JP2016141903A - Method for producing sheet-like material with textured surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-like material with a surface feeling comparable with that of natural leather having a grain pattern.SOLUTION: There is provided a method for producing a sheet-like material with a textured surface, which is obtained by subjecting a sheet-like material comprising a polymeric elastomer and a fibrous base material including an ultrafine fiber having an average fiber diameter of 0.1 to 7 μm to surface treatment. The producing method includes the steps of, in the following order: (i) raising a surface of a sheet-like material having a polymeric elastomer between ultrafine fibers of the fibrous base material including the ultrafine fibers or between bundles of the ultrafine fibers; (ii) imparting unevenness patterns 1, 2 on the surface of the raised sheet-like material by an embossing roll with unevenness patterns on the surface thereof; and (iii) subjecting the sheet-like material imparted unevenness patterns 1, 2 thereon to crumpling treatment in water.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a surface-treated sheet-like product having nappings.

  Suede-like sheet-like materials and nubuck-like sheet-like materials having nappings mainly composed of ultrafine fibers and a polymer elastic body have excellent characteristics not found in natural leather, such as durability and uniformity. It has been used for clothing, chair upholstery and automotive interior materials. In recent years, a quality closer to that of natural leather has been demanded, and in particular, a sheet-like material having a texture pattern that is a characteristic of natural leather has been demanded.

  So far, studies have been made to impart a texture pattern to a suede-like sheet-like material or a nubuck-like sheet-like material. For example, a method using an emboss roll has been proposed (see Patent Documents 1 and 2). However, in this proposal, the sheet-like material is compressed by a wrinkled embossing roll to form a wrinkled concave portion on the surface of the sheet-like material to give a wrinkled pattern. When a wrinkled pattern is applied to the sheet-like material having napping such as an object or a nubuck-like sheet by an embossing roll, the surface of the wrinkled pattern that has become a concave portion becomes smooth because the napped surface is aligned. Is reflected and whitened (see FIG. 1). FIG. 1 is a schematic plan view for exemplifying and explaining a textured pattern of a conventional sheet-like material, which will be described later.

  In other words, the wrinkle pattern of natural leather is a wrinkle-like pattern that appears darker and darker than the surface, whereas the wrinkle pattern of the embossing roll proposed above is natural and light and dark due to whitening of the wrinkle-like pattern. Since it is reversed, it has a different impression from natural leather.

  As another method, a texture pattern is applied with an embossing roll, and at the same time, a resin liquid is applied only to the concave portions, and then only the ultrafine fibers of the convex portions are raised, and the napped portions and the silver surface portion made of ultrafine fibers on the surface. There has been proposed a method for realizing a nubuck-like appearance with a mixture (see Patent Documents 3 and 4). However, this proposed method has a problem that an appearance defect occurs due to a difference in color developability between the surface fibers and the resin.

  Furthermore, as another method, a method is proposed in which a heat-shrinkable woven or knitted fabric integrated with an ultrafine fiber nonwoven fabric containing a polymer elastic body is shrunk to give the sheet surface an uneven pattern similar to the texture of natural leather. (See Patent Document 5). However, the wrinkle pattern obtained by this proposal is rough, and it is considered difficult to control the expression of the wrinkle pattern.

  Thus, the actual situation is that a surface-like sheet-like material having a texture pattern comparable to that of natural leather has not been obtained so far.

JP 59-9282 JP 2002-105870 A JP 2003-113582 A JP 2005-146446 A JP 2012-136801 A

  Therefore, an object of the present invention is to provide a method for producing a surface-treated sheet-like product having a surface feeling comparable to natural leather having a texture pattern.

The present invention relates to a surface-treated sheet-like material obtained by subjecting a sheet-like material comprising a fibrous base material comprising ultrafine fibers having an average fiber diameter of 0.1 μm to 7 μm and a polymer elastic body to surface treatment. In which the following steps (i) to (iii) are performed in this order.
(I) a step of raising the surface of a sheet-like material having a polymer elastic body between ultrafine fibers or a bundle of ultrafine fibers of a fibrous base material comprising ultrafine fibers;
(Ii) a step of providing a concavo-convex pattern on the surface of the raised sheet by an embossing roll having a concavo-convex pattern on the surface;
(Iii) A step of squeezing the sheet provided with the uneven pattern in water.

  According to a preferred aspect of the method for producing a surface-treated sheet-like material of the present invention, the polymer elastic body contains polyurethane as a main component.

  Moreover, according to the preferable aspect of the manufacturing method of the surface processed sheet-like material of this invention, it is carrying out shrinkage | contraction process simultaneously with the hot water of the temperature of 110 degreeC or more in the case of the said stagnation process.

  Moreover, according to the preferable aspect of the manufacturing method of the surface treatment sheet-like material of this invention, the said fiber base material is that the said ultrafine fiber and woven / knitted fabric are entangled and integrated.

  Moreover, according to the preferable aspect of the manufacturing method of the surface-treated sheet-like material of the present invention, the woven or knitted fabric has a dry heat area shrinkage rate in a dry heat treatment at a temperature of 100 ° C. for 5 minutes and a temperature of 140 ° C. for 5 minutes. The difference from the dry heat area shrinkage ratio in the dry heat treatment is in the range of 10% to 25%.

  According to the present invention, it is possible to obtain a surface-treated sheet-like product having a surface feeling comparable to natural leather having a texture pattern.

  The surface-treated sheet-like material obtained by the present invention has a texture pattern in which the surface has raised hairs and is formed by a plurality of convex portions separated by concave portions. After imparting a wrinkle pattern with embossing rolls, etc., by dispersing the smoothed fibers in the recesses, which are wrinkled parts, by scouring, the whitening of the recesses is eliminated and the surface looks inferior to natural leather. Is.

FIG. 1 is a schematic plan view for illustrating a texture pattern of a conventional surface-treated sheet-like material. FIG. 2 is a schematic plan view for illustrating the texture pattern of the surface-treated sheet-like material manufactured according to the present invention.

The present invention relates to a surface-treated sheet-like material obtained by subjecting a sheet-like material comprising a fibrous base material comprising ultrafine fibers having an average fiber diameter of 0.1 μm to 7 μm and a polymer elastic body to surface treatment. The following steps (i) to (iii) are performed in this order.
(I) a step of raising the surface of a sheet-like material having a polymer elastic body between ultrafine fibers or a bundle of ultrafine fibers of a fibrous base material comprising ultrafine fibers;
(Ii) a step of providing a concavo-convex pattern on the surface of the raised sheet by an embossing roll having a concavo-convex pattern on the surface;
(Iii) A step of squeezing the sheet provided with the uneven pattern in water.

  By carrying out the steps (i) to (iii) in this order, in the sheet-like material having a wrinkled pattern, the smoothened fibers of the concave portions on the surface are dispersed, and the whitening of the concave portions is eliminated and the leather is dark blue. A surface-treated sheet-like material having no surface feeling can be obtained.

  First, said process (i) is demonstrated in detail.

  Examples of ultrafine fibers contained in the fibrous base material include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, polylactic acid and other polyesters, 6-nylon and 66-nylon, etc. Various synthetic fibers made of polyamide, acrylic polymer, polyethylene, polypropylene, thermoplastic cellulose, and the like can be used.

  Of these, synthetic fibers made of polyester such as polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate are particularly preferably used from the viewpoint of excellent strength, dimensional stability, light resistance and dyeability.

  Moreover, the fiber obtained from a recycling raw material or a plant-derived raw material can be used from a viewpoint of environmental consideration. Furthermore, ultrafine fibers of different materials can be mixed in the sheet-like material.

  According to various purposes, inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, antibacterial agents, etc. should be added to the polymer that forms ultrafine fibers. Can do.

  It is important that the average single fiber diameter of the ultrafine fibers constituting the surface-treated sheet-like material obtained in the present invention is 0.1 μm or more and 7 μm or less. By setting the average single fiber diameter to 7 μm or less, preferably 5 μm or less, and more preferably 4 μm or less, a surface-treated sheet-like material that is flexible, dense, and has a soft touch surface quality is obtained. Further, when applying a texture pattern by an embossing roll, which will be described later, it is possible to impart a highly durable texture pattern because the fibers are easily crimped.

  On the other hand, by setting the average single fiber diameter to 0.1 μm or more, preferably 0.7 μm or more, more preferably 1 μm or more, color development after dyeing, fiber dispersibility at the time of raising treatment such as grinding with sandpaper, etc. , And has an excellent effect on the ease of judgment.

  The cross-sectional shape of the ultrafine fiber may be a round cross section, but a fiber having an irregular cross section such as an ellipse, a flat shape, a polygon such as a triangle, a sector shape, or a cross shape may be employed.

  The ultrafine fibers contained in the fibrous base material are made of ultrafine fibers by direct spinning or by dissolving and removing two component thermoplastic resins with different solvent solubility from sea components and island components using a solvent or the like. Sea-island composite fibers used as fibers, two-component thermoplastic resins, peelable composite fibers that are split into ultrafine fibers by alternately disposing the cross sections of the fibers radially or in layers and separating and separating each component Can be adopted. Among them, the sea-island type composite fiber can give an appropriate void between island components, that is, between ultrafine fibers inside the fiber bundle by removing the sea component, and is also preferable from the viewpoint of texture and surface quality. Used.

  For the sea-island type composite fiber, a sea-island type compound base is used, and a method using a polymer inter-array in which the sea component and the island component are mutually aligned and spun, and the sea component and the island component are mixed. However, a sea-island type composite fiber by a method using a polymer array is preferably used in that an ultrafine fiber 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 fibrous base material. By using a nonwoven fabric, a uniform and elegant appearance and texture can be obtained.

  As a form of the nonwoven fabric, either a short fiber nonwoven fabric or a long fiber nonwoven fabric may be used. However, when emphasis is placed on texture and quality, a short fiber nonwoven fabric is preferably used.

  The fiber length of the ultrafine fiber in the case of a short fiber nonwoven fabric is preferably 25 to 90 mm. By setting the fiber length 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 excellent wear resistance can be obtained. The fiber length is more preferably 35 to 80 mm, and particularly preferably 40 to 70 mm.

  When a short fiber nonwoven fabric is used as the nonwoven fabric, the ultrafine fibers (or ultrafine fiber-generating fibers) are preferably crimped and cut into a predetermined length to obtain raw cotton. A known method can be used for crimping or cutting.

  Next, the obtained raw cotton is made into a fiber web with a cross wrapper or the like and entangled to obtain a nonwoven fabric. A needle punch, a water jet punch, or the like can be used as a method for obtaining a nonwoven fabric by entanglement of a fiber web.

  A woven fabric and a knitted fabric (hereinafter collectively referred to as “woven fabric”) can be inserted into the fibrous base material. By inserting a woven or knitted fabric, the strength of the sheet-like material can be improved.

  The average single fiber diameter of the fibers constituting the woven or knitted fabric is preferably about 0.3 to 10 μm.

  The woven or knitted fabric is preferably shrinkable. The shrinkage of the woven or knitted fabric may be manifested by any method of heat treatment, chemical or solvent treatment, mechanical treatment, or other treatment methods. From the viewpoint of productivity, a preferred embodiment is one that shrinks by heat treatment. By using a woven or knitted fabric that shrinks by heat treatment, when the kneading treatment is performed at a high temperature in the subsequent step (iii), the sheet-like material is highly shrunk to improve the dense feeling, and the wrinkle pattern imparted to the surface of the sheet-like material The line of the concave part becomes thinner, and the lightness and darkness of the uneven part becomes more like genuine leather.

  The shrinkage characteristics of a woven or knitted fabric when using a heat-shrinkable knitted or knitted fabric include a dry heat area shrinkage ratio in a dry heat treatment at a temperature of 100 ° C. for 5 minutes and a dry heat area in a dry heat treatment at a temperature of 140 ° C. for 5 minutes. The difference from the shrinkage rate is preferably in the range of 10% to 25%. In the course of the production process of the surface-treated sheet-like product of the present invention, for example, in the drying step after the generation treatment of ultrafine fibers, heat at a temperature of around 100 ° C. may be applied, but the woven / knitted fabric at 100 ° C. and 140 ° C. By designing the difference in area shrinkage at a temperature of 0 ° C. to be 10% or more, it is possible to prevent the woven or knitted fabric from losing its shrinkability due to such a thermal history in the intermediate process. In addition, by making the difference in shrinkage rate at temperatures of 100 ° C. and 140 ° C. 25% or less, the difference in shrinkage between the nonwoven fabric layer and the woven / knitted fabric layer in the fibrous base material is optimized, and good touch and uniformity are achieved. It is easy to achieve both a good external appearance.

  As a method of entanglement of a nonwoven fabric (fiber web) and a woven or knitted fabric, a method of laminating one woven or knitted fabric on a nonwoven fabric (fiber web), a method of sandwiching a nonwoven fabric (fiber web) between two woven or knitted fabrics, For example, a method of sandwiching a knitted fabric between two non-woven fabrics (fiber webs). In terms of workability and efficiency, a method in which a nonwoven fabric (fiber web) is sandwiched between two woven or knitted fabrics is a preferred embodiment.

  Next, as a method of obtaining a sheet-like material having a polymer elastic body between the ultrafine fibers or the ultrafine fiber bundles of the fibrous base material, a treatment for expressing the ultrafine fibers from the ultrafine fiber expression type fibers was performed. A treatment for imparting the polymer elastic body may be performed later, or a treatment for imparting the ultrafine fiber from the ultrafine fiber expression type fiber may be performed after the treatment for imparting the polymer elastic body. When the ultrafine fiber expression treatment is performed first, the polymer elastic body grips the ultrafine fiber, so that the ultrafine fiber does not fall off and can be used for a longer period of time. When the polymer elastic body is applied first, the polymer elastic body has a structure in which the ultrafine fibers are not gripped, so that a sheet having a good texture can be obtained. Which is performed first can be appropriately selected depending on the type of the elastic polymer used. The ultrafine fiber expression treatment can be performed by immersing a fibrous base material made of the ultrafine fiber expression type fiber in a solvent and dissolving and removing the sea component.

  When the ultrafine fiber-expressing fiber is a sea-island type composite fiber, as the solvent for dissolving and removing the sea component, when the sea component is polyethylene, polypropylene, and polystyrene, an organic solvent such as toluene or trichlorethylene can be used. Further, when the sea component is a copolyester or polylactic acid, an aqueous alkali solution such as sodium hydroxide can be used. When the sea component is a water-soluble thermoplastic polyvinyl alcohol resin, hot water can be used.

  The polymer elastic body used in the present invention is a polymer compound having rubber elasticity that 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.

  By using a polymer elastic body mainly composed of polyurethane, it is possible to obtain a sheet-like material having a solid tactile sensation, a leather-like appearance and physical properties that can withstand actual use.

  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 obtained by a reaction of a polymer diol, an organic diisocyanate and a chain extender is preferably used.

  As the polymer diol, for example, polycarbonate-based, polyester-based, polyether-based, silicone-based, and fluorine-based diols can be adopted, and a copolymer combining these can also be used.

  From the viewpoint of texture, polyether diols are preferably used. Also, from the viewpoint of hydrolysis resistance, polycarbonate-based and polyether-based diols are preferably used, and from the viewpoint of heat resistance including light resistance and embossing roll embossing rolls, polycarbonate-based and polyester-based diols are used. Preferably used. Furthermore, from the viewpoint of the balance between hydrolysis resistance, heat resistance and light resistance, polycarbonate-based and polyester-based diols are preferably used, and polycarbonate-based diols are particularly preferably used.

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

  Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol. Linear alkylene glycol, and branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and 2-methyl-1,8-octanediol Alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol. In the present invention, either a polycarbonate diol obtained from a single alkylene glycol or a copolymerized polycarbonate diol obtained from two or more alkylene glycols is preferably used.

  Examples of the polyester diol include polyester diols obtained by condensing various low molecular weight polyols and polybasic acids.

  Examples of the low molecular weight polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,2-dimethyl-1,3. -Propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol And one or more selected from cyclohexane-1,4-dimethanol can be used. Further, addition products obtained by adding various alkylene oxides to bisphenol A can also be used.

  Examples of the polybasic acid include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and One type or two or more types selected from hexahydroisophthalic acid can be used.

  Examples of the polyether-based diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymerized diols combining them.

  The number average molecular weight of the polymer diol used in the present invention is preferably 500 to 4000. By making the number average molecular weight preferably 500 or more, more preferably 1500 or more, it is possible to prevent the texture of the sheet-like material from becoming hard. Moreover, the intensity | strength as a polyurethane is maintainable by making a number average molecular weight into 4000 or less, More preferably 3000 or less preferably.

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

  Examples of the chain extender include amine chain extenders such as ethylenediamine and methylenebisaniline, and diol chain extenders such as ethylene glycol. Moreover, the polyamine obtained by making polyisocyanate and water react can also be used as a chain extender.

  If desired, a crosslinking agent can be used in combination with polyurethane for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like. The cross-linking agent may be an external cross-linking agent added as a third component to the polyurethane, or may be an internal cross-linking agent that introduces a reactive site that becomes a cross-linked structure in advance in the polyurethane molecular structure, and both are preferably used. In the present invention, it is preferable to use an internal crosslinking agent from the viewpoint that the crosslinking points can be formed more uniformly in the polyurethane molecular structure and the reduction in flexibility can be reduced.

  As the crosslinking agent, a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a silanol group, or a melamine resin can be used. However, if the crosslinking proceeds excessively, the polyurethane tends to harden and the texture of the sheet-like material tends to harden, so that a crosslinking agent having a silanol group is preferably used in terms of the balance between reactivity and flexibility.

  When water-dispersed polyurethane is used in the present invention, it is preferable 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. Further, any combination of a cationic and nonionic internal emulsifier and a combination of an anionic and nonionic internal emulsifier can be employed. Among these, nonionic internal emulsifiers are preferably used in that they are excellent in light resistance compared to cationic internal emulsifiers, and are not adversely affected by neutralizing agents as compared to anionic internal emulsifiers.

  The polymer elastic body used in the present invention contains a polyester-based, polyamide-based, polyolefin-based elastomer resin, acrylic resin, ethylene-vinyl acetate resin, or the like as long as the performance and texture as a binder are not impaired. Can do.

  In addition, the polymer elastic body includes various additives, for example, pigments such as carbon black, flame retardants such as phosphorus, halogen and inorganic, antioxidants such as phenol, sulfur and phosphorus, benzoate UV absorbers such as triazole, benzophenone, salicylate, cyanoacrylate and oxalic acid anilides, light stabilizers such as hindered amines and benzoates, hydrolysis stabilizers such as polycarbodiimide, plasticizers, electric resistance An inhibitor, a surfactant, a coagulation adjusting agent, a dye, and the like can be contained.

  As a method of fixing the polymer elastic body to the fibrous base material, there is a method of impregnating the fiber base material with a solution of the polymer elastic body and performing wet coagulation or dry coagulation. You can choose.

  The content of the elastic polymer in the sheet-like material can be appropriately adjusted in consideration of the type and texture and physical properties of the polyurethane used. The content of the polymer elastic body with respect to the sheet-like material is preferably 10% by mass or more and 100% by mass or less, and more preferably 20% by mass or more and 50% by mass or less.

  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 is protected by the water-soluble resin, and on the surface of the fiber constituting the fiber bundle of the ultrafine fiber, The directly joined portions are not continuous but intermittent, and the adhesion area can be moderately suppressed. As a result, it is possible to obtain an artificial leather having a soft texture 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 applying the water-soluble resin to the fibrous base material include a method in which the fibrous base material is impregnated with an aqueous solution of the water-soluble resin and dried.

  It is also preferable to subject the fibrous base material before applying the polymer elastic body to a heat shrinkage treatment at 80 to 100 ° C. by warm water or steam treatment in order to improve the fineness of the fibers.

  The application amount of the water-soluble resin is preferably 1 to 50% by mass relative to the mass of the fibrous base material before application. A favorable texture is obtained by making application amount into 1 mass% or more. Further, by setting the applied amount to 50% by mass or less, an artificial leather 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 fibrous base material in the subsequent process increases, it is possible to increase the density of the artificial leather and the tactile feel. The application amount of the water-soluble resin is more preferably 3% by mass or more and 30% by mass or less, and particularly preferably 5% by mass or more and 20% by mass or less. The applied water-soluble resin is removed with hot water or the like after the polymer elastic body is applied.

  Next, the surface of the sheet-like material composed of the fibrous base material and the polymer elastic body is raised. By having raised napping by raising, it can be set as a favorable suede tone or nubuck tone sheet.

  The raising treatment can be performed by a method of grinding using sandpaper, roll sander or the like. A lubricant such as a silicone emulsion can be applied before the raising treatment. In addition, applying an antistatic agent prior to the raising treatment is a preferable aspect because grinding powder generated from the sheet by grinding becomes difficult to accumulate on the sandpaper.

  In addition, the sheet-like material composed of the fibrous base material and the polymer elastic body may be divided into half or several sheets in the sheet thickness direction after the polymer elastic body is provided.

  Next, said process (ii) is demonstrated. In step (ii), a concavo-convex pattern is imparted to the surface of the sheet-like material raised in step (i) by an embossing roll having a concavo-convex pattern on the surface. Genuine leather with a wrinkled pattern is a wrinkled pattern formed by a plurality of convex portions on the surface divided by the wrinkled concave portions. By using the surface portion of the sheet as a concave portion and the wrinkle portion as a convex portion, a concavo-convex pattern can be imparted to the raised sheet surface. The shape of the wrinkle pattern is mainly an ellipse or a polygon, but there is no particular limitation, and the target wrinkle pattern of natural leather can be referred to.

  It is important that the embossing pattern is applied by processing with an embossing roll from the viewpoint of surface touch and quality.

  The roll temperature at the time of applying the embossed roll using the embossing roll may be adjusted as appropriate depending on the configuration and thickness of the sheet-like material, but is preferably 100 ° C. or higher and 180 ° C. or lower. By setting the roll temperature to 100 ° C. or higher, it is possible to obtain a shape-retaining property at the time of stagnation treatment or practical use in step (iii), and by setting the roll temperature to 180 ° C. or lower, a sheet shape It is possible to suppress deterioration of a polymer elastic body mainly composed of ultrafine fibers and polyurethane constituting the object. The roll temperature is more preferably 110 ° C. or more and 170 ° C. or less, and particularly preferably 120 ° C. or more and 160 ° C. or less. Moreover, it is a preferable aspect to heat a receiving roll and to process it from a viewpoint of the shape retaining property of a wrinkle pattern.

  Next, said process (iii) is demonstrated. In the step (iii), the sheet-like material to which the concavo-convex pattern is given in the step (ii) is squeezed in water.

  By subjecting the sheet-like material provided with the uneven pattern to a scouring treatment in water, the fibers are dispersed again, and the concave portions are not whitened, so that a surface feel comparable to natural leather can be obtained.

  FIG. 1 is a schematic plan view for exemplifying a texture pattern of a conventional sheet-like material. The concave portion 1 is formed into a continuous and branched wrinkled pattern, and the convex portion 2 is surrounded by the wrinkled concave portion 1 and has an independent shape. Since the concave portion 1 is crimped by an embossing roll, the surface fibers appear smooth and whitened. However, since the convex portion 2 is raised, the wrinkled concave portion 1 appears brighter. This is the opposite of natural leather.

  On the other hand, FIG. 2 is a schematic plan view for illustrating the texture pattern of the surface-treated sheet-like material obtained in the present invention. The concave portion 3 forms a continuous and branched wrinkled pattern, and the convex portion 4 is surrounded by the wrinkled concave portion 3 and has an independent shape. The recess 3 is once smoothed and whitened by being pressure-bonded by an embossing roll. However, in the next step (iii), the above-mentioned sheet is squeezed in water to disperse the fibers again, thereby eliminating the whitening of the recess. The surface looks inferior to leather.

  As a method for carrying out the stagnation treatment in water, it can be carried out by a known method, but since the stagnation effect is particularly high, it is preferable to carry out the stagnation treatment using a liquid flow dyeing machine.

  It is also preferable to simultaneously perform the shrinkage treatment with hot water at a temperature of 110 ° C. or higher, more preferably 120 ° C. or higher during the stagnation treatment in water. By doing so, the sheet-like material to which the concavo-convex pattern is imparted contracts, the lines of the concave portions of the embossed pattern become thin, and the lightness and darkness of the surface concavo-convex pattern becomes more like genuine leather. Furthermore, when a woven or knitted fabric having heat shrinkability is inserted into the fibrous base material, the sheet-like material is further shrunk, and the effect of further reducing the lines of the concave portions of the texture pattern is obtained. Since it becomes small, it is preferable.

  In the method for producing a surface-treated sheet-like material of the present invention, dyeing can be performed. The dye can be selected according to the ultrafine fibers constituting the sheet-like material. For example, when the ultrafine fiber is made of polyester fiber, a disperse dye can be used, and when the ultrafine fiber is made of polyamide fiber, an acid dye or a metal-containing dye can be used. When dyeing with a disperse dye, it is preferable to perform reduction cleaning after dyeing. In addition, a dyeing assistant can be used for the purpose of improving the uniformity and reproducibility of dyeing.

  Dyeing may be performed simultaneously with the itch treatment.

  In addition, the surface-treated sheet-like material obtained in the present invention can be subjected to a finishing agent treatment such as a softening agent such as silicone or an antistatic agent. Finishing agent treatment can be performed after dyeing or in the same bath as dyeing.

  The surface-treated sheet-like material obtained in the present invention contains, for example, a dye, a pigment, a softener, a texture adjusting agent, an anti-pilling agent, an antibacterial agent, a deodorant, a water repellent, a light proofing agent, a weathering agent, and the like. This is also a preferred embodiment.

  Moreover, it is preferable that the surface-treated sheet-like material obtained by the present invention has a surface composed of only ultrafine fibers. A good touch can be obtained when the surface is made of only ultrafine fibers. When a resin or the like is applied to the surface of the sheet-like material, the touch is inferior compared to that made of only ultrafine fibers due to roughness or catching.

  The surface-treated sheet-like material obtained by the method for producing a surface-treated sheet-like material of the present invention has a wrinkle pattern that is not inferior to that of natural leather. It can be suitably used as an interior material having a very elegant appearance for a skin material such as a seat or a ceiling in a vehicle room such as a train and an aircraft. In addition, shirts, jackets, bags, belts, wallets, etc., clothing materials used for some of them, casual shoes, sports shoes, men's shoes, women's shoes, upper shoes, trims, etc., mobile terminals and personal computers It can be suitably used for exteriors and case materials such as mobile phones and smartphones, and other industrial materials.

<Evaluation method>
(1) Polymer melt flow rate (MFR)
4-5 g of polymer sample pellets are placed in a cylinder of an MFR meter electric furnace, and using a Toyo Seiki melt indexer (S101), the load is 2160 gf and the temperature is 285 ° C. The amount (g) was measured. The same measurement was repeated 3 times, and the average value was defined as MFR.

(2) Average single fiber diameter A scanning electron microscope (SEM) photograph of the cross-section of the sheet-like material was taken, 100 round or nearly elliptical fibers were selected at random, and the single fiber diameter was measured to be 100. The average value of was calculated.

(3) Average height difference between the concave and convex portions of the sheet-like material A scanning electron microscope (SEM) photograph of a cross section including the concave and convex portions of the sheet-like material was taken, and the concave and convex portions were randomly selected at 10 locations. The height difference was measured and the average value was calculated. The unit is μm, and the first decimal place is rounded off.

(4) Appearance quality (light and dark texture)
10 healthy adult males and 10 adult females each, with a total of 20 evaluators, with the wrinkled pattern and the surface of the wrinkled pattern of the sheet-like material, judged the darker one, and judged the darker part to be dark .

<Notation of chemical substances>
-PU: Polyurethane-PTMG: Polytetramethylene glycol with a number average molecular weight of 2000-PCL: Polycaprolactone with a number average molecular weight of 2000-MDI: 4,4'-diphenylmethane diisocyanate-DMF: N, N-dimethylformamide-PET: Polyethylene terephthalate -PVA: Polyvinyl alcohol.
EG: ethylene glycol.

<Polyurethane (PU) types>
(1) Organic solvent polyurethane I (PU-I)
・ Polyisocyanate: MDI
Polyol: PTMG 70% by mass, PCL 30% by mass
-Chain extender: EG
-Solvent: DMF.

[Example 1]
(raw cotton)
Polyethylene terephthalate (PET) having an MFR of 48 is used as the island component, polystyrene having an MFR of 65 is used as the sea component, and a sea-island type die having a number of islands of 16 islands / hole is used. The spinning temperature is 285 ° C. Sea-island composite fibers were melt-spun under the conditions of an island / sea mass ratio of 80/20, a discharge rate of 1.2 g / min · hole, and a spinning speed of 1100 m / min. Next, the fiber is stretched 2.8 times in an oil solution bath for spinning at a temperature of 90 ° C., crimped using an indentation type crimping machine, and then cut to a length of 51 mm to obtain a single fiber A raw cotton of a sea-island type composite fiber having a fineness of 3.8 dtex was obtained.

(fabric)
PET was discharged from a spinneret with 72 holes at a spinning temperature of 295 ° C., and was drawn at a spinning speed of 1650 m / min to obtain an undrawn yarn. Further, using a hot roll-hot plate drawing machine, the drawn yarn was drawn at a draw ratio of 2.8 times to obtain a drawn filament of 72 filaments with a total fineness of 84 dtex.

  Using the above-mentioned drawn yarn twisted 2500 times / m (twisting coefficient 22900) as both the weft and the warp of the woven fabric, the weave density is warp 69 / 2.54 cm and weft 69 / A 2.54 cm plain woven fabric was produced.

(Fiber web)
Using the above-mentioned raw cotton, a card web and a cross wrapping process were performed, and needle punching was performed at a punch number of 600 / cm ² to obtain a fiber web.

(Fiber base material)
The above-mentioned plain woven fabric is inserted above and below the above-mentioned fiber web and needle punched with a punch number of 2900 / cm ² to integrate the above-mentioned fiber web and the above-mentioned fabric, the thickness is 3.0 mm, and the density is 0 A fibrous substrate of .24 g / cm ³ was obtained.

(Shrink treatment, application of water-soluble resin and dissolution removal of sea components)
After shrinking the fibrous base material with hot water at a temperature of 96 ° C., the saponification degree is 88%, impregnated with a 12% by mass PVA aqueous solution, and squeezed at a target weight of 10% by mass with respect to the solid fiber content. And dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet with PVA. Next, this sheet with PVA was immersed in trichlorethylene to dissolve and remove the sea components of the sea-island type composite fiber to obtain a sheet with PVA after sea removal treatment.

(Applying polymer elastic body)
The sheet with PVA after the sea removal treatment is impregnated with a DMF solution of polyurethane-I (PU-I) adjusted to a solid content concentration of 12% by mass, and squeezed at a target weight of 25% by mass with respect to the fiber content of the solid content. The polyurethane was coagulated in an aqueous solution having a DMF concentration of 30% by mass. Thereafter, PVA and DMF were removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet with polyurethane.

(Half and brushed)
The polyurethane-coated sheet is cut in half in the thickness direction, and the half-cut surface is ground with an endless sandpaper of sandpaper count 240 to form a raised surface, and the thickness is adjusted simultaneously with the formation of the raised surface. A napped sheet of 00 mm was obtained.

(Give a wrinkle pattern)
A wrinkle with a depth of 300 μm, with a wrinkled pattern of a plurality of concave parts consisting of independent ellipses and polygons with a convex part with a continuous wrinkle part and a surface part divided into convex parts with respect to the above raised sheet Using the embossed roll on which the pattern was applied, the embossing roll temperature was set to 160 ° C., and the temperature of the receiving roll was set to 150 ° C. to obtain a textured napped sheet.

(Itching treatment / dyeing)
A leather-like sheet (surface-treated sheet-like material) is obtained by dyeing the above-mentioned textured napped sheet using a liquid dyeing machine at a temperature of 130 ° C. at the same time as the sagging treatment and drying using a dryer. )

  The average height difference between the concave and convex portions of the obtained leather-like sheet (surface-treated sheet-like material) was 230 μm. The concave fibers compressed and smoothed by the embossing roll at the time of applying the wrinkle pattern were dispersed and no whitening occurred, and the surface was inferior to natural leather. The results are shown in Table 1.

[Example 2]
(raw cotton)
PET with an MFR of 48 is used as the island component, polystyrene with an MFR of 65 is used as the sea component, a sea island type composite die with an island number of 36 islands / hole is used, the spinning temperature is 280 ° C., the island / sea mass Sea-island type composite fibers were melt-spun under the conditions of a ratio of 55/45, a discharge rate of 1.3 g / min / hole, and a spinning speed of 1300 m / min. Next, the film was stretched 3.6 times in an oil solution bath for spinning at a temperature of 90 ° C., subjected to a crimping process using an indentation type crimping machine, and then cut into a length of 51 mm. A raw cotton of a sea-island type composite fiber having a fiber fineness of 2.9 dtex was obtained.

(Weaving-half cutting and raising treatment)
A napped sheet was obtained in the same manner as in Example 1 except that the above raw cotton was used.

(Give a wrinkle pattern)
A wrinkle with a depth of 300 μm, with a wrinkled pattern of a plurality of concave parts consisting of independent ellipses and polygons with a convex part with a continuous wrinkle part and a surface part divided into convex parts with respect to the above raised sheet Using the embossed roll on which the pattern was applied, the embossing roll temperature was set to 170 ° C., and the temperature of the receiving roll was set to 150 ° C. to obtain a textured napped sheet.

(Itching treatment and dyeing)
The above-mentioned textured napped sheet is dyed at the same time as the scouring treatment using a liquid dyeing machine at a temperature of 130 ° C., and dried using a dryer. Product).

  The average height difference between the concave and convex portions of the obtained leather-like sheet (surface-treated sheet-like material) was 220 μm. The concave fibers compressed and smoothed by the embossing roll at the time of applying the wrinkle pattern were dispersed and no whitening occurred, and the surface was inferior to natural leather. The results are shown in Table 1.

[Example 3]
(raw cotton)
The island component is made of PET with an MFR of 48, and the sea component is polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate with an MFR of 95. The sea-island composite fiber was melt-spun at a spinning temperature of 285 ° C., an island / sea mass ratio of 30/70, a discharge rate of 1.3 g / min / hole, and a spinning speed of 1250 m / min. Next, it is stretched 3.7 times in an oil solution bath for spinning at a temperature of 60 ° C., crimped using an indentation type crimping machine, and then cut to a length of 51 mm to obtain a single fiber A raw cotton of a sea-island type composite fiber having a fineness of 2.8 dtex was obtained.

(Woven fabric to fibrous base material)
A fibrous base material was obtained in the same manner as in Example 1 except that the raw cotton was used.

(Shrinkage treatment and dissolution and removal of sea components)
After shrinking the fibrous base material with hot water at a temperature of 96 ° C., it is immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. for 30 minutes to remove sea components. Thus, a fibrous base material after sea removal treatment was obtained.

(Applying water-soluble resin)
The fibrous base material after the above sea removal treatment is impregnated with a PVA aqueous solution of 12% by mass with a saponification degree of 88%, and is squeezed with a target amount of 10% by mass with respect to the fiber content of solids, and hot air at a temperature of 110 ° C. And dried for 10 minutes to obtain a sheet with PVA.

(Application of polymer elastic body to dyeing)
A leather-like sheet (surface-treated sheet-like material) was obtained in the same manner as in Example 1 except that the above sheet with PVA was used. The average height difference between the concave and convex portions of the obtained leather-like sheet (surface-treated sheet-like material) was 210 μm. Since the fibers of the concave portions compressed and smoothed by the embossing roll at the time of applying the wrinkle pattern are dispersed, whitening is eliminated and the quality is inferior to natural leather. The results are shown in Table 1.

[Example 4]
(raw cotton)
Raw cotton was obtained in the same manner as in Example 1.

(Fiber web / Fiber base)
A non-woven fabric (felt) having a thickness of 3.0 mm and a density of 0.21 g / cm ³ by performing needle punching with a punch number of 3500 / cm ² using the above-described raw cotton, through a card and cross-wrapper process. Got. This was used as the fibrous base material of this example.

(Shrinkage treatment ~ dyeing)
A leather-like sheet (surface-treated sheet-like material) was obtained in the same manner as in Example 1 except that the above fibrous base material was used.

  The average height difference between the concave and convex portions of the obtained leather-like sheet (surface-treated sheet-like product) was 200 μm. When the wrinkle pattern was applied, the fibers in the concave portions that were compressed and smoothed by the embossing roll were dispersed and whitening was suppressed. The results are shown in Table 1.

[Example 5]
(Raw cotton to wrinkle pattern)
In the same manner as in Example 1, a textured napped sheet was obtained.

(Itching process)
The above textured napped sheet is subjected to a sag treatment using a liquid dyeing machine at a temperature of 20 ° C. and then dried using a dryer to obtain a leather-like sheet (surface-treated sheet-like material). Obtained.

  The average height difference between the concave and convex portions of the obtained leather-like sheet (surface-treated sheet-like material) was 190 μm. When the wrinkle pattern was applied, the fibers in the concave portions that were compressed and smoothed by the embossing roll were dispersed and whitening was suppressed. The results are shown in Table 1.

[Comparative Example 1]
(Raw cotton-brushed)
In the same manner as in Example 1, a napped sheet was obtained.

(staining)
The raised sheet was dyed at the same time as the squeezing treatment using a liquid dyeing machine at a temperature of 130 ° C., and dried using a dryer to obtain a dyed raised sheet.

(Give a wrinkle pattern)
With respect to the above-mentioned dyed napped sheet, the wrinkle portion is a continuous convexly branched convex portion, the surface portion is divided into convex portions, and a plurality of concave and convex concave wrinkle patterns with a depth of depth. Using an embossing roll with a 300 μm embossed pattern, the embossing roll temperature was set to 160 ° C., and the receiving roll temperature was set to 150 ° C. to obtain a leather-like sheet (surface-treated sheet-like material). The obtained leather-like sheet (surface-treated sheet-like material) has a concave portion with a continuous and branched wrinkle portion, and the fine fibers are smooth, and the surface portion is divided by the concave portion and is composed of a plurality of independent ellipses and polygons. A wrinkled pattern with napped edges is provided on the convex part of the slab, and the average height difference between the concave part and the convex part is 290 μm. In addition, the wrinkle portion was whitened and brighter than the surface portion, and was light and dark different from natural leather. The results are shown in Table 1.

[Comparative Example 2]
(Raw cotton to wrinkle pattern)
In the same manner as in Example 1, a textured napped sheet was obtained.

(staining)
The above-mentioned embossed napped sheet was dyed under a temperature condition of 130 ° C. using a beam dyeing machine and dried using a drier to obtain a leather-like sheet (surface-treated sheet-like material).

  The average height difference between the concave and convex portions of the obtained leather-like sheet (surface-treated sheet-like material) was 280 μm. The concave fibers compressed and smoothed by the embossing roll at the time of applying the wrinkle pattern maintained smoothness, the wrinkled portion was whitened and brighter than the surface portion, and light and dark different from natural leather. The results are shown in Table 1.

1: Concave part 2: Convex part 3: Concave part 4: Convex part

Claims (5)

A method for producing a surface-treated sheet-like material, wherein a surface material is applied to a sheet-like material comprising a fibrous base material comprising an ultrafine fiber having an average fiber diameter of 0.1 μm to 7 μm and a polymer elastic body And the manufacturing method of the surface processed sheet-like thing characterized by performing the process of following (i)-(iii) in this order.
(I) a step of raising the surface of a sheet-like material having a polymer elastic body between ultrafine fibers or a bundle of ultrafine fibers of a fibrous base material comprising ultrafine fibers;
(Ii) a step of providing a concavo-convex pattern on the surface of the raised sheet by an embossing roll having a concavo-convex pattern on the surface;
(Iii) A step of squeezing the sheet provided with the concavo-convex pattern in water.   The method for producing a surface-treated sheet-like product according to claim 1, wherein the polymer elastic body contains polyurethane as a main component.   The method for producing a surface-treated sheet-like material according to claim 1 or 2, wherein the shrinkage treatment is simultaneously performed with hot water having a temperature of 110 ° C or higher during the stagnation treatment.   The manufacturing method of the surface-treated sheet-like material in any one of Claims 1-3 in which the said ultrafine fiber and woven / knitted fabric are entangled and integrated with the said fibrous base material.   The difference between the dry heat area shrinkage ratio in the dry heat treatment at 100 ° C. for 5 minutes and the dry heat area shrinkage ratio in the dry heat treatment at 140 ° C. for 5 minutes in the woven or knitted fabric is 10% or more and 25% or less. The manufacturing method of the surface processed sheet-like material in any one of Claims 1-4 which is inside.