JP2018096006A - Sheet-like object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-like object excellent in light resistance, and fogging resistance while having tactile feeling of a natural nubuck leather, and piloerection feeling of a natural suede leather.SOLUTION: A sheet-like object of the present invention is a fiber structure comprising an ultra-fine fiber having an average single fiber diameter of not less than 0.1 μm and not greater than 8 μm, and satisfies all of the following conditions (1)-(3). (1) A discontinuous resin layer is formed on a piloerection surface. (2) The resin layer is constituted by not less than 2 layers. (3) The resin layer contains a light resistant agent and a porous inorganic filler.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a sheet-like material that has a feel of natural nubuck leather and a raised feeling of natural suede leather, and is excellent in light resistance and fogging resistance.

  A suede-like artificial leather made of ultrafine fibers and a polymer elastic body has excellent properties not found in natural leather in terms of durability and uniformity. Taking advantage of these features, suede-like artificial leather has been used in a wide range of applications such as clothing, furniture, and automotive interior materials. In recent years, further diversification needs have arisen, and the development of artificial leather having a quality other than suede is desired.

  Examples thereof include artificial leathers such as silvered tones and nubuck tones. Unlike suede leather, natural nubuck leather is obtained by raising the silver surface of leather. For this reason, it has the feature of having a wet tactile sensation while having a surface fineness and flatness such as leather with silver. However, none of the artificial leather and synthetic leather imitating the existing natural nubuck leather has achieved sufficient quality and texture compared to the natural nubuck leather.

  For nubuck-like artificial leather, for example, after a resin liquid is applied to the napped surface of a fiber sheet made of ultrafine fibers, it is further chemically and / or mechanically divided to expose the napped fibers. It has been proposed (see Patent Document 1). However, the proposed method has a problem of light resistance such that the resin layer on the surface is deteriorated by ultraviolet rays or the like.

  Moreover, as a synthetic leather excellent in light resistance in the resin layer on the surface, a method of impregnating the resin layer with a light resistance agent has been proposed (see Patent Document 2). However, in this proposal, synthetic leather whose entire surface layer is a resin layer is not a wet tactile sensation like natural nubuck leather, and fogging resistance due to sublimation of the light-resistant agent by heat is a problem.

  Moreover, as a method excellent in suppressing fogging from the resin layer, a method of adding a porous fogging inhibitor to the resin layer has been proposed (see Patent Document 3). However, in this proposal, the surface is composed only of a resin, and further, since a light-resistant agent for improving light resistance is not added, the resin layer on the surface is deteriorated by ultraviolet rays or the like, and light resistance Was insufficient.

Japanese Patent No. 3409554 JP 2014-65983 A JP 2008-156620 A

  Accordingly, an object of the present invention is to provide a sheet structure excellent in light resistance and fogging resistance, which is a fiber structure composed of ultrafine fibers and has the feel of natural nubuck leather and the nap of natural suede leather. There is to do.

The present invention is to solve the above problems, and the sheet-like material of the present invention is a fiber structure comprising ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 8 μm or less, At least one surface of the fiber structure has nap and satisfies the following (1) to (3).
(1) A discontinuous resin layer is formed on the raised surface,
(2) The resin layer is composed of two or more layers,
(3) The resin layer contains a light-proofing agent and a porous inorganic filler.

  Here, the discontinuous resin layer means that the resin layer formed on the surface of the sheet-like material of the present invention is irregularly and discontinuously arranged on the surface of the sheet-like material. On the surface of the sheet-like material of the invention, the resin layer and the raised portions are irregularly and discontinuously arranged, and the surface layer state where the raised portions exist between the resin portions scattered in an island shape. say.

  According to a preferred aspect of the sheet-like material of the present invention, the resin layer has a three-layer structure.

  According to a preferred embodiment of the sheet-like material of the present invention, the total thickness of the resin layer is 0.001 to 0.4 mm.

  According to a preferred embodiment of the sheet-like material of the present invention, the molecular weight of the light proofing agent is 300 or more and 100,000 or less.

  According to a preferred aspect of the sheet-like material of the present invention, the fiber structure includes a polymer elastic body inside.

  According to a preferred aspect of the sheet-like material of the present invention, the fiber structure includes a reinforcing cloth made of a woven or knitted fabric inside.

  According to a preferred embodiment of the sheet-like material of the present invention, the porous inorganic filler is at least one selected from the group consisting of montmorillonite, saponite, hectorite and fluorinated mica.

  According to the present invention, it is possible to obtain a sheet-like product that has a feel close to natural nubuck leather and a raised feeling of natural suede leather, and is further excellent in light resistance and fogging resistance. In addition, since the surface resin layer contains a light-resistant agent and a porous inorganic filler in combination, the light resistance of the sheet-like material can be maintained for a long time by suppressing sublimation due to heat of the light-resistant agent that causes fogging. Can do.

FIG. 1 is a schematic plan view of the surface of a sheet-like material produced according to the present invention.

The sheet-like material of the present invention is a fiber structure composed of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 8 μm or less, and at least one surface of the fiber structure has napped, and the following ( It is a sheet-like material characterized by satisfying all of 1) to (3).
(1) A discontinuous resin layer is formed on the raised surface,
(2) The resin layer is composed of two or more layers,
(3) The resin layer contains a light-proofing agent and a porous inorganic filler.

  That is, the sheet-like material of the present invention is composed of a fiber structure mainly composed of ultrafine fibers having an average single fiber diameter of 0.1 to 8 μm, and at least one surface of the fiber structure has napped, A sheet-like material in which a discontinuous resin layer is formed on the raised surface, the resin layer is two or more, and the resin layer contains a light-proofing agent and a porous inorganic filler.

  The sheet-like material of the present invention is composed of a fiber structure composed of ultrafine fibers having an average single fiber diameter of 0.1 to 8 μm. The average single fiber diameter of the ultrafine fibers is preferably 0.3 μm or more and 7 μm or less, and more preferably 0.5 μm or more and 6 μm or less.

  When the average single fiber diameter of the ultrafine fibers is less than 0.1 μm, the strength of the sheet-like material is insufficient. In addition, when the average single fiber diameter exceeds 8 μm, the texture of the sheet-like material becomes hard and the surface quality of the sheet-like material is lowered because it is difficult to form delicate napping, and when the fiber structure is a nonwoven fabric Further, the entanglement of the fibers becomes insufficient and the wear resistance of the sheet-like material is lowered.

  As the ultrafine fibers constituting the sheet-like material of the present invention, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyester such as polyethylene 2,6-naphthalene dicarboxylate, polyamide such as 6-nylon, 66-nylon, Various synthetic fibers made of polymers such as acrylic polyethylene and polypropylene can be used. Among these, polyester fibers made of polymers such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate are preferably used because of their excellent strength, dimensional stability, light resistance, and dyeability. Moreover, unless the objective of this invention is impaired, the ultrafine fiber of a different raw material can also be mixed with a fiber structure.

  Addition of inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, UV absorbers, conductive agents, heat storage agents and antibacterial agents to the ultrafine fibers that make up the fiber structure can do.

  As the cross-sectional shape of the ultrafine fiber constituting the fiber structure, a cross-sectional shape of a polygonal shape such as an ellipse, a flat shape, and a triangle, a cross-sectional shape such as a sector shape and a cross shape can be adopted in addition to a round cross-section.

  Examples of the fiber structure used in the present invention include woven fabrics, knitted fabrics, non-woven fabrics, and fiber structures filled with a polymer elastic body in these fiber structures, and are required for each use and purpose. It can be properly used according to cost and characteristics. Woven fabrics and knitted fabrics are preferably used in terms of cost, and non-woven fabrics and fiber structures filled with a polymer elastic body are preferably used in terms of quality due to fullness and fine napping.

  When a woven or knitted fabric is used as the fiber structure, examples of the woven fabric include plain weave, twill weave, satin weave, and various fabrics based on these woven structures. As the knitted fabric, any of a knitted fabric represented by warp knitting, weft knitting represented by tricot knitting, lace knitting, and various knitted fabrics can be employed.

  When nonwoven fabric is used as the fiber structure, it is expressed in various categories such as general short fiber nonwoven fabric, long fiber nonwoven fabric, needle punch nonwoven fabric, papermaking nonwoven fabric, spunbond nonwoven fabric, melt blown nonwoven fabric, and electrospun nonwoven fabric. All nonwoven fabrics can be applied. Here, non-woven fabrics are preferable in terms of quality due to a solid texture and fine napping.

  A fiber structure in which a polymer elastic body is filled in these fiber structures is more preferably used in that the durability of the sheet-like material and the wear resistance of the surface of the sheet-like material are excellent.

  Furthermore, in the sheet-like product of the present invention, it is preferable that a woven or knitted fabric is included in the structure from the viewpoint of excellent mechanical strength.

  When the sheet-like material includes a woven or knitted fabric, a synthetic fiber made of polyester, polyamide, polyethylene, polypropylene, or a copolymer thereof is suitably used as the yarn constituting the woven or knitted fabric. Among these, synthetic fibers made of polyester, polyamide and copolymers thereof can be used alone or in combination or mixed. In addition, filament yarns, spun yarns, blended yarns of filaments and short fibers, and the like can be used as the yarns constituting the woven or knitted fabric.

  The woven or knitted fabric included in the sheet-like material includes a composite fiber in which two or more kinds of polymers are combined in a side-by-side type or an eccentric core-sheath type (hereinafter, sometimes referred to as a side-by-side type composite fiber). A woven or knitted fabric can also be used. For example, in a side-by-side type composite fiber composed of two or more types of polymers having a difference in intrinsic viscosity (IV), different internal strains occur between the two components due to stress concentration on the high viscosity side during stretching. Due to this internal strain, the high-viscosity side contracts greatly due to the difference in elastic recovery rate after stretching and the difference in heat shrinkage in the heat treatment process, and strain occurs in the single fiber to express a three-dimensional coil type crimp. This three-dimensional coil-type crimp develops stretchability as artificial leather.

  Examples of the woven fabric contained in the sheet-like material include plain weave, twill weave, satin weave, and various fabrics based on these woven structures. As the knitted fabric, any of a knitted fabric represented by warp knitting, weft knitting represented by tricot knitting, lace knitting, and various knitted fabrics can be employed. Among them, a woven fabric is preferable from the viewpoint of processability, and a plain woven fabric is preferably used particularly in terms of cost. Further, the woven density of the woven fabric can be appropriately set according to the total fineness of the yarn and the equipment and conditions for intertwining the nonwoven fabric and the knitted fabric described later.

  In a preferred embodiment, the fiber structure constituting the sheet-like material of the present invention contains a polymer elastic body therein. By including the polymer elastic body inside, the form stability of the sheet-like material and the wear resistance of the surface are improved.

  When the polymer structure includes a polymer elastic body, polyurethane, SBR, NBR, acrylic resin, or the like can be used as the polymer elastic body. Among them, polyurethane is preferably used as a main component. It is an aspect. By using polyurethane, it is possible to obtain a composite sheet-like product having a tactile sensation with a sense of fullness, a leather-like appearance, and physical properties that can withstand actual use.

  When using polyurethane as the polymer elastic body contained in the fiber structure, both organic solvent-based polyurethane used in a state dissolved in an organic solvent and water-dispersed polyurethane used in a state dispersed in water are used. Can be adopted. As the polyurethane, a polyurethane obtained by a reaction of a polymer diol, an organic diisocyanate and a chain extender is preferably used.

  When water-dispersed polyurethane is used as the polymer elastic body inside the fiber structure, it is a preferred embodiment to use an internal emulsifier in order to disperse the polyurethane in water. Examples of the internal emulsifier include cationic internal emulsifiers such as quaternary amine salts, anionic internal emulsifiers such as sulfonates and carboxylates, and nonionic internal emulsifiers such as polyethylene glycol. Any of a combination of a nonionic internal emulsifier and a combination of an anionic and nonionic internal emulsifier can be employed.

  Various types of additives, for example, pigments such as carbon black, flame retardants such as phosphorus-based, halogen-based, and inorganic-based materials, phenol-based, sulfur-based, and phosphorus-based oxidizing agents are used in the polymer elastic body inside the fiber structure. UV absorbers such as inhibitors, benzotriazoles, benzophenones, salicylates, cyanoacrylates and oxalic acid anilides, light stabilizers such as hindered amines and benzoates, hydrolysis stabilizers such as polycarbodiimides, A plasticizer, an antistatic agent, a surfactant, a coagulation modifier, a dye, and the like can be contained.

  The content of the polymer elastic body in the fiber structure can be appropriately adjusted in consideration of the type of polymer elastic body to be used, the method for producing the polymer elastic body, the texture and physical properties. The content of the polymer elastic body is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and still more preferably 15% by mass with respect to the mass of the sheet-like material. It is 45 mass% or less. By setting the content ratio of the polymer elastic body to 5% by mass or more, the sheet strength can be obtained and the entangled state can be maintained by binding the fibers, while the content ratio is 80% by mass or less. By doing, it can prevent that a texture becomes hard.

  In the present invention, it is important that the fiber structure has napping on at least one surface thereof. By having the raised surface, the adhesiveness with the subsequent resin layer is excellent, and furthermore, the surface texture close to that of genuine leather can be obtained by the raised fiber exposed on the surface of the sheet-like material.

  Further, it is important that a discontinuous resin layer is formed on the raised surface, and the resin layer is composed of two or more layers, and the resin layer has a three-layer structure. This is a preferred embodiment. As described above, the discontinuous resin layer is a surface layer in which resin portions are scattered in islands on the surface of a sheet-like material, and napped portions exist between the resin portions. Say state.

  Moreover, it is preferable that the ratio for which the discontinuous resin part accounts to the sheet-like material surface is 10 to 90%, More preferably, it is 20 to 80%. When the above ratio is less than 10%, not only the wear resistance is inferior, but also a nubuck-like surface feeling and tactile sensation cannot be obtained, and when the above ratio exceeds 90%, a suede-like texture is obtained. The air permeability is lost and the feeling of napping cannot be obtained.

  FIG. 1 is a schematic plan view for illustrating the surface form of a sheet-like material obtained in the present invention. In the surface form of the sheet-like material in FIG. 1, the raised portions 1 are continuous and branched, and the resin portion 2 is surrounded by the raised portions 1 and has an independent shape.

  By forming the resin layer in a non-continuous manner, sufficient air permeability of the sheet-like material is secured in the napped portion which is a non-resin portion, and when the sheet-like material is bent, the resin layer is cracked. It is possible to maintain good quality and texture.

  Moreover, when the resin layer is two or more layers, a sheet-like material having excellent wear resistance, which is required to be more durable, such as an automobile seat or a sofa can be obtained. When the resin layer is one layer, the wear resistance is poor.

  The resin used in the resin layer in the present invention is a polymer compound having rubber elasticity that preferably expands and contracts, and examples thereof include polyurethane, SBR, NBR, and acrylic resin. Among these, a polymer elastic body mainly composed of polyurethane, specifically, a polymer elastic body composed of polyurethane of 50% by mass or more is preferably used from the viewpoint of balance between texture and physical properties.

  Examples of the polyurethane include an organic solvent-based polyurethane used in a state dissolved in an organic solvent, and a water-dispersed polyurethane used in a state dispersed in water, and both can be employed in the present invention.

  As the polyurethane used in the present invention, a polyurethane having a structure in which a polyol, a polyisocyanate, and a chain extender are appropriately reacted can be used.

  As the polyol, for example, polycarbonate-based diol, polyester-based diol, polyether-based diol, silicone-based diol, fluorine-based diol, or a copolymer obtained by combining these can be used. Of these, polycarbonate diols and polyester diols are preferably used from the viewpoint of light resistance. Furthermore, from the viewpoint of hydrolysis resistance and heat resistance, a polycarbonate diol is preferably used. However, in the adhesive layer in the present invention, a polyether diol or a polyester diol is used because of its adhesion to the surface of the fiber structure. Preferably used.

  The polycarbonate diol can be produced by transesterification of an alkylene glycol and a carbonate ester or a reaction of phosgene or chloroformate ester with an alkylene glycol.

  Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and the like. Linear alkylene glycol, branched alkylene glycol such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, Alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

  In the present invention, either a polycarbonate diol obtained from a single alkylene glycol or a copolymerized polycarbonate diol obtained from two or more kinds of alkylene glycols can be used.

  Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and xylylene diisocyanate, and aromatic polyisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. Can be used in combination. Among them, aromatic polyisocyanates such as diphenylmethane diisocyanate are preferred when importance is attached to durability and heat resistance, and aliphatics such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferred when light resistance is important. A polyisocyanate is preferably used.

  As the chain extender, for example, amine chain extenders such as ethylenediamine and methylenebisaniline, diol chain extenders such as ethylene glycol, and polyamine obtained by reacting polyisocyanate with water can be used.

  The resin used in the resin layer in the present invention can contain an elastomer resin such as polyester, polyamide, and polyolefin, acrylic resin, ethylene-vinyl acetate resin, and the like as long as the wear resistance and texture are not impaired. . These resins include various additives such as pigments such as carbon black, flame retardants such as phosphorus, halogen and inorganic, antioxidants such as phenol, sulfur and phosphorus, hindered amines. And a light stabilizer such as benzoate, a hydrolysis stabilizer such as polycarbodiimide, a plasticizer, an antistatic agent, a surfactant, a coagulation regulator, and a dye.

  In the present invention, it is important that the resin layer contains a light-proofing agent and also contains a porous inorganic filler.

  The light-resistant agent and the porous inorganic filler are preferably included in the surface layer of the resin layer, more preferably included in two or more layers including the surface layer, and further preferably included in three or more layers including the surface layer. It is.

  The content (solid content) of the light stabilizer contained in the resin layer is preferably 0.5 to 10% by mass, more preferably 1 to 9% by mass, and more specifically 2 to 8% by mass or less. It is. When the content of the light proofing agent is less than 0.5% by mass, deterioration of the resin layer with time, particularly with light, cannot be suppressed, and yellowing or durability of the resin layer may be deteriorated. Moreover, when content of a light-resistant agent exceeds 10 mass%, the membrane | film | coat intensity | strength of resin may be impaired and the abrasion resistance of a sheet-like material may fall.

  Further, as the light stabilizer used in the present invention, specifically, benzotriazole, benzophenone, triazine, cyanoacrylate, oxanilide, salicylate, formamidine, carbazide, benzoate, nickel complex , Hindered amines, and cinnamic acid esters, and the like. These can be used alone or in combination of two or more. Of these, benzotriazole-based light stabilizers are preferably used from the viewpoint of good heat resistance and high absorption performance with respect to ultraviolet wavelengths.

  Moreover, it is preferable that the number average molecular weights of a light resistance agent are 300-100,000, More preferably, it is 350-50000, More preferably, it is 400-10,000. If the number average molecular weight of the light resisting agent is less than 300, it is likely to volatilize by heat and may cause fogging.

  It is preferable that content (solid content) of the porous inorganic filler contained in a resin layer is 0.1-10 mass%, More preferably, it is 0.5-8 mass%, More preferably, it is 1-5. % By mass.

  When the content of the porous filler is less than 0.1% by mass, the fogging resistance may be deteriorated because the volatile components cannot be retained in the pores. On the other hand, if the content of the porous filler exceeds 10% by mass, the surface-like feel of the cloth-like leather may become rough, and further, the film strength of the resin may be impaired and the wear resistance of the sheet-like material may be lowered.

  The porous inorganic filler used in the present invention is mainly a layered clay mineral, for example, a silicate mineral having a layered structure, a tetrahedron composed of silicic acid, an octahedron including Al, Mg, and the like. It is a substance having a layered structure in which etc. are laminated. Examples of such materials include montmorillonite, saponite, hectorite, piderite, stevensite, nontronite, vermiculite, halloysite, mica, fluorinated mica, kaolinite, pyrophyllolite and the like. The product may be a product or a synthetic product. Further, zirconium phosphate, swellable mica treated with fluorine, and the like can also be used. These may be used individually by 1 type, and can also be used in combination of 2 or more type. Of these layered inorganic compounds, montmorillonite, saponite, hectorite, fluorinated mica and the like are preferably used.

  Moreover, it is preferable that the total thickness of the resin layer of this invention is 0.001-0.4 mm. When the total thickness is less than 0.001, the wear resistance tends to be inferior, and when the total thickness exceeds 0.4 mm, the texture is hard. The total thickness is more preferably 0.01 to 0.3 mm, and still more preferably 0.05 to 0.25 mm.

  The thickness of each layer of the resin layer is preferably 0.001 to 0.02 mm for the first layer and the second layer, and preferably 0.008 to 0.06 mm for the third layer. The first layer and the second layer each have a maximum of about 0.065 mm, and the third layer has a maximum of about 0.25 mm.

  Next, a method for producing the sheet-like material of the present invention will be described.

  The ultrafine fibers constituting the sheet-like material of the present invention can be obtained by using ultrafine fiber expression type fibers composed of two or more kinds of polymer substances having different solubility in a solvent.

  As ultrafine fiber expression type fiber, two-component thermoplastic resins with different solubility in solvent are used as sea component and island component, and the sea component is dissolved and removed using solvent to make island component into ultrafine fiber. It is possible to employ a composite fiber or a peelable composite fiber in which the fiber surface is split into ultrafine fibers by alternately disposing the fiber surface in a radial or multilayered manner and separating it by solvent treatment. . Above all, the sea-island type composite fiber can provide an appropriate gap between island components, that is, between the ultrafine fibers inside the fiber bundle by removing the sea component, so from the viewpoint of flexibility and texture of the base material. Preferably used.

  For the production of sea-island type composite fibers, a sea-island-type composite base is used, and a polymer inter-array system in which two components, the sea component and the island component, are spun together, and the two components, the sea component and the island component, are mixed. A mixed spinning method in which spinning is performed can be used, but a sea-island type composite fiber manufacturing method by a polymer array system is more preferably used in that ultrafine fibers having a uniform fineness can be obtained.

  It is a preferable aspect that the ultrafine fibers are in the form of a nonwoven fabric (ultrafine fiber web) in the fiber structure. By using a nonwoven fabric, a uniform and elegant appearance and texture can be obtained. The form of the nonwoven fabric (extra fine fiber web) may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric, but a short fiber nonwoven fabric is preferably used when emphasis is placed on texture and quality.

  When the short fiber nonwoven fabric is used, the fiber length of the ultrafine fiber is preferably 25 mm or more and 90 mm or less. By setting the fiber length of the ultrafine fiber to 90 mm or less, good quality and texture can be obtained, and by setting the fiber length to 25 mm or more, a sheet-like product having good wear resistance can be obtained.

  In the present invention, the obtained ultrafine fiber-generating fiber is preferably crimped and cut into a predetermined length to obtain a nonwoven raw cotton. The ultrafine fiber generating fiber can be used as a long-fiber nonwoven fabric without being cut into a predetermined length, but when emphasizing the texture and quality, it is preferable to cut into a predetermined length to obtain a short-fiber nonwoven fabric. . Similarly, when emphasis is placed on texture and quality, the fiber length of the short fibers is preferably 25 mm or more and 90 mm or less in consideration of wear resistance due to entanglement. A known method can be used for crimping or cutting.

  Next, the obtained raw cotton is made into a fiber web by a cross wrapper or the like and entangled to obtain a nonwoven fabric. As a method for obtaining a nonwoven fabric by entanglement of fiber webs, needle punch, water jet punch or the like can be used. Further, the basis weight of the fiber web can be appropriately set in consideration of the design of the final product, the dimensional change in the subsequent process, the characteristics of the processing machine, and the like.

  It is also a preferable aspect to obtain a laminated sheet of a nonwoven fabric and a woven / knitted fabric made of ultrafine fiber generating fibers by entangled and integrating a woven / knitted fabric and a fiber structure made of ultrafine fiber generating fibers. A method such as needle punching or water jet punching can be used as a method for intertwining both. Among these, the entanglement process by the needle punch is a preferable aspect from the viewpoint of the bonding property and the quality of the product. From the viewpoint of densification, the laminated sheet of the fiber structure and woven / knitted fabric made of ultrafine fiber-generating fibers thus obtained is subjected to dry heat and / or wet heat in the stage before applying the polymer elastic body. It is a preferable embodiment that the resin is shrunk and further densified. This shrinkage treatment can be performed before or after the development of the ultrafine fibers, but can also be performed after the development. However, in the point that the characteristics of the sea component polymer of the ultrafine fiber generation type fiber can be used for the shrinkage, before the ultrafine fibers are generated. It is a preferable aspect to perform the shrinkage treatment.

  Moreover, it is preferable that the range of the area shrinkage rate of the lamination sheet in this shrinking process is 15% or more and less than 35%. By setting the area shrinkage rate to 15% or more, an effect of improving the quality due to the shrinkage can be preferably obtained. In addition, by setting the area shrinkage rate to less than 35%, it is possible to leave room for shrinkage in the woven or knitted fabric integrated with the nonwoven fabric, so that it is possible to efficiently shrink after the polymer elastic body is applied later. Become. The range of the area shrinkage rate is more preferably 13% or more and less than 30%, and further preferably 15% or more and less than 25%.

  The method for producing a sheet-like product according to the present invention is a method of treating a laminated sheet of a fiber structure composed of the above-described ultrafine fiber generating fiber and a woven or knitted fabric to express ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 8 μm or less. Including the step of Examples of the ultrafine fiber generation treatment method include a method in which one of the resins constituting the ultrafine fiber generation type fiber is dissolved with a solvent. In particular, for the ultrafine fiber-generating sea-island composite fiber in which the sea component is made of an easily soluble polymer and the island component is made of a hardly soluble polymer, a method of dissolving the sea component is preferable.

  As the solvent for dissolving the sea component, when the sea component is a polyolefin such as polyethylene or polystyrene, an organic solvent such as toluene or trichloroethylene is used. When the sea component is polylactic acid or copolymer polyester, an aqueous alkali solution such as sodium hydroxide can be used. Further, this ultrafine fiber generation processing (sea removal treatment) can be performed by immersing a fiber entangled body made of ultrafine fibers in a solvent and squeezing it.

  Subsequently, the fiber structure containing the obtained ultrafine fibers is subjected to a treatment for imparting a polymer elastic body. A method of performing either the treatment for expressing the ultrafine fiber from the ultrafine fiber expression type fiber or the treatment for imparting the polymer elastic body may be employed. When the ultrafine fiber expression treatment is performed first, the polymer elastic body holds the ultrafine fiber, so that the ultrafine fiber does not fall off and can be used for a longer period of time. Further, when the polymer elastic body is applied first, since the polymer elastic body has a structure in which the ultrafine fibers are not gripped, an artificial leather having a good texture can be obtained. Which is performed first can be appropriately selected depending on the type of polyurethane to be used.

  Moreover, when providing a polymeric elastic body after the expression process of an ultrafine fiber, it is preferable to provide the process of providing a water-soluble resin between both processes. By providing the step of applying the water-soluble resin, the surface of the fiber constituting the fiber bundle of the ultrafine fiber and the woven or knitted fabric is protected by the water-soluble resin, and on the surface of the fiber constituting the fiber bundle of the ultrafine fiber and the woven or knitted fabric. In addition, the portions directly bonded to the polymer elastic body exist intermittently rather than continuously, and the adhesion area can be moderately suppressed. As a result, it is possible to obtain an artificial leather having a high stretchability when a soft texture or a woven or knitted fabric made of a composite fiber such as a side-by-side type is used while having a good hand feeling due to the polymer elastic body. .

  As such a water-soluble resin, polyvinyl alcohol, polyethylene glycol, saccharides, starch and the like can be used. Among them, polyvinyl alcohol having a saponification degree of 80% or more is preferably used.

  Examples of the method for imparting the water-soluble resin to the fiber entangled body include a method of impregnating the fiber structure with an aqueous solution of the water-soluble resin and drying. From the viewpoint of suppressing the shrinkage of the woven or knitted fabric, the drying conditions such as the drying temperature and the drying time are preferably controlled so that the temperature of the fiber entangled body to which the water-soluble resin is applied is suppressed to 110 ° C. or lower.

  It is preferable that the application amount of the water-soluble resin is 1 to 30% by mass with respect to the mass of the fiber entangled body immediately before application. By setting the applied amount to 1% by mass or more, in the case of a sheet-like material using a woven or knitted fabric made of a composite fiber such as a good texture and side-by-side type, good stretch properties can be obtained. In addition, when the applied amount is 30% by mass or less, a sheet shape having good workability and good physical properties such as wear resistance can be obtained. In addition, since the amount of the polymer elastic body that can be imparted to the fiber entangled body increases in the subsequent process, the density of the sheet-like material and the tactile sensation can be increased.

  In the method for producing a sheet-like product of the present invention, a method of laminating a sheet in which a woven or knitted fabric is laminated on a nonwoven fabric, which is a precursor, before application of a polymer elastic body, as needed, before applying the polymer elastic body is It is known as a method of improving Generally, the napped-tone artificial leather that has undergone the process of shrinking the nonwoven fabric is improved in quality because the napped density increases.

  In the method for producing a sheet-like product of the present invention, a step of half-cutting a fiber structure (artificial leather precursor sheet) provided with a polymer elastic body in the plane direction can be performed. By including a half-cutting process, the productivity of artificial leather can be improved. For example, when adopting a method of laminating a nonwoven fabric layer composed of ultrafine fiber-generating fibers as a method of laminating a woven or knitted fabric, the precursor sheet is cut in half and the inner surface is a raised surface However, this is a preferred embodiment as a method for achieving precise quality.

  It is important that the sheet-like material of the present invention has napping on at least one side. The napping treatment can be performed by buffing the surface of the fiber structure using a sandpaper or a roll sander. In particular, by using sandpaper, uniform and dense napping can be formed. Furthermore, in order to form uniform napping on the surface of the fiber structure, it is preferable to reduce the grinding load.

  The sheet-like material of the present invention is suitably dyed. The dyeing is preferably carried out using a high-temperature and high-pressure dyeing machine in order to soften the texture of the dyed sheet using disperse dyes, cationic dyes or other reactive dyes.

  Furthermore, if necessary, finishing treatments such as softeners such as silicone, antistatic agents, water repellents, flame retardants, and light resistance agents can be applied, and the finishing treatment can be performed after dyeing or in the same bath as dyeing. it can. For the flame-retardant treatment, known halogen-based flame retardants such as bromine and chlorine and non-halogen-based flame retardants such as phosphorus can be used. It can also be applied by coating.

  In the sheet-like material of the present invention, a discontinuous resin layer is formed on the raised surface, and the resin layer has a layer structure of two or more layers. Furthermore, it is a more preferable aspect that the resin layer has a three-layer structure including an adhesive layer, an intermediate layer, and a surface layer. Here, the adhesive layer has an adhesive function between the sheet-like material, the intermediate layer, and the resin layer of the surface layer.

  The method for forming the resin layer in the present invention is not particularly limited as long as it can be applied discontinuously on the surface of the fiber structure to be a sheet-like material, but a screen method such as a flat screen or a rotary screen, or gravure coating A method of drying to form a resin layer after application by a method, etc., and after forming a discontinuous resin film on a supporting base fiber such as a release paper, an adhesive is applied to the surface of the resin film, Examples include a method of forming a resin layer by pasting and bonding to a surface to be a fiber structure and peeling a release paper.

  Furthermore, in order to make a resin layer into two layers or three layers, it can form by repeating said method twice or three times. Moreover, about said method, the same method may be repeated and it can also be used in combination of 2 or more types.

  The sheet-like material of the present invention obtained from the above has the feel of natural nubuck leather and the feeling of napping and breathability of natural suede leather, and is further excellent in light resistance and fogging resistance. It can be suitably used widely from furniture, chairs and vehicle interior materials to which leather is used, to clothing applications.

  Next, an example is given and the sheet-like material of the present invention is explained in detail.

[Measuring method and processing method for evaluation]
(1) Average single fiber diameter of ultrafine fibers:
Take a scanning electron microscope (SEM) photograph of the cross section of the sheet of the sheet, select 100 circular or near-circular elliptical fibers, measure the single fiber diameter, and calculate the average value of 100 It was calculated by doing. In the case where an ultrafine fiber having an irregular cross section was adopted, the diameter of the circumscribed circle of the ultrafine fiber was defined as the single fiber diameter, and the same calculation was performed.

(2) Total thickness of the resin layer on the surface of the sheet-like material:
A cross section perpendicular to the planar direction and the machine direction of the sheet-like material was cut out and placed on the sample stage so that the cross section was not distorted. Subsequently, using a scanning electron microscope (SEM, VE-7800 manufactured by Keyence Corporation), 10 sheets of the cross section of the sheet-like sample piece were photographed at different magnifications of 200 times. From each of these captured images, when the direction parallel to the cross section is horizontal, the napped layer side of the cross section is up, and the other surface is down, the highest position z1 of the resin layer and the lowest position z2 of the resin layer The distance between the two points was obtained, and the total thickness of the resin layer was calculated. Furthermore, the average value of 10 values obtained by calculation was defined as the total thickness of the resin layer.

(3) Light resistance of sheet surface:
Using a xenon weather meter manufactured by Suga Test Instruments Co., Ltd., the sheet-like material is irradiated with light having a wavelength of 300 to 400 nm, an irradiance of 150 W / m ² , a black panel temperature of 73 ± 3 ° C., a chamber temperature of 38 ° C., and a relative humidity. After performing a forced deterioration treatment with light irradiation at 50 ± 5% for 144 hours, the degree of color change of the sheet-like material after irradiation is determined using the gray scale for color change of JIS L0804 (2004). Judgment was performed by class judgment of 9 steps from 1 to 5 in increments of 0.5. The n number was set to 3, and the remaining grades excluding the best grade and the worst grade were used as the evaluation results. For example, if the n = 3 class judgment is grade 3, grade 3 and grade 4, the evaluation result is grade 3, and if grade 3, grade 4 and grade 4, the assessment result is grade 4. In the present invention, grade 3 or higher was regarded as acceptable.

(4) Fogging resistance of sheet material:
Three samples with a diameter of 80 cm are collected. A fogging test is performed by heating at 80 ° C. for 3 hours in a glass sag acceleration test apparatus (window screen fogging tester WF-2, manufactured by Suga). Next, the reflectance of the glass plate (110 mm × 110 mm square shape, thickness 3 mm) after the fogging test is measured with a gonioglossimeter (manufactured by Suga; UGV-5) using a halogen lamp as a light source. The measurement angle (incident angle and light receiving angle) is 60 degrees, the sample is rotated 90 degrees, and measurement is performed 4 times per sample (360 degrees by 4 times 90 degrees). , R2, R3, and R4, the reflectance R after the fogging test is calculated by the following equation.
R = (R1 + R2 + R3 + R4) / 4.

The fogging resistance referred to in the present invention is obtained from the R value and the following R0 value by the following equation.
・ Fog resistance (%) = R / R0 × 100
That is, here, R0, R2, R3 and R4 are the reflectance (%) of the glass plate after the fogging test, R is the average value of R1, R2, R3 and R4, and R0 is the value before the fogging test. It is the reflectance (%) of the glass plate. In the present invention, the average value was calculated by setting the number of n to 3 (3 samples), and the numbers after the decimal point were rounded off. In the evaluation judgment, the fogging resistance was 90% or more.

(5) Evaluation of surface texture of sheet-like material:
The surface tactile sensation of the sheet-like material was evaluated by sensory inspection of 10 subjects. Compared with the dense and wet tactile sensation of natural nubuck, those judged by 8 or more people to have a dense and wet tactile sensation (double circle: ◎), and those judged by 5-7 (single circle: ◯), those determined by 3-4 persons (triangle: Δ), and those determined by 2 persons or less were classified as (×). Double circle and single circle were accepted. In this determination, those having a natural nubuck-like feel are high.

(6) Evaluation of surface texture of sheet-like material:
The surface napping feeling of the sheet-like material was evaluated by a sensory test of 10 subjects. Compared with the feeling of napping of natural suede, 8 or more people judged that they had a suede-like napping feeling (double circle: ◎), 5-7 people judged (single circle: 〇), Those determined by 3-4 persons were classified as (triangle: Δ), and those determined by 2 persons or less were classified as (x). Double circle and single circle were accepted. In this determination, those having a natural suede-like feel are high.

(7) Evaluation of abrasion resistance on the surface of the sheet-like material:
Regarding the sheet-like material to be evaluated, one circular test piece having a diameter of 120 mm was collected from an arbitrary place and tested by the Taber abrasion test method of Section 6.1 of ASTM D3884. In the test, the CS # 10 wear wheel was subjected to 1000 rotation wear at 4.9 N, and then the wear state of the surface of the sheet-like object was observed. The grade was judged according to the evaluation. In the evaluation of the present invention, grades 3 to 5 were regarded as acceptable.
-Grade 5: No difference from the pre-test condition.
-Fourth grade: Slight cracking or peeling of the surface resin layer is observed, but it is hardly noticeable.
・ Third class: Clearly, cracking and peeling of the surface resin layer are observed, but not noticeable.
・ Second grade: Slightly significant cracking or peeling of the surface resin layer.
・ First grade: The surface resin layer is cracked and peeled off.

[Example 1]
<Raw cotton>
Polyethylene terephthalate is used as the island component, polystyrene is used as the sea component, a sea-island type composite die having 16 islands is melt-spun at an island / sea mass ratio of 80/20, and then drawn and crimped. After that, it was cut into a length of 51 mm to obtain a sea-island type composite fiber raw cotton.

<Laminated web (nonwoven fabric) and laminated sheet with woven / knitted fabric>
In order to form a laminated web (nonwoven fabric) through a card and cross wrapping process using the above-mentioned raw material of sea-island type composite fiber, 100 w / cm ² in order to suppress a fabric wrinkle due to a sudden width change after the fabric bonding Needle punching was performed with the number of punches. Separately, a single yarn composed of a single component having an intrinsic viscosity (IV) of 0.65 and a multifilament (84 dtex, 72 filaments) having a twist number of 2500 T / m is used for the weft, and the intrinsic viscosity (IV) is 0.65. This is a single yarn composed of a single component, and a multifilament (84 dtex, 72 filaments) having a twist number of 2500 T / m is used as a warp. The weave density is 97 warp / 2.54 cm, and the weft is 76 strands / 2.54 cm. A plain fabric was woven. The obtained plain woven fabric was laminated on the upper and lower sides of the laminated web (nonwoven fabric).

Thereafter, a needle punch is applied at a punch number (density) of 2500 / cm ² , and a laminate composed of a nonwoven fabric made of ultrafine fiber-generating fibers having a basis weight of 740 g / m ² and a thickness of 3.4 mm and a heat-shrinkable woven fabric. A sheet was obtained.

<Fiber structure>
By treating the laminated sheet obtained in the above step with hot water at a temperature of 96 ° C. to shrink, then impregnating with an aqueous PVA (polyvinyl alcohol) solution and drying with hot air at a temperature of 110 ° C. for 10 minutes, A sheet substrate having a PVA mass of 7.6% by mass relative to the mass of the laminated sheet was obtained. The sheet substrate thus obtained is immersed in trichlorethylene to dissolve and remove polystyrene as a sea component, and a seawater-removed sheet in which ultrafine fibers having an average single fiber fineness of 4.4 μm are intertwined with a plain fabric. Got. The seawater-free sheet composed of the non-woven fabric and the plain fabric thus obtained was immersed in a polyurethane DMF (dimethylformamide) solution adjusted to a solid content concentration of 12%, and then a DMF concentration of 30%. The polyurethane was coagulated in an aqueous solution. Thereafter, PVA and DMF are removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes, whereby a fiber structure in which the polyurethane mass is 27% by mass with respect to the total mass of the ultrafine fibers made of island components and the above-mentioned plain fabric. A precursor sheet of the product was obtained.

  The fiber structure precursor sheet thus obtained is cut in half in the thickness direction and the non-woven fabric layer inside the precursor sheet is cut in half, and the cut sheet surface is ground with an endless sandpaper of sandpaper number 320 Then, a raised surface was formed on the surface layer portion to obtain a fiber structure having a thickness of 0.81 mm. The fiber structure thus obtained was subjected to shrinkage treatment and dyeing at the same time under a temperature condition of 120 ° C. using a liquid dyeing machine, and then dried with a dryer to obtain a fiber structure. Obtained.

<Resin layer formation>
A polyurethane DMF (dimethylformamide) solution adjusted to a solid content concentration of 25% contains 4% by mass of a polyurethane solid content ratio and a benzotriazole-based light-resisting agent having a molecular weight of 448 (TINSFINN 234 manufactured by BASF). Adjust the solution to contain 2% by mass of the porous inorganic filler montmorillonite, repeat the rotary coating method 3 times on the raised surface of the fiber structure obtained in the previous step, and discontinuously coat the surface A polyurethane resin layer having a thickness of 0.2 mm was formed using the three-layer structure. Further, the resin layer portions are dotted in an island shape on the surface, and the resin portions and napped portions are irregularly and discontinuously arranged, and the ratio of the resin portion to the fiber structure surface is 60%. It was. The sheet-like material obtained in this way was excellent in light touch and fogging resistance while having the feel of natural nubuck leather and the natural nap of suede leather. The results are shown in Table 1.

[Example 2]
<Raw cotton>
Polyethylene terephthalate is used as the island component, polystyrene is used as the sea component, and a sea-island type composite base with 100 islands is used for melt spinning at an island / sea mass ratio of 80/20, followed by drawing and crimping. After that, it was cut into a length of 51 mm to obtain a sea-island type composite fiber raw cotton.

<Laminated web (nonwoven fabric) and laminated sheet with woven / knitted fabric-resin layer formation>
The average single fiber diameter of the ultrafine fibers is 0.3 μm and the surface is dotted with island-like resin layers in the same manner as in Example 1 except that the sea-island type composite fiber raw cotton is used. The resin portion and the napped portion were irregularly and discontinuously arranged, and a ratio of the resin portion to the fabric surface was 70%. The sheet-like material obtained in this way was good in that it had the feel of natural nubuck leather and the nap of natural suede leather, and was excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Example 3]
<Raw cotton>
Polyethylene terephthalate is used as the island component, polystyrene is used as the sea component, and a sea-island type composite die having 8 islands is melt-spun at an island / sea mass ratio of 80/20, and then drawn and crimped. After that, it was cut into a length of 51 mm to obtain a sea-island type composite fiber raw cotton.

<Laminated web (nonwoven fabric) and laminated sheet with woven / knitted fabric-fiber structure>
A fiber structure in which the average single fiber diameter of the ultrafine fibers was 7.0 μm was obtained in the same manner as in Example 1 except that the above-mentioned sea-island type composite fiber was used.

<Resin layer formation>
A polyurethane DMF (dimethylformamide) solution adjusted to a solid content concentration of 25%, followed by 6% by mass of a polyurethane solid content ratio and a benzotriazole-based molecular weight 316 light-resistant agent (TINUVINN 326 manufactured by BASF) were further added. The solution was adjusted to contain 3% by mass of the porous inorganic filler montmorillonite, and the rotary coating method was repeated three times on the raised surface of the fiber structure obtained in the above process, and the surface was discontinuous. A polyurethane resin layer having a thickness of 0.2 mm was formed by the coated three-layer structure. In addition, the resin layer portions are dotted in an island shape on the surface, and the resin portions and the napped portions are irregularly and discontinuously arranged, and the ratio of the resin portion to the fiber structure surface is 60%. there were. The sheet-like material thus obtained has a larger average single fiber diameter of the ultrafine fibers than Example 1, so that the surface feel and the nap feel are slightly inferior, but the feel of natural nubuck leather and the natural suede are slightly inferior. It had a feeling of napping of leather and was excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Example 4]
<Raw cotton>
Polyethylene terephthalate is used as the island component, polystyrene is used as the sea component, a sea-island type composite die having 36 islands is melt-spun at an island / sea mass ratio of 55/45, and then drawn and crimped. After that, it was cut into a length of 51 mm to obtain a sea-island type composite fiber raw cotton.

<Laminated web (nonwoven fabric) and laminated sheet with woven / knitted fabric>
Using the above-mentioned raw material of sea-island type composite fiber, a laminated web is formed through a card and cross wrapping process, and the number of punches is 100 / cm ^{2 in} order to suppress fabric wrinkles due to a sudden change in width after fabric bonding. Needle punched. Separately, it is a side-by-side type composite yarn having a composite ratio (mass%) of 50:50 made of PET having an intrinsic viscosity (IV) of 0.78 and PET having an intrinsic viscosity (IV) of 0.51, and the twist number is 1500 T / m. Multifilaments (56 dtex, 12 filaments) are used as weft yarns, and multifilaments (84 dtex, 72 filaments) having a twist of 2500 T / m and a single yarn having an intrinsic viscosity (IV) of 0.65 are used as warp yarns. A plain fabric having a weaving density of warp 69 / 2.54 cm and weft 83 / 2.54 cm was woven. The obtained plain woven fabric was laminated on the upper and lower sides of the laminated web.

Thereafter, a needle punch is applied at a punch number (density) of 2500 / cm ² , and a nonwoven fabric made of ultrafine fiber generating fibers having a basis weight of 560 g / m ² and a thickness of 2.3 mm, and a heat-shrinkable woven fabric. A laminated sheet was obtained.

<Fiber structure>
By treating the laminated sheet obtained in the above step with hot water at a temperature of 96 ° C. to shrink, then impregnating with an aqueous PVA (polyvinyl alcohol) solution and drying with hot air at a temperature of 110 ° C. for 10 minutes, A sheet substrate having a PVA mass of 4.0 mass% with respect to the laminated sheet mass was obtained. The sheet substrate thus obtained is immersed in trichlorethylene to dissolve and remove the polystyrene as a sea component, and the sea removal sheet is formed by intertwining ultrafine fibers having an average single fiber fineness of 2.1 μm and a plain fabric. Got. The seawater-free sheet composed of the nonwoven fabric and the plain fabric thus obtained was immersed in a polyurethane DMF (dimethylformamide) solution adjusted to a solid content concentration of 12%, and then a DMF concentration of 30%. The polyurethane was coagulated in an aqueous solution. Thereafter, PVA and DMF are removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes, whereby a fiber structure in which the polyurethane mass is 20% by mass with respect to the total mass of the ultrafine fibers made of island components and the above-mentioned plain fabric A precursor sheet of the product was obtained.

  The fiber structure precursor sheet thus obtained is half-cut in the thickness direction and the nonwoven fabric layer inside the fiber structure precursor sheet is vertically cut, and the half-cut sheet surface is the endless number of sandpaper count 320. By grinding with sandpaper, a raised surface was formed on the surface layer portion to obtain a raw artificial leather machine having a thickness of 0.46 mm. The fiber structure living machine thus obtained is subjected to shrinkage treatment and dyeing at the same time under a temperature condition of 120 ° C. using a liquid dyeing machine, and then dried in a dryer to obtain a fiber structure. Obtained.

<Resin layer formation>
A polyurethane DMF (dimethylformamide) solution adjusted to a solid content concentration of 25%, followed by 4% by mass of polyurethane solids mass ratio, benzotriazole-based molecular weight 448 light stabilizer (TINUVINN 234 made by BASF), and polyurethane solids The solution was adjusted to contain 2% by mass of the porous inorganic filler montmorillonite, and the gravure coating technique was repeated twice on the raised surface of the fiber structure obtained in the above process, and the surface was discontinuous. A polyurethane resin layer having a thickness of 0.2 mm was formed with a coated two-layer structure. Further, the resin layer portions are dotted in an island shape on the surface, the resin portions and the napped portions are irregularly and discontinuously arranged, and the ratio of the resin portion to the fabric surface is 30%. . The sheet-like material obtained in this way was good in that it had the feel of natural nubuck leather and the nap of natural suede leather, and was excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Example 5]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure using fibers having an average single fiber diameter of 4.3 μm was obtained.

<Resin layer formation>
A polyurethane DMF (dimethylformamide) solution adjusted to a solid content concentration of 25%, followed by 6% by mass of polyurethane solids mass ratio, benzophenone-based light-proofing agent with a molecular weight of 326 (BASF CHIMASSORB 81), and polyurethane solids Adjust the solution to contain 3% by mass of the porous inorganic filler montmorillonite by mass ratio, repeat the rotary coating method 3 times on the raised surface of the fiber structure obtained in the above process, and discontinuously coat the surface A three-layer polyurethane resin layer was formed. In addition, the resin layer portions are dotted in an island shape on the surface, and the resin portions and the napped portions are irregularly and discontinuously arranged, and the ratio of the resin portion to the fiber structure surface is 60%. there were. The sheet-like material obtained in this way was good in that it had the feel of natural nubuck leather and the nap of natural suede leather, and was excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Example 6]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.2 μm.

<Resin layer formation>
A polyurethane DMF (dimethylformamide) solution adjusted to a solid content concentration of 25%, followed by 8% by mass of a polyurethane solid content mass ratio, a benzotriazole molecular weight 225 light stabilizer (LA-32 manufactured by ADEKA), and polyurethane Adjust the solution to contain 4% by mass of the solid content mass ratio and the porous inorganic filler montmorillonite, and repeat the rotary coating method three times on the raised surface of the fiber structure obtained in the above process, discontinuously surface A polyurethane resin layer having a thickness of 0.2 mm was formed in a three-layer structure coated with. In addition, the resin layer portions are dotted in an island shape on the surface, and the resin portions and the napped portions are irregularly and discontinuously arranged, and the ratio of the resin portion to the fiber structure surface is 60%. there were. The sheet-like material thus obtained has a light fogging agent with a lower molecular weight than that of Example 1, so that the fogging resistance is slightly inferior, but has the feel of natural nubuck leather and the feeling of napping of natural suede leather. However, it was also excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Example 7]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.3 μm.

<Resin layer formation>
A sheet-like material was obtained in the same manner as in Example 1 except that the polyurethane solid mass ratio and the porous inorganic filler were changed to saponite. The sheet-like material obtained in this way was good in that it had the feel of natural nubuck leather and the napping feeling of natural suede leather, and was further excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Example 8]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.3 μm.

<Resin layer formation>
A sheet-like material was obtained in the same manner as in Example 1, except that 1% by mass of a polyurethane solid content weight ratio and a benzotriazole-based molecular weight 448 light-resistant agent (TINUVIN 234 manufactured by BASF) was contained. The sheet-like material obtained in this way has a light resistance slightly lower than that of Example 1, so that the light resistance is slightly inferior, but has a natural nubuck leather feel and a natural suede leather nap. However, it was also excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Example 9]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.4 μm.

<Resin layer formation>
10 mass% of polyurethane solid content mass ratio, benzotriazole-based molecular weight 448 light-resistant agent (TINUVIN 234 manufactured by BASF) was contained, and polyurethane solid content mass ratio and montmorillonite of a porous inorganic filler were contained 5 mass%. Except for this, a sheet-like material was obtained in the same manner as in Example 1. Since the sheet-like material thus obtained has a larger amount of light-resistant agent compared to Example 1, the abrasion resistance is slightly inferior, but the feel of natural nubuck leather and the feeling of napping of natural suede leather are achieved. Furthermore, it was excellent in light resistance and fogging resistance while having it. The results are shown in Table 1.

[Example 10]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.4 μm.

<Resin layer formation>
A sheet-like material was obtained in the same manner as in Example 1 except that the polyurethane solid content mass ratio and the porous inorganic filler montmorillonite were added in an amount of 0.1% by weight. The sheet-like material thus obtained has a slightly lower fogging resistance because the amount of the porous inorganic filler added is smaller than that in Example 1, but the feel of natural nubuck leather and the napped of natural suede leather While having a feeling, it was excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Example 11]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.3 μm.

<Resin layer formation>
A sheet-like material was obtained in the same manner as in Example 1 except that the polyurethane solid content mass ratio and the porous inorganic filler montmorillonite were contained at 10 mass%. The sheet-like material thus obtained has a slightly inferior surface feel because the amount of the porous inorganic filler added is larger than that of Example 1, but the feel of natural nubuck leather and the feeling of napping of natural suede leather are somewhat poor. Furthermore, it was excellent in light resistance and fogging resistance. The results are shown in Table 1.

[Comparative Example 1]
<Raw cotton>
Polyethylene terephthalate is used as the island component, polystyrene is used as the sea component, and a sea-island type composite die having 8 islands is melt-spun at an island / sea mass ratio of 80/20, and then drawn and crimped. After that, it was cut into a length of 51 mm to obtain a sea-island type composite fiber raw cotton.

<Entangled body (laminated sheet) of nonwoven fabric and woven / knitted fabric to fiber structure>
A fiber structure was obtained in the same manner as in Example 1 except that the above-mentioned sea-island type composite fiber was used, using ultrafine fibers having an average single fiber diameter of 8.5 μm.

<Resin layer formation>
A sheet-like material was obtained in the same manner as Example 1. Although the sheet-like material obtained in this way is excellent in light resistance and fogging resistance, the average single fiber diameter of the ultrafine fibers is too large, so it does not have the feel of natural nubuck leather and is natural. The suede leather was also inferior to the raised feeling. The results are shown in Table 1.

[Comparative Example 2]
<Laminated cotton to laminated web (nonwoven fabric) and laminated sheet with woven / knitted fabric>
In the same manner as in Example 1, a laminated sheet composed of a nonwoven fabric composed of ultrafine fiber-generating fibers having an average single fiber diameter of 4.2 μm and a heat-shrinkable fabric was obtained.

<Fiber structure>
A fiber structure was obtained in the same manner as in Example 1 except that the endless sandpaper was not ground and the napped surface was not formed on the surface layer portion.

<Resin layer formation>
A sheet-like material was obtained in the same manner as in Example 1. The sheet-like material thus obtained has the feel of natural nubuck leather and is excellent in light resistance and fogging resistance, but has no raised surface on the surface layer portion, so natural suede leather There was no feeling of napping at all, and it was inferior to the touch feeling similar to the conventional synthetic leather. The results are shown in Table 1.

[Comparative Example 3]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.1 μm.

<Resin layer formation>
A polyurethane resin layer with a uniform three-layer structure and a thickness of 0.2 mm is formed by a rotary coating method. The resin layer portion is dotted in an island shape on the surface, and the resin portion and the napped portion are regularly and continuously. A sheet-like material was obtained in the same manner as in Example 1 except that it was arranged. The sheet-like material thus obtained has a raised feeling of suede leather and is excellent in light resistance and fogging resistance, but the resin part and the raised part are arranged regularly and continuously. The crack of this was developed and the feel of natural nubuck leather was inferior. The results are shown in Table 1.

[Comparative Example 4]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.0 μm.

<Resin layer formation>
A sheet-like material was obtained in the same manner as in Example 1 except that a single polyurethane resin layer whose surface was discontinuously coated was formed. Further, on the surface, the resin layer portions are dotted in an island shape, and the resin portions and the napped portions are irregularly and discontinuously arranged, and the ratio of the resin portion to the fabric surface is 8%. It was. Although the sheet-like material obtained in this way is excellent in light resistance and fogging resistance, the ratio of the resin portion to the fabric surface is too low, so that a natural nubuck-like surface feel and feel can be obtained. Rather, the suede leather had a strong nap and a poor wear resistance. The results are shown in Table 1.

[Comparative Example 5]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure using fibers having an average single fiber diameter of ultrafine fibers of 3.9 μm was obtained.

<Resin layer formation>
A sheet-like material was obtained in the same manner as in Example 1 except that the polyurethane resin did not contain a porous inorganic filler. The sheet-like material thus obtained has the feel of natural nubuck leather and the nap of suede leather, and further has light resistance, but contains a porous inorganic filler in the polyurethane resin. As a result, the fogging resistance was poor. The results are shown in Table 1.

[Comparative Example 6]
<Raw cotton to fiber structure>
In the same manner as in Example 1, a fiber structure was obtained using fibers having an average single fiber diameter of 4.1 μm.

<Resin layer formation>
A sheet-like material was obtained in the same manner as in Example 1 except that the polyurethane resin did not contain a light proofing agent and a porous inorganic filler. Although the sheet-like material thus obtained has the feel of natural nubuck leather and the nap of suede leather, it does not contain a light-resistant agent and a porous inorganic filler in the polyurethane resin. The fogging resistance was poor. The results are shown in Table 1.

1: Napped portion 2: Resin portion

Claims (7)

It is a fiber structure composed of ultrafine fibers having an average single fiber diameter of 0.1 to 8 μm, and at least one surface of the fiber structure has raised hairs, and all of the following (1) to (3) are satisfied. A sheet-like material characterized by that.
(1) A discontinuous resin layer is formed on the raised surface,
(2) The resin layer is composed of two or more layers,
(3) The resin layer contains a light resistance agent and a porous inorganic filler. The sheet-like material according to claim 1, wherein the resin layer has a three-layer structure.   The sheet-like material according to claim 1 or 2, wherein the total thickness of the resin layer is 0.001 to 0.4 mm.   The sheet-like article according to any one of claims 1 to 3, wherein the light-proofing agent has a molecular weight of 300 or more and 100,000 or less.   The sheet structure according to any one of claims 1 to 4, wherein the fiber structure includes a polymer elastic body therein.   The sheet structure according to any one of claims 1 to 5, wherein the fiber structure includes a reinforcing cloth made of a woven or knitted fabric.   The sheet-like material according to any one of claims 1 to 6, wherein the porous inorganic filler is at least one selected from the group consisting of montmorillonite, saponite, hectorite and fluorinated mica.