JP2010203021A - Sheet material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lightweight sheet material having excellent appearance, feeling, and further extension ratio and extension recovery ratio. <P>SOLUTION: The sheet material includes: ultrafine fibers having an average fiber diameter of 0.3-7 μm of the single fibers; a polymer elastic body containing a polyurethane as a main ingredient; and a woven fabric. In the sheet material, one of warp yarns and weft yarns composing the woven fabric is a yarn formed from two or more polyethylene terephthalate-based polymers having a difference in intrinsic viscosity (IV), and containing side-by-side type or eccentric core-sheath type conjugated fibers. The other contains fibers formed from one polyethylene terephthalate-based polymer, and having a hollow part in the cross section of the single fibers. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a sheet-like material, specifically a leather-like sheet-like material.

  Sheets composed mainly of ultrafine fibers and polymer elastic bodies have excellent features not found in natural leather, and their use has been increasing year by year for clothing, chair upholstery, automobile interior materials, and the like. Recently, a sheet excellent in stretchability in one direction has been demanded particularly from the viewpoint of a feeling of wear in the use of clothing and a moldability in the use of materials. Various studies have been made on such demands.

  For example, Patent Document 1 describes a method of inserting a woven or knitted fabric using polytrimethylene terephthalate fibers into a base fabric for artificial leather as described above. This method utilizes the stretch properties resulting from the crystal structure of polytrimethylene terephthalate, but the movement of the woven or knitted fabric is strong due to the high density nonwoven fabric intertwined with single fibers and the applied polyurethane. It was restrained and its stretchability was low.

  Patent Document 2 discloses a method of inserting a woven or knitted fabric using a latently crimped yarn made of high-shrinkage polyester and low-shrinkage polyester. However, the leather-like sheet was still insufficient as a stretch property in one direction.

JP-A-11-269975 JP 2000-336581 A

  An object of this invention is to provide the sheet-like material excellent in the stretch property in one direction and the stretch back property especially.

  That is, the present invention is a sheet-like material comprising ultrafine fibers having an average fiber diameter of 0.3 to 7 μm, a polymer elastic body, and a woven fabric, and one of the warp or the weft constituting the woven fabric, A sheet-like material comprising a composite fiber in which two or more kinds of polymers are combined in a side-by-side type or an eccentric core-sheath type, and the other includes a fiber having a hollow portion in a single fiber cross section .

  According to the present invention, it is possible to obtain a sheet-like material particularly excellent in stretchability in one direction and stretchback property.

It is a scanning electron microscope (SEM) photograph of the cross section of a sheet-like object for confirming the cavity of the thread | yarn in a textile fabric.

  The sheet-like material of the present invention comprises ultrafine fibers. The extra fine fibers can provide a suede-like or nubuck-like appearance and texture.

  As the ultrafine fibers constituting the sheet-like material of the present invention, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyester such as polyethylene 2,6-naphthalene dicarboxylate, polyamide such as 6-nylon, 66-nylon, Various synthetic fibers such as acrylic polyethylene and polypropylene can be used. Among these, polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate are preferable because they are excellent in strength, dimensional stability, light resistance, and dyeability. Also, ultrafine fibers of different materials may be mixed.

  Depending on various purposes, inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, antibacterial agents, etc. are added to the polymer forming the ultrafine fibers. It is also preferable.

  It is important that the average single fiber diameter of the ultrafine fibers constituting the sheet material is 0.3 to 7 μm. By setting the thickness to 7 μm or less, preferably 5 μm or less, more preferably 4 μm or less, the sheet-like material is excellent in flexibility and napped quality. On the other hand, when the thickness is 0.3 μm or more, preferably 0.7 μm or more, more preferably 1 μm or more, the coloring property after dyeing and the dispersibility of fibers during brushing treatment such as grinding with sandpaper are excellent. .

  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.

  The ultrafine fibers are preferably non-woven fabrics in the sheet form. By using a nonwoven fabric, a uniform and elegant appearance and texture can be obtained.

  The form of the nonwoven fabric (ultrafine fiber web) may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric, but a short fiber nonwoven fabric is preferred 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 it to 90 mm or less, good quality and texture are obtained, and by setting it to 25 mm or more, a sheet-like material that can withstand abrasion resistance and repeated expansion and contraction can be obtained. For example, when very short short fibers are used in the papermaking method, the fibers are often dropped and the nap on the surface disappears or the short fibers are entangled by repeated expansion and contraction, and the quality of the sheet-like material is significantly deteriorated. Will be. In order to suppress this, increasing the amount of the polymer elastic body such as polyurethane leads to hardening of the texture and deterioration of the stretchability. However, if the fiber length is in the above-mentioned range, it becomes a structure in which the ultrafine fibers are tightly entangled, so that the entanglement between the fibers is not unraveled due to the dropout of many fibers or repeated expansion and contraction. It is possible to maintain high quality.

  The sheet-like material of the present invention also comprises a polymer elastic body. The polymer elastic body can provide a sense of fulfillment, a leather-like appearance, and physical properties that can withstand actual use. The polymer elastic body is a polymer having rubber elasticity that expands and contracts, and examples thereof include polyurethane, SBR, NBR, and acrylic resin. Among these, those mainly composed of polyurethane, specifically, those composed of 50% by mass of polyurethane are preferable in terms of balance between texture and physical properties.

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

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

  As the polyol, a polycarbonate-based diol, a polyester-based diol, a polyether-based diol, a silicone-based diol, a fluorine-based diol, or a copolymer combining these may be used. Among these, polycarbonate diols and polyester diols are preferably used from the viewpoint of light resistance. Furthermore, in order to make a structure having a cavity around the composite fiber constituting the fabric in the sheet, a shrinkage treatment is performed under a high temperature condition, but a polycarbonate system is more preferable in that it has heat resistance that can withstand this high temperature condition. .

  The polycarbonate diol can be produced by transesterification of an alkylene glycol and a carbonate ester or a reaction of phosgene or chloroformate ester with an alkylene glycol. Examples of the alkylene glycol include linear chains such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol. Alkylene glycol, branched alkylene glycol such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,4 -Alicyclic diols such as cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, pentaerythritol and the like. Either a polycarbonate diol obtained from a single alkylene glycol or a copolymerized polycarbonate diol obtained from two or more types of alkylene glycols may be used.

  Examples of the polyisocyanate include aliphatic systems such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and aromatic systems such as diphenylmethane diisocyanate and tolylene diisocyanate, and these may be used in combination. Among them, aromatic groups such as diphenylmethane diisocyanate are preferable when importance is attached to durability and heat resistance, and aliphatic systems such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate are preferable when importance is attached to light resistance. .

  As the chain extender, amines such as ethylenediamine and methylenebisaniline, diols such as ethylene glycol, and polyamines obtained by reacting polyisocyanate with water can be used.

  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. As an internal emulsifier, a cation type such as a quaternary amine salt, an anion type such as a sulfonate and carboxylate, a nonionic type such as polyethylene glycol, and a combination of a cationic type and a nonionic type, a combination of an anionic type and a nonionic type Either is acceptable. Of these, nonionic ones are preferable in that they are superior in light resistance compared to cationic ones, and have no adverse effects due to neutralizing agents compared to anionic ones.

  The polymer elastic body may contain an elastomer resin such as polyester, polyamide, or polyolefin, an acrylic resin, an ethylene-vinyl acetate resin, or the like as long as the performance and texture as a binder are not impaired. Various additives such as pigments such as carbon black, flame retardants such as phosphorus, halogen and inorganic, antioxidants such as phenol, sulfur and phosphorus, benzotriazole, benzophenone and salicylate UV absorbers such as cyanoacrylates and oxalic acid anilides, light stabilizers such as hindered amines and benzoates, hydrolysis stabilizers such as polycarbodiimides, plasticizers, antistatic agents, surfactants, coagulation It may contain adjusting agents, dyes and the like.

  The content of the elastic polymer may be appropriately adjusted in consideration of the type of polyurethane to be used, the production method, texture, and stretchability described below.

  The sheet-like material of the present invention comprises a woven fabric. The form as a sheet-like material is stabilized by the woven fabric, and further, stretchability and stretchback property can be obtained as described later.

  The sheet-like material of the present invention comprises a composite fiber (hereinafter referred to as “side-by-side type composite fiber”) in which one of warp or weft of a fabric is composited in a side-by-side type or an eccentric core-sheath type. This is very important. For example, in a side-by-side type composite fiber composed of two or more types of polymers having a difference in intrinsic viscosity (IV), different internal strains occur between the two components due to stress concentration on the high viscosity side during stretching. Due to this internal strain, the high viscosity side contracts greatly due to the difference in elastic recovery rate after stretching and the heat shrinkage difference in the heat treatment process, and strain occurs in the single fiber to express a three-dimensional coil type crimp. This three-dimensional coil-type crimp develops stretchability as a sheet-like material. Further, due to the strong shrinkage force of the fabric, the surface of the sheet-like material has a high fiber density, and it is possible to obtain a fine and high-quality quality and a good touch.

  As a combination of polymers constituting the composite fiber such as side-by-side type, two or more kinds of polyethylene terephthalate (PET) polymers having a difference in intrinsic viscosity are preferable. For example, when using a side-by-side type composite fiber that shrinks from a low temperature and easily develops crimps, it is difficult to control the timing at which crimps develop, and its stretchability is sufficient when incorporated into a sheet-like material. However, because side-by-side type composite fibers using PET develop crimps at a relatively high temperature, it is easy to control the timing at which crimps develop, and even when incorporated into a sheet-like material. Stretching properties can be fully exhibited.

  The PET-based polymer is a polymer having a structure whose main component is a structure obtained by copolymerizing terephthalic acid or a derivative thereof and ethylene glycol or a derivative thereof. The main component is based on a polyethylene terephthalate-based polymer. It is preferably 50% by weight or more. Moreover, you may contain the copolymerization component in which formation of another ester bond is possible. Examples of the copolymerizable compound include dicarboxylic acids such as isophthalic acid, succinic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, sebacic acid, sodium 5-isophthalate, ethylene glycol, diethylene glycol, butanediol, neopentyl glycol, Examples include diols such as cyclohexanedimethanol, polyethylene glycol, and polypropylene glycol.

  The intrinsic viscosity of the PET polymer can be set to a desired viscosity by appropriately adjusting the polymerization time, temperature, catalyst amount and copolymerization component.

  The difference between the highest and lowest viscosity of two or more types of polymers forming a composite fiber such as side-by-side type. When two types of polymers are used, the difference in intrinsic viscosity between the two types of polymers is 0. .2 or more is preferable for obtaining excellent stretchability as a sheet-like material.

  The composite ratio of the high-viscosity component and the low-viscosity component in the case of consisting of two types of polymers is as follows. The amount ratio of the low viscosity component is preferably 75:25 to 35:65, and more preferably 65:35 to 45:55.

As a twist coefficient concerning the thread | yarn which comprises a side-by-side type or an eccentric core-sheath type composite fiber, 5000-25000 are preferable by the definition by a following formula. By making it 5000 or more, more preferably 8000 or more, it is possible to prevent the yarn from being damaged when the sheet is entangled with the ultrafine fiber-expressing fiber in the subsequent processing, and 25000 or less, more preferably 20000. Sufficient stretch property can be acquired by setting it as follows.
The twist coefficient K is obtained by the following equation.
K = T × D ^0.5
Here, K: Twisting coefficient T: Number of twists per 1 m of yarn length (times)
D: Yarn fineness (dtex).

  Moreover, it is preferable that the thread | yarn which comprises composite fibers, such as a side-by-side type, is a structure (henceforth a hollow structure) which has a cavity inside a thread within a sheet-like thing. The hollow structure of the yarn is a structure in which the composite fiber constituting the yarn does not exist at the center of the yarn. Further, a polymer elastic body or the like may exist in the cavity inside the yarn. By having a hollow structure, excellent stretch properties are expressed in the sheet-like material, and further, the sheet-like material is swollen and voids are given to the inside of the sheet-like material, thereby providing a flexible texture and an appropriate repulsive force. A hand-held feeling is obtained.

  As will be described later, the hollow structure of the yarn comprising the composite fiber such as the side-by-side type is obtained by interlacing the woven fabric with the ultrafine fiber-expressing fiber and forming a sheet, and then kneading and shrinking under a condition of 110 ° C. or higher. Obtainable.

  In addition, the sheet-like material of the present invention has a cross section of a single fiber in the direction perpendicular to the other side of the woven warp or weft of the composite fiber such as the side-by-side type composite fiber, that is, in the direction perpendicular to the side of the side-by-side type composite fiber. It is important to include a fiber having a hollow portion (hereinafter referred to as “hollow fiber”).

  By arranging the hollow fibers in the orthogonal direction of the side-by-side type composite fiber, it is possible to impart higher stretchability and stretch back property to the direction of the yarn in which the side-by-side type composite fiber is arranged. The mechanism is presumed as follows. In other words, the side-by-side type composite fiber contracts when the crimp is developed, and if the contraction is suppressed, the crimp is also suppressed. However, when the side-by-side type composite fiber is crimped, the hollow of the hollow fiber is crushed. Thus, it is considered that the contraction was absorbed, and as a result, the crimp expression of the side-by-side type composite fiber was not impaired, and a larger stretch margin could be included.

  Further, since side-by-side type composite fibers develop crimps by shrinkage, the fabric and thus the obtained sheet-like material tends to have a higher basis weight, but by using hollow fibers in combination, a lighter sheet-like material is obtained. be able to. If the yarn of the fabric is reduced for the purpose of weight reduction or the fiber diameter is reduced, the strength of the sheet-like material is reduced, or the fabric is entangled between the fabric and the ultrafine fiber expression type fiber due to damage with the needle needle. The fibers are cut and the fibers are exposed on the sheet surface, resulting in problems such as deterioration in appearance quality.

  The hollow ratio of the hollow fiber is preferably 10 to 40%. By setting it to 10% or more, the effect of improving the stretch property and stretch back property as described above can be obtained. Moreover, by setting it as 40% or less, it can prevent that a hollow part is crushed before the wall part of a hollow fiber breaks or a crimp expression process.

  Further, the number of hollow portions in the cross section of the hollow fiber is preferably one. By setting it as one, the hollow of the hollow fiber is apt to be crushed when the side-by-side type composite fiber is crimped, and the shrinkage is easily absorbed.

  As the polymer forming the hollow fiber, PET, polytrimethylene terephthalate (PTT), or the like can be employed.

  Examples of the texture of the woven fabric include plain weave, twill weave and satin weave, and plain weave is preferable from the viewpoint of cost.

  The sheet-like product of the present invention preferably 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 fastener, a weatherproof agent and the like.

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

  The ultrafine fiber can be obtained by using an ultrafine fiber expression type fiber composed of two or more kinds of polymer substances having different solubility in a solvent. After entanglement of the ultrafine fiber-expressing fiber and the woven fabric in advance, by treating with a solvent and expressing the ultrafine fiber, a sheet-like material in which the ultrafine fiber and the woven fabric are entangled without damaging the ultrafine fiber. Obtainable.

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

  For the sea-island type composite fiber, a sea-island type composite base is used, and a polymer inter-array system in which the two components of the sea and the island are mutually arranged and spun, and the mixed spinning in which the two components of the sea and the island are mixed and spun. Although a system etc. can be used, the sea island type composite fiber by a polymer array system is more preferable at the point from which the ultrafine fiber of uniform fineness is obtained.

  In the case of a short fiber 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.

  The obtained raw cotton is preferably made into a web with a cross wrapper or the like and used for entanglement with the woven fabric.

  As a method for producing a composite fiber such as a side-by-side type, two or more kinds of polymers are merged into a side-by-side type or an eccentric core-sheath type by a die, discharged from a discharge hole, cooled and solidified, and an oil agent is applied. May be manufactured by a two-step method in which stretching or stretching false twisting is performed, or may be manufactured by a direct spinning stretching method in which the yarn is stretched as it is without being wound once after spinning.

  As a method for producing hollow fibers, for example, a polymer flow in which slit-like discharge holes are arranged in a broken-line circle shape or the like is used to join adjacent polymer flows after discharge so as to surround the hollow portion. Can be formed. After discharge, this is cooled and solidified, and after applying oil, it may be produced by a two-step method in which it is wound up and then stretched or stretched false twisted. It may be produced by a direct spinning drawing method. Alternatively, it is possible to obtain a hollow fiber by spinning a fiber with a core-sheath structure using an easy-eluting component as a core component and eluting the core, but it is possible to obtain a hollow stably without problems such as poor decentering. In view of the simplicity of the process and the process, a method of directly forming a hollow structure using a die in which slit-like discharge holes are arranged as described above is preferable.

  The ultrafine fiber expression type fiber and the fabric are entangled. As the method, needle punch, water jet punch or the like can be used.

  The entangled body of the ultrafine fiber-expressing fiber and the woven fabric is preferably subjected to heat shrink treatment by hot water or steam treatment to improve the denseness of the fiber. However, if crimps develop at this stage, the crimp is fixed by the polymer elastic body to be applied later without any additional allowance for crimps, and the stretch property is inhibited. Is preferably low enough to suppress the occurrence of crimp, and specifically, 100 ° C. or lower is preferable.

  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, since the polymer elastic body holds the ultrafine fiber, the ultrafine fiber does not fall off even during repeated expansion and contraction, and it can withstand longer use. 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 one is performed first may be appropriately selected depending on the type of polyurethane to be used.

  The ultrafine fiber expression treatment can be performed by immersing an entangled body of sea-island type composite fiber and fabric in a solvent to dissolve and remove sea components.

  When the ultrafine fiber-expressing fiber is a sea-island composite fiber, an organic solvent such as toluene or trichloroethylene can be used as a solvent for dissolving and removing the sea component when the sea component is polyethylene, polypropylene, or polystyrene. 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 the polymer elastic body to the entangled body, there is a method of impregnating a solution of the polymer elastic body into a sheet and performing wet coagulation or dry coagulation, and may be appropriately selected depending on the type of polyurethane 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 water-soluble resin, the surface of the composite fiber such as the fiber bundle of the ultrafine fiber and the side-by-side type is protected by the water-soluble resin, and the surface of the fiber bundle of the ultrafine fiber and the side-by-side type composite 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 a sheet-like material that has a good hand feeling due to the polymer elastic body and is excellent in soft texture and high stretchability.

  As such a water-soluble resin, polyvinyl alcohol having a saponification degree of 80% or more is preferable.

  As a method for applying the water-soluble resin, there is a method in which an aqueous solution of the water-soluble resin is impregnated and dried. As drying conditions such as drying temperature and drying time, it is preferable to suppress the temperature of the sheet-like product itself to 110 ° C. or less in order to suppress the occurrence of crimp of the composite fiber such as a side-by-side type.

  The application amount of the water-soluble resin is preferably 1 to 30% by mass with respect to the sheet-like material immediately before application. By setting the content to 1% by mass or more, good texture and stretchability can be obtained. Moreover, by setting it as 30 mass% or less, a thing with favorable workability and physical properties, such as abrasion resistance, is obtained.

  The provided water-soluble resin may be removed with hot water or the like before the shrinkage treatment described below.

  Next, it is preferable to perform a shrinking treatment in which the sheet-like material is kneaded under heat and shrunk. By performing such a shrinkage treatment, crimps of the side-by-side type composite fiber are expressed, and good stretch properties can be obtained. Furthermore, a good texture, touch and quality can be obtained.

  The crimp is preferably developed after the entanglement treatment or the application of the polymer elastic body. For example, by developing crimps after the entanglement process, the fiber is cut at the time of entanglement and the appearance quality of the sheet-like material is deteriorated, or a structure having a cavity inside the yarn made of a composite fiber such as a side-by-side type It can be prevented from being crushed. In addition, by expressing the crimp after the application of the polymer elastic body, it is possible to prevent the crimp from being fixed by the polymer elastic body in the state where there is no allowance for further crimping and the stretch property being inhibited. .

  For example, a liquid dyeing machine can be used for the shrinking treatment.

  The temperature for the shrinking treatment is preferably 110 ° C. or higher. By setting the temperature to 110 ° C. or higher, more preferably 120 ° C. or higher, and more preferably 125 ° C. or higher, the side-by-side type composite fiber is easily crimped and the woven fabric is further contracted. It is easy to obtain a structure having a cavity, and high stretchability can be obtained. On the other hand, thermal degradation of the polymer elastic body can be prevented by setting it to 150 ° C. or lower, more preferably 135 ° C. or lower.

  Moreover, you may dye | stain simultaneously with a shrinkage | contraction process. What is necessary is just to select dye according to the ultrafine fiber which comprises a sheet-like material. For example, when the ultrafine fiber is made of polyester, a disperse dye can be used, and when the ultrafine fiber is made of polyamide, an acid dye or a metal-containing dye can be used. When dyed with disperse dyes, reduction washing may be performed after dyeing.

  It is also preferable to use a dyeing assistant for the purpose of improving the uniformity and reproducibility of dyeing.

  Moreover, you may give finishing agents processing, such as softening agents, such as silicone, and an antistatic agent. The finishing treatment may be performed after dyeing or in the same bath as dyeing.

  The sheet-like product of the present invention preferably has raised fibers of ultrafine fibers on at least one surface in order to achieve a raised texture. The raising treatment is preferably performed between the application of the polymer elastic body and the shrinking treatment or after the shrinking treatment.

  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 may be applied before the raising treatment. In addition, it is preferable to apply an antistatic agent before the raising treatment because grinding powder generated from the sheet by grinding becomes difficult to deposit on the sandpaper.

  Further, the sheet-like material may be divided into two or more sheets in the thickness direction of the sheet before the polymer elastic body is applied or contracted.

[Evaluation methods]
(1) Intrinsic Viscosity 0.8 g of sample polymer is dissolved in 10 mL of orthochlorophenol (hereinafter abbreviated as OCP), and the relative viscosity ηr is obtained by the following equation using an Ostwald viscometer at 25 ° C. ) Was calculated.
ηr = η / η ₀ = (t × d) / (t ₀ × d ₀ )
Intrinsic viscosity IV = 0.0242ηr + 0.2634
Here, η: viscosity of polymer solution η ₀ : viscosity of OCP t: time of dropping of solution (second)
d: density of the solution (g / cm ³ )
t ₀ : OCP fall time (seconds)
d ₀ : Density of OCP (g / cm ³ ).

(2) Average single fiber diameter A scanning electron microscope (SEM) photograph of the cross section of the sheet was taken, 100 circular fibers close to a circle or a circle were selected at random, and the average value of 100 fibers was measured by measuring the single fiber diameter. It was calculated by calculating.

(3) Confirmation of the cavity of the composite fiber yarn in the fabric Take a scanning electron microscope (SEM) photograph of the cross section of the sheet, select the circular or nearly elliptical yarn constituting the fabric, and shown in FIG. I drew an approximate circle. Subsequently, a line A connecting the outer periphery of the yarn and the center of the approximate circle is drawn, the length of the portion B where the line A and the fiber overlap is measured, and the ratio of the length of the line B to the length of the line A is determined. taking measurement. This was performed for 10 pieces, and when the average of 10 pieces was 80% or less, it was determined that the structure had a cavity inside the yarn.

(4) Elongation rate The elongation rate of the sheet-like material was measured by JIS L 1096 (1999) 8.14.1 B method (constant load method).
In the present invention, the level (target value) of a good elongation rate is 15 to 35%.

(5) Elongation recovery rate The elongation recovery rate of the sheet-like material was measured according to JIS L 1096 (1999) 8.14.2 B-1 method (constant load method). The holding interval was 50 cm, and the standing time after removing the load was 1 hour.
In the present invention, the level (target value) of a good elongation recovery rate is 80 to 100%.

For (6) product basis weight resulting sheet material was weighed 25 cm × 20 cm, it was calculated by converting the weight per 1 m ^2.

(7) Appearance quality 10 healthy adult men and 10 adult women each, with a total of 20 evaluators, were evaluated visually and sensory evaluation as follows, and the highest evaluation was defined as appearance quality. In the present invention, good levels are “◯” and “Δ”.
○: The dispersion state of the fibers is good and the appearance is also good.
Δ: There are portions where the dispersion state of the fibers is slightly poor, but the appearance is reasonably good.
X: Overall, the fiber dispersion state is very poor and the appearance is poor.

(8) Texture Twelve healthy adult males and 10 adult females were evaluated with a total of 20 evaluators, and the following evaluation was made by tactile sensation. Further, when the evaluation results were broken in the same number, the texture with the poor evaluation was taken as the texture. In the present invention, a good level is “◎” or “◯”.
A: Very flexible.
○: Flexible.
Δ: Hard
X: Very hard.

(9) Pilling Evaluation As a Martindale abrasion tester, James H. Heal & Co. The model 406 made by using the company's ABRASIVE CLOTH SM25 as a standard friction cloth, a load equivalent to 12 kPa was applied, and the appearance of the sample after being rubbed under conditions of 20,000 wear times was visually observed and evaluated. . The evaluation criteria were grade 5 when the appearance of the sample was not changed from before friction, grade 1 when the appearance of many hairballs was graded, and the grade was divided by 0.5 grade.

[Notation of chemical substances]
PU: Polyurethane PTMG: Polytetramethylene glycol PCL with number average molecular weight 2000: Polycaprolactone PNMOC with number average molecular weight 2000: Derived from 1,9-nonanediol and 2-methyl-1,8-octanediol with number average molecular weight 2000 Copolycarbonate diol PHMPC: copolymerized polycarbonate diol derived from 1,6-hexanediol having a number average molecular weight of 2000 and 3-methyl-1,5-pentanediol MDI: 4,4′-diphenylmethane diisocyanate H12MDI: dicyclohexylmethane Diisocyanate DMF: N, N-dimethylformamide PET: polyethylene terephthalate PVA: polyvinyl alcohol.

[Polyurethane type]
(1) Organic solvent polyurethane I (PU-I)
Polyisocyanate: MDI
Polyol: PTMG 70%, PCL 30%
Chain extender: EG
(2) Organic solvent-based polyurethane II (PU-II)
Polyisocyanate: MDI
Polyol: PNMOC 60%, PHMPC 40%
Chain extender: EG
(3) Water-dispersed polyurethane III (PU-III)
Polyisocyanate: H12MDI
Polyol: PHMPC
Chain extender: Water (diamine obtained by reaction of isocyanate and water)
Internal emulsifier: Diol compound having polyethylene glycol in the side chain Internal cross-linking agent: γ- (2-aminoethyl) aminopropyltrimethoxysilane.

[Example 1]
(raw cotton)
PET is used as the island component, polystyrene is used as the sea component, and a sea-island type composite die having 36 islands is used to melt and spin at an island / sea mass ratio of 55/45, and then stretched and crimped. , And cut into 51 mm to obtain a raw material of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

(fabric)
(Side-by-side type composite fiber yarn)
A PET having an intrinsic viscosity (IV) of 0.78 and a PET having an intrinsic viscosity (IV) of 0.51 were separately melted and combined at a spinning temperature of 295 ° C. from a 12-hole side-by-side composite spinneret at a mass ratio of 50:50. The yarn was discharged and taken up at a spinning speed of 1450 m / min to obtain an undrawn yarn. Further, using a hot roll-hot plate drawing machine, the film was drawn at a draw ratio of 2.6 times to obtain a side-by-side type composite fiber yarn of 56 dtex, 12 filaments.

(Hollow fiber yarn)
PET having an intrinsic viscosity (IV) of 0.65 is discharged from a spinneret of 12 holes (for 12 filaments) in which three slit-shaped discharge holes are arranged in a circle / filament broken line at a spinning temperature of 295 ° C. The yarn was taken up at a spinning speed of 2300 m / min, and was drawn twice without being wound once to obtain a hollow fiber yarn having 82 dtex, 12 filaments, and a hollow rate of 32%.

(Weaving)
The side-by-side type composite fiber yarn is subjected to a twist of 1500 times / m (twisting factor 11200) as a weft, and the hollow fiber yarn is subjected to a twist of 500 times / m (twisting factor 4500) as a warp. A plain fabric having a weaving density of warp 69 / 2.54 cm and weft 83 / 2.54 cm was produced.

(Entanglement)
Using the raw cotton, a laminated web is formed through a card and a cross-wrapper process, needle punching is performed with a number of punches of 600 / cm ² , and then the fabric is inserted above and below the web to punch 2900 / cm ² A needle punch was applied in the number of pieces to bond the web and the woven fabric to obtain an entangled sheet.

(Providing water-soluble resin and sea removal)
The entangled sheet is shrunk with hot water at 96 ° C., impregnated with a 12% by mass PVA aqueous solution, squeezed with a target weight of 20% by mass with respect to the solid fiber, and dried with hot air at a temperature of 110 ° C. for 10 minutes. A sheet with PVA was obtained. This PVA-attached sheet was immersed in trichlorethylene to dissolve and remove sea components, and a seawater-removed sheet obtained by intertwining the ultrafine fiber bundle with the woven fabric was obtained.

(Applying polymer elastic body)
The sea removal sheet is impregnated with a DMF solution of polyurethane I adjusted to a solid content concentration of 12% by mass, and squeezed with a target amount of 20% by mass with respect to the fiber content of the solid content, and the polyurethane is solidified in an aqueous solution with a DMF concentration of 30% by mass. I was damned. Thereafter, PVA and DMF were removed with hot water and dried with hot air at 110 ° C. for 10 minutes to obtain a sheet with polyurethane.

(Half-cut, brushed, shrinking treatment and dyeing)
The polyurethane-coated sheet was cut in half in the thickness direction, and the half-cut surface was ground with an endless sandpaper having a sandpaper count of 240, to obtain a raised sheet having a raised surface.
The raised sheet was subjected to shrinkage treatment and dyeing with a liquid dyeing machine at 130 ° C., and dried with a drier to obtain a leather-like sheet.
The obtained leather-like sheet had good stretchability in the horizontal direction.

[Example 2]
(raw cotton)
The same one as used in Example 1 was used.

(fabric)
A hollow fiber yarn similar to that used in Example 1 was twisted 500 times / m (twisting coefficient 4500) as a weft, and a side-by-side composite fiber yarn similar to that used in Example 1 was 1500. A plain woven fabric having a weaving density of warp 69 / 2.54 cm and weft 84 / 2.54 cm was produced using a twisted yarn / m (twisting coefficient 11200) as a warp.

(Entanglement-shrinkage treatment and dyeing)
A leather-like sheet was obtained in the same manner as in Example 1 except that the above woven fabric was used.
The obtained leather-like sheet had good stretchability in the vertical direction.

[Example 3]
(raw cotton)
PET is used as the island component, polystyrene is used as the sea component, and a sea-island type composite die having 16 islands is melt-spun at an island / sea mass ratio of 80/20, and then stretched and crimped. , And cut into 51 mm to obtain a raw material of sea-island type composite fiber having a single fiber fineness of 3.8 dtex.

(fabric)
The same one as used in Example 1 was used.

(Entanglement-shrinkage treatment and dyeing)
A leather-like sheet was obtained in the same manner as in Example 1 except that the raw cotton and polyurethane II were used.
The obtained sheet had good stretchability in the horizontal direction.

[Example 4]
(raw cotton)
The same one as used in Example 3 was used.

(fabric)
The same one as used in Example 1 was used.

(Entanglement)
An entangled sheet was obtained in the same manner as in Example except that the raw cotton and the woven fabric were used.

(Applying water-soluble resin)
The entangled sheet is shrunk with hot water at 96 ° C., impregnated with a 12% by mass PVA aqueous solution, squeezed with a target weight of 20% by mass with respect to the solid fiber, and dried with hot air at a temperature of 110 ° C. for 10 minutes. A sheet with PVA was obtained.

(Applying polymer elastic body)
The above-mentioned sheet with PVA is impregnated in a DMF solution of polyurethane II adjusted to a solid content concentration of 12% by mass, squeezed with a target applied amount of 20% by mass with respect to the fiber content of the solid content, and solidified in an aqueous solution having a DMF concentration of 30% by mass. I was damned. Thereafter, PVA and DMF were removed with hot water and dried with hot air at 110 ° C. for 10 minutes to obtain a sheet made of sea-island type composite fiber, woven fabric and polyurethane.

(Sea removal)
The sheet made of the sea-island type composite fiber, the woven fabric and the polyurethane was immersed in trichlorethylene to dissolve and remove the sea component to obtain a sheet made of the ultrafine fiber bundle, the woven fabric and the polyurethane.

(Half-shrinking and dyeing)
A leather-like sheet was obtained in the same manner as in Example 1 except that the above-mentioned ultrafine fiber bundle, a fabric and a sheet made of polyurethane were used.
The obtained leather-like sheet had good stretchability in the horizontal direction.

[Example 5]
(raw cotton)
An island / sea weight ratio of 55/45 using PET as an island component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate as a sea component, and a sea-island type composite base having 36 islands. After being melt-spun, after stretching and crimping, it was cut to 51 mm to obtain a sea-island composite fiber raw cotton having a single fiber fineness of 2.8 dtex.

(fabric)
The same one as used in Example 1 was used.

(Entanglement)
An entangled sheet was obtained in the same manner as in Example 1 except that the raw cotton was used.

(Applying polymer elastic body)
The entangled sheet was shrunk with hot water at 96 ° C. and then dried with hot air at a drying temperature of 110 ° C. for 5 minutes.

  Next, it is impregnated with a water-dispersed polyurethane III adjusted to a solid content concentration of 20% by mass, squeezed at a target amount of 30% by mass with respect to the solids fiber content, dried with hot air at a drying temperature of 120 ° C. for 10 minutes, A sheet made of woven fabric and polyurethane was obtained.

(Sea removal)
The above-mentioned sea-island type composite fiber, woven fabric and polyurethane sheet are immersed in a 15 g / L sodium hydroxide aqueous solution heated to 80 ° C. and treated for 30 minutes to remove sea components of the sea-island type fiber, A sheet made of woven fabric and polyurethane was obtained.

(Half-shrinking and dyeing)
A leather-like sheet was obtained in the same manner as in Example 1 except that a sheet made of the above ultrafine fibers, woven fabric and polyurethane was used.

  The obtained leather-like sheet had good stretchability in the horizontal direction.

[Comparative Example 1]
(raw cotton)
The same one as used in Example 1 was used.

(fabric)
(Normal fiber yarn)
PET having an intrinsic viscosity (IV) of 0.65 was discharged from a spinneret having 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-thermoplate drawing machine, drawing was performed at a draw ratio of 2.8 times to obtain a drawn yarn of 84 dtex and 72 filaments.

(Weaving)
The same side-by-side type composite fiber yarn used in Example 1 was twisted 1500 times / m (twisting coefficient 11200) as a weft, and the normal fiber yarn was 2500 times / m (twisting coefficient 22900). A plain woven fabric with a weaving density of warp 69 / 2.54 cm and weft 84 / 2.54 cm was produced using the twisted warp.

(Entanglement-shrinkage treatment and dyeing)
A leather-like sheet was obtained in the same manner as in Example 1 except that the above woven fabric was used.

  The obtained leather-like sheet was stretchable in the horizontal direction.

[Comparative Example 2]
(raw cotton)
The same one as used in Example 1 was used.

(fabric)
The normal fiber yarn used in Comparative Example 1 was subjected to a twist of 2500 times / m (twisting coefficient 22900) for both the weft and the warp. The weave density was 69 warp / 2.54 cm, 69 weft / A 2.54 cm plain woven fabric was produced.

(Entanglement-shrinkage treatment and dyeing)
A leather-like sheet was obtained in the same manner as in Example 1 except that the above woven fabric was used.

  The obtained leather-like sheet was not stretchable.

[Comparative Example 3]
(raw cotton)
The same one as used in Example 1 was used.

(fabric)
The side-by-side type composite fiber yarn used in Example 1 was twisted 1500 times / m (twisting coefficient 11200) for both the weft and the warp, and the weave density was 83 warp / 2.54 cm and the weft 83. A plain / 2.54 cm plain woven fabric was produced.

(Entanglement-shrinkage treatment and dyeing)
A leather-like sheet was obtained in the same manner as in Example 1 except that the above woven fabric was used.

  Table 1 summarizes the conditions and results of the above Examples and Comparative Examples.

  Since the sheet-like material of the present invention is excellent in appearance, texture, elongation rate and elongation recovery rate, and is lightweight, it can be used for skins and wall materials of furniture and chairs, as well as vehicles such as automobiles, trains, and aircraft. It can be suitably used as an interior material having a very elegant appearance for a skin material such as a seat or ceiling in a room. Furthermore, it can be suitably used as shirts, jackets, bags, belts, wallets, etc., clothing materials used for some of them, casual shoes, sports shoes, men's shoes, shoes for women's shoes, trims, etc. it can.

Claims (2)

  A sheet-like material comprising an ultrafine fiber having an average fiber diameter of 0.3 to 7 μm, a polymer elastic body, and a woven fabric, wherein one of warp or weft constituting the woven fabric is composed of two or more kinds of polymers. A sheet-like material comprising a composite fiber composited in a side-by-side type or an eccentric core-sheath type, and the other comprising a fiber having a hollow portion in a single fiber cross section.   The sheet-like object according to claim 1, wherein the fiber having the hollow portion has one hollow portion in a single fiber cross section.