JP2006274456A - Leather-like sheet-shaped product and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a leather-like sheet-shaped product excellent in biodegradability and durability and a method for producing the same. <P>SOLUTION: The leather-like sheet-shaped product comprises a super fine nonwoven fabric (A) containing at least a biodegradable aliphatic polyester fiber and substantially constituted of a fiber material in which filaments having 0.0001-0.5 dtex monofilament fineness are mutually interlaced. The leather-like sheet-shaped product is produced by interlacing the filaments able to generate the superfine biodegradable aliphatic polyester fiber having at least 0.0001-0.5 dtex by needle punching, generating the superfine fiber and bringing the same to the super fine fiber nonwoven fabric (A), subsequently overlapping the same with a woven fabric or a knit fabric (B), interlacing them by treating with a high speed fluid under at least 10 MPa pressure and dying the same. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a leather-like sheet having biodegradability and durability and a method for producing the same.

  The leather-like sheet-like material called “artificial leather” or “synthetic leather” that has been put on the market is mainly composed of ultrafine fibers made of aromatic polyester such as polyethylene terephthalate and polyamide such as nylon 6 and a polymer elastic body. Compared to natural leather, it is superior in lightness and easy care, and is widely used for various purposes.

  In general, as a method for producing such artificial leather or synthetic leather, after impregnating a fiber sheet material with a polymer elastic body solution such as polyurethane, the fiber sheet material is immersed in water or an organic solvent aqueous solution. Thus, a method of wet coagulating the polymer elastic body is employed (for example, see Patent Document 1).

  In recent years, awareness of global environmental conservation has increased, and in order to reduce the environmental impact at the time of disposal, materials with a little environmental impact have been demanded.

  For example, sea island type composite fiber staples capable of generating ultrafine fibers are entangled by needle punch method, and then the sea components are dissolved to form ultrafine fiber sheet-like material, which is subjected to high-speed fluid treatment, polyurethane, etc. There is a method of obtaining a leather-like sheet-like material without using a polymer elastic body (see, for example, Patent Document 2). With this method, a leather-like sheet consisting only of fibers is obtained without using polyurethane, so it is easier to recycle than a leather-like sheet using conventional polyurethane, but it is discarded without being recycled. There was a problem that what was landfilled at that time remained undecomposed in the soil.

On the other hand, in order to reduce the environmental load at the time of disposal, a leather-like sheet-like material made of polyurethane using polyester diol has been proposed as an ultrafine fiber of aliphatic polyester having biodegradability and a polymer elastic body ( For example, see Patent Document 3). However, the leather-like sheet produced by this method has a problem that its strength tends to decrease due to hydrolysis of polyurethane, and its durability is poor.
JP 2003-89985 A JP 2005-54345 A JP 2001-214380 A

  An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a leather-like sheet material excellent in biodegradability and durability and a method for producing the same.

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

  That is, one embodiment of the leather-like sheet-like material of the present invention is substantially composed of fibers having a single fiber fineness of 0.0001 to 0.5 dtex, which include at least biodegradable aliphatic polyester fibers. It consists of the nonwoven fabric comprised from a fiber material.

  One embodiment of the method for producing a leather-like sheet according to the present invention is to entangle a 0.0001-0.5 dtex fiber capable of generating at least biodegradable aliphatic polyester ultrafine fiber by a needle punch. After that, ultrafine fibers are generated to form an ultrafine fiber non-woven fabric (A), and then superposed on the woven fabric or knitted fabric (B) and subjected to high-speed fluid treatment at a pressure of at least 10 MPa, and then dyed. It is characterized by that.

  In another embodiment of the method for producing a leather-like sheet of the present invention, fibers capable of generating an aliphatic polyester ultrafine fiber having biodegradability of at least 0.0001 to 0.5 dtex are entangled by a needle punch. Later, superficially woven or knitted fabric (B) is superposed to generate ultrafine fibers by high-speed fluid treatment at a pressure of at least 10 MPa to form ultrafine fiber non-woven fabric (A), entangled, and then dyed It is.

  According to the present invention, it is possible to provide a leather-like sheet-like material excellent in biodegradability without substantially using a polymer elastic body such as polyurethane as a fiber binder, and clothing, bags, shoes, It can be suitably used for sheets, materials and the like.

  The leather-like sheet-like material of the present invention is composed of a non-woven fabric containing at least biodegradable aliphatic polyester ultra-fine fibers, thereby providing biodegradability and texture and surface feeling like natural leather. It becomes possible to obtain the leather-like sheet | seat which has.

  The term “biodegradable” as used herein means that it can be decomposed by microorganisms in a natural environment such as natural fibers such as wool, hair and cellulose fibers. Polylactic acid fibers and the like are also biodegradable because they are degraded by microorganisms after hydrolysis.

  The ultrafine fiber nonwoven fabric (A) used in the present invention is made of a fiber having at least a biodegradable aliphatic polyester fiber and having a single fiber fineness of 0.0001 to 0.5 dtex.

  The single fiber fineness is preferably 0.001 to 0.3 dtex, more preferably 0.005 to 0.15 dtex. If it is less than 0.0001 dtex, the strength decreases, which is not preferable. On the other hand, if it exceeds 0.5 dtex, the texture becomes stiff, and entanglement becomes insufficient, resulting in problems such as deterioration in surface quality and wear resistance. In addition, as long as the effect of this invention is not impaired, the fiber of the single fiber fineness exceeding said range may be contained.

  Although it does not specifically limit as aliphatic polyester which has biodegradability, For example, polylactic acid, polycaprolactone, polyglycolic acid, polybutylene succinate etc. can be used. Moreover, if the single fiber fineness is within the above range, other fibers can be used in combination as long as the effects of the present invention are not impaired.

  Moreover, although it does not specifically limit as fiber length, since an ultrafine fiber nonwoven fabric (A) is used for the surface of a leather-like sheet, when using a short fiber, fiber length is 1-10 cm mainly. Preferably, it is 1.5 to 8 cm, more preferably 2 to 6 cm. If fibers exceeding 10 cm are contained, the surface quality deteriorates, which is not preferable. Moreover, it is not preferable that the fiber length is less than 1 cm because the fiber is easily entangled and the strength and durability of the sheet are lowered. In addition, in the range which does not impair the effect of this invention, the fiber of the fiber length outside this range may be contained.

  On the other hand, as will be described later, when three or more layers of ultrafine fiber nonwoven fabric (A) / woven fabric or knitted fabric (B) / short fiber nonwoven fabric (C) are stacked, the short fiber nonwoven fabric (C) used on the back surface has an inhibition of flexibility. It is preferable that the fiber length is 0.1 to 1 cm in terms of few points.

  The method for producing so-called ultrafine fibers whose single fiber fineness is in the above-mentioned range is not particularly limited, and it is produced as a nonwoven fabric such as a spunbond method, a melt blow method, an electrospinning method, a flash spinning method, etc. in addition to a normal filament spinning method. It may be a system to do. In addition, as a means of obtaining ultrafine fibers, a method of directly spinning ultrafine fibers, spinning fibers that are usually fine and capable of generating ultrafine fibers (hereinafter referred to as ultrafine fiber-generating fibers), and then producing ultrafine fibers A method of generating fibers may also be used.

  In the present invention, these ultrafine fibers can be entangled with each other to improve wear resistance. Most of the conventional leather-like sheets made of ultrafine fibers have a structure in which ultrafine fiber bundles are entangled. However, in the present invention, the expected wear resistance effect is obtained by entanglement of ultrafine fiber bundles. I can't. That is, wear resistance can be improved by forming a structure in which ultrafine fibers are entangled with each other. In addition, the ultrafine fiber bundle may be contained in the range which does not impair the effect of this invention.

  Further, a leather-like sheet-like material generally called synthetic leather or artificial leather is obtained by adding a polymer elastic body such as polyurethane to a nonwoven fabric or a fiber material in which a nonwoven fabric and a nonwoven fabric are integrated. Polyester elastomer made of polyethylene propyl alcohol, polyurethane using polypropylene adipate glycol and polyurethane using polyester diol, polybutylene, polybutylene terephthalate and polycaprolactone diol, etc. is degradable in soil or compost, The polymer elastic body made of the polyurethane is likely to be reduced in strength by hydrolysis, and the durability and surface quality are likely to be reduced.

  In the present invention, in order to prevent deterioration of durability and surface quality due to hydrolysis, it is preferable that the substrate is substantially made of a fiber material. Here, “consisting essentially of a fiber material” means that the macromolecular elastic body is not substantially observed when the surface or cross section is observed with an SEM, a microscope or the like.

  In addition, for example, functional agents such as fine particles, dyes, softeners, softeners, texture modifiers, anti-pilling agents, antibacterial agents, deodorants, water repellents, light proofing agents, and antifungal agents impair the effects of the present invention. It may be included within a range. In addition, entanglement of the ultrafine fiber nonwoven fabric (A) and the woven fabric or knitted fabric (B), which are constituent elements in the present invention, can improve the tensile strength and tear strength, impart drapeability, and the like. preferable. The woven fabric or the knitted fabric (B) may be a single woven fabric or a knitted fabric, or may be both a woven fabric and a knitted fabric. The structure of the woven or knitted fabric (B) is not particularly limited, and various structures can be used depending on the purpose. For the purpose of improving the tensile strength and tear strength, it is preferable to use a woven fabric. Examples of the woven structure include plain weave and twill weave. In addition, for the purpose of improving drape, it is preferable to use a knitted fabric. Examples of the knitted structure include a circular knitting and a flat knitting. On the other hand, a double knitting is more preferable in terms of handling. Moreover, it is preferable that it is warp knitting from the point of productivity or ease of handling, for example, a tricot is mentioned.

  Moreover, it is preferable that said textile fabric or knitted fabric (B) contains the fiber which has biodegradability. The fiber having biodegradability is not particularly limited, and for example, cellulose fibers such as aliphatic polyester and cotton, and animal hair such as wool can be used. Among these biodegradable fibers, it is preferable to use an aliphatic polyester fiber because an arbitrary fineness can be easily obtained. Moreover, if it is a range which does not impair the effect of this invention, fibers other than a biodegradable fiber can be used together.

  The fineness of the fiber used for the woven fabric or the knitted fabric (B) is preferably 100 dtex or less, more preferably 85 dtex or less, and even more preferably 50 dtex or less. If it exceeds 100 dtex, it is not preferable because the drapeability deteriorates when it is made into a knitted fabric. The lower limit is not particularly limited, and the thinner the film, the better the drape. However, 10 dtex or more is preferable from the viewpoint of excellent handleability. The single fiber fineness is preferably 0.1 to 3 dtex. Exceeding 3 dtex is not preferable because the drapeability is lowered. Further, the lower limit is not particularly limited, but if it is less than 0.1 dtex, the fiber strength is lowered, so that the single yarn is easily broken, and the drapability tends to deteriorate, which is not preferable.

Although the basis weight of the woven or knitted fabric (B) can be appropriately adjusted fit basis weight of the leather-like sheet, it is preferable that in the case of apparel applications is 30 to 150 g / ^{m 2,} with 40 to 100 g / ^{m 2} More preferably. If it is less than 30 g / m ² , the form is unstable, the handleability is poor, and it becomes difficult to obtain improved strength and draping due to entanglement with the ultrafine fiber nonwoven fabric. Moreover, since it exists in the tendency for a softness | flexibility to fall when it exceeds 150 g / m < ² >, it is unpreferable. The woven density and knitting density are not particularly limited, but in consideration of the addition of entanglement with single fiber nonwoven fabric, strength, and drapeability, the woven fabric usually has a warp yarn density of 50 to 180 yarns / An inch, a weft density of 30 to 130 yarns / inch, and a knitted fabric of 20 to 60 gauge can be used.

  Further, when there is a product surface and a back surface, and the back surface also requires quality, a short fiber nonwoven fabric mainly containing at least biodegradable aliphatic polyester having a fiber length of 0.1 to 1.1 cm. (C) is further entangled, and it is preferable to have a three-layer structure in which the surface is an ultrafine fiber nonwoven fabric (A), the intermediate layer is a woven fabric or a knitted fabric (B), and the back surface is a short fiber nonwoven fabric (C). In order not to increase the overall basis weight more than necessary, the short fiber nonwoven fabric (C) preferably has a low basis weight, and is preferably manufactured by a papermaking method that can easily reduce the basis weight.

  Moreover, in order to make the back surface quality and flexibility compatible, the single fiber fineness of the short fiber nonwoven fabric (C) is preferably 0.001 to 0.5 dtex, and 0.01 to 0.3 dtex. More preferably. If the single fiber fineness is less than 0.001 decidex, it is difficult to obtain a non-woven fabric having a uniform basis weight by the paper making method, and if it exceeds 0.5 decitex, the quality of the back surface is lowered and it is difficult to obtain a high-class feeling. .

  In the total weight of the leather-like sheet comprising the ultrafine fiber nonwoven fabric (A) and the woven fabric or knitted fabric (B), or the ultrafine fiber nonwoven fabric (A), the woven fabric or knitted fabric (B), and the short fiber nonwoven fabric (C), the ultrafine fiber The nonwoven fabric (A) is preferably 40 to 80% by weight, and more preferably 60 to 80% by weight. When the ultrafine fiber nonwoven fabric (A) is less than 40% by weight, the texture is close to that of a brushed woven fabric or knitted fabric, and it is difficult to obtain a high-quality feeling as a leather-like sheet material, and when it exceeds 80% by weight, the woven fabric or knitted fabric (B). It becomes difficult to sufficiently obtain the effect of adding strength and drapeability by entanglement.

  In addition, in order to impart biodegradability to the leather-like sheet material, a fiber having biodegradability in the composition ratio of the ultrafine fiber nonwoven fabric (A), the woven fabric or the knitted fabric (B), or the short fiber nonwoven fabric (C). It is preferable to contain 40% by weight or more because the shape easily collapses due to physical action after the biodegradable fiber is decomposed. Furthermore, it is more preferable that the biodegradable fiber is contained in an amount of 60% by weight or more, and more preferably 80% by weight or more. It may be 100% by weight. Further, in each constituent ratio of the ultrafine fiber nonwoven fabric (A), the woven fabric or the knitted fabric (B), or the short fiber nonwoven fabric (C) contained in the leather-like sheet material, 40% by weight or more of biodegradable fibers are included. Preferably, each contains 60% by weight or more, more preferably each contains 80% by weight or more, and most preferably each contains 100% by weight. When the composition ratio of the biodegradable fiber is less than 40% by weight, the biodegradable fiber is not easily disintegrated after being decomposed, and the original shape is retained.

  The biodegradable aliphatic polyester constituting the leather-like sheet of the present invention preferably has a melting point of 120 ° C. or higher. If the melting point is less than 120 ° C., if the dyeing temperature is set to 120 ° C. or higher in order to improve the dyeing property, the fibers are fused with each other, and the texture becomes harder or the surface raised quality deteriorates.

  Among the aliphatic polyesters, polylactic acid is preferable because it has a high melting point of 170 ° C. and the raw material is derived from natural products. Here, the melting point is a melting point peak temperature obtained by differential scanning calorimetry (DSC measurement).

  The polylactic acid is more preferably composed mainly of L-lactic acid and / or D-lactic acid. The molecular weight of polylactic acid is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 200,000 or more. A molecular weight of less than 50,000 is not preferable because problems such as a decrease in spinnability, fiber properties such as strength, and a decrease in product physical properties occur.

  In addition, hydrolysis resistance can be improved by blocking the carboxyl terminal group of polylactic acid with a terminal blocking agent such as a carbodiimide compound, an epoxy compound, an oxazoline compound, an aziridine compound, a diol compound, or a long-chain alcohol compound. ,preferable.

The basis weight of the leather-like sheet of the present invention is preferably 100 to 350 g / m ² , more preferably 120 to 300 g / m ² , and further preferably 140 to 250 g / m ² . If it is less than 100 g / m ² , the strength is lowered, the woven fabric or the knitted fabric (B) can be easily seen on the surface, and the quality is lowered. When it exceeds 350 g / m ² , it is difficult to entangle the ultrafine fibers with each other, and durability is lowered, which is not preferable. The apparent fiber density is preferably 0.27 to 0.50 g / cm ³ , more preferably 0.28 to 0.45 g / cm ³ , and still more preferably 0.29 to 0.40 g / cm ³ . is there. If it is less than 0.27 g / cm ³ , the abrasion resistance and durability are particularly lowered, which is not preferable. On the other hand, if it exceeds 0.50 g / cm ³ , flexibility is lowered, which is not preferable.

  In addition, the leather-like sheet-like material of the present invention has at least one surface raised in order to obtain an excellent surface appearance like natural leather, and gives a smooth touch of suede and nubuck and an excellent lighting effect. Is preferred.

  However, since the leather-like sheet-like material having napping shows a tendency that its abrasion resistance tends to decrease, the leather-like sheet-like material of the present invention contains fine particles for the purpose of improving the abrasion resistance. Is preferred. 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 these 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. When the thickness is less than 0.001 μm, it is difficult to obtain the expected effect, and when it exceeds 30 μm, the washing durability is lowered due to dropping. For the average particle diameter, a measurement method suitable for each material and size, for example, a BET method, a laser method, or a Coulter method is employed.

  The amount of these fine particles can be appropriately adjusted within a range in which the effect of the present invention can be exerted, but is preferably 0.01 to 8% by weight, more preferably 0.02 to 5% by weight, still more preferably. Is 0.05 to 2% by weight. If it is 0.01 weight% or more, the improvement effect of abrasion resistance can be exhibited notably, and the effect tends to become large, so that the amount is increased. However, if it exceeds 8%, the texture becomes hard, which is not preferable.

  It is more preferable to use a mixture of fine particles having different average particle diameters because the packing density of the fine particles with respect to the fibers is increased and the wear resistance is further improved.

  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. It does not specifically limit as a softening agent, What is generally used for a textile fabric, a knitted fabric, etc. is suitably selected according to a fiber kind. For example, in the dyeing note 23rd edition (Issue Color Co., Ltd., issued on August 31, 2002), it is possible to appropriately select the materials described in the names of the texture finish and the soft finish, Of these, silicone emulsions are preferable in view of excellent flexibility effects, and silicone emulsions modified with amino or epoxy are more preferable. When these softeners are included, the wear resistance tends to decrease. Therefore, the amount of the softener and the amount of the fine particles can be appropriately adjusted while balancing the target texture and the wear resistance. preferable. Therefore, the amount is not particularly limited. However, if the amount is too small, the effect cannot be exerted. If the amount is too large, there is a sticky feeling, and the amount is usually in the range of 0.01 to 10% by weight.

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

  First, a method for producing the ultrafine fiber nonwoven fabric (A) in the leather-like sheet of the present invention will be described. The production method of the ultrafine fiber having a single fiber fineness constituting the ultrafine fiber nonwoven fabric (A) in the range of 0.0001 to 0.5 dtex is not particularly limited. For example, a method of directly spinning the ultrafine fiber, a fiber having a normal fineness There is a method of spinning fibers that can generate ultrafine fibers (ultrafine fiber-generating fibers) and then generating ultrafine fibers. 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 form a sea-island state. The method for obtaining this fiber is not particularly limited. For example, (1) 2 A method of blending and spinning a polymer of two or more components in a chip state, (2) a method of kneading a polymer of two or more components in advance to form a chip and then spinning, and (3) 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 a machine pack, and a method of using a die such as Japanese Patent Publication Nos. 44-18369 and 54-116417. In the present invention, any method can be used to satisfactorily produce, but the method (4) is preferably employed because the selection of the polymer is easy.

  In the method (4), 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, more preferably 0.4 to 0.97, and 0.5 to 0.8. Further preferred. If it is less than 0.3, the removal rate of sea components increases, which is not preferable in terms of cost. On the other hand, if it exceeds 0.99, the island components are likely to merge with each other, which is not preferable in terms of spinning stability.

  When ultrafine fibers are obtained from sea-island type fibers, the island components become the intended ultrafine fibers. The polymer of the aliphatic polyester having biodegradability used for the island component is not particularly limited, and can be appropriately selected and used as long as it can be fiberized. -Polylactic acid mainly composed of lactic acid and / or D-lactic acid. 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 sea component polymer. 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, polyvinyl alcohol, polyethylene glycol or copolymers thereof, JP-A 61-29120, JP-A 63-165516, Hot water-soluble polymers such as hot water-soluble polyesters described in JP-A-63-159520, JP-A-1-272820, etc., 5-sodium sulfoisophthalic acid, sodium dodecylbenzenesulfonate, bisphenol A compound, Polyester obtained by copolymerization of isophthalic acid, adipic acid, dodecadioic acid, cyclohexyl carboxylic acid, or the like can be used. Polystyrene is preferable from the viewpoint of spinning stability, but a hot water-soluble polymer and a copolyester having a sulfone group are preferable because they can be easily removed without using an organic solvent. 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 preferable combination is to use polylactic acid mainly composed of L-lactic acid and / or D-lactic acid as an island component and a copolymer polyester having polystyrene or sulfone group as a 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 fiber, compounding 2 or more components in a nozzle | cap | die.

  Next, the obtained short fibers are made into a non-woven fabric. As the method, a dry method in which a web is obtained using a card, a cross wrapper, or a random web, or a wet method such as a paper making method can be employed. In the present invention, a dry method combining a needle punching method and a high-speed fluid treatment method is preferred in that the structure of the leather-like sheet of the present invention can be easily achieved. The basis weight of the leather-like sheet-like material can be adjusted as appropriate depending on the amount of fibers used for making the nonwoven fabric and the basis weight of the woven or knitted fabric (B) to be intertwined.

Next, a method for producing by a dry method preferably employed in the present invention will be described, but the present invention is not limited thereto. First, a web obtained by using a card, a cross wrapper, or the like has a fiber apparent density of preferably 0.12 to 0.30 g / cm ³ , more preferably 0.15 to 0.25 g / cm ³ by needle punching. And When it is less than 0.12 g / cm ³ , the entanglement is insufficient, and it is difficult to obtain desired physical properties such as tensile strength, tear strength, and wear resistance. The upper limit is not particularly defined, but if it exceeds 0.30 g / cm ³ , problems such as breakage of the needle needle and remaining of the needle hole are not preferable.

  Moreover, when performing needle punching, it is preferable that the single fiber fineness of an ultrafine fiber generation type | mold fiber is 1-10 dtex, 2-8 dtex is more preferable, and 2-6 dtex is further more preferable. When the single fiber fineness is less than 1 dtex or exceeds 10 dtex, the entanglement by the needle punch becomes insufficient, and it becomes difficult to obtain an ultra-fine short fiber nonwoven fabric with good physical properties.

The needle punch in the present invention is not a role as temporary fixing for obtaining simple process passability, and it is preferable to sufficiently entangle the fibers. Therefore, the driving density is preferably 100 / cm ² or more, more preferably 500 / cm ² or more, and still more preferably 1000 / cm ² or more.

  The nonwoven fabric thus obtained is preferably shrunk by dry heat and / or wet heat, and further densified.

  Next, it is preferable that the ultrafine fibers are entangled by performing a high-speed fluid treatment after the ultrafine treatment, simultaneously with the ultrafine treatment, or at the same time as the ultrafine treatment. Although it is possible to combine high-speed fluid treatment with ultrafine treatment, it is preferable to perform high-speed fluid treatment even after at least most of the ultrafine treatment is completed, in order to further promote the entanglement between ultrafine fibers, It is preferable to perform high-speed fluid processing after performing ultrafine processing.

  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 miniaturization by applying a physical stimulus, for example, a method of applying pressure between rollers in addition to a method of giving an impact such as the above needle punch method or water jet punch method, Examples include a method of performing ultrasonic treatment.

  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.

  Moreover, since it is preferable on the working environment without using a solvent, it is one of the preferable aspects of this invention to use a hot water soluble polymer for an island component.

  In addition, 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 water jet punch, a sea island type fiber made of water-soluble sea components is used. , A method of removing and entanglement by water jet punch, using two or more sea-island fibers with different alkali decomposition rates, decomposing easily soluble components through an alkali treatment liquid, and finally removing and entanglement by water jet punch The method of performing a process etc. are mentioned.

  In this way, the ultrafine fiber nonwoven fabric (A) to be entangled with the woven fabric or the knitted fabric (B) can be produced.

  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 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. In particular, when the diameter exceeds 0.15 mm, the entanglement property between the ultrafine fibers is lowered, the surface becomes easy to peach, and the surface smoothness is also not preferred. Therefore, it is preferable that the nozzle hole diameter is small, but if it is less than 0.06 mm, nozzle clogging is likely to occur.

  Further, for the purpose of achieving uniform entanglement in the thickness direction and / or improving the smoothness of the nonwoven fabric surface, the treatment is preferably repeated a number of times. The water flow 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 treat at least once with a pressure of 10 MPa or more in order to obtain a desired physical property such as tensile strength, tear strength, and wear resistance at a high degree by entanglement of ultrafine fibers. Preferably there is. 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, and preferably 40 MPa. 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 Thus, it is possible to obtain an ultra-fine short fiber nonwoven fabric in which ultra-fine fibers are entangled to such an extent that the surface properties such as abrasion resistance can be improved. In addition, you may perform a water immersion process before performing a water jet punch process. Furthermore, in order to improve the surface quality, a method of relatively moving the nozzle head and the nonwoven fabric, or a method of inserting a wire mesh between the nonwoven fabric and the nozzle after the entanglement and performing a watering treatment can be performed. Further, before performing the high-speed fluid processing, it is preferable to perform split processing on two or more sheets perpendicular to the thickness direction.

  Moreover, the manufacturing method of a textile fabric or a knitted fabric (B) is not specifically limited, According to the structure | tissue which requires, the loom and knitting machine suitable for it can be used. Examples of the loom include an air jet loom, a water jet loom, and a fly shuttle loom.

  Examples of the knitting machine include a flat knitting machine, a circular knitting machine, a tricot machine, and a Russell machine. As a method of entanglement of the woven fabric or knitted fabric (B) thus obtained with the nonwoven fabric, various methods other than the entanglement method using means such as needle punch and high-speed fluid treatment, the adhesion method, and the like can be used. Or it can employ | adopt in combination. Among these, the method by entanglement is preferable in that it has excellent drape properties, and it is more preferable to use high-speed fluid treatment in that it can be entangled without damaging the woven fabric or the knitted fabric (B).

  Furthermore, when intertwining another short fiber nonwoven fabric (C), the manufacturing method of this nonwoven fabric is not specifically limited, It can use suitably according to various uses. For example, it is possible to obtain excellent wear resistance on both sides by overlapping and intertwining the above-described ultrafine fiber nonwoven fabric (A). Moreover, in order to attach importance to low basis weight and flexibility, it may be manufactured by a papermaking method.

  In addition, it is preferable to adjust the entanglement degree of the ultrafine fiber nonwoven fabric (A) as appropriate by means of laminating. That is, when laminating the ultrafine fiber nonwoven fabric (A) and the woven fabric or knitted fabric (B) by entanglement, the degree of entanglement of the ultrafine fiber nonwoven fabric (A) itself is kept low, and it is overlapped with the woven fabric or knitted fabric (B). Entangling is preferable in terms of improving peel strength and wear resistance. For example, it is preferable that the ultrafine fiber nonwoven fabric (A) is mainly in a state where the ultrafine fiber bundles are entangled, that is, the above-described method, preferably a nonwoven fabric that is ultrafine after needle punching, and the woven fabric or knitted fabric (B) is overlapped on this Intertwined with a water jet punch. On the other hand, when the ultrafine fiber nonwoven fabric (A) and the woven fabric or knitted fabric (B) are overlapped by bonding, it is preferable from the viewpoint of wear resistance that the ultrafine fiber nonwoven fabric (A) itself has a high entanglement strength. For example, the ultrafine fiber nonwoven fabric (A) is bonded after the ultrafine fibers are mainly intertwined with each other. When the ultrafine fiber nonwoven fabric (A) and the woven fabric or knitted fabric (B) are entangled using a high-speed fluid, after the ultrafine fiber nonwoven fabric (A) and the woven fabric or knitted fabric (B) are overlapped, from the ultrafine fiber nonwoven fabric (A) side It is preferable to process.

  When the short fiber nonwoven fabric (C) is produced by a papermaking method, a web prepared by a papermaking method prepared in advance (hereinafter referred to as a papermaking web) and a fabric or knitted fabric (B) are entangled with each other, the fabric or A method of forming a papermaking web all at once on the knitted fabric (B) can be adopted, and if possible, a method of forming a laminated sheet at once is preferable in terms of cost. In particular, when the paper web is entangled, it becomes difficult to uniformly entangle the fine web nonwoven fabric (A) and the woven fabric or knitted fabric (B) by increasing the density. Alternatively, after the knitted fabric (B) is entangled, it is preferable to entangle the ultrafine fiber nonwoven fabric (A). Entanglementing them can be expected to improve strength, add drape, and improve back surface quality. Thereafter, high-speed fluid processing is performed.

  The production method of the papermaking web is not particularly limited. For example, fibers having a fiber length of 0.1 to 1 cm made of an aliphatic polyester having biodegradability such as polylactic acid mainly composed of L-lactic acid and / or D-lactic acid are used. It can be produced by beating in water containing a water-soluble resin, etc., and making a dispersion on a wire mesh or the like by dispersing it at a concentration of about 0.0001 to 0.1%. When the papermaking web is formed on the woven fabric or the knitted fabric (B) at once, the web can be produced by placing the woven fabric or the knitted fabric (B) on the wire mesh and then making the paper.

  When obtaining a leather-like sheet-like material having suede-like or nubuck-like napping, napping treatment with sandpaper or a brush is preferably performed. Such napping treatment can be performed before or after dyeing, which will be described later, or before and after dyeing. However, since the coloring of sandpaper and brushes occurs when dyeing is performed, it is preferably performed before dyeing. Moreover, although it can also carry out after application | coating of the microparticles | fine-particles mentioned later, since it shows the tendency for napping to come out, it is preferable after performing microparticles | fine-particles provision.

  The laminated sheet thus obtained is then dyed. The method is not particularly limited, and the dyeing machine used may be any of a liquid dyeing machine, a thermosol dyeing machine, a high-pressure jigger dyeing machine, etc., but the texture of the obtained leather-like sheet is excellent. It is preferable to dye using a liquid dyeing machine.

  In the case of dyeing, disperse dyes can be used as in the case of polyethylene terephthalate fibers. In addition, for example, when polylactic acid containing L-lactic acid and / or D-lactic acid as a main component is used, dyeing at a high temperature causes a decrease in strength due to hydrolysis, so the dyeing temperature is 110 ° C. to 120 ° C. It is preferable. If it is less than 110 ° C, the dyeability is poor.

  Moreover, in leather-like sheet-like materials mainly composed of fiber materials, after dyeing for the purpose of improving the smoothness of the surface and / or obtaining a semi-silvery surface, it is compressed 0.1 to 0.8 times You can also

  In the present invention, it is preferable to apply fine particles because the wear resistance can be improved. By applying the fine particles, it is possible to obtain an effect of giving a feel such as a dry feeling or a squeaky feeling. The means for applying the fine particles is not particularly limited and can be appropriately selected from a pad method, a method using a liquid dyeing machine and a jigger dyeing machine, and a spraying method. The same applies to the case where a softening agent is applied. From the viewpoint of cost, it is preferable to apply the softening agent simultaneously with the fine particles.

  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) Single fiber fineness The composite fiber fineness was measured according to JIS L1013-8.3.1A method (2001), and the value calculated from the number of islands and the weight ratio was defined as the single fiber fineness.
(2) Fiber length It measured according to JIS L1015-8.4.1C method (2001).
(3) Per unit area It measured according to JIS L1096-8.4.1 (2001).
(4) Apparent density It was measured according to JIS L1096-8.10.1 (2001).
(5) Biodegradability test A sample having a length of 30 cm and a width of 30 cm was prepared and embedded in a compost at 60 ° C. at a depth of 10 cm, and the change in shape was examined. If the shape was broken, it was judged to have biodegradability.

Example 1
Polystyrene (Asahi Kasei: Stylon) as the sea component, polylactic acid having a melting point of 168 ° C., a weight average molecular weight of 120,000, and an L-form ratio of 98 mol% as the island component, and a sea-island type compound spinneret with 36 islands, An undrawn yarn having a sea / island ratio of 55/45% by weight was wound up. The spinning temperature was 260 ° C., and the take-up speed was 1200 m / min.

  Subsequently, the undrawn yarn was drawn at a drawing temperature of 80 ° C. and a heat setting temperature of 120 ° C. using a normal hot roll-hot roll drawing machine. The draw ratio was adjusted so that the elongation of the drawn yarn was 35%. This stretched yarn bundle is crimped by about 15 threads / 2.54 cm with a crimper, then cut to a length of 51 mm, and the single fiber fineness of the composite fiber is 3 dtex. A sea-island composite fiber staple was obtained.

A web was prepared by passing the staple through a card and a cross wrapper. Subsequently, it was processed with a 1 barb-type needle punch at a driving density of 2000 pieces / cm ² to obtain a composite short fiber nonwoven fabric having an apparent fiber density of 0.22 g / cm ³ .

  Next, it is immersed in an aqueous solution of polyvinyl alcohol (PVA) 12% having a polymerization degree of 500 and a saponification degree of 88% heated to about 95 ° C. so as to have an adhesion amount of 25% with respect to the nonwoven fabric weight in terms of solid content. Simultaneously with the impregnation, a shrinkage treatment was carried out for 2 minutes, followed by drying at 100 ° C. to remove moisture. The obtained sheet was treated with trichrene at about 30 ° C. until the polystyrene was completely removed, and ultrafine fibers having a single fiber fineness of about 0.046 dtex were obtained. Subsequently, using a standard type wood splitting machine manufactured by Murota Manufacturing Co., Ltd., splitting was performed in two perpendicular to the thickness direction to obtain an ultrafine fiber nonwoven fabric (A).

Also, using poly-L lactic acid having a melting point of 168 ° C., a weight average molecular weight of 120,000, and an L-form ratio of 98 mol%, it was introduced into a melt spinning pack at a spinning temperature of 220 ° C. and taken at 3000 m / min to obtain an undrawn yarn. Obtained. Next, the undrawn yarn is drawn 1.2 times at a drawing temperature of 90 ° C. and a heat setting temperature of 120 ° C. using a hot roll-hot roll drawing machine to obtain a drawn yarn consisting of 56 dtex and 12 filaments, By using the drawn yarn, a plain woven fabric (B) having a weave density of 136 / inch in length, 96 in width / inch, and a basis weight of 77 g / m ² was produced.

Also, by using a polylactic acid having a melting point of 168 ° C., a weight average molecular weight of 120,000, and an L-form ratio of 98 mol%, a polylactic acid ultrafine fiber having a single fiber of 0.2 dtex and a fiber length of 0.5 cm is obtained by a direct spinning method. A short fiber nonwoven fabric (C) of 20 g / m ² was prepared by papermaking.

  Next, the plain woven fabric (B) and the short fiber nonwoven fabric (C) are overlapped, and the diameter of the hole is 0.1 mm from the surface of the short fiber nonwoven fabric (C). It processed with the pressure of 7 MPa at the processing rate of / min, and obtained the laminated body of the textile fabric (B) and the short fiber nonwoven fabric (C). Next, the laminate and the ultrafine fiber nonwoven fabric (A) are overlapped, and a water jet punch composed of a nozzle head having a pore diameter of 0.1 mm and an interval of 0.6 mm from the ultrafine fiber nonwoven fabric (A) side is 7 m / min. The treatment was carried out 3 times at 17 MPa at a treatment speed, and then the treatment was carried out 3 times at 17 MPa from the short fiber nonwoven fabric (C) side, and entanglement was carried out together with the removal of PVA.

  Next, napping of the ultrafine fiber nonwoven fabric (A) is performed with sandpaper, and “Sumikaron Blue S-BBL200” (manufactured by Sumika Chemtex Co., Ltd.) is used at 120 ° C. with a liquid dyeing machine. And stained at 45 minutes. The obtained non-woven fabric was made of a softener (amino-modified silicone emulsion “Silicoran AN980SF” manufactured by one company) and fine particles (colloidal silica “Snowtex 20L” manufactured by Nissan Chemical Industries, Ltd., average particle size 0.04 to 0.05 μm. : BET method) soaked in an aqueous solution containing 2.0% colloidal silica, dried at 100 ° C. while brushing, and composed of ultrafine fiber nonwoven fabric (A) and plain fabric (B) A leather-like sheet was obtained.

  The leather-like sheet-like material thus obtained had a dense structure in which ultrafine fibers were entangled with each other, and the ultrafine fibers and the woven fabric were entangled, and had a suede-like appearance. The composition ratio of the ultrafine fiber nonwoven fabric (A) in the total weight of the leather-like sheet was 50% by weight. The composition ratio of the biodegradable fiber was 100% by weight for the ultrafine fiber nonwoven fabric (A), the plain fabric (B), and the short fiber nonwoven fabric (C).

  The leather-like sheet-like material has sufficient durability for use by entanglement of the woven fabric, and its biodegradability was evaluated. As a result, the shape was broken and the biodegradability was excellent. The evaluation results are shown in Table 1.

Example 2
Polystyrene (Asahi Kasei: Stylon) is used as the sea component, polyethylene terephthalate is used as the island component, the number of islands is 36, the sea / island ratio is 55/45% by weight, the single fiber fineness of the composite fiber is 3 dtex, and the number of crimps is 15 mountains / 2. A polystyrene / polyethylene terephthalate sea-island composite fiber staple having a length of 54 cm and a length of 51 mm was obtained.

  A non-woven fabric was prepared in the same manner as in Example 1 except that the staple and the staple of polystyrene / polylactic acid similar to that in Example 1 were mixed at a mixing ratio = 50/50% by weight. A ′) was obtained.

Next, except that the weft of the plain woven fabric (B) of Example 1 was changed to 56 dtex, 12 filament polyethylene terephthalate fiber, a plain woven fabric was prepared with the same woven density, and the woven density was 136 warps / inch, A plain fabric (B ′) having a width of 96 pieces / inch and a basis weight of 79 g / m ² was produced.

Next, superfine fiber nonwoven fabric (A ′) and plain woven fabric (B ′) are overlapped, with a water jet punch composed of nozzle heads with an interval of 0.6 mm, with a pore diameter of 0.1 mm from the ultrafine fiber nonwoven fabric (A) side, The treatment was performed 3 times at 17 MPa at a treatment speed of 7 m / min, and then 3 times at 17 MPa from the plain woven fabric (B) side, and entanglement was performed together with the removal of PVA.
Next, napping, dyeing, softener and fine particles were applied in the same manner as in Example 1, and drying was performed at 100 ° C. while brushing to obtain a leather-like sheet.

  The leather-like sheet-like material thus obtained had a dense structure in which ultrafine fibers were entangled with each other, and the ultrafine fibers and the woven fabric were entangled, and had a suede-like appearance. The composition ratio of the ultrafine fiber nonwoven fabric (A ′) in the total weight of the leather-like sheet is 58% by weight, and the composition ratio of the biodegradable fiber is 50% by weight of the ultrafine fiber nonwoven fabric (A ′). The plain fabric (B ′) was 59% by weight.

  This leather-like sheet was sufficiently durable for use by entanglement of the fabric. Further, when the biodegradability was evaluated, the biodegradability was inferior to that of Example 1, but the shape was broken and the biodegradability was sufficient. The evaluation results are shown in Table 1.

Example 3
Polylactic acid having a melting point of 168 ° C., a weight average molecular weight of 120,000, and an L-form ratio of 98 mol% is used as the first component, nylon 6 is used as the second component, the single fiber fineness is 2.4 dtex, and the number of crimps is 15 peaks / 2. A staple of 24 split-divided composite fibers having a composite ratio of 1: 1 and similar to the cross-sectional shape shown in FIG.

A web was prepared by passing the staple through a card and a cross wrapper. Subsequently, it processed with the implantation density of 2000 pieces / cm < ² > with the 1 barb type needle punch, and obtained the composite short fiber nonwoven fabric of the fiber apparent density 0.24g / cm < ³ >.

  Next, it is immersed in an aqueous solution of polyvinyl alcohol (PVA) 12% having a polymerization degree of 500 and a saponification degree of 88% heated to about 95 ° C. so as to have an adhesion amount of 25% with respect to the nonwoven fabric weight in terms of solid content. Simultaneously with the impregnation, a shrinkage treatment was carried out for 2 minutes, followed by drying at 100 ° C. to remove moisture.

  The obtained sheet was split into two pieces perpendicular to the thickness direction using a standard type splitting machine manufactured by Murota Manufacturing Co., Ltd. to obtain a composite short fiber nonwoven fabric.

  Next, the composite short fiber nonwoven fabric and the same plain fabric (B) as in Example 1 were overlapped, and a water jet punch composed of nozzle heads with a diameter of 0.1 mm from the composite long fiber nonwoven fabric side and 0.6 mm intervals was used. Treated 3 times at 20 MPa at a treatment speed of 2 m / min, splits the composite fiber with PVA removal, splits almost all the composite fiber consisting of polylactic acid and nylon 6 with a single fiber fineness of about 0.1 dtex And an ultrafine fiber nonwoven fabric (A ″) entangled with each other.

  Next, after further treatment with 20 Mpa three times from the ultrafine fiber nonwoven fabric (A ″) side, the treatment was performed three times at 20 MPa from the plain woven fabric (B) side to perform entanglement.

  Next, napping of the ultrafine fiber nonwoven fabric (A ″) is performed with sandpaper, and “LANACRON Navy S-G KWL 150%” (manufactured by Ciba Specialty Chemicals Co., Ltd.) is used with a liquid dyeing machine. The sample was stained at 100 ° C. for 60 minutes. The obtained non-woven fabric was made of a softener (amino-modified silicone emulsion “Silicoran AN980SF” manufactured by one company) and fine particles (colloidal silica “Snowtex 20L” manufactured by Nissan Chemical Industries, Ltd., average particle size 0.04 to 0.05 μm. : BET method) and squeezed to 2.0% colloidal silica, and then dried at 100 ° C. while brushing to obtain a leather-like sheet.

  The leather-like sheet-like material thus obtained had a dense structure in which ultrafine fibers were entangled with each other, and the ultrafine fibers and the woven fabric were entangled, and had a suede-like appearance. The composition ratio of the ultrafine fiber nonwoven fabric (A ″) in the total weight of the leather-like sheet is 59% by weight, and the composition ratio of the biodegradable fiber is 50 for the ultrafine fiber nonwoven fabric (A ″). % By weight and plain fabric (B) was 100% by weight.

  This leather-like sheet was sufficiently durable for use by entanglement of the fabric. Further, when the biodegradability was evaluated, the biodegradability was inferior to that of Example 1, but the shape was broken and the biodegradability was sufficient. The evaluation results are shown in Table 1.

Comparative Example 1
Using the same polystyrene / polyethylene terephthalate staples as in Example 2, a web was produced through a card and a cross wrapper. Subsequently, it processed with the implantation density of 2000 pieces / cm < ² > with the 1 barb type needle punch, and obtained the composite short fiber nonwoven fabric of the fiber apparent density 0.22g / cm < ³ >. Next, it is immersed in an aqueous solution of polyvinyl alcohol (PVA) 12% having a polymerization degree of 500 and a saponification degree of 88% heated to about 95 ° C. so as to have an adhesion amount of 25% with respect to the nonwoven fabric weight in terms of solid content. Simultaneously with the impregnation, a shrinkage treatment was carried out for 2 minutes, followed by drying at 100 ° C. to remove moisture. The obtained sheet was treated with trichrene at about 30 ° C. until the polystyrene was completely removed, and ultrafine fibers having a single fiber fineness of about 0.046 dtex were obtained.

  Subsequently, using a standard splitting machine manufactured by Murota Manufacturing Co., Ltd., splitting was performed into two pieces perpendicular to the thickness direction to obtain an ultrafine fiber nonwoven fabric (A ′ ″).

Next, a plain woven fabric (B ″) composed of 56 dtex 12-filament polyethylene terephthalate fibers having a warp density of 136 / inch, width of 96 / inch, and a basis weight of 80 g / m ² is applied to a fine fiber nonwoven fabric (A ′ ″). ), And processed three times at 17 MP at a processing speed of 5 m / min with a water jet punch having a nozzle diameter of 0.1 mm from the monofilament nonwoven fabric (A ′ ″) side and a nozzle head with a spacing of 0.6 mm. Then, the PVA was removed three times from the plain fabric (B ″) side at 17 MPa for entanglement.

  Next, napping, dyeing, softening agent and fine particle application were performed in the same manner as in Example 1 and dried at 100 ° C. while brushing to obtain a leather-like sheet.

  The leather-like sheet-like material thus obtained had a dense structure in which ultrafine fibers were entangled with each other, and the ultrafine fibers and the woven fabric were entangled, and had a suede-like appearance. Further, the composition ratio of the ultrafine fiber nonwoven fabric (A ′ ″) in the total weight of the leather-like sheet is 60% by weight, and the composition ratio of the fiber having biodegradability is the ultrafine fiber nonwoven fabric (A ′ ″). The plain fabric (B ″) was 0%.

  This leather-like sheet was not biodegradable. The evaluation results are shown in Table 1.

3 is a cross-sectional view of a peelable split composite fiber obtained in Example 3. FIG.

Explanation of symbols

1: Component 1
2: Component 2
3: Hollow part

Claims (15)

From the ultrafine fiber nonwoven fabric (A) which is composed of a fiber material substantially including an aliphatic polyester fiber having biodegradability and intertwined with fibers having a single fiber fineness of 0.0001 to 0.5 dtex. A leather-like sheet characterized by The leather-like sheet-like article according to claim 1, wherein the woven or knitted fabric (B) containing at least biodegradable fibers is laminated. The leather-like sheet-like product according to claim 2, wherein a short fiber nonwoven fabric (C) having a fiber length of 0.1 to 1 cm and containing at least biodegradable aliphatic polyester fiber is laminated. The leather-like sheet-like material according to claim 2 or 3, wherein the ultrafine fiber nonwoven fabric (A) is 40 to 80% in a composition ratio in the total weight. The composition of the ultrafine fiber nonwoven fabric (A), the woven fabric or the knitted fabric (B), or the short fiber nonwoven fabric (C) contains 40% by weight or more of biodegradable fibers. The leather-like sheet-like material according to crab. The leather-like sheet material according to any one of claims 1 to 5, wherein the biodegradable aliphatic polyester is a polyester mainly composed of L-lactic acid and / or D-lactic acid. Basis weight 100~350g / ^{m 2,} leather-like sheet according to claim 1, apparent density, characterized in that a 0.27~0.50g / cm ^3,. The leather-like sheet-like product according to any one of claims 1 to 7, wherein at least one surface has napping. Fine leather is contained, The leather-like sheet-like material in any one of Claims 1-8 characterized by the above-mentioned. At least 0.0001 to 0.5 decitex of the biodegradable aliphatic polyester ultrafine fibers that can be generated are entangled with a needle punch, and then the ultrafine fibers are generated to form the ultrafine fiber nonwoven fabric (A), and then A method for producing a leather-like sheet, characterized in that it is superposed on a woven fabric or a knitted fabric (B), subjected to high-speed fluid treatment at a pressure of at least 10 MPa, entangled, and then dyed. At least a pressure of at least 10 MPa is superimposed on the woven fabric or the knitted fabric (B) after the fibers capable of generating an aliphatic polyester ultrafine fiber having biodegradability of at least 0.0001 to 0.5 dtex are entangled with a needle punch. A method for producing a leather-like sheet, characterized in that ultrafine fibers are generated by high-speed fluid treatment to form an ultrafine fiber nonwoven fabric (A), entangled, and then dyed. The method for producing a leather-like sheet-like material according to claim 10 or 11, wherein, in the high-speed fluid treatment, the short fiber nonwoven fabric (C) produced by the papermaking method is entangled with the woven fabric or the knitted fabric (B). The short fiber non-woven fabric (C) and the woven fabric or knitted fabric (B) produced by the paper making method are overlapped, entangled by high-speed fluid treatment, and then the ultra-fine fiber non-woven fabric (A) or the non-woven fabric capable of generating ultra-fine fibers is stacked, and the high-speed fluid treatment is performed. The method for producing a leather-like sheet-like product according to claim 12, wherein the ultrafine and / or entanglement is performed. The method for producing a leather-like sheet according to any one of claims 10 to 13, wherein napping treatment is performed before dyeing. The method for producing a leather-like sheet according to any one of claims 10 to 16, wherein fine particles are provided after dyeing.

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