscosity of adhesive resin (Pa s) The viscosity (Pa·s) of the adhesive resin was measured before application using a Tokyo Keiki "B-type viscometer" at 25°C, in accordance with JIS K7117:1999 "Plastics - Liquid, emulsion or dispersion resins - Measurement method of apparent viscosity using a Brookfield rotational viscometer."

[0210] (4) Physical properties of laminates (4-1) Thickness (mm) The thickness (mm) of the laminate was measured and calculated using the "Peacock Dial Thickness Gauge H" manufactured by Ozaki Seisakusho Co., Ltd. as a thickness measuring instrument, according to the method described above.

[0211] (4-2) Weight (g / m 2 ) Laminate weight (g / m 2 ) was measured and calculated by the method described above.

[0212] (4-3) Failure mode when attempting to peel, peel strength when peeling (N / cm) The fracture mode when attempting to peel and the peel strength (N / cm) when peeling were evaluated, measured, and calculated using an Instron "Model: 3343" tensile tester according to the method described above.

[0213] (4-4) Color development The color development of the laminate was evaluated by 10 healthy adult panelists according to the following criteria, and the evaluation result given by the largest number of people was adopted. In the present invention, a good level is "grade 4 to 5." Grade 5: The color was very vivid, or the color depth and brilliance were outstanding, and the appearance was good. Level 4: A rating between Level 5 and Level 3. Grade 3: Overall the color is vivid, but there are some areas that are not so good. Level 2: A rating between Level 3 and Level 1. Grade 1: Overall impression was dull and the appearance was poor.

[0214] (4-5) Surface quality (grade) The surface quality of the laminate was evaluated by 10 healthy adult panelists using the following criteria. The evaluation was based on the result with the largest number of participants. The surface quality was evaluated by placing the laminate (23) on an inspection table (22) parallel to the floor (21) as shown in Figure 2, and visually inspecting the laminate (23) at a 45° angle from the plane of the inspection table so that the line (25) connecting the visual inspection position (24) and the laminate (23) was 50 cm long. A 32W fluorescent lamp (26) was installed 150 cm above the top of the inspection table in the vertical direction. The surface quality evaluation was performed by placing the laminate (23) directly below the fluorescent lamp (26), i.e., in a position where a perpendicular line (27) could be drawn from the laminate to the fluorescent lamp. A surface quality rating of grades 4 to 5 was considered good. Grade 5: The fibers were uniformly raised, the fibers were well dispersed, and the appearance was good. Level 4: A rating between Level 5 and Level 3. Grade 3: The fiber standing condition was somewhat poor in some areas. Level 2: A rating between Level 3 and Level 1. Grade 1: Overall, the fiber standing and dispersion were very poor, and the appearance was poor.

[0215] (4-6) Evaluation of bent parts after press forming (grade) To evaluate the bent portion after press molding (grade), a top-hat-shaped molded specimen with a diameter of 45 mm, a height of 10 mm, and a maximum expansion ratio of 120% at the bent portion was prepared using a male / female cylindrical container lid mold, and evaluation was performed. Specifically, the laminate was left to stand in an oven heated to 200°C for 5 minutes, and then pressed at a pressure of 0.1 MPa for 30 seconds using a heated press set to 55°C to obtain a molded specimen. The appearance quality of the bent portion of this specimen was visually evaluated, with grades 4 to 5 being considered good. The expansion ratio was calculated using the following steps (a) to (d). (a) Ten evaluation samples of A4 size (210 mm x 297 mm) were taken from any position of the laminate before molding. (b) A 5 mm x 5 mm grid was drawn on the surface of the epidermis layer side of the collected evaluation sample. (c) The area of ​​the grid drawn on the surface layer side of the evaluation sample obtained by molding was measured using a digital microscope, "VHX-5000" manufactured by Keyence Corporation, with the magnification adjusted to 20 times. (d) The area of ​​the measured square was divided by the original area before molding to obtain the expansion rate (%). Grade 5: Appearance was very good (no deterioration in quality due to increased exposure of polyurethane on the surface of the laminate after processing). Level 4: A rating between Level 5 and Level 3. Grade 3: Fair (there is an increase in the amount of polyurethane exposed on the surface of the laminate after processing, and a deterioration in quality is observed.) Level 2: A rating between Level 3 and Level 1. Grade 1: The appearance was poor (the amount of exposed polyurethane on the surface of the laminate after processing had increased significantly, and the quality had deteriorated significantly).

[0216] (4-7) Discoloration evaluation (grade) after press molding To evaluate (grade) discoloration after press molding, the laminate was left to stand in an oven heated to 200°C for 5 minutes, and then pressed at a pressure of 0.1 MPa for 30 seconds using a heated press set to 55°C to obtain a laminate sample. This sample was compared with the surface before molding and judged using the gray scale for discoloration specified in JIS L0804:2004 "Gray scale for discoloration," with grade 4 or higher being considered a pass.

[0217] (4-8) Rubbing fastness (grade) A 30 x 200 mm test piece was taken from the laminate and attached to a Gakushin Type II friction tester (JIS L0849:2013 "Test Method for Color Fastness to Friction"). A dry and sweaty white cotton cloth was placed over the friction element. The friction load was set to 1.96 N, and the test piece was rubbed 200 times at a speed of 30 strokes per minute over a distance of 100 mm. After the test, the degree of staining of the sample after the friction test was assessed using the staining gray scale specified in JIS L0805:2005 "Staining Gray Scale." A grade of 4 or higher was considered pass. The sweaty cloth was a white cotton cloth immersed in artificial sweat for 10 minutes. The artificial sweat solution was prepared by dissolving the following ingredients in distilled water to make 1 L. Disodium hydrogen phosphate dodecahydrate (reagent) as specified in JIS K9019:2021: 8g Sodium chloride: 8g, as specified in JIS K8150:2006 "Sodium chloride (reagent)" 5g of acetic acid as specified in JIS K8355:2006 "Acetic acid (reagent)".

[0218] [Chemical Substances] The abbreviations for chemical substances used in the examples and comparative examples have the following meanings: (ultrafine fiber resin) PET: Polyethylene terephthalate PLA: Polylactic acid (pigment) CB: Carbon black (Resin related to ultrafine fibers) P1: Polyethylene terephthalate with an intrinsic viscosity (IV value) of 0.72 P2: A masterbatch in which carbon black (average particle size: 0.02 μm, coefficient of variation (CV) of particle size: 20%) is contained as a black pigment in the above P1 at a content of 20% by mass relative to the mass of the masterbatch. P3: Melt flow rate (MFR) 30 g / 10 min, melting point 170 °C, solid density 1.240 g / cm 3 Polylactic acid P4: A masterbatch in which carbon black (average particle size: 0.02 μm, coefficient of variation (CV) of particle size: 20%) is contained as a black pigment in the above P3 at a content of 20 mass% relative to the mass of the masterbatch. P5: A masterbatch in which cobalt aluminate (average particle size: 0.05 μm, coefficient of variation (CV) of particle size: 30%, "TM Blue 3490E" manufactured by Dainichiseika Color & Chemicals Co., Ltd.) is contained as a blue pigment in the above P1 at a content of 20 mass% relative to the mass of the masterbatch. (Polycarbonate-based polyurethane) PCPU: Polycarbonate polyurethane C9 / C8 2m: A copolymer polycarbonate diol having a number average molecular weight of 2000, represented by the following general formula (4) and derived from 1,9-nonanediol and 2-methyl-1,8-octanediol.

[0219] [ka]

[0220] (In the formula, n and m are positive integers, and the copolymer is a random copolymer. R represents an aliphatic hydrocarbon group, either (CH2)9 or CH2-CH(CH3)-(CH2)6.) C6 / C5 3m : A copolymer polycarbonate diol having a number average molecular weight of 2000, represented by the following general formula (5) and derived from 1,6-hexanediol and 3-methyl-1,5-pentanediol.

[0221] [ka]

[0222] (In the formula, x and y are positive integers, and the copolymer is a random copolymer. R represents an aliphatic hydrocarbon group of either (CH2)6 or (CH2)2-CH(CH3)-(CH2)2.) C6 / C6: A copolymeric polycarbonate diol having a number average molecular weight of 2000, represented by the following general formula (6), and derived from 1,6-hexanediol:

[0223] [ka]

[0224] (In the formula, x and y are positive integers, and the copolymer is a random copolymer. R represents an aliphatic hydrocarbon group of (CH2)6.) C4 / C10: A copolymer polycarbonate diol having a number average molecular weight of 2000, represented by the following general formula (7), and derived from 1,4-butanediol and 1,10-decanediol.

[0225] [ka]

[0226] (wherein x and y are positive integers, and the copolymer is a random copolymer. R is (CH2)4 or (CH2) 10 ) PTMG: Polytetramethylene glycol with a number average molecular weight of 2000 PCL: Polycaprolactone diol with a number average molecular weight of 2000 (others) MDI: 4,4'-diphenylmethane diisocyanate DMF: N,N-dimethylformamide PU: Polyurethane EG: ethylene glycol.

[0227] Here, the following Production Examples 1 to 4 show production examples of polyurethane solutions used in the Examples and Comparative Examples.

[0228] [Manufacturing Example 1] Polyols: C9 / C8 2m 60 parts by mass of C6 / C5 3m 40 parts by mass of MDI as the organic diisocyanate, DMF was used as a solvent in a four-neck separable flask equipped with a condenser so that the molar ratio of total polyol to MDI was 1:3, and the mixture was stirred and reacted under a nitrogen atmosphere while being controlled at a temperature in the range of 40°C to 60°C.

[0229] Then, EG was diluted in DMF as a chain extender and added dropwise to the reaction mixture while controlling the temperature within the range of 50-60°C. After that, the mixture was gradually diluted with DMF, and after about 10 hours, a polycarbonate-based polyurethane solution with a solids content of 25% was obtained.

[0230] The solution was then diluted with DMF to a solids concentration of 13% by mass, yielding a DMF solution S1 of polycarbonate-based polyurethane X.

[0231] [Manufacturing Example 2] A DMF solution S2 of polyurethane α was obtained in the same manner as in Production Example 1, except that 70 parts by mass of PTMG and 30 parts by mass of PCL were used as the polyols.

[0232] [Manufacturing Example 3] A DMF solution S3 of polyurethane β was obtained in the same manner as in Production Example 1, except that 100 parts by mass of C6 / C6 was used as the polyol.

[0233] [Manufacturing Example 4] Polyols: C9 / C8 2m A DMF solution S4 of polycarbonate-based polyurethane Y was prepared in the same manner as in Production Example 1, except that 60 parts by mass of and 40 parts by mass of C6 / C6 were used.

[0234] [Manufacturing Example 5] As polyol, 50 parts by mass of C4 / C10 and 50 parts by mass of C6 / C5 3m A DMF solution S5 of polycarbonate-based polyurethane Y was prepared in the same manner as in Production Example 1, except that 50 parts by mass of and were used.

[0235] [Example 1] (1) Formation of the epidermal layer <Step of forming ultrafine fiber-forming fibers> Polystyrene was used as the sea component, and a polymer consisting of P1 and P2 mixed at a mass ratio of P1:P2 = 95:5 was used as the island component. Melt spinning was performed under the conditions of a conjugation ratio of 20 mass% of the sea component and 80 mass% of the island component, with 16 islands per filament. Next, the ultrafine fiber-forming fiber was stretched 2.7 times in a spinning oil bath at 90°C to obtain an islands-in-sea type composite fiber with an average single fiber diameter of 20 μm.

[0236] <Step of forming a fiber structure> Next, the obtained islands-in-the-sea composite fiber was cut into a fiber length of 51 mm to form a staple, which was then passed through a card and a cross wrapper to form a fiber web, which was then needle-punched to a thickness of 2.1 mm and an apparent density of 0.22 g / cm.3 A fiber structure (short fiber nonwoven fabric) was produced.

[0237] <Process for forming ultrafine fibers> The obtained fiber structure was immersed in trichloroethylene and squeezed with a mangle 10 times to obtain a sheet made of ultrafine fibers from which the sea component of the islands-in-sea type composite fiber had been removed.

[0238] <Step of applying polycarbonate-based polyurethane> The sheet made of the ultrafine fibers was immersed in a DMF solution S1 of polycarbonate-based polyurethane X, and then the sheet immersed in the DMF solution S1 of polycarbonate-based polyurethane X in an aqueous solution with a DMF concentration of 30% by mass was immersed in hot water at 90°C to remove the DMF, thereby solidifying the polycarbonate-based polyurethane X. Thereafter, the sheet was dried with hot air at a temperature of 110°C for 10 minutes, yielding a sheet-like material to which the polycarbonate-based polyurethane X was imparted.

[0239] <Step of polishing the sheet-like object> The sheet-like material obtained as described above was cut in half by slicing it perpendicularly to the thickness direction, and the non-cut surface (the surface opposite to the surface formed by cutting in half) was ground with sandpaper of sandpaper grit size 180 to obtain a green fabric having raised nap.

[0240] <Process of dyeing grey fabric> The greige fabric obtained as described above was dyed with a black dye using a jet dyeing machine at a temperature of 120°C. After that, it was dried in a dryer to obtain ultrafine fibers with an average single fiber diameter of 4.4 μm, a thickness of 0.7 mm, and a basis weight of 226 g / m. 2 The artificial leather thus obtained had a nap coverage of 85% and a dye content of 3% by mass.

[0241] (2) Formation of laminate <Backing layer> Foamed resin sheet made of polyolefin resin (thickness 2.4 mm, basis weight 170 g / m 2, foaming ratio 15 times) was used.

[0242] <Adhesive resin> A two-component polyurethane adhesive was used as the adhesive. The two components were mixed to prepare a mixture of 100 parts by mass of the main component, the polyol compound, and 25 parts by mass of the isocyanate compound. The viscosity of this mixture was 5 Pa·s. This two-component polyurethane adhesive resin (abbreviated as "PUA" in Tables 1 to 6) was applied to release paper using a gravure roll. The amount of adhesive resin applied was 41 g / m 2 It was decided.

[0243] <Step of forming laminate> The adhesive resin on the release paper was dried in a drying oven controlled at a temperature between 80°C and 100°C. The adhesive resin was then transferred to the backing layer. The surface of the backing layer to which the adhesive resin had been transferred was then placed on the half-cut surface of the skin layer, and the laminate was obtained by pressing at 80°C and 2 MPa for 60 seconds to cure the adhesive and form an adhesive resin. The resulting laminate had good color development and friction resistance in the skin layer, and maintained high surface quality even after press molding, while also maintaining sufficient peel strength. The results are shown in Tables 1 and 2.

[0244] [Example 2] (1) In the step of forming the fiber structure in the formation of the surface layer, a fiber structure (short fiber nonwoven fabric) with a fiber web thickness of 2.1 mm was used, but a fiber structure (short fiber nonwoven fabric) with a fiber web thickness of 1.7 mm was used, resulting in a thickness of 0.6 mm and a basis weight of 155 g / m 2 The artificial leather was used, and further, in the <step of forming a laminate> of (2) forming a laminate, the amount of adhesive resin applied was 32 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the above conditions were met. The obtained laminate had good color development and friction fastness in the surface layer, and maintained high surface quality even after press molding, while also achieving sufficient peel strength. The results are shown in Tables 1 and 2.

[0245] [Example 3] (1) In the step of forming the fiber structure in the formation of the surface layer, a fiber structure (short fiber nonwoven fabric) with a fiber web thickness of 2.1 mm was used, but a fiber structure (short fiber nonwoven fabric) with a fiber web thickness of 2.8 mm was used, resulting in a thickness of 0.8 mm and a basis weight of 300 g / m 2 The artificial leather was used, and further, in the <step of forming a laminate> of (2) forming a laminate, the amount of adhesive resin applied was 32 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the above conditions were met. The obtained laminate had good color development and friction fastness in the surface layer, and maintained high surface quality even after press molding, while also achieving sufficient peel strength. The results are shown in Tables 1 and 2.

[0246] [Example 4] (1) In the process of polishing the sheet material for forming the surface layer, sandpaper with a grit size of 180 was used, but when sandpaper with a grit size of 100 was used, the surface was polished to a weight of 232 g / m. 2 , artificial leather with a nap coverage of 70% was used, and further, in the <step of forming a laminate> of (2) forming a laminate, the amount of adhesive resin applied was 42 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the following was used: Although slight cracks were observed in the bent portions after press molding, the obtained laminate had good color development and friction fastness in the surface layer, and also had sufficient peel strength. The results are shown in Tables 1 and 2.

[0247] [Example 5] (2) In forming the laminate, the backing layer is a polyester knitted fabric (fineness 110T / 48f, basis weight 340g / m 2 , front structure 10 / 34, back structure 10 / 12), and in the <process of forming a laminate>, the amount of adhesive resin applied was 40 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the above conditions were met. The obtained laminate had good color development and friction fastness in the surface layer, and maintained high surface quality even after press molding, while also achieving sufficient peel strength. The results are shown in Tables 1 and 2.

[0248] [Example 6] (1) In the step of applying polycarbonate-based polyurethane to the surface layer, DMF solution S1 of polycarbonate-based polyurethane X was used, but it was replaced with DMF solution S4 of polycarbonate-based polyurethane Y to obtain a surface layer with a basis weight of 218 g / m. 2 The artificial leather was used, and further, in the step of forming a laminate in (2), the amount of adhesive resin applied was 41 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the peel strength of the obtained laminate was slightly inferior, but the surface layer had good color development and friction fastness, and the surface quality was high even after press molding. The results are shown in Tables 1 and 2.

[0249] [Example 7] (1) In the process of forming the skin layer, P1 and P2 were used as island components, but P3 and P4 were used instead, resulting in a basis weight of 192 g / m 2 The artificial leather thus obtained was used, and further, in the <step of forming a laminate> of (2) forming a laminate, the amount of adhesive resin applied was 40 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the above conditions were met. The obtained laminate had good color development and friction fastness in the surface layer, and maintained high surface quality even after press molding, while also achieving sufficient peel strength. The results are shown in Tables 3 and 4.

[0250] [Example 8] (1) In the step of forming the skin layer, P1 and P2 were used as island components, but P1 and P5 were used instead, resulting in a basis weight of 235 g / m 2 The artificial leather thus obtained was used, and further, in the <step of forming a laminate> of (2) forming a laminate, the amount of adhesive resin applied was 40 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the above conditions were met. The obtained laminate had good color development and friction fastness in the surface layer, and maintained high surface quality even after press molding, while also achieving sufficient peel strength. The results are shown in Tables 3 and 4.

[0251] [Example 9] (1) After the process of dyeing the grey fabric to form the skin layer, the following process of forming a resin layer is added to form a fabric with a basis weight of 385 g / m 2 In the step of forming a laminate in (2), the amount of adhesive resin applied is 40 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the following was used: Although slight cracks were observed in the bent portions after press molding, the obtained laminate had good color development and friction fastness in the surface layer, and also had sufficient peel strength. The results are shown in Tables 3 and 4.

[0252] <Step of forming resin layer> The first layer was made of polyether-based polyurethane, and the second and third layers were made of polycarbonate-based polyurethane. The rotary coating method was repeated three times on the nap-bearing side of the artificial leather to form three discontinuous polyurethane resin layers. The surface was dotted with islands of resin, with a nap coverage rate of 40% and a total polyurethane resin layer thickness of 0.2 mm.

[0253] [Example 10] (1) In the process of dyeing the grey fabric to form the surface layer, by increasing the dye concentration, the dye content in the artificial leather becomes 7% by mass and the basis weight becomes 225 g / m. 2 The artificial leather used was 40g / m 2 A laminate was obtained in the same manner as in Example 1, except that the rubbing resistance of the obtained laminate was slightly inferior, but the surface layer had good color development, high surface quality even after press molding, and sufficient peel strength. The results are shown in Tables 3 and 4.

[0254] [Example 11] (1) In the step of applying polycarbonate-based polyurethane to the surface layer, DMF solution S1 of polycarbonate-based polyurethane X was used, but it was replaced with DMF solution S5 of polycarbonate-based polyurethane Y to form a surface layer with a basis weight of 220 g / m. 2A laminate was obtained in the same manner as in Example 1, except that the artificial leather obtained in Example 1 was used. The resulting laminate had good color development and friction fastness in the surface layer, and maintained high surface quality even after press molding, while also achieving sufficient peel strength. The results are shown in Tables 3 and 4.

[0255] [Example 12] (2) A laminate was obtained in the same manner as in Example 1, except that a polyolefin-based adhesive containing neither an isocyanate compound nor its reaction product was used as the adhesive in the formation of the laminate. The resulting laminate had sufficient peel strength, although it was slightly inferior to the other examples. In addition, the surface layer had good color development and friction fastness, and high surface quality even after press molding. The results are shown in Tables 3 and 4.

[0256] [Comparative Example 1] (1) The process of applying polycarbonate polyurethane to form the surface layer was replaced with the process of applying polyurethane α to form a surface layer with a weight of 208 g / m. 2 The artificial leather was used, and further, in the step of forming a laminate in (2), the amount of adhesive resin applied was 41 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the above conditions were met. Although the obtained laminate had good color development and friction fastness in the surface layer, cracks were observed throughout the laminate even after press molding, and the laminate had poor peel strength from the backing material. The results are shown in Tables 5 and 6.

[0257] <Step of adding polyurethane α> The sheet made of ultrafine fibers was immersed in a DMF solution S2 of polyurethane α, and then the sheet immersed in the DMF solution S2 of polyurethane α in an aqueous solution with a DMF concentration of 30% by mass was immersed in hot water at 90°C to remove the DMF and coagulate the polyurethane α. The sheet was then dried with hot air at 110°C for 10 minutes to obtain a sheet-like material to which polyurethane α was imparted.

[0258] Comparative Example 2 (1) The process of applying polycarbonate polyurethane to form the surface layer was replaced with the process of applying polyurethane β to form a surface layer with a weight of 220 g / m. 2 The artificial leather thus obtained was used, and further, in the <step of forming a laminate> of (2) forming a laminate, the amount of adhesive resin applied was 40 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the above conditions were met. The resulting laminate had good color development and friction fastness in the surface layer, but the texture of the surface layer was hard, cracks were observed throughout the laminate even after press molding, and the laminate had poor peel strength from the backing material. The results are shown in Tables 5 and 6.

[0259] <Step of adding polyurethane β> The sheet made of the ultrafine fibers was immersed in a DMF solution S3 of polyurethane β, and then the sheet immersed in the DMF solution S3 of polyurethane α in an aqueous solution with a DMF concentration of 30% by mass was immersed in hot water at 90°C to remove the DMF and coagulate the polyurethane β. Thereafter, the sheet was dried with hot air at a temperature of 110°C for 10 minutes to obtain a sheet-like material to which polyurethane β was imparted.

[0260] Comparative Example 3 (1) In the process of forming ultrafine fiber-developing fibers in the skin layer formation, P1 and P2 were used as island components, but instead only P1 was used. Furthermore, in the process of dyeing the gray fabric, the dye concentration was increased, resulting in an artificial leather with a dye content of 7% by mass and a basis weight of 210 g / m. 2 The artificial leather was used, and further, in the <step of forming a laminate> of (2) forming a laminate, the amount of adhesive resin applied was 42 g / m 2 A laminate was obtained in the same manner as in Example 1, except that the above conditions were met. The obtained laminate had sufficient peel strength and no cracks were observed after press molding, but the color development and color fastness of the surface layer and the surface quality after press molding were poor. The results are shown in Tables 5 and 6.

[0261] Comparative Example 4 (2) A laminate was obtained in the same manner as in Comparative Example 2, except that a polyolefin-based adhesive containing neither an isocyanate compound nor its reaction product was used as the adhesive in the formation of the laminate. The resulting laminate had good friction resistance in the surface layer, but the texture of the surface layer was hard, and cracks were observed throughout even after press molding, resulting in a laminate with poor peel strength from the backing material. The results are shown in Tables 5 and 6.

[0262] [Table 1]

[0263] [Table 2]

[0264] [Table 3]

[0265] [Table 4]

[0266] [Table 5]

[0267] [Table 6]

[0268] As shown in Tables 1 to 4, the laminates of Examples 1 to 12 contained black pigment in the ultrafine fibers of the skin layer, and the polyurethane in the skin layer was two types of polycarbonate-based polyurethane with specific skeletons, so that all of the laminates had good color development and friction resistance in the skin layer, while also achieving sufficient peel strength.

[0269] On the other hand, as shown in Tables 5 and 6, when a polyurethane without a polycarbonate skeleton was used as the polyurethane in the skin layer, as in the laminate of Comparative Example 1, crosslinking points with the adhesive resin were not formed, resulting in a laminate with poor peel strength from the backing material.

[0270] Furthermore, when only one type of polycarbonate-based polyurethane was used in the polyurethane skeleton of the skin layer, as in the laminates of Comparative Examples 2 and 4, the resulting skin layer was very rigid, and no crosslinking points were formed with the adhesive resin, resulting in a laminate with poor peel strength from the backing material.

[0271] In addition, when the ultrafine fibers did not contain a black pigment, as in the laminate of Comparative Example 3, the dye deteriorated upon heating, causing a significant change in the hue of the ultrafine fibers, resulting in a laminate with poor color development and friction fastness of the surface layer after high-temperature press molding. [Explanation of symbols]

[0272] 11: Laminate 12a: Ultra-fine fiber 12b: Polycarbonate-based polyurethane 12c: Ultrafine fiber bundle 13: Backing layer 14: Adhesive resin 15: Boundary between backing layer and adhesive resin 16: Normal line to the boundary between the backing layer and adhesive resin and the interface of the adhesive resin on the surface layer side 17: Ultra-fine fibers closest to the backing layer 18: Perpendicular line from the boundary between the backing layer and adhesive resin to the surface of the backing layer side 19: Perpendicular line from the microfiber closest to the backing layer to the surface of the epidermis layer 20: Boundary between adhesive resin and skin layer 21: Floor 22: Examination table 23: Laminate 24: Visual inspection location 25: Line connecting the visual inspection position and the laminate 26: Fluorescent Light 27: Perpendicular line from laminate to fluorescent lamp

Claims

1. A laminate comprising a surface layer containing artificial leather and a backing layer laminated together via an adhesive resin, The artificial leather includes a fiber structure and a polycarbonate-based polyurethane, the fiber structure includes ultrafine fibers made of a polyester resin containing a black pigment and / or a chromatic pigment, The polycarbonate-based polyurethane has a skeleton represented by the following general formula (1) and a skeleton represented by the following general formula (2), or It has a skeleton represented by general formula (2) and a skeleton represented by general formula (3), The backing layer is at least one material selected from the group consisting of woven or knitted fabrics, nonwoven fabrics, and foamed resin sheets. Laminate. 【Chemistry 1】 (In the formula, R １ and R ２ are aliphatic hydrocarbon groups having 7 to 11 carbon atoms, and may be the same or different. n and m are positive integers, and R １ and R ２ are different, it is a block copolymer or a random copolymer.) 【Chemistry 2】 (In the formula, R ３ and R ４ are aliphatic hydrocarbon groups having 3 to 6 carbon atoms, and may be the same or different. In addition, x and y are positive integers, and R ３ and R ４ are different, it is a block copolymer or a random copolymer.) 【Transformation 3】 (In the formula, R ５ is an aliphatic hydrocarbon group having 3 to 5 carbon atoms, and R ６ is an aliphatic hydrocarbon group having 8 to 12 carbon atoms. Furthermore, a and b are positive integers, and R ５ and R ６ is a block copolymer or a random copolymer.

2. The laminate according to claim 1 , wherein the adhesive resin is a polyurethane resin.

3. The peel strength when the surface layer is peeled from the laminate is 7 N / cm or more and 16 N / cm or less, The failure mode at the time of peeling is cohesive failure of the adhesive resin, a material failure of the backing layer; Interfacial failure or mixed interfacial / cohesive failure between the adhesive resin and the backing layer; The laminate according to claim 1 or 2, wherein

4. The laminate according to claim 1 or 2, wherein the nap coverage of the surface layer is 70% or more and 100% or less.

5. The laminate according to claim 1 or 2, further comprising a resin layer on at least a portion of the surface of the skin layer.

6. The laminate according to claim 1 or 2, wherein the dye content of the surface layer is 3% by mass or less.

7. A method for producing the laminate according to claim 1 or 2, A method for manufacturing a laminate, comprising the steps of applying an adhesive to one surface of sheet A which will become the backing layer, placing sheet B which will become the skin layer on the surface coated with the adhesive, and curing the adhesive to integrate sheet A and sheet B via an adhesive resin which is the cured product of the adhesive.

8. The method for producing a laminate according to claim 7, wherein the adhesive is a two-component polyurethane adhesive comprising an isocyanate compound and a polyol compound.

9. An interior material comprising the laminate according to claim 1 or 2.

10. A vehicle part comprising the laminate of claim 1 or 2.

11. A piece of furniture comprising the laminate of claim 1 or 2.

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