JP4973170B2 - Leather-like sheet and manufacturing method thereof - Google Patents

Description

The present invention relates to a leather-like sheet material excellent in drapeability and stretchability, forming a beautiful silhouette, and excellent in wearing feeling, and a method for producing the same.

  Leather-like sheet-like materials such as artificial leather have excellent properties not found in natural leather, such as flexibility, easy care, and uniform physical properties, so they can be used in various applications including clothing and materials. in use.

  In recent years, the demand for each application has also been at a high level, and in the application of clothing, a material excellent in drape and stretch properties is required in order to obtain a silhouette at the time of wearing and a comfortable wearing feeling. In addition, in materials such as car seats, ceiling materials, and sofas, stretchability is required to improve workability when bonding.

  In order to solve these problems, a method for obtaining a leather-like sheet having stretch properties has also been studied. For example, two fibers having different solubility are aligned and one fiber is formed by twisting yarn. There is a method in which a woven fabric formed by using a fabric is integrated with an ultrafine fiber nonwoven fabric by needle punching or water jet, and then one of the fibers of the woven fabric is dissolved to form a coil spring (for example, Patent Document 1). . According to this method, although it is possible to obtain stretch properties, it is necessary to dissolve the fibers constituting the fabric. Therefore, if the fibers are not sufficiently dissolved, the stretchability may be insufficient, or the fibers used for the ultrafine fibers and the fabric may be used. The combination of the polymers is limited, and there is a problem that sufficient drape cannot be obtained due to adhesion of the elastic polymer to the fabric.

  Further, a latent shrinkable woven fabric is formed by using latently crimpable fiber yarns such as false twisted yarns and composite yarns composed of two or more components having different heat shrinkage properties as latent shrinkable fibers. There is a method of obtaining a stretchable artificial leather by providing a polymer elastic body after forming a laminated entangled body of a shrinkable woven fabric and an ultrafine fiber nonwoven fabric (for example, Patent Document 2). In this method, it is not necessary to dissolve the fibers of the woven fabric, and the problem of polymer combination can be solved. However, since the polymer elastic body is used, the problem of drapability remains unsolved.

  In recent years, due to growing awareness of global environmental conservation and health, materials that are gentle on the body and have low environmental impact, such as residual organic solvents and no generation of toxic gases when discarded, and materials with excellent recyclability are being demanded. . In particular, residual organic solvents used when impregnating a polymer elastic body and generation of toxic gases when discarded are regarded as problems.

In order to solve this problem, a method not using a polymer elastic body has been studied. For example, sea island type composite fiber staples that can generate ultrafine fibers are entangled by needle punch method, and then the ultrafine fiber nonwoven fabric obtained by dissolving sea components and two polytrimethylene terephthalate side-by-side with different intrinsic viscosities There is a method of obtaining a leather-like sheet-like material excellent in wear resistance and stretch without using a polymer elastic body by laminating latent crimped fabrics made of type composite fibers and applying high-speed fluid treatment ( For example, Patent Document 3). However, in this method, it is difficult to maintain the drape when the front and back surfaces of the leather-like sheet are formed of ultrafine fibers, and when the leather-like sheet is thick, a drape is excellent. I couldn't.
JP 2000-154478 A JP 2000-336581 A JP 2005-256268 A

  The present invention provides a leather-like sheet-like material having a structure in which a woven fabric using ultrafine fiber nonwoven fabric and latently crimped fiber is intertwined and integrated, has a low environmental load at the time of disposal, and has excellent drape and stretch properties. It is intended to provide a manufacturing method.

  In order to solve the above-described problems, the present invention has the following configuration.

That is, an ultrafine fiber nonwoven fabric having an average fiber fineness of 0.001 to 0.5 dtex is entangled and integrated with the woven fabric by the needle punch method , and the twist coefficient of the yarn constituting the woven fabric is 7000 to 20000, One surface of the sheet-like material is made of continuous ultrafine fibers in the surface direction intertwined with each other, and the other surface is formed by ultrafine fibers discontinuous in the surface direction, with a drape coefficient of 0.35 to 0. 5. A leather-like sheet-like material substantially made of a fiber material having an elongation rate of 10 to 35% in at least one of the vertical direction and the horizontal direction.
Twist coefficient K = T × D ^0.5
Where T: number of twists per 1 m of yarn length (times)
D: Yarn fineness (decitex).

Moreover, the manufacturing method of the leather-like sheet material of the present invention uses 1-8 decitex composite fiber short fibers capable of generating ultrafine fibers having an average fiber fineness of 0.001-0.5 decitex, After producing the short fiber web (a) by the needle punch method, the following steps (1) to (4) are performed.
(1) The process of producing the fiber structure which piled up the textile fabric (b) on the at least single side | surface of the short fiber web (a), and made it intertwined and integrated by the needle punch method.
(2) Generating ultrafine fibers from a fiber structure entangled and integrated by the needle punch method, making the short fiber web (a) an ultrafine fiber nonwoven fabric, and allowing the short fibers to penetrate in the thickness direction of the fabric (b), A step of forming a fiber structure in which the short fiber web (a) and the woven fabric (b) are intertwined and integrated, and one surface has a surface formed by discontinuous ultrafine fibers .
(3) A step of performing high-speed fluid treatment on a fiber structure made of an ultrafine fiber nonwoven fabric in which only one side obtained by the steps of (1) to (2) is continuously intertwined in the surface direction at a fluid pressure of 10 MPa or more.
(4) A shrinking step of shrinking 5 to 30% in the vertical direction and the horizontal direction after performing the high-speed fluid treatment.

  According to the above-described leather-like sheet-like material of the present invention and the method for producing the same, a leather-like sheet-like material having a draping property and a stretch property that is not found in natural leather is obtained with less environmental impact at the time of disposal. Can provide a good silhouette and wearing feeling when worn, and materials excellent in three-dimensional formability as materials such as car seats and furniture.

  The leather-like sheet-like material of the present invention is substantially composed of a fiber material, and ultrafine fibers having an average fiber fineness of 0.001 to 0.5 dtex are entangled and integrated with the woven fabric. One surface of the object is composed of continuous ultrafine fibers in the surface direction intertwined with each other, the other surface is formed by discontinuous ultrafine fibers in the surface direction, and the drape coefficient is 0.35 to 0.5. And the elongation percentage is 10 to 35% in at least one of the vertical and horizontal directions.

  The leather-like sheet-like material of the present invention has a feature that a drape coefficient is small and a beautiful silhouette along the shape can be expressed, and is specified by the JIS L 1096 (1999) 8.19.7 G method (drape coefficient). The drape coefficient is preferably 0.300 to 0.500, more preferably 0.350 to 0.450, and still more preferably 0.350 to 0.400. If the drape coefficient is less than 0.300, a beautiful silhouette can be expressed, but there is no rebound and it is too flexible and the texture of woven or knitted fabric is unreliable, and the high-quality texture of artificial leather is lost. If the drape coefficient exceeds 0.500, it will be difficult to express a beautiful silhouette along the shape.

  In addition, the leather-like sheet-like material of the present invention is characterized by excellent stretchability, and at least one elongation rate in the vertical or horizontal direction is defined by JIS L 1096 (1999) 8.14.1 A method. The elongation ratio is preferably 10.0 to 35.0%, more preferably 15.0 to 25.0%, and the elongation ratio in the vertical and horizontal directions is 10.0 to 35.0%. More preferably it is. If the elongation rate is less than 10% in at least one of the vertical or horizontal directions, the stretchability is insufficient, and it is not preferable because it feels stretchy when worn, and when it is used as a car seat or furniture skin material. However, moldability is lowered, and workability at the time of molding is lowered. On the other hand, if the elongation rate exceeds 35%, the shape tends to be shifted even by light pulling at the time of sewing, which is not preferable because the sewing property tends to be lowered and the elongation recovery rate tends to be lowered.

  In order to achieve the drape coefficient and elongation rate, it is important that the ultrafine fiber nonwoven fabric and the woven fabric are intertwined and integrated. When the ultrafine fiber nonwoven fabric is entangled with the woven fabric, it is possible to obtain a beautiful silhouette and stretchability along a shape that cannot be obtained with the ultrafine fiber nonwoven fabric alone.

For example, in the case where ultrafine fiber nonwoven fabric and woven fabric are bonded together with an adhesive, etc. without entanglement and integration, a material with high stress among the materials of ultrafine fiber nonwoven fabric, woven fabric, or adhesive when pulling or bending However, the drape coefficient and elongation rate of the present invention cannot be achieved.
Furthermore, the leather-like sheet-like material of the present invention is composed of ultrafine fibers that are continuous in the surface direction in which one surface is intertwined with each other, and the other surface is formed by ultrafine fibers that are discontinuous in the surface direction. is important. The term “continuous in the plane direction” as used herein means that the fabric constituting the leather-like sheet is almost completely covered by the ultrafine fibers, and the fabric is not exposed on the surface. In most cases, the fabric is made of ultrafine fibers, but when the surface is observed visually or with an optical microscope, SEM, or the like, the fabric is exposed. In the leather-like sheet-like material of the present invention, since there is a discontinuous surface in such a surface direction, the tension of the fiber when bent is reduced, so the leather-like sheet has a small drape coefficient and forms a good silhouette. A sheet-like material can be obtained. Therefore, the effect of the present invention cannot be obtained with a leather-like sheet-like material composed of ultrafine fibers whose both surfaces are continuous in the surface direction.

  Further, in the leather-like sheet of the present invention, being substantially composed of a fiber material means that the binder composed of a polymer elastic body such as polyurethane is less than 5% by weight, preferably the binder is composed of fibers. Less than 3% by weight, more preferably less than 1% by weight of the fiber, most preferably no binder. When the content of the polymer elastic body is small, a soft texture with no rubber feeling can be achieved, and various effects such as high color development, high light resistance, and yellowing resistance can be achieved.

  The leather-like sheet of the present invention is most preferably one that does not contain a polymer elastic body such as a polyether-based fiber or a polyurethane-based fiber such as spandex. However, it does not deviate from the effects of the present invention. It does not matter if the body is included.

  In the leather-like sheet material of the present invention, the ultrafine fiber nonwoven fabric is composed of ultrafine fibers having an average short fiber fineness of 0.001 to 0.5 dtex. The average single fiber fineness is preferably 0.005 to 0.3 dtex, more preferably 0.01 to 0.15 dtex. If the average single fiber fineness is less than 0.001 dtex, it is not preferable because the strength of the leather-like sheet is lowered and it is difficult to obtain a dark product by dyeing. In addition, if the average single fiber fineness exceeds 0.5 dtex, the texture of the leather-like sheet becomes stiff, and the fiber entanglement becomes insufficient, resulting in a decrease in the surface quality of the leather-like sheet. Or problems such as a decrease in wear resistance occur. In addition, a fiber having a single fiber fineness of less than 0.001 dtex or a fiber having a single fiber fineness of more than 0.5 dtex may be included as long as the effects of the present invention are not impaired. The content of fibers having a single fiber fineness of less than 0.001 dtex and fibers having a single fiber fineness of more than 0.5 dtex is preferably 30% or less of the fibers constituting the short fiber nonwoven fabric, and 10% or less. More preferably, it is even more preferable that it is not contained at all.

  In the leather-like sheet-like material of the present invention, the average fiber length of the above-mentioned ultrafine fibers is preferably composed of short fibers of 20 to 100 mm, more preferably 25 to 80 mm, and further preferably 30 to 60 mm. If the average fiber length exceeds 100 mm, the surface quality deteriorates, which is not preferable. On the other hand, if the average fiber length is less than 20 mm, the abrasion resistance of the leather-like sheet is lowered.

  The content of fibers having a fiber length of more than 100 mm and fibers having a fiber length of less than 20 mm is most preferably not included, but the content of fibers having a fiber length of less than 20 mm and fibers having a fiber length of more than 100 mm Is a friction that is less than 10% of the fibers constituting the short fiber nonwoven fabric and measured according to JIS L 1096 (1999) 8.17.5 E method (Martindale method) furniture load (12 kPa) In terms of strength, the surface on which the ultrafine fibers are formed is included if the wear loss of the test cloth is 8 mg or less after 20,000 rubbing in the pilling position setting (THREE DRIVE ROLLERS = POSITION B) of the Martindale abrasion tester. May be.

  Further, in the leather-like sheet-like material of the present invention, these ultrafine fibers are intertwined with each other and the surface and / or the back surface of the leather-like sheet-like material is formed, so that the surface feel like natural leather is obtained. And is particularly important for improving wear resistance. Here, forming a surface means that it can be confirmed that a layer is formed when a cross section in the vertical or horizontal direction is observed.

  Most of the conventional leather-like sheets made of ultrafine fibers have a structure in which ultrafine fibers are entangled in a bundle of fibers. However, a structure entangled in the state of a fiber bundle cannot provide sufficient wear resistance as in the present invention. In the present invention, it is necessary for the ultrafine fibers to have a structure in which the ultrafine fibers are intertwined with each other in order to improve the wear resistance. In addition, the structure which was entangled in the state of the fiber bundle may be included in the range which does not impair the effect of this invention.

  The average monofilament fineness is in the above-mentioned range, the polymer used for so-called ultrafine fibers is not particularly limited, for example, polyester, polyamide, polypropylene, polyethylene, etc. From the viewpoint of dyeability and strength, polyester and polyamide are preferable, and polyester is more preferable in consideration of dyeability with a fabric used as a component of the present invention.

  The polyester is not particularly limited as long as it is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, and can be used as an ultrafine fiber generating fiber. It is not a thing.

  Specifically, for example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis (2-chlorophenoxy) Examples include ethane-4,4′-dicarboxylate.

  In the leather-like sheet-like material of the present invention, the most commonly used polyethylene terephthalate or a polyester copolymer mainly containing ethylene terephthalate units can be preferably used.

  As the polyamide, for example, polymers such as nylon 6, nylon 66, nylon 610, and nylon 12 can be employed.

  In the present invention, in order to prevent the fabric from being exposed and obtain a beautiful silhouette, the thickness of the leather-like sheet of the present invention is preferably 0.45 to 1.5 mm, 1.0 mm is more preferable, 0.5 to 1.0 mm is more preferable, and 0.55 to 0.8 mm is still more preferable.

  The fibers constituting the fabric used in the leather-like sheet of the present invention are preferably composite fibers in which two or more kinds of polyester polymers are joined in a side-by-side type or an eccentric core-sheath type. The woven fabric using these fibers has an effect of exhibiting excellent drape and elongation rate in a leather-like sheet. As long as the woven fabric includes such a composite fiber, a normal fiber may be included as long as the effects of the present invention are not impaired. For example, the composite fiber and normal fiber can be combined and used as a composite yarn.

  Further, the composite fiber joined in the side-by-side type or the eccentric core-sheath type may be used for either the warp yarn or the weft yarn, and a normal fiber may be used for the other.

  The polyester polymer is, for example, a polymer such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate. In addition, two or more kinds of polyesters means that two or more kinds of polyesters having different physical and / or chemical properties are used. That is, two or more kinds of polyesters joined to the side-by-side type or the eccentric core-sheath type means that two or more kinds of polyesters having different physical and / or chemical properties are side-by-side type or It means that it is joined to an eccentric core-sheath type. Thereby, crimp can be expressed in the composite fiber due to physical or chemical factors. In view of easy expression of crimps, it is preferable to use two or more polyesters having different heat shrinkability. Thereby, crimping can be easily expressed by heat-treating and shrinking the composite fiber. By producing crimps in the composite fiber, a leather-like sheet having excellent drape and elongation can be obtained. Examples of the polyester having different heat shrinkage include those having different polymerization degrees of polymers and blends of different polymers. In the present invention, a low-viscosity polyester having an intrinsic viscosity of 0.35 to 0.55 and an intrinsic viscosity of 0.65 to 0 are obtained in that a leather-like sheet having excellent spinnability and excellent rebound is obtained. A composite fiber in which .85 high-viscosity polyester is composited is preferable. In this case, in general, the high-viscosity polyester has higher heat shrinkability than the low-viscosity polyester. In order to obtain a leather-like sheet having excellent drape and elongation, the intrinsic viscosity difference between the low viscosity polyester and the high viscosity polyester is preferably in the range of 0.20 to 0.40. As the intrinsic viscosity [η], a value measured as an orthochlorophenol solution at a temperature of 25 ° C. was used.

The composite ratio of the two or more polyester polymers is high shrinkage component: low shrinkage component = 75 in terms of the yarn homogeneity and the dimensional uniformity of the coil in the fiber length direction when the crimp is expressed. The range of 25-35: 65 (weight%) is preferable, and the range of 65: 35-45: 55 is more preferable.
The composite form may be either a side-by-side type or an eccentric core-sheath type, but a side-by-side type is preferred in that a leather-like sheet-like material having excellent resilience in addition to drape and stretchability can be obtained.

  The average single fiber fineness of the composite fiber is not particularly limited, but 1 to 15 dtex is preferable in that a stretch recovery rate is high and a fabric having a soft texture can be obtained.

  In the leather-like sheet material of the present invention, when observing a cross-sectional photograph of the leather-like sheet material in the vertical direction or the horizontal direction, the warp yarn or the horizontal yarn of the woven fabric has a length direction in the central portion of the spiral shape. It is preferable to form a hollow structure. It is not necessary for all fibers contained in the woven fabric to have such a structure. Even if such a hollow structure is formed in part, the spiral shape is stretched when pulled, and the stretch rate of the leather-like sheet is increased. There is an effect of improving. For example, such a hollow spiral shape can be generated by shrinking a latent crimped yarn and expressing crimp by a difference in shrinkage rate.

Moreover, in the preferable manufacturing method which manufactures the leather-like sheet-like material mentioned later of this invention by twisting to this composite fiber, there exists an effect which suppresses the single yarn breakage of a textile fabric. At this time, the twist factor K represented by the following formula is 7000 to 20000 in that the single yarn breakage during integration by the needle punch method can be suppressed, and further, the elongation rate of the leather-like sheet can be improved. It is preferable that it is 9000-18000.
Twist coefficient K = T × D ^0.5
Where T: number of twists per 1 m of yarn length (times)
D: Fineness of yarn (Decitex)
The structure of the woven fabric is not particularly limited, and examples of the woven fabric include plain weave, twill weave and satin weave. Of these, plain weaving is preferred because there are many constraint points of the yarn, a firm woven fabric can be obtained, and damage due to needle punching can be suppressed.

The basis weight of the woven fabric can be appropriately adjusted according to the basis weight of the leather-like sheet. The basis weight of the woven fabric is preferably 40.0 to 170.0 g / m ² in terms of obtaining a leather-like sheet having excellent handleability, drape coefficient, and elongation rate, and is preferably 50.0 to 150.0 g / m ^2. m ² is more preferable, and 60.0 to 120.0 g / m ² is even more preferable.

  The weight ratio of the woven fabric is preferably 20 to 70%, more preferably 25 to 60% of the entire leather-like sheet-like material, from a high-quality texture and a balance between the drape coefficient and the elongation rate. More preferably, it is ˜50%.

  Moreover, the number of nodes of the leather-like sheet-like material of the present invention is preferably 6 to 10 in terms of obtaining a beautiful silhouette, more preferably 6 to 10, and further preferably 7 to 10. . Further, the drape coefficient decreases as the number of nodes of the leather-like sheet increases, but if the number of nodes is too large, it becomes difficult to obtain a leather-like texture, so approximately 10 is the upper limit. The number of nodes is the average value obtained by counting the number of folds in the front and back projections obtained by the JIS L 1096 (1999) 8.19.7 G method (drape coefficient).

  Furthermore, the elongation recovery rate defined by the JIS L 1096 (1999) 8.14.2 A method in the vertical and horizontal directions of the leather-like sheet of the present invention is preferably 85.0 to 100%, More preferably, it is 90.0 to 100%. An elongation recovery rate of less than 85.0% is not preferable because distortion occurs due to expansion and contraction during use, causing loss of shape.

  In the leather-like sheet material of the present invention, the formation direction of the ultrafine fiber nonwoven fabric is the vertical direction, and the width direction of the ultrafine fiber nonwoven fabric is the horizontal direction. The formation direction of the ultrafine fiber nonwoven fabric can generally be determined from a plurality of factors such as the fiber orientation direction, streak traces by needle punching or high-speed fluid treatment, and treatment traces. If it is impossible to estimate and judge the vertical direction for reasons such as conflicting judgments due to these multiple factors, lack of clear orientation, or streak traces, the maximum tensile strength The vertical direction is the vertical direction, and the direction perpendicular thereto is the horizontal direction.

  The leather-like sheet-like material of the present invention is less likely to fall off due to friction and has excellent durability, and is used for a load for furniture (12 kPa) of JIS L 1096 (1999) 8.17.5 E method (Martindale method). In the abrasion resistance test measured according to the above, after the surface of the ultrafine fiber is rubbed 20000 times with the setting of the Martindale abrasion tester's pilling position (THREE DRIVE ROLLERS = POSITION B), the abrasion loss of the test cloth is 8 mg or less. It is preferable that The wear loss is more preferably 6 mg or less, and even more preferably 4 mg or less. On the other hand, the lower limit is not particularly limited, and the leather-like sheet of the present invention can be obtained with almost no wear loss.

Since the drape coefficient and elongation rate characteristic of the leather-like sheet material of the present invention can be obtained and the exposure of the fabric can be suppressed, the basis weight of the leather-like sheet material is 130.0 to 300.0 g / m. preferably ² is, more preferably 140.0~280.0g / ^{m 2,} further preferably 150.0~260.0g / ^{m 2.} In the leather-like sheet material of the present invention, it is preferable that at least one surface of the leather-like sheet material is raised to obtain an excellent surface appearance like natural leather. As the raised state, it is preferable to have a suede or nubuck smooth touch and an excellent lighting effect.
In addition, it is preferable to attach a binder made of a polymer elastic body such as polyurethane to the fiber at less than 5% by weight because the wear resistance can be improved without hardening the texture, and less than 3% by weight. More preferably, it is more preferably less than 1% by weight.
Furthermore, the leather-like sheet-like material can also have an effect of giving a feel such as dry feeling and squeaky feeling by including fine particles. The material of the fine particles is not particularly limited as long as it is insoluble in water, and examples thereof include inorganic substances such as silica, colloidal silica, titanium oxide, aluminum and mica, and organic substances such as melamine resin.

  The average particle diameter of the fine particles is preferably 0.001 to 30 μm, more preferably 0.01 to 20 μm, and still more preferably 0.05 to 10 μm. The average particle diameter of the fine particles can be measured using a measurement method suitable for each material and size, for example, a BET method, a laser method, a dynamic scattering method, a Coulter method, or the like. In the present invention, the volume (mass) average particle diameter determined using the BET method is particularly preferable. The amount of these fine particles can be appropriately adjusted within a range where the effects of the present invention can be exhibited. The content of the fine particles is preferably 0.01 to 10% by weight of the leather-like sheet material in that the texture of the leather-like sheet material does not become hard and an effect of improving the wear resistance is obtained, and 0.02 to 5%. % By weight is more preferable, and 0.05 to 1% by weight is more preferable. In addition, it is also preferable to use a small amount of resin in combination in order to prevent fine particles from falling off and improve durability.

  Moreover, in order to obtain a soft texture and a smooth surface touch, the leather-like sheet of the present invention preferably contains a softening agent. As the softening agent, it is preferable to appropriately select one generally used for woven or knitted fabrics according to the fiber type. For example, in the 23rd edition of Dyeing Note (Issue Color Co., Ltd., issued on August 31, 2002), those described under the names of texture finish and soft finish can be appropriately selected. Among these, a silicone emulsion is preferable in terms of excellent flexibility effect, and an amino-modified or epoxy-modified silicone emulsion is more preferable. When these softeners are contained, the wear resistance tends to decrease. Therefore, the amount of the softener is preferably adjusted as appropriate while balancing the target texture and wear resistance. Therefore, the amount thereof is not particularly limited, but is preferably in the range of 0.01 to 10% by weight of the leather-like sheet-like material in terms of balance between texture and wear resistance and suppression of stickiness.

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

The method for producing a leather-like sheet according to the present invention uses a staple fiber of 1-8 dtex composite fiber capable of generating ultrafine fibers having an average fiber fineness of 0.001-0.5 dtex, and a needle punch. After producing the short fiber web (a) by the method, the following steps (1) to (4) are performed.
(1) The process of producing the fiber structure which piled up the textile fabric (b) on the at least single side | surface of the short fiber web (a), and made it intertwined and integrated by the needle punch method.
(2) A step of generating ultrafine fibers from a fiber structure entangled and integrated by the needle punch method to make the short fiber web (a) an ultrafine fiber nonwoven fabric.
(3) A step of performing high-speed fluid treatment on a fiber structure made of an ultrafine fiber nonwoven fabric in which only one side obtained by the steps of (1) to (2) is continuously intertwined in the surface direction at a fluid pressure of 10 MPa or more.
(4) A shrinking step of shrinking 5 to 30% in the vertical direction and the horizontal direction after performing the high-speed fluid treatment.

  First, a production method for obtaining a fiber structure in which the ultrafine fiber nonwoven fabric and the woven fabric are intertwined and integrated in the leather-like sheet-like material of the present invention will be described, but the present invention is not limited thereto.

  The method for producing ultrafine fibers having an average single fiber fineness constituting the ultrafine fiber nonwoven fabric of the leather-like sheet of the present invention in the range of 0.001 to 0.5 dtex is not particularly limited. For example, the ultrafine fibers are directly spun. There is a method of spinning a fiber (ultrafine fiber generation type fiber) that is a fiber having a normal fineness and capable of generating an ultrafine fiber, and then generating an ultrafine fiber. Examples of methods using ultrafine fiber generating fibers include, for example, means such as a method of removing sea components after spinning sea-island fibers, and a method of spinning and splitting split-type fibers to make them ultrafine. Can do. Among these, in the present invention, ultrafine fibers can be obtained easily and stably, and the structure of the leather-like sheet of the present invention can be easily achieved by the preferred production method of the present invention described later. In addition, it is preferable to produce a sea-island type fiber or a split-type fiber. More preferably, it is made of fibers.

  The term “sea-island type fiber” as used herein refers to a fiber in which two or more components are combined and mixed at an arbitrary stage to obtain a sea-island state. The method for obtaining this fiber is not particularly limited. For example, (i) 2 A method of blending and spinning a polymer of more than two components in a chip state, (ii) a method of kneading a polymer of two or more components in advance to form a chip and then spinning, and (iii) spinning a polymer of two or more components in a molten state And a method of mixing using a static kneader or the like in the pack of the machine, and (iv) a method of manufacturing using a die such as JP-B No. 44-18369 and JP-A No. 54-116417. In the present invention, it can be satisfactorily produced by any method, but the method (iv) is preferably employed in that the polymer can be easily selected.

  In the method (iv), the cross-sectional shape of the island fiber obtained by removing the sea-island fiber and the sea component is not particularly limited, and examples thereof include a circle, polygon, Y, H, X, W, C, and π type. Can be mentioned. Further, the number of polymer species to be used is not particularly limited, but it is preferably 2 to 3 components in consideration of spinning stability, and particularly preferably composed of 2 components of sea 1 component and island 1 component. . In addition, the component ratio at this time is preferably 0.3 to 0.99 by weight ratio of island fibers to sea-island fibers in terms of spinning stability and cost, and more preferably 0.4 to 0.97. 0.5 to 0.8 is more preferable.

  When ultrafine fibers are obtained from sea-island type fibers, the island components become the intended ultrafine fibers. The polymer used for the island component is not particularly limited, and those that can be made into fibers can be appropriately selected and used. However, the polyesters and polyamides described above are preferably used in the present invention. In addition, the polymer used as the sea component is not particularly limited as long as it is incompatible with the island component, but it is a chemical that is more soluble and degradable with respect to the solvent and chemicals used than the polymer of the island component. It is preferable that it has a property. Depending on the selection of the polymer constituting the island component, for example, polyolefins such as polyethylene and polystyrene, α-oleins having 4 or less carbon atoms such as ethylene, propylene, 1-butene and isobutene, methyl vinyl ether, ethyl vinyl ether, n- Water-soluble thermoplastic polyvinyl alcohol, polyethylene glycol, or copolymer components such as vinyl ethers such as propyl vinyl ether, i-propyl vinyl ether and n-butyl vinyl ether are present in polyvinyl alcohol in an amount of 1 to 20 mol% Copolymers thereof, hot water-soluble polyesters described in JP-A-61-29120, JP-A-63-165516, JP-A-63-159520, JP-A-1-272820, etc. Hot water-soluble polymer, 5-sodium sulfoisophthalic acid, sodium dodecylbenzenesulfonate, bisphenol A compound, isophthalic acid, adipic acid, can be used Dodekajion acid, polyester obtained by copolymerizing cyclohexyl carboxylic acid, polylactic acid and the like.

  Polystyrene is preferable from the viewpoint of spinning stability, but it can be easily removed with an aqueous solution of water or alkali without using an organic solvent, and a hot water-soluble polymer or a copolyester having a sulfone group or a polyester is less in terms of environmental load. More preferred are lactic acid and water-soluble thermoplastic polyvinyl alcohol. The copolymerization ratio is preferably 5 mol% or more from the viewpoint of processing speed and stability, and 20 mol% or less from the viewpoint of ease of polymerization, spinning and stretching. In the present invention, a preferred combination is to use a copolymerized polyester having polyethylene terephthalate as the island component and polystyrene or sulfone group as the sea component. To these polymers, inorganic particles such as titanium oxide particles may be added to the polymer in order to improve the concealing property. In addition, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storages, etc. Materials, antibacterial agents, etc. can be added according to various purposes.

  The polymer spun in this way can be stretched and crystallized. For example, after drawing an unstretched yarn, it can be stretched 1 to 3 stages by wet heat or dry heat, or both. In addition, when using split type | mold fiber, it can mainly carry out according to the manufacturing method of the above-mentioned sea-island type | mold fiber, compounding 2 or more components within a nozzle | cap | die.

  The 1-8 dtex composite fiber capable of generating ultrafine fibers thus obtained is crimped and cut by a conventional method to obtain short fibers. Next, a short fiber web (a) can be obtained by a dry method using a card, a cross wrapper, a random weber, or a wet method such as a papermaking method. In the present invention, a short fiber web having a wide basis weight from low basis weight to high basis weight can be obtained. The dry method is preferred because it is obtained.

  Next, the manufacturing method of the woven fabric (b) to be intertwined with the ultrafine fiber nonwoven fabric will be described. In order to obtain the elongation rate and elongation recovery rate that are the characteristics of the present invention, the effect of the present invention is not obtained even if intertwined with any woven fabric, for example, when a relaxation treatment is performed on the woven fabric alone, It is preferable to use a woven fabric having an elongation rate of 10 to 35% in at least one of the vertical and horizontal directions, and an elongation recovery rate of 85 to 100% in the vertical and horizontal directions. The higher the stretch rate and the stretch recovery rate of the woven fabric, the higher the stretch rate and the stretch recovery rate of the leather-like sheet. In order to obtain the woven fabric (b) having the elongation rate and the elongation recovery rate in such a range, for example, two or more kinds of polyester polymers are formed side by side along the fiber length direction as fibers constituting the woven fabric. It is preferable to use a latently crimped yarn that is a bonded composite fiber or an eccentric core-sheath type composite fiber that forms a core-sheath structure in which two or more kinds of polyester polymers are eccentric. The method for producing such a composite fiber is not particularly limited, but known methods described in, for example, JP-B 63-42021, JP-A-4-308271, JP-A-11-43835, and the like. The method can be applied. Also, when woven and non-woven fabrics are entangled and integrated with a needle punch, a method of firmly bonding fibers from the viewpoint of suppressing the breakage of single fibers of the fabric and preventing the texture-like hardening of the leather-like sheet, cover It is preferable to employ a method for reducing the factor to the limit, a method for setting the fiber twist coefficient in a specific range, and the like. Of these methods, the method of setting the fiber twist coefficient in a specific range is particularly preferably used in terms of improving the process stability and the stretchability of the resulting leather-like sheet. At this time, the twist coefficient of the fiber is preferably 7000 to 20000, and more preferably 9000 to 18000. In addition, a well-known method can be employ | adopted for the provision method of a twist.

  By using such a fiber and using a loom suitable for the required tissue, the fabric (b) used in the method for producing the leather-like sheet of the present invention is obtained. The weaving method of the fabric (b) is not particularly limited, and a loom suitable for the required structure can be used. Examples of the loom include an air jet loom, a water jet loom, and a fly shuttle loom. At this time, if the weaving density is lowered too much, the elongation recovery rate of the woven fabric is reduced, and if the weaving density is raised too much, the fiber is easily damaged by the needle punch, so there may be a proper space between the warp yarn and the weft yarn. preferable. Since this space varies depending on the type of needle to be used, it is preferable to change it appropriately.

  Next, the woven fabric (b) and the short fiber web (a) obtained in this way are overlapped and subjected to needle punching to be entangled and integrated (step (1)).

In that case, the basis weight is less than 40 g / m ² of fabric (b), drape coefficient of the leather-like sheet, the number of nodes, elongation, can not achieve the extension recovery rate, drape exceeds basis weight 170 g / m ² coefficients Is large and the number of nodes is small, so that the fabric weight (b) is preferably in the range of 40 to 170 g / m ² . In the present invention, in order to set the thickness of the finally obtained leather-like sheet material to 0.45 mm to 1.0 mm, short fibers are used so that the basis weight of the leather-like sheet material is 130 to 300 g / m ^2. It is preferable to appropriately combine the weights of the web (a) and the fabric (b).

  As a method of overlapping the short fiber web (a) and the woven fabric (b), the woven fabric (b) may be stacked on at least one side of the short fiber web (a). Specifically, (A) the short fiber web (a ) / Woven fabric (b), (B) (A) needle punched two sheets, fabric (b) / short fiber web (a) / short fiber web (a) / woven fabric (b) And (C) a method of making the woven fabric (b) / short fiber web (a) / woven fabric (b), by performing needle punching on the superposed short fiber web (a) and the woven fabric (b), A fiber in which short fibers constituting the short fiber web (a) are entangled with each other, the short fibers are penetrated in the thickness direction of the woven fabric (b), and the short fiber web (a) and the woven fabric (b) are entangled and integrated. While obtaining a structure, it can be in a state in which one side has a surface formed by ultrafine fibers discontinuous in the surface direction. . In the case of overlapping by the method (A), the exposure of the composite fibers constituting the woven fabric (b) on the short fiber web (a) surface is suppressed by needle punching only from the surface of the short fiber web (a). Is preferable.

  In addition, the entangled and woven fabric (b), when entangled and integrated, does not develop crimps due to refining by a softener or the like, and by shrinkage by a relaxation process such as a liquid dyeing machine. Is preferably used in the state of latent crimped yarn. When the shrinkage treatment is performed, the space between the warp yarn and the weft yarn is reduced, and there is a high possibility that the single yarn of the composite fiber of the fabric (b) is cut by the needle. If single yarn breakage occurs, the strength of the woven fabric (b) decreases, and the elongation recovery rate of the resulting leather-like sheet decreases, which is not preferable. Furthermore, crimps are developed due to the shrinkage, and the fabric (b) is easily stretched by the process tension, and not only the process passability is lowered, but also the stretch rate is lowered by the stretch of the fabric (b) by the process tension. Therefore, it is not preferable.

  At least the crimp expression of the composite fiber of the woven fabric (b) is preferably performed after the short fiber web (a) and the woven fabric (b) are entangled and integrated by a needle punch, whereby the drape coefficient, the number of nodes, The elongation rate and the elongation recovery rate can be improved.

  Needle punch conditions for obtaining the leather-like sheet-like material of the present invention are not particularly limited, and can be appropriately changed according to the basis weight of the short fiber web (a) and the fabric (b) to be used. The needle elongation is preferably at least at a needle depth such that the barb portion of the needle penetrates from the front side to the back side of the fabric (b). Thereby, by exposing the back side of the fabric (b) with the short fibers, the fabric can be prevented from being exposed, and when the leather-like sheet is formed, the front and back surfaces can be formed by the ultrafine fibers intertwined with each other. .

The number of needle punches for sufficiently intertwining and integrating the short fiber web (a) and the woven fabric (b) is preferably 800 to 4000 / cm ² when a one barb needle is used, and 1000 to 3500. / Cm ² is more preferable, and 1200 to 3000 / cm ² is more preferable. In this process, the short fibers are passed through the fabric (b) and sufficiently entangled and integrated to improve the followability of the ultrafine fibers with respect to the movement of the fabric due to bending or stretching when the leather-like sheet is formed. Therefore, the drape coefficient, the number of nodes, and the expansion rate can be improved.

  In addition, when the number of barbs of the needle to be used is larger than that of one barb, the entanglement efficiency is increased, so that the number of needle punches can be reduced. In that case, the number of needle punches can be changed as appropriate.

Thus obtained, the apparent density of the fibrous structure is preferably 0.12~0.4g / cm ^3, more preferably 0.15~0.35g / cm ^3. When the apparent density of the fiber structure is less than 0.12 g / cm ³ , the entanglement of the short fiber web (a) itself and the integration with the fabric (b) become insufficient, and peeling occurs as described above. Or the drape coefficient and the number of nodes tend to decrease. Moreover, although an upper limit is not prescribed | regulated in particular, when it exceeds 0.4 g / cm < ³ >, since there exists a tendency for the single fiber of a textile fabric (b) to be damaged or a cut | disconnection, it is unpreferable.

  In order to perform needle punching, the average single fiber fineness of the composite fiber constituting the short fiber web (a) is preferably 1 to 8 dtex, more preferably 2 to 7 dtex, and 3 to 6 dtex. Further preferred. When the single fiber fineness is less than 1 dtex or exceeds 8 dtex, the composite fiber is not easily applied to the barb of the needle, and the entanglement of the short fiber web (a) itself and the woven fabric (b) are difficult to be integrated. This is not preferable because of its tendency.

  Next, the obtained fiber structure is preferably shrunk by dry heat or wet heat, or both to increase the density. Thereby, when it is set as a leather-like sheet-like thing, a dense napping can be obtained and surface quality can be improved. In addition, crimping can be caused in the composite fiber of the fabric (b), which is a latent crimped yarn, by this shrinking treatment.

  Subsequently, the ultrafine fiber nonwoven fabric is obtained by subjecting the composite fiber of the short fiber web (a) to ultrafine fiber (step (2)). The ultrafine treatment method is not particularly limited, and examples thereof include a mechanical method and a chemical method. The mechanical method is a method of miniaturizing by applying a physical stimulus. For example, in addition to the method of giving an impact such as the needle punch method and the high-speed fluid processing described above, a method of pressurizing between rollers, Examples include a method of performing sonication. It is possible to combine high-speed fluid processing with ultrafine processing, but it is preferable to perform high-speed fluid processing at least after the microminiaturization processing has been completed, in order to promote the entanglement between ultrafine fibers. More preferably, the high-speed fluid treatment is performed after the treatment.

  As a method of performing ultrafine treatment and high-speed fluid treatment at the same time, for example, using a split split type composite fiber, a method of splitting and entanglement by a water jet punch, a sea island type fiber composed of a water-soluble sea component, A method of removing and entanglement with a jet punch, two or more sea island type fibers with different alkali decomposition rates, and after decomposing easily soluble components through an alkali treatment liquid, final removal and entanglement treatment with a water jet punch The method of performing etc. is mentioned. By such a method, the short fiber web (a) can be made into ultrafine fibers.

  Examples of the chemical method include a method in which at least one component constituting the sea-island fiber is subjected to changes such as swelling, decomposition, and dissolution with hot water or a chemical. In the present invention, a scientific method is preferable in that uniform ultrafine fibers can be obtained. In the case of using polystyrene as the sea component, it is possible to perform ultrafine processing by using trichlorethylene. Note that it is preferable that the fiber structure is impregnated with a resin and then subjected to an ultrafine treatment because the elongation during the ultrafine treatment can be suppressed and the surface fluffing can be suppressed.

  The resin used in the ultrafine treatment is preferably a water-soluble resin that can be easily removed by a high-speed fluid treatment performed in the subsequent steps, and examples thereof include polyvinyl alcohol (hereinafter abbreviated as PVA). it can.

  In addition, it is more preferable to make ultrafine fibers with water or an alkaline aqueous solution without using an organic solvent in that the influence on the environment is small. The alkaline solution here is an aqueous solution having a pH of 7 to 14, and the chemical used is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, calcium hydroxide, magnesium hydroxide and the like can be mentioned.

  There are no particular restrictions on the means for forming ultrafine fibers with water or an aqueous solution comprising the agent. For example, a polymer such as polyethylene terephthalate or nylon 6 is used as the island component, and water-soluble thermoplastic polyvinyl alcohol is used as the sea component. Examples thereof include a method of using a polymer that can be dissolved in hot water such as a base resin, or a polymer having a high hydrolysis rate with an alkaline aqueous solution with respect to island components, such as polylactic acid and a copolyester having 5-sodium sulfoisophthalic acid. The treatment method using water or an alkaline aqueous solution is not particularly limited, and is a method of heating with steam after padding the solution, a method of running in a hot bath such as an open soaper or a vibro washer, or liquid dyeing. The processing method etc. can be mentioned, Each may be processed individually or in combination of several methods. Further, if necessary, a penetrant such as a surfactant can be used in combination to improve the penetrability of amines such as triethanolamine and diethanolamine, weight loss accelerators, and water and aqueous alkali solutions into the fiber structure. In the present invention, since the short fiber web and the woven fabric are integrated, elongation can be suppressed even in the case of ultrafine fiber formation using an aqueous solution that cannot be reinforced by PVA.

  Moreover, when performing a split process, the hardness of a fiber structure can be raised by impregnating PVA resin, and process passability can be improved. The split treatment can be performed either before or after the ultrafine fiber formation, but when the fiber structure is thin, it is preferable to perform the split treatment before the ultrafine fiber formation.

  In the case of the fiber structure in which the above-described (A) is superposed by the ultrafine processing, the ultrafine fibers are continuously present in the surface direction on one side of the woven fabric (b), and are entangled three-dimensionally. On the other surface, a discontinuous surface is formed in the surface direction in which ultrafine fibers penetrate perpendicularly to the fabric (b). In the present invention, it is important to obtain a fiber structure having such a structure before performing high-speed fluid treatment. Since one surface of the woven fabric (b) is a surface in which the above-described ultrafine fibers penetrate vertically and is discontinuous in the surface direction, the fiber tension at the time of bending is reduced, so the drape coefficient is small and good A leather-like sheet that forms a silhouette can be obtained. That is, in the fiber structure in which the short fiber web (a) and the woven fabric (b) are overlapped like the short fiber web (a) / woven fabric (b) / short fiber web (a), both surfaces of the woven fabric (b) are surfaces. Since it becomes the surface of the ultrafine fiber continuous in the direction, the drape coefficient becomes large and the effect of the present invention cannot be obtained.

  In addition, conventional leather-like sheets are impregnated with a polymer elastic body such as polyurethane before or after the ultrathinning treatment, but when the ultrafine fiber or fabric is hardened with the polymer elastic body, the drape coefficient is high and the number of nodes The leather-like sheet-like material characteristic of the present invention cannot be obtained, and the reduction of the environmental load at the time of disposal, which is the object of the present invention, cannot be achieved.

  The fiber structure in which the ultrafine fiber obtained is generated is low in abrasion resistance and is not suitable for practical use. Therefore, next, high-speed fluid processing is performed (step (3)). By performing high-speed fluid treatment, the ultrafine fibers are highly entangled with each other, so that high abrasion resistance can be obtained as a leather-like sheet-like material without impregnation with a polymer elastic body such as polyurethane.

  Here, in the case of the fiber structure in which the above-described (B) and (C) are stacked, before performing the high-speed fluid treatment, the layer of ultrafine fibers between the upper and lower fabrics (b) is arranged in the thickness direction. A fiber structure similar to (A) can be obtained by splitting the two vertically. The split processing method is not particularly limited, and can be performed using a slicing machine or the like. Further, if necessary, split processing can be performed on two or more sheets perpendicular to the thickness direction.

  As the high-speed fluid processing, it is preferable to perform water jet punch processing using a water flow in terms of the working environment. At this time, it is preferable to perform the water in a columnar flow state. The columnar flow is usually obtained by ejecting from a nozzle having a diameter of 0.06 to 1.0 mm at a fluid pressure of 1 to 60 MPa. In order to obtain efficient entanglement and good surface quality, this treatment preferably has a nozzle diameter of 0.06 to 0.15 mm and an interval of 5 mm or less, and a diameter of 0.06 to 0.12 mm. The interval is more preferably 1 mm or less. These nozzle specifications do not need to be all the same when processing multiple times. For example, a nozzle having a large hole diameter and a small hole diameter can be used in combination, but the nozzle having the above configuration is used at least once. It is preferable. A smaller nozzle hole diameter is preferable, but if it is less than 0.06 mm, nozzle clogging is likely to occur, and this is not preferable because there is a problem that the cost increases due to the necessity of highly filtering water.

  Further, in order to achieve uniform entanglement in the thickness direction and / or to improve the smoothness of the surface of the nonwoven fabric, the high-speed fluid treatment is preferably repeated many times. At that time, when the PVA resin is used in the ultrafine treatment, the PVA resin will not stick to each other unless the PVA resin is removed by the water flow, and the effect of improving the abrasion resistance cannot be obtained. After it disappears, it is necessary to perform high-speed fluid treatment repeatedly several times. The water pressure is appropriately selected according to the basis weight of the nonwoven fabric to be treated, and the higher the basis weight, the higher the pressure. Furthermore, it is important to process at a pressure of 10 MPa or more, preferably 15 MPa or more, in order to highly entangle the ultrafine fibers and obtain the desired physical properties such as tensile strength, tear strength, and wear resistance. . Further, the upper limit is not particularly limited, but the cost increases as the pressure increases, and in the case of a low-weight nonwoven fabric, the nonwoven fabric tends to be non-uniform, and fluff may be generated by cutting the fiber. Or less, more preferably 30 MPa or less. By doing so, for example, in the case of ultrafine fibers obtained from ultrafine fiber generation type fibers, it is common that the ultrafine fiber bundles in which the ultrafine fibers are converged are entangled, but almost entanglement by the ultrafine fiber bundles is observed It is possible to obtain a fiber structure in which ultrafine fibers are entangled to such an extent that they are not. In addition, you may perform a water immersion process before performing a water jet punch process. In order to further improve the surface quality, a method of relatively moving the nozzle head and the nonwoven fabric, or a method of sprinkling the fiber structure after entanglement by inserting a wire mesh or the like between the nozzles is performed. You can also.

  In the method for producing a leather-like sheet of the present invention, the relative speed (so-called processing speed) between the nozzle head and the fiber structure when performing high-speed fluid treatment is not particularly limited, and the basis weight of the fiber structure or Although it can be appropriately changed depending on conditions such as water pressure, the processing speed is usually preferably 4 m / min or more, and more preferably 6 m / min or more in consideration of productivity.

  Further, in the method for producing a leather-like sheet-like material of the present invention, the woven fabric integrated with the ultrafine fiber nonwoven fabric after high-speed fluid treatment (in order to reduce the drape coefficient of the leather-like sheet-like material and improve the number of nodes and the elongation rate) It is important to shrink b) (step (4)).

  The shrinking method is not particularly limited, and the shrinking method can be performed by dry heat or wet heat, or both. As the timing for shrinking the woven fabric (b), after the high-speed fluid treatment, shrinkage may be performed in any step such as after napping, during dyeing, after dyeing, or after dyeing, or in multiple steps in a plurality of steps. It is preferable to shrink at the same time as dyeing in terms of omitting the process. In addition, when wrinkles occur during dyeing, it is preferable to further shrink by dyeing after shrinking at a temperature that does not cause wrinkles before dyeing.

  In the shrinkage treatment, crimping occurs in the composite fiber constituting the woven fabric (b) by being contracted by 5 to 30% in the longitudinal direction and the horizontal direction of the fiber structure, and resistance when bent. This is preferable because the drape coefficient is reduced and the elongation rate is improved, and it is more preferable that the shrinkage is 8 to 15%. Further, if the shrinkage rate is less than 5%, a sufficient elongation rate cannot be obtained, and if the shrinkage rate exceeds 30%, wrinkles occur during shrinkage or the elongation recovery rate tends to decrease, resulting in loss of shape. Since it becomes easy to do, it is not preferable.

  Further, in order to obtain a leather-like sheet-like material having suede-like or nubuck-like napping, it is preferable to perform napping treatment with sandpaper or a brush. Such napping treatment can be performed before or after dyeing, which will be described later. However, since the colored fibers adhere to the sandpaper or the brush when dyeing is performed, it is preferable to perform the dyeing process before dyeing.

  Next, a leather-like sheet-like material having suede-like or nubuck-like napping can be obtained by dyeing the raised fiber structure. The dyeing method is not particularly limited, and the dyeing machine to be used may be any of a liquid dyeing machine, a thermosol dyeing machine, a high-pressure jigger dyeing machine, etc., but the liquid dyeing is advantageous in that the texture of the obtained leather-like sheet is excellent. It is preferable to dye using a machine. Although the conditions for dyeing are not particularly limited, it is preferably performed at 100 to 140 ° C. for 1 to 60 minutes using a liquid flow dyeing machine. The treatment time is more preferably 10 to 60 minutes.

  Moreover, in order to further improve the abrasion resistance of the leather-like sheet material, a binder made of a polymer elastic body such as polyurethane can be provided. The binder may be applied at any stage before the napping treatment or after the napping treatment, but is preferably applied after the napping treatment in terms of obtaining surface smoothness, and the binder is added after the napping treatment. In the state, it is more preferable to perform napping treatment with sandpaper or a brush. As a means for providing a binder made of a polymer elastic body such as polyurethane, a pad method, a method using a liquid dyeing machine or a jigger dyeing machine, a spraying method, etc. can be appropriately selected.

  The means for applying fine particles and a softening agent to the leather-like sheet can also be performed by the same means as the binder. The fine particles and softening agent are preferably applied after dyeing. If applied before dyeing, the effect may be reduced due to omission during dyeing or uneven dyeing may occur, which is not preferable.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured by the method described below.

(1) Twist factor K
The yarn twist coefficient K was determined by the following equation.
Twist coefficient K = T × D ^0.5
Where T: number of twists per 1 m of yarn length, D: yarn fineness (decitex)
Here, the number of twists T per 1 m of yarn length means the number of untwisting when untwisting under a load of 90 × 10 ⁻³ cN / dtex with an electric tester and completely untwisting. It is the value divided by the yarn length.

(2) Weight per unit area, thickness, apparent density The basis weight was measured by the method described in JIS L 1096 8.4.2 (1999). Further, the thickness was measured with a dial thickness gauge (manufactured by Ozaki Mfg. Co., Ltd., trade name “Peacock H”), and the apparent density was determined by dividing the basis weight value by the thickness value.

(3) Measurement of fineness The cross section of the nonwoven fabric was observed with an optical microscope. 100 fiber cross-sections were selected at random, the cross-sectional area was measured, and the number average of 100 fiber cross-sectional areas was determined. From the average value of the obtained fiber cross-sectional area and the specific gravity of the fiber, the fineness was obtained by calculation. The specific gravity of the fiber was measured based on JIS L 1015 8.14.2 (1999).

(4) Measurement of fiber length 100 fibers were each extracted from arbitrary three places of a nonwoven fabric, and fiber length was measured. The number average of 300 measured fiber lengths was determined.

(5) Drape coefficient, number of nodes The draping property of the leather-like sheet conforms to JIS L 1096 (1999) 8.19.7 G method (drape coefficient), and the drape tester (model: YD-100, Daiei Kagaku Co., Ltd.) Measured using Seiki Seisakusho. The measurement was carried out by changing to the condition of “rotating the sample table for 2 minutes” instead of the condition of “vibrating the sample table up and down three times” defined in JIS. This condition is a standard use condition of the measuring device. The number of folds counted from the projection obtained by the drape coefficient test was defined as the number of nodes. In addition, the measurement was performed 3 times each on the front and back, and the average value was taken as these values.

(6) Elongation rate In JIS L 1096 (1999) 8.14.1 A method (constant speed extension method), the elongation rate of the sheet-like material was measured (the gripping interval was 20 cm).

  Further, the elongation recovery rate of the sheet-like material was determined by the JIS L 1096 (1999) 8.14.2 A method (repeated constant speed extension method) (repeated constant speed extension method) (the gripping interval is 20 cm). In the table, the values obtained are rounded off to the nearest decimal place.

(7) Martindale abrasion test A test piece having a diameter of 3.8 cm was taken from the leather-like sheet, and the weight was measured. According to JIS L 1096 (1999) 8.17.5 E method (Martindale method) Furniture load (12 kPa), the surface where the ultrafine fibers are formed is set to the pilling position of the Martindale abrasion tester (THREE DRIVE ROLLERS = POSITION) A wear resistance test was carried out in B). When rubbed 20000 times, the testing machine was stopped, and the weight loss of the test piece after the test with respect to that before the test was evaluated.

(8) Silhouette evaluation A jacket was made of a leather-like sheet, and 10 people wore it at 7 hours / day for one week. During the wearing period, people were allowed to live as usual, and the silhouette was not lost before and after wearing, or 10 people evaluated in 3 stages by sensory evaluation, and the worst evaluation was taken as the evaluation value.
Good: A, Somewhat bad: B, Bad: C

(9) Wearing feeling A jacket was made of a leather-like sheet, and 10 people wore it for 7 hours / day for 1 week. During the wearing period, people were allowed to live as usual, and the comfort at the time of wearing was evaluated in four stages by sensory evaluation, and the worst evaluation was taken as the evaluation value.
Wear feeling Good: A, Normal: B, Somewhat bad: C, Bad: D.

Reference example 1
A low-viscosity component made of 100% polyethylene terephthalate having an intrinsic viscosity of 0.40 and a high-viscosity component made of polyethylene terephthalate having an intrinsic viscosity of 0.75 were bonded to the side-by-side at a weight composite ratio of 50:50, and spun and stretched A composite fiber of 56 dtex 12 filaments was obtained. This was twisted at 800 T / m (twisting coefficient 5987) by S twisting and steam set at 65 ° C. This yarn was used as warp yarn and weft yarn, the woven structure was plain, and a woven fabric (1) having a woven density of 93 × 64 pieces / 2.54 cm and 44 g / m ² was produced.

Reference example 2
A woven fabric was produced under the same conditions except that the number of twists of the conjugate fiber of Reference Example 1 was 1500 T / m (twisting coefficient 11225) to produce a 51 g / m ² woven fabric (2).

Reference example 3
Using the conjugate fiber of Reference Example 1, the S was twisted at 2400 T / m (twisting coefficient 17960), and steam setting was performed at 75 ° C. Similarly, a Y-twisted 2400 T / m (twisting coefficient 17960) twisted yarn was set at 75 ° C. and steam set. S warp yarn and Z twist yarn are alternately arranged on the warp yarn, and the weaving structure is plain weave using S twist yarn on the weft yarn, producing a woven fabric with a woven density of 93 × 64 / 2.54 cm. 57 g / m ² of woven fabric (3) was produced.

Reference example 4
A woven fabric was produced in the same manner as in Reference Example 3 except that the steam set temperature was 95 ° C, and a woven fabric (4) of 63 g / m ² was produced.

Reference Example 5
A fabric was produced under the same conditions except that the number of twists in Reference Example 3 was 3000 T / m (twist coefficient 22450), and a fabric (5) of 60 g / m ² was produced.

Reference Example 6
A polyethylene terephthalate component having an intrinsic viscosity of 0.66 was spun and drawn to obtain a composite fiber of 56 dtex 48 filaments. This was twisted by S twisting at 2400 T / m (twisting coefficient 17960) and steam set at 75 ° C. Similarly, a Y-twisted 2400 T / m (twisting coefficient 17960) twisted yarn was set at 75 ° C. and steam set. S warp yarn and Z twist yarn are alternately arranged on the warp yarn, and the weaving structure is plain weave using S twist yarn on the weft yarn, producing a woven fabric with a woven density of 93 × 64 / 2.54 cm. , 60 g / m ² of woven fabric (6) was produced.

Reference Example 7
Using the yarn of Reference Example 3, a 44 gauge, 77 g / m ² double circular knitting was prepared to obtain a knitted fabric (1).

Example 1
A sea island type composite short fiber having an average single fiber fineness of 3 dtex, 36 islands, and an average fiber length of 51 mm consisting of 45 parts of polystyrene as a sea component and 55 parts of polyethylene terephthalate as an island component is passed through a card machine and a cross wrapper to have a basis weight of 157 g / An m ² short fiber web was prepared. The web obtained was overlapped with the fabric (2) produced in Reference Example 2, and 1600 pieces were needle punched alternately from the surface of the short fiber web and the surface of the fabric (2) using a 1 barb type needle punch machine. Needle-punched at a driving density of / cm ² to obtain a fiber structure having a basis weight of 211 g / m ² , a thickness of 1.36 mm, and a fiber apparent density of 0.155 g / cm ³ . Next, it was immersed in an aqueous solution of 1.3% PVA with a polymerization degree of 500 and a saponification degree of 88% heated to 83 ° C. for 2 minutes, and then heated to 95 ° C. with a polymerization degree of 500 and a saponification degree of 88% (PVA ) Soaked in a 1.3% aqueous solution for 2 minutes, impregnated with PVA so as to impregnate the fiber structure with an amount of 5% in terms of solid content, and simultaneously subjected to shrinkage treatment, 5.5% in the vertical direction, Shrink 14.1% in the horizontal direction. Then, it dried at 100 degreeC and removed the water | moisture content. Next, this fiber structure was treated with tricrene at 30 ° C. until the polystyrene was completely removed, thereby expressing ultrafine fibers having an average single fiber fineness of 0.046 dtex from the composite short fibers. As a result, one surface of the fabric (2) is a surface in which the microfibers are continuously present in the surface direction and is intertwined three-dimensionally, and the other surface is the surface of the fabric (2). A fiber structure was obtained in which ultrafine fibers penetrated vertically and formed with discontinuous surfaces in the surface direction.

From the surface in which the ultrafine fibers of this fiber structure are continuous in the plane direction and entangled three-dimensionally, a water jet punching machine having a nozzle head with a hole diameter of 0.1 mm and an interval of 0.6 mm is 5 m. Water jet punching was performed three times at a pressure of 17 MPa at a processing speed of / min. In addition, after performing the water jet punch process of the 2nd time, the stickiness of PVA disappeared and PVA was able to be removed. Next, a water jet punching process was performed three times at a pressure of 17 MPa from a surface discontinuous in the surface direction in which ultrafine fibers penetrated perpendicularly to the fabric (2). By this treatment, the ultrafine fibers on both sides of the woven fabric (2) have a structure in which the ultrafine fibers are entangled with each other with little entanglement due to the fiber bundle.
Subsequently, the surface of the obtained fiber structure was napped with sandpaper. Further, the fiber structure was subjected to a flow dyeing machine using a “Sumikaron Blue S-BBL200” (manufactured by Sumika Chemtex Co., Ltd.) at a concentration of 20% owf at 120 ° C. for 45 minutes. Stained. In addition, it was shrink | contracted 16.6% in the length direction and 15.8% in the horizontal direction by dyeing | staining.

The obtained sheet is immersed in an aqueous solution containing a softening agent (nonionic softening agent “ELSOFT N-500 CONK” manufactured by One Company, Ltd.) and fine particles (colloidal silica “Aldac SP-65” manufactured by one company, Inc.). Then, it was squeezed with mangles so that the colloidal silica content was 0.1%, and then dried at 100 ° C. while brushing.
The leather-like sheet thus obtained has a dense structure in which ultrafine fibers having an average fineness of 0.049 dtex form layers on both sides of the fabric (2), and the ultrafine fibers are intertwined with each other. It was. Moreover, it was 46.7 mm when the average fiber length of the ultrafine fiber was measured.

  This leather-like sheet was measured for drape coefficient and number of nodes, elongation rate and elongation recovery rate. The drape coefficient was 0.433, the number of nodes was 7 and the drape coefficient was excellent, and the elongation rate was 16.9% vertical. The stretch recovery rate was 33.2%, the length was 93.0%, and the width was 88.5%. The wear loss after the Martindale abrasion test was 0.9 mg, which was a good result. A jacket was made of this leather-like sheet and the silhouette and wearability were evaluated. As a result, good results were obtained in both silhouette and wear. The evaluation results are shown in Table 1.

Example 2
A leather-like sheet was obtained in the same manner as in Example 1 except that the woven fabric (3) produced in Reference Example 3 was used. In the production of the leather-like sheet, the shrinkage treatment with the PVA aqueous solution shrinks 5.0% in the vertical direction and 12.1% in the horizontal direction, and 12.7% in the vertical direction and 12.7% in the horizontal direction for dyeing. Shrinkage by 13.4%.

  This leather-like sheet is made of ultrafine fibers on the front and back surfaces. When the drape coefficient and the number of nodes, and the elongation rate and the extension recovery rate are measured, the drape coefficient is 0.421 and the number of nodes is 7 The rate is 12.6% vertically, 24.2% horizontally, and the recovery rate is 94.5% vertically and 92.9% horizontally. Although the stretchability is slightly inferior to Example 1, the draping property and the stretch property are good. It was excellent. Further, the weight loss after the Martindale abrasion test was 0.7 mg, which was a good result. A jacket was made from this leather-like sheet and the silhouette and wearability were evaluated. As a result, good results were obtained in the silhouette and the wearability. The evaluation results are shown in Table 1.

Example 3
Except that when the short fiber web and the woven fabric (3) prepared in Reference Example 3 were overlapped and needle punched, only the surface of the short fiber web was needle punched at a driving density of 1800 pieces / cm ^2. In the same manner as in No. 2, a leather-like sheet was obtained.

  In the production of the leather-like sheet, the shrinkage treatment with the PVA aqueous solution shrinks 5.5% in the vertical direction and 12.4% in the horizontal direction, and 13.8% in the vertical direction and 14. Shrinkage 0%.

  This leather-like sheet is made of ultrafine fibers on the front and back surfaces. When the drape coefficient and the number of nodes, the elongation rate and the extension recovery rate were measured, the drape coefficient was 0.409, the number of nodes was 7, and the elongation rate. The length is 13.7%, the width is 26.5%, the stretch recovery rate is 94.4% and the width is 91.8%. Although the stretchability is slightly inferior to Example 1, it is excellent in drape and stretchability. The surface quality of the surface of the ultrafine fiber penetrating the fabric (3) was superior to the leather-like sheet-like material obtained in Example 1 or Example 2. Further, the weight loss after the Martindale abrasion test was 1.2 mg, which was a good result. A jacket was made of this leather-like sheet and the silhouette and wearability were evaluated. As a result, good results were obtained in both silhouette and wear. The evaluation results are shown in Table 1.

Comparative Example 1
The fabric was used in the same manner as in Example 1 except that the fabric (1) prepared in Reference Example 1 was used. When the short fiber nonwoven fabric and the fabric were entangled and integrated with the needle punch, the fabric was damaged. However, a leather-like sheet could not be obtained.

Comparative Example 2
A leather-like sheet was obtained in the same manner as in Example 1 except that the woven fabric (5) produced in Reference Example 5 was used. This leather-like sheet shrinks 2.0% in the vertical direction and 9.4% in the horizontal direction by shrinkage treatment with an aqueous PVA solution, and 7.8% in the vertical direction and 10% in the horizontal direction when dyeing. .2% contraction.

  This leather-like sheet is made of ultra-fine fibers on the front and back surfaces. When the drape coefficient and the number of nodes, the elongation rate and the elongation recovery rate were measured, the drape coefficient was 0.519, the number of nodes was 5, and the elongation rate. The length was 7.4%, the width was 12.6%, the stretch recovery rate was 92.5%, the width was 92.3%, and the drape was inferior. The wear loss after the Martindale abrasion test was 0.6 mg, which was a good result. A jacket was made with this leather-like sheet, and the silhouette and the feeling of wearing were evaluated. The result was that the silhouette was slightly poor. The evaluation results are shown in Table 1.

Comparative Example 3
A leather-like sheet was obtained in the same manner as in Example 1 except that the woven fabric (6) obtained in Reference Example 6 was used. This leather-like sheet shrinks 2.7% in the vertical direction and 8.2% in the horizontal direction by shrinkage treatment with an aqueous PVA solution, and 6.4% in the vertical direction and 8 in the horizontal direction for dyeing. .1% contraction.

  This leather-like sheet is made of ultra-fine fibers on the front and back surfaces. When the drape coefficient, the number of nodes, the elongation rate, and the extension recovery rate were measured, the drape coefficient was 0.530, the number of nodes was 5, and the elongation rate. The length was 6.1%, the width was 8.7%, and the stretch recovery rate was 87.6% and the width was 90.4%. The weight loss after the Martindale abrasion test was 0.8 mg, which was a good result, but was inferior to the drapeability and elongation recovery rate as compared with Examples 1 to 3. A jacket was made with this leather-like sheet, and the silhouette and the feeling of wear were evaluated. The result was that the silhouette and the wearability were slightly poor. The evaluation results are shown in Table 1.

Comparative Example 4
A leather-like sheet was obtained in the same manner as in Example 3 except that the woven fabric used was changed to the knitted fabric (1) obtained in Reference Example 7. This leather-like sheet is contracted by 3.5% in the vertical direction and 11.9% in the horizontal direction by shrinkage treatment with an aqueous PVA solution, and 13.8% in the vertical direction and 14% in the horizontal direction by dyeing. .3% contraction.

  The leather-like sheet was measured for the drape coefficient and the number of nodes, the elongation rate and the elongation recovery rate. As a result, the drape coefficient was 0.294, the number of nodes was 7, the elongation rate was 13.6% vertical, 25.1 horizontal. %, And the elongation recovery rate was 83.9% vertically and 79.3% horizontally. In addition, the weight loss after the Martindale abrasion test was a good result of 3.2 mg, but compared with Examples 1 to 3, the draping property was excellent, but the elongation recovery rate was greatly inferior. In addition, although the front and back surfaces of the leather-like sheet are formed of ultrafine fibers, the composite fiber of the fabric that has been broken by a single yarn protrudes from the surface when the needle is punched, and the surface quality is improved with a rough touch. It was inferior. In addition, the texture was soft and closer to the woven or knitted fabric than the artificial leather, and it was not as high quality as the artificial leather. A jacket was made with this leather-like sheet, and the silhouette and wearability were evaluated. As a result, the shape was lost and the feeling of wear was poor. The evaluation results are shown in Table 1.

Comparative Example 5
When it was produced in the same manner as in Example 3 except that the water jet punching was not performed, the ultrafine fibers dropped off due to dyeing, and a leather-like sheet-like product could not be obtained.

Example 4
A sea island type composite short fiber having an average single fiber fineness of 3 dtex, 36 islands, and an average fiber length of 51 mm consisting of 45 parts of polystyrene as a sea component and 55 parts of polyethylene terephthalate as an island component is passed through a card machine and a cross wrapper to have a basis weight of 157 g / An m ² web was made. The web obtained was overlapped with the woven fabric (4) produced in Reference Example 4, and needle punching was performed only from the surface of the short fiber web at a driving density of 1000 pieces / cm ² using a 1 barb type needle punching machine, A fiber structure having an apparent fiber density of 0.146 g / cm ³ was obtained. This fiber structure was overlapped with the short fiber webs on the inside, and alternately needle punched at a driving density of 1000 / cm ² alternately from both sides. The basis weight was 403 g / m ² and the thickness was 2.70 mm. A fiber structure having an apparent fiber density of 0.149 g / cm ³ was obtained.

  Next, it was immersed in an aqueous solution of 1.3% PVA with a polymerization degree of 500 and a saponification degree of 88% heated to 83 ° C. for 2 minutes, and then heated to 95 ° C. with a polymerization degree of 500 and a saponification degree of 88% (PVA ) Soaked in 1.3% aqueous solution for 2 minutes, impregnated with PVA so as to impregnate the fiber structure to 5% in terms of solid content, and at the same time performed shrinkage treatment, 2.9% in the vertical direction, Shrink 10.1% in the horizontal direction. Then, it dried at 100 degreeC and removed the water | moisture content. Next, this fiber structure was treated with tricrene at 30 ° C. until the polystyrene was completely removed, thereby expressing ultrafine fibers having an average single fiber fineness of 0.046 dtex from the composite short fibers. Next, using a standard splitting machine manufactured by Murota Manufacturing Co., Ltd., the ultrafine fiber layer between the fabrics (3) was split into two pieces perpendicular to the thickness direction. Subsequent water jet punching, napping, dyeing, softening agent and fine particle application were performed in the same manner as in Example 1 to obtain a leather-like sheet.

  In addition, this leather-like sheet contracted by 11.7% in the vertical direction and 9.4% in the horizontal direction by dyeing.

  This leather-like sheet is made of ultra-fine fibers on the front and back surfaces. When the drape coefficient and the number of nodes, the elongation rate and the elongation recovery rate were measured, the drape coefficient was 0.387, the number of nodes was 7, and the elongation rate. Has a length of 11.4%, a width of 18.8%, a stretch recovery rate of 92.5%, and a width of 91.0%. Although the stretchability is slightly inferior to those of Examples 1 to 3, the draping property is excellent. Met. Further, the weight loss after the Martindale abrasion test was 1.1 mg, which was a good result.

The average fineness of the ultrafine fibers in this leather-like sheet was 0.050, and the average fiber length was 26.4 mm.
A jacket was made of this leather-like sheet and the silhouette and wearability were evaluated. As a result, good results were obtained in both silhouette and wear. The evaluation results are shown in Table 1.

Example 5
A sea island type composite short fiber having an average single fiber fineness of 3 dtex, 36 islands, and an average fiber length of 51 mm consisting of 45 parts of polystyrene as a sea component and 55 parts of polyethylene terephthalate as an island component is passed through a card machine and a cross wrapper, and the basis weight is 320 g / An m ² short fiber web was prepared. The fabric (4) prepared in Reference Example 4 was overlapped on both sides of the obtained web, and both sides were alternately needle punched at a driving density of 1800 pieces / cm ² using a 1 barb type needle punch machine. Of 437 g / m ² , a thickness of 2.68 mm, and an apparent fiber density of 0.163 g / cm ³ was obtained.

  Next, it was immersed in an aqueous solution of 1.3% PVA with a polymerization degree of 500 and a saponification degree of 88% heated at 83 ° C. for 2 minutes, and then heated to 95 ° C. with a polymerization degree of 500 and a PVA with a saponification degree of 88%. It is immersed in a 3% aqueous solution for 2 minutes and impregnated with PVA so that the fiber structure has an adhesion amount of 5% in terms of solid content. At the same time, shrinkage treatment is performed, and 3.6% in the vertical direction and in the horizontal direction. 13.9% contraction. Then, it dried at 100 degreeC and removed the water | moisture content. Next, this fiber structure was treated with tricrene at 30 ° C. until the polystyrene was completely removed, thereby expressing ultrafine fibers having an average single fiber fineness of 0.046 dtex from the composite short fibers. Next, using a standard splitting machine manufactured by Murota Manufacturing Co., Ltd., the ultrafine fiber layer between the fabrics (4) was split into two pieces perpendicular to the thickness direction. Subsequent water jet punching, dyeing, softening agent and fine particle application were performed in the same manner as in Example 1 to obtain a leather-like sheet.

  The leather-like sheet contracted by 10.8% in the vertical direction and 9.8% in the horizontal direction by dyeing.

  This leather-like sheet is made of ultra-fine fibers on the front and back surfaces. When the drape coefficient and the number of nodes, the elongation rate and the extension recovery rate were measured, the drape coefficient was 0.374, the number of nodes was 7, and the elongation rate. Has a length of 12.5%, a width of 19.0%, a stretch recovery rate of 92.0% and a width of 91.3%, which is slightly inferior in stretchability to Examples 1 to 3, but excellent in drapeability. Met. Further, the weight loss after the Martindale abrasion test was 0.7 mg, which was a good result.

The average fineness of the ultrafine fibers in this leather-like sheet was 0.050, and the average fiber length was 27.8 mm.
A jacket was made of this leather-like sheet and the silhouette and wearability were evaluated. As a result, good results were obtained in both silhouette and wear. The evaluation results are shown in Table 1.

Comparative Example 6
A sea island type composite short fiber having an average single fiber fineness of 3 dtex, 36 islands, and an average fiber length of 51 mm consisting of 45 parts of polystyrene as a sea component and 55 parts of polyethylene terephthalate as an island component is passed through a card machine and a cross wrapper to have a basis weight of 157 g / Short fiber webs of m ² and 62 g / m ² were made. The obtained two types of webs were overlapped on both sides of the fabric (2) prepared in Reference Example 2, alternately needle punched, needle punched at a driving density of 1600 pieces / cm ² , and the basis weight was 294 g / m ² . A fiber structure having a thickness of 1.84 mm and an apparent fiber density of 0.160 g / cm ³ was obtained. Next, it was immersed in an aqueous solution of 1.3% PVA with a polymerization degree of 500 and a saponification degree of 88% heated to 83 ° C. for 2 minutes, and then heated to 95 ° C. with a polymerization degree of 500 and a saponification degree of 88% (PVA ) Soaked in a 1.3% aqueous solution for 2 minutes, impregnated with PVA so as to impregnate the fiber structure with a solid content equivalent to 5%, and simultaneously contracted, It contracted 13.7% in the horizontal direction. Then, it dried at 100 degreeC and removed the water | moisture content.

  Next, this fiber structure was treated with tricrene at 30 ° C. until the polystyrene was completely removed, thereby expressing ultrafine fibers having an average single fiber fineness of 0.046 dtex from the composite short fibers. As a result, a fiber structure was obtained in which both sides of the woven fabric (2) had a surface in which ultrafine fibers penetrated perpendicularly to the woven fabric (2) and the ultrafine fibers were continuously present in the surface direction.

Subsequent water jet punching, dyeing, softening agent and fine particle application were performed in the same manner as in Example 1 to obtain a leather-like sheet.
In addition, this leather-like sheet contracted 15.7% in the vertical direction and 14.6% in the horizontal direction by dyeing.

  This leather-like sheet is made of ultra-fine fibers on the front and back surfaces. When the drape coefficient and the number of nodes, the elongation rate and the extension recovery rate were measured, the drape coefficient was 0.531, the number of nodes was 7, and the elongation rate. The length was 16.0%, the width was 24.1%, and the stretch recovery rate was 92.0% and the width was 92.1%. The stretchability was excellent, but the drape was poor. In addition, the weight loss after the Martindale abrasion test was as good as 1.0 mg.

The average fineness of the ultrafine fibers in this leather-like sheet was 0.049, and the average fiber length was 44.6 mm.
A jacket was made with this leather-like sheet, and the silhouette and wearability were evaluated. The result was that the silhouette was somewhat poor. The evaluation results are shown in Table 1.

Example 6
A sea island type composite short fiber having an average single fiber fineness of 3 dtex, 36 islands, and an average fiber length of 51 mm consisting of 45 parts of polystyrene as a sea component and 55 parts of polyethylene terephthalate as an island component is passed through a card machine and a cross wrapper, and the basis weight is 140 g / An m ² short fiber web was prepared. The web (2) produced in Reference Example 2 was overlapped on the obtained web, and needle punching was alternately performed from the surface of the short fiber web and the surface of the fabric (2) using a 1 barb type needle punching machine. Needle-punched at a driving density of / cm ² to obtain a fiber structure having a basis weight of 225 g / m ² , a thickness of 1.41 mm, and an apparent fiber density of 0.160 g / cm ³ . Next, it was immersed in an aqueous solution of 1.3% PVA with a polymerization degree of 500 and a saponification degree of 88% heated to 83 ° C. for 2 minutes, and then heated to 95 ° C. with a polymerization degree of 500 and a saponification degree of 88% (PVA ) Soaked in a 1.3% aqueous solution for 2 minutes, impregnated with PVA so as to impregnate the fiber structure with a solid content equivalent to 5%, and simultaneously contracted, The shrinkage was 13.8% in the horizontal direction. Then, it dried at 100 degreeC and removed the water | moisture content. Next, this fiber structure was treated with tricrene at 30 ° C. until the polystyrene was completely removed, thereby expressing ultrafine fibers having an average single fiber fineness of 0.046 dtex from the composite short fibers. Thereby, the same fiber structure as Example 1 was obtained.

  From the surface in which the ultrafine fibers of this fiber structure are continuous in the plane direction and are entangled three-dimensionally, a water jet punch machine having a nozzle diameter of 0.12 mm and an interval of 0.6 mm is used for 5 m. Water jet punching was performed three times at a pressure of 17 MPa at a processing speed of / min. Next, a water jet punching process was performed three times at a pressure of 17 MPa from a surface discontinuous in the surface direction in which ultrafine fibers penetrated perpendicularly to the fabric (2). By this treatment, the ultrafine fibers on both sides of the woven fabric (2) have a structure in which the ultrafine fibers are entangled with each other with little entanglement due to the fiber bundle.

  Subsequently, the surface of the obtained fiber structure was napped with sandpaper. The fiber structure subjected to napping treatment is dipped in an aqueous solution containing a water-based urethane resin ("Evaphanol AP12" manufactured by Nikka Chemical Co., Ltd.) and a migration inhibitor ("Neo Sticker N" manufactured by Nikka Chemical Co., Ltd.). After squeezing the liquid, drying was performed at 130 ° C. for 2 minutes. As a result of measuring the weight after drying, the weight was increased by 4% compared with that before application of the water-based urethane resin. After applying the water-based urethane resin, the surface of the fiber structure was further napped with sandpaper.

  The obtained fibrillar structure was subjected to a flow dyeing machine using a “Sumikaron Blue S-BBL200” (manufactured by Sumika Chemtex Co., Ltd.) at a concentration of 20% owf at 120 ° C. for 45 minutes. Stained. In addition, due to dyeing, the shrinkage was 14.2% in the vertical direction and 15.0% in the horizontal direction.

  Next, it is immersed in an aqueous solution containing a softening agent (“Nonion-based softening agent“ ELSOFT N-500 Conch ”, manufactured by One Corporation) and an antistatic agent (“ Nicepol FL ”, Nikka Chemical Co., Ltd.) After squeezing, it was dried at 100 ° C. while brushing.

  In the leather-like sheet thus obtained, as in Example 1, ultrafine fibers having an average fineness of 0.049 dtex formed layers on both sides of the fabric (2), and the ultrafine fibers were intertwined with each other. It was a dense structure.

The leather-like sheet was measured for the drape coefficient and the number of nodes, the elongation rate and the elongation recovery rate. As a result, the drape coefficient was 0.470, the number of nodes was 7, and the drape coefficient was excellent. The stretch recovery rate was 32.5%, the length was 93.2%, and the width was 89.0%. The weight loss after the Martindale abrasion test was 4.1 mg, which was a good result. A jacket was made of this leather-like sheet and the silhouette and wearability were evaluated. As a result, good results were obtained in both silhouette and wear. The evaluation results are shown in Table 1.
Example 7
Copolymer polyester containing 8 mol% of 5-sodiumsulfoisophthalic acid as sea component based on total acid component, average single fiber fineness consisting of 70 parts of polyethylene terephthalate as island component, 3.3 dtex, 36 islands, average fiber length of 51 mm The sea-island type composite short fiber was passed through a card machine and a cross wrapper to produce a short fiber web having a basis weight of 300 g / m ² . Using this short fiber web, the basis weight was 482 g / m ² , the thickness was 2.8 mm, and the apparent fiber density was 0.172 g / in the same manner as in Example 5 except that the needle punch driving density was 2400 / cm ^2. A cm ³ fiber structure was obtained.

  Next, it was immersed in an aqueous solution of 1.3% PVA with a polymerization degree of 500 and a saponification degree of 88% heated at 83 ° C. for 2 minutes, and then heated to 95 ° C. with a polymerization degree of 500 and a PVA with a saponification degree of 88%. It is immersed in a 3% aqueous solution for 2 minutes and impregnated with PVA so as to impregnate the fiber structure with a solid content equivalent to 5%. At the same time, shrinkage treatment is performed, and 4.9% in the vertical direction and in the horizontal direction. The shrinkage was 10.6%. Then, it dried at 100 degreeC and removed the water | moisture content. Next, using a standard splitting machine manufactured by Murota Manufacturing Co., Ltd., the ultrafine fiber layer between the fabrics (4) was split into two pieces perpendicular to the thickness direction. Thereafter, the fiber structure was subjected to a split treatment, immersed in a sodium hydroxide solution, squeezed with a mangle, and then subjected to steam treatment to develop ultrafine fibers, followed by washing with water and drying.

  Thereby, one surface of the woven fabric (4) is a surface in which the microfibers are continuously present in the surface direction and is intertwined three-dimensionally, and the other surface is the surface of the woven fabric (4). A fiber structure in which ultrafine fibers penetrated perpendicularly and a surface in which the ultrafine fibers were discontinuous was formed in the surface direction was obtained.

  The subsequent processing was performed in the same manner as in Example 6. At the time of dyeing, the shrinkage was 8.1% in the vertical direction and 6.6% in the horizontal direction.

  The leather-like sheet thus obtained has a dense structure in which ultrafine fibers having an average fineness of 0.041 dtex form layers on both sides of the fabric (4), and the ultrafine fibers are intertwined with each other. It was.

  The leather-like sheet was measured for drape coefficient and number of nodes, elongation rate and elongation recovery rate. As a result, the drape coefficient was 0.492, the number of nodes was 6 and the drape coefficient was excellent, and the elongation rate was 11.6% vertically. The stretch recovery rate was 15.0%, the length was 91.9%, and the width was 92.7%. The weight loss after the Martindale abrasion test was 6.2 mg, which was a good result. A jacket was made of this leather-like sheet and the silhouette and wearability were evaluated. As a result, good results were obtained in both silhouette and wear. The evaluation results are shown in Table 1.

ADVANTAGE OF THE INVENTION According to this invention, the environmental impact at the time of disposal can be provided, and the leather-like sheet-like material which has the drape property and stretch property which are not in natural leather can be provided.
The leather-like sheet-like material of the present invention can be suitably used in fields where three-dimensional formability is required, such as clothing, car seats and furniture that require a good silhouette and wearing feeling.

Claims (14)

An ultra-fine fiber nonwoven fabric having an average fiber fineness of 0.001 to 0.5 dtex is entangled and integrated with the woven fabric by a needle punch method, and the twisting coefficient of the yarn constituting the woven fabric is 7000 to 20000. One surface of the object is composed of continuous ultrafine fibers in the surface direction intertwined with each other, the other surface is formed by discontinuous ultrafine fibers in the surface direction, the drape coefficient is 0.35 to 0.5, A leather-like sheet-like material substantially consisting of a fiber material having an elongation rate of 10 to 35% in at least one of the vertical direction and the horizontal direction.
Twist coefficient K = T × D ^0.5
Where T: number of twists per 1 m of yarn length (times)
D: Yarn fineness (decitex). The fibers constituting the woven fabric form a core-sheath structure in which two or more types of polyester polymers are bonded side by side along the fiber length direction, or two or more types of polyester polymers are eccentric. The leather-like sheet-like material according to claim 1, wherein the yarn is composed of an eccentric core-sheath type composite fiber, and the twisting coefficient of the yarn constituting the woven fabric is 7,000 to 20,000.
Twist coefficient K = T × D ^0.5
Where T: number of twists per 1 m of yarn length (times)
D: Yarn fineness (decitex). The leather-like sheet material according to claim 1 or 2, wherein the thickness is 0.45 mm to 1.5 mm. The leather-like sheet material according to any one of claims 1 to 3, wherein the number of nodes is 6 to 10. The leather-like sheet-like product according to any one of claims 1 to 4, wherein a longitudinal recovery rate and a horizontal recovery rate are 85 to 100%. The leather-like sheet according to any one of claims 1 to 5, wherein in the abrasion test in the Martindale method, the weight loss when the surface on which the ultrafine fibers are formed is 20000 times is 8 mg or less. . After producing a short fiber web (a) by a needle punch method using short fibers of 1-8 decitex composite fibers capable of generating ultrafine fibers having an average fiber fineness of 0.001-0.5 dtex, The manufacturing method of the leather-like sheet-like material characterized by performing the process of the following (1)-(4).
(1) The process of producing the fiber structure which piled up the textile fabric (b) on the at least single side | surface of the short fiber web (a), and made it intertwined and integrated by the needle punch method.
(2) Generating ultrafine fibers from a fiber structure entangled and integrated by the needle punch method, making the short fiber web (a) an ultrafine fiber nonwoven fabric, and allowing the short fibers to penetrate in the thickness direction of the fabric (b), A step of forming a fiber structure in which the short fiber web (a) and the woven fabric (b) are intertwined and integrated, and one surface has a surface formed by discontinuous ultrafine fibers .
(3) A step of performing high-speed fluid treatment on a fiber structure made of an ultrafine fiber nonwoven fabric in which only one side obtained by the steps of (1) to (2) is continuously intertwined in the surface direction at a fluid pressure of 10 MPa or more.
(4) A shrinking step of shrinking 5 to 30% in the vertical direction and the horizontal direction after performing the high-speed fluid treatment. 8. The method for producing a leather-like sheet-like material according to claim 7, wherein when punching the short fiber web (a) and the woven fabric (b), the needle punch is performed only from the surface of the short fiber web (a). After the two fiber structures obtained in the step (1) are overlapped so that the short fiber webs (a) sides are in contact with each other, and further made into a fiber structure entangled and integrated by the needle punch method, The method according to claim 7 or 8, wherein the steps (2) to (4) are performed. In the step of (1), after producing a fiber structure that is piled up so as to be woven fabric (b) / short fiber web (a) / woven fabric (b) and entangled and integrated by the needle punch method, (2 The method of manufacturing a leather-like sheet according to claim 8, wherein the steps (4) to (4) are performed. The method for producing a leather-like sheet according to any one of claims 7 to 10, wherein the step (2) is performed using water or an aqueous alkali solution. One component of 1-8 decitex composite fiber capable of generating ultrafine fibers having an average fiber fineness of 0.001-0.5 dtex is polyethylene terephthalate or a polyester copolymer mainly containing ethylene terephthalate units, polylactic acid, It is a water-soluble thermoplastic polyvinyl alcohol-type resin, The manufacturing method of the leather-like sheet-like material in any one of Claims 7-11 characterized by the above-mentioned. The leather-like product according to any one of claims 6 to 12, wherein after the step (1), the step is split into two or more perpendicular to the thickness direction, and then the steps (2) to (4) are performed. Manufacturing method of sheet-like material. After the step (2), the leather is split into two or more pieces perpendicular to the thickness direction, and then the steps (3) to (4) are performed. Manufacturing method of sheet-like material.