JP6354337B2 - Sheet - Google Patents

Description

  The present invention relates to a sheet-like material, and particularly preferably relates to a sheet-like material having napping.

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. If a wrinkled pattern is applied to an embossing roll on a sheet-like material such as an object or a nubuck-like sheet-like material, the surface of the wrinkled pattern that is a concave portion becomes a smooth surface with the raised hairs aligned. Is reflected and whitened (see FIG. 2). 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 has a natural wrinkle and shadow due to whitening of the wrinkle-like pattern. Since it is the opposite, the impression is different from natural leather.

  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 3). 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 2012-136801 A

  An object of the present invention is to provide a sheet-like material having a surface feeling comparable to natural leather having a texture pattern.

The sheet-like material of the present invention is a sheet-like material comprising an ultrafine fiber having an average fiber diameter of 0.1 μm or more and 7 μm or less and a polymer elastic body mainly composed of polyurethane. surface is a ultrafine fibers, and has a nap, and a convex portion and wrinkle portion, have a grain pattern formed by a plurality of recesses that are separated by the convex portion, the the surface of the sheet It is a sheet-like material characterized in that the fibers in the recessed portion are pressure-bonded .

  According to a preferred aspect of the sheet-like material of the present invention, the surface of the sheet-like material having the texture pattern is composed of only ultrafine fibers.

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

Sheet of this invention, the surface is made of ultrafine fibers and having a nap, and a convex portion as a wrinkle portion, those having a grain pattern is formed by a plurality of recesses that are separated by the protrusion is there. When a wrinkle pattern is given by an embossing roll or the like, the wrinkled part is a convex part and the surface part is a concave part. Since the convex part of the wrinkle part is not pressure-bonded, the fiber maintains napping, so it looks darker and darker than the concave part. Thereby, by aligning the shade of the surface with natural leather, a sheet-like material having a surface feeling comparable to natural leather having a textured pattern is obtained.

FIG. 1 is a schematic plan view illustrating a texture pattern of a sheet-like material of the present invention. FIG. 2 is a schematic plan view illustrating a textured pattern of a conventional sheet-like material.

The sheet-like material of the present invention is a sheet-like material comprising an ultrafine fiber having an average fiber diameter of 0.1 μm or more and 7 μm or less and a polymer elastic body mainly composed of polyurethane. surface is a ultrafine fibers, and has a nap, and a convex portion and wrinkle portion, have a grain pattern formed by a plurality of recesses that are separated by the convex portion, the the surface of the sheet It is a sheet-like product formed by pressure-bonding the fibers in the recessed portion .

  The sheet-like material of the present invention includes ultrafine fibers as described above, and the fine appearance and texture of suede and nubuck can be obtained with the ultrafine fibers.

  Examples of the ultrafine fiber constituting the sheet-like product of the present invention include, for example, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalene dicarboxylate and polyester such as polylactic acid, 6-nylon and 66- Various synthetic fibers made of polyamide such as nylon, acrylic polymer, polyethylene, polypropylene and thermoplastic cellulose 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. Is also a preferred embodiment.

  It is important that the average single fiber diameter of the ultrafine fibers constituting the sheet-like material of 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 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 may be a polygonal shape such as an ellipse, a flat shape, or a triangle, or an irregular cross-section such as a sector shape or a cross shape.

  It is a preferable aspect that the ultrafine fibers are in the form of a nonwoven fabric (ultrafine fiber web) in the sheet-like material. By using a nonwoven fabric, a uniform and elegant appearance and texture can be obtained.

  The form of the non-woven fabric (ultrafine fiber web) may be either a short-fiber non-woven fabric or a long-fiber non-woven fabric, but a short-fiber non-woven fabric is preferably used when emphasis is placed on texture and quality.

  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.

  A nonwoven fabric or a knitted fabric can be inserted into the nonwoven fabric for the purpose of improving the strength. The average single fiber diameter of the fibers constituting such a woven or knitted fabric is preferably about 0.3 to 10 μm.

  The sheet-like material of the present invention also comprises a polymer elastic body mainly composed of polyurethane. The polymer elastic body is a polymer compound having rubber elasticity that expands and contracts, and examples of the polymer elastic body include polyurethane, SBR, NBR, and an acrylic resin. Moreover, the main component here means that the weight of polyurethane is more than 50% by mass with respect to the mass of the entire polymer elastic body.

  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. 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, 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 said crosslinking agent, the compound which has an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group, etc. can be used. However, if the crosslinking proceeds excessively, the polyurethane tends to harden and the texture of the sheet-like material tends to become hard, 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. Any of a combination of a 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 as compared with cationic internal emulsifiers and are not adversely affected by neutralizing agents as compared with 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.

  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 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.

  It is also preferable that the sheet-like material of the present invention contains, for example, a dye, a pigment, a softening agent, a texture adjusting agent, an anti-pilling agent, an antibacterial agent, a deodorant, a water repellent, a light proofing agent, and a weathering agent. It is.

Moreover, in the sheet-like material of the present invention, it is preferable that the density of the entire sheet-like material is 0.20 g / cm ³ or more and 0.60 g / cm ³ or less. By setting the density to 0.20 g / cm ³ or more, the physical properties of the sheet-like product itself can be secured, and by setting the density to 0.60 g / cm ³ or less, the texture of the sheet-like product is good. It will be something. The density of the entire sheet is preferably not more than 0.25 g / cm ³ or more 0.50 g / cm ^3, more preferably not more than 0.30 g / cm ³ or more 0.45 g / cm ^3.

It is important that the sheet-like material of the present invention has napped fibers of at least one surface. By having napping, it can be set as a favorable suede-like or nubuck-like sheet-like material. Moreover, it is important for the sheet-like material of the present invention that the surface of the sheet-like material is composed of only ultrafine fibers. This is because a good touch can be obtained when the surface of the sheet-like material is composed 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 a sheet-like material consisting of only ultrafine fibers due to roughness or catching.

Sheet of this invention, the surface having a napped, the protrusions and wrinkles section, have a grain pattern formed by a plurality of recesses that are separated by the convex portion, the the surface of the sheet It is important that the portion of the fiber that has become a recess is pressed . Generally, a wrinkle pattern is imparted to a sheet-like material as a concave portion. This is because the wrinkled part of the natural leather wrinkle part is a concave part, but if a wrinkle pattern is given to the sheet-like material having napping by an embossing roll or the like, the fibers on the surface of the pressed concave part become smooth, The light is reflected and whitened. However, in natural leather, the wrinkled recesses are darker and darker than the surface, so the wrinkled pattern with the wrinkled recesses formed by embossing rolls has an unnatural quality because the shadow is reversed. There is a problem of end. Although this problem does not occur in a silver-finished product having a coating layer of resin or the like, it is likely to occur in a nap-like sheet-like material having fine irregularities due to ultrafine fibers, and is a specific problem.

  In the present invention, in order to match the shade with the natural leather, a wrinkle pattern having a wrinkled portion as a convex portion is provided. That is, it has a texture pattern formed by a plurality of concave portions divided by convex portions. As a result, the fibers on the surface portion other than the wrinkle portion appear smooth and whitened, and the wrinkle portion appears darker and darker, and the shade is the same as that of natural leather. As a result, the sheet-like product of the present invention has a quality comparable to natural leather. Further, in the present invention, the unevenness of the seat surface is opposite to that of natural leather, but it does not feel unnatural by arranging the shadows.

  Further, the wrinkle pattern of the present invention has a convex portion as a wrinkle portion, but this convex portion is continuous and branched, and is a pattern like a wrinkle of natural leather. In addition, the convex part which is the surface part is divided into wrinkle-like concave parts and is independent, and the shape is mainly an ellipse or polygon, but there is no particular limitation, and the target natural leather wrinkle pattern is referred to be able to.

Next, the texture pattern will be described with reference to the drawings.
FIG. 1 is a schematic plan view illustrating a texture pattern of a sheet-like material of the present invention. The convex part 1 forms a continuous and branched wrinkled pattern, and the concave part 2 is surrounded by the wrinkled convex part 1 and has an independent shape. Since the concave portion 2 is pressure-bonded by an embossing roll, the surface fibers are smooth and appear white. However, since the convex portion 1 is raised, the wrinkled pattern of the convex portion 1 is darker. It looks dark and has the same shade as natural leather.
On the other hand, FIG. 2 is a schematic plan view illustrating a textured pattern of a conventional sheet-like material. The concave portion 3 is formed into a continuous and branched wrinkled pattern, and the convex portion 4 is surrounded by the wrinkled concave portion 3 and has an independent shape. Since the concave portion 3 is pressure-bonded by an embossing roll, the surface fibers are smooth and appear white. However, since the convex portion 4 is raised, the wrinkled concave portion 3 looks brighter and thinner. This is the opposite of natural leather.
Next, an example of a method for producing the sheet-like material of the present invention will be described.

  In the present invention, as a means for obtaining ultrafine fibers constituting the sheet-like material, it is preferable to use ultrafine fiber generating fibers. A nonwoven fabric formed by entanglement of ultrafine fibers (bundles) can be obtained by entanglement of ultrafine fiber-generating fibers in advance to obtain a nonwoven fabric, followed by ultrafinening of the fibers.

  The ultra-fine fiber generation type fiber is a sea-island type composite in which two component thermoplastic resins with different solvent solubility are used as sea components and island components, and the sea components are dissolved and removed using a solvent to remove the island components. It is possible to employ a peelable composite fiber that splits fibers into ultrafine fibers by alternately disposing fibers or two-component thermoplastic resin in a radial or multilayered cross section and separating each component. Among them, the sea-island type composite fiber is preferably used also from the viewpoint of texture and surface quality because it can provide an appropriate gap between the island components by removing the sea component, that is, between the ultrafine fibers inside the fiber bundle. .

  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.

  When a short fiber nonwoven fabric is used as the nonwoven fabric, the obtained ultrafine fiber-expressing fiber is 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.

  It is also a preferable aspect that the non-woven fabric is subjected to heat shrink treatment by hot water or steam treatment in order to improve the fineness of the fibers.

  The ultrafine fiber expression treatment can be performed by immersing a nonwoven fabric made of sea-island composite fibers in a solvent to dissolve and remove sea components.

  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.

As a method of fixing a polymer elastic body mainly composed of polyurethane to a sheet made of a nonwoven fabric, there is a method of impregnating a sheet of a polymer elastic body into a sheet and performing wet coagulation or dry coagulation, depending on the type of polyurethane used. You can choose.
A method in which either the treatment for developing the ultrafine fiber from the ultrafine fiber expression type fiber or the treatment for imparting the polymer elastic body can be employed first. 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 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 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 a method for applying the water-soluble resin to the fiber entangled body include a method of impregnating a nonwoven fabric with an aqueous solution of the water-soluble resin and drying it.

  The application amount of the water-soluble resin is preferably 1 to 50% by mass with respect to the mass of the fiber entangled body immediately 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 fiber entangled body increases in the subsequent process, the artificial leather can be densified and the tactile sensation can be increased. The application amount of the water-soluble resin is more preferably 3% or more and 30% or less, and particularly preferably 5% or more and 20% or less. The applied water-soluble resin is removed with hot water or the like after the polymer elastic body is applied.

  In the sheet-like material of the present invention, it is important to have napped fibers of at least one surface for raising the nap. The raising treatment is preferably performed after the step of applying the elastic polymer having polyurethane as a main component.

  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.

  The sheet-like product of the present invention can be dyed. 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.

  Moreover, it is also a preferable aspect to use a dyeing assistant for the purpose of improving the uniformity and reproducibility of dyeing.

Further, the sheet-like material of 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.
Further, the sheet may be divided into half or several sheets in the sheet thickness direction after applying the polymer elastic body.

Sheet of this invention, the protrusions and wrinkles unit, it is important to impart grain pattern that is formed by a plurality of recesses that are separated by the protrusion. A known method such as processing using an embossing roll or printing can be used as the method for applying the embossed pattern, but it is preferable to apply the embossing roll by processing using 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 durability that does not lose the wrinkle pattern even in actual use, and by setting the roll temperature to 180 ° C. or lower, the ultrafine fibers and polyurethane constituting the sheet-like material can be obtained. It is possible to suppress the deterioration of the polymer elastic body having the main component. 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 from a viewpoint of the endurance of a wrinkle pattern to heat a receiving roll and to process it.

  The timing of applying the texture pattern can be performed either before or after dyeing. When the grain pattern is imparted before dyeing, the surface is disturbed by the dyeing and a natural surface feeling is obtained. On the other hand, when the grain pattern is imparted after dyeing, a clear grain pattern can be imparted.

  The sheet-like material of the present invention is a sheet-like material having a texture pattern comparable to that of natural leather, and is used for the skin and wall materials of furniture and chairs, as well as seats and ceilings in vehicle interiors such as automobiles, trains and aircraft. Can be suitably used as an interior material having a very elegant appearance. The sheet-like product of the present invention further includes shirts, jackets, bags, belts, wallets, etc., and clothing materials, casual shoes, sports shoes, men's shoes, women's shoes, etc. used for some of them. , Trim, etc., can be suitably used for exterior and case materials of mobile terminals, personal computers, mobile phones, smartphones, and other industrial materials.

<Evaluation method>
(1) Polymer melt flow rate (MFR):
4-5 g of sample pellets are placed in a cylinder of an MFR electric furnace and the amount of resin extruded in 10 minutes under a load of 2160 gf and a temperature of 285 ° C. using a Toyo Seiki melt indexer (S101) (g) Was measured. The same measurement was repeated 3 times, and the average value was defined as MFR.

(2) Average single fiber diameter:
By taking a scanning electron microscope (SEM) photograph of the cross section of the sheet-like material, selecting 100 circular or nearly elliptical fibers at random, measuring the single fiber diameter, and calculating the average value of 100 Calculated.

(3) Difference in average height between concave and convex portions:
Calculated by taking a scanning electron microscope (SEM) photograph of the cross section including the concave and convex portions of the sheet-like material, measuring the height difference between the concave and convex portions at 10 randomly selected points, and calculating the average value. did. The unit is μm, and the first decimal place is rounded off.

(4) Appearance quality (shaded shading):
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. Melt spinning was performed 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, it 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, then cut to a length of 51 mm, and single fiber fineness A raw cotton of 3.8 dtex sea-island type composite fiber 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. Furthermore, it was drawn at a draw ratio of 2.8 times using a hot roll-hot plate type drawing machine to obtain a drawn yarn having a total fineness of 84 dtex and 72 filaments.

  The drawn yarn obtained as described above is subjected to a twist of 2500 times / m (twisting coefficient 22900) for both the weft and the warp, and the weaving density is warp 69 / 2.54 cm, 69 weft. /2.54 cm plain fabric was produced.

(Entanglement)
Using the raw cotton obtained as described above, a laminated fiber web is formed through a card and a cross wrapping process, and needle punching is performed with a number of punches of 600 pieces / cm ² , and then the plain fabric is made into fibers. Inserted above and below the web and needle punched with a punch number of 2900 / cm ² to integrate the laminated fiber web and fabric, intertwining with a thickness of 3.0 mm and a density of 0.24 g / cm ³ A sheet (felt) was obtained.

(Shrinkage, water-soluble resin application, sea removal)
The entangled sheet obtained as described above is shrunk with hot water at a temperature of 96 ° C. and then impregnated with a PVA aqueous solution of 12% by mass with a saponification degree of 88%, and a target weight for the solid fiber content. The sheet was squeezed at 10% by mass and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet with PVA. Next, the sheet with PVA thus obtained was immersed in trichlorethylene to dissolve and remove sea components, thereby obtaining a sheet with seawater-free PVA formed by intertwining the ultrafine fiber bundle with the fabric.

(Applying polymer elastic body)
The sheet with seawater-free PVA obtained as described above was impregnated with a DMF solution of polyurethane-I (PU-I) adjusted to a solid content concentration of 12% by mass, and a target weight of 25 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 obtained as described above is cut in half in the thickness direction, and the half-cut surface is ground with an endless sandpaper with sandpaper count 240 to form a raised surface, and the thickness adjustment is performed simultaneously with the formation of the raised surface. And a napped sheet having a thickness of 1.00 mm was obtained.

(staining)
The raised sheet obtained as described above was dyed under a temperature condition of 130 ° C. using a liquid dyeing machine, and dried using a dryer to obtain a leather-like sheet.

(Give a wrinkle pattern)
With respect to the leather-like sheet obtained as described above, the wrinkled part is a continuous and branched concave part, and the surface part is divided into concave parts, and a plurality of convex and convex embossed polygonal patterns, Using an embossing roll having a texture pattern with a depth of 300 μm, the embossing roll temperature was set to 160 ° C., and the receiving roll temperature was set to 150 ° C. to obtain a wrinkled leather-like sheet (sheet-like material). . The obtained wrinkled leather-like sheet (sheet-like material) is raised with raised portions where the wrinkle portions are continuous and branched, and the surface portion is divided by the raised portions and is composed of a plurality of independent ellipses and polygons. The embossed pattern in which the ultrafine fibers are smooth in the concave portion is given, and the average height difference between the concave portion and the convex portion is 270 μm. In addition, the wrinkle portion was darker and darker than the surface portion, and had the same shadow as 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 Melt spinning was performed 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 fiber is 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 sea-island type composite fiber having a fineness of 2.9 dtex was obtained.

(Textile to half-cut, brushed)
A napped sheet was obtained in the same manner as in Example 1 except that the raw cotton obtained as described above was used.

(Give a wrinkle pattern)
With respect to the raised sheet obtained as described above, the wrinkle portion is a continuous and branched concave portion, the surface portion is divided into concave portions, and an uneven oval and polygonal convex texture pattern with a depth of Using an embossing roll with a 300 μm embossed pattern, the embossing roll temperature was set to 170 ° C., and the temperature of the receiving roll was set to 150 ° C. to obtain an embossed napped sheet. The resulting wrinkled-applied napped sheet has raised nap at the convex part where the wrinkle part is continuous and branched, and the surface part is separated by the convex part, and the ultrafine fibers are smoothed by a plurality of independent oval and polygonal concave parts. The wrinkle pattern is given.

(staining)
The wrinkled napped sheet obtained as described above is dyed under a temperature condition of 130 ° C. using a liquid dyeing machine, and dried using a drier to give a wrinkled leather-like sheet (sheet-like) Product). The resulting wrinkled leather-like sheet (sheet-like material) had a wrinkled portion as a convex portion and a surface portion provided with a concave wrinkle pattern, and the average height difference between the concave portion and the convex portion was 240 μm. In addition, the wrinkle portion was darker and darker than the surface portion, and had the same shadow as 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 melt spinning was performed 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, then cut to a length of 51 mm, and single fiber fineness A raw cotton of 2.8 dtex sea-island type composite fiber was obtained.

(Woven fabric-entangled)
An entangled sheet (felt) was obtained in the same manner as in Example 1 except that the raw cotton obtained as described above was used.

(Shrinkage and sea removal)
The entangled sheet obtained as described above was shrunk with hot water at a temperature of 96 ° C. and then immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. for 30 minutes. The sea component was removed to obtain a sea removal sheet in which ultrafine fibers and fabric were intertwined.

(Applying water-soluble resin)
The sea removal sheet obtained as described above was impregnated with a PVA aqueous solution of 12% by mass with a saponification degree of 88%, 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. It dried for 10 minutes and obtained the sheet | seat with desealing PVA.
(Applying polymer elastic body to applying texture pattern)
A wrinkled leather-like sheet (sheet-like material) was obtained in the same manner as in Example 1 except that the sheet with seawater-free PVA obtained as described above was used. The obtained wrinkled leather-like sheet (sheet-like material) is raised with raised portions where the wrinkle portions are continuous and branched, and the surface portion is divided by the raised portions and is composed of a plurality of independent ellipses and polygons. The embossed pattern in which the ultrafine fibers are smooth in the concave portions is given, and the average height difference between the concave portions and the convex portions is 290 μm. In addition, the wrinkle portion was darker and darker than the surface portion, and had the same shadow as natural leather. The results are shown in Table 1.

[Comparative Example 1]
(Raw cotton to dyeing)
A leather-like sheet was obtained in the same manner as in Example 1.

(Give a wrinkle pattern)
For the leather-like sheet obtained as described above, the wrinkled part is a continuous convexly branched convex part, and the surface part is divided into convex parts, with a plurality of concave textured patterns consisting of an ellipse and a polygon. Using an embossing roll with a texture pattern with a depth of 300 μm, the embossing roll temperature is set to 160 ° C. and the receiving roll temperature is set to 150 ° C. to obtain a wrinkled leather-like sheet (sheet-like material). It was. The resulting wrinkled leather-like sheet (sheet-like material) has a plurality of ovals and polygons which are separated by recesses and the surface part is separated by recesses where the wrinkle parts are continuous and branched. 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 wrinkled part was whitened and brighter than the surface part, and had a shadow different from that of natural leather. The results are shown in Table 1.

[Comparative Example 2]
(Raw cotton-half cut, brushed)
In the same manner as in Example 2, a napped sheet was obtained.

(Give a wrinkle pattern)
For the leather-like sheet obtained as described above, the wrinkled part is a continuous convexly branched convex part, the surface part is divided into convex parts, and the concave and convex concave pattern consisting of an independent ellipse and polygon. Using an embossing roll having an embossed pattern having a thickness of 300 μm, the embossing roll temperature was set to 170 ° C. and the receiving roll temperature was set to 150 ° C. to obtain a wrinkled-applied napped sheet. The obtained wrinkle-applied napped sheet has a concave portion in which the wrinkle portion is continuous and branched, and the ultrafine fibers are smooth, and the surface portion is separated by the concave portion, and the napped portion is raised by an independent oval and polygonal convex portion. The wrinkle pattern was given.

(staining)
The wrinkled napped sheet obtained as described above is dyed under a temperature condition of 130 ° C. using a liquid dyeing machine, and dried using a drier to give a wrinkled leather-like sheet (sheet-like) Product). The obtained wrinkled leather-like sheet (sheet-like material) had a wrinkled portion as a concave portion and a surface portion provided with a wrinkle pattern of a plurality of convex portions, and the average height difference between the concave portion and the convex portion was 280 μm. . In addition, the wrinkled part was whitened and brighter than the surface part, and had a shadow different from that of natural leather. The results are shown in Table 1.

[Comparative Example 3]
(raw cotton)
Polyethylene terephthalate (PET) with an MFR of 48 is used as the island component, polystyrene with an MFR of 65 is used as the sea component, and a sea island type composite die having an island number of 8 islands / hole is used. The spinning temperature is 285 ° C. The melt spinning was performed under the conditions of an island / sea mass ratio of 80/20, a discharge rate of 1.8 g / min / hole, and a spinning speed of 1100 m / min. Next, it is stretched 2.5 times in an oil solution bath for spinning at a temperature of 90 ° C., crimped using an indentation type crimping machine, and then cut into a length of 51 mm to obtain a single fiber fineness. A raw cotton of 7.2 dtex sea-island type composite fiber was obtained.
(Weaving to texture pattern)
A wrinkled leather sheet (sheet-like material) was obtained in the same manner as in Example 1 except that the raw cotton obtained as described above was used. The obtained wrinkled leather-like sheet (sheet-like material) is raised with raised portions where the wrinkle portions are continuous and branched, and the surface portion is divided by the raised portions and is composed of a plurality of independent ellipses and polygons. A textured pattern in which the ultrafine fibers are slightly smooth at the concave portions is given, and the average height difference between the concave portions and the convex portions is 200 μm, and the pattern is slightly weak. In addition, the wrinkle portion was slightly darker and darker than the surface portion, and had the same shadow as natural leather. The results are shown in Table 1.

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

Claims (1)

It is a sheet-like material comprising ultrafine fibers having an average fiber diameter of 0.1 μm or more and 7 μm or less and a polymer elastic body mainly composed of polyurethane, and the surface of the sheet-like material is composed of ultrafine fibers, and napped has, and a convex portion and wrinkle portion, have a grain pattern formed by a plurality of recesses that are separated by the convex portion, the fibers of said recess and is part on the surface of the sheet is crimped A sheet-like material characterized by being made.

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