Laminate, interior material including same, vehicle component, and furniture

Abstract

The present invention addresses the problem of providing a laminate with which it is possible to maintain color development and friction fastness in a surface layer even after high-temperature press molding, and with which it is possible to achieve sufficient peel strength.　A laminate according to the present invention comprises a surface layer containing artificial leather and a backing layer laminated together via an adhesive resin, wherein: the artificial leather includes a fiber structure and a polycarbonate-based polyurethane; the fiber structure includes ultrafine fibers composed 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 layer is at least one selected from the group consisting of woven or knitted fabrics, non-woven fabrics, and foamed resin sheets. (In formula (1), R1 and R2 are each a C7-11 aliphatic hydrocarbon group and may be the same or different. In addition, (n) and (m) are positive integers, and when R1 and R2 are different from each other, block copolymerization or random copolymerization is carried out.) (In formula (2), R3 and R4 are each a C3-6 aliphatic hydrocarbon group and may be the same or different. In addition, (x) and (y) are positive integers, and when R3 and R4 are different from each other, block copolymerization or random copolymerization is carried out.) (In formula (3), R5 is a C3-5 aliphatic hydrocarbon group and R6 is a C8-12 aliphatic hydrocarbon group. In addition, (a) and (b) are positive integers, and R5 and R6 are each a block copolymer or a random copolymer.)

Description

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

[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.

[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 including a non-porous thermoplastic elastomer layer and a decorative layer containing a fiber structure disposed on the outer surface of the thermoplastic elastomer layer, the composite layer being formed by combining the surface layer of the thermoplastic elastomer layer with the surface layer of the fiber structure contained in the decorative layer. It is described 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 provides a high 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.

[0005] JP 2017-61051 A International Publication No. 2017 / 056465

[0006] When these laminates are used for various purposes, they are press-molded at high temperatures (approximately 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 therefore, although 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 narrowed, 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.

[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 comprising a surface layer including artificial leather and a backing layer laminated together via an adhesive resin, wherein the artificial leather includes a fiber structure and a polycarbonate-based polyurethane, the fiber structure includes 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 the following general formula (1) and a skeleton represented by the following general formula (2), or has a skeleton represented by the following general formula (2) and a skeleton represented by the following general formula (3), and the backing layer is at least one material selected from the group consisting of woven or knitted fabrics, nonwoven fabrics, and foamed resin sheets.

[0013]

[0014] (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.)

[0015]

[0016] (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.)

[0017]

[0018] (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.

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

[0020] [3] The laminate according to [1] or [2], wherein the peel strength when the surface layer is peeled from the laminate is 7 N / cm or more and 16 N / cm or less, and the failure mode during the peeling is either cohesive failure of the adhesive resin, material failure of the backing layer, or interfacial failure between the adhesive resin and the backing layer, or a mixture of interfacial failure and cohesive failure.

[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], 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] above, comprising the steps of applying an adhesive to one surface of sheet A that will become the backing layer, placing sheet B that will become the skin layer on the surface that has been coated with the adhesive, and curing the adhesive to integrate sheet A and sheet B via an adhesive resin that is the cured product of the adhesive.

[0025] [8] The method for producing a laminate according to [7], 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].

[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.

[0030] Fig. 1 is a cross-sectional schematic 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, and Fig. 2 is a conceptual perspective view illustrating and explaining a method for evaluating the surface quality of a laminate according to the present invention.

[0031] The laminate of the present invention is a laminate formed by laminating a surface layer containing artificial leather and a backing 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 having a skeleton represented by the following general formula (1) and a skeleton represented by the following general formula (2), or having a skeleton represented by the following general formula (2) and a skeleton represented by the following general formula (3), and 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]

[0033] (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.)

[0034]

[0035] (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.)

[0036]

[0037] (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 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 present invention.

[0038] [Fiber structure] First, a fiber structure according to one embodiment of the present invention (hereinafter also referred to as "this embodiment") is composed of ultrafine fibers made of a polyester resin containing a black pigment and / or a 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 containing mainly 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, the difference in intrinsic viscosity (IV value) of the polyesters used is preferably 0.50 or less, and more preferably 0.30 or less, from the viewpoint of compatibility between the two or more components.

[0043] In the present invention, the intrinsic viscosity is calculated by the following method: (i) 0.8 g of a sample polymer is dissolved in 10 mL of orthochlorophenol, and (ii) the relative viscosity η is 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. ｒ = η / η ０ = (t × d) / (t ０ ×d ０ ) ... (formula). Intrinsic viscosity (IV value) = 0.0242η ｒ +0.2634 ... (where η is the viscosity of the polymer solution, η ０ is the viscosity of orthochlorophenol, t is the solution drop time (seconds), and d is the solution density (g / cm ３ ), t ０ is the fall time of orthochlorophenol (seconds), d ０ is the density of orthochlorophenol (g / cm ３ ) and ).

[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 pigment, chromatic pigment The polyester resin in this embodiment contains a black pigment and / or a chromatic pigment. Here, in the present invention, the term "chromatic pigment" refers to a pigment with a color such as red, blue, green, or yellow. Specifically, the black pigment and / or chromatic pigment are pigments having ... ＊ a ＊ b ＊ In the color space, saturation (C ＊) is 10 or more. When the polyester resin contains a black pigment and / or a chromatic pigment (hereinafter, these may be abbreviated simply as "pigment" as a general term for black pigment, chromatic pigment, or a mixture of black pigment and chromatic pigment), a laminate having a surface layer that is resistant to discoloration even when exposed to heat during press molding is obtained.

[0046] Preferred examples of black pigments include carbonaceous black pigments such as carbon black and graphite, and oxide-based black pigments such as triiron tetroxide and copper-chromium composite oxides. In particular, it is more preferred that the black pigment is carbon black, from the viewpoints that a fine particle diameter 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 Color & Chemicals Co., Ltd.), iron oxide (e.g., "TM Red 8270" manufactured by Dainichiseika Color & Chemicals Co., Ltd.), and cobalt aluminate (e.g., "TM Blue 3490E" manufactured by Dainichiseika Color & 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 what 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, thereby 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 friction 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 the 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 a significant decrease in yarn strength due to falling off of small particles from 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 that it 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 coefficient of variation of the particle size of the pigment are values ​​measured and calculated by the following methods. (i) A laminate or a single skin layer before lamination is obtained, and a test piece of 10 mm square or larger is randomly taken from the sample. An ultrathin section of 5 μm to 10 μm thick is prepared so that the longitudinal cross section of the test piece (a cross section where the cross sections of the skin layer and backing layer can be observed if the test piece is a laminate) can be observed. (ii) The cross section of the laminate in the ultrathin section is observed at 10,000x magnification using a transmission electron microscope (TEM, for example, the "H7700" model manufactured by Hitachi High-Technologies Corporation). (iii) In the cross section of the test piece, 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 are photographed. (iv) Using image analysis software (for example, "VW-9000" manufactured by Keyence Corporation), measure the circle-equivalent diameter of 20 pigment particle diameters contained within a 2.3 μm × 2.3 μm field of view of the observed image. If there are fewer than 20 pigment particles contained within the 2.3 μm × 2.3 μm field of view, select another fiber that allows 20 measurements and measure them. (v) Calculate the average value (arithmetic mean) and coefficient of variation (CV) for the particle diameters measured at the 20 points. 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 diameter (%) = (standard deviation of particle diameter) / (arithmetic mean of particle diameter) × 100 (formula).

[0051] When measurements are made using a fiber structure containing ultrafine fibers, ultrathin sections having 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, the surface layer is carefully peeled off, and the backing layer and layers other than the artificial leather of the surface layer are removed. If the surface layer is obtained before lamination, the layers other than the artificial leather of the surface layer are removed. If the artificial leather is obtained alone, it can be evaluated from (ii) without performing the above-mentioned removal process. (ii) A piece of artificial leather approximately 8 to 20 cm square is immersed in N,N-dimethylformamide (DMF) and boiled for at least 2 hours to dissolve only the polyurethane, and the remaining ultrafine fibers are collected and their mass is measured. This is the mass (g) of the ultrafine fibers before dissolution. (iii) For the collected ultrafine fibers, the polyester resin is dissolved using a mixture of phenol and tetrachloroethane, the pigment is extracted, and the mixture is filtered using a filter with a mesh size of 0.45 μm or equivalent. The mass of the residue remaining on the filter is measured. This is the mass (g) of the residue on the filter. (iv) The residue obtained in (iii) is subjected to elemental analysis to calculate the ratio of black pigment and chromatic pigment. (v) The ratio (mass%) of pigment contained in the ultrafine fibers is calculated using the following formula, and the obtained value is rounded to one decimal place. (Mass (g) of residue on filter × ratio of black pigment and chromatic pigment) / (Mass (g) of ultrafine fibers before dissolution) × 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 a 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) A laminate or a single skin layer before lamination is obtained, and test pieces of 10 mm or more square are randomly taken. Ultrathin sections of 5 μm to 10 μm thick are prepared 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 section is taken at 1000x magnification using a scanning electron microscope (SEM, for example, Keyence Corporation's "VHX-D500 / D510"). (iii) Of the cross sections of the test pieces in the ultrathin section, circular or nearly circular elliptical fibers in the skin layer that appear to have a single fiber diameter of 15.0 μm or less are considered to be ultrafine fibers. Ten of these ultrafine fibers are randomly selected, and the single fiber diameter of each is measured. (iv) Calculate the arithmetic mean value of the 10 single fiber diameters and round to the nearest tenth.

[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 by press molding into a laminate. However, cross-sectional shapes of irregular cross sections such as oval, triangle, and other polygonal (including those with rounded corners), sector, cross, hollow, Y-shaped, T-shaped, and U-shaped cross sections 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 a cross-sectional shape that the ultrafine fiber to be measured originally has, or a shape close to circular."

[0059] (4) Fiber Structure 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. 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 primarily made 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). By using a fiber structure as a substrate primarily made 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 are available in the form of long-fiber nonwoven fabrics mainly composed of filaments, and short-fiber nonwoven fabrics mainly composed of fibers of 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 highly dense surface for the skin layer when raised.

[0061] When a short-fiber nonwoven fabric is used, 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. If the manufacturing process can be identified, the average fiber length can also be calculated by that method. (i) When measuring from a laminate, the surface layer is carefully peeled off, and the backing layer and layers other than the artificial leather surface layer are removed. If the surface layer is obtained before lamination, the layers other than the artificial leather surface layer are removed. If the artificial leather is obtained alone, evaluation can be performed starting from (ii) without the above-mentioned removal process. (ii) The artificial leather is immersed in N,N-dimethylformamide (DMF) and boiled for 2 hours or more 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, Keyence Corporation's "VHX-D500 / D510" model). (iv) Ten ultrafine fibers are randomly selected from the collected fibers, and the fiber length of each is measured. (v) Calculate the arithmetic average of the lengths of the 10 fibers and round down to an integer.

[0063] [Polycarbonate-based polyurethane] The artificial leather included in the laminate of this embodiment contains, in addition to the fiber structure, a polycarbonate-based polyurethane. This polycarbonate-based polyurethane has 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]

[0065] (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.)

[0066]

[0067] (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.)

[0068]

[0069] (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.

[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 likely to have an amorphous structure, and when bonded to a backing layer with an adhesive resin, it has a high affinity with the adhesive resin, and high peel strength can be obtained 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] In addition, R represented by the general formula (1) １ and R ２ , R represented by the general formula (2) ３ and R ４ may each be the same aliphatic hydrocarbon group, but as in the case of general formula (3), if they are different aliphatic hydrocarbon groups, the polyurethane is more likely to have an amorphous structure, and when the polyurethane is 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 a polycarbonate-based polyurethane has all of the skeletons shown in general formulas (1), (2), and (3) and the structure needs to be confirmed, the following method can be used for evaluation. (i) Randomly collect three test pieces measuring 10 cm x 10 cm from the sample. (ii) If the 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 surface layer, leaving only the artificial leather surface layer. In the case of the surface layer before the sample is laminated, remove any layers other than the artificial leather surface layer. If the sample is artificial leather alone, evaluation begins with (iii). In the case of a fiber structure to which a polycarbonate-based polyurethane has been applied before the sample is laminated, evaluation begins with (iv). (iii) Remove 30% of the artificial leather layer in the thickness direction from both surfaces, excluding the napped portions, by polishing 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, and the solution was １ H-NMR measurement.

[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, the alkylene glycol 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 general formula (1), can be straight-chain alkylene glycols such as 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc., or branched alkylene glycols such as 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2,8-dimethyl-1,9-nonanediol, etc. Copolymerized polycarbonate diols obtained from straight-chain alkylene glycols obtained from 1,9-nonanediol and 2-methyl-1,8-octanediol, etc., and branched alkylene glycols, are particularly preferred, as they have a high affinity with adhesive resins when bonded to a backing layer with an adhesive resin, thereby achieving high peel strength between the skin 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 from which the polycarbonate diol B having a polycarbonate skeleton with a short-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms represented by the general formula (2) can be obtained includes linear alkylene glycols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, and branched alkylene glycols such as propylene glycol, neopentyl glycol, and 3-methyl-1,5-pentanediol. Copolymerized polycarbonate diols obtained from linear 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 with 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 such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, and 1,3-butanediol are used as the alkylene glycol (a1) having 3 to 5 carbon atoms. Examples of the alkylene glycol (a2) having 8 to 12 carbon atoms include linear alkylene glycols such as 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol, and branched alkylene glycols such as 5-methyl-2,4-heptanediol, 2-methyl-1,7-heptanediol, and 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 copolymeric polycarbonate diol C becomes high, resulting in a hard texture, and when it has 13 or more carbon atoms, the crystallinity of the copolymeric 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 thus achieves high peel strength between the surface layer and the backing layer. Copolymerized polycarbonate diols obtained from 1,4-butanediol and 1,10-decanediol, etc., 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 texture 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 group of the alkylene glycol in the polycarbonate diols A and B, i.e., R １ and R ２ , or R ３ and R ４ may be the same or different, but more preferably, by using a copolymer of two kinds of alkylene glycols, the polyurethane is more likely to have an amorphous structure, and when bonding with the backing layer by adhesive, the affinity with the adhesive (adhesive resin) is higher, and a high peel strength can be obtained 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 the backing layer is even better, and further, the crosslinking reaction derived from the adhesive proceeds at the interface with the polycarbonate-based polyurethane, involving the polycarbonate-based polyurethane, and so an even higher peel strength can be obtained between the surface 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 evaluation using gas chromatography (for example, GC-14B manufactured by Shimadzu Corporation and DB-WAX manufactured by J&W as a column) with 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 making the content of the polycarbonate-based polyurethane 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 by the polycarbonate-based polyurethane can be further strengthened, and the abrasion resistance of the artificial leather in the surface layer can be further improved. On the other hand, by making the content of the polycarbonate-based polyurethane preferably 60% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, not only can the artificial leather have higher flexibility, but also, even when the laminate is partially stretched by press molding, the laminate is flexible enough to easily conform to the molding die, and the surface layer is free of cracks or tears.

[0085] In the present invention, the content of polycarbonate-based polyurethane in 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 sample is a laminate, the surface layer is carefully peeled off from the test piece, and the backing layer and layers other than the artificial leather of the surface layer are removed, leaving only the artificial leather layer of the surface layer. In the case of the surface layer before the sample is laminated, the layers other than the artificial leather of the surface layer are removed. If the sample is artificial leather alone, evaluation begins with (iii). In the case of a fiber structure to which polycarbonate-based polyurethane has been applied before the sample is laminated, evaluation begins with (iv). (iii) 30% of the artificial leather layer in the thickness direction is removed from both surfaces, excluding the napped portions, by polishing 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 mean value (%) of the three test pieces is rounded to the nearest whole number 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)) x 100 (formula).

[0086] The number average molecular weight of the polycarbonate-based polyurethane can be determined by evaluating a 0.125 wt % N,N-dimethylformamide solution using gel permeation chromatography (for example, HLC-8220GPC manufactured by Tosoh Corporation, using Guard column α, TSKgel α-M, also manufactured by Tosoh Corporation, as the column).

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

[0088] [Artificial Leather] The surface layer of the laminate of the present 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 sufficiently 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 effect 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, the surface skin layer is carefully peeled off, and the backing layer and layers other than the artificial leather of the surface skin layer are removed. If the surface skin layer is obtained before lamination, the layers other than the artificial leather of the surface skin layer are removed. If the artificial leather is obtained alone, evaluation can be performed starting from (ii) without performing the above-mentioned removal work. (ii) With a lint brush or the like used to invert the nap of the napped portion on the surface of the artificial leather of the surface skin layer, a thin slice 1 mm thick is prepared in the cross-sectional direction 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, etc.). (iv) In the SEM image, 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 value (arithmetic mean) of the heights of the layer consisting only of ultrafine fibers measured at the 10 points is calculated, and the decimal point is discarded to obtain an integer value.

[0092] Of course, in order 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 particularly preferably a sheet-like shape. The components of the laminate will be described in order.

[0094] (1) Skin Layer The skin 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 surface layer is measured and calculated by the following method. (i) When the artificial leather of the surface layer has a napped portion on its surface, the nap of 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 an observation magnification of 30 to 90 times so that the presence of nap can be seen. (ii) Using image analysis software (having a function to calculate the area ratio of a specified pixel, for example, "ImageJ" from the National Institutes of Health (NIH)), the nap coverage of a total actual area of ​​9 mm2 is measured and calculated. ２ Total area of ​​the raised hair portion (mm ２ ) was calculated and used as the nap-standing coverage rate. The percentage of the total area was calculated by using image analysis software on the photographed SEM image to correct the 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 the 256-level image was binarized by setting 128 as the threshold, and the part (white part) where the pixel value of the grayscale image was 128 to 255 was considered to be the nap-standing part. In addition, in calculating the nap-standing coverage rate, if a substance that is not nap-standing, such as polyurethane being exposed or dust being attached, is calculated as nap-standing and has a significant impact on the nap-standing coverage rate, the image is manually edited and the color tone of the non-napped substance is set to 0, and that part is calculated as a non-napped 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, which 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, the term "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 of the content measured and calculated by the method described below is 0.05% by mass.

[0099] The dye content in the surface layer used in the laminate of the present invention is calculated by the following method. (i) When measuring from the laminate, the surface layer is carefully peeled off and all layers other than the surface layer of the backing layer are removed. If the surface layer alone is obtained before lamination, evaluation can be performed starting from (ii) without performing the above-mentioned removal process. (ii) 5 g of the surface layer is immersed in 30 mL of dimethylformamide or the like and refluxed at 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 to separate into methanol solution A in which the dye is dissolved and coagulated polymeric elastomer. (iv) The coagulated polymeric elastomer is dissolved in 20 mL of dimethylformamide or the like and reprecipitated in 200 mL of methanol to obtain methanol solution B in which the dye is dissolved. (v) Methanol solutions A and B are mixed, and solids are removed using a 0.45 μm mesh filter or equivalent. The residue obtained by distilling the methanol under reduced pressure is used as the dye, and its mass is measured. (vi) The dye content in the skin layer is calculated using the following formula, and the result is rounded to the nearest whole number: Dye content (mass %) = ((mass of dye) / (mass of skin layer)) × 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) A laminate or a single skin layer before lamination is obtained. If the sample has nap, a lint brush or the like is used to lay down the nap on the surface of the skin layer, and a 1 mm-thick thin section is prepared in the cross-sectional direction perpendicular to the longitudinal direction of the laminate. (ii) The cross-section of the skin layer of the laminate is observed at 90x magnification using an SEM (e.g., Keyence Corporation's "VHX-D500 / D510"). (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, as shown in FIG. 1. (iv) Calculate the average (arithmetic mean) of the lengths (mm) measured at the 10 points and round off to one decimal place.

[0102] 1 is a cross-sectional conceptual diagram illustrating and explaining one embodiment of the laminate of the present invention, in which a surface layer and a backing layer are laminated via an adhesive resin. The laminate (11) is formed by laminating a backing layer (13) and an artificial leather containing a fiber structure including ultrafine fiber bundles (12c) composed of ultrafine fibers (12a) and a 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 has 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, 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 an observation magnification of 30 to 90 times so that the presence of napped can be seen. (ii) Using image analysis software (having a function to calculate the area ratio of a specified pixel, for example, "ImageJ" from the National Institutes of Health (NIH)), 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, the napped portion on the surface is laid down using a lint brush or the like, and the observation image is taken using an SEM (for example, "VHX-D500 / D510" manufactured by Keyence Corporation) at an observation magnification of 30 to 90 times so that the presence of napped can be seen. ２ Total area of ​​resin portion (mm ２ The ratio of the total area is calculated and used as the area ratio of the resin portion of the skin layer. The total area ratio 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 the 256-level image by setting 128 as the threshold, and regarding the parts of the grayscale image where the pixel value is 0 to 127 (black part) as 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, spunlace 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. The polymer constituting the nonwoven fabric, i.e., the polymer that is the main component of the fibers constituting the nonwoven fabric (the polymer that accounts for 60% by mass of the polymers constituting the fibers), includes 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] Among these, it is more preferable that the backing layer is 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 can provide a laminate that combines material strength and moldability. Here, the term "main component" means the component that is the most abundant by mass among the components contained. Note that 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. The thickness of the backing layer is preferably 0.1 mm or more, more preferably 0.2 mm or more, and even more preferably 0.3 mm or more, so that the laminate has better peel strength and material strength, and has excellent shape retention after molding. On the other hand, the thickness of the backing layer is preferably 5.0 mm or less, more preferably 4.5 mm or less, and even more preferably 4.0 mm or less, so that the laminate has better moldability and is more flexible.

[0112] The thickness of the backing layer is measured and calculated using the following method: (i) A 1 mm-thick thin section is prepared in the cross-sectional direction 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, such as a Keyence VHX-D500 / D510 model). (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 FIG. 1. If the adhesive has penetrated the backing layer, the boundary is considered to be the top end of the backing layer that is incorporated into the adhesive resin (14). (iv) Calculate the average (arithmetic mean) of the lengths (mm) measured at the 10 points and round off to one decimal place.

[0113] (3) Adhesive Resin: The adhesive resin in this embodiment can be appropriately selected from 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 crosslinking reactions originating from the adhesive resin, resulting in high peel strength between the skin layer and the backing layer, making it preferable. Similarly, when the adhesive resin is acrylic resin, it is easy to form carbonyl bonds, resulting in high peel strength between the skin layer and the backing layer, making it preferable.

[0114] As described below, the polyurethane resin may be a two-component polyurethane adhesive comprising 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 making the thickness of the adhesive resin preferably 5 μm or more, more preferably 75 μm or more, and even more preferably 125 μm or more, the laminate has high moldability, which further suppresses wrinkles during molding of the laminate. Furthermore, by making the thickness of the adhesive resin preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 300 μm or less, the laminate becomes more flexible.

[0116] The thickness of the adhesive resin is measured and calculated by the following method: (i) Three 3 cm square test pieces are taken from any location on the laminate at equal 4 cm intervals in the longitudinal direction. (ii) The taken test pieces are cut parallel to the thickness direction. (iii) In the cross section exposed by cutting in the thickness direction, the boundary between the skin layer and the backing layer, which contains at least the adhesive resin, is observed at 500x magnification using a scanning electron microscope (SEM, for example, Keyence Corporation's "VHX-D500 / D510"). (iv) A 500 μm x 500 μm area containing 500 or more ultrafine fiber cross sections is defined in the boundary and photographed. Here, the "area containing 500 or more ultrafine fiber cross sections" refers to a region in the cross section of the boundary between the skin layer and the backing layer observed in (iii) above, in which the number of ultrafine fibers that can be observed in the cut cross section is 500 or more. (v) Calculate the average (arithmetic mean) of the thickness (μm) of the adhesive resin present in the above-mentioned region. The thickness of the adhesive resin here means the length of the perpendicular line (16) to the boundary (15) between the backing layer and the adhesive resin and the interface of the adhesive resin on the skin layer side (area with voids of 1 μm or more), as shown in Figure 1. Note that if the adhesive has penetrated the backing layer, the interface of the adhesive resin on the backing layer side (area 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 preferably 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 during the peeling is either cohesive failure of the adhesive resin, material failure of the backing layer, or interfacial failure between the adhesive resin and the backing layer, or a mixture of interfacial failure and cohesive failure.

[0118] A peel strength of preferably 7 N / cm or more, more preferably 8 N / cm or more, 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 a value measured in accordance with "6.3.1 Tensile strength and elongation (ISO method)" of JIS L1913:2010 "Test methods for general nonwoven fabrics," and a nonwoven fabric having an average tensile strength of 200 N / 5 cm or more in any two orthogonal directions is considered to be "high strength."

[0121] The peel strength is measured in accordance with JIS K6854-2:1999 "Adhesive - Peel Adhesion Strength Test Method," and refers to the peel strength between the skin layer and the backing layer when peeled at an angle of 180°. Specifically, it is measured and calculated by the following method: (i) A test piece measuring 150 mm length x 25 mm width is cut from the laminate. (ii) One end of the test piece is immersed in ethanol, immediately removed, and half of the skin layer is peeled off. (iii) After sufficient drying, the test piece is placed in a tensile tester (e.g., Instron Model 3343) with the skin layer side as the "flexible adherend" and the backing layer side as the "rigid adherend," and pulled 30 mm or more at a gripping speed of 100 mm / min, and the maximum strength is read. (iv) The failure mode is determined according to the following criteria: - Peeling due to failure within the skin layer: material failure of the skin layer - Peeling due to failure within the backing layer: material failure of the backing layer - Peeling between the adhesive resin and the skin layer: interfacial failure between the adhesive resin and the skin layer - Peeling between the adhesive resin and the backing layer: interfacial failure between the adhesive resin and the backing layer - Peeling due to failure within the adhesive resin: cohesive failure of the adhesive resin - If multiple failure modes are observed, it is judged to be mixed. For example, if there is both a section where peeling occurs between the adhesive resin and the backing layer and a section where peeling occurs due to failure within the adhesive resin, it is considered to be "mixed interfacial failure / cohesive failure between the adhesive resin and the backing layer."

[0122] In the laminate of this embodiment, the depth of the adhesive resin filling the skin layer is preferably 5 μm or more and less than 95 μm. This filling depth is preferably 5 μm or more, more preferably 15 μm or more, and even more preferably 25 μm or more, resulting in a laminate with excellent peel strength between the skin layer and the backing layer. On the other hand, a filling depth of 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 is measured and calculated by the following method: (i) Three 3 cm square test pieces are taken at equal 4 cm intervals in the longitudinal direction from any location on the laminate. (ii) The taken test pieces are cut parallel to the thickness direction. (iii) In the cross section exposed by cutting in the thickness direction, the boundary between the skin layer and the backing layer, which contains at least the adhesive resin, is observed at 500x magnification using a SEM (e.g., Keyence Corporation's "VHX-D500 / D510"). (iv) A 500 μm × 500 μm region containing 500 or more ultrafine fiber cross sections is defined in the boundary portion. Here, the region containing 500 or more ultrafine fiber cross sections refers to a region in the cross section observed in (iii) above where 500 or more ultrafine fibers can be observed as cut cross sections. (v) Calculate the average (arithmetic mean) of the filling depth (μm) of adhesive resin, etc. present in the region. The filling depth here refers to the distance from the center of the ultrafine fiber (17) closest to the backing layer (13) among the ultrafine fibers whose entire periphery is covered with the adhesive resin, as illustrated in FIG. 1, to the point where a void of 1 μm or more exists along a 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, each 5 cm long and 5 cm wide, are randomly taken from the laminate. (ii) The thickness of the test pieces in (i) is measured to the nearest 0.01 mm using a thickness measuring device (for example, the "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) is calculated and rounded 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 basis weight is preferably 170 g / m or less. ２ More preferably, 200 g / m ２ By setting the density to 1000 g / m or more, 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 or less, more preferably 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, each 30 cm long and 30 cm wide, are randomly taken from the laminate. (ii) The mass of the test pieces (i) is measured. (iii) The mass per unit area of ​​each test piece is calculated using the following formula: Mass per unit area (g / m ２ ) = mass of test piece (g) / area of ​​test piece (m ２ (iv) The arithmetic mean value (g / m) of the mass per unit area obtained in (iii) 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 formed 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 shape of the openings can be any shape depending on the desired design, and can be round, oval, polygonal (flat, triangular, etc.), sectoral, cross, hollow, Y-shaped, T-shaped, U-shaped, or other irregular shapes. The arrangement pattern of the openings is not particularly limited and may be arranged regularly or irregularly, but from the viewpoint of exerting uniform strength throughout the laminate, it is preferable that the openings be arranged regularly at a predetermined interval. From the viewpoint of achieving both breathability and strength of the laminate, the opening diameter is preferably 0.1 mm or more and 3.0 mm or less, and the opening ratio is preferably 20% or less from the viewpoint of maintaining strength, resistance to deformation of the opening holes, and resistance to fraying around the holes.

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

[0131] (1) Formation of the Surface Layer The surface layer of this embodiment is the aforementioned artificial leather, and it is preferable to form this artificial leather by including the following steps: Step (1-1): Step of forming ultrafine fiber-developing fibers Step (1-2): Step of forming a fiber structure Step (1-3): Step of forming ultrafine fibers Step (1-4): 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): Step of polishing the sheet-like material Step (1-6): Step of dyeing the greige material Step (1-7): Other finishing steps It goes without saying that the sheet-like material obtained may be used as artificial leather not only if it has undergone only steps (1-1) to (1-4), but also if it has undergone one or more steps of steps (1-5), (1-6), and (1-7) in addition to steps (1-1) to (1-4). Each step will be described in detail below.

[0133] <Step (1-1): Step of forming ultrafine fiber-developing fiber> In this step, an ultrafine fiber-developing fiber having an islands-in-sea composite structure is formed, which is composed 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 fiber is preferred from the viewpoint of the 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] As a method for incorporating a pigment into the island portions, either the pigment and polyester resin may be directly kneaded to a predetermined amount, or a method of mixing a masterbatch with polyester resin chips and spinning them can be used. Among these, the method of mixing the polyester resin chips with a masterbatch is preferred because it allows the amount of pigment contained in the ultrafine fibers to be appropriately adjusted. The pigment content in the masterbatch is preferably in the range of 10% by mass or more and 40% by mass or less. The pigment content in the ultrafine fibers is preferably in the range of 0.1% by mass or more and 2.0% by mass or less.

[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 portions of an islands-in-sea type composite fiber is measured and calculated by the following method. (i) Ten 20 cm long islands-in-sea type composite fibers are bundled together. (ii) The sea portion is dissolved and removed from the sample obtained in (i), and then the sample is air-dried. (iii) The sample is subjected to 10 tests (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 according to "8.5.1 Standard Time Test" in "8.5 Tensile Strength and Elongation" of JIS L1013:2010 "Test Methods for Chemical Fiber Filament Yarns." (iv) The arithmetic mean value (cN / dtex) of the test results obtained in (iii) is rounded to one decimal place.

[0139] <Step (1-2): Step of forming a fiber structure> This step is for forming a fiber structure containing the ultrafine fiber development type 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 the 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 0.45g / cm or more ３ The apparent density is preferably 0.15 g / cm or less. ３ By setting the apparent density at 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 water-soluble resin can be added to the fiber structure by impregnating the fiber structure with an aqueous solution of a water-soluble resin such as polyacrylamide (PAA), polyvinyl alcohol (PVA), or carboxymethyl cellulose, followed by drying. Adding a water-soluble resin to the fiber structure before the "step of forming ultrafine fibers" in step (1-3) fixes the fibers, resulting in a fiber structure that is less susceptible to dimensional changes due to process tension, etc., 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 napped 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) 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 applying 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] Methods for fixing the polycarbonate-based polyurethane to the fiber structure after impregnating the fiber structure with the polycarbonate-based polyurethane solution 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 solvent is coagulated; 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 before this polishing to obtain two sheet-like materials.

[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] <Step (1-6): Step of Dyeing the Grey Machine> In this step, the grey machine is dyed. Note that in the present case, an embodiment in which no dyeing is performed is also preferred. Considering discoloration due to exposure to molding, thermal history, and the like, the most preferred embodiment is to use no dye or to limit the amount of dye used to the small amount required for toning. When dyeing, examples of dyeing methods that can be used include flow dyeing using a jigger dyeing machine or a flow 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. Among these, it is preferable to use a flow dyeing machine because it can provide a soft texture and also in terms of quality and dignity.

[0159] <Step (1-7): Other Finishing Steps> If necessary, the obtained sheet-like material or greige machine 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] <Skin 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, a bending resistance in the longitudinal direction of the skin layer of preferably 300 mm or less, more preferably 250 mm or less, and even more preferably 200 mm or less can further suppress the occurrence of wrinkles and sagging during the lamination process with the backing layer, thereby further improving the operability of the lamination process.

[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, the skin layer is carefully peeled off and the layers other than the skin layer of the backing material layer are removed. If a single skin layer before lamination is obtained, evaluation can be performed starting from (ii) without performing the above-mentioned removal work. (ii) Five 30 x 2 cm test pieces are taken in the longitudinal direction from any position on the skin layer. (iii) The skin layer is measured according to Method A (45° cantilever method) described in 8.21.1 of "Bending Resistance" in JIS L1096:2010 "Testing Methods for Woven and Knit Fabrics," and the average value of the five pieces is calculated.

[0166] The longitudinal direction of the skin layer in the present invention is determined by the following method. When the longitudinal direction can be determined from the appearance of the skin layer, i.e., when the winding direction of the skin layer roll can be uniquely determined, this direction is considered to be 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) An arbitrary direction is determined within the plane of the skin layer, and the test is performed along that direction according to "6.3.1 Tensile Strength and Elongation (ISO Method)" of JIS L1913:2010 "Test Methods for General Nonwoven Fabrics." (ii) The test is also performed in the same way 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 this is considered to be the tensile strength of the skin layer in each direction. (iv) The direction with the highest measured value is considered to be the longitudinal direction of the skin layer. When there are two or more directions with the highest tensile strength, the direction perpendicular to these directions in which the tensile strength is lower is defined as the longitudinal direction of the skin layer. When there are two or more directions with the highest tensile strength and the tensile strengths perpendicular to these directions are also equal, for example, when the tensile strengths in all four directions are equal, any of the four directions is defined as 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 having a rich feel and an excellent texture. ２ or less, more preferably 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 surface 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, each 30 cm long and 30 cm wide, are randomly taken from the surface layer to be used in the laminate. (ii) The mass of the test pieces in (i) is measured. (iii) The mass per unit area of ​​each test piece is calculated using the following formula: Mass per unit area (g / m ２ ) = mass of test piece (g) / area of ​​test piece (m ２ (iv) The arithmetic mean value (g / m) of the mass per unit area obtained in (iii) ２ ) is rounded down to an integer value.

[0169] (2) Formation of the Laminate 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 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 suppress the VOCs emitted when the adhesive is dried, and further to suppress the VOC emissions from the obtained 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 step 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 the backing layer are temporarily bonded. Therefore, the crosslinking reaction between the isocyanate compound and the adhesive resin of the polycarbonate polyurethane of the sheet B that forms the surface layer proceeds more easily, resulting in improved peel strength between the surface layer and the backing layer.

[0175] In addition to the isocyanate compound and the 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 5 to 30 parts by weight of an isocyanate compound per 100 parts by weight of the polyol compound, which is the main component. By using 5 or more parts by weight 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 or less parts by weight of the isocyanate compound, the pot life of the adhesive can be further extended, improving operability.

[0177] 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 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. The use of 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 that 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 that 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 uniformly.

[0179] The amount of adhesive applied to the backing layer is 15 g / m2 in terms of 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. ２ More 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 or less, more preferably 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 even better peel strength and material strength and even better shape retention after molding can be obtained. ２ or less, more preferably 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 will be the backing layer in this embodiment, 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, each 30 cm long and 30 cm wide, are randomly taken from the backing layer to be used in the laminate before lamination. (ii) The mass of the test pieces (i) is measured. (iii) The mass per unit area of ​​each test piece is calculated using the following formula: Mass per unit area (g / m ２ ) = mass of test piece (g) / area of ​​test piece (m ２ (iv) The arithmetic mean value (g / m) of the mass per unit area obtained in (iii) ２ ) is rounded down to an integer value.

[0182] A laminate can then be obtained by overlapping and pressing the adhesive-coated surface of Sheet A, which will serve as the backing layer, and the back surface of Sheet B, which will serve as the skin (the surface of the laminate that does not serve as the design surface). 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 performing pressure bonding using 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 molecular motion of the adhesive between the backing layer and the skin layer and of the polyurethane in the skin layer becomes more active, which facilitates the crosslinking reaction caused by the adhesive and allows for 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, thereby achieving higher peel strength between the skin layer and the backing layer. A temperature of 200° C. or lower, more preferably 140° C. or lower, provides a laminate of even higher quality.

[0186] The pressure of the calender roll in this case is preferably 10 N / cm or more and 1000 N / cm or less. By setting it to preferably 20 N / cm or more, more preferably 30 N / cm or more, the adhesive can easily penetrate into the interior of the ultrafine fiber bundle, and the peel strength can be improved. On the other hand, by setting it 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, a steam temperature of 100°C or lower, more preferably 90°C or lower, can provide 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 molded 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.

[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 Methods] 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 Skin Layer (1-1) Physical Properties of the Fiber Structure (1-1-1) Average Particle Diameter (μm) and Coefficient of Variation of Particle Diameter (%) of Black Pigments and Chromatic Pigments Included in Ultrafine Fibers The average particle diameter (μm) of the black pigments and chromatic pigments included in ultrafine fibers was measured and calculated by the method described above using a transmission electron microscope (TEM) "H7700" manufactured by Hitachi High-Technologies Corporation and image analysis software "VW-9000" manufactured by Keyence Corporation.

[0196] (1-1-2) Pigment Content (% by mass) in Ultrafine Fibers The pigment content (% by mass) in 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 (μm) of Ultrafine Fibers The average single fiber diameter (μm) of ultrafine fibers was measured and calculated by the above-described 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 (% by mass) of Polycarbonate-Based Polyurethane in the Skin Layer The content (% by mass) of polycarbonate-based polyurethane in the skin layer was measured and calculated by the method described above.

[0199] (1-3) Physical Properties of the Epidermal Layer (1-3-1) Pile Length (μm) of Artificial Leather The pile length (μm) was measured and calculated using a scanning electron microscope (SEM) model VHX-D500 / D510 manufactured by Keyence Corporation, according to the method described above.

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

[0201] (1-3-3) Pile coverage rate (%), surface area ratio (%) of resin layer The pile coverage rate (%) and surface area ratio (%) of resin layer were measured and calculated by the above-mentioned method using "VHX-D500 / D510 type" manufactured by Keyence Corporation as SEM and "ImageJ" of the National Institutes of Health (NIH) as 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 SEM "VHX-D500 / D510" manufactured by Keyence Corporation, according to 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 ) Weight of backing layer (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" manufactured by Keyence Corporation, according to the method described above.

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

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

[0210] (4) Physical Properties of the Laminate (4-1) Thickness (mm) The thickness (mm) of the laminate was measured and calculated using a "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 ) Weight per unit area of ​​laminate (g / m ２ ) was measured and calculated by the method described above.

[0212] (4-3) Breakdown mode when peeling is attempted, and peel strength (N / cm) when peeling The evaluation of the breakdown mode when peeling is attempted and the peel strength (N / cm) when peeling are evaluated, measured, and calculated using a tensile tester manufactured by Instron, Model: 3343, according to the method described above.

[0213] (4-4) The color development of the color-developing laminate was evaluated by 10 healthy adult panelists according to the following criteria, and the evaluation result with the largest number of participants was adopted. In the present invention, a good level is "grade 4 to grade 5." Grade 5: The color was very vivid, or the color depth and brightness were outstanding, and the appearance was good. Grade 4: An evaluation between grades 5 and 3. Grade 3: The color was vivid overall, but there were some parts that were slightly less good. Grade 2: An evaluation between grades 3 and 1. Grade 1: The 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, with the evaluation result with the largest number of participants being adopted. The surface quality was evaluated by placing the laminate (23) on an inspection table (22) parallel to the floor (21) as shown in FIG. 2 , and visually inspecting the laminate (23) at a 45° angle from the plane of the inspection table so that the length of the line (25) connecting the visual inspection position (24) and the laminate (23) was 50 cm. A 32 W fluorescent lamp (26) was installed on the inspection table, 150 cm above the top surface 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. Grades 4 to 5 of surface quality were considered to be good. Grade 5: There was uniform fiber nap, the fiber dispersion was good, and the appearance was good. Grade 4: An evaluation between grades 5 and 3. Grade 3: There were some areas where the fiber nap was not quite good. Grade 2: An evaluation between grades 3 and 1. Grade 1: Overall, the fiber nap and dispersion were very poor, and the appearance was poor.

[0215] (4-6) Evaluation (Grade) of Bends After Press Molding For the evaluation (grade) of bends after press molding, a top-hat-shaped molded specimen with a diameter of 45 mm, a height of 10 mm, and a maximum bend expansion ratio of 120% was prepared using a male / female cylindrical container lid mold, and evaluation was performed. Specifically, the laminate was placed 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 bends 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 A4-sized (210 mm x 297 mm) evaluation samples were taken from any location on the pre-molded laminate. (b) A 5 mm x 5 mm grid was drawn on the surface of the skin layer side of the collected evaluation samples. (c) The area of ​​the grids drawn on the surface layer side of the evaluation sample obtained by molding was measured using a digital microscope, Keyence Corporation's "VHX-5000," adjusted to 20x magnification. (d) The measured grid area was divided by the original area before molding to obtain the expansion rate (%). Grade 5: The appearance was very good (there was no deterioration in quality due to increased exposure of polyurethane on the surface of the laminate after processing). Grade 4: A rating between Grades 5 and 3. Grade 3: Fair (there was an increase in exposure of polyurethane on the surface of the laminate after processing, and deterioration in quality was observed). Grade 2: A rating between Grades 3 and 1. Grade 1: The appearance was poor (there was a significant increase in exposure of polyurethane on the surface of the laminate after processing, and deterioration in quality was significant).

[0216] (4-7) Evaluation (grade) of discoloration after press molding For the evaluation (grade) of 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 skin before molding and judged using the discoloration gray scale specified in JIS L0804:2004 "Gray scale for discoloration," with grade 4 or higher being considered a pass.

[0217] (4-8) Rubbing Fastness (Class) 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 Rubbing"). White cotton cloth of each condition, dry cloth and sweat 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 reciprocations per minute over a distance of 100 mm. After the test, the degree of staining of the sample after the friction test was determined using the staining gray scale specified in JIS L0805:2005 "Staining Gray Scale," with a grade of 4 or higher being considered a pass. The sweat cloth refers to a white cotton cloth immersed in artificial sweat for 10 minutes. The artificial sweat solution was prepared by dissolving the following in distilled water to make 1 L. - 8 g of disodium hydrogen phosphate dodecahydrate as specified in JIS K9019:2021 "disodium hydrogen phosphate dodecahydrate (reagent)", - 8 g of sodium chloride as specified in JIS K8150:2006 "sodium chloride (reagent)", - 5 g of acetic acid as specified in JIS K8355:2006 "acetic acid (reagent)".

[0218] [Notation of Chemical Substances, etc.] The meanings of the abbreviations of chemical substances, etc. used in the examples and comparative examples are as follows: (Resin of ultrafine fibers) PET: polyethylene terephthalate PLA: polylactic acid (Pigment) CB: carbon black (Resin related to ultrafine fibers) P1: polyethylene terephthalate having an intrinsic viscosity (IV value) of 0.72 P2: 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 20 mass% relative to the mass of the masterbatch P3: melt flow rate (MFR) of 30 g / 10 min, melting point of 170° C., solid density of 1.240 g / cm ３P4: Masterbatch obtained by adding 20% ​​by mass of carbon black (average particle size: 0.02 μm, coefficient of variation (CV) of particle size: 20%) as a black pigment to the masterbatch in the amount of 20% by mass relative to the mass of the masterbatch in the above P3. P5: Masterbatch (polycarbonate-based polyurethane) obtained by adding 20% ​​by mass of 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.) as a blue pigment to the masterbatch in the amount of 20% by mass relative to the mass of the masterbatch in the above P1. PCPU: Polycarbonate-based polyurethane C9 / C8 ２ｍ : A copolymerized 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]

[0220] (wherein n and m are positive integers, and the copolymer is a random copolymer. R is (CH ２ ) ９ Or CH ２ -CH(CH ３ )-(CH ２ ) ６ ) C6 / C5 ３ｍ : A copolymerized 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]

[0222] (wherein x and y are positive integers, and the copolymer is a random copolymer. R is (CH ２ ) ６ Or (CH ２ ) ２ -CH(CH ３ )-(CH ２ ) 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]

[0224] (wherein x and y are positive integers, and the copolymer is a random copolymer. R is (CH ２ ) 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]

[0226] (wherein x and y are positive integers, and the copolymer is a random copolymer. R is (CH ２ ) ４ Or (CH ２ ) 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] The following Production Examples 1 to 4 show production examples of polyurethane solutions used in the Examples and Comparative Examples.

[0228] [Production Example 1] Polyol: C9 / C8 ２ｍ 60 parts by mass of C6 / C5 ３ｍ 40 parts by mass of the above and MDI as an organic diisocyanate were charged into a four-neck separable flask equipped with a condenser so that the molar ratio of the total amount of polyol to MDI was 1:3, and the mixture was reacted with stirring under a nitrogen atmosphere while controlling the temperature within the range of 40°C to 60°C.

[0229] Then, EG as a chain extender was diluted in DMF and added dropwise to the reaction mixture while controlling the temperature in the range of 50 to 60°C. After that, the mixture was gradually diluted with DMF, and after about 10 hours, a polycarbonate-based polyurethane solution with a solid 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] [Production 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] [Production 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] [Production Example 4] Polyol: 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] [Production Example 5] 50 parts by mass of C4 / C10 polyol 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 Skin Layer <Step of Forming Ultrafine Fiber-Containing Fiber> Using polystyrene as the sea component and a polymer obtained by mixing P1 and P2 in a mass ratio of P1:P2 = 95:5 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, and the number of islands was 16 islands / 1 filament. Next, the ultrafine fiber-container fiber was drawn 2.7 times in a spinning oil bath heated to 90°C to obtain an islands-in-sea type composite fiber having an average single fiber diameter of 20 µm.

[0236] <Step of forming a fiber structure> Next, the obtained islands-in-sea type 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] <Step of forming ultrafine fibers> The obtained fiber structure was immersed in trichloroethylene and squeezed with a mangle, which was repeated 10 times to obtain a sheet made of ultrafine fibers from which the sea component of the islands-in-sea type composite fibers 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 coagulating the polycarbonate-based polyurethane X. Thereafter, the sheet was dried with hot air at a temperature of 110°C for 10 minutes, thereby obtaining a sheet-like material to which the polycarbonate-based polyurethane X had been applied.

[0239] <Step of grinding the sheet-like material> The sheet-like material obtained as described above was sliced ​​perpendicularly in the thickness direction to cut it in half, 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] <Step of dyeing the greige 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. Thereafter, the fabric was dried in a dryer to obtain ultrafine fibers having 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%. The dye content in the resulting artificial leather was 3% by mass.

[0241] (2) Formation of Laminate <Backing Layer> A foamed resin sheet (thickness 2.4 mm, basis weight 170 g / m) made of a polyolefin resin. ２ , expansion ratio 15 times) was used.

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

[0243] <Step of forming a laminate> The adhesive resin on the release paper was placed in a drying oven with the oven temperature controlled between 80°C and 100°C and dried. 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 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 into an adhesive resin. The resulting laminate had good color development and friction fastness in the skin 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.

[0244] [Example 2] (1) In the step of forming a fiber structure in the formation of the surface layer, a fiber structure (short fiber nonwoven fabric) having a fiber web thickness of 2.1 mm was used, but a fiber structure (short fiber nonwoven fabric) having 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 thus obtained was used, and further, in the step of forming a laminate in (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 a fiber structure in the formation of the surface layer, a fiber structure (short fiber nonwoven fabric) having a fiber web thickness of 2.1 mm was used, but a fiber structure (short fiber nonwoven fabric) having 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 ２The artificial leather thus obtained was used, and further, in the step of forming a laminate in (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 step of polishing the sheet-like material in the formation of the surface layer, sandpaper with a grit size of 180 was used, but sandpaper with a grit size of 100 was used for grinding, resulting in a basis weight of 232 g / m ２ , and artificial leather with a nap coverage of 70% was used. Furthermore, in the <Step of forming a laminate> of (2) Formation of 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> was a polyester knitted fabric (fineness 110T / 48f, basis weight 340 g / m ２ , front structure 10 / 34, back structure 10 / 12), and in the <step 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 form the surface layer, the DMF solution S1 of polycarbonate-based polyurethane X was used, but the DMF solution S4 of polycarbonate-based polyurethane Y was used instead. ２ The artificial leather thus obtained was used, and further, in the step of forming a laminate in (2) forming a laminate, the amount of adhesive resin applied was set to 41 g / m２ 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 step of forming ultrafine fiber-developing fibers in the formation of 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 in (2) forming a laminate, the amount of adhesive resin applied was set to 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 ultrafine fiber-developing fibers in the formation of 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 in (2) forming a laminate, the amount of adhesive resin applied was set to 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 step of dyeing the grey fabric in the formation of the skin layer, the following step of forming a resin layer was 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 on the nap-bearing side of the artificial leather. The rotary coating method was repeated three times to form three discontinuous polyurethane resin layers covering the surface. The resin portions were scattered in islands on the surface, the nap coverage rate was 40%, and the total thickness of the polyurethane resin layer was 0.2 mm.

[0253] [Example 10] (1) In the step of dyeing the grey fabric in the formation of the surface layer, the dye concentration was increased to obtain an artificial leather with a dye content of 7% by mass and a basis weight of 225 g / m ２ The artificial leather was used, and 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 abrasion 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 form the surface layer, the DMF solution S1 of polycarbonate-based polyurethane X was used, but the DMF solution S5 of polycarbonate-based polyurethane Y was used instead. ２ A 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 <step of applying polycarbonate-based polyurethane> for forming the surface layer was being carried out, but the following <step of applying polyurethane α> was carried out instead, and the basis weight was 208 g / m ２ The artificial leather thus obtained was used, and further, in the step of forming a laminate in (2) forming a laminate, the amount of adhesive resin applied was set to 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, thereby coagulating the polyurethane α. Thereafter, the sheet was dried with hot air at a temperature of 110° C. for 10 minutes, thereby obtaining a sheet-like material to which polyurethane α was added.

[0258] [Comparative Example 2] (1) The <step of applying polycarbonate-based polyurethane> for forming the surface layer was being carried out, but the following <step of applying polyurethane β> was carried out instead, and the basis weight was 220 g / m ２ The artificial leather thus obtained was used, and further, in the step of forming a laminate in (2) forming a laminate, the amount of adhesive resin applied was set to 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 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, thereby coagulating the polyurethane β. Thereafter, the sheet was dried with hot air at a temperature of 110° C. for 10 minutes, thereby obtaining a sheet-like material to which polyurethane β was added.

[0260] [Comparative Example 3] (1) In the step of forming ultrafine fiber-developing fibers in the formation of the skin layer, P1 and P2 were used as island components, but only P1 was used. Furthermore, in the step of dyeing the greige fabric, the dye concentration was increased, so that the dye content in the artificial leather was 7% by mass and the basis weight was 210 g / m. ２ The artificial leather thus obtained was used, and further, in the step of forming a laminate in (2) forming a laminate, the amount of adhesive resin applied was set to 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 obtained laminate had good friction fastness 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]

[0263]

[0264]

[0265]

[0266]

[0267]

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

[0269] On the other hand, as shown in Tables 5 and 6, when a polyurethane not having 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 due to 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.

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

Claims

1. A laminate comprising a surface layer including artificial leather and a backing layer laminated together via an adhesive resin, wherein the artificial leather includes a fiber structure and a polycarbonate-based polyurethane, the fiber structure includes 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 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), and the backing layer is at least one material selected from the group consisting of woven or knitted fabrics, nonwoven fabrics, and foamed resin sheets. (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.) (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.) (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. A laminate according to claim 1 or 2, wherein the peel strength when the surface layer is peeled from the laminate is 7 N / cm or more and 16 N / cm or less, and the failure mode during the peeling is either cohesive failure of the adhesive resin, material failure of the backing layer, or interfacial failure or a mixture of interfacial failure and cohesive failure between the adhesive resin and the backing layer.

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, which has 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 a laminate according to claim 1 or 2, 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 together 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. Furniture comprising the laminate of claim 1 or 2.

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