JP2019060060A - Sheet-like product - Google Patents

Abstract

To provide a sheet-like product comprising an interlaced fiber of a nonwoven fabric made of ultra fine fiber and a fabric that are laminated and interlaced for integration, the interlaced fiber being impregnated with an elastomer, the sheet-like product having a soft texture with less hardening of the texture due to fire retardancy, while having excellent strength and fire retardancy.SOLUTION: A sheet-like product comprises an interlaced fiber of a nonwoven fabric made of ultra fine fiber having an average single fiber diameter of 0.1 to 8 μm and a fabric that are laminated and interlaced for integration and an elastic polymer. The fiber constituting the fabric comprises a polyphenylene sulfide fiber.SELECTED DRAWING: None

Description

  The present invention relates to a sheet-like material, and more specifically, the present invention is formed by impregnating a polymer entangled body in which a non-woven fabric composed of microfibers and a woven fabric are laminated and entangled and integrated. The present invention relates to a sheet-like material having excellent strength and flame retardancy.

  A sheet-like product mainly composed of a fiber entangled body such as a non-woven fabric made of ultrafine fibers and a polymer elastic body has excellent characteristics which natural leathers do not have, such as durability and uniformity, among which So-called suede-like artificial leather, in which the surface is buffed to form extrafine fiber naps, is used not only as a clothing material but also in various fields such as vehicle interior materials, furniture interior materials and building materials.

  When suede-like artificial leather is used for a skin material such as a vehicle interior material, distortion may occur in the skin material due to repeated use over a long period of time, so the woven and knitted fabric is entangled and integrated in the nonwoven fabric or on one side. A method of making an artificial leather with high strength, low elongation, and a high degree of flexibility has been proposed (see Patent Document 1).

  Furthermore, although suede-like artificial leather is often required to have high flame-retardant performance in the above-mentioned fields, it is necessary to constitute a woven or knitted fabric with a polymer elastic body such as polyurethane constituting nonwoven suede-like artificial leather or nonwoven fabric. Fibers are known to be very difficult to flame retardant.

  Therefore, for example, as a method for imparting flame retardancy to a suede-like artificial leather, a resin composition containing an acrylic ester resin as a main component and containing an aromatic phosphate ester and a metal oxide is used as a back surface of a suede-like artificial leather. A method for achieving flame retardancy by applying to the above has been proposed (see Patent Document 2). However, in order to obtain a high degree of flame retardancy by this proposal, it is necessary to impart a large amount of the flame retardant resin composition, and as a result, there is a problem that the texture of the suede-like artificial leather is cured.

  As a method of suppressing the hardening of texture of suede-like artificial leather by incombustibility, a method of applying a flame retardant phosphorus copolymer polyester to a woven or knitted fabric integrated with a non-woven fabric has been proposed (see Patent Documents 3 and 4) ). However, in this proposal, there is a problem that sufficient strength of a sheet-like material can not be obtained by using a phosphorus copolymerized polyester which is inferior in strength to polyester which is not copolymerized as a component of a woven or knitted fabric.

Japanese Patent Application Laid-Open No. 62-78281 Japanese Patent Application Publication No. 2004-036011 JP 2004-169197 A JP, 2006-112006, A

  Therefore, an object of the present invention is a sheet-like product in which a polymer elastic body is impregnated in a fiber entangled body in which a non-woven fabric made of ultrafine fibers and a woven fabric are laminated and entangled and integrated, It is an object of the present invention to provide a sheet-like material having a soft texture, which is excellent, but in which curing of the texture due to inflammability is reduced.

  The present invention solves the above-mentioned problems, and the sheet-like material of the present invention is formed by laminating a non-woven fabric and a woven fabric consisting of ultrafine fibers having an average single fiber diameter of 0.1 to 8 μm and entanglement It is a sheet-like article which consists of a fiber entangled body and an elastic polymer which are made, and which is characterized in that the fiber which constitutes the above-mentioned textiles contains polyphenylene sulfide fiber.

  According to a preferred embodiment of the sheet-like material of the present invention, the above-mentioned sheet-like material contains a phosphorus-based and / or inorganic-based flame retardant.

  According to a preferred embodiment of the sheet material of the present invention, the above-mentioned flame retardant is not present in the surface layer of the leather-like sheet material.

  According to a preferred embodiment of the sheet material of the present invention, 40% by mass or more of the fibers constituting the woven fabric are polyphenylene sulfide fibers.

  According to a preferred embodiment of the sheet material of the present invention, 100% by mass of the fibers constituting the woven fabric is polyphenylene sulfide fiber.

  According to the present invention, it is possible to obtain a sheet material excellent in strength and flame retardancy that can endure repeated use, which is important in vehicle interior materials. In addition, it is possible to obtain a sheet-like material which has been a problem with the conventional sheet-like material excellent in strength and flame retardancy, and is reduced in feeling of curing such as curing and tackiness due to flame retardancy and in strength.

  The sheet-like article of the present invention is a sheet-like article comprising an entangled member and an elastic polymer, in which a non-woven fabric and a woven fabric made of ultrafine fibers having an average single fiber diameter of 0.1 to 8 μm are laminated and entangled and integrated. The fibers constituting the woven fabric are sheet-like materials containing polyphenylene sulfide fibers.

  As a kind of microfiber which constitutes the nonwoven fabric used by the present invention, a natural fiber, a regenerated fiber, a semi synthetic fiber, a synthetic fiber etc. can be used, for example. Among them, in view of durability, in particular mechanical strength, heat resistance and light resistance, synthetic fibers are preferable, and polyester fibers are particularly preferably used.

  When a synthetic fiber is used as the ultrafine fiber, the polymer forming the ultrafine fiber may be an inorganic particle such as titanium oxide particles, a lubricant, a pigment, a heat stabilizer, an ultraviolet light absorber, or a conductive material depending on various purposes. Agents, heat storage agents, antimicrobial agents, etc. can be added.

  It is important that the average single fiber diameter of the microfibers be 0.1 to 8 μm. By setting the average single fiber diameter to 8 μm or less, it is possible to obtain a sheet-like material excellent in fine and soft touch surface quality. On the other hand, when the average single fiber diameter is 0.1 μm or more, excellent effects are obtained in color development and fastness after dyeing. The average single fiber diameter of the microfibers is preferably in the range of 1 μm to 6 μm, and more preferably in the range of 1.5 μm to 4.5 μm.

  The cross-sectional shape of the microfibers is preferably a round cross-section from the viewpoint of processing operability, but it is preferably an oval, a flat, a polygon such as flat and triangular, a sector and a cross, a hollow, Y, T, and U It is also possible to adopt a cross-sectional shape of a cross section such as a mold.

  For the average single fiber diameter, take a scanning electron microscope (SEM) photograph of the cross section of the sheet-like material, randomly select 10 circular or nearly circular elliptical fibers, measure the single fiber diameter, and average 10 Calculated by calculating the value. When an ultrafine fiber of atypical cross section is employed, the cross sectional area of the single fiber is first measured, and the diameter of the single fiber is determined by calculating the diameter when the cross section is regarded as circular.

  It is important that the microfibers be in the form of a non-woven in the sheet form. By using a non-woven fabric, it is possible to obtain a uniform and elegant appearance and texture when raising the surface.

  As the form of the non-woven fabric, both long-fiber non-woven fabrics and short-fiber non-woven fabrics can be used, but short-fiber non-woven fabrics are preferable since they have a large number of naps on the product surface and are easy to obtain an elegant appearance.

  The fiber length of the microfibers when using a short fiber non-woven fabric is preferably 25 to 90 mm. By setting the fiber length to 90 mm or less, good quality and texture can be obtained, and by setting the fiber length to 25 mm or more, a sheet-like product having excellent abrasion resistance can be obtained. The fiber length is more preferably 35 to 80 mm, still more preferably 40 to 70 mm.

Basis weight of the nonwoven fabric constituting the sheet is measured by JIS L1913 (2010) 6.2, is preferably in the range of 50 to 400 g / ^{m 2,} more preferably in the range of 80~300g / ^{m 2} . When the basis weight of the non-woven fabric is less than 50 g / m ² , the sheet-like material becomes paper-like and the texture is poor. Moreover, when the fabric weight of a nonwoven fabric exceeds 400 g / m < ² >, there exists a tendency for the texture of a sheet-like thing to become hard.

  In the sheet-like material of the present invention, it is important to laminate the fabric on one side or the other side of the non-woven fabric and to entangle and integrate them in order to improve the strength and the form stability.

  It is important to contain polyphenylene sulfide fiber as a fiber which constitutes textiles used for a sheet-like article of the present invention. The polyphenylene sulfide fiber has properties of high strength and flame retardancy, and the strength and flame retardancy of the sheet material are greatly improved by using the woven fabric containing the polyphenylene sulfide fiber.

  The content of polyphenylene sulfide fibers in the woven fabric is preferably 40% by mass or more, and more preferably 100% by mass, because the sheet-like material has sufficient flame retardancy.

  When the fabric contains fibers other than polyphenylene sulfide fibers, examples of fibers other than polyphenylene sulfide fibers include synthetic fibers such as polyester fibers, polyamide fibers and acrylic fibers, but from the viewpoint of color fastness, non-woven fabrics are constituted. It is preferable that it is the same material as the ultrafine fiber to be used.

  When the woven fabric contains fibers other than polyphenylene sulfide fibers, the fibers constituting the woven fabric may be a cross-woven fabric of polyphenylene sulfide fibers and fibers other than polyphenylene sulfide fibers, and the warp and / or weft may not be polyphenylene sulfide fibers and polyphenylene sulfide fibers. Twisted yarn with fibers can be used.

Basis weight of the fabric is measured by JIS L1096 (2010) 8.3, is preferably in the range of 20 to 200 g / ^{m 2,} more preferably in the range of 30 to 150 g / ^{m 2.} If the fabric weight of the woven fabric is less than 20 g / m ² , the form stability of the woven fabric becomes poor, and wrinkles are generated when the woven fabric is inserted between the non-woven fabric and the non-woven fabric, or when the fabric is superposed on the non-woven fabric surface. It becomes difficult to stack. When the fabric weight of the woven fabric exceeds 200 g / m ² , the structure of the woven fabric becomes dense, and entanglement between the non-woven fabric and the woven fabric tends to be difficult.

  The thickness of the woven fabric is preferably 0.1 mm to 0.4 mm, more preferably 0.15 mm to 0.3 mm, as measured by JIS L1096 (2010) 8.4. By setting the thickness of the woven fabric to 0.1 mm or more, it becomes possible to impart better form stability to the sheet-like material. Further, by setting the thickness to 0.4 mm or less, napped fiber density unevenness due to the unevenness of the woven fabric in the sheet-like material can be suppressed, and a more excellent surface quality can be maintained.

  As types of fibers constituting the fabric, filament yarns, spun yarns, innovative spun yarns, mixed composite yarns of filament yarns and spun yarns, etc. can be used, but spun yarns have many fluffs on the surface due to their structure. It is more preferable to use a filament since it becomes a defect when the fluff falls off and is exposed to the surface when the nonwoven fabric and the fabric are entangled, it is more preferable to use a multifilament as the filament.

  It is preferable that the fiber diameter of the single fiber of the fiber which comprises textiles is 1-50 micrometers, More preferably, it is 3-40 micrometers, More preferably, it is 5-30 micrometers. By setting the fiber diameter of the single fiber to 50 μm or less, a sheet-like material excellent in flexibility is obtained, and by setting the fiber diameter of the single fiber to 1 μm or more, the shape stability of the product as a sheet-like material is improved. Do.

  The total fineness of the yarn constituting the woven fabric is measured in accordance with JIS L1013 (2010) 8.3b (simple method), preferably 30 dtex to 170 dtex, more preferably 50 dtex to 150 dtex, and still more preferably 70 dtex to 130 dtex. By setting the total fineness to 170 dtex or less, a sheet-like material excellent in flexibility is obtained, and by setting the total fineness to 30 dtex or more, the shape stability of the product as a sheet-like material is improved. At this time, it is preferable that the total deniers of the multifilaments of the warp and the weft be the same total denier.

  Moreover, it is a preferable aspect to make the yarn which comprises textiles into a strong twist yarn, and it is preferable that the twist number of the yarn which comprises textiles is 700T / m-4500T / m.

  Although the basic texture of the fabric may be twill or satin, a plain texture that is less likely to be dislocated is preferably used.

  The weave density of the woven fabric is preferably adjusted so that in the sheet-like material, both of the warp yarns and weft yarns have a density of 40 yarns / 2.54 cm to 200 yarns / 2.54 cm. By setting the weave density of the fabric constituting the sheet-like material to 40 / 2.54 cm or more, a sheet-like material excellent in the form stability can be obtained. On the other hand, the texture of the sheet can be made flexible by setting the weave density of the fabric constituting the sheet to 200 / 2.54 cm or less.

  Since the polymer elastic body constituting the sheet-like material of the present invention is a binder for gripping the ultrafine fibers constituting the sheet-like material, the polymer elasticity used is considered in consideration of the soft texture of the sheet-like material of the present invention As the body, polyurethane, SBR, NBR, acrylic resin and the like can be mentioned. Among them, it is a preferred embodiment to use polyurethane as a main component. By using polyurethane, it is possible to obtain a sheet having a solid feel, a leather-like appearance, and physical properties that endure actual use. Further, the main component referred to herein means that the mass of polyurethane is more than 50% by mass with respect to the mass of the whole polymer elastic body.

  When polyurethane is used in the present invention, either an organic solvent-based polyurethane used in a state of being dissolved in an organic solvent or a water-dispersed polyurethane used in a state of being dispersed in water can be employed. Further, as the polyurethane, a polyurethane obtained by the reaction of a polymer diol, an organic diisocyanate and a chain extender is preferably used.

  In addition, the polymer elastic body, according to the purpose, various additives, for example, pigments such as carbon black, flame retardants such as phosphorus based, halogen based and inorganic based, oxidation such as phenol based, sulfur based and phosphorus based Inhibitors, UV absorbers such as benzotriazole type, benzophenone type, salicylate type, cyanoacrylate type and oxalylic acid anilide type, light stabilizers such as hindered amine type and benzoate type, hydrolysis resistant stabilizers such as polycarbodiimide, A plasticizer, an antistatic agent, a surfactant, a coagulation regulator, a dye and the like can be contained.

  The content of the polymeric elastic body in the sheet-like material can be appropriately adjusted in consideration of the type of polymeric elastic body to be used, the method of producing the polymeric elastic body, and the feel and physical properties. The content of the polymer elastic body is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 45% by mass, and still more preferably 20% by mass with respect to the mass of the fiber entangled body The content is 40% by mass or less. When the content of the polymer elastic body is less than 10% by mass, the bonding between the fibers by the polymer elastic body is weak, and the abrasion resistance of the sheet material tends to be inferior. Moreover, when content of a polymeric elastic body exceeds 60 mass%, there exists a tendency for the feel of a sheet-like thing to become hard.

  In the sheet-like material of the present invention, it is a preferred embodiment to have raised hair on the surface. The napped hair may be provided only on the surface of the sheet-like material, or on both sides. In the case of having a nap on the surface, the nap form has a nap length and direction flexibility such that a so-called finger mark is emitted when the direction of the nap changes when the finger is traced from the viewpoint of design effect Is preferred. More specifically, the nap length of the surface is preferably 100 μm or more and 400 μm or less, and more preferably 150 μm or more and 350 μm or less. The surface napped hair length is an SEM photograph of the cross section of the sheet material at 50 times magnification with the napped hair of the sheet material upside-down, and the height of the napped hair portion (layer consisting of ultrafine fibers) is measured at 10 points and averaged. Calculated by calculating the value.

  The sheet-like material of the present invention preferably contains a flame retardant. When the flame retardant is contained, as a type of the flame retardant, a phosphorus-based and / or inorganic-based flame retardant which does not generate harmful substances at the time of combustion is preferably used.

Examples of phosphorus-based flame retardants include polyphosphate-based flame retardants such as ammonium polyphosphate (for example, Exflam APP 204 (manufactured by Wellchem), Exolit AP 462 (manufactured by Clariant)), and nitrogen-containing organic phosphates such as guanidine phosphate Flame retardants (for example, Bigol No. 415 (made by Daikyo Chemical Co., Ltd.)), aromatic phosphate ester flame retardants such as triphenyl phosphate, trixylenyl phosphate (for example, TPP (Daihachi Kogyo Co., Ltd.) Company company)),
In addition, as an inorganic flame retardant, flame retardants such as aluminum hydroxide, titanium oxide, zinc oxide, expansive graphite, magnesium hydroxide, calcium carbonate, zinc borate, ammonium polyphosphate and red phosphorus may be used. Although it is possible, it is preferable to use a polyphosphate flame retardant which is excellent in processability and durability.

  The flame retardant is preferably contained together with a binder resin such as an acrylic resin, a urethane resin, a polyester resin, and a vinyl acetate resin. As the binder resin, an acrylic resin is preferably used from the viewpoint of adhesion and heat resistance. Hereinafter, the binder resin containing a flame retardant may be described as a resin containing a flame retardant.

  The resin containing the above-mentioned flame retardant further contains aluminum hydroxide, magnesium hydroxide, metal oxide and the like as a flame retardant auxiliary, and as a thickener for improving daily stability and production workability. It is possible to add polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, an alkali-thickening acrylic resin, ethylene oxide higher fatty acid ester, etc., and further, as a softener, liquid paraffin, polyethylene glycol, etc.

  Although the flame retardant-containing resin may be contained in the entire sheet-like material or may be contained only on the back side of the sheet-like material, it does not impair the touch and fastness of the surface. Preferably, it is contained only on the back side of the sheet-like material and does not exist on the surface side.

  The surface layer referred to here is the napped layer when the sheet-like material has napped hairs, and is the uppermost one of the three divided in the thickness direction with the front side of the sheet-like material up when there is no napped hair. It means the layer.

  The applied amount of the resin containing the flame retardant is the mass (solid content mass) at the time of drying with respect to the sheet-like material in order to exert good flame retardancy within a range that does not impair the soft feeling of the sheet-like material. It is preferable that it is 3-25 mass%. The amount of the resin containing the flame retardant is more preferably 5 to 20% by mass, still more preferably 8 to 18% by mass.

  It is preferable that the thickness of the sheet-like material of this invention measured by a JIS L1913 (2010) 6.1 A method is the range of 0.2-1.2 mm. When the thickness of the sheet-like material is smaller than 0.2 mm, the processability at the time of production is deteriorated, and when the thickness is larger than 1.2 mm, the flexibility of the sheet-like material tends to be impaired. The thickness of the sheet is more preferably 0.3 to 1.1 mm, still more preferably 0.4 to 1 mm.

  The sheet-like material of the present invention preferably has a tensile strength of 50 to 200 N / cm as measured according to JIS L1913 (2010) 6.3.1. When the tensile strength is 50 N / cm or more, the form stability of the sheet is excellent, and when the tensile strength is 200 N / cm or less, the sheet is excellent in moldability. The tensile strength is more preferably 70 to 180 N / cm, still more preferably 80 to 150 N / cm.

  The sheet material of the present invention preferably has a bending resistance of 30 to 120 mm as measured by JIS L1913 (2010) 6.7a (cantilever method). When the bending resistance is 30 mm or more, the fullness of the sheet-like material is excellent, and when the bending resistance is 120 mm or less, the texture is soft and the molding property is excellent. The bending resistance is more preferably 35 to 100 mm, still more preferably 40 to 80 mm.

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

  In the present invention, as means for obtaining the ultrafine fibers constituting the sheet-like material, it is a preferred embodiment to use an ultrafine fiber-represented fiber. The ultrafine fiber-represented fiber is entangled in advance to form a non-woven fabric, and then the ultra-thin fiber is obtained to obtain a non-woven fabric in which the ultra-fine fiber bundle is entangled.

  As an ultrafine fiber expression type fiber, two component thermoplastic resins having different solvent solubility are used as a sea component and an island component, and the sea component is dissolved and removed using a solvent or the like to make the island component an ultrafine fiber A sea-island type composite fiber, or a release type composite fiber or the like in which bicomponent thermoplastic resins are alternately arranged in radial or multi-layered fiber cross sections and separated into components by peeling and dividing each component into ultrafine fibers etc. Can. Above all, by removing the sea component, the sea-island composite fiber can provide an appropriate gap between the island components, that is, between the ultrafine fibers inside the fiber bundle, so that the viewpoint of the texture and surface quality of the sheet Are also preferably used.

  The sea-island type composite fiber uses a sea-island type composite spinneret, and uses a polymer mutual alignment body in which two components of a sea component and an island component are mutually arranged and spun, and a mixture of two components of a sea component and an island component Although a mixed spinning method of spinning by spinning can be used, a sea-island composite fiber according to a method using a polymer mutual arrangement is preferably used from the viewpoint of obtaining ultrafine fibers with a uniform single fiber fineness.

  Further, as the form of the non-woven fabric, as described above, a short fiber non-woven fabric or a long fiber non-woven fabric can be used, but in the case of a short fiber non-woven fabric, fibers oriented in the thickness direction of the sheet are compared to the long fiber non-woven fabric It is possible to obtain a high degree of compactness on the surface of the sheet-like material when it is raised.

  In the case of using a staple fiber nonwoven fabric as the nonwoven fabric, the obtained ultrafine fiber-represented fiber is preferably crimped and cut into a predetermined length to obtain a raw cotton. A well-known method can be used for crimp processing and cut processing.

  Next, the obtained raw cotton is made into a fiber web with a cross wrapper or the like, and entangled to obtain a non-woven fabric. Needle punching, water jet punching, or the like can be used as a method of entanglement of the fiber web to obtain a non-woven fabric.

  Furthermore, the obtained non-woven fabric and fabric are laminated and entangled and integrated. For entanglement integration of the non-woven fabric and the fabric, after laminating the fabric on one side or both sides of the non-woven fabric, or after sandwiching the fabric between a plurality of non-woven fabric webs, The fibers of the fabric can be intertwined.

  In the needle used for needle punching, the number of needle barbs is preferably 1 to 9. By preferably providing at least one needle barb, efficient fiber entanglement is possible. On the other hand, fiber damage can be suppressed by setting the needle barb to preferably 9 or less.

  The number of composite fibers, such as ultrafine fiber-represented fibers, caught by the barbs is determined by the shape of the barbs and the diameter of the composite fibers. Therefore, the barb shape of the needle used in the needle punching process has a kickup of 0 to 50 μm, an undercut angle of 0 to 40 °, a throat depth of 40 to 80 μm, and a throat length of 0. A 5 to 1 mm barb is preferably used.

The number of punchings is preferably 1000 to 8000 per cm ² . By setting the number of punchings to preferably 1000 / cm ² or more, compactness can be obtained and a highly accurate finish can be obtained. On the other hand, by setting the number of punchings to preferably 8000 / cm ² or less, deterioration in processability, fiber damage and strength reduction can be prevented.

  By setting the barb direction of the needle of the needle punch to 90 ± 25 ° which is preferably orthogonal to the traveling direction of the woven fabric and the non-woven fabric, it becomes difficult to catch the weft yarn of the fragile woven fabric.

  Moreover, when performing a water jet punch process, it is preferable to perform water in the state of a columnar flow. Specifically, it is a preferable embodiment to eject water at a pressure of 1 to 60 MPa from a nozzle having a diameter of 0.05 to 1.0 mm.

It is preferable that the apparent density of the nonwoven fabric which consists of a composite fiber (ultrafine fiber expression type | mold fiber) after a needle punch process or a water jet punch process is 0.15-0.45 g / cm < ³ >. By setting the apparent density to preferably 0.15 g / cm ³ or more, sufficient shape stability and dimensional stability of the artificial leather base material can be obtained. On the other hand, by setting the apparent density to preferably 0.45 g / cm ³ or less, a sufficient space for applying the polymer elastic body can be maintained.

  It is also a preferred embodiment that the above-mentioned non-woven fabric is subjected to a heat shrinking treatment with warm water or steam in order to improve the fineness of the fibers.

  Next, the non-woven fabric may be impregnated with an aqueous solution of a water-soluble resin and dried to give the water-soluble resin. By applying the water-soluble resin to the non-woven fabric, the fibers are fixed and the dimensional stability is improved.

  Next, the obtained non-woven fabric is treated with a solvent to develop ultrafine fibers with an average single fiber diameter of 0.1 to 8 μm.

  The ultrafine fiber expression treatment can be performed by immersing a non-woven fabric composed of sea-island composite fibers in a solvent to dissolve and remove the sea component of the sea-island composite fibers.

  When the ultrafine fiber expression type fiber is a sea-island type composite fiber, an organic solvent such as toluene or trichloroethylene can be used as a solvent for dissolving and removing the sea component when the sea component is polyethylene, polypropylene and polystyrene. When the sea component is copolyester or polylactic acid, an aqueous alkaline solution such as sodium hydroxide can be used. When the sea component is a water-soluble thermoplastic polyvinyl alcohol resin, hot water can be used.

  Next, a non-woven fabric (fiber entangled body) is impregnated with a solvent solution of a polymer elastic body and solidified to give a polymer elastic body. As a method of fixing the polymer elastic body to the non-woven fabric, there is a method of impregnating a solution of the polymer elastic body into the non-woven fabric (fiber entangled body) and then wet coagulating or dry coagulating. These methods can be selected as appropriate.

  From the viewpoint of production efficiency, it is preferable that the sheet-like material to which the polymer elastic body is applied be semi-cut in the thickness direction.

  The surface of the sheet-like or semi-cut sheet-like material to which the polymeric elastomer is applied can be subjected to a raising treatment. A raising process can be given by the method of grinding etc. using a sandpaper, a roll sander, etc. The raising treatment can be applied only to the surface of the sheet-like material or to both surfaces.

  In the case of applying a raising treatment, a lubricant such as a silicone emulsion can be applied prior to the raising treatment. In addition, the addition of the antistatic agent before the raising treatment makes it difficult for the grinding powder generated from the sheet by grinding to be deposited on the sandpaper. Thus, a sheet is formed.

  The above-mentioned sheet-like material can be subjected to a dyeing process as required. The dyeing process may be, for example, flow dyeing process using a jigger dyeing machine or a flow dyeing machine, dyeing process such as thermosol dyeing process using a continuous dyeing machine, roller printing, screen printing, ink jet printing, sublimation It is possible to use printing on the napped surface by printing, vacuum sublimation printing, or the like. Among them, it is preferable to use a jet-flow dyeing machine from the viewpoint of quality and quality, since a soft feeling can be obtained. Moreover, various resin finishing processes can be given after dyeing | staining as needed.

  In addition, the sheet-like material described above can be provided with designability on the surface thereof as needed. For example, post processing such as drilling processing such as perforation, embossing processing, laser processing, pin sonic processing, and printing processing can be performed.

  As a method of applying the resin containing the flame retardant to the sheet, for example, using an apparatus such as a rotary screen, knife roll coater, gravure roll coater, kiss roll coater, and calendar coater, the back side of the sheet is It is possible to adopt a method of applying (back coating), a method of applying to the whole sheet material by a pad dry method, or the like.

  As a drying method after giving resin containing a flame retardant, it can dry using dryers, such as a tenter dryer.

  The sheet material of the present invention is excellent in strength and flame retardancy and has a soft texture, so it can be used in various fields such as interior materials for vehicles, materials for furniture interior, and construction materials, but it is particularly high strength and flame retardant It is suitably used in an interior material for vehicles where performance is required.

  Next, the sheet-like material of the present invention and the method for producing the same will be described by way of examples.

<Evaluation method>
(1) Average single fiber diameter:
For the average single fiber diameter, take a scanning electron microscope (SEM) photograph of the cross section of the sheet-like material, randomly select 10 circular or nearly circular elliptical fibers, measure the single fiber diameter, and average 10 Calculated by calculating the value. When an ultrafine fiber of atypical cross section was employed, the cross sectional area of the single fiber was first measured, and the diameter of the single fiber was determined by calculating the diameter when the cross section was regarded as circular.

(2) Flame-retardant performance test of sheet material:
FMVSS (US Federal Motor Vehicle Safety Standard) No. The horizontal burning rate was measured based on the automotive interior material burning test standard 302, and the flame resistance performance of the sheet was evaluated according to the following criteria.
-When self-erasing before reaching A marked line, the judgment classification is set as "A self-erasing in marked line" and it is judged as a pass.

  When the self-extinguishing exceeds the A marked line, the combustion distance is within 50 mm, and the combustion time is within 60 seconds, the judgment category is “self-extinguishing”, and is regarded as a pass.

  -Although self-extinguishing does not occur, when the burning rate between the marked lines is 4 inches / minute or less (about 101.6 mm / minute) or less, the judgment category is set as "combustion at a specified speed or less" and it is regarded as passing.

  · If the burning rate between the marked lines exceeds 4 inches / minute (about 101.6 mm / minute) without self-extinguishing, the judgment category is set as "combustion exceeding specified speed" and is rejected.

(3) Tensile strength of sheet material:
It measured based on JIS L1913 (2010) 6.3.1. The measurement was made at five points in any direction of the sheet, and the average value was taken as the tensile strength of the sheet.

(4) Stiffness of sheet-like material:
It measured based on JIS L1913 (2010) 6.7a (cantilever method). The measurement was performed at six points in any direction of the sheet, and the average value was taken as the hardness of the sheet.

(5) Surface touch of sheet:
The surface touch of the sheet was evaluated by sensory evaluation as described below, with a total of 20 persons, 10 healthy adults and 10 females each, and the most frequent evaluation was surface touch of the sheet. And Moreover, when evaluation results were cracked by the same number, the one with bad evaluation was made into the surface touch of a sheet-like article. In the present invention, good levels are "◎" and "○".
:: Smooth surface touch, no sticky feeling,
○: The surface touch is smooth but somewhat sticky,
:: The surface touch is smooth but quite sticky,
X: The surface touch is rough.

<Description of chemical substance>
It is written with the following code.
DMF: N, N-dimethylformamide PVA: polyvinyl alcohol PPS: polyphenylene sulfide.

Example 1
<Raw cotton>
Using polyethylene terephthalate (PET) having an inherent viscosity (IV) of 0.718 as the island component, using polystyrene having an MFR of 65 as the sea component, and using a sea-island composite spinneret having 16 islands / hole. Melt spinning was performed under the conditions of a spinning temperature of 285 ° C., an island / sea mass ratio of 80/20, a discharge amount of 1.2 g / min · hole, and a spinning speed of 1100 m / min. Then, it is drawn 2.8 times in an oil solution bath for spinning at a temperature of 90 ° C., crimped using an push-type crimper, and then cut into a length of 51 mm, and the single fiber fineness There was obtained a raw cotton of a 3.8 dtex sea-island composite fiber.

<Entanglement, fabric bonding>
Next, using the raw cotton of the islands-in-sea type composite fiber described above, a laminated web is formed through a card and a cross-wrapping process, and 100 yarns / cm ² to suppress fabric wrinkles due to rapid width change after fabric bonding. Needle punching was performed with the number of punches.

Subsequently, using a twisted yarn obtained by twisting 2500 T / m on polyphenylene sulfide fiber ("Torcon" (registered trademark) manufactured by Toray Industries, Inc., 84 dtex, 72 filaments) for both weft and warp, the weave density is A plain weave of 95 / 2.54 cm and 76 / 2.54 cm was laminated on the upper and lower sides of the laminated web. Thereafter, needle punching was performed with a number of punches of 2500 / cm ² to obtain a entangled sheet having a basis weight of 700 g / m ² and a thickness of 3.0 mm.

<Application of water-soluble resin, sea removal and compression>
The entangled sheet obtained as described above is shrunk with hot water at a temperature of 96 ° C., and after being impregnated with a 5% by mass aqueous solution of PVA (polyvinyl alcohol) having a degree of saponification of 88%, it is rolled The film was dried while migrating the PVA with hot air at a temperature of 120 ° C. for 10 minutes to obtain a sheet with PVA of 7.5% by mass with respect to the mass of the sheet substrate. Dissolving and removing the sea component and compressing the PVA-attached sheet were carried out by immersing the thus-obtained sheet with PVA in trichloroethylene and performing squeezing and compression 10 times with a mangle to give PVA. A dewatered PVA-attached sheet in which ultrafine fiber bundles are intertwined is obtained.

<Application of polymer elastic body>
The dewatered PVA-attached sheet obtained as described above is dipped in a DMF (dimethylformamide) solution of polyurethane adjusted to a solid concentration of 11.3%, squeezed with a roll, and then polyurethane in an aqueous solution with a DMF concentration of 30% Solidified. Thereafter, the PVA and DMF are removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet with polyurethane having a thickness of 2.2 mm and a polyurethane mass of 27% by mass based on the mass of the fibrous substrate I got

<Half and Brushed>
The polyurethane-coated sheet obtained as described above is semi-cut vertically in the thickness direction, and the semi-cut surface is ground with an endless sand paper of sandpaper number 180, 0.25 mm, and a napped surface is formed. A napped sheet of 0.85 mm was obtained.

<Staining and finishing>
The napped sheet obtained as described above is dyed with a black dye under a temperature condition of 120 ° C. using a jet flow dyeing machine and then dried in a dryer at a temperature of 100 ° C. A flame retardant containing 70% by mass of silicon oxide-based resin-treated ammonium polyphosphate (manufactured by Wellchem, phosphorus content: 28% by mass) as a flame retardant component, and after curing using a screen coater on the back of the napped sheet The coating process is performed so that the solid content mass of the resin containing the flame retardant is 40 g / m ^2, and then the drying process is performed for 7 minutes at a temperature of 100 ° C., and the average short fiber diameter of the microfibers is 4 A sheet having a thickness of .4 μm, a basis weight of 412 g / m ² and a thickness of 1 mm was obtained. The obtained sheet-like material was excellent in strength and flame retardancy, and had good surface touch and flexibility. The results are shown in Table 1.

Example 2
The average short fiber diameter of the ultrafine fibers is 4.4 μm in the same manner as in Example 1 except that the warp of the woven fabric is changed to a twisted yarn made of polyethylene terephthalate fibers having an intrinsic viscosity (IV) of 0.65. A sheet of 409 g / m ² and a thickness of 1 mm was obtained. The obtained sheet-like material was excellent in strength and flame retardancy, and had good surface touch and flexibility. The results are shown in Table 1.

[Example 3]
Except that a twisted yarn (84 dtex, 72 filaments) in which a polyethylene terephthalate fiber having an intrinsic viscosity (IV) of 0.65 and a polyphenylene sulfide fiber similar to that of Example 1 were used in 1: 1 was used for the warp and weft of the woven fabric In the same manner as in Example 1, a sheet having an average short fiber diameter of ultrafine fibers of 4.4 μm, a basis weight of 405 g / m ² and a thickness of 1 mm was obtained. The obtained sheet-like material was excellent in strength and flame retardancy, and had good surface touch and flexibility. The results are shown in Table 1.

Example 4
As a flame retardant processing agent, Vigor No. 2 containing a guanidine phosphate derivative as a main component. An extremely thin film was prepared in the same manner as in Example 1 except that using 415 (made by Daikyo Chemical Co., Ltd.) and applying the pad-dry method so that the amount of the flame retardant processing agent was the same as in Example 1. A sheet having an average short fiber diameter of 4.4 μm, a basis weight of 411 g / m ² and a thickness of 1 mm was obtained. The obtained sheet-like material was excellent in strength and flame retardancy, and although somewhat sticky, had a good surface touch and flexibility. The results are shown in Table 1.

[Example 5]
The average short fiber diameter of the microfibers is 4.4 μm and the basis weight is 450 g / m in the same manner as in Example 1 except that the solid content mass of the resin containing the flame retardant is 80 g / m ^2. A sheet having a thickness of 1 mm was obtained with m ² . The obtained sheet-like material had high strength and a good surface touch, and although it was somewhat inferior in flexibility, it had particularly excellent flame retardancy. The results are shown in Table 1.

[Example 6]
Spinning is performed using polyethylene terephthalate having an intrinsic viscosity (IV) of 0.718 as the island component, using polystyrene having an MFR of 18 as the sea component, and a sea-island composite spinneret having 16 islands / hole. After melt spinning at a temperature of 285 ° C. and an island component / sea component mass ratio of 55/45, it is drawn, crimped using a push-fit crimper, and then cut into a length of 51 mm. A raw cotton of a sea-island composite fiber having a single fiber fineness of 3.0 dtex was obtained.

A sheet-like material having an average short fiber diameter of ultrafine fibers of 3.1 μm, a basis weight of 414 g / m ² and a thickness of 1 mm was obtained in the same manner as in Example 1 except that this raw cotton was used. The obtained sheet-like material was excellent in strength and flame retardancy, and had good surface touch and flexibility. The results are shown in Table 1.

[Example 7]
Spinning is performed using polyethylene terephthalate having an intrinsic viscosity (IV) of 0.718 as an island component, using polystyrene having an MFR of 18 and having an island number of 36 islands / hole as a sea component. After melt spinning at a temperature of 285 ° C. and an island component / sea component mass ratio of 20/80, it is drawn, crimped using a push-in crimper, and then cut into a length of 51 mm. A raw cotton of a sea-island composite fiber with a single fiber fineness of 1.6 dtex was obtained.

A sheet material having an average short fiber diameter of ultrafine fibers of 0.9 m, a basis weight of 408 g / m ² and a thickness of 1 mm was obtained in the same manner as in Example 1 except that this raw cotton was used. The obtained sheet-like material was excellent in strength and flame retardancy, and had good surface touch and flexibility. The results are shown in Table 2.
[Example 8]
Using polyethylene terephthalate with an intrinsic viscosity (IV) of 0.718 as the island component, polystyrene with an MFR of 18 as the sea component, and an island-in-hole composite nozzle having 8 islands / hole, the spinning temperature is After melt spinning with an island component / sea component mass ratio of 70/30 at 285 ° C., it is drawn, crimped using a push-fit crimper, and then cut into 51 mm lengths to be single A raw cotton of a sea-island composite fiber having a fiber fineness of 7.3 dtex was obtained.

A sheet-like material having an average short fiber diameter of ultrafine fibers of 7.7 μm, a basis weight of 409 g / m ² and a thickness of 1 mm was obtained in the same manner as in Example 1 except that this raw cotton was used. The obtained sheet-like material was excellent in strength and flame retardancy, and had good surface touch and flexibility. The results are shown in Table 2.

Comparative Example 1
The average short fiber diameter of the ultrafine fibers is 4.4 μm in the same manner as in Example 1 except that the warp and weft of the woven fabric are changed to twisted yarns made of polyethylene terephthalate fibers having an intrinsic viscosity (IV) of 0.65. A sheet having a basis weight of 412 g / m ² and a thickness of 1 mm was obtained. Although the obtained sheet-like material is excellent in strength, and has good surface touch and flexibility, it is significantly inferior in flame retardancy. The results are shown in Table 2.

Comparative Example 2
The average short fiber diameter of the ultrafine fibers is 4.4 μm and the basis weight is 462 g / in the same manner as in Comparative Example 1 except that the solid content mass of the resin containing the flame retardant is 80 g / m ^2. A sheet having a thickness of 1 mm was obtained with m ² . The obtained sheet has high strength and good surface touch, and has excellent flame retardancy but is inferior in flexibility. The results are shown in Table 2.

Comparative Example 3
The average short fiber diameter of the ultrafine fibers is 4 in the same manner as in Example 1 except that a twisted yarn made of phosphorus copolymerized polyethylene terephthalate fiber having a phosphorus atom concentration of 0.5 mass% is used for the warp and weft of the woven fabric. A sheet having a thickness of 4 mm and a basis weight of 413 g / m ² and a thickness of 1 mm was obtained. Although the obtained sheet-like material had a good surface touch, excellent flame retardancy and flexibility, it was inferior in strength. The results are shown in Table 2.

  As shown in Examples 1 to 8 in Table 1 and Table 2, in a sheet-like product obtained by impregnating a high-polymer elastic body in a fiber entangled body in which a non-woven fabric and a fabric made of microfibers are laminated and entangled and integrated. When the fibers constituting the woven fabric contain polyphenylene sulfide, the strength, flame retardancy, flexibility and surface touch are excellent.

  On the other hand, as shown in Table 2, when the polyphenylene sulfide fiber is not contained in the fibers constituting the woven and knitted fabric as in Comparative Examples 1 and 2, the flame retardancy is insufficient or the flame retardancy is compensated. The addition of a large amount of the flame retardant causes a lack of flexibility. In addition, as in Comparative Example 3, when a phosphorus-copolymerized polyester fiber is used as a fiber constituting a woven fabric, the strength is insufficient as compared with a sheet-like material using a woven fabric containing polyphenylene sulfide fiber. Become.

Claims (5)

  A sheet-like article comprising a fiber entangled body and a polymer elastic body in which a non-woven fabric and a woven fabric made of ultrafine fibers having an average single fiber diameter of 0.1 to 8 μm are laminated and entangled and integrated, A sheet-like material, wherein the fibers contain polyphenylene sulfide fibers.   The sheet-like material according to claim 1, which contains a phosphorus-based flame retardant and / or an inorganic flame retardant.   The sheet-like material according to claim 2, wherein the flame retardant is not present in the surface layer of the sheet-like material.   The sheet-like material according to any one of claims 1 to 3, wherein 40% by mass or more of the fibers constituting the woven fabric are polyphenylene sulfide fibers.   The sheet-like material according to any one of claims 1 to 3, wherein 100% by mass of the fibers constituting the woven fabric is polyphenylene sulfide fiber.