JP4835181B2 - Leather-like product, molded body thereof, and method for producing leather-like product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a leather-like material which has high grade leather like appearance or touch and also having good moldability, shape retention and a good grade, a molded body comprising it and a manufacturing method of the leather-like material. <P>SOLUTION: The leather-like material is obtained by laminating a skin layer comprising an extremely fine fiber nonwoven fabric (A) with a decitex of 0.0001-0.5, a weldable fiber nonwoven fabric (B) containing weldable fibers and a knitted fabric (C). Further, molded body has the leather-like material arranged on its surface. The leather-like material is manufactured by laminating the fine fiber nonwoven fabric (A) with an average monofilament fineness of 0.0001-0.5 decitex and a laminated sheet, which is obtained by superposing the weldable fiber nonwoven fabric (B) and the knitted fabric (C) to subject them to high speed fluid treatment, to form a laminated sheetlike article and subjected the laminated sheetlike article to molding and welding treatment. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a leather-like article having a leather-like appearance and touch, and excellent in moldability and form retention, a molded article comprising the same, and a method for producing the same.

  Leather-like sheets such as artificial leather and synthetic leather are used for bags, shoes, furniture, automobile interior materials, and the like in order to give the surface appearance and a high-quality touch. And with the complication of molding shape in recent years, various leather-like sheets excellent in moldability have been studied (for example, Patent Document 1). As a result, the moldability of the leather-like sheet has been improved, and it has become possible to deal with complex shapes, but for applications that require mold form retainability, the form retainability was insufficient. .

On the other hand, as a technique for improving the shape retention of a polyurethane-containing leather-like sheet, a sheet-like laminate in which a nonwoven fabric containing heat-fusible fibers is laminated on the leather-like sheet is known (for example, patents) Reference 2). With this laminate, shape retention is good, but since the sheet is easily plastically deformed, there is a problem in quality such that once it is stretched, it does not return to its original shape and becomes wrinkled. In addition, lamination of a leather-like sheet-like material and a nonwoven fabric containing fusion fibers is performed with an adhesive, but there is a problem that peeling occurs due to differences in extensibility, density, and the like of both sheets due to molding.
JP 2003-20573 A JP-A-7-216756

  In view of the background of the above-mentioned prior art, the present invention provides a leather-like article having a leather-like appearance and touch, moldability, shape retention, and good quality, and a molded article comprising the same, and a method for producing the same. To do.

In order to solve the above problems, the present invention employs the following means. That is, the leather-like material of the present invention has a skin layer composed of a polyester ultrafine fiber nonwoven fabric (A) having an average single fiber fineness of 0.0001 to 0.5 dtex and a melting point of fibers constituting the ultrafine fiber nonwoven fabric (A). A fusion fiber nonwoven fabric (B) including a fusion fiber made of a copolyester having a melting point lower by at least ° C. and a woven or knitted fabric (C) are laminated.

  Further, the molded article of the present invention is characterized in that such a leather-like material is arranged on the surface.

Moreover, the manufacturing method of the leather-like thing of this invention is 10 degreeC from melting | fusing point of the fiber which comprises the polyester extra fine fiber nonwoven fabric (A) of average monofilament fineness 0.0001-0.5 dtex, and an extra fine fiber nonwoven fabric (A). A laminated sheet obtained by laminating a fused fiber nonwoven fabric (B) containing a fused fiber made of a copolyester having a low melting point and a woven / knitted fabric (C) and a laminated sheet obtained by performing high-speed fluid treatment. Then, a molding fusion treatment is performed.

  According to the present invention, leather that has a leather-like high-grade appearance that is particularly suitable for indoor interiors, automobile interior materials, and miscellaneous goods, and that has a high-grade surface appearance that is obtained from good moldability and form retention. You can provide something like that.

  The present invention has been intensively studied on the above-mentioned problems, that is, leather-like products having a leather-like appearance and touch, moldability, shape retention, and good quality, and the ultrafine fiber nonwoven fabric (A) and woven / knitted fabric (C ) And the fused fiber nonwoven fabric (B) have been investigated to solve the above problems all at once.

  The leather-like product of the present invention has a configuration in which the ultrafine fiber nonwoven fabric (A) constitutes the skin layer, and the fused fiber nonwoven fabric (B) and the woven / knitted fabric (C) are laminated. When the ultrafine fiber nonwoven fabric layer (A) forms the skin layer, it becomes possible to obtain a high-grade appearance, a smooth touch, an elegant lighting effect, and the like. Furthermore, by laminating the fused fiber nonwoven fabric (B) and the woven or knitted fabric (C), it becomes possible to achieve both form stability and moldability, which are the effects of the present invention. The order of lamination of the leather-like material is not particularly limited, and other than the ultrafine fiber nonwoven fabric (A) / fused fiber nonwoven fabric (B) / woven / knitted fabric (C) (hereinafter abbreviated as A / B / C) A / C / B, A / C / B / A, A / B / C / A, etc. Further, even if other nonwoven fabrics are laminated between the respective layers, the effects of the present invention are not impaired. Can be combined freely. In particular, when the woven or knitted fabric (C) forms the back surface (for example, A / B / C), it is preferable to laminate a non-woven fabric composed of ultrafine fibers in order to improve the quality of the back surface. Moreover, it is preferable that the fused fiber nonwoven fabric (B) and the woven or knitted fabric (C) are directly laminated from the viewpoint of achieving both form stability and moldability.

  The lamination state is not particularly limited, and can be appropriately selected such as adhesion and entanglement. However, it is difficult to generate wrinkles and irregularities, and the quality of the leather-like material is excellent. It is preferable that In particular, it is preferable that the fused fiber nonwoven fabric (B) and the woven or knitted fabric (C) are laminated by entanglement in view of excellent shape stability and moldability. The shape is not particularly limited, and may be a sheet shape or a three-dimensional shape by molding.

  The ultrafine fiber nonwoven fabric (A) constituting the leather-like material of the present invention comprises ultrafine fibers having an average single fiber fineness of 0.0001 to 0.5 dtex. The average single fiber fineness is preferably 0.001 to 0.3 dtex, more preferably 0.005 to 0.15 dtex. If the average single fiber fineness is less than 0.0001 dtex, the strength of the leather-like material is lowered, which is not preferable. If the average single fiber fineness exceeds 0.5 decitex, the texture of the leather-like sheet becomes stiff, the fiber entanglement becomes insufficient, the quality of the leather-like material is lowered, and the wear resistance is reduced. It is not preferable because a problem such as reduction occurs. In addition, a fiber having a single fiber fineness of less than 0.0001 dtex or a fiber having a single fiber fineness of more than 0.5 dtex may be included as long as the effect of the present invention is not impaired. The content of fibers having a single fiber fineness of less than 0.0001 dtex and fibers having a single fiber fineness of more than 0.5 dtex is preferably 30% or less of the fibers constituting the ultrafine fiber nonwoven fabric (A). % Or less is more preferable, and it is most preferable that it is not contained at all.

  As the ultrafine fiber, a thermoplastic polymer, particularly a fiber made of a polymer such as polyester, polylactic acid, polyamide, polypropylene, polyethylene or the like is preferably used. Fibers excellent in rubber-like elasticity such as polyether ester fibers and polyurethane fibers such as so-called spandex are not preferable.

  The polyester is not particularly limited as long as it can be fiberized. Specifically, for example, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis (2- Chlorophenoxy) ethane-4,4′-dicarboxylate and the like. Of these, the most commonly used polyethylene terephthalate or a polyester copolymer mainly containing ethylene terephthalate units is preferably used.

  Examples of the polyamide include polymers having an amide bond such as nylon 6, nylon 66, nylon 610, nylon 12, and the like.

  Although the average fiber length of the ultrafine fiber is not particularly limited, it is preferably 10 to 100 mm, more preferably 15 to 80 mm, and more preferably 20 to 60 mm in consideration of the surface lighting effect, wear resistance, quality, and the like. More preferably it is. The content of fibers having an average fiber length of more than 100 mm and fibers having a fiber length of less than 10 mm is preferably 30% or less, more preferably 10% or less of the fibers constituting the ultrafine fiber nonwoven fabric (A) in number. Most preferably it is not included.

  In the present invention, the ultrafine fiber nonwoven fabric (A) is not in a state where the ultrafine fiber bundles found in the conventional sheet are intertwined, but that these ultrafine fibers are intertwined with each other, In particular, it is preferable in terms of improving wear resistance, surface quality, and form stability.

  Moreover, if the fusion fiber nonwoven fabric (B) which comprises the leather-like thing of this invention contains a fusion fiber, it will not specifically limit. By the fused fiber, the leather-like material of the present invention can exhibit a high-quality leather-like shape and obtain good shape retention. The fused fiber in the present invention is a fiber made of a polymer having a property that the fiber is melted by heat, alkali or acidic aqueous solution, an organic solvent, and the like, and has a function of adhering to other fibers by the melted portion. Say. Since the fusion function can be exerted if the polymer is present on the fiber surface, the configuration mode is not particularly limited. For example, in addition to the fiber composed only of the polymer, the sheath portion in the core-sheath composite fiber Or a fiber in which the polymer is arranged on one side of a side-by-side type composite fiber.

  In the present invention, in particular, a heat-fusible fiber that is fused by heating is preferable in terms of ease of molding. Here, the melting point of the fusion fiber is preferably a temperature equal to or higher than the heat history of the step of laminating with the ultrafine fiber nonwoven fabric (A) and the woven / knitted fabric (C), and is preferably 100 ° C. or higher in terms of process controllability. 110 ° C. or higher is more preferable, and 120 ° C. or higher is more preferable. Further, when the ultrafine fiber nonwoven fabric (A) is dyed, the upper limit is preferably 200 ° C. or less, more preferably 180 ° C. or less, and even more preferably 160 ° C. or less, because there is a concern of fastness or color developability. .

  The fusible polymer is not particularly limited to polyamide, polyester, polyolefin, etc., but can be dyed with the same dye as the ultrafine fiber constituting the ultrafine fiber nonwoven fabric (A), and the ultrafine fiber is dissolved. Select those that can be fused without any conditions. From the viewpoint of dyeability and adhesiveness, it is preferable to select the same type of polymer. For example, if the ultrafine fiber nonwoven fabric (A) is a polyester, it is preferable to select a fused fiber made of a copolyester.

  Here, in the case of selecting a fiber to be fused by heat, the temperature management by the fusion treatment is easy when the fused fiber is made of a polymer having a melting point of 10 ° C. or higher, preferably 20 ° C. or higher, than the ultrafine fiber. This is preferable. Of these polymers, polyesters, particularly copolymer polyesters based on polyethylene terephthalate, are more preferred in view of ease of handling, strength, and heat resistance. The copolyester is not particularly limited, but for example, it can be changed to terephthalic acid, aromatic carboxylic acid such as isophthalic acid or naphthalenedicarboxylic acid, or aliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid, or changed to ethylene glycol and diethylene glycol. Hexylene glycol, polyalkylene glycol, and the like, which can be appropriately copolymerized and used.

  The fineness of the fused fiber is not particularly limited. For example, a fiber of 0.0001 to 30 dtex can be used, but if it is 3 dtex or less, preferably 1 dtex or less, the flexibility of the leather-like material and the fused fiber This is preferable because there is an effect such as an increase in fusion efficiency due to an increase in the contact area.

  The fiber length of the fused fiber is not particularly limited, but is preferably a short fiber in terms of excellent appearance of leather-like material and excellent peel strength and moldability, more preferably 1 to 100 mm, and 1 to 10 mm. The short fiber is more preferable. If it is 100 mm or less, the unevenness | corrugation by melt | fusion of a fused fiber does not appear on the surface, but it is preferable at the point which is excellent in surface quality. Moreover, if it is 1 mm or more, it exists in the tendency which is more excellent in form retainability.

  It is preferable that the nonwoven fabric has a more uniform and high density of fibers and is present in layers in the cross section of the leather-like material in terms of preventing deterioration of the surface quality of the leather-like material and satisfying shape retention. In addition, the presence of a layer in the present invention means that when the cross section is observed, it can be visually recognized that the nonwoven fabric forms a layer.

  The ratio of the fusion fiber to the fusion fiber nonwoven fabric (B) is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 30% or more in terms of more excellent shape retention. % Or more is more preferable, and 60% or more is more preferable. Other fibers may be included in addition to the fusion fibers, and the inclusion of 0.0001 to 0.5 dtex ultrafine fibers as the other fibers means that the fusion fiber nonwoven fabric (B) is made into another layer, For example, when laminating by entanglement with ultrafine fiber nonwoven fabric (A) or woven or knitted fabric (C), the entanglement is improved and the peel strength is improved, and when exposed to the surface, there is a concern that the surface quality is lowered. It is preferable because it is not present. Moreover, it is preferable at the time of the shaping | molding before melt | fusion, the followable | trackability to a type | mold improves and a more fine unevenness | corrugation can be formed. In addition, before laminating | stacking by entanglement, it is preferable at the point of the ease of handling at the time of lamination | stacking that it is temporarily adhered by water-soluble polymers, such as polyvinyl alcohol.

  The woven or knitted fabric (C) constituting the leather-like product of the present invention is a generic term for woven fabric and knitted fabric. The woven fabric is not particularly limited in structure such as plain weave, twill weave and satin weave, but plain weave is preferred in terms of cost and excellent surface smoothness of the nonwoven fabric after lamination. Moreover, as a knitted fabric, a circular knitting, a tricot, Russell, etc. are good, However It does not specifically limit. By the woven or knitted fabric, wrinkles can be prevented at the time of molding, and good quality can be obtained. In particular, the elongation specified by JIS L 1096 (1999) 8.14.1 A method should be 2 to 50%, preferably 5 to 30%, more preferably 10 to 25% in both the vertical and horizontal directions. Is preferred. If it is 2% or more, it is preferable in terms of facilitating molding into deeper irregularities, and if it is 50% or less, it is preferable in terms of ease of handling during lamination. Furthermore, it is preferable that the elongation recovery rate specified by JIS L 1096 (1999) 8.14.2 A method is 70 to 100% in terms of improving the followability to the mold and improving the quality. In the present invention, the warp direction of the woven or knitted fabric means a warp direction in the case of a woven fabric, a wale in the case of a knitted fabric, and a horizontal direction means a weft direction in the case of a woven fabric and a course in the case of a knitted fabric. .

  When the so-called stretch woven or knitted fabric described above is selected as the woven or knitted fabric (C) in the present invention, it is applied to applications requiring flexibility such as a sofa seat material in which a conventional stretch leather-like sheet is used. Further, by imparting form retention, which is an effect of the present invention, it becomes possible to manufacture a sheet having a complicated shape that has not been possible in the past while maintaining flexibility. In this case, in order to maintain flexibility, in addition to considering a manufacturing method such as fusing treatment only for a necessary portion, optimization is appropriately made in relation to the fused fiber nonwoven fabric (B) such as reducing the amount of fused fiber. It is preferable.

  The fibers constituting the woven or knitted fabric of the present invention are not particularly limited in addition to ordinary drawn yarns, processed yarns, etc., but mainly two or more kinds of polyesters in terms of the above-mentioned purpose, cost, and ease of handling. Is preferably a composite fiber bonded side-by-side along the fiber length direction, or an eccentric core-sheath type composite fiber forming a core-sheath structure in which two or more kinds of polyesters are eccentric. As long as such a composite fiber is included, a normal fiber may be included as long as the effects of the present invention are not impaired. That is, for example, the composite fiber and another fiber may be combined to be used as a composite yarn, or in the case of a woven fabric, the composite fiber is used only for weft or warp, and the other is used as another fiber. May be used.

  Here, the polyester constituting the woven or knitted fabric is a polymer such as polyethylene terephthalate, polytrimethylene terephthalate, or polybutylene terephthalate. The term “two or more polyester polymers” means that two or more polyester polymers 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, by performing a relaxation process, crimps can be easily expressed and a woven or knitted fabric excellent in stretchability can be obtained. Examples of polyesters having different heat shrinkability include polymers having different intrinsic viscosities and different degrees of polymerization, blends of different polymers, and the like.

  Moreover, stretchability can be improved as at least 1 sort (s) is polytrimethylene terephthalate among polyester. In particular, polytrimethylene terephthalate is preferably used as the high shrinkage component because it has excellent stretch properties. In this case, the low shrinkage component of the composite fiber may be a fiber-forming polyester that has good interfacial adhesiveness with polytrimethylene terephthalate, which is a high shrinkage component, and has stable yarn forming properties. However, in consideration of mechanical properties, chemical properties and raw material prices, polytrimethylene terephthalate, polyethylene terephthalate, and polybutylene terephthalate having fiber forming ability are preferable.

  Here, the polytrimethylene terephthalate is a polyester obtained using terephthalic acid as a main acid component and 1,3-propanediol as a main glycol component. However, it may contain a copolymer component capable of forming another ester bond at a ratio of 20 mol%, more preferably 10 mol% or less. Examples of copolymerizable compounds include dicarboxylic acids such as isophthalic acid, succinic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, sebacic acid, and 5-sodium sulfoisophthalic acid, ethylene glycol, diethylene glycol, butanediol, and neopentyl glycol. And diols such as cyclohexanedimethanol, polyethylene glycol, and polypropylene glycol, but are not limited thereto.

  Further, if necessary, the fibers constituting the woven or knitted fabric (C) may be colored, such as titanium dioxide as a matting agent, fine particles such as silica and alumina as a lubricant, hindered phenol derivatives as an antioxidant, and the like. A pigment or the like may be added.

  It is preferable that the intrinsic viscosity difference of the polymer which forms the said composite fiber is 0.01-0.4. If it is 0.01 or more, the stretchability is improved, and if it is 0.4 or less, the spinning stability is good. At this time, a composite fiber in which a low-viscosity polyester having 0.35 to 0.55 and a high-viscosity polyester having an intrinsic viscosity of 0.65 to 0.85 are combined is preferable. In this case, in general, the high-viscosity polyester has higher heat shrinkability than the low-viscosity polyester. As the intrinsic viscosity IV, a value measured as an orthochlorophenol solution at a temperature of 25 ° C. was used.

  The composite ratio of two or more polyester polymers is preferably in the range of high shrinkage component: low shrinkage component = 75: 25 to 35:65 (% by weight), from 65:35 to 45, from the viewpoint of yarn production. : The range of 55 is more preferable.

  The average single fiber fineness of the composite fiber constituting the woven or knitted fabric (C) is not particularly limited, but 1 to 15 dtex is preferable in terms of excellent moldability, handleability, and surface quality.

  The leather-like material of the present invention is preferably substantially made of a fiber material and does not substantially contain a polymer elastic body. Usually, a leather-like sheet retains physical properties such as tensile strength, tear strength, and abrasion resistance, so that it contains 10 to 60% of a polymer elastic body such as polyurethane, which is present in a film form inside the nonwoven fabric. This tends to hinder the formation of fine irregularities when molding, and is not preferable for molding applications. On the other hand, when it is substantially made of a fiber material, moldability is further improved and recyclability is also preferable. Usually, a leather-like material excluding a polymer elastic body cannot satisfactorily obtain a leather-like material in the production process, and physical properties such as abrasion resistance cannot withstand practical use. However, it is possible to obtain a leather-like material substantially made of a fiber material by the production method of the present invention described later. In the present invention, the fine fiber nonwoven fabric (A), the fused fiber nonwoven fabric (B), and the fibers constituting the woven or knitted fabric (C) constituting the leather-like material are preferably 80 to 100% by weight, and more preferably 90 to 90% by weight. 100% by weight is preferably polyester from the viewpoint of recyclability.

  Here, “consisting essentially of a fiber material” means that it is composed only of a fiber material that is a constituent element of a general leather-like sheet-like material and a fiber material of a polymer elastic body. However, more specifically, when the surface is observed with an SEM, a microscope or the like, it means that the polymer elastic body is not substantially observed as a film-like body observed in a general leather-like material. It is. Preferably, a polymer elastic body is not observed even in a form other than a film form, but a processing agent used in post-processing, for example, a dye, a softening agent, an abrasion resistance improving agent, various fastness improving agents, anti-electricity resistance Agents or fine particles may be contained in the leather-like sheet of the present invention.

  The leather-like material of the present invention can be used as a silver surface tone or napped tone depending on its use and purpose, but in particular, the surface appearance by the ultrafine fiber nonwoven fabric (A) can be effectively used and molded. In terms of excellent quality by processing, it is preferably napped.

In addition, the leather-like material of the present invention preferably has a density of 0.25 g / cm ³ or more, more preferably 0.29 g / cm ³ or more, in terms of improving wear resistance. More preferably, it is 30 g / cm ³ or more. The upper limit of the apparent fiber density is not particularly limited, but it is preferably 0.80 g / cm ³ or less because of excellent handling during molding.

Basis weight of the leather-like material of the present invention is preferably 150 to 800 g / ^{m 2,} more preferably 150~600g / ^{m 2,} more preferably from 200~450g / ^{m 2.} If the basis weight of the leather-like sheet is 150 g / m ² or more, better surface quality can be obtained, and if it is 800 g / m ² or less, the form retainability is more excellent, which is preferable.

  The thickness of the leather-like material of the present invention is preferably 0.1 to 5.0 mm, more preferably 0.5 to 2.5 mm. If it is 0.1 mm or more, a leather-like product having excellent surface quality can be easily obtained, and if it is 5.0 mm or less, it tends to be excellent in mold followability during molding.

  The basis weight uses a value obtained based on the method described in JIS L 1096 8.4.2 (1999). In addition, when a test piece cannot be collected with a size of 20 cm square, it is converted from the area that can be collected to obtain a measured value. The thickness is measured with a dial thickness gauge (manufactured by Ozaki Mfg. Co., Ltd., trade name “Peacock (registered trademark) H”), and the basis weight value is divided by the thickness value to obtain the apparent fiber density.

  In addition, the leather-like material of the present invention forms an ultrafine fiber non-woven fabric in an abrasion resistance test measured according to JIS L 1096 (1999) 8.17.5 E method (Martindale method) furniture load (12 kPa). The wear loss of the test cloth after wearing 20000 times in the pilling position setting B (THREE DRIVE ROLLERS = POSITION B) is 20 mg or less and the number of pills is 5 or less. Is preferred. The wear loss is more preferably 15 mg or less, and still more preferably 10 mg or less. The number of pills is more preferably 3 or less, and even more preferably 1 or less. If the wear loss is 20 mg or less, the fluff hardly adheres to clothes or the like in actual use. On the other hand, the lower limit is not particularly limited, and a leather-like product of the present invention can be obtained which has almost no weight loss. In addition, when the number of generated pills exceeds 5, the quality is deteriorated due to a change in appearance when used, which is not preferable.

Further, the breathability of the leather-like material is preferably 10 cc / cm ² / sec or less from the viewpoint of improving moldability, more preferably 8.0 cc / cm ² / sec or less, and 5.0 cc / More preferably, it is cm ² / sec or less. The lower limit is not particularly limited, and is preferably as different as 0 cc / cm ² / sec.

  The value obtained by the JIS L 1096 8.27.1 (1999) A method (fragile type) is used as the air flow rate here.

  Since the leather-like material of the present invention has an excellent surface appearance and touch, the molded body in which the leather-like material of the present invention is arranged on the surface should be molded and used for indoor interiors, automotive interior materials, miscellaneous goods, etc. Can do.

  Next, as an example of a preferable method for producing the leather-like product of the present invention, the method for producing the leather-like product of the present invention will be described.

  The production method of the ultrafine fiber constituting the ultrafine fiber nonwoven fabric (A) constituting the leather-like material of the present invention is not particularly limited, and besides the ordinary filament spinning method, the spunbond method, the melt blow method, the electrospinning method, the flash spinning method. The method of manufacturing as a nonwoven fabric, such as a method, may be used. In addition, as a means for obtaining ultrafine fibers, a method of directly spinning ultrafine fibers, a fiber having a fineness and capable of generating ultrafine fibers (hereinafter referred to as ultrafine fiber-generating fibers), and then spinning ultrafine fibers are obtained. A method of generating fibers may also be used.

  Here, as a method of obtaining ultrafine fibers using ultrafine fiber generation type fibers, specifically, a method of removing sea components after spinning sea-island type fibers, or splitting after spinning of split-type fibers Thus, it is possible to adopt means such as a method of ultra-thinning.

  Among these means, in the present invention, it is preferable to produce ultrafine fibers from the viewpoint that ultrafine fibers can be obtained easily and stably. Further, when a leather-like sheet is used, the same kind is used. It is more preferable to manufacture with an island-in-sea fiber in that an ultrafine fiber made of the same kind of polymer that can be dyed with a dye can be easily obtained.

It does not specifically limit as a method of obtaining a sea-island type fiber, For example, the method etc. which are described in the following (1)-(4) are mentioned.
(1) A method of spinning by blending two or more polymers in a chip state.
(2) A method in which a polymer of two or more components is kneaded in advance to form a chip and then spun.
(3) A method in which two or more polymers in a molten state are mixed in a spinning machine pack with a static kneader or the like.
(4) A method of manufacturing using a die such as Japanese Patent Publication No. 44-18369 and Japanese Patent Application Laid-Open No. 54-116417.

  In the present invention, it can be satisfactorily produced by any of the methods, but the method (4) is most preferable 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. For example, the shape is round, polygonal, Y-shaped, H-shaped, X-shaped. Examples include a mold, a W-shape, a C-shape, and a π-shape.

  When the fiber is once obtained and made into a non-woven fabric, the method may be a wet method or a dry method, but the dry method is preferred from the viewpoint of less fiber falling off during friction.

  The fiber length is preferably cut to 10 to 70 mm for the dry method and 0.1 to 20 mm for the wet method.

  As a preferable manufacturing method as a dry method, a short fiber nonwoven fabric is manufactured by a needle punch method using 1 to 10 dtex ultrafine fiber generating short fibers capable of generating ultrafine fibers, and then ultrafinened to obtain an ultrafine fiber nonwoven fabric. A method is mentioned. In addition, it is preferable that the short fiber nonwoven fabric of the ultrafine fiber generating fiber is excellent in surface quality and shape stability when it is shrunk by dry heat or wet heat, or both, and further densified.

In order to obtain a leather-like material consisting essentially of a fiber material in the present invention, it is preferable to perform high-speed fluid treatment in the state of ultrafine fibers, as will be described later, but generation of ultrafine fibers before making ultrafine fibers. It is preferable that needle punching is sufficiently performed in the state of the mold short fiber nonwoven fabric. For example, needle punching is performed until the apparent fiber density is preferably 0.12 to 0.3 g / cm ³ , more preferably 0.15 to 0.25 g / cm ³ . The upper limit is not particularly specified, but if it exceeds 0.3 g / cm ³ , problems such as breakage of the needle needle and remaining of the needle hole are not preferable. In this case, it is preferable to use a needle of 1 to 9 barbs and a needle density of 1000 to 4000 needles / cm ² .

  In the fused fiber nonwoven fabric (B) constituting the leather-like material of the present invention, the fibers arranged in a single component or a composite component of the fused polymer are directly formed into a nonwoven fabric by a spunbond method, a melt blow method, or the like. The fused fiber obtained by stretching can be wound once and then cut as necessary to produce a short fiber nonwoven fabric. In the present invention, it is preferable to use a short fiber nonwoven fabric that is particularly leather-like and excellent in moldability, but in this case, as described above, it is cut to 10 to 70 mm for the dry method and 0.1 to 20 mm for the wet method. It is preferable to do. In the case where the fusion fiber and other fibers are mixed, for example, the fibers can be mixed after being cut.

  Among these production methods, production by a wet method is particularly preferable in that the fusion fiber layer can be designed to be thinner and the moldability can be improved, and the lamination with the woven or knitted fabric (C) can be facilitated. When the thickness of the fusion layer exceeds 3.0 mm, the moldability tends to be lowered, and good lamination becomes difficult when lamination is performed with a high-speed fluid. From this viewpoint, the thickness of the fusion layer is preferably 2.0 mm or less, more preferably 1.0 mm or less, and further preferably 0.5 mm or less. These thicknesses can be easily manufactured by a wet method. The fused fiber nonwoven fabric (B) of the present invention preferably contains 0.001 to 0.5 decitex ultrafine fibers, but it can be easily carried out if it is a wet method even when it is mixed. Is possible. When manufacturing by a wet method, after cutting the fiber to a desired length, if necessary, fibers other than fusion fibers such as ultrafine fibers are mixed to produce a slurry, and a paper web is created by a wet papermaking method . At this time, the drying temperature is preferably set to be equal to or lower than the melting point of the fused fiber.

  In the case of producing a woven fabric as the woven or knitted fabric (C) of the present invention, it is produced by a loom such as a shuttleless loom such as a water jet loom or an air jet loom, a fly shuttle loom, a tappet loom, a dobby loom, or a jacquard loom. can do. In the case of producing a knitted fabric, the weft knitting can be produced by, for example, a weft knitting machine or a circular knitting machine, and the warp knitting can be produced by a tricot machine, a Milanese machine, a Russell machine or the like.

  In the case of a stretch woven or knitted fabric, for example, a composite fiber in which two or more kinds of polyester polymers are bonded side by side along the fiber length direction, or two or more kinds of polyester polymers are eccentric. It is preferable to use an eccentric core-sheath type composite fiber forming a core-sheath structure and to make this a woven or knitted fabric from the viewpoint of cost and ease of handling. The production method of the composite fiber is not particularly limited, but for example, it is obtained by forming a side-by-side composite flow using two types of polyester polymers and then discharging the composite fiber from a discharge hole for obtaining a desired cross-sectional shape. Can do. After the discharged yarn is cooled and solidified, it may be produced by a two-step method in which it is wound once and then stretched or stretched false twisted. Alternatively, it may be directly stretched by drawing directly after spinning. It may be manufactured.

  In order to stably manufacture such a composite fiber, the intrinsic viscosity of each component and the intrinsic viscosity difference between the components are important. Even in the case of a composite fiber, it is not practical if the viscosity of one side component is too low to have fiber forming ability, or conversely, it is too high to require a special spinning device. Further, the difference in viscosity between the components determines the degree of yarn bending (bending phenomenon) immediately below the discharge hole, which greatly affects the yarn-making property.

  The obtained knitted or knitted fabric is subjected to a relaxation treatment and contracted as necessary, and an intermediate set is performed. When performing the relaxation treatment, the treatment is carried out at a temperature of 80 to 140 ° C. by a continuous spread relaxation treatment machine such as an open soaper, a relaxer, or a softer, or a batch type treatment machine such as a jigger, wins, or a liquid dyeing machine. Prior to the relaxation treatment using the liquid dyeing machine, it is preferable to perform the pre-shrinkage with a continuous spreading-type continuous relaxation treatment machine from the viewpoint that uniform shrinkage treatment can be performed. Moreover, an intermediate | middle set can be performed at 100-190 degreeC.

  The ultrafine fiber nonwoven fabric (A), the fused fiber (B) and the woven / knitted fabric (C) thus obtained are then laminated. As the means, it can be performed by adhesion, entanglement or the like, but in terms of flexibility, lamination by entanglement is preferable. When laminating by entanglement, it can be performed, for example, by needle punching or high-speed fluid processing, and in particular, a high speed that does not damage the woven or knitted fabric of the present invention and can obtain a good surface quality of leather-like material. Fluid treatment is preferred.

  As the high-speed fluid processing, water jet punch processing is preferable from the viewpoint of the working environment. At this time, the water flow is preferably performed in a columnar flow state. The columnar flow is usually obtained by ejecting at a pressure of 1 to 60 MPa from a nozzle having a diameter of fluid injection holes of 0.06 to 1.0 mm. In this treatment, in order to obtain efficient entanglement and good surface quality, the diameter of the nozzle (fluid injection hole) is preferably 0.06 to 0.15 mm, the nozzle interval is preferably 5 mm or less, and the diameter is 0. 0.06 to 0.12 mm, and the nozzle 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.

  Further, in order to achieve uniform entanglement in the thickness direction and / or to improve the smoothness of the nonwoven fabric surface, it is preferable to perform high-speed fluid treatment repeatedly many times. Moreover, the water flow pressure is appropriately determined according to the basis weight of the nonwoven fabric to be treated, and the higher the basis weight, the higher the pressure.

  Furthermore, in the present invention, in order to obtain a leather-like material substantially composed of a fiber material, it is preferable to treat at least once with a pressure of 10 MPa or more for the purpose of highly entanglement of ultrafine fibers. It is more preferable to perform the treatment once at a pressure of 15 MPa or more. In addition, the upper limit is not particularly limited, but the cost increases as the pressure increases, and the nonwoven fabric may be non-uniform if the basis weight is low, or fluff may be generated due to fiber cutting, which is preferable. Is 40 MPa or less, more preferably 30 MPa or less.

  In the present invention, a polymer elastic body can be provided as necessary. In this case, the polymer elastic body is impregnated in the state of a solution or a dispersion. In terms of excellent working environment, it is particularly preferable to impregnate in the state of an aqueous dispersion dispersed in water. A heat-sensitive gelling agent, a crosslinking agent, a stabilizer, a penetrating agent, and the like may be added to the dispersion of the water-dispersed polymer elastic body.

  After impregnating the dispersion of the water-dispersed polymer elastic body, the nonwoven fabric containing the dispersion is heated with dry heat, hot water, hot water, atmospheric or high-pressure steam, microwaves, etc. to gel (solidify) ) Process. For example, an apparatus for heating with steam includes an atmospheric steamer, a high temperature steamer, and the like. It is preferable to use an apparatus that can use both steam and microwave because a high migration preventing effect can be obtained.

  In order to obtain a surface with a silver tone, a surface layer portion made of a polymer elastic body may be further formed on the surface by coating or lamination.

  On the other hand, in order to finish the surface of the raised hair, an appropriate method such as buffing with sandpaper or the like can be employed.

  Furthermore, dyeing with a liquid dyeing machine is preferred in that a high-quality surface appearance can be obtained. Further, after dyeing, various functional processing such as water repellent processing, antibacterial processing, anti-pill processing, or high color processing can be performed in addition to soft processing.

  The laminated sheet thus obtained is made into a leather-like article or molded article having excellent shape retention when heated at a temperature equal to or higher than the melting point of the fusion fiber, preferably higher than the melting point by 20 ° C. The leather-like material of the present invention has a good moldability due to the presence of the woven or knitted fabric, and in particular, by using a stretchable woven or knitted fabric, wrinkles can be suppressed with respect to the uneven shape. When fusing, it is preferable to fuse sufficiently in applications that do not consider the texture at all, such as housings, cases, ceiling materials, interior materials, etc. In necessary applications, it is preferable to adjust appropriately such as weakening the degree of fusion. In addition, when performing heat molding, in addition to performing under no pressure, it is possible to pressurize simultaneously with or after heating. It is preferable to apply pressure in terms of more excellent surface quality, molded shape, and the like. Moreover, when using for a sheet | seat material etc., after shaping | molding once, it is preferable to shape | mold with a hot air etc.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, the following method was used for the measuring method of each physical-property value in an Example.

  In addition, Reference Examples 1 to 3 described below describe the manufacturing conditions of the woven fabric and the nonwoven fabric used in the examples.

A. Intrinsic viscosity IV
0.8 g of the sample polymer was dissolved in 10 ml of orthochlorophenol (hereinafter abbreviated as OCP), the relative viscosity ηr was determined from the following equation using an Ostwald viscometer at 25 ° C., and the intrinsic viscosity IV was calculated.
ηr = η / η0 = (t × d) / (t0 × d0)
Intrinsic viscosity IV = 0.0242ηr + 0.2634
Where η: viscosity of the polymer solution η0: viscosity of the OCP t: drop time of the solution (seconds)
d: Density of solution (g / cm ³ )
t0: OCP fall time (seconds)
d0: OCP density (g / cm ³ ).

B. Elongation rate of woven or knitted fabric Measured with a gripping interval of 20 cm in JIS L 1096 (1999) 8.14.1 A method (constant speed elongation method).

C. Elongation recovery rate of woven or knitted fabric Measured according to JIS L 1096 (1999) 8.14.2 A method (repeated constant speed elongation method) with a grip interval of 20 cm.

D. The basis weight, thickness, and fiber apparent density of the leather-like material were measured by the method described in JIS L 1096 8.4.2 (1999). The thickness was measured with a dial thickness gauge (manufactured by Ozaki Seisakusho, trade name “Peacock (registered trademark) H”), and the apparent fiber density was determined by dividing the basis weight value by the thickness value.

E. Martindale Abrasion Test for Leather-Like Material A test piece having a diameter of 3.8 cm was taken from the leather-like material and weighed. In accordance with JIS L 1096 (1999) 8.17.5 E method (Martindale method) Furniture load (12 kPa), the skin layer formed by the ultrafine fiber nonwoven fabric is set to the pilling position setting B (THREE) using a Martindale abrasion tester. A wear resistance test was performed with DRIVE ROLLERS = POSITION 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. Moreover, the number of pills was counted from the appearance of the test piece after the test.

F. Formability of leather-like materials The occurrence of wrinkles was visually evaluated in three stages (○: no wrinkles, Δ: some wrinkles, ×: wrinkles)
Example 1
A web was prepared through a card and a cross wrapping using sea island type short fibers having a single fiber fineness of 3 dtex, 36 islands and a 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. Then, 1 is treated with implantation density of 1500 / cm ² at barb type needle punch machine to obtain a short fiber non-woven fabric of fibers apparent density 0.21 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 give an adhesion amount of 25% based on the weight of the nonwoven fabric. Simultaneously with the impregnation of PVA, a shrinkage treatment was performed for 2 minutes, and dried 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. Next, using a standard splitting machine manufactured by Murota Manufacturing Co., Ltd., splitting was performed by splitting the sheet into two pieces in a direction perpendicular to the thickness direction, and an ultrafine fiber nonwoven fabric having a fiber-equivalent basis weight of 108 g / m ² ( A) was obtained.

  Next, a low-viscosity component consisting of 100% polyethylene terephthalate having an IV of 0.50 and a high-viscosity component consisting of polyethylene terephthalate having an IV of 0.75 are bonded to the side-by-side at a weight composite ratio of 50:50, and spinning and stretching. As a result, a composite fiber of 56 dtex 12 filaments was obtained. This was additionally twisted at 1500 T / m and steam set at 65 ° C. Using this yarn, a 2/2 oblique fabric with a warp density of 95 / 2.54 cm and a weft density of 85 / 2.54 cm was produced.

  The obtained woven fabric was treated at 95 ° C. with a continuous expansion relaxer, further treated at 110 ° C. with a liquid dyeing machine, and then subjected to an intermediate setting at 180 ° C. with an overfeed rate of 3% (C ) The stretch rate of this woven fabric was 6.3% in the vertical direction and 24.9% in the horizontal direction, and the recovery rate in the stretch was 89.9% in the vertical direction and 83.3% in the horizontal direction.

On the other hand, 6 polyethylene terephthalate fibers (melting point: 170 ° C., 2.1 dtex, fiber length: 5 mm) and polyethylene terephthalate fibers (melting point: 260 ° C., 0.1 dtex, fiber length: 5 mm) copolymerized with 30 mol% of isophthalic acid. : The slurry mixed by 4: was produced, and the fused fiber nonwoven fabric (B) of 35 g / m < ² > of fiber conversion basis weights was manufactured with the papermaking method.

Moreover, the paper-making web (D) of 33 g / m < ² > of fiber conversion basis weights was produced by the paper-making method using the polyethylene terephthalate fiber (0.1 decitex, fiber length 5mm).

  The non-woven fabric and the woven fabric thus obtained are first superposed so as to be B / D, and the water jet punch machine has a nozzle diameter of 0.1 mm from the paper-making web (D) side and nozzle heads with an interval of 0.6 mm. The water jet punching process was performed three times at a processing speed of 5 m / min and a pressure of 6 MPa. Subsequently, the fusion fiber nonwoven fabric (B) was overlapped so as to be B / C / D, and water jet punching was similarly performed from the fusion fiber nonwoven fabric side. Next, the ultrafine fiber nonwoven fabric (A) is overlapped so as to be A / B / C / D, and from the ultrafine fiber nonwoven fabric (A) side, using the same nozzle head, a processing speed of 5 m / min, a pressure of 10, 15, Water jet punching was performed at 20 MPa. Subsequently, the water jet punch process was similarly performed from the back side (D) side.

  Next, after raising the surface of the ultrafine fiber nonwoven fabric (A) with sandpaper, "Sumikaron (registered trademark) Blue S-BBL200" (manufactured by Sumika Chemtex Co., Ltd.) was used with a liquid dyeing machine. Staining was carried out at 110 ° C. for 60 minutes at a concentration of 20% owf. The obtained sheet contains a softening agent (amino-modified silicone emulsion “Aldac (registered trademark) AN980SF” manufactured by One Corporation) and fine particles (colloidal silica “Snowtex (registered trademark) 20L” manufactured by Nissan Chemical Industries, Ltd.). It was immersed in an aqueous solution and squeezed so that the content of colloidal silica was 0.1%, and then dried at 100 ° C. while brushing.

The leather-like sheet thus obtained was then molded using a mold heated to 180 ° C. The leather-like product thus obtained was excellent in surface quality, having a basis weight of 224 g / m ² , a thickness of 0.64 mm, a fiber apparent density of 0.350 g / cm ³ , and a moldability of “◯”. As a result of the Martindale abrasion test, one pill was found and the weight loss was 5 mg.

Comparative Example 1
A leather-like product was obtained in the same manner as in Example 1 except that the fabric (C) was not used. The surface quality of the leather-like material obtained in this way was excellent, but since there was no woven fabric, wrinkles due to nesting or loosening occurred in the ultrafine fiber nonwoven fabric layer at the deeply drawn part of the formwork, and the moldability Was x.

Comparative Example 2
A leather-like material was obtained in the same manner as in Example 1 except that the fused fiber nonwoven fabric (B) was not used. Although the leather-like product thus obtained was excellent in surface quality, it could not be molded by heat treatment because there was no fused nonwoven fabric.

Comparative Example 3
A single fiber fineness 5.1 decitex polyethylene terephthalate was cut to 51 mm, and then a short fiber nonwoven fabric was obtained at a needle density of 100 / cm ^{2 with} a needle punch. Subsequently, this was processed in the same manner as in Example 1 instead of the ultrafine fiber nonwoven fabric (A). The non-woven fabric obtained in this manner was pilled and peeled by dyeing, and a leather-like appearance could not be obtained.

Claims (18)

From a skin layer composed of a polyester ultrafine fiber nonwoven fabric (A) having an average single fiber fineness of 0.0001 to 0.5 dtex, and a copolymer polyester having a melting point that is 10 ° C. or more lower than the melting point of the fibers constituting the ultrafine fiber nonwoven fabric (A) A leather-like article comprising a fusion fiber nonwoven fabric (B) containing a fusion fiber and a woven or knitted fabric (C). The leather-like article according to claim 1, wherein the fusion fiber nonwoven fabric (B) and the woven or knitted fabric (C) are laminated by entanglement. The leather-like product according to claim 1 or 2, wherein the leather-like product is substantially composed of a fiber material. The leather-like article according to any one of claims 1 to 3, wherein the fusion fiber nonwoven fabric contains 30 to 100% by weight of the fusion fiber. The leather-like article according to any one of claims 1 to 4, wherein the fibers constituting the fused fiber nonwoven fabric (B) are short fibers having a fiber length of 1 to 10 mm. The leather-like article according to any one of claims 1 to 5, wherein the fiber constituting the fused fiber nonwoven fabric (B) is a fused fiber having a melting point of 100 to 200 ° C. The leather-like material according to any one of claims 1 to 6, wherein 80 to 100% by weight of the constituent fiber is polyester. The leather-like material according to any one of claims 1 to 7, wherein the leather-like material has napped surfaces. The leather-like article according to any one of claims 1 to 8, wherein the woven or knitted fabric (C) has an elongation rate of 2 to 50% and an elongation recovery rate of 70 to 100%. The fibers constituting the woven or knitted fabric (C) mainly form a composite fiber in which two or more kinds of polyesters are bonded side-by-side along the fiber length direction, or a core-sheath structure in which two or more kinds of polyesters are eccentric. The leather-like article according to claim 1, wherein the leather-like article is an eccentric core-sheath type composite fiber. The leather-like product has a wear loss of 20 mg or less when the surface is worn 20000 times in the abrasion test in the Martindale method, and the number of pills is 5 or less. Item 11. A leather-like article according to any one of Items 1 to 10. The leather-like product according to any one of claims 1 to 11, wherein the leather-like product has a thickness of 0.1 to 5.0 mm. A molded article comprising the leather-like article according to any one of claims 1 to 12 disposed on a surface thereof. A fusion fiber comprising a polyester ultrafine fiber nonwoven fabric (A) having an average single fiber fineness of 0.0001 to 0.5 dtex and a copolyester having a melting point lower by 10 ° C. or more than the melting point of the fibers constituting the ultrafine fiber nonwoven fabric (A). A leather characterized by laminating a laminated fiber sheet obtained by superimposing a fusion fiber nonwoven fabric (B) containing woven fabric and knitted fabric (C) on a high-speed fluid treatment to form a laminated sheet, followed by molding and fusion treatment A method of manufacturing the like. The ultrafine fiber nonwoven fabric (A) has an average single fiber fineness of 0.0001 to 0.5 dtex, and can generate ultrafine fibers having an average fiber length of 1 to 10 cm, and has an average single fiber fineness of 1 to 10 dtex. 15. The method for producing a leather-like article according to claim 14, wherein the generation-type short fibers are obtained by entanglement of the generated short fibers with a needle punch and then generating ultrafine fibers by ultrafine processing. In Claim 14 or 15, the fusion fiber nonwoven fabric (B) and the woven or knitted fabric (C) are stacked and subjected to high-speed fluid treatment, and then the ultrafine fiber nonwoven fabric (A) is stacked on the laminated sheet to further increase the speed. A method for producing a leather-like article, comprising performing a fusion treatment after performing a fluid treatment. The method for producing a leather-like product according to any one of claims 14 to 16, wherein the fused fiber nonwoven fabric (B) is produced by a papermaking method. The method for producing a leather-like article according to any one of claims 14 to 17, wherein the woven or knitted fabric (C) has an elongation rate of 5 to 50% and an elongation recovery rate of 70 to 100%.