JP5035117B2 - Sheet material and method for producing the same - Google Patents

Description

  The present invention relates to a sheet-like material and a manufacturing method thereof.

  Sheet-like materials mainly composed of ultrafine fibers and polymer elastic bodies have excellent characteristics not found in natural leather, and their use has spread year by year for clothing, chair upholstery, automobile interior materials, and the like. Recently, a sheet-like material excellent in stretchability has been demanded from the viewpoint of a feeling of wear especially for clothing and from a moldability viewpoint for materials.

  In producing such a sheet-like material, the nonwoven fabric is impregnated with an organic solvent solution of polyurethane, and then the fiber sheet-like material is immersed in water or an organic solvent solution which is a non-solvent of polyurethane to wet-solidify the polyurethane. The method is generally adopted. As such an organic solvent, a water-miscible organic solvent such as N, N'-dimethylformamide is used.

  However, since organic solvents such as N, N′-dimethylformamide used in polyurethane as described above are highly harmful to the human body and the environment, the conventional organic solvents have recently been used in the production of sheet-like materials. A method of using a polyurethane aqueous dispersion in which polyurethane is dispersed in water instead of a type of polyurethane has been studied.

  Unlike the conventional solution in which polyurethane is dissolved in an organic solvent, the polyurethane aqueous dispersion is an emulsion in which polyurethane is dispersed in water and therefore does not contain an organic solvent.

  Under such circumstances, a sheet-like material having stretch properties using a polyurethane aqueous dispersion is being studied.

  For example, Patent Document 1 describes a method of inserting a woven or knitted fabric using polytrimethylene terephthalate fibers. Although it uses the stretch properties resulting from the crystal structure of polytrimethylene terephthalate, in the case of a sheet-like material, a high-density nonwoven fabric in which single fibers are entangled with each other, and a given polyurethane, The movement was firmly restrained and the stretchability was low. Furthermore, since the fiber length of the ultrafine fibers forming the nonwoven fabric is as short as 20 mm or less, entanglement is released by repeated expansion and contraction, leading to deterioration of quality.

  Patent Document 2 describes a method of inserting a woven or knitted fabric using a woven or knitted fabric using polyurethane fibers. However, it is known that polyurethane deteriorates with time, and its stretchability disappears with long-term use. In addition, since the fiber length of the ultrafine fibers is short as in Patent Document 1, entanglement between the ultrafine fibers is released by repeatedly expanding and contracting, leading to deterioration in quality.

  Furthermore, Patent Document 3 describes a method of applying a fabric using a composite fiber composed of two or more polyester polymers, one component of which is made of polytrimethylene terephthalate. However, polytrimethylene terephthalate is sensitive to heat and tends to shrink. Therefore, when a sheet-like material is processed by applying this woven fabric, crimps appear in an unintended process due to heat applied during the processing, and as a result, the sheet-like material tends to have poor stretchability. In addition, since the fiber length of the ultrafine fibers is short as in Patent Document 1, entanglement between the ultrafine fibers is released by repeatedly expanding and contracting, leading to deterioration in quality.

That is, until now, a sheet-like material excellent in appearance, texture, elongation rate and elongation recovery rate using an aqueous polyurethane dispersion without using an organic solvent has not been obtained.
JP-A-11-269975 JP 2004-91999 A JP 2005-60859 A

  In view of the background of such prior art, the present invention is to provide a sheet-like product excellent in appearance, texture, elongation rate and elongation recovery rate and environmentally friendly, and a method for producing the same.

That is, the present invention relates to a woven or knitted fabric including a yarn comprising a side-by-side type or eccentric core-sheath type composite fiber formed from two or more types of polyethylene terephthalate polymers having a difference in intrinsic viscosity (IV), and an average single fiber. fineness consists of a 0.5dtex following ultrafine fibers or 0.001Dtex, contains a self-emulsifiable polyurethane, and the yarn comprising a side-by-side or eccentric core-sheath composite fiber is that having a tunnel structure It is a sheet-like thing characterized by this.

Moreover, this invention is a method of manufacturing the sheet-like material of this invention, Comprising: The manufacturing method of a sheet-like material characterized by including the process of following (1)-(4).
(1) A step of intertwining the woven or knitted fabric with ultrafine fiber-generating fibers made of two or more types of polymers having different solubility in a solvent.
(2) A step of impregnating and coagulating a liquid obtained by dispersing self-emulsifying polyurethane in water to give the self-emulsifying polyurethane.
(3) A step of expressing an ultrafine fiber having an average single fiber fineness of 0.001 dtex or more and 0.5 dtex or less from the ultrafine fiber generating fiber with a solvent.
(4) A step of shrinking the woven or knitted fabric in the sheet-like material by kneading under a condition of 110 ° C. or higher.

  According to the present invention, it is possible to obtain a sheet-like material excellent in appearance, texture, elongation rate and elongation recovery rate and environmentally friendly, and a method for producing the same.

  The sheet-like product of the present invention comprises a woven or knitted fabric. It is important that the woven or knitted fabric includes a yarn including a fiber formed from a polyethylene terephthalate polymer. This is because it has the most suitable characteristics in the manufacture of sheet-like materials. For example, when a sheet-like material of the present invention is produced using a woven or knitted fabric made of a composite fiber using polytrimethylene terephthalate, polytrimethylene terephthalate has a heat-sensitive property and thus is easily contracted by heat. Therefore, when a sheet-like material is processed by applying this woven fabric, crimps appear in an unintended process due to heat applied during the processing, and as a result, the sheet-like material tends to have poor stretchability. On the other hand, a composite fiber using polyethylene terephthalate is suitable for the method for producing a sheet-like product of the present invention because crimps develop at a relatively high temperature.

  The polyethylene terephthalate polymer is a polymer having a structure mainly composed of a copolymer of terephthalic acid or a derivative thereof and ethylene glycol or a derivative thereof. 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.

  Moreover, it is also preferable to add titanium dioxide as a matting agent, silica or alumina fine particles as a lubricant, hindered phenol derivatives, coloring pigments or the like as an antioxidant to a polyethylene terephthalate polymer, if necessary. .

  The woven or knitted fabric in the sheet-like product of the present invention includes a yarn comprising a side-by-side or eccentric core-sheath type composite fiber formed from two or more kinds of polyethylene terephthalate polymers having a difference in intrinsic viscosity (IV). is important. Such a composite fiber has different internal strains 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 contraction force of the woven or knitted fabric, the surface of the sheet-like product has a high fiber density, and it is possible to obtain a fine and high-grade quality and a good touch.

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

  When two or more types of polyethylene terephthalate polymers forming a side-by-side or eccentric core-sheath type composite fiber are the difference between the highest and the lowest in viscosity, and two types of polyethylene terephthalate polymers The difference in intrinsic viscosity between the two types of polyethylene terephthalate polymers is preferably 0.2 or more in order to obtain excellent stretch properties as a sheet-like material.

  As a composite ratio of the high viscosity component and the low viscosity component in the case of comprising two types of polyethylene terephthalate polymers, in terms of yarn production, homogeneity of coil dimensions in the fiber length direction, and formation of a tunnel structure described later, 75:25 to 35:65 is preferable, and 65:35 to 45:55 is more preferable as the amount ratio of the high viscosity component to the low viscosity component.

  As the fiber cross-sectional shape of the composite fiber, a round cross-section, a triangular cross-section, a multi-lobe cross-section, a flat cross-section, an X-type cross-section, and various other irregular cross-sections can be adopted. From the viewpoint of cross section, light weight, heat retention, and rebound, a hollow section is preferable, and a triangular section is preferable from the viewpoint of dry texture.

The twist coefficient of the twist applied to the yarn comprising the side-by-side or eccentric core-sheath type composite fiber is preferably 5000 to 25000. By making it 5000 or more, more preferably 8000 or more, it is possible to prevent the yarn from being damaged when a sheet is produced by being entangled with the ultrafine fiber generating 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 yarn comprising the side-by-side type or the eccentric core-sheath type composite fiber has a tunnel structure in the sheet-like material. Here, the tunnel structure is a structure in which the outer peripheral portion of the yarn is formed of fibers, but no fiber is present in the center portion of the yarn. The degree of the tunnel structure is preferably such that the thickness of the outer peripheral portion is 80% or less of the yarn radius. A polymer elastic body or the like may exist inside the tunnel structure.
By having a tunnel 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, so that a flexible texture and appropriate repulsive force are fulfilled. A hand-held feeling is obtained.

  As will be described later, the yarn constituting the woven or knitted fabric has a tunnel structure by entangled the woven or knitted fabric with the ultrafine fiber generating fiber and then squeezed and shrunk under a condition of 110 ° C. or higher.

  In the present invention, the woven or knitted fabric is a generic term for woven fabric and knitted fabric. 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. In the case of a knitted fabric, circular knitting, tricot, raschel and the like are preferable.

  The knitted or knitted fabric used in the present invention is preferably a woven or knitted fabric composed entirely of such composite fibers, but may contain other fibers as long as the effects of the present invention are not impaired.

  For example, it is also possible to use the composite fiber only for the weft or only for the warp to give stretchability in the horizontal direction or the vertical direction.

  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. Of these, polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate are preferably used from the viewpoints of strength, dimensional stability, light resistance, and dyeability. Moreover, the sheet-like material may be configured by mixing ultrafine fibers of different materials.

  In addition, in these polymers, in order to improve the concealability, addition of inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, antibacterial agents, etc. Addition according to various purposes is also preferable.

  It is important that the average single fiber fineness of the ultrafine fibers constituting the sheet-like material is 0.001 dtex or more and 0.5 dtex or less from the viewpoint of flexibility and napped quality of the sheet-like material. Preferably it is 0.3 dtex or less, More preferably, it is 0.2 dtex or less. On the other hand, it is preferably 0.005 dtex or more, more preferably 0.01 dtex or more, from the viewpoint of dispersibility of fibers during raising process such as coloring after dyeing or grinding with sandpaper, and ease of spreading. .

  The average single fiber fineness of the ultrafine fibers is obtained by taking a scanning electron microscope (SEM) photograph of a sheet-like material or the surface of the sheet, and randomly selecting 100 circular or near-elliptical elliptical fibers. Is calculated by converting the specific gravity of the material polymer into fineness, and further calculating the average value.

  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 nonwoven fabric (ultrafine fiber web) constituting the sheet-like material of the present invention may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric, but a short fiber nonwoven fabric is preferable when emphasis is placed on texture and quality. When the short fiber nonwoven fabric is used, the fiber length is preferably 25 mm or more and 90 mm or less. 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.

  It is important that the sheet-like material of the present invention contains a self-emulsifying polyurethane. The self-emulsifying polyurethane has a hydrophilic so-called internal emulsifier in its molecular structure and can be stably dispersed in water without using an emulsifier such as a surfactant. Since the self-emulsifying type polyurethane does not need to use an emulsifier such as an activator, it has higher water resistance in the sheet-like product than the forced emulsification type polyurethane use. Can be prevented from falling off.

  Self-emulsifying polyurethane, which is a kind of water-dispersed polyurethane, has a higher hydrophilicity than organic solvent-based polyurethane, and therefore is more easily softened when the polyurethane is wetted with water. Therefore, when the woven or knitted fabric made of the composite fiber in the sheet is contracted, the polyurethane is softened by getting wet with water, and the shrinkage inhibition of the woven or knitted fabric can be suppressed. Furthermore, since the amount of internal emulsifier used to disperse polyurethane in water is larger than that of forced emulsification type polyurethane, self-emulsification type polyurethane can suppress inhibition of shrinkage of woven and knitted fabrics more. is there. Therefore, the present invention becomes a sheet-like material excellent in stretchability.

  The self-emulsifying polyurethane present in the internal space of the sheet-like material preferably has a nonporous structure. Since the self-emulsifying polyurethane has a non-porous structure, it becomes stronger in physical force such as stagnation as compared with the porous structure, so that the pilling resistance, wear resistance, etc. of the sheet-like material are improved. The term “non-porous structure” as used herein means that when a scanning electron microscope (SEM) photograph of a cross section of a sheet-like material is observed at a magnification of 300 times, pores of 5 μm or more cannot be seen in the self-emulsifying polyurethane portion. .

  The self-emulsifying polyurethane existing in the internal space of the sheet-like material is obtained by impregnating a sheet made of woven or knitted fabric made of composite fibers and a sheet made of ultrafine fibers with a solution obtained by dispersing the self-emulsifying polyurethane in water. . Since the self-emulsifying polyurethane has a hydrophilic so-called internal emulsifier in its molecular structure, it can be stably dispersed in water without using an emulsifier such as a surfactant.

  The self-emulsifying polyurethane is usually handled in a state of being dispersed in water, and can be obtained from the manufacturer in this state. This is because once dried, it cannot be dispersed in water again.

  Internal emulsifiers are any of cationic systems such as quaternary amine salts, anionic systems such as sulfonates and carboxylates, nonionic systems such as polyethylene glycol, combinations of cationic systems and nonionic systems, and combinations of anionic systems and nonionic systems. However, the cationic internal emulsifier is inferior in light resistance such as yellowing, and the anionic internal emulsifier is preferably a nonionic internal emulsifier because it may cause a harmful effect due to the neutralizing agent.

  As the self-emulsifying polyurethane used in the present invention, those having a structure obtained by appropriately reacting polyol, polyisocyanate, chain extender, and internal crosslinking agent in addition to the internal emulsifier 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. Of these, polycarbonate diols and polyether diols are preferably used from the viewpoint of hydrolysis resistance, and polycarbonate diols are more preferable from the viewpoints of light resistance and heat resistance.

  The polycarbonate-based diol can be produced by an ester exchange reaction between an alkylene glycol and a carbonate ester, or a reaction between phosgene or chloroformate ester and 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. Of these, aliphatic systems such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferable from the viewpoint of 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.

  An internal cross-linking agent is a compound having a crosslinkable functional group that is introduced into the molecular structure in advance when a self-emulsifying polyurethane is synthesized as part of a self-emulsifying polyurethane molecule. Thus, durability such as hydrolysis resistance of the self-emulsifying polyurethane can be remarkably improved. An internal emulsifier is preferably used, and the type thereof is not particularly limited, but a compound having a silanol group forming a siloxane bond is preferable.

  The self-emulsifying polyurethane may have 3% by weight or more and 30% by weight or less of polyethylene glycol with respect to the total weight of the self-emulsifying polyurethane. By having polyethylene glycol, heat-sensitive gelling properties can be imparted, and migration can be suppressed and a flexible sheet-like product can be formed when self-emulsifying polyurethane is imparted. Furthermore, the property that the self-emulsifying polyurethane itself becomes soft when wetted with water can be imparted, and inhibition of shrinkage of the woven or knitted fabric can be suppressed in a later step. However, in the case of a self-emulsifying type polyurethane that is self-emulsified with a nonionic internal emulsifier, if it is too little, it becomes difficult to self-emulsify, and if it is too much, physical properties such as water resistance and strength of the polyurethane film are likely to deteriorate. The content of polyethylene glycol with respect to the total weight of polyurethane is more preferably 5% by weight or more and 20% by weight or less.

  In the present invention, the self-emulsifying polyurethane may be used alone or in combination of two or more, and other polymers may be used in combination.

  Examples of other polymers include water-dispersible and water-soluble polymers such as acrylic and silicone.

  Self-emulsifying polyurethanes are pigments such as carbon black, dyes, anti-fungal agents, weathering agents such as antioxidants and UV absorbers, flame retardants, penetrating agents and lubricants, anti-blocking agents such as silica and titanium oxide, and antistatic agents. It is also preferable to contain a surfactant such as an agent, an antifoaming agent such as silicone, a filler such as cellulose, and a coagulation modifier.

  In the sheet-like product of the present invention, the content of the self-emulsifying polyurethane with respect to the ultrafine fibers and the woven / knitted fabric is preferably 20% by weight or more and 100% by weight or less. By setting it to 20% by weight or more, it is possible to obtain wear resistance and form retention that can withstand repeated expansion and contraction. By making it 100% by weight or less, it is possible to prevent the texture of the sheet-like material from becoming hard, and when the shrinkage of the woven or knitted fabric is performed in a later step, the shrinkage of the woven or knitted fabric is not inhibited and the stretch property can be expressed. . More preferably, they are 30 to 90 weight%, More preferably, they are 35 to 85 weight%.

  The sheet-like material of the present invention contains functional agents such as dyes, pigments, softeners, texture modifiers, anti-pilling agents, antibacterial agents, deodorants, water repellents, light proofing agents, and weathering agents. Is also preferable.

  Next, the manufacturing method of the sheet-like material of this invention is demonstrated.

The manufacturing method of the sheet-like object of the present invention includes the following steps (1) to (4).
(1) A woven or knitted fabric including a yarn comprising a composite fiber of a side-by-side type or an eccentric core-sheath type formed from two or more types of polyethylene terephthalate polymers having a difference in intrinsic viscosity, and 2 different in solubility in a solvent. A process of entanglement with ultrafine fiber-generating fibers composed of more than one type of polymer.
(2) A step of impregnating and coagulating a liquid obtained by dispersing self-emulsifying polyurethane in water to give the self-emulsifying polyurethane.
(3) A step of expressing an ultrafine fiber having an average single fiber fineness of 0.001 dtex or more and 0.5 dtex or less from the ultrafine fiber generating fiber with a solvent.
(4) A step of shrinking the woven or knitted fabric under a condition of 110 ° C. or higher.

  By carrying out the steps (1) to (4), a sheet-like material excellent in appearance, texture, elongation rate and elongation recovery rate can be obtained.

  First, step (1) will be described.

  In the step (1), a woven or knitted fabric including a yarn comprising a composite fiber of a side-by-side type or an eccentric core-sheath type formed from two or more types of polyethylene terephthalate polymers having a difference in intrinsic viscosity, and solubility in a solvent Are entangled with ultrafine fiber-generating fibers made of two or more types of polymers having different qualities.

  For example, in the case of a side-by-side type composite fiber, a high-viscosity polyethylene terephthalate polymer is arranged on one of two types of polyethylene terephthalate polymer and a low-viscosity polyethylene terephthalate polymer is arranged on the other side. After joining at the upper part of the discharge hole to form a side-by-side composite flow, it can be obtained by discharging from the discharge hole for obtaining a desired cross-sectional shape. After the discharged yarn is cooled and solidified, it may be produced by a two-step method in which it is wound once and then stretched or stretched false twisted. Alternatively, it may be directly stretched by drawing directly after spinning. It may be manufactured.

  In the present invention, as the ultrafine fibers constituting the sheet, ultrafine fiber-generating fibers composed of two or more kinds of polymer substances having different solubility in a solvent are used. After the ultrafine fiber generating fiber and the woven or knitted fabric are entangled in advance, a sheet-like product formed by entanglement of the ultrafine fiber and the woven or knitted fabric can be obtained by treating with a solvent and making the fibers ultrafine.

  As ultra-fine fiber generation 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 adopt a fiber or a peelable composite fiber in which the two-component thermoplastic resin is alternately arranged in a radial or multilayered manner on the fiber surface and separated into fine fibers by solvent separation and separation. 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.

  The obtained ultrafine fiber-generating fiber is preferably crimped and cut into a predetermined length to obtain raw cotton (web).

  A known method can be used for crimping or cutting. The obtained raw cotton is made into a web with a cross wrapper or the like, and then the fiber is entangled with the woven or knitted fabric to make a sheet.

  Known methods such as needle punching and water jet punching can be used as a method for obtaining a sheet by entanglement of fibers and woven or knitted fabric.

  The obtained sheet may be subjected to shrinkage treatment by hot water or steam treatment in order to improve the fineness of the fibers. However, if the shrinkage treatment is performed at a high temperature, crimps of the woven or knitted fabric will be manifested, and if self-emulsifying polyurethane is applied in the next step in this state, care must be taken because it becomes a sheet-like product with poor stretchability. . When the shrinkage treatment is performed, it is preferably performed at 100 ° C. or lower.

  Next, process (2) is demonstrated.

  In step (2), a self-emulsifying polyurethane is impregnated and solidified by impregnating and coagulating a liquid in which self-emulsifying polyurethane is dispersed in water (hereinafter also referred to as “self-emulsifying polyurethane aqueous dispersion”).

  In applying the self-emulsifying type polyurethane water dispersion to the sheet, for example, impregnating the sheet with the self-emulsifying type polyurethane water dispersion, or applying and dry-solidifying the sheet, after impregnating the sheet with the polyurethane water dispersion, There are a method of heat-coagulation by heat and heat drying, a method of heat-coagulation by hot coagulation in hot water, and a combination thereof.

  In addition, when drying temperature is too low, drying time will become long, From this point, 80 degreeC or more is preferable, More preferably, it is 90 degreeC or more. On the other hand, if the drying temperature is too high, it may cause thermal degradation of the self-emulsifying polyurethane. From such a point, 180 ° C. or lower is preferable, and 160 ° C. or lower is more preferable. Further, it is preferable that the crimp of the side-by-side type or eccentric core-sheath type composite fiber in the knitted or knitted fabric is not expressed at this stage but is expressed in the step (4) described later. From this point, 120 ° C. or lower is preferable, and 110 ° C. or lower is more preferable.

  The polyurethane water dispersion used in the production of the present invention is a polyurethane water dispersion dispersed in water as an emulsion, and is a self-emulsifying polyurethane water dispersion containing no emulsifier such as a surfactant.

  When a forced emulsification type polyurethane aqueous dispersion containing an emulsifier such as a surfactant is used, the surface of the obtained sheet-like material is sticky due to the emulsifier, so a washing step is required, and the processing step Will increase the cost.

  The self-emulsifying polyurethane is usually handled in a state of being dispersed in water, and can be obtained from the manufacturer in this state. This is because once dried, it cannot be dispersed in water again.

  The self-emulsifying polyurethane aqueous dispersion used in the present invention may contain a water-soluble organic solvent in an amount of 0 to 40% by weight with respect to the aqueous dispersion in order to improve storage stability and film forming property. However, it is preferable that the organic solvent is contained in an amount of 0% by weight or more and 1% by weight or less because of concerns such as release of the organic solvent into the atmosphere due to heating during film formation and residual organic solvent in the final product.

  The self-emulsifying polyurethane is not particularly limited as long as it is an aqueous dispersion dispersed in water, but a polycarbonate-based self-emulsifying polyurethane aqueous dispersion is preferred from the viewpoint of hydrolysis resistance.

  The concentration of the self-emulsifying polyurethane aqueous dispersion (content of the self-emulsifying polyurethane relative to the self-emulsifying polyurethane aqueous dispersion) is 10% by weight or more and 50% by weight from the viewpoint of storage stability of the self-emulsifying polyurethane aqueous dispersion. The following is preferred.

  The self-emulsifying polyurethane aqueous dispersion preferably has a thermal gelation temperature. By having a thermal gelation temperature, it is possible to suppress the polyurethane migration phenomenon when the sheet is impregnated and dried. However, if the heat-sensitive gelation temperature is too low, there is a high possibility of gelation in the storage of the polyurethane water dispersion, and if it is too high, the migration phenomenon cannot be suppressed, so it is preferably 55 ° C. or higher and 90 ° C. or lower.

  The self-emulsifying polyurethane aqueous dispersion preferably has a heat-sensitive gelation property alone, but for the purpose of imparting the heat-sensitive gelation property to the self-emulsifying polyurethane water dispersion or lowering the heat-sensitive gelation temperature, It is also preferable to add inorganic salts such as calcium, sodium sulfate, and potassium sulfate.

  In addition, when applying a self-emulsifying polyurethane aqueous dispersion, a pigment such as carbon black, a dye, an antifungal agent, a light-resistant agent such as an antioxidant or an ultraviolet absorber, a flame retardant, a penetrating agent or a lubricant. It is also preferable to add an antiblocking agent such as silica or titanium oxide, an antistatic agent, an antifoaming agent such as silicone, a filler such as cellulose, a polyurethane coagulation adjusting agent, or the like.

  Step (2) may be performed either before or after step (3).

  Next, process (3) is demonstrated.

  In the step (3), ultrafine fibers having an average single fiber fineness of 0.001 dtex or more and 0.5 dtex or less are expressed from the ultrafine fiber generation type fiber by a solvent. When the ultrafine fiber generating fiber is a sea-island type composite fiber, the sea component includes polyethylene, polypropylene, polystyrene, copolymerized polyester such as sodium 5-sulfoisophthalate or polyethylene glycol, polylactic acid, water-soluble thermoplastic polyvinyl Alcohol resins and the like can be used.

  Solvents that dissolve sea components include organic solvents such as toluene and trichlorethylene in the case of polyethylene, polypropylene, and polystyrene. Alcohol aqueous solutions such as sodium hydroxide and water-soluble thermoplastic polyvinyl alcohol in the case of copolymer polyester and polylactic acid. In the case of a resin, hot water can be used, and it can be removed by immersing the sea-island type composite fiber in a solvent and performing a stenosis.

  Next, process (4) is demonstrated.

  In the step (4), a sheet-like material composed of a woven or knitted fabric, ultrafine fibers, and self-emulsifying polyurethane is squeezed under a condition of 110 ° C. or higher to shrink the woven or knitted fabric.

  By imparting sag to the sheet-like material under conditions of 110 ° C. or higher, shrinkage and crimping of the yarn composed of the composite fiber constituting the woven or knitted fabric can be expressed, and stretch properties can be imparted to the sheet-like material. . As a result, stretchability is imparted to the sheet-like material, and a good texture, touch and quality can be obtained.

  In order to give a stagnation to the sheet at a temperature of 110 ° C. or higher, a liquid dyeing machine or the like can be used, and a known dyeing machine can be used.

  The treatment temperature needs to be 110 ° C. or higher, and if the treatment is performed at a higher temperature, the yarns are more easily crimped and the woven or knitted fabric is more easily shrunk, preferably 120 ° C. or higher, more preferably 125 ° C. That's it. However, if the treatment is carried out at an excessively high temperature, the polymer elastic body containing polyurethane as a main component is thermally deteriorated. Therefore, the temperature is preferably 150 ° C. or less, more preferably 135 ° C. or less.

  In the present invention, in this step (4), it is important to heat the sheet-like material at a high temperature to perform a shrinkage treatment of the woven or knitted fabric, thereby expressing the crimp of the yarn. For example, when a knitted or knitted fabric that has been contracted and crimped in advance is inserted in step (1), the fibers of the woven or knitted fabric are cut by an entanglement process such as a needle punch, and the fibers are exposed on the sheet surface. The appearance quality may deteriorate, the stretchability may deteriorate, the feeling of holding, and the quality may deteriorate. Further, when polyurethane is applied in the step (2) after the knitted or knitted fabric is crimped, the form of the sheet-like product itself is fixed, and the stretch property is hardly exhibited. Therefore, in the present invention, it is preferable that the woven or knitted fabric in the sheet-like material is shrunk after being integrated as a sheet-like material so that the yarn composed of the composite fiber has a tunnel structure.

Moreover, you may dye | stain simultaneously with the shrinkage | contraction process in a process (4). The dye is not particularly limited, and may be selected according to the ultrafine fibers constituting the sheet-like material. For example, disperse dyes can be used if the sheet is made of polyester-based ultrafine fibers, and acidic dyes or metal-containing dyes can be used if they are made of polyamide-based ultrafine fibers.
When dyed with disperse dyes, reduction washing may be performed after dyeing.

  Moreover, it is preferable to use a dyeing assistant during dyeing for the purpose of improving the uniformity and reproducibility of dyeing. Further, a finishing agent treatment such as a softening agent such as silicone or an antistatic agent may be applied, and the finishing treatment may be performed after dyeing or in the same bath as dyeing.

  The sheet-like material of the present invention may be a nap-like sheet-like material having napped fibers of at least one surface. For that purpose, it is preferable to perform a raising process between the step (3) and the step (4) or after the step (4).

  The raising treatment for forming napping on the surface of the sheet-like material can be performed by a grinding method using a sandpaper or a roll sander. 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 the grinding powder generated from the sheet-like material by grinding tends to be difficult to deposit on the sandpaper.

  Further, the sheet-like material may be divided into half or several sheets in the sheet thickness direction before the step (2), before the step (3) or before the step (4).

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example, this invention is not limited only to a following example.

[Evaluation method]
(1) Intrinsic viscosity IV
0.8 g of the sample polymer was dissolved in 10 mL of orthochlorophenol (hereinafter abbreviated as OCP), the relative viscosity ηr was determined from the following equation using an Ostwald viscometer at 25 ° C., and the intrinsic viscosity IV 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) Twisting coefficient The yarn is untwisted under a load of 90 × 10 ⁻³ cN / dtex by an electric tester, and the number of untwisting when completely untwisted is divided by the yarn length after untwisting. The number T of twists was calculated | required and also the twist coefficient K was calculated | required by following Formula.
K = T × D ^0.5
Here, K: Twisting coefficient T: Number of twists per 1 m of yarn length (times)
D: Yarn fineness (dtex).

(3) Average single fiber fineness A scanning electron microscope (SEM) photograph of the surface of a sheet or sheet-like material is taken, 100 round or nearly elliptical fibers are selected at random, and the fiber diameter is measured to obtain a fiber. It calculated by converting into the fineness from the specific gravity (polyethylene terephthalate is 1.38 g / cm ³ ), and calculating the average value of 100.

(4) Confirmation of the tunnel structure of the yarn in the woven or knitted fabric Take a scanning electron microscope (SEM) photograph of the cross section of the sheet, select the circular or nearly elliptical yarn that forms the woven or knitted fabric, An approximate circle was drawn as shown in FIG. continue,
A line A connecting the outer periphery of the yarn and the center of the approximate circle was drawn, the length of the part B where the line A and the fiber overlap each other was measured, and the ratio of the length of the line B to the length of the line A was measured. This was measured every 30 degrees with respect to the circular arc part where the outer peripheral part can be confirmed, and the average value was obtained as the degree of fullness of the fiber.

(5) Stretch properties Stretch properties were evaluated based on the stretch rate and stretch recovery rate. For each direction of the sheet, if both the stretch rate and stretch recovery rate exceed the target values, the evaluation is "○", and the evaluation is "good", if either or both do not exceed the target, "X", fail It was. Also, if either the vertical direction or the horizontal direction, or both pass, it is judged as a sheet with stretch properties, and in the overall evaluation, it is judged as “O”, and if both are rejected, it is judged as rejected, It was set as “x”.

-Elongation rate The elongation rate of the sheet-like material was measured in JIS L 1096 (2005) 8.14.1 B method (constant load method).
In the present invention, a good level (target value) is an expansion rate of 15% to 35%.

-Extension recovery rate The extension recovery rate of the sheet-like material was measured in JIS L 1096 (2005) 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, a good level (target value) is an elongation recovery rate of 80% or more and 100% or less.

(6) Appearance quality The surface quality of leather-like sheet-like materials is the highest, with 10 healthy adult men and 10 adult women each, with a total of 20 evaluators evaluated by visual and sensory evaluation as follows. The evaluation was the 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.

(7) Texture 10 healthy adult men and 10 adult women each, with a total of 20 evaluators, the following evaluation was made by tactile sensation, and the most frequent evaluation was used as the texture. 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

(8) Pilling Evaluation Pilling evaluation of the sheet-like material was conducted by James H. as a Martindale abrasion tester. 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, and grade 1 when many pills were generated, and the grade was divided into 0.5 grades.

[Notation of chemical substances]
PU: Polyurethane C5C6PC: Copolymer of pentamethylene carbonate diol and hexamethylene carbonate diol Polycarbonate polyol 3MPC: Poly (3-methylpentane carbonate) polyol PHC: Polyhexamethylene carbonate H12MDI: Dicyclohexylmethane diisocyanate HDI: Hexamethylene diisocyanate PET: Polyethylene terephthalate NaOH: Sodium hydroxide [Polyurethane type]
(1) Self-emulsifying polyurethane water dispersion I (PU-I)
Polyisocyanate: H12MDI
Polyol: C5C6PC
Internal emulsifier: Diol compound chain extender having polyethylene glycol in the side chain: Water (diamine obtained by reaction of isocyanate and water)
Internal cross-linking agent: γ- (2-aminoethyl) aminopropyltrimethoxysilane (2) Self-emulsifying polyurethane water dispersion II (PU-II)
Polyisocyanate: HDI
Polyol: 3MPC
Internal emulsifier: dimethylolpropionic acid triethylamine salt chain extender: water (diamine obtained by reaction of isocyanate and water)
Internal cross-linking agent: γ- (2-aminoethyl) aminopropyltrimethoxysilane (3) forced emulsification type polyurethane III (PU-III)
Polyisocyanate: H12MDI
Polyol: PHC
Internal emulsifier: None External emulsifier: Nonionic surfactant Internal cross-linking agent: None (Manufacture of woven and knitted fibers)
<Production Example 1>
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 the composite ratio (wt%) was 50:50 from a 12-hole composite spinneret at a spinning temperature of 295 ° C. The yarn was discharged and taken up at a spinning speed of 1450 m / min to obtain a 12 filament side-by-side composite structure undrawn yarn.
Further, using a hot roll-thermoplate drawing machine, drawing was carried out at a draw ratio of 2.6 times to obtain a drawn yarn of 56 dtex and 12 filaments.

<Production Example 2>
PET having an intrinsic viscosity (IV) of 0.78 as a core and PET having an intrinsic viscosity (IV) of 0.51 as a sheath are melted separately, and a composite ratio (wt%) is obtained from a 12-hole composite spinneret at a spinning temperature of 295 ° C. The yarn was discharged at 50:50 and taken up at a spinning speed of 1450 m / min to obtain a 12 filament eccentric core-sheath type composite structure undrawn yarn.
Further, using a hot roll-thermoplate drawing machine, drawing was carried out at a draw ratio of 2.6 times to obtain a drawn yarn of 56 dtex and 12 filaments.

<Production Example 3>
PET having an intrinsic viscosity (IV) of 0.65 was discharged from a 72-hole composite spinneret at a spinning temperature of 295 ° C. and taken up at a spinning speed of 1650 m / min to obtain 72-filament 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.

(Manufacture of textiles)
<Production Example 4>
A twisted yarn obtained by twisting the drawn yarn obtained in Production Example 1 at 1500 times / m (twisting factor 11200) as a weft, and a drawn yarn obtained in Production Example 3 at 2500 times / m (twisting factor 22900). A plain woven fabric was produced using the twisted yarns subjected to.

<Production Example 5>
A plain woven fabric was produced using the twisted yarn obtained in Production Example 1 with a twist of 1500 times / m (twisting coefficient 11200) as both the weft and the warp.

<Production Example 6>
A twisted yarn obtained by twisting the drawn yarn obtained in Production Example 2 at 1500 times / m (twisting factor 11200) as a weft, and a drawn yarn obtained in Production Example 3 at 2500 times / m (twisting factor 22900) A plain woven fabric was produced using the twisted yarns subjected to.

<Production Example 7>
A plain weave fabric was produced using the twisted yarn obtained in Production Example 3 twisted 2500 times / m (twisting coefficient 22900) for both the weft and the warp.

<Production Example 8>
A twisted yarn obtained by twisting the drawn yarn obtained in Production Example 1 at 1500 times / m (twisting factor 11200) as a weft, and a drawn yarn obtained in Production Example 3 at 2500 times / m (twisting factor 22900). A plain woven fabric was produced using the twisted yarns subjected to.
The obtained woven fabric was treated with a liquid dyeing machine at 130 ° C. for 30 minutes, and then dried at 130 ° C. using a pin tenter to produce a woven fabric in which wefts were crimped.

(Manufacture of sheet-like materials)
<Example 1>
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.

Using this raw material of sea-island type composite fiber, a laminated web is formed through a card and cross wrapping process, needle punched at a number of punches of 600 / cm ² , and then the fabric produced in Production Example 4 is placed above and below the web. The sheet was inserted, needle punched at a punch number of 2900 / cm ² , and the web and the fabric were bonded together to obtain a sheet.

  The 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, impregnation with self-emulsifying polyurethane aqueous dispersion I (PU-I) and hot air drying at a drying temperature of 120 ° C. for 10 minutes so that the weight of polyurethane relative to the weight of the island component and the fabric is 51% by weight. A sheet-like material having polyurethane added thereto was obtained.

  Next, this sheet-like material is immersed in an aqueous solution of sodium hydroxide having a concentration of 15 g / L heated to 80 ° C. and treated for 30 minutes to remove sea components of sea-island type fibers, and consists of ultrafine fibers, woven / knitted fabric and polyurethane. A sheet was obtained. It was confirmed by scanning electron microscope (SEM) observation of the surface of the sheet material that the average single fiber fineness was 0.04 dtex.

  Then, the sheet-like material was cut in half in the thickness direction, and the raised surface was formed by grinding the half-cut surface using an endless sandpaper having a sandpaper count of 240.

  The sheet-like material thus obtained was subjected to shrinkage treatment and dyeing simultaneously at 130 ° C. with a liquid dyeing machine, and then dried with a dryer to obtain a sheet-like material.

  As a result of observing the cavities of the threads in the woven fabric, it was confirmed that cavities exist in the wefts. Further, the obtained sheet-like product had a horizontal elongation rate of 25% and an elongation recovery rate of 92%, and had good stretchability in the horizontal direction. The appearance quality, texture, and pilling evaluation were also good results.

<Example 2>
An island / sea weight ratio of 80/20 using PET as an island component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate as a sea component, and using a sea-island type composite die having 16 islands. After being melt-spun, after stretching and crimping, it was cut to 51 mm to obtain a raw material of sea-island type composite fiber having a single fiber fineness of 3.8 dtex.

Using this raw material of sea-island type composite fiber, a laminated web is formed through a card and cross wrapping process, needle punched at a number of punches of 300 / cm ² , and then the woven fabric produced in Production Example 5 is placed on the top and bottom of the web. The sheet was inserted, needle punched with a punch number of 3400 / cm ² , and the web and the woven fabric were bonded together to obtain a sheet.

  The 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, impregnation with self-emulsifying polyurethane aqueous dispersion II (PU-II) and hot air drying at a drying temperature of 120 ° C. for 10 minutes so that the weight of polyurethane relative to the weight of the island component and the fabric is 43% by weight. A sheet-like material having polyurethane added thereto was obtained.

  Next, this sheet-like material is immersed in an aqueous solution of sodium hydroxide having a concentration of 15 g / L heated to 80 ° C. and treated for 30 minutes to remove sea components of sea-island type fibers, and consists of ultrafine fibers, woven / knitted fabric and polyurethane. A sheet was obtained. It was confirmed by scanning electron microscope (SEM) observation of the surface of the sheet-like material that the average single fiber fineness was 0.19 dtex.

  Then, the sheet-like material was cut in half in the thickness direction, and the raised surface was formed by grinding the half-cut surface using an endless sandpaper having a sandpaper count of 240.

  The sheet-like material thus obtained was subjected to shrinkage treatment and dyeing simultaneously at 130 ° C. with a liquid dyeing machine, and then dried with a dryer to obtain a sheet-like material.

  As a result of observing the cavities of the threads in the woven fabric, it was confirmed that cavities exist in the warp and weft. In addition, the obtained sheet-like material has a horizontal elongation of 20%, an elongation recovery rate of 91%, a vertical elongation rate of 18%, and an elongation recovery rate of 85%, which is good in both the horizontal and vertical directions. There was a good stretch. The appearance quality, texture, and pilling evaluation were also good results.

<Example 3>
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.

Using this raw material of sea-island type composite fiber, a laminated web is formed through a card and cross wrapping process, needle punched at a number of punches of 600 / cm ² , and then the fabric produced in Production Example 4 is placed above and below the web. The sheet was inserted, needle punched at a punch number of 2900 / cm ² , and the web and the fabric were bonded together to obtain a sheet.

  The 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.

  Subsequently, it was immersed in a 15 g / L aqueous sodium hydroxide solution heated to 80 ° C. and treated for 20 minutes to remove sea components of the sea-island fibers, thereby obtaining a sea-removal sheet composed of ultrafine fibers and woven or knitted fabric. It was confirmed by scanning electron microscope (SEM) observation of the surface of the sheet material that the average single fiber fineness was 0.04 dtex.

  The sheet made of ultrafine fibers and woven fabric is impregnated with self-emulsifying polyurethane aqueous dispersion I (PU-I) and dried with hot air at a drying temperature of 120 ° C. for 10 minutes, so that polyurethane relative to the weight of the island component and the woven fabric is obtained. A sheet-like material to which polyurethane was added so that the weight was 24% by weight was obtained.

  Then, the sheet-like material was cut in half in the thickness direction, and the raised surface was formed by grinding the half-cut surface using an endless sandpaper having a sandpaper count of 240.

  The sheet-like material thus obtained was subjected to shrinkage treatment and dyeing simultaneously at 130 ° C. with a liquid dyeing machine, and then dried with a dryer to obtain a sheet-like material.

  As a result of observing the cavities of the threads in the woven fabric, it was confirmed that cavities exist in both the wefts. Further, the obtained sheet-like material had a horizontal elongation rate of 18% and an elongation recovery rate of 95%, and had good stretchability in the horizontal direction. The appearance quality, texture, and pilling evaluation were also good results.

<Example 4>
PET was used as the island component, polystyrene was used as the sea component, and a sea-island type composite die having 36 islands was melt-spun at an island / sea weight ratio of 55/45. After stretching and crimping, 51 mm To obtain a raw material of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

Using this raw material of sea-island type composite fiber, a laminated web is formed through a card and cross wrapping process, needle punched at a number of punches of 600 / cm ² , and then the fabric produced in Production Example 4 is placed above and below the web. The sheet was inserted, needle punched at a punch number of 2900 / cm ² , and the web and the fabric were bonded together to obtain a sheet.

  The 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, impregnation with self-emulsifying polyurethane aqueous dispersion I (PU-I) and hot air drying at a drying temperature of 120 ° C. for 10 minutes so that the weight of polyurethane relative to the weight of the island component and the fabric is 69% by weight. A sheet-like material having polyurethane added thereto was obtained.

  This sheet-like material was dissolved and removed from sea components in trichlorethylene to obtain a sheet-like material comprising ultrafine fibers, woven fabric and polyurethane. The average single fiber fineness was 0.05 detex by observation with a scanning electron microscope (SEM) of the cross section of the sheet-like material.

  Then, the sheet-like material was cut in half in the thickness direction, and the raised surface was formed by grinding the half-cut surface using an endless sandpaper having a sandpaper count of 240.

  The sheet-like material thus obtained was subjected to shrinkage treatment and dyeing simultaneously at 130 ° C. with a liquid dyeing machine, and then dried with a dryer to obtain a sheet-like material.

  As a result of observing the cavities of the threads in the woven fabric, it was confirmed that cavities exist in the wefts. Further, the obtained sheet-like product had a horizontal elongation rate of 27% and an elongation recovery rate of 87%, and had good stretchability in the horizontal direction. The appearance quality, texture, and pilling evaluation were also good results.

<Example 5>
Except for using the woven fabric produced in Production Example 8 and setting the amount of polyurethane to 47%, the same treatment as in Example 1 was performed to obtain a sheet-like material having a raised surface. The sheet-like material thus obtained was dyed with a liquid dyeing machine at 130 ° C. and then dried with a dryer to obtain a sheet-like material.

  As a result of observing the cavities of the yarns in the woven fabric, no cavities existed for both the warp and the weft. Further, the obtained sheet-like material had a good texture, and although the pilling evaluation was slightly low in grade, it was sufficient for practical use. Further, the fibers of the woven fabric were exposed on the product surface, and although the appearance quality was slightly inferior to the other examples, it was sufficient for practical use.

<Example 6>
A sheet-like material was obtained in the same manner as in Example 1 except that the woven fabric produced in Production Example 6 was used and the amount of polyurethane applied was 49%.

  As a result of observing the cavities of the threads in the woven fabric, it was confirmed that cavities exist in the wefts. Further, the obtained sheet-like product had a horizontal elongation rate of 20% and an elongation recovery rate of 88%, and had good stretchability in the horizontal direction. The appearance quality, texture, and pilling evaluation were also good results.

<Comparative Example 1>
A sheet-like material was obtained in the same manner as in Example 1 except that the woven fabric (ordinary woven fabric) prepared in Production Example 7 was used and the amount of polyurethane was 53%.

  As a result of observing the cavities of the yarns in the woven fabric, no cavities existed for both the warp and the weft. Further, the obtained sheet-like material was good in appearance quality, texture, and pilling evaluation, but was not stretchable.

<Comparative example 2>
A sheet-like material was obtained in the same manner as in Example 1 except that the forced emulsification type polyurethane aqueous dispersion III (PU-III) was used and the amount of polyurethane was 56%.

  As a result of observing the cavities of the threads in the woven fabric, it was confirmed that cavities exist in the wefts. Moreover, although the obtained sheet-like material had good stretchability in the horizontal direction and good texture, the pilling evaluation was poor, and the appearance quality was poor due to poor fiber dispersion.

  Since the sheet-like material of the present invention is excellent in appearance, texture, elongation rate and elongation recovery rate, it can be used for furniture and chair skin materials and wall materials, and also in seats in vehicles such as automobiles, trains and aircraft. It can be suitably used as an interior material having a very elegant appearance for skin materials such as roofs and ceilings. 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.

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 woven / knitted fabric.

Claims (7)

A woven or knitted fabric including yarns containing side-by-side type or eccentric core-sheath type composite fibers formed from two or more types of polyethylene terephthalate polymers having a difference in intrinsic viscosity (IV), and an average single fiber fineness of 0.001 dtex. consists or more 0.5dtex following ultrafine fibers, containing a self-emulsifiable polyurethane, and the yarn comprising a side-by-side or eccentric core-sheath composite fiber, characterized in Rukoto to have a tunnel structure Sheet material. The result composite fibers of side-by-side or eccentric core-sheath type from two polyethylene terephthalate polymers, the intrinsic viscosity difference between the two kinds of polyethylene terephthalate polymers is 0.2 or more, according to claim 1 Sheet material. The sheet-like object according to claim 1 or 2 , wherein the fiber length of the ultrafine fiber is 25 mm or more and 90 mm or less. The sheet-like material according to any one of claims 1 to 3 , wherein the self-emulsifying polyurethane contains 3% by mass or more and 30% by mass or less of polyethylene glycol with respect to the total mass. The sheet-like material according to any one of claims 1 to 4 , wherein the self-emulsifying polyurethane has a siloxane bond in its molecular structure. A method for producing a sheet-like material according to any one of claims 1 to 5 , comprising the following steps (1) to (4).
(1) A step of intertwining the woven or knitted fabric with ultrafine fiber-generating fibers made of two or more types of polymers having different solubility in a solvent.
(2) A step of impregnating and coagulating a liquid obtained by dispersing self-emulsifying polyurethane in water to give the self-emulsifying polyurethane.
(3) A step of expressing an ultrafine fiber having an average single fiber fineness of 0.001 dtex or more and 0.5 dtex or less from the ultrafine fiber generating fiber with a solvent.
(4) A step of shrinking the woven or knitted fabric in the sheet-like material by kneading under a condition of 110 ° C. or higher. The manufacturing method of the sheet-like material of Claim 6 which passes through the process of said (1)-(4) in order of (1), (2), (3), (4).