Composite body, vehicle interior material including same, vehicle component, seat

Abstract

The present invention addresses the problem of providing a sheet that has favorable surface quality and texture as well as favorable strength and flame-retardance performance without being susceptible to seam spotting. The present invention relates to a composite body that is formed by adjacently layering an artificial leather and a woven or knitted article a. The artificial leather includes: a fiber structure that includes a base material composed of ultrafine fibers as a constituent element; and a polymer elastic body. The woven or knitted article a includes modacrylic fibers. An adhesive resin is present in spots between the artificial leather and the woven or knitted fabric a.

Description

Composites and vehicle interior materials, vehicle parts, and seats containing the composites

[0001] The present invention relates to a composite in which an artificial leather and a woven or knitted fabric are laminated adjacent to each other.

[0002] Artificial leather, which mainly contains a fiber structure containing ultrafine fibers and a polymeric elastomer, is more durable than natural leather and can be made to have uniform quality, and is therefore used in a variety of fields, including vehicle interior materials, interior goods, shoes, clothing, etc. When this artificial leather is used for vehicle seats, furniture, etc., it is required to have properties such as strength and flame retardancy in addition to good surface quality and texture.

[0003] Various proposals have been made to impart strength and flame retardancy to artificial leather. For example, Patent Document 1 proposes a flame-retardant artificial leather characterized by being characterized in that an artificial leather comprising a thermoplastic synthetic fiber fabric made of woven, knitted, or nonwoven fabric and a polymeric elastomer impregnated therein is impregnated with a flame-retardant resin composition containing ammonium polyphosphate that has been treated to make it difficult to dissolve in water, a triazine-based flame retardant having a specific range of water solubility, and a binder resin. Patent Document 1 also describes that the production method described in Patent Document 1 can provide a flame-retardant artificial leather that has excellent flame retardancy without impairing the inherent soft texture of the artificial leather, and that has excellent edge resistance by suppressing the occurrence of scratches (which will be described later), and that has excellent heat resistance by suppressing discoloration of the resin composition even when exposed to high temperatures.

[0004] Patent Document 2 proposes a flame-retardant leather-like sheet substrate comprising a nonwoven fabric in which ultrafine fibers are three-dimensionally entangled and a polymeric elastomer, in which at least a portion of the ultrafine fibers are made of an organic phosphorus component copolymerized polyester and the polymeric elastomer is made of a polycarbonate-based polyurethane copolymerized with an organic phosphorus component. It also describes that this configuration results in a halogen-free, excellent flame retardancy, and extremely excellent durability of the flame retardancy.

[0005] Furthermore, Patent Document 3 proposes an artificial leather having an apparent density within a specific range, which comprises a nonwoven fabric in which a blend of fibers mainly composed of polyester shrinkable fiber, latent crimp fiber, and meta-aramid fiber is entangled and in which the shrinkage and crimping of each fiber are manifested, and which is characterized by the content of each fiber being specific.It is stated that this configuration results in significantly improved texture and flame retardancy compared to conventional artificial leathers having the same apparent density.

[0006] JP 2013-227685 A JP 2002-201574 A JP 2008-133578 A

[0007] Incidentally, a known technique for imparting flame retardancy to artificial leather is to apply a water-soluble flame retardant such as guanidine phosphate to the entire artificial leather. However, this method has problems such as the loss of the smooth feel of the raised nap on the surface of the artificial leather, and when the artificial leather absorbs moisture and undergoes a process of drying, the moisture causes the guanidine phosphate to dissolve and migrate to the surface, forming ring-shaped stains, a phenomenon known as "edge marks," which significantly impairs the design of the artificial leather.

[0008] The technology proposed in Patent Document 1 makes it possible to obtain artificial leather that is less harsh and has a certain level of flame retardancy while maintaining a smooth surface. However, because a flame-retardant resin composition containing a binder resin is added, there is room for improvement in the texture and drape of the artificial leather.

[0009] On the other hand, in the technology proposed in Patent Document 2, the polymer elastomer, which is an important constituent substance for imparting strength and texture to artificial leather, is polyurethane copolymerized with an organic phosphorus component, and therefore the design results in a lower texture and durability compared to ordinary polymer elastomers.

[0010] Furthermore, the technology proposed in Patent Document 3 involves blending multiple types of fibers, such as polyester fibers and meta-aramid fibers, in the fiber structure of the artificial leather, making it difficult to achieve uniform nap raising and dyeing, resulting in uneven surface quality.

[0011] The present invention has been made in consideration of the above circumstances, and its object is to provide a sheet that is smooth and has good surface quality and texture, as well as strength and flame retardancy.

[0012] As a result of extensive research conducted by the inventors in order to achieve the above object, it was discovered that by laminating artificial leather with a woven or knitted fabric containing a specific flame-retardant fiber to form a composite, and by having an adhesive resin present in a dispersed state between the layers of the artificial leather and the woven or knitted fabric, a composite having good surface quality and texture as well as strength and flame retardancy can be obtained.

[0013] The present invention has been completed based on these findings, and provides the following inventions.

[0014] [1] A composite formed by adjacently laminating an artificial leather and a woven or knitted fabric (a), wherein the artificial leather comprises: a fiber structure including, as a component, a substrate made of ultrafine fibers; and a polymeric elastomer; the woven or knitted fabric (a) comprises modacrylic fibers; and an adhesive resin is present discretely between the layers of the artificial leather and the woven or knitted fabric (a).

[0015] [2] The composite according to [1], wherein the content of polyester fiber in the woven or knitted fabric a is 5% by mass or more and 50% by mass or less.

[0016] [3] The composite according to [1] or [2], wherein the content of modacrylic fiber in the composite is 20% by mass or more and 50% by mass or less.

[0017] [4] The composite according to any one of [1] to [3], wherein the fiber structure further comprises a woven or knitted fabric b.

[0018] [5] A vehicle interior material comprising the composite according to any one of [1] to [4].

[0019] [6] A vehicle part comprising the composite material according to any one of [1] to [4].

[0020] [7] A seat comprising the composite according to any one of [1] to [4].

[0021] According to the present invention, a composite can be obtained which is smooth and has good surface quality and texture, as well as excellent strength and flame retardancy.

[0022] FIG. 1 is a cross-sectional view of an artificial leather illustrating and explaining a method for measuring and calculating nap length for the composite artificial leather of the present invention. FIG. 2 is a conceptual perspective view illustrating and explaining one embodiment of an adhesive resin for the composite of the present invention (arranged in a dot pattern). FIG. 3 is a conceptual perspective view illustrating and explaining one embodiment of an adhesive resin for the composite of the present invention (arranged in a grid pattern). FIG. 4 is a conceptual perspective view illustrating and explaining one embodiment of an adhesive resin for the composite of the present invention (arranged in a stripe pattern). FIG. 5 is a conceptual perspective view illustrating and explaining one embodiment of an adhesive resin for the composite of the present invention (arranged in a random mesh pattern). FIG. 6 is a conceptual perspective view illustrating and explaining a form of an adhesive resin that is not a composite of the present invention (a state in which the adhesive resin is present substantially over the entire surface). FIG. 7 is a conceptual perspective view illustrating and explaining a form of an adhesive resin that is not a composite of the present invention (a state in which the adhesive resin is arranged only at the end of woven or knitted fabric a). FIG. 8 is a perspective conceptual diagram illustrating and explaining the form of the adhesive resin of the present invention that is not a composite (a state in which the adhesive resin is locally disposed only in a part of the woven or knitted fabric a).

[0023] The composite of the present invention is a composite formed by adjacently laminating an artificial leather and a woven or knitted fabric (a), wherein the artificial leather comprises a fiber structure including a substrate composed of ultrafine fibers as a component, and a polymeric elastomer, the woven or knitted fabric (a) comprises modacrylic fibers, and an adhesive resin is present in a dispersed state between the layers of the artificial leather and the woven or knitted fabric. These components will be described in detail below, but the present invention is not limited to the scope described below as long as it does not deviate from the gist of the present invention, and various modifications are possible within the scope of the present invention.

[0024] In the present invention, the term "woven or knitted fabric" is a general term for woven fabrics and knitted fabrics.

[0025] [Substrate Composed of Ultrafine Fibers] First, the artificial leather according to the composite of the present invention includes a fiber structure, and the fiber structure includes a substrate composed of ultrafine fibers as a constituent element.

[0026] The ultrafine fibers are preferably made of a thermoplastic resin. Examples of thermoplastic resins that can be formed into fibers include polyester-based resins such as "polyethylene terephthalate, polybutylene terephthalate, and polyester elastomers," polyamide-based resins such as "polyamide 6, polyamide 66, and polyamide elastomers," polyurethane-based resins, polyolefin-based resins, and acrylonitrile-based resins. However, polyester-based resins are preferred from the viewpoints of durability, particularly mechanical strength and heat resistance. In this invention, "polyester-based resin" refers to a resin in which the molar fraction of the polyester unit in the repeating units is 80 mol % to 100 mol %. Unless otherwise specified, the term "...-based resin" is used in the same sense.

[0027] Examples of the polyester resin include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate. Among these, polyethylene terephthalate, which is the most widely used, or a polyester copolymer containing mainly ethylene terephthalate units is preferably used.

[0028] If necessary, inorganic particles such as titanium oxide particles, lubricants, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, antibacterial agents, etc. can be added to the above-mentioned thermoplastic resins within the scope of the present invention. In particular, when the artificial leather is to be colored deeply, it is preferable that the thermoplastic resin constituting the ultrafine fibers contains a black pigment such as carbon black and / or a chromatic pigment such as nickel titanium yellow.

[0029] In the present invention, ultrafine fibers refer to fibers having a single fiber diameter of 15.0 μm or less, and the average single fiber diameter of these ultrafine fibers is preferably 0.1 μm or more and 10.0 μm or less. By setting the average single fiber diameter of the ultrafine fibers to a range of preferably 0.1 μm or more, more preferably 0.5 μm or more, a composite having excellent color development after dyeing, light fastness, and friction fastness, as well as stability during spinning, can be obtained. On the other hand, by setting the average single fiber diameter of the ultrafine fibers to a range of preferably 10.0 μm or less, more preferably 8.0 μm or less, a composite having excellent surface quality that is dense and soft to the touch can be obtained.

[0030] In the present invention, the average single fiber diameter of ultrafine fibers refers to a value measured and calculated by the following method. (i) A scanning electron microscope (SEM, for example, Keyence Corporation's "VHX-D500 / D510" model) is used to photograph the cross section of the artificial leather from among the cross sections of the composite, and 10 fibers that are considered to be circular or nearly circular elliptical ultrafine fibers (fibers that appear to be 15.0 μm or less) are randomly selected and their single fiber diameter is measured. However, if the measured single fiber diameter exceeds 15.0 μm, that fiber is not an ultrafine fiber, and another ultrafine fiber is selected and its single fiber diameter is measured. (ii) The arithmetic mean of the single fiber diameters of the 10 fibers is calculated and rounded to one decimal place.

[0031] The cross-sectional shape of the ultrafine fibers according to the present invention is preferably round, since this facilitates stable formation of ultrafine fibers for artificial leather in the composite production stage and results in a composite with an excellent balance of quality, texture, and strength, but cross-sectional shapes such as oval, polygonal (e.g., flat, triangular), fan, cross, hollow, Y-shaped, T-shaped, and U-shaped cross-sections can also be used as appropriate depending on the properties desired for the composite. In this case, the average single fiber diameter of the ultrafine fibers is determined by first measuring the cross-sectional area of ​​a single fiber and then calculating the diameter when the cross section is considered to be circular.

[0032] The substrate according to the present invention is made of the ultrafine fibers. Such substrates may be in the form of nonwoven fabrics, woven or knitted fabrics, or fabrics containing both, and can be appropriately selected depending on the cost and properties required for each application or purpose.

[0033] Among these, the substrate is preferably a nonwoven fabric. When the substrate is such that the surface of the artificial leather is raised, the composite has a rich texture and excellent quality due to the fine nap.

[0034] When the substrate is a nonwoven fabric, the nonwoven fabric may be in the form of a long-fiber nonwoven fabric mainly composed of filaments, or a short-fiber nonwoven fabric mainly composed of fibers of 100 mm or less. A long-fiber nonwoven fabric is preferred because it results in a composite with excellent strength. On the other hand, a short-fiber nonwoven fabric allows more fibers to be oriented in the thickness direction of the artificial leather than a long-fiber nonwoven fabric, and when the surface of the artificial leather is raised, it results in a composite with a high degree of density on the surface.

[0035] When a short-fiber nonwoven fabric is used, the fiber length of the ultrafine fibers is preferably 25 mm or more and 90 mm or less. By setting the upper limit of the fiber length range to preferably 90 mm or less, more preferably 80 mm or less, and even more preferably 70 mm or less, a composite having good quality and texture can be obtained. On the other hand, by setting the lower limit of the fiber length range to preferably 25 mm or more, more preferably 35 mm or more, and even more preferably 40 mm or more, a composite having excellent abrasion resistance can be obtained.

[0036] It is also preferable that the composite contains a woven or knitted fabric made of the ultrafine fibers as a component. Such a fiber structure allows for a composite with excellent uniformity in thickness and quality.

[0037] [Fiber Structure] The fiber structure according to the present invention includes, as a constituent element, a substrate made of the ultrafine fibers.

[0038] Furthermore, it is also preferable that the fiber structure further includes a woven or knitted fabric b. Specifically, the woven or knitted fabric b is laminated inside the substrate or on one surface of the substrate. In particular, when the composite has openings, it is preferable that the woven or knitted fabric b is a woven fabric, as this results in a composite that can ensure strength. Note that "the composite has openings" refers to the presence of portions in which holes (through openings) penetrate the composite in the thickness direction. This woven or knitted fabric b is different from the woven or knitted fabric a described below, and the woven or knitted fabric b is mainly composed of fibers other than modacrylic fibers. Here, "a woven or knitted fabric mainly composed of fibers other than modacrylic fibers" refers to a woven or knitted fabric (including those that do not contain modacrylic fibers) in which the modacrylic fiber content of the fibers constituting the woven or knitted fabric is 1.0 mass % or less (including those that do not contain modacrylic fibers).

[0039] The type of fiber constituting the woven or knitted fabric b is preferably a filament yarn, a spun yarn, or a composite yarn made of a filament yarn and a spun yarn, and from the standpoint of durability, particularly mechanical strength, it is more preferable to use a multifilament made of a polyester resin or a polyamide resin.

[0040] The average single fiber diameter of the fibers constituting the woven or knitted fabric (b) is preferably 1 μm or more and 50 μm or less. By setting the upper limit of this range of average single fiber diameter to preferably 50 μm or less, more preferably 15 μm or less, and even more preferably 13 μm or less, a composite with excellent flexibility is obtained. Furthermore, even if the fibers of the woven or knitted fabric (b) are exposed on the surface of the composite, the hue difference with the pigment-containing ultrafine fibers after dyeing is small, resulting in a composite without impairing the uniformity of the surface hue. On the other hand, by setting the lower limit of the range of average single fiber diameter of the fibers constituting the woven or knitted fabric (b) to 1 μm or more, more preferably 8 μm or more, and even more preferably 9 μm or more, a composite with high dimensional stability is obtained.

[0041] In the present invention, the average single fiber diameter of the fibers constituting the woven or knitted fabric b is a value measured and calculated by taking a scanning electron microscope (SEM, for example, "VHX-D500 / D510" manufactured by Keyence Corporation) photograph of the cross section of the composite, randomly selecting 10 fibers constituting the woven or knitted fabric b, measuring the single fiber diameters of the selected fibers, calculating the arithmetic average of the 10 fibers, and rounding off to one decimal place.

[0042] When the fibers constituting the woven or knitted fabric b are multifilaments, the total fineness of the multifilaments is preferably 30 dtex or more and 170 dtex or less. With regard to the range of the total fineness of the yarns constituting the woven or knitted fabric b, if the upper limit is 170 dtex or less, a composite with excellent flexibility can be obtained. On the other hand, with regard to the range of the total fineness of the yarns constituting the woven or knitted fabric b, if the lower limit is 30 dtex or more, not only is the shape stability of the composite product improved, but also, when the nonwoven fabric and the woven or knitted fabric b are entangled and integrated by needle punching or the like, the fibers constituting the woven or knitted fabric b are less likely to be exposed on the surface of the composite, which is preferable. In this case, it is preferable that the total fineness of the multifilaments of the warp and weft yarns be the same.

[0043] The total fineness of the yarns constituting the woven or knitted fabric b refers to the value measured and calculated according to "8.3.1 Correct fineness b) Method B (simplified method)" of "8.3 Fineness" in JIS L1013:2010 "Testing methods for chemical fiber filament yarns."

[0044] In this case, the fiber structure according to the present invention is preferably formed by entangling the substrate and the woven / knitted fabric b together. Such a fiber structure results in a composite with excellent strength and shape stability, particularly when the composite has openings. In the present invention, "the substrate and the woven / knitted fabric b are entangled together" refers to a state in which there are multiple portions where the ultrafine fibers constituting the substrate and the fibers constituting the woven / knitted fabric b are entangled, and the substrate and the woven / knitted fabric b are integrated.

[0045] [Polymer elastomer] The artificial leather of the composite of the present invention contains a polymer elastomer. In this specification, "containing a polymer elastomer" refers to a state in which the polymer elastomer is contained in the central 40% of the artificial leather in the composite, excluding the 30% of the thickness from both surfaces excluding the napped portion. This can be determined by the following procedures (1) to (7). (1) With the napped surface of the artificial leather laid flat using a lint brush or the like, a thin section 1 mm thick is prepared in the thickness direction of the artificial leather from a randomly selected position in the artificial leather. (2) Using a scanning electron microscope (SEM, for example, Keyence Corporation's "VHX-D500 / D510"), the cross section of the thin section prepared in (1) is observed in the central 40% of the thickness from both surfaces excluding the 30% of the thickness. (3) The presence or absence of substances other than the fibers that make up the fiber structure is confirmed in the SEM image. (4) If any substances other than the fibers constituting the fiber structure are present, remove them by peeling or otherwise applying them to the surface layer of the artificial leather. (5) Remove 30% of the artificial leather in the thickness direction from both surfaces, excluding the napped portion, by polishing or otherwise removing them, leaving only the central 40%. (6) Dissolve the test piece from (5) in N,N-dimethylformamide (DMF) and hexafluoro-2-propanol (HFIP), respectively, and confirm the presence or absence of a polymeric elastomer by performing a compositional analysis of the solute in the DMF solution and the insoluble matter in HFIP after dissolution. The presence or absence of a polymeric elastomer is confirmed in the compositional analysis, for example, by infrared spectroscopy (IR). (7) If the structure of a polymeric elastomer, described below, is confirmed in either the solute in the DMF solution or the insoluble matter in HFIP, it is deemed to contain a polymeric elastomer.

[0046] Since this polymeric elastomer is a binder that holds the ultrafine fibers that make up the artificial leather, in consideration of the soft feel of the composite of the present invention, it is preferable to use polyurethane as the main component of the polymeric elastomer used. Note that, in the present invention, "main component" means that the mass of polyurethane is more than 50% by mass of the total mass of the polymeric elastomer.

[0047] In the present invention, the polyurethane preferably used as the polymeric elastomer can be either an organic solvent-based polyurethane, which is used in a dissolved state in an organic solvent, or a water-dispersed polyurethane, which is used in a dispersed state in water. Here, in the present invention, a water-dispersed polyurethane refers to a polyurethane that has a hydrophilic group and a solubility in DMF of less than 40 g / 100 g-DMF (less than 40 g of the polyurethane can be dissolved in 100 g of DMF). Conversely, a polyurethane that has a solubility in DMF of 40 g / 100 g-DMF or more (40 g or more of the polyurethane can be dissolved in 100 g of DMF) is considered to be an organic solvent-based polyurethane resin.

[0048] In the present invention, the polyurethane preferably used as the polymeric elastomer can be used in combination with a crosslinking agent in order to improve water resistance, abrasion resistance, hydrolysis resistance, etc. The crosslinking agent may be an external crosslinking agent added to the polyurethane as a third component, or an internal crosslinking agent that preliminarily introduces reactive points that form a crosslinked structure into the molecular structure of the polyurethane. An internal crosslinking agent is more preferred from the viewpoint of reducing a decrease in flexibility because it can form uniform crosslinking points within the molecular structure of the polyurethane.

[0049] Furthermore, the polymeric elastomer may contain various additives depending on the purpose, such as flame retardants such as "phosphorus-based, halogen-based, and inorganic-based" antioxidants, "phenol-based, sulfur-based, and phosphorus-based" antioxidants, ultraviolet absorbers such as "benzotriazole-based, triazine-based, benzophenone-based, salicylate-based, cyanoacrylate-based, and oxalic acid anilide-based" ultraviolet absorbers, light stabilizers such as "hindered amine-based and benzoate-based" stabilizers, hydrolysis-resistant stabilizers such as "carbodiimide-based and oxazoline-based" stabilizers, plasticizers, antistatic agents, surfactants, coagulation adjusters, carbon black, and dyes.

[0050] Generally, the content of the polymeric elastomer in the artificial leather can be adjusted appropriately taking into consideration the type of polymeric elastomer used, the manufacturing method of the polymeric elastomer, and the texture and physical properties. In the present invention, however, the content of the polymeric elastomer is preferably 2% by mass or more and 50% by mass or less, based on the mass of the artificial leather. Regarding the range of the polymeric elastomer content, if the lower limit is preferably 2% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, the bonding between the fibers by the polymeric elastomer during the stage of obtaining the artificial leather can be strengthened, resulting in a composite with excellent strength. Meanwhile, regarding the range of the polymeric elastomer content, if the upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, the composite not only has a soft texture but also is capable of suppressing dye staining of other fabrics washed at the same time.

[0051] In the present invention, the polymer elastomer content (mass %) in the artificial leather is measured and calculated using the following procedure: (1) Three 10 cm x 10 cm test pieces are randomly collected from the composite. (2) If a substance is applied to the surface of the artificial leather in the composite, remove that layer by peeling or other methods. (3) Remove 30% of the thickness of both surfaces of the artificial leather, excluding the napped portion, by polishing or other methods, leaving only the central 40%. (4) In the method (7) for confirming whether or not the polymer elastomer is present, if the polymer elastomer structure is confirmed in the solute side of the DMF solution, perform procedure (5); if the polymer elastomer structure is confirmed in the insoluble side of the HFIP, perform procedure (6), and calculate the polymer elastomer content. If the polymer elastomer structure is confirmed in both DMF and HFIP, the larger of the values ​​calculated in procedures (5) and (6) is used as the polymer elastomer content. (5) The test piece is immersed in DMF and 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 polymer elastomer content: (sample mass (g) before dissolution - sample mass (g) after dissolution and drying) / (sample mass (g) before dissolution) x 100 ... (formula). (6) The test piece is immersed in HFIP and 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 polymer elastomer content: (sample mass (g) after dissolution) / (sample mass (g) before dissolution) x 100 ... (formula).

[0052] [Artificial Leather] The artificial leather according to the composite of the present invention includes the fiber structure and the polymeric elastomer. The artificial leather according to the composite of the present invention preferably has nap on the surface not adjacent to the woven or knitted fabric a, and further preferably has a surface resin layer on the napped surface.

[0053] In other words, in the present invention, the raised nap may be present only on the surface of the artificial leather that is not adjacent to the woven or knitted fabric a, as described above, or may be present on both surfaces. In the case where the raised nap is present on the surface that is not adjacent to the woven or knitted fabric a, from the viewpoint of design effect, it is preferable that the raised nap has a length and directional flexibility that is such that when the raised nap changes direction when the artificial leather is traced with a finger, a mark is left, that is, a so-called finger mark is produced.

[0054] More specifically, the nap length on the surface is preferably 200 μm or more and 500 μm or less. With regard to this nap length range, if the lower limit is preferably 200 μm or more, more preferably 250 μm or more, the nap on the surface covers the polymeric elastomer inside the substrate and suppresses exposure of the polymeric elastomer on the surface of the artificial leather not adjacent to the woven or knitted fabric a, resulting in a composite with uniform color development. Furthermore, when the woven or knitted fabric b is entangled and integrated with the nonwoven fabric constituting the artificial leather, it is preferable to set the nap length on the surface within the above range, since this can sufficiently cover the fibers of the woven or knitted fabric b near the surface of the artificial leather. On the other hand, with regard to the nap length range, if the upper limit is preferably 500 μm or less, more preferably 450 μm or less, a composite with excellent design effect and abrasion resistance is obtained.

[0055] In the present invention, the nap length of an artificial leather is measured and calculated by the following method. (1) The nap on the surface having nap is raised using a lint brush or the like. (2) With the nap raised, two images of the cross section of the artificial leather are taken at 120x magnification using a scanning electron microscope (SEM: for example, Keyence Corporation's "VHX-D500 / D510"). (3) As shown in FIG. 1, the layer of the cross section consisting only of fibers oriented in the thickness direction is designated as the nap-raising portion (2). The length from the intersection of the fibers oriented in the thickness direction and the fibers oriented in the plane direction of the artificial leather to the tip of the nap is defined as the nap length (μm), and this length is measured at 10 points. (4) Step (3) is repeated for all cross sections, and the arithmetic average of the nap lengths (μm) is calculated and rounded to one decimal place.

[0056] In the present invention, when the surface resin layer is present, the surface resin layer may be a continuous layer (in which case the surface of the composite has a grain finish) or a discontinuous layer (in which case the surface of the composite has a semi-grain finish).

[0057] The surface resin layer is preferably made of one or more resins selected from the group consisting of styrene-butadiene rubber, nitrile rubber, acrylic resin, epoxy resin, polyurethane resin, and natural resin, and among these, polyurethane resin is preferred from the viewpoints of flexibility and abrasion resistance.

[0058] In the present invention, the resin used in the surface resin layer may contain, to the extent that the effects of the present invention are not impaired, elastomer resins such as polyesters, polyamides, and polyolefins, acrylic resins, ethylene-vinyl acetate resins, etc. Furthermore, these resins may contain various additives, for example, pigments such as carbon black, phosphorus-, halogen-, and inorganic-based flame retardants, phenol-, sulfur-, and phosphorus-based antioxidants, hindered amine- and benzoate-based light stabilizers, hydrolysis-resistant stabilizers such as polycarbodiimides, plasticizers, antistatic agents, surfactants, coagulation adjusters, and dyes.

[0059] [Woven / Knitted Fabric a] The woven / knitted fabric a of the composite of the present invention contains modacrylic fiber. This modacrylic fiber refers to a fiber containing acrylonitrile, with an acrylonitrile content of 35% by mass or more and less than 85% by mass. The modacrylic fiber generates an inert gas upon combustion, thereby helping to self-extinguish the flame on the surface of the composite. The composite is formed by laminating artificial leather adjacent to the woven / knitted fabric a containing modacrylic fiber, which has voids between the fibers, making the artificial leather, which is structurally prone to combustibility, less flammable.

[0060] Preferably, the woven or knitted fabric (a) further contains polyester fiber, and the polyester fiber content is preferably 5% by mass or more and 50% by mass or less. When the lower limit of the polyester fiber content is preferably 5% by mass or more, more preferably 10% by mass or more, a composite with excellent strength is obtained. On the other hand, when the upper limit of the polyester fiber content is preferably 50% by mass or less, more preferably 45% by mass or less, a composite with excellent flame retardancy is obtained.

[0061] The content ratios of modacrylic fiber and polyester fiber in this woven / knitted fabric a are values ​​that are measured and calculated for the remaining woven / knitted fabric a after removing everything other than woven / knitted fabric a from the composite by peeling or polishing, according to "Part 1: Fiber identification" of JIS L1030-1:2012 "Testing methods for blending ratios in textile products" and "5. Dissolving method" or "6. Dissolution method" of "Part 2. Fiber blending ratio" of JIS L1030-2:2012 "Testing methods for blending ratios in textile products."

[0062] Examples of the woven or knitted fabric a of the composite of the present invention include plain weave, twill weave, satin weave, and various woven fabrics based on these weave structures, as well as warp knitting, weft knitting represented by tricot knitting, lace knitting, and various knitted fabrics based on these knitting structures. Either woven or knitted fabrics can be used.

[0063] In particular, in consideration of the adhesive strength with the artificial leather, the material strength of the woven / knitted fabric a, and the flexibility and flame retardancy of the composite, it is preferable that the woven / knitted fabric a be a woven fabric. By doing so, the composite has excellent adhesive strength between the artificial leather and the woven / knitted fabric a, and also has excellent flexibility and flame retardancy.

[0064] [Composite] The composite of the present invention is formed by adjacently laminating an artificial leather and a woven or knitted fabric a. An adhesive resin is present in a dispersed state between the layers of the artificial leather and the woven or knitted fabric a. Here, "the adhesive resin is present in a dispersed state between the layers of the artificial leather and the woven or knitted fabric a" specifically refers to a state in which the adhesive resin is arranged in a dot pattern as shown in Figure 2, a state in which the adhesive resin is arranged in a grid pattern as shown in Figure 3, a state in which the adhesive resin is arranged in a stripe pattern as shown in Figure 4, or a state in which the adhesive resin is arranged in a random mesh pattern as shown in Figure 5, but does not refer to a state in which the adhesive resin is present over substantially the entire surface as shown in Figure 6, a state in which the adhesive resin is arranged only at the edge of the woven or knitted fabric a as shown in Figure 7, or a state in which the adhesive resin is arranged locally only in a portion of the woven or knitted fabric a as shown in Figure 8, etc.

[0065] The adhesive resin according to the present invention can be appropriately selected from, for example, polyurethane, acrylic resin, silicone resin, polyolefin, polyamide, epoxy resin, vinyl chloride, polyester, etc., depending on the material and shape of the woven or knitted fabric (a). Among these, polyurethane or acrylic resin is preferable, taking into consideration flexibility and adhesive strength at high temperatures. Polyurethane, which provides high adhesive strength and flexibility, is particularly preferable. The polyurethane is preferably a moisture-curing reactive hot-melt adhesive, or a two-component type that is mixed with an isocyanate or a chain extender.

[0066] The modacrylic fiber content in the composite is preferably 20% by mass or more and 50% by mass or less. When the lower limit of the modacrylic fiber content is preferably 20% by mass or more, more preferably 25% by mass or more, the composite has excellent flame retardancy. On the other hand, when the upper limit of the modacrylic fiber content is preferably 50% by mass or less, more preferably 45% by mass or less, the composite has excellent strength.

[0067] In the present invention, the content of modacrylic fiber in the composite is a value measured and calculated in accordance with "Part 1: Fiber identification" of JIS L1030-1:2012 "Testing methods for blending ratios in textile products" and "5. Dissolution method" or "6. Dissolution method" of "Part 2: Fiber blending ratio" of JIS L1030-2:2012 "Testing methods for blending ratios in textile products."

[0068] The composite of the present invention has a basis weight of 200 g / m ２ 900g / m or more ２ The lower limit of the range of the weight per unit area of ​​the composite is preferably 200 g / m or less. ２ More preferably, 250 g / m ２ More preferably, 300 g / m ２ By setting the weight of the composite to 900 g / m or more, a composite having a solid feel and excellent texture can be obtained. ２ or less, more preferably 800 g / m ２ More preferably 700 g / m or less ２ The above conditions result in a flexible composite with excellent moldability.

[0069] In the present invention, the basis weight of a composite is a value measured and calculated by the following method. (i) Three test pieces each measuring 5 cm x 5 cm are randomly taken from the composite. (ii) The mass of the composite is measured to one decimal place. (iii) The mass of the composite is divided by the area of ​​the test piece to calculate the basis weight of each composite sample. The arithmetic mean value (g / m) of the three test pieces is calculated. ２ ) shall be rounded to the nearest whole number.

[0070] The composite according to the present invention preferably has a thickness of 0.2 mm or more and 5.0 mm or less, as measured by "6.1.1 Method A" of "6.1 Thickness (ISO Method)" of JIS L1913:2010 "Testing Methods for General Nonwoven Fabrics." With regard to the thickness range of the composite, the lower limit is preferably 0.2 mm or more, more preferably 0.3 mm or more, and even more preferably 0.4 mm or more, so that the composite not only has excellent processability during production but also has a solid feel and an excellent texture. On the other hand, with regard to the thickness range of the composite, the upper limit 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 composite has excellent moldability and flexibility.

[0071] In the present invention, the thickness of the composite is a value measured and calculated by the following method: (i) 2500 mm from the composite ２ (ii) Apply a pressure of 0.5 kPa to the upper circular horizontal plate of a thickness gauge (e.g., Ozaki Seisakusho's "Dial Thickness Gauge H-1A") and adjust the zero point. (iii) Using the thickness gauge, apply a pressure of 0.5 kPa to the test piece for 10 seconds and measure the thickness to the nearest 0.01 mm. (iv) Calculate the arithmetic mean value (mm) of the 10 test pieces and round off to three decimal places.

[0072] The composite of the present invention preferably has an average tensile strength in any two orthogonal directions, as measured according to "6.3.1 Tensile strength and elongation (ISO method)" of JIS L1913:2010 "Testing methods for general nonwoven fabrics," of 100 N / 5 cm or more and 2000 N / 5 cm. An average tensile strength of 100 N / 5 cm or more, more preferably 150 N / 5 cm or more, and even more preferably 200 N / 5 cm or more, is preferred because it provides excellent shape stability and durability. Furthermore, an average tensile strength of 2000 N / 5 cm or less, more preferably 1800 N / 5 cm or less, and even more preferably 1500 N / 5 cm or less results in a composite with excellent moldability.

[0073] The tensile strength can be adjusted by the basis weight and density of the artificial leather, the density of the laminated woven or knitted fabric a and the inserted woven or knitted fabric b, and the total fineness of the constituent yarns.

[0074] Here, the composite of the present invention is characterized by excellent flame retardancy, and is preferably a composite that passes the flame retardancy evaluation described below.

[0075] The flame retardancy of this composite was evaluated based on the flammability test standard (horizontal burning rate) for automotive interior materials in the Federal Motor Vehicle Safety Standard (FMVSS) No. 302. A test specimen (350 mm x 100 mm) was held horizontally, a 38 mm flame was applied for 15 seconds, and the burning rate over the 254 mm distance between the A and B marks was measured according to the following criteria: If the flame self-extinguished before reaching the A mark, the composite was rated as "non-flammable" and passed. If the flame self-extinguished beyond the A mark, the burning distance was within 50 mm, and the burning time was within 60 seconds, the composite was rated as "self-extinguishing" and passed. If the flame did not self-extinguish but the burning rate between the marks was 80 mm / min or less, the composite was rated as "burning at or below the specified rate" and passed. If the flame did not self-extinguish but the burning rate between the marks exceeded 80 mm / min, the composite was rated as "burning above the specified rate" and failed.

[0076] The flame retardancy can be adjusted by the content of modacrylic fiber in the woven or knitted fabric a and the basis weight of the artificial leather and the woven or knitted fabric a.

[0077] When the composite of the present invention is used as an interior material for a vehicle, it is required to have high breathability, particularly in order to be compatible with a seat ventilation system, and therefore it is also preferable that the composite have a plurality of openings.

[0078] The "opening" in the present invention is not limited to a portion where a hole (through opening) penetrates through the composite in the thickness direction, but also includes, for example, a case where the openings of the artificial leather and the woven / knitted fabric a do not overlap in the planar position and do not form a through opening. An example of the latter is a form in which an opening is formed in advance in the artificial leather and then laminated on the woven / knitted fabric a.

[0079] The openings may have any shape depending on the desired design, including round, oval, polygonal (e.g., flat, triangular), sectoral, cross, hollow, Y-shaped, T-shaped, and U-shaped irregular shapes. The arrangement pattern of the openings is not particularly limited and may be regular or irregular. However, from the viewpoint of achieving uniform breathability and strength throughout the composite, it is preferable for the openings to be arranged regularly at predetermined intervals. From the viewpoint of achieving both breathability and strength in the composite, the pore size of the openings is preferably 0.1 mm or more and 3.0 mm or less. The opening ratio is preferably 20% or less from the viewpoint of maintaining strength and dimensional stability.

[0080] In the present invention, the "opening ratio" refers to the ratio of the total area of ​​the openings to the surface area of ​​the composite.

[0081] [Method for producing a composite] The method for producing a composite of the present invention preferably includes a step of dispersing an adhesive resin between the layers of the artificial leather and the woven or knitted fabric a. Details of these steps are described below.

[0082] (1) Process for Forming Artificial Leather First, with regard to the fiber structure for artificial leather, methods for forming a substrate composed of ultrafine fibers include a method of directly spinning fibers having the above-mentioned average single fiber diameter to obtain a substrate, a method of first forming a sheet composed of ultrafine fiber-developing fibers described below and then developing ultrafine fibers having the above-mentioned average single fiber diameter from the sheet to form a substrate (a method via a sheet composed of ultrafine fiber-developing fibers), etc. Among these, the method of first passing through a sheet composed of ultrafine fiber-developing fibers is preferred from the viewpoint of excellent operability and the ability to obtain fibers with a uniform single fiber diameter.

[0083] As the ultrafine fiber-forming fiber, an islands-in-sea type composite fiber is used, in which thermoplastic resins having different solvent solubilities are used as a sea part (easily soluble polymer) and an island part (slightly soluble polymer), and the sea part is dissolved and removed using a solvent or the like to form the island part fibers having the above-mentioned average single fiber diameter. The use of islands-in-sea type composite fiber is preferred from the viewpoint of soft texture and surface quality of the composite, because it is possible to provide appropriate gaps between the island parts, i.e., between the ultrafine fibers within the fiber bundle, when the sea part is removed.

[0084] As a method for spinning ultrafine fiber-producing fibers having an islands-in-sea composite structure, a method using a spinneret for islands-in-sea composite fibers, in which the sea part and island part fibers are mutually arranged and spun, is preferred from the viewpoint of obtaining ultrafine fibers with a uniform single fiber diameter.

[0085] As the sea component of the islands-in-sea type composite fiber, polyethylene, polystyrene, copolymer polyesters copolymerized with "sodium sulfoisophthalic acid or polyethylene glycol," etc., polylactic acid, polyvinyl alcohol, and copolymers thereof can be used, but from the viewpoints of spinnability and ease of elution, polystyrene and copolymer polyesters are preferably used.

[0086] When the islands-in-sea type composite fiber is used, the strength of the island component fibers is preferably 2.0 cN / dtex or more. By setting the strength of the island component fibers to preferably 2.0 cN / dtex or more, more preferably 2.3 cN / dtex or more, and even more preferably 2.8 cN / dtex or more, the abrasion resistance of the composite can be improved and a decrease in friction fastness due to fiber shedding can be suppressed.

[0087] In the present invention, the strength of the island components of an islands-in-sea type composite fiber is a value measured and calculated by the following method. (1) Ten 20 cm long islands-in-sea type composite fibers are bundled together. (2) The sea component is dissolved and removed from the sample obtained in (1), and then the sample is air-dried. (3) Ten tests are conducted (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 "Testing Methods for Chemical Fiber Filament Yarns." (4) The arithmetic mean value (cN / dtex) of the test results obtained in (3) is rounded to one decimal place.

[0088] When the substrate is a nonwoven fabric, the spun ultrafine fiber-developing fibers are opened and then formed into a fiber web using a cross wrapper or the like, and the web is entangled to obtain a fiber structure containing the nonwoven fabric as a constituent element. Methods that can be used to obtain a fiber structure containing the nonwoven fabric as a constituent element by entangling the fiber web include needle punching and water jet punching.

[0089] As mentioned above, the nonwoven fabric can be in the form of either a short fiber nonwoven fabric or a long fiber nonwoven fabric. However, when the nonwoven fabric is a short fiber nonwoven fabric, the number of fibers oriented in the thickness direction of the artificial leather is greater than when it is a long fiber nonwoven fabric, and when the composite is raised, a high degree of density and soft texture can be obtained on the surface.

[0090] When the nonwoven fabric is a staple fiber nonwoven fabric, the islands-in-sea type composite fibers obtained in the step of forming the islands-in-sea type composite 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.

[0091] When a short-fiber nonwoven fabric is used, the average fiber length of the ultrafine fiber-developing 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 a soft feel can be obtained. 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 composite with excellent abrasion resistance can be obtained.

[0092] Furthermore, in an embodiment in which the fiber structure further includes a woven or knitted fabric b as a constituent element, a sheet made of ultrafine fiber development type fiber obtained by the above-mentioned method and the woven or knitted fabric b can be laminated and entangled together. To entangle the sheet made of ultrafine fiber development type fiber and the woven or knitted fabric b, the woven or knitted fabric b can be laminated on one or both sides of the sheet made of ultrafine fiber development type fiber, or the woven or knitted fabric b can be sandwiched between multiple sheets made of ultrafine fiber development type fiber, and the fibers of the sheet made of ultrafine fiber development type fiber and the woven or knitted fabric b can be entangled together by needle punching, water jet punching, or the like.

[0093] The apparent density of a sheet made of ultrafine fiber-developing fibers after needle punching or water jet punching (hereinafter abbreviated as "entangled sheet"; including those entangled and integrated with woven or knitted fabric b) 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 to 0.45 g / cm or more, even if excessive tension is applied during the manufacturing process, the fibers are less likely to slip through or stretch, the denseness of the fibers is improved, and a composite having good appearance quality can be obtained. ３ By setting the above, it is possible to maintain sufficient space for providing the polymeric elastomer and maintain voids in the cross section, thereby making it possible to obtain a composite having a soft feel.

[0094] It is also a preferred embodiment that the entangled sheet is subjected to a heat shrinking treatment using hot water or steam in order to improve the denseness of the fibers.

[0095] Next, the entangled sheet can be impregnated with an aqueous solution of a water-soluble resin and then dried to impart a water-soluble resin. By imparting a water-soluble resin to the entangled sheet, the fibers are fixed and dimensional stability is improved. Here, in the present invention, the water-soluble resin refers to a resin that is soluble in water or hot water (water at 80°C to 100°C), and specific examples include polyacrylamide, polyvinyl alcohol, and carboxymethyl cellulose.

[0096] The resulting entangled sheet can then be treated with a solvent or solution to produce ultrafine fibers. This treatment is one method for forming ultrafine fibers having an average single fiber diameter of 1.0 μm or more and 10.0 μm or less. Hereinafter, the entangled sheet in which ultrafine fibers have been produced will be referred to as an ultrafine fiber sheet.

[0097] The formation of the ultrafine fiber sheet by this method can be carried out by immersing the entangled sheet in a solvent or solution to dissolve and remove the sea component of the islands-in-sea type composite fibers.

[0098] As a solvent for dissolving and removing the sea component, when the sea component is polyethylene or polystyrene, an organic solvent such as toluene or trichloroethylene can be used. When the sea component is a copolymer polyester or polylactic acid, an alkaline aqueous solution such as an aqueous sodium hydroxide solution can be used. When the sea component is a water-soluble thermoplastic polyvinyl alcohol, hot water can be used.

[0099] Then, a sheet with a polymer elastomer containing the polymer elastomer can be formed by impregnating an ultrafine fiber sheet or an entangled sheet with the solution of the polymer elastomer and solidifying the polymer elastomer. Methods for solidifying the polymer elastomer include a method in which an ultrafine fiber sheet or an entangled sheet is impregnated with a solution of the polymer elastomer, followed by wet coagulation or dry coagulation, and these methods can be selected appropriately depending on the type of polymer elastomer used.

[0100] When polyurethane is selected as the polymeric elastomer, the solvent preferably used is N,N-dimethylformamide, dimethyl sulfoxide, etc., when the polyurethane is an organic solvent-based polyurethane. When the polyurethane is a water-dispersible polyurethane, a water-dispersible polyurethane liquid in which polyurethane is dispersed in water as an emulsion may be used.

[0101] When an elastomer is added to the entangled sheet, after the formation of the sheet with the elastomer, it is possible to develop ultrafine fibers by treating the sheet with a solvent or solution. The specific procedures are the same as those described above.

[0102] In this manner, a sheet-like material can be formed that includes a fiber structure containing a substrate composed of ultrafine fibers as a component and a polymeric elastomer. This can be directly sent to a subsequent process as artificial leather, or one surface of the obtained sheet-like material can be subsequently ground to form a napped artificial leather. From the viewpoint of production efficiency, it is also preferred to cut the sheet-like material in half in the thickness direction to form two pieces of artificial leather before grinding the surface of the artificial leather.

[0103] Specifically, one surface of the sheet-like material (including a sheet-like material cut in half) can be ground using sandpaper, a roll sander, etc. A lubricant such as a silicone emulsion can be applied to the surface of the sheet-like material before grinding.

[0104] Although the product that has undergone the above steps may be used as is as artificial leather, it is preferable to subject it to various post-processing steps, as in the general method of producing artificial leather, and it goes without saying that the artificial leather that has undergone post-processing is also considered to be artificial leather in the present invention.

[0105] First, it is also preferable to dye the artificial leather. Examples of the dyeing method include jet dyeing using a jigger dyeing machine or jet dyeing machine, dip dyeing such as thermosol dyeing using a continuous dyeing machine, or printing on the napped surface by roller printing, screen printing, inkjet printing, sublimation printing, vacuum sublimation printing, etc. Among these, jet dyeing using a jet dyeing machine is preferred in terms of obtaining a soft texture and quality and grade.

[0106] The basis weight of the artificial leather according to the composite of the present invention is measured according to "6.2 Mass per unit area (ISO method)" of JIS L1913:2010 "General nonwoven fabric testing method", and the basis weight is 50 g / m ２ More than 600g / m ２ The weight of the artificial leather is preferably 50 g / m or less. ２ More preferably, 80 g / m ２ By setting the weight of the artificial leather to 600 g / m or more, a composite having a more substantial feel and excellent texture can be obtained. ２ or less, more preferably 500 g / m ２ A more flexible composite can be obtained by:

[0107] Furthermore, if necessary, a design can be applied to the surface. For example, post-processing such as perforation, embossing, laser processing, pinsonic processing, and printing can be performed. Of course, it is also preferable to perform these post-processing treatments on the artificial leather before dyeing.

[0108] (2) Step of distributing adhesive resin (step of forming a composite) Subsequently, adhesive resin is dispersed between the layers of the artificial leather and the woven or knitted fabric a, thereby obtaining a composite.

[0109] In the manufacturing method of the composite according to the present invention, the basis weight of the woven or knitted fabric a in the manufacturing stage of the composite is 50 g / m ２ More than 300g / m ２ The weight of the woven or knitted fabric a is preferably 50 g / m or less. ２More preferably, 70 g / m ２ By setting the weight of the woven or knitted fabric a at 300 g / m, a composite having excellent flame retardancy and strength can be obtained. ２ More preferably, 250 g / m ２ This allows a composite with excellent flexibility to be obtained.

[0110] In the present invention, the basis weight of the woven or knitted fabric a in the manufacturing stage of the composite refers to the value measured in accordance with "6.2 Mass per unit area (ISO method)" of JIS L1913:2010 "Testing methods for general nonwoven fabrics."

[0111] In the method for producing a composite according to the present invention, the tensile strength of the woven or knitted fabric a during the production of the composite is preferably 80 N / 5 cm or more and 1500 N / 5 cm or less, as an average value of the tensile strength in any two orthogonal directions. Setting this average tensile strength to 80 N / 5 cm or more, more preferably 100 N / 5 cm or more, and even more preferably 150 N / 5 cm or more, is preferred because it provides excellent shape stability and durability when formed into a composite. Furthermore, setting the average tensile strength to 1500 N / 5 cm or less, more preferably 1200 N / 5 cm or less, and even more preferably 1000 N / 5 cm or less, provides excellent moldability when formed into a composite.

[0112] In the present invention, the tensile strength of the woven or knitted fabric a at the production stage of the composite refers to the value measured in accordance with "6.3.1 Tensile strength and elongation (ISO method)" of JIS L1913:2010 "Testing methods for general nonwoven fabrics."

[0113] The adhesive for the composite of the present invention can be applied in a predetermined amount using a device such as a rotary screen, knife roll coater, gravure roll coater, kiss roll coater, or calendar coater. As long as the amount applied is accurate, the hot-melt resin serving as the adhesive resin can be directly dispensed onto the woven or knitted fabric (a), or a nonwoven fabric composed of the adhesive resin (as long as the adhesive resin can be dispersed as described above) can be placed on top of the fabric. Among these methods, in order to achieve a good texture for the composite, it is preferable to use a rotary screen or gravure roll coater to dispose the adhesive resin in a dispersed state, as illustrated in Figures 2 to 5. This prevents the composite from becoming hardened in texture or losing breathability.

[0114] In the bonding method for the composite of the present invention, when the adhesive resin is a wet-curing resin, the bonding is promoted by placing the composite in an appropriate temperature and humidity environment (also called "curing"). When a thermoplastic resin is used as the adhesive resin, the composite is integrated by thermocompression bonding. For thermocompression bonding, a method such as a heat roll can be used.

[0115] The amount of adhesive resin can be changed depending on the surface condition of the woven or knitted fabric (a) or artificial leather to be bonded and the type of adhesive resin. ２ 80g / m or more ２ The amount of the adhesive resin is preferably 2 g / m or less. ２ More preferably, 5 g / m ２ By adjusting the amount of the adhesive resin to 80 g / m or more, the adhesive strength between the layers is improved. ２ or less, more preferably 70 g / m ２ By setting the following, the flexibility of the composite becomes good.

[0116] [Vehicle interior materials, seats] The composite of the present invention is smooth and has good surface quality and texture, as well as strength and flame retardancy, and is therefore suitable for a wide range of applications, including clothing applications, miscellaneous goods applications, shoe and bag applications, vehicle interior materials, seats, substrates for polishing pads, various polishing cloths, wiping cloths, and other industrial materials.

[0117] Among these, vehicle interior materials containing the composite are preferred because they can take advantage of the excellent flame retardancy and strength properties. Such vehicle interior materials are interior materials used for vehicle parts such as automobile steering wheels, horn switches, shift knobs, dashboards, instrument panels, glove boxes, floor carpets, floor mats, ceiling linings, sun visors, and assist grips, and it is more preferred that these vehicle parts contain the composite. Note that the term "vehicle" in the present invention includes automobiles, aircraft, railway vehicles, ships, as well as carriages, carriages, rickshaws, and other vehicles, as well as some industrial, construction, and agricultural machinery capable of carrying humans or animals, such as excavators, crane trucks, tractors, and combine harvesters.

[0118] Alternatively, seats containing the composite are also preferred because they can take advantage of the properties in applications requiring flame retardancy and strength. It is more preferable that at least a portion of the covering material of the headrest, seat, armrest, footrest, etc., for example, the portion that comes into direct contact with the seated person, is made of the composite. Of course, the seat of the present invention can be used not only for vehicles such as automobiles, aircraft, railway vehicles, and ships, but also for homes, offices, and stores. The term "seat" as used in the present invention also includes chairs, benches, sofas, couches, stools, and floor chairs.

[0119] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0120] [Measurement Methods and Evaluation Processing Methods] Unless otherwise specified, the measurements of each physical property were carried out according to the above-mentioned methods.

[0121] (1) Average Single Fiber Diameter of Ultrafine Fibers (μm): The average single fiber diameter of ultrafine fibers was measured and calculated by the above-mentioned method using a scanning electron microscope "VHX-D500 / D510" manufactured by Keyence Corporation.

[0122] (2) Pile Length (μm): The pile length of the artificial leather was measured and calculated by the above-mentioned method using a scanning electron microscope, "VHX-D500 / D510 model" manufactured by Keyence Corporation.

[0123] (3) Thickness (mm): The thickness of the composite was measured and calculated using a "Dial Thickness Gauge H-1A" manufactured by Ozaki Manufacturing Co., Ltd. as a thickness measuring instrument, according to the method described above. The thickness of the artificial leather was measured and calculated in the same manner as the thickness of the composite.

[0124] (4) Weight (g / m ２ The basis weight of the composite was measured and calculated by the method described above. The basis weights of the artificial leather and woven / knitted fabric a were measured and calculated in the same manner as the thickness of the composite.

[0125] (5) Tensile strength (N / 5 cm): The tensile strength of the composite was measured and calculated by the above-mentioned method using a tensile tester, Model: 3343, manufactured by Instron. The tensile strength of the artificial leather and woven / knitted fabric a was measured and calculated in the same manner as the thickness of the composite.

[0126] (6) Weave Density (Counts / 2.54 cm) The weave density of woven / knitted fabric a was measured and calculated by the following method. (i) Five test pieces measuring 6 cm x 6 cm were randomly taken from woven / knitted fabric a. (ii) The number of warp and weft threads present in a 5.08 cm section was counted. (iii) The number of warp and weft threads present in a 5.08 cm section was divided by 2 to calculate the weave density of the warp and weft threads of each sample. The arithmetic mean value (counts / 2.54 cm) of the five test pieces was rounded to one decimal place to calculate the weave density of woven / knitted fabric a.

[0127] (7) Modacrylic Fiber Content (% by Mass) in Woven / Knit Fabric a The modacrylic fiber content in woven / knit fabric a was evaluated by the dissolution method described above. The specific method was as follows: (i) Three test pieces measuring 10 cm x 10 cm were randomly taken from woven / knit fabric a. (ii) The test pieces were immersed in DMF to dissolve the modacrylic fiber, and then dried at 25°C for 24 hours. The mass ratio of the test pieces before and after dissolution was calculated using the following formula, and the arithmetic mean value (%) of the three test pieces was rounded to one decimal place to calculate the modacrylic fiber content: (Sample mass (g) before dissolution - Sample mass (g) after dissolution and drying) / (Sample mass (g) before dissolution) x 100 (formula).

[0128] (8) Content (% by mass) of modacrylic fiber in the composite The content (% by mass) of modacrylic fiber in the composite was evaluated and measured by the following method. (i) The weight of the modacrylic fiber calculated when evaluating the content (% by mass) of modacrylic fiber in the woven or knitted fabric a was multiplied by 100 to obtain the basis weight (g / m ２ (ii) The weight per unit area of ​​the modacrylic fiber was divided by the weight per unit area of ​​the composite, and the result was multiplied by 100 to calculate the content (mass%) of the modacrylic fiber in the composite.

[0129] (9) Opening ratio (%) of composite: The opening ratio of the composite was determined by taking a photograph of a 20 cm × 20 cm composite surface using an electron microscope (for example, "Digital Microscope VHX-1000" manufactured by Keyence Corporation), determining the sum of the areas of the openings using a "circle area measurement" function, and calculating the ratio to the composite surface. This procedure was carried out for five samples, and the opening ratio was determined by arithmetic average.

[0130] (10) Combustibility of Composite (mm / min): The flammability of the composite was evaluated according to the method described above.

[0131] (11) Composite Edges: The composite edges were evaluated by placing the composite on urethane foam, dropping 3 cc of water onto the surface, leaving it to dry naturally, and then observing whether there were any abnormalities in appearance such as ring stains on the sample surface. If ring stains or the like were clearly visible to the naked eye, the result was rated as "present."

[0132] (12) Surface Quality of Composites: A total of 20 healthy adult males and females, 10 of whom were healthy, conducted a sensory evaluation of the surface quality of the composites. Composites measuring 200 mm square or larger were evaluated on a 5-point scale as shown below, with the most common evaluation being taken as the surface quality. In the present invention, a satisfactory level is "grade 3 to grade 5." Note that this evaluation was not conducted for Example 5, which had a surface resin layer. Grade 5: The surface of the composite was smooth to the touch, and finger marks were visible. Grade 4: An evaluation between grades 5 and 3. Grade 3: The surface of the composite felt frictional resistance, but finger marks were visible. Grade 2: An evaluation between grades 3 and 1. Grade 1: The surface of the composite felt frictional resistance, and almost no finger marks were visible.

[0133] (13) Texture of the Composite: A total of 20 healthy adult men and women, 10 of whom were healthy, conducted a sensory evaluation. The composite was cut into 300 mm square pieces and evaluated as follows based on the feel when gripped in the palm of the hand, with the most common evaluation being taken as the texture of the composite. In the case of a tie, the higher evaluation was taken as the texture of the composite. In the present invention, a good level is "Grade 3 or 4." Grade 4: Soft and drapeable, good texture Grade 3: Slightly soft and drapeable, good texture Grade 2: Slightly stiff, poor drapeability, poor texture Grade 1: Stiff, no drapeability, poor texture

[0134] [Artificial Leather] The artificial leathers used in the Examples and Comparative Examples were produced as illustrated in the following Production Examples 1-A to 1-D.

[0135] [Production Example 1-A] (Artificial leather A) (Islands-in-sea type composite fiber) Using polystyrene as the sea part and polyethylene terephthalate (referred to as PET in Table 1) having an intrinsic viscosity (IV value) of 0.72 as the island parts, an islands-in-sea type composite fiber was obtained with a conjugation ratio of 20 mass % of the sea part and 80 mass % of the island parts, with 16 islands / filament and an average single fiber diameter of 20 μm.

[0136] (Entangled sheet) The obtained islands-in-sea composite fibers were cut into staples with a fiber length of 51 mm, and the staples were passed through a card and a cross wrapper to form a fiber web. The fiber web was needle-punched to a basis weight of 550 g / m ２ An entangled sheet having a thickness of 2.50 mm was produced.

[0137] (PVA-attached sheet) The entangled sheet obtained as described above was shrunk with hot water at 96°C. The entangled sheet shrunk with hot water was then impregnated with an aqueous solution of polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) with a saponification degree of 88%, which had been adjusted to a concentration of 5% by mass. The sheet was then squeezed with a roll and dried with hot air at 125°C for 10 minutes while causing migration of the PVA, to obtain a PVA-attached sheet with a PVA mass of 45% by mass relative to the sheet mass.

[0138] (Ultrafine fiber sheet) The PVA-attached sheet obtained by entanglement of the ultrafine fiber bundles was immersed in trichloroethylene, squeezed with a mangle, and compressed 10 times to dissolve and remove the sea component (sea removal) and compress the PVA-attached sheet, thereby obtaining an ultrafine fiber sheet.

[0139] The ultrafine fiber sheet obtained as described above was immersed in a DMF solution of polyurethane containing organic solvent-based polyurethane as the main component, adjusted to a solids concentration of 12% by mass, and then the polyurethane resin was coagulated in an aqueous solution of DMF concentration of 30% by mass. Thereafter, the sheet was dried with hot air at a temperature of 110° C. for 10 minutes to obtain a sheet with a polymer elastomer having a thickness of 2.00 mm.

[0140] (Sheet-like product) The polymeric elastomer-attached sheet obtained as described above was cut in half in the thickness direction, and the surface formed by cutting in half (the half-cut surface) was ground with endless sandpaper of sandpaper count 240, thereby obtaining a sheet-like product having nap and a thickness of 0.60 mm.

[0141] The napped sheet thus obtained was dyed with a black dye using a jet dyeing machine at a temperature of 125°C, and then dried in a dryer to obtain artificial leather having ultrafine fibers with an average single fiber diameter of 4.4 µm. The results are shown in Table 1.

[0142] [Production Example 1-B] (Artificial Leather B) A DMF (dimethylformamide) solution of polyurethane adjusted to a solid content of 30% was applied to the napped surface (surface) of the artificial leather of Production Example 1-A by gravure coating, and then dried to obtain 10 g / m ２ An artificial leather was obtained in the same manner as in Production Example 1-A, except that the surface resin layer was formed as follows. The results are shown in Table 1.

[0143] [Production Example 1-C] (Artificial Leather C) The entangled sheet of Production Example 1-A was woven into a woven fabric with a basis weight of 450 g / m ２ An artificial leather was obtained in the same manner as in Production Example 1-A, except that a sheet with a 1.50 mm thick elastomer was produced, and then a napped sheet with a 0.45 mm thick material was produced. The results are shown in Table 1.

[0144] [Production Example 1-D] (Artificial Leather D) An artificial leather was obtained in the same manner as in Production Example 1-A, except that the entangled sheet in Production Example 1-A was replaced with the following entangled sheet, and a sheet with a polymer elastomer having a thickness of 2.30 mm was produced, followed by a sheet-like product with a napped thickness of 0.90 mm. The results are shown in Table 1. (Entangled Sheet of Production Example 1-D) A plain weave fabric (woven / knitted fabric b) made from yarns spun with polyethylene terephthalate having an intrinsic viscosity (IV value) of 0.72, with a warp and weft single fiber diameter of 10 μm, a twist of 2500 T / m, and a weave density of 95 × 76 (warp × weft) per 2.54 cm (1 inch), was sandwiched between the top and bottom of a fiber web to form a woven fabric / fiber web / woven fabric laminate, and the laminate was needle-punched to form an artificial leather with a basis weight of 700 g / m. ２ An entangled sheet having a thickness of 3.00 mm was produced.

[0145]

[0146] [Woven and knitted fabric a] The woven and knitted fabrics a used in the examples and comparative examples were prepared as exemplified in the following Production Examples 2-A to 2-F.

[0147] [Production Example 2-A] (Woven / knitted fabric a-A) The following woven / knitted fabric a was obtained. The results are shown in Table 2. Warp yarn 1: Spun yarn of modacrylic fiber with an LOI value of 32 (referred to as "MOD" in Table 2). Staple fiber fineness: 1.7 dtex. Staple fiber length: 38 mm. Spun yarn fineness: 295 dtex. Number of twists: 15 / 2.54 cm. Warp yarn 2: Multifilament of polyethylene terephthalate (referred to as "PET" in Table 2). Staple fiber single yarn fineness: 3.1 dtex. Number of multifilament single yarns (filament count): 96. Total multifilament fineness: 330 dtex. Weft yarn 1: Spun yarn of modacrylic fiber with an LOI value of 32 (MOD). Staple fiber fineness: 1.7 dtex. Staple fiber length: 38 mm. Spun yarn fineness: 295 dtex.・Number of twists: 15 / 2.54cm Weft 2: ・Polyethylene terephthalate multifilament (PET) ・Single filament fineness of long fibers: 3.1 dtex ・Number of single multifilament yarns (filament count): 96 ・Total fineness of multifilament: 330 dtex Weave: ・Plain weave in which warp yarns 1 and 2 are woven at a density ratio of 100:0 (only warp yarn 1 is used), and weft yarns 1 and 2 are woven at a density ratio of 50:50 Weave density: Warp direction: Weft direction = 74 threads / 2.54cm: 58 threads / 2.54cm Other characteristics: ・Weight: 170g / m ２ .

[0148] [Production Example 2-B] (Woven / Knitted Fabric a-B) A woven / knitted fabric a was obtained in the same manner as in Production Example 2-A, except that the weave of Production Example 2-A was changed to the following weave. ２ The results are shown in Table 2. Weave: A plain weave in which weft yarn 1 and weft yarn 2 were woven together at a density ratio of 80:20.

[0149] [Production Example 2-C] (Woven / Knitted Fabric a-C) A woven / knitted fabric a was obtained in the same manner as in Production Example 2-A, except that the weave of Production Example 2-A was changed to the following weave. ２ The results are shown in Table 2. Weave: A plain weave in which weft yarn 1 and weft yarn 2 were interwoven at a density ratio of 5:95.

[0150] [Production Example 2-D] (Woven / Knitted Fabric a-D) A woven / knitted fabric a was obtained in the same manner as in Production Example 2-A, except that the weave of Production Example 2-A was changed to the following weave. ２ The results are shown in Table 2. Weave: A plain weave in which weft yarn 1 and weft yarn 2 were woven together at a density ratio of 100:0 (only weft yarn 1 was used).

[0151] [Production Example 2-E] (Woven / Knitted Fabric a-E) A woven / knitted fabric a was obtained in the same manner as in Production Example 2-A, except that the weave of Production Example 2-A was changed to the following weave. ２ The results are shown in Table 2. Weave: A plain weave in which warp yarns 1 and 2 were interwoven at a density ratio of 0:100 (only warp yarn 2 was used) and weft yarns 1 and 2 were interwoven at a density ratio of 0:100. [Production Example 2-F] (Woven / Knitted Fabric a-F) A woven / knitted fabric a was obtained in the same manner as in Production Example 2-A, except that warp yarn 1 and weft yarn 1 in Production Example 2-A were changed to the following warp yarn 3 and weft yarn 3. The basis weight was 190 g / m ２ The results are shown in Table 2. Warp yarn 3: Spun yarn of meta-aramid fiber with an LOI value of 32 (denoted as "MET" in Table 2) Weft yarn 3: Spun yarn of meta-aramid fiber with an LOI value of 32 (MET).

[0152]

[0153] [Example 1] Artificial leather A was used as the artificial leather, woven / knitted fabric a-A was used as the woven / knitted fabric a, and a moisture-curing reactive urethane adhesive with a melt viscosity of 2000 mPa·s at 125°C was used as the adhesive resin. The adhesive resin was applied to the surface (back surface) opposite to the napped surface of this artificial leather A using a gravure roll coater in the pattern shown in Figure 2 (dot shape, adhesive resin basis weight: 10 g / m ２ The dots were spaced apart with a center-to-center distance of 1.2 mm. Then, woven / knitted fabrics a-A were layered and nipped with a pair of calendar rolls with the roll surface temperature set to 90°C. This was then cured for 24 hours in an environment with an ambient temperature of 25°C and a relative humidity of 50%, to obtain a composite. The results are shown in Table 3.

[0154] Example 2 A composite was obtained in the same manner as in Example 1, except that woven / knitted fabric a-A was changed to woven / knitted fabric a-B. The results are shown in Table 3.

[0155] Example 3 A composite was obtained in the same manner as in Example 2, except that artificial leather A was changed to artificial leather B. The results are shown in Table 3.

[0156] Example 4 A composite was obtained in the same manner as in Example 1, except that woven / knitted fabric a-A was changed to woven / knitted fabric a-C. The results are shown in Table 3.

[0157] Example 5 A composite was obtained in the same manner as in Example 1, except that artificial leather A was changed to artificial leather C. The results are shown in Table 3.

[0158] Example 6 A composite was obtained in the same manner as in Example 1, except that the artificial leather A was changed to the artificial leather D and the woven / knitted fabric a was changed to the woven / knitted fabric a-D. The results are shown in Table 3.

[0159] [Example 7] A composite was obtained in the same manner as in Example 1, except that artificial leather A was changed to artificial leather D, and openings were formed in the obtained composite using a punching board with needles (needle diameter: 1.4 mm, vertical pitch: 5 mm, horizontal pitch: 5 mm, opening rate: 12%) to form a composite with openings. The results are shown in Table 3.

[0160]

[0161] Comparative Example 1: Woven / knitted fabric a-A was changed to woven / knitted fabric a-E, and the resulting composite was coated with guanidine phosphate as a flame retardant in an amount of 15 g / m ２ A composite to which a flame retardant had been impregnated by immersion was obtained in the same manner as in Example 1, except that the composite was immersed in an aqueous guanidine phosphate solution so that the composition satisfies the following formula:

[0162] Comparative Example 2 A flame retardant containing 70% by mass of silicon oxide resin-treated ammonium polyphosphate (manufactured by Wellchem, phosphorus content 28%, nitrogen content 14%) was applied to the surface of the composite facing the woven or knitted fabric a-E using a screen coater, and then dried at 100°C for 7 minutes to obtain a dried coating amount of the resin containing the flame retardant of 70 g / m ２ A composite body having a back surface coated with a resin containing a flame retardant was obtained in the same manner as in Comparative Example 1, except that the above-mentioned conditions were changed. The results are shown in Table 4.

[0163] [Comparative Example 3] Woven or knitted fabrics a-D were not laminated, and a flame retardant containing 70% by mass of silicon oxide resin-treated ammonium polyphosphate (manufactured by Wellchem, phosphorus content 28%, nitrogen content 14%) was applied to the surface of the composite on the woven or knitted fabric a side using a screen coater, followed by drying at a temperature of 100°C for 7 minutes, resulting in a dry adhesion amount of the resin containing the flame retardant of 70 g / m ２ A composite body having a flame retardant coating on the back side was obtained in the same manner as in Example 6, except that the above-mentioned conditions were met. The results are shown in Table 4.

[0164] Comparative Example 4 A composite was obtained in the same manner as in Example 6, except that woven / knitted fabric aD was changed to woven / knitted fabric aF. The results are shown in Table 4.

[0165] Comparative Example 5: Woven / knitted fabric a-D was changed to woven / knitted fabric a-A, and in the step of forming a composite, a moisture-curing polyurethane resin was applied at 25 g / m ２ A composite was obtained in the same manner as in Example 6, except that the coating amount was adjusted to 100%. The results are shown in Table 4.

[0166]

[0167] The composites obtained in Examples 1 to 7 were all smooth and had good surface quality and texture, as well as good strength and flame retardancy.

[0168] On the other hand, the composite of Comparative Example 1 was rough and had poor surface quality. The composites of Comparative Examples 2, 3, and 5 all had poor texture. The composite of Comparative Example 4 had poor flame retardancy.

[0169] 1: Composite 2: Raised portion 3: Boundary line between raised portion and other portion (line connecting intersection of fibers oriented in the thickness direction and fibers oriented in the surface direction of the artificial leather) 4: Arrow indicating distance from intersection of fibers oriented in the thickness direction and fibers oriented in the surface direction of the artificial leather to tip of raised portion 5: Artificial leather 6: Woven / knitted fabric a 7: Adhesive resin

Claims

1. A composite comprising artificial leather and woven / knitted fabric (a) laminated adjacent to each other, wherein the artificial leather comprises: a fiber structure including, as a component, a substrate made of ultrafine fibers; and a polymeric elastomer; the woven / knitted fabric (a) comprises modacrylic fibers; and an adhesive resin is present discretely between the layers of the artificial leather and the woven / knitted fabric (a).

2. The composite according to claim 1, wherein the content of polyester fiber in the woven or knitted fabric (a) is 5% by mass or more and 50% by mass or less.

3. The composite according to claim 1 or 2, wherein the modacrylic fiber content in the composite is 20% by mass or more and 50% by mass or less.

4. The composite according to claim 1 or 2, wherein the fiber structure further comprises a woven or knitted fabric (b).

5. A vehicle interior material comprising the composite of claim 1 or 2.

6. A vehicle part comprising the composite of claim 1 or 2.

7. A seat comprising the composite of claim 1 or 2.

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