WO2014042241A1 - シート状物の製造方法及びこの製造方法より得られるシート状物 - Google Patents
シート状物の製造方法及びこの製造方法より得られるシート状物 Download PDFInfo
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- WO2014042241A1 WO2014042241A1 PCT/JP2013/074833 JP2013074833W WO2014042241A1 WO 2014042241 A1 WO2014042241 A1 WO 2014042241A1 JP 2013074833 W JP2013074833 W JP 2013074833W WO 2014042241 A1 WO2014042241 A1 WO 2014042241A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using knitted fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
- D06N3/0036—Polyester fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
- D06M11/05—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof with water, e.g. steam; with heavy water
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/105—Resistant to abrasion, scratch
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/06—Building materials
- D06N2211/063—Wall coverings
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
- D06N2211/106—Footwear
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/14—Furniture, upholstery
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/24—Personal care
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/26—Vehicles, transportation
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
Definitions
- the present invention reduces the amount of organic solvent used in the manufacturing process by using water-dispersed polyurethane as the binder resin, and in an environmentally friendly sheet-like material, achieves both good flexibility and high-grade appearance quality,
- the present invention relates to a method for producing a sheet-like material having good wear resistance.
- a sheet-like material mainly composed of a fibrous base material and polyurethane has excellent characteristics not found in natural leather and is widely used for various applications.
- a leather-like sheet-like material using a polyester-based fibrous base material is excellent in light resistance, and therefore its use has been expanded year by year for clothing, chair upholstery, automobile interior materials, and the like.
- the obtained fibrous base material is mixed with water which is a non-solvent of polyurethane or an organic solvent / water mixed solution.
- water which is a non-solvent of polyurethane or an organic solvent / water mixed solution.
- the organic solvent that is a solvent for such polyurethane a water-miscible organic solvent such as N, N-dimethylformamide (DMF) is used.
- DMF N, N-dimethylformamide
- PVA polyvinyl alcohol
- the former water-dispersed polyurethane impregnation step uses PVA having a saponification degree of 98% and a polymerization degree of 500, but since the polymerization degree is low, the dropping into the water-dispersed polyurethane liquid is suppressed. It was something that could not be done. And when PVA melt
- the present invention relates to an environment-friendly sheet-like manufacturing method that reduces the use of organic solvents in the manufacturing process, and provides a sheet that has both an elegant appearance with napping and a soft texture and has good wear resistance.
- a method for producing a product is provided.
- the sheet-like material manufacturing method of the present invention is a sheet-like material manufacturing method characterized in that the following steps a, b, and c are performed in this order.
- a. A step of imparting 0.1 to 50% by mass of PVA having a saponification degree of 98% or more and a polymerization degree of 800 to 3500 to the fibrous base material based on the mass of fibers contained in the fibrous base material, b. Providing a water-dispersible polyurethane to the fibrous base material to which the PVA is applied, c.
- the fibrous base material in the steps a, b and c is mainly composed of ultrafine fibers or ultrafine fiber expression type fibers having an average single fiber diameter of 0.3 to 7 ⁇ m.
- the fibrous base material is mainly composed of ultrafine fibers as a component
- a step of expressing the ultrafine fibers from the ultrafine fiber-expressing fibers before applying the polyvinyl alcohol is performed, and the fibrous base material is
- an ultrafine fiber-expressing fiber is a main constituent
- the polyvinyl alcohol is removed and at the same time, the ultrafine fiber-expressing fiber is removed from the ultrafine fiber-expressing fiber. It is a manufacturing method which performs the process of expressing a fiber.
- the step of developing ultrafine fibers is a step of treating with an alkaline aqueous solution.
- the fibrous base material in the steps a, b, and c comprises an ultrafine fiber having an average single fiber diameter of 0.3 to 7 ⁇ m as a main constituent, It is a manufacturing method which passes through the process of expressing an ultrafine fiber from the fibrous base material which uses an ultrafine fiber expression type fiber as a main structural component before the process a.
- the fibrous base material in the steps a, b, and c comprises ultrafine fibers having an average single fiber diameter of 0.3 to 7 ⁇ m as a main constituent, After providing water-dispersible polyurethane to a fibrous base material containing an ultrafine fiber-expressing fiber as a main constituent before step a and expressing the ultrafine fiber from the fibrous base material provided with the water-dispersible polyurethane This is a production method through the step a (with reinforcing polyurethane).
- the fibrous base material in the steps a, b and c has an ultrafine fiber-expressing fiber as a main constituent, and after the step c, the ultrafine fiber is used.
- This is a production method through a step of expressing ultrafine fibers having an average single fiber diameter of 0.3 to 7 ⁇ m from a fibrous base material containing expression type fibers as a main constituent.
- the tensile strength of the PVA is 400 to 800 kg / cm 2 .
- the fibrous base material is intertwined with ultrafine fibers or ultrafine fiber-expressing fibers having an average single fiber diameter of 0.3 to 7 ⁇ m and woven fabric and / or knitted fabric. It is integrated.
- the density of the sheet material obtained by the method for producing a sheet material of the present invention is 0.2 to 0.7 g / cm 3 .
- the sheet-like material manufacturing method of the present invention is a sheet-like material manufacturing method characterized in that the following steps a, b, and c are performed in this order.
- a. A step of imparting 0.1 to 50% by mass of PVA having a saponification degree of 98% or more and a polymerization degree of 800 to 3500 to the fibrous base material based on the mass of fibers contained in the fibrous base material, b. Providing a water-dispersible polyurethane to the fibrous base material to which the PVA is applied, c.
- PVA is removed, in the vicinity of the surface layer of the fibrous base material to which a large amount of PVA has adhered, a large gap is formed between the fiber and the polyurethane, and the surface appearance of the sheet-like material that has undergone the napping process becomes a bundle.
- the fibrous base material is an ultrafine fiber having an average single fiber diameter of 0.3 to 7 ⁇ m or an ultrafine fiber expression type fiber as a main constituent
- the fibrous base material is When using ultrafine fibers as the main constituent, performing the step of expressing the ultrafine fibers from the ultrafine fiber-expressing fibers before applying PVA, and the fibrous base material using the ultrafine fiber-expressing fibers as the main constituent
- a process of developing ultrafine fibers from the ultrafine fiber-expressing fibers is performed.
- the timing of sea removal treatment may be selected according to the desired characteristics of the obtained sheet-like material.
- the fibrous base material of the sheet-like material obtained by the present invention uses an ultrafine fiber expression type fiber, and the ultrafine fiber expressed from the ultrafine fiber expression type fiber is a main constituent.
- the fiber can be made ultrafine by passing through the subsequent ultrafine fiber process, and an elegant surface appearance can be obtained.
- the average single fiber diameter of the ultrafine fiber obtained from the ultrafine fiber-expressing type fiber through the fiber ultrafine process is 0.3 to 7 ⁇ m.
- the average single fiber diameter is set to 7 ⁇ m or less, more preferably 6 ⁇ m or less, and even more preferably 5 ⁇ m or less, it is possible to obtain a sheet-like product having excellent flexibility and napping quality.
- the average single fiber diameter is set to 0.3 ⁇ m or more, more preferably 0.7 ⁇ m or more, and even more preferably 1 ⁇ m or more, the bundle of fibers at the time of napping such as coloring after dyeing or grinding with sandpaper is used. Excellent dispersibility and ease of handling.
- the fiber constituting the fibrous base material used in the present invention is not particularly limited.
- polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polylactic acid; 6-nylon and 66-nylon, etc.
- Fibers made of polyamide, acrylic, polyethylene, polypropylene, and melt-spinnable thermoplastic resins such as thermoplastic cellulose can be used.
- polyester fibers are preferably used from the viewpoints of strength, dimensional stability, and light resistance. Further, from the viewpoint of environmental consideration, fibers obtained from recycled raw materials and plant-derived raw materials are preferable.
- the fibrous base material may be configured by mixing fibers of different materials.
- the ultrafine fiber-expressing type fiber As the ultrafine fiber-expressing type fiber, (a) a two-component thermoplastic resin having different solvent solubility is used as a sea component and an island component, and the sea component is dissolved and removed using a solvent or the like to remove the island component from the ultrafine fiber. Adopting sea-island type fibers and (b) peelable composite fibers that split two components of thermoplastic resin radially or in multiple layers on the fiber cross section and split each component into ultrafine fibers. can do.
- the sea-island type fibers can be preferably used also from the viewpoint of the flexibility and texture of the sheet-like material because an appropriate void can be imparted between the island components, that is, between the ultrafine fibers, by removing the sea components. .
- sea-island type fiber for example, a sea-island type composite base is used, and a sea-island type composite fiber in which two components of the sea component and the island component are arranged and spun together; There are mixed spinning fibers.
- Sea-island type composite fibers are preferably used from the viewpoint that ultrafine fibers having a uniform fineness can be obtained, and that a sufficiently long ultrafine fiber is obtained and contributes to the strength of the sheet-like material.
- the island component of the sea-island fiber is not particularly limited.
- polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polylactic acid; polyamides such as 6-nylon and 66-nylon; acrylics; polyethylenes; polypropylenes And fibers made of melt-spinnable thermoplastic resin such as thermoplastic cellulose can be used.
- polyester fibers are preferably used from the viewpoints of strength, dimensional stability, and light resistance. Further, from the viewpoint of environmental consideration, fibers obtained from recycled raw materials and plant-derived raw materials are preferable.
- the fibrous base material may be configured by mixing fibers of different materials.
- the island component of the sea-island fiber may be the same as the fiber constituting the fibrous base material.
- Sea-island type fiber ultrafine treatment can be performed by immersing the sea-island type fiber in a solvent and squeezing the solution.
- a solvent for dissolving the sea component an organic solvent such as toluene or trichloroethylene is used when the sea component is polyethylene, polypropylene or polystyrene, and an alkali such as sodium hydroxide is used when the sea component is a copolymerized polyester or polylactic acid.
- An aqueous solution can be used.
- hot water can be used. From the viewpoint of environmental considerations of the process, a sea removal treatment with an aqueous alkali solution such as sodium hydroxide or hot water is preferable.
- the sea component of the sea-island fiber is not particularly limited, and for example, polyethylene; polypropylene; polystyrene; copolymer polyester obtained by copolymerization with sodium sulfoisophthalate or polyethylene glycol, and polylactic acid; PVA can be used.
- polyethylene polypropylene
- polystyrene polystyrene
- copolymer polyester obtained by copolymerization with sodium sulfoisophthalate or polyethylene glycol
- polylactic acid PVA
- a copolyester or polylactic acid obtained by copolymerizing alkali-decomposable sodium sulfoisophthalate or polyethylene glycol that can be decomposed without using an organic solvent, and hot water-soluble PVA are preferable. .
- the cross-sectional shape of the fiber constituting the fibrous base material is not particularly limited, and may be a round cross-section, but adopts a polygonal shape such as an ellipse, a flat shape, and a triangular shape, or a deformed cross-section shape such as a sector shape and a cross shape. Also good.
- the average single fiber diameter of the fibers constituting the fibrous base material is preferably 0.3 to 20 ⁇ m.
- the thickness is more preferably 0.7 to 15 ⁇ m, particularly preferably 1 to 7 ⁇ m.
- the woven fabric, knitted fabric, non-woven fabric and the like can be adopted as the form of the fibrous base material of the present invention. Especially, since the surface appearance of the sheet-like material at the time of surface raising treatment is favorable, a nonwoven fabric is preferably used.
- the non-woven fabric may be either a short-fiber non-woven fabric or a long-fiber non-woven fabric, but the long-fiber non-woven fabric has fewer fibers facing the thickness direction of the sheet-like material when raised, than the short-fiber non-woven fabric. Is low and the surface appearance tends to be inferior, short fiber nonwoven fabrics are preferably used.
- the fiber length of the short fiber in the short fiber nonwoven fabric is preferably 25 to 90 mm. By setting the fiber length to 25 mm or more, a sheet-like material having excellent abrasion resistance can be obtained by entanglement. In addition, when the fiber length is 90 mm or less, a sheet-like material having excellent texture and quality can be obtained.
- the fiber length is more preferably 30 to 80 mm.
- Needle punch or water jet punch can be employed as a method of entanglement of non-woven fibers or fiber bundles.
- the non-woven fabric has a structure in which bundles of ultrafine fibers (ultrafine fiber bundles) are intertwined. Since the ultrafine fibers are entangled in a bundle state, the strength of the sheet-like material is improved.
- the nonwoven fabric of such an embodiment can be obtained by causing the ultrafine fibers to develop after entanglement of the ultrafine fiber-expressing fibers in advance.
- the ultrafine fiber or the ultrafine fiber bundle constitutes a non-woven fabric
- it may be intertwined with the woven fabric or the knitted fabric for the purpose of improving the strength.
- plain weave, twill weave, satin weave, etc. are mentioned, and plain weave is preferably used from the viewpoint of cost.
- plain weave is preferably used from the viewpoint of cost.
- circular knitting, tricot, Russell and the like can be mentioned.
- the average single fiber diameter of the fibers constituting the woven or knitted fabric is preferably 0.3 to 20 ⁇ m.
- the PVA applied to the fibrous base material has a saponification degree of 98% or more and a polymerization degree of 800 to 3500.
- degree of saponification 98% or more, it is possible to prevent PVA from dissolving in the water-dispersed polyurethane liquid when the water-dispersed polyurethane is applied.
- PVA is dissolved in the water-dispersed polyurethane liquid, not only is the effect sufficient to protect the surface of the ultrafine fibers constituting napped fibers, but also the water-dispersed polyurethane liquid in which PVA is dissolved is used as a fibrous base.
- PVA is taken into the polyurethane and it becomes difficult to remove the PVA later. Therefore, the adhesive state between the polyurethane and the fibers cannot be stably controlled, and the texture becomes hard.
- the solubility of PVA in water varies depending on the degree of polymerization.
- the degree of polymerization is less than 800, PVA is dissolved in the water-dispersed polyurethane liquid when water-dispersed polyurethane is applied.
- the polymerization degree of PVA is larger than 3,500, the viscosity of the PVA aqueous solution becomes high, and when the fibrous base material is impregnated with the PVA aqueous solution, it cannot be penetrated into the fibrous base material.
- PVA preferably has a viscosity of 10 to 50 mPa ⁇ s at 20 ° C. in a 4% by mass aqueous solution.
- a viscosity of 10 to 50 mPa ⁇ s at 20 ° C. in a 4% by mass aqueous solution.
- an appropriate migration structure can be obtained inside the fibrous base material during drying, and a balance of physical properties such as flexibility, surface appearance, and abrasion resistance of the sheet-like material can be obtained.
- the fibrous base material can be easily impregnated by setting it to 50 mPa ⁇ s or less, more preferably 40 mPa ⁇ s or less.
- the glass transition temperature of PVA is preferably 70 to 100 ° C.
- the glass transition temperature is preferably 70 to 100 ° C.
- the glass transition temperature By setting the glass transition temperature to 70 ° C. or higher, more preferably 75 ° C. or higher, softening in the drying process can be prevented, the dimensional stability of the fibrous base material can be obtained, and the surface appearance of the sheet-like material can be deteriorated. Can be suppressed.
- the glass transition temperature to 100 ° C. or lower, more preferably 95 ° C. or lower, it is possible to prevent the fiber base material from becoming too hard and deterioration in process passability.
- the melting point of PVA is preferably 200 to 250 ° C.
- the melting point is preferably 200 to 250 ° C.
- the melting point By setting the melting point to 200 ° C. or higher, more preferably 210 ° C. or higher, softening in the drying process can be prevented, dimensional stability of the fibrous base material can be obtained, and deterioration of the surface appearance of the sheet-like material can be suppressed. Can do.
- the melting point to 250 ° C. or lower, more preferably 240 ° C. or lower, it is possible to prevent the fiber base material from becoming too hard and the process passability from being deteriorated.
- the tensile strength of the PVA film is preferably 400 to 800 kg / cm 2 .
- the tensile strength is a value obtained by measuring a 100 ⁇ m thick PVA film in an atmosphere of a temperature of 20 ° C. and a humidity of 65%.
- the amount of PVA applied to the fibrous base material is 0.1 to 50% by mass, preferably 1 to 45% by mass, based on the fiber mass of the fibrous base material.
- the method for imparting PVA to the fibrous base material is not particularly limited, and various methods commonly used in this field can be adopted.
- PVA is dissolved in water, impregnated into the fibrous base material, and dried by heating.
- the method to do is preferable from a viewpoint which can provide uniformly. If the temperature is too low, the drying time is required to be long. If the temperature is too high, the PVA is insolubilized and cannot be dissolved and removed later. Therefore, drying is preferably performed at 80 to 160 ° C.
- the temperature is more preferably 110 to 150 ° C.
- the drying time is usually 1 to 20 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes from the viewpoint of processability.
- a preferable temperature for the heat treatment is 80 to 180 ° C.
- a more preferable temperature is 100 ° C. to 160 ° C.
- water-dispersed polyurethane is applied to the fibrous base material to which PVA is applied.
- the water dispersion-type polyurethane provided before a sea removal process aims at reinforcement, you may provide to the fiber base material to which PVA is not provided.
- the water-dispersed polyurethane to be applied to the fibrous base material after PVA is preferably 1 to 80% by mass with respect to the fibrous base material, but the purpose is mainly the durability of the product (especially wear resistance). If the amount is too small, the physical properties, durability, etc. of the obtained sheet-like material cannot withstand practical use, so 2-50% by mass is more preferred.
- the fibrous base material in the steps a, b, and c is mainly composed of ultrafine fibers having an average single fiber diameter of 0.3 to 7 ⁇ m.
- the water-dispersible polyurethane is applied to the fibrous base material, and after the ultrafine fibers are expressed from the fibrous base material to which the water-dispersible polyurethane has been applied,
- the water-dispersed polyurethane may be applied to the same type or different types of water-dispersed polyurethane.
- the water-dispersed polyurethane includes (I) a forced emulsification type polyurethane that is forcibly dispersed and stabilized using a surfactant, and (II) a hydrophilic structure in the polyurethane molecular structure, and a surfactant is present.
- the self-emulsifying type polyurethane can be dispersed / stabilized in water without being used, but any of them may be used in the present invention.
- the method for applying the water-dispersible polyurethane to the fibrous base material is not particularly limited, but a method of impregnating and applying the water-dispersible polyurethane liquid to the fibrous base material, solidifying, and heating and drying can be uniformly applied. Therefore, it is preferable.
- the polyurethane liquid can be coagulated by dry coagulation, wet heat coagulation, wet coagulation, or a combination thereof by impregnating and applying a polyurethane liquid to a fibrous base material.
- the concentration of the water-dispersible polyurethane liquid is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, from the viewpoint of storage stability of the water-dispersible polyurethane liquid. It is.
- the polyurethane liquid used in the present invention may contain a water-soluble organic solvent in an amount of 40% by mass or less based on the polyurethane liquid in order to improve storage stability and film forming property. From this point, the content of the organic solvent is preferably 1% by mass or less.
- water-dispersed polyurethane liquid used in the present invention those having heat-sensitive coagulation properties are preferable.
- polyurethane can be uniformly applied in the thickness direction of the fibrous base material.
- heat-sensitive coagulation refers to the property that when a polyurethane liquid is heated, the fluidity of the polyurethane liquid decreases and solidifies when it reaches a certain temperature (thermal coagulation temperature).
- a polyurethane liquid is applied to a fibrous base material, and then solidified by dry coagulation, wet heat coagulation, wet coagulation, or a combination thereof, and dried to give polyurethane to the fibrous base material.
- the heat-sensitive coagulation temperature of the water-dispersed polyurethane liquid is preferably 40 to 90 ° C.
- the heat-sensitive coagulation temperature is preferably 40 to 90 ° C.
- a thermal coagulant may be added as appropriate in order to set the thermal coagulation temperature as described above.
- heat-sensitive coagulants include inorganic salts such as sodium sulfate, magnesium sulfate, calcium sulfate, and calcium chloride; radical reactions such as sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and benzoyl peroxide are initiated. Agents and the like.
- the wet heat coagulation temperature is preferably equal to or higher than the heat sensitive coagulation temperature of polyurethane, and is preferably 40 to 200 ° C.
- the wet heat solidification temperature is preferably 40 ° C. or higher, more preferably 80 ° C. or higher, the time to solidification of the polyurethane can be shortened to further suppress the migration phenomenon.
- the wet heat coagulation temperature is set to 200 ° C. or lower, more preferably 160 ° C. or lower, it is possible to prevent thermal degradation of polyurethane and PVA.
- the wet coagulation temperature is not less than the heat-sensitive coagulation temperature of polyurethane and is preferably 40 to 100 ° C.
- the dry solidification temperature and the drying temperature are preferably 80 to 180 ° C.
- the dry solidification temperature and the drying temperature are preferably 80 to 180 ° C.
- the productivity is excellent.
- the dry coagulation temperature and the drying temperature is set to 180 ° C. or lower, more preferably 160 ° C. or lower, it is possible to prevent thermal degradation of polyurethane and PVA.
- polyurethane used in the present invention a polyurethane obtained by a reaction of a polymer diol, an organic diisocyanate and a chain extender is preferable.
- the polymer diol is not particularly limited.
- polycarbonate-based, polyester-based, polyether-based, silicone-based, and fluorine-based diols can be used, and a copolymer obtained by combining these may be used.
- polycarbonate-based and polyether-based diols are preferably used.
- polycarbonate and polyester are preferably used.
- polycarbonate-based and polyester-based diols are more preferable, and polycarbonate-based diols are particularly preferably used.
- the polycarbonate diol can be produced by a transesterification reaction between an alkylene glycol and a carbonate ester, or a reaction between phosgene or chloroformate ester and an alkylene glycol.
- the alkylene glycol is not particularly limited.
- ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10 -Linear alkylene glycol such as decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, etc.
- Branched alkylene glycols alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
- alicyclic diols such as 1,4-cyclohexanediol
- aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
- Either a polycarbonate diol obtained from a single alkylene glycol or a copolymerized polycarbonate diol obtained from two or more types of alkylene glycols may be used.
- polyester-based diol examples include polyester diols obtained by condensing various low molecular weight polyols and polybasic acids.
- the low molecular weight polyol is not particularly limited, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,2-dimethyl.
- -1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1 , 4-diol, and cyclohexane-1,4-dimethanol can be used.
- addition products obtained by adding various alkylene oxides to bisphenol A can also be used.
- the polybasic acid is not particularly limited, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, One type or two or more types selected from terephthalic acid and hexahydroisophthalic acid may be mentioned.
- the polyether diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymer diols obtained by combining them.
- the number average molecular weight of the polymer diol used in the present invention is preferably 500 to 4000.
- strength as a polyurethane is maintainable by making a number average molecular weight into 4000 or less, More preferably, 3000 or less.
- the organic diisocyanate is not particularly limited. These may be used, and these may be used in combination. Among these, aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferably used from the viewpoint of light resistance.
- the chain extender is not particularly limited, and amine chain extenders such as ethylenediamine and methylenebisaniline, and diol chain extenders such as ethylene glycol can be used. Moreover, the polyamine obtained by making polyisocyanate and water react can also be used as a chain extender.
- a crosslinking agent may be used in combination for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like.
- the cross-linking agent may be an external cross-linking agent added as a third component to the polyurethane, or may be an internal cross-linking agent that introduces a reaction point that becomes a cross-linked structure in advance in the polyurethane molecular structure.
- an internal cross-linking agent it is preferable to use an internal cross-linking agent from the viewpoint that the cross-linking points can be formed more uniformly in the polyurethane molecular structure and the reduction in flexibility can be reduced.
- crosslinking agent a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group, or the like can be used.
- the crosslinking proceeds excessively, the polyurethane tends to harden and the texture of the sheet-like material also tends to harden. Therefore, those having a silanol group are preferably used in terms of the balance between reactivity and flexibility.
- the polyurethane used in the present invention preferably has a hydrophilic group in the molecular structure.
- a hydrophilic group in the molecular structure By having a hydrophilic group in the molecular structure, the dispersion / stability of the water-dispersed polyurethane can be improved.
- hydrophilic group examples include a cation system such as a quaternary amine salt, an anion system such as a sulfonate and carboxylate, a nonionic system such as polyethylene glycol, a combination of a cationic system and a nonionic system, and an anionic system and a nonionic system. Any hydrophilic group of the combination of systems can be employed. Of these, nonionic hydrophilic groups that are free from yellowing caused by light and harmful effects caused by a neutralizing agent are particularly preferably used.
- a neutralizing agent is required.
- the neutralizing agent is a tertiary amine such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine and dimethylethanolamine.
- amines are generated and volatilized by heat during film formation and drying, and released outside the system. For this reason, in order to suppress the release of air and the deterioration of the working environment, it is essential to introduce a device for recovering volatile amines.
- the amine does not volatilize by heating and remains in the final product sheet, it may be discharged to the environment when the product is incinerated.
- the anionic hydrophilic group neutralizing agent is an alkali metal such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or a hydroxide of an alkaline earth metal
- the polyurethane part is wetted with water.
- alkalinity in the case of a nonionic hydrophilic group, since a neutralizing agent is not used, there is no need to worry about deterioration due to hydrolysis of polyurethane.
- the water-dispersed polyurethane used in the present invention is optionally made of various additives, for example, pigments such as carbon black, flame retardants such as phosphorus, halogen, silicone and inorganic, phenol, sulfur and phosphorus.
- Antioxidants such as benzotriazoles, benzophenones, salicylates, cyanoacrylates and oxalic acid anilides, light stabilizers such as hindered amines and benzoates, and hydrolysis resistance of polycarbodiimides Stabilizers, plasticizers, antistatic agents, surfactants, thickeners, softeners, water repellents, coagulation regulators, dyes, preservatives, antibacterial agents, deodorants, cellulose particles, fillers such as microballoons , And inorganic particles such as silica and titanium oxide.
- an inorganic system such as sodium bicarbonate, an organic system such as 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], etc.
- a foaming agent may be contained.
- the content ratio of polyurethane to the sheet-like material of the present invention is preferably 1 to 80% by mass.
- the ratio of the polyurethane is preferably 1% by mass or more, more preferably 5% by mass or more, it is possible to obtain sheet strength and prevent the fibers from falling off.
- the blending ratio of polyurethane is 80% by mass or less, more preferably 70% by mass or less, it is possible to prevent the texture from becoming hard and to obtain good napped quality.
- the content ratio of polyurethane to the sheet-like material is the sum thereof.
- the water-dispersed polyurethane to be applied to the fibrous base material before the ultrafine fiber is preferably 1 to 30% by mass with respect to the fibrous base material. Further, it is a reinforcement of the fibrous base material, and if it is applied too much, the texture of the obtained sheet-like material becomes hard, so 2 to 20% by mass is more preferable.
- the fiber ultrafine treatment (sea removal treatment) of the sea-island fiber can be performed by immersing the sea-island fiber in a solvent and squeezing the solution.
- a solvent for dissolving the sea component an organic solvent such as toluene or trichloroethylene is used when the sea component is polyethylene, polypropylene or polystyrene, and an alkali such as sodium hydroxide is used when the sea component is a copolyester or polylactic acid.
- An aqueous solution can be used. Further, when the sea component is PVA, hot water can be used. From the viewpoint of environmental considerations of the process, a sea removal treatment with an aqueous alkali solution such as sodium hydroxide or hot water is preferable.
- a flexible sheet-like material is obtained by removing PVA from the polyurethane-added sheet.
- the method for removing PVA is not particularly limited, but for example, it is preferable to dissolve and remove the sheet by immersing the sheet in hot water at 60 to 100 ° C. and squeezing with a mangle if necessary.
- a PVA is applied to a fibrous base material having an ultrafine fiber-expressing fiber as a main constituent, polyurethane is applied, and when PVA is removed from a sheet after the polyurethane is applied, the ultrafine fiber is simultaneously removed with PVA. You may pass through the process of making an ultrafine fiber express from an expression type fiber.
- the method for producing a sheet-like product of the present invention may include a step of half-cutting in the thickness direction after applying water-dispersed polyurethane to at least a fibrous base material provided with PVA.
- the PVA is largely adhered to the surface layer of the fibrous base material and is less adhered to the inner layer by migration.
- a small amount of water-dispersed polyurethane adheres to the side with a large amount of PVA, and a large amount of water-dispersed polyurethane to a side with a small amount of PVA.
- a sheet-like material having an attached structure is obtained.
- the surface on which a large amount of PVA is adhered (the surface on which less water-dispersed polyurethane adheres) is used as the napped surface of the sheet-like material, there is a gap between the polyurethane and the ultrafine fibers constituting the napped by the addition of PVA. Is generated, the degree of freedom is given to the fibers constituting the nap, the surface texture becomes flexible, and a good appearance quality and soft touch can be obtained.
- the raised hair is short because the fibers constituting the raised hair are strongly held by the polyurethane.
- a good appearance quality with a dense feeling is obtained, and the wear resistance is also good.
- production efficiency can be improved by including the process of half-cutting in the sheet thickness direction.
- the sheet-like material may be raised to form napped on the surface.
- the method for forming napping is not particularly limited, and various methods that are usually performed in this field, such as buffing with sandpaper or the like, can be used.
- the napped length is preferably 0.2 to 1 mm.
- silicone or the like may be applied as a lubricant to the polyurethane-applied sheet-like material before the raising treatment.
- a lubricant By applying a lubricant, raising by surface grinding becomes possible easily, and the surface quality becomes very good, which is preferable.
- an antistatic agent may be applied before the raising treatment, which is a preferred embodiment because the application of the antistatic agent makes it difficult for grinding powder generated from the sheet-like material to be deposited on the sandpaper by grinding.
- the sheet can be dyed.
- a dyeing method various methods commonly used in this field can be adopted. However, since the sheet-like material can be softened by giving a stagnation effect simultaneously with the dyeing of the sheet-like material, a liquid dyeing machine is used. The method used is preferred.
- the dyeing temperature is preferably 80 to 150 ° C., although it depends on the type of fiber. By setting the dyeing temperature to 80 ° C. or higher, more preferably 110 ° C. or higher, it is possible to efficiently dye the fibers. On the other hand, the deterioration of the polyurethane can be prevented by setting the dyeing temperature to 150 ° C. or lower, more preferably 130 ° C. or lower.
- the dye used in the present invention may be selected in accordance with the type of fiber constituting the fibrous base material, and is not particularly limited.
- a disperse dye can be used for a polyester fiber, and a polyamide fiber. If so, an acid dye or a metal-containing dye can be used, and further a combination thereof can be used. When dyed with disperse dyes, reduction washing may be performed after dyeing.
- a dyeing assistant during dyeing.
- a dyeing assistant By using a dyeing assistant, the uniformity and reproducibility of dyeing can be improved.
- a finishing agent treatment using, for example, a softener such as silicone, an antistatic agent, a water repellent, a flame retardant, a light proofing agent, and an antibacterial agent can be performed.
- the density of the sheet-like material of the present invention is preferably 0.2 to 0.7 g / cm 3 .
- the density is preferably 0.2 to 0.7 g / cm 3 .
- Viscosity of PVA aqueous solution The viscosity at 20 ° C. of a 4 mass% PVA aqueous solution was measured by the rotational viscometer method described in 3.11.1 of JIS K6726 (1994) polyvinyl alcohol test method.
- the average single fiber diameter was obtained by taking a scanning electron microscope (SEM) photograph of the surface of a fibrous base material or sheet-like material at a magnification of 2000 times, randomly selecting 100 fibers, and the single fiber diameter. was calculated by calculating the average value.
- SEM scanning electron microscope
- the outer circumference circle diameter of the irregular cross section was calculated as the single fiber diameter.
- the number of samplings corresponding to each existing number ratio is selected and calculated to be a total of 100. did.
- the fibers of the reinforcing woven fabric or knitted fabric are excluded from the sampling target in the measurement of the average single fiber diameter.
- the surface appearance of the sheet-like material is 5 as follows by visual and sensory evaluation, with 20 adult men and 10 adult women each in good health as a total of 20 evaluators. A stepped evaluation was performed, and the highest evaluation was defined as the surface appearance. As for the surface appearance, Grade 3 to Grade 5 were good. Grade 5: There is uniform fiber napping, the fiber dispersion state is good, and the appearance is good. Grade 4: Evaluation between grade 5 and grade 3. Third grade: The dispersion state of the fibers is slightly poor, but there are fiber nappings and the appearance is reasonably good. Second grade: An evaluation between the third grade and the first grade. First grade: Overall, the dispersion state of the fibers is very poor, or the fibers are long and the appearance is poor.
- Example 1-1 (Nonwoven fabric for fibrous base materials) Polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate was used as the sea component, and polyethylene terephthalate was used as the island component, with a composite ratio of 45 mass% sea component and 55 mass% island component. / 1 filament, sea island type composite fiber having an average single fiber diameter of 17 ⁇ m was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
- the nonwoven fabric for fibrous base material is immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and treated for 30 minutes to obtain a sea removal sheet from which sea components of sea-island type composite fibers have been removed. It was. The average single fiber diameter on the surface of the sea removal sheet was 3 ⁇ m.
- PVA having a saponification degree of 99% and a polymerization degree of 1400 (NM-14 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-coated sheet having a PVA adhesion amount of 10 mass% with respect to the fiber mass of the seawater-removed sheet.
- the seawater sheet provided with the above PVA is impregnated with the above polyurethane liquid, treated in a moist and hot atmosphere at a temperature of 100 ° C. for 5 minutes, then dried with hot air at a drying temperature of 120 ° C. for 5 minutes, and further at 150 ° C.
- a polyurethane-coated sheet was obtained so that the amount of polyurethane adhered to the fiber mass of the nonwoven fabric was 30% by mass.
- the PVA removal sheet is cut in half in the thickness direction, and the surface opposite to the half-cut surface is brushed by grinding using a 240 mesh endless sandpaper, then dyed with disperse dye using a circular dyeing machine, and then reduced and washed. To obtain a sheet.
- the surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 1-2 (Fabric base fabric) A 84 dtex / 36 filament polyethylene terephthalate fiber was used for both warp and weft, and a plain fabric for a fibrous base material having a warp density of 123 / 2.54 cm and a warp density of 98 / 2.54 cm was woven.
- the fabric to which the above PVA is applied is impregnated with the above polyurethane liquid, treated in a moist and hot atmosphere at a temperature of 100 ° C. for 5 minutes, then dried with hot air at a drying temperature of 120 ° C. for 5 minutes, and further at a temperature of 150 ° C.
- a sheet provided with polyurethane was obtained so that the amount of polyurethane adhered to the fiber mass of the nonwoven fabric was 10% by mass.
- the surface of the sheet from which the PVA was removed was brushed by grinding using a 320 mesh endless sandpaper, then dyed with a disperse dye using a circular dyeing machine and subjected to reduction cleaning to obtain a sheet.
- the surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 1-3 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for a fibrous base material as in Example 1-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 1100 (NM-11, manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the above-described PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-attached sheet having a PVA adhesion amount of 15 mass% with respect to the fiber mass of the seawater-removed sheet.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 1-4 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for a fibrous base material as in Example 1-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 2600 (NH-26 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the above PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-coated sheet in which the amount of PVA adhered to the fiber mass of the seawater-removed sheet was 5 mass%.
- Example 1-5 Nonwoven fabric for fibrous base materials
- the sea component polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used, and as the island component, polyethylene terephthalate is used.
- the sea component is 20% by mass and the island component is 80% by mass.
- the obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching.
- the nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
- the nonwoven fabric for fibrous base material was treated in the same manner as in Example 1-1 to obtain a sea removal sheet from which sea components of the sea-island composite fibers were removed.
- the average single fiber diameter on the surface of the sea removal sheet was 4.4 ⁇ m.
- a polyurethane-applied sheet was obtained in the same manner as in Example 1-1.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 1-6 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for a fibrous base material as in Example 1-1 was used.
- a polyurethane-applied sheet was obtained in the same manner as in Example 1-1.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 1-7 (Nonwoven fabric for fibrous base materials)
- the sea component polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used, and as the island component, polyethylene terephthalate is used.
- the sea component is 20% by mass and the island component is 80% by mass.
- / 1 filament sea island type composite fiber having an average single fiber diameter of 30 ⁇ m was obtained.
- the obtained sea-island type composite fiber is cut into a fiber length of 51 mm to form a staple, a fiber web is formed through a card and a cross wrap, and a PET 84 dtex-72 filament on both sides of the web is a strong twisted yarn having a twist of 2000 T / m.
- the plain woven fabric used was laminated and made into a nonwoven fabric by needle punching.
- the nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
- the nonwoven fabric for fibrous base material was treated in the same manner as in Example 1-1 to obtain a sea removal sheet from which sea components of the sea-island composite fibers were removed.
- the average single fiber diameter on the surface of the sea removal sheet was 4.4 ⁇ m.
- a polyurethane-applied sheet was obtained in the same manner as in Example 1-1.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 1-8 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for a fibrous base material as in Example 1-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 1000 (PVA110 manufactured by Kuraray Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the above-described PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-attached sheet having a PVA adhesion amount of 15 mass% with respect to the fiber mass of the seawater-removed sheet.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 1-9 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for a fibrous base material as in Example 1-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 1400 (NM-14 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the above-described PVA liquid, and was heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-applied sheet having a PVA adhesion amount of 10% by mass with respect to the fiber mass of the seawater-removed sheet.
- the seawater sheet provided with the above PVA is impregnated with the above-mentioned polyurethane liquid, dried with hot air at a drying temperature of 120 ° C. for 8 minutes, and further subjected to dry heat treatment at a temperature of 150 ° C. for 2 minutes, whereby a nonwoven fabric fiber is obtained.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 1-1 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for a fibrous base material as in Example 1-1 was used.
- PVA having a saponification degree of 87% and a polymerization degree of 500 (GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1.
- the obtained sheet-like material is not uniformly applied due to partial dissolution of PVA in the water-dispersed polyurethane liquid, the surface appearance is poor in the state of fiber dispersion, and there is no dull feeling of denseness, The texture was hard.
- Example 1-2 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for a fibrous base material as in Example 1-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 500 (NL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared in an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1.
- the obtained sheet-like material is not uniformly applied due to partial dissolution of PVA in the water-dispersed polyurethane liquid, the surface appearance is poor in the state of fiber dispersion, and there is no dull feeling of denseness, The texture was hard.
- Example 1-3 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for a fibrous base material as in Example 1-1 was used.
- Example 1-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 1-1.
- the obtained sheet-like material was soft in texture, but because of too much PVA, the fiber was not sufficiently gripped by polyurethane, the surface appearance was too long and the wear was poor, and the wear resistance was poor Met.
- Example 1-4 A sheet-like material was obtained in the same manner as in Example 1-1 except that the PVA liquid was not prepared and the PVA was not applied or removed. The texture of the obtained sheet was hardened. Further, the surface appearance was poor with no raised hairs.
- Table 1 shows the evaluation results of the sheet-like materials obtained in Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-4.
- Example 2-1 (Nonwoven fabric for fibrous base materials) Polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate was used as the sea component, and polyethylene terephthalate was used as the island component, with a composite ratio of 45 mass% sea component and 55 mass% island component. / 1 filament, sea island type composite fiber having an average single fiber diameter of 17 ⁇ m was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
- PVA having a saponification degree of 99% and a polymerization degree of 1400 (NM-14 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the nonwoven fabric for a fibrous base material is impregnated with the above PVA liquid, and heated and dried at a temperature of 140 ° C. for 10 minutes.
- the adhesion amount of PVA to the island component mass of the sea-island fiber of the nonwoven fabric for a fibrous base material is 10 mass. % PVA application sheet was obtained.
- the sheet provided with the above PVA is impregnated with the above polyurethane liquid, treated in a humid and hot atmosphere at a temperature of 100 ° C. for 5 minutes, then dried with hot air at a drying temperature of 120 ° C. for 5 minutes, and further at a temperature of 150 ° C.
- a sheet provided with polyurethane was obtained so that the amount of polyurethane adhered to the mass of the island component of the nonwoven fabric was 30% by mass.
- the sheet from which the PVA was removed was immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and treated for 30 minutes to obtain a sea removal sheet from which sea components of the sea-island composite fibers were removed. .
- the average single fiber diameter on the surface of the sea removal sheet was 3 ⁇ m.
- the sea removal sheet is cut in half in the thickness direction, and the surface opposite to the half-cut surface is brushed by grinding using a 240 mesh endless sandpaper, then dyed with disperse dye using a circular dyeing machine, and reduced and washed. To obtain a sheet.
- the surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 2-2 (Nonwoven fabric for fibrous base materials)
- the sea component polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used, and as the island component, polyethylene terephthalate is used.
- / 1 filament sea island type composite fiber having an average single fiber diameter of 30 ⁇ m was obtained.
- the obtained sea-island type composite fiber was cut into a fiber length of 51 mm to be a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching.
- the nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
- the sheet from which the PVA was removed was subjected to a fiber ultrafine treatment in the same manner as in Example 2-1, to obtain a seawater-removed sheet from which sea components of the sea-island type composite fibers were removed.
- the average single fiber diameter on the surface of the sea removal sheet was 4.4 ⁇ m.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 2-3 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 2-1 was used.
- Example 2-1 In the same manner as in Example 2-1, except that the PVA liquid similar to that in Example 2-1 was used and the amount of PVA adhered was changed by adjusting the squeezing after impregnation, the sea-island fiber of the nonwoven fabric for fibrous base material was used. A PVA-added sheet having a PVA adhesion amount of 20% by mass relative to the island component mass was obtained.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 2-4 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 2-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 1100 (NM-11, manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the nonwoven fabric for a fibrous base material is impregnated with the above PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes.
- the adhesion amount of PVA to the island component mass of the sea-island fiber of the nonwoven fabric for a fibrous base material is 15 mass. % PVA application sheet was obtained.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 2-5 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 2-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 2600 (NH-26 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the nonwoven fabric for fibrous base material is impregnated with the above PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes, and the adhesion amount of PVA to the island component mass of the sea island fiber of the nonwoven fabric for fibrous base material is 5 mass. % PVA application sheet was obtained.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 2-6 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 2-1 was used.
- the nonwoven fabric for fibrous base material provided with the above PVA is impregnated with the above polyurethane liquid, treated in a moist and hot atmosphere at a temperature of 100 ° C. for 5 minutes, then dried with hot air at a drying temperature of 120 ° C. for 5 minutes, and By performing a dry heat treatment at a temperature of 150 ° C. for 2 minutes, a sheet provided with polyurethane so that the amount of polyurethane attached to the mass of the island component of the nonwoven fabric was 30% by mass was obtained.
- the sheet provided with the polyurethane was immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and treated for 40 minutes to remove PVA and remove the sea components of the sea-island composite fibers.
- a sea removal sheet was obtained.
- the average single fiber diameter on the surface of the sea removal sheet was 3 ⁇ m.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 2-7 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 2-1 was used.
- the seawater sheet provided with the above PVA is impregnated with the above-mentioned polyurethane liquid, dried with hot air at a drying temperature of 120 ° C. for 8 minutes, and further subjected to dry heat treatment at a temperature of 150 ° C. for 2 minutes, whereby a nonwoven fabric fiber is obtained.
- the sheet from which the PVA was removed was subjected to a fiber ultrafine treatment in the same manner as in Example 2-1, to obtain a seawater-removed sheet from which sea components of the sea-island type composite fibers were removed.
- the average single fiber diameter on the surface of the sea removal sheet was 3 ⁇ m.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 2-1 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 2-1 was used.
- PVA having a saponification degree of 87% and a polymerization degree of 500 (GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1.
- the obtained sheet-like material is not uniformly applied due to partial dissolution of PVA in the water-dispersed polyurethane liquid, the surface appearance is poor in the state of fiber dispersion, and there is no dull feeling of denseness, The texture was hard.
- Example 2-2 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 2-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 500 (NL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared in an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1.
- the obtained sheet-like material is not uniformly applied due to partial dissolution of PVA in the water-dispersed polyurethane liquid, the surface appearance is poor in the state of fiber dispersion, and there is no dull feeling of denseness, The texture was hard.
- Example 2-3 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 2-1 was used.
- Example 2-1 In the same manner as in Example 2-1, except that the PVA liquid similar to that in Example 2-1 was used and the amount of PVA adhered was changed by adjusting the squeezing after impregnation, the sea-island fiber of the nonwoven fabric for fibrous base material was used. A PVA-added sheet having a PVA adhesion amount of 55% by mass relative to the island component mass was obtained.
- Example 2-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 2-1.
- the obtained sheet-like material was soft in texture, but because of too much PVA, the fiber was not sufficiently gripped by polyurethane, the surface appearance was too long and the wear was poor, and the wear resistance was poor Met.
- Example 2-4 A sheet-like material was obtained in the same manner as in Example 2-1, except that the preparation of the PVA liquid and the addition / removal of PVA were not performed. The texture of the obtained sheet was hardened. Further, the surface appearance was poor with no raised hairs.
- Table 2 shows the evaluation results of the sheet-like materials obtained in Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-4.
- Example 3-1 (Nonwoven fabric for fibrous base materials) Polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate was used as the sea component, and polyethylene terephthalate was used as the island component, with a composite ratio of 45 mass% sea component and 55 mass% island component. / 1 filament, sea island type composite fiber having an average single fiber diameter of 17 ⁇ m was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
- the nonwoven fabric for fibrous base material is impregnated with the first-stage polyurethane liquid, treated for 5 minutes in a humid heat atmosphere at a temperature of 100 ° C., then dried with hot air at a drying temperature of 120 ° C. for 5 minutes, and further 150
- a first-stage polyurethane-applied sheet was obtained so that the amount of the first-stage polyurethane adhered to the mass of the island component of the nonwoven fabric was 3% by mass.
- the polyurethane-coated sheet was immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and treated for 30 minutes to obtain a sea removal sheet from which sea components of the sea-island composite fibers were removed.
- the average single fiber diameter on the surface of the sea removal sheet was 3 ⁇ m.
- PVA having a saponification degree of 99% and a polymerization degree of 1400 (NM-14 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-coated sheet having a PVA adhesion amount of 10 mass% with respect to the fiber mass of the seawater-removed sheet.
- the seawater-free sheet provided with the above PVA is impregnated with the above-mentioned second-stage polyurethane liquid, treated in a moist and hot atmosphere at a temperature of 100 ° C. for 5 minutes, then dried with hot air at a drying temperature of 120 ° C. for 5 minutes, and By performing a dry heat treatment at a temperature of 150 ° C. for 2 minutes, a sheet provided with the second-stage polyurethane was obtained so that the adhesion amount of the second-stage polyurethane with respect to the fiber mass of the nonwoven fabric was 30% by mass.
- the PVA-removed sheet is cut in half in the thickness direction, and the surface opposite to the half-cut surface is brushed by grinding using a 240 mesh endless sandpaper, and then dyed with a disperse dye using a circular dyeing machine and reduced. Washing was performed to obtain a sheet. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 3-2 (Nonwoven fabric for fibrous base materials)
- the sea component polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used, and as the island component, polyethylene terephthalate is used.
- the sea component is 20% by mass and the island component is 80% by mass.
- the obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching.
- the nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
- a first-stage polyurethane-added sheet was obtained in the same manner as Example 3-1.
- a sea removal sheet was obtained in the same manner as in Example 3-1.
- the average single fiber diameter on the surface of the sea removal sheet was 4.4 ⁇ m.
- a second-stage polyurethane-added sheet was obtained in the same manner as Example 3-1.
- Example 3-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 3-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 3-3 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 3-1 was used.
- a first-stage polyurethane-added sheet was obtained in the same manner as Example 3-1.
- PVA having a saponification degree of 99% and a polymerization degree of 1100 (NM-11, manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the PVA liquid and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-attached sheet having a PVA adhesion amount of 15% by mass with respect to the fiber mass of the seawater-free sheet.
- Example 3-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 3-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 3-4 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 3-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 2600 (NH-26 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- Example 3-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 3-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 3-5 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 3-1 was used.
- a first-stage polyurethane-added sheet was obtained in the same manner as Example 3-1.
- the seawater sheet provided with the above PVA is impregnated with the above-mentioned polyurethane liquid, dried with hot air at a drying temperature of 120 ° C. for 8 minutes, and further subjected to dry heat treatment at a temperature of 150 ° C. for 2 minutes, whereby a nonwoven fabric fiber is obtained.
- Example 3-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 3-1. The surface appearance of the obtained sheet-like material was good, had a soft texture, and had good wear resistance.
- Example 3-1 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 3-1 was used.
- PVA having a saponification degree of 87% and a polymerization degree of 500 (GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-coated sheet having a PVA adhesion amount of 10 mass% with respect to the fiber mass of the seawater-removed sheet.
- Example 3-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 3-1.
- the obtained sheet-like material is not uniformly applied due to partial dissolution of PVA in the water-dispersed polyurethane liquid, the surface appearance is poor in the state of fiber dispersion, and there is no dull feeling of denseness, The texture was hard.
- Example 3-2 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 3-1 was used.
- PVA having a saponification degree of 99% and a polymerization degree of 500 (NL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared in an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.
- the seawater-removed sheet was impregnated with the PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-coated sheet having a PVA adhesion amount of 10 mass% with respect to the fiber mass of the seawater-removed sheet.
- Example 3-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 3-1.
- the obtained sheet-like material is not uniformly applied due to partial dissolution of PVA in the water-dispersed polyurethane liquid, the surface appearance is poor in the state of fiber dispersion, and there is no dull feeling of denseness, The texture was hard.
- Example 3-3 (Nonwoven fabric for fibrous base materials) The same nonwoven fabric for fibrous base material as in Example 3-1 was used.
- Example 3-1 (Half-cut, brushed, dyed, reduced cleaning) A sheet was obtained in the same manner as in Example 3-1.
- the obtained sheet-like material was soft in texture, but because of too much PVA, the fiber was not sufficiently gripped by polyurethane, the surface appearance was too long and the wear was poor, and the wear resistance was poor Met.
- Example 3-4 A sheet-like material was obtained in the same manner as in Example 3-1, except that the preparation of the PVA liquid and the addition / removal of PVA were not performed. The texture of the obtained sheet was hardened. Further, the surface appearance was poor with no raised hairs.
- Table 3 shows the evaluation results of the sheet-like materials obtained in Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-4.
- the sheet-like materials obtained in Examples 3-1 to 3-5 all had a good surface appearance, a soft texture, and good wear resistance.
- most of the sheet-like materials obtained in Comparative Examples 3-1 to 3-4 had a poor surface appearance, and most of them had a hard texture.
- the sheet-like material obtained by the present invention includes furniture, chairs and wall materials, interior materials having a very elegant appearance as a skin material such as seats, ceilings and interiors in vehicle interiors such as automobiles, trains and aircraft, shirts, Jackets, casual shoes, sports shoes, uppers and trims for shoes such as men's shoes and women's shoes, bags, belts, wallets, etc., clothing materials used for some of them, wiping cloth, polishing cloth, CD curtains, etc. It can be suitably used as an industrial material.
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- Engineering & Computer Science (AREA)
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- Chemical & Material Sciences (AREA)
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
a.繊維質基材にケン化度が98%以上、かつ重合度が800~3500であるPVAを繊維質基材に含まれる繊維質量に対し0.1~50質量%付与する工程、
b.該PVAが付与された繊維質基材に水分散型ポリウレタンを付与する工程、
c.該水分散型ポリウレタンを付与した繊維質基材から、PVAを除去する工程。
a.繊維質基材にケン化度が98%以上、かつ重合度が800~3500であるPVAを繊維質基材に含まれる繊維質量に対し0.1~50質量%付与する工程、
b.該PVAが付与された繊維質基材に水分散型ポリウレタンを付与する工程、
c.該水分散型ポリウレタンを付与した繊維質基材から、PVAを除去する工程。
(1)PVA水溶液の粘度
JISK6726(1994)ポリビニルアルコール試験方法の3.11.1記載の回転粘度計法により、4質量%PVA水溶液の20℃の粘度を測定した。
10質量%PVA水分散液を5cm×10cm×1cmのポリエチレン製トレーに入れ、8時間25℃で風乾後、120℃の温度の熱風乾燥機で2時間熱処理して厚さ100μmのPVA乾式膜を得た。このPVA乾式膜について、JISL1096(2010)8.14.1記載のA法(ストリップ法)に従い、引張試験機にて抗張力を測定した。
平均単繊維直径は、繊維質基材またはシート状物表面の走査型電子顕微鏡(SEM)写真を倍率2000倍で撮影し、繊維をランダムに100本選び、単繊維直径を測定して平均値を計算することで算出した。
繊維質基材またはシート状物を構成する繊維が異形断面の場合は、異形断面の外周円直径を単繊維直径として算出した。また、円形断面と異形断面が混合している場合、単繊維直径が大きく異なるものが混合している場合等は、それぞれの存在本数比率に応じたサンプリング数を計100本となるように選び算出した。ただし、繊維質基材に補強用の織物や編物が挿入されているような場合には、当該補強用の織物や編物の繊維は、平均単繊維直径の測定においてサンプリング対象からは除外した。
JISL1096(2010)8.21.1記載のA法(45°カンチレバー法)に基づき、タテ方向とヨコ方向へそれぞれ2cm×15cmの試験片を作成し、45°の斜面を有する水平台に置き、試験片を滑らせて試験片の一端の中央点が斜面と接したときのスケールを読んだ。試験片5枚での平均値を求め、剛軟度とした。
シート状物の表面外観は、健康状態の良好な成人男性と成人女性各10名ずつ、計20名を評価者として、目視と官能評価によって下記のように5段階評価し、最も多かった評価を表面外観とした。表面外観は、3級~5級を良好とした。
5級:均一な繊維の立毛があり、繊維の分散状態は良好で、外観は良好である。
4級:5級と3級の間の評価である。
3級:繊維の分散状態はやや良くない部分があるが、繊維の立毛はあり、外観はまずまず良好である。
2級:3級と1級の間の評価である。
1級:全体的に繊維の分散状態は非常に悪い、または繊維の立毛が長く、外観は不良である。
ナイロン6からなる直径0.4mmのナイロン繊維を繊維の長手方向に垂直に長さ11mmに切ったものを100本そろえて束とし、この束を直径110mmの円内に6重の同心円状に97個(中心に1個、直径17mmの円に6個、直径37mmの円に13個、直径55mmの円に19個、直径74mmの円に26個、直径90mmの円に32個、それぞれの円において等間隔に)配置した円形ブラシ(ナイロン糸9700本)を用い、荷重8ポンド(約3629g)、回転速度65rpm、回転回数50回の条件で、シート状物の円形サンプル(直径45mm)の表面を摩耗せしめ、その前後のサンプルの質量変化を測定し、5サンプルの平均値を摩耗減量とした。
(繊維質基材用不織布)
海成分として、5-スルホイソフタル酸ナトリウムを8mol%共重合したポリエチレンテレフタレートを用い、島成分として、ポリエチレンテレフタレートを用い、海成分45質量%、島成分55質量%の複合比率で、島数36島/1フィラメント、平均単繊維直径17μmの海島型複合繊維を得た。得られた海島型複合繊維を繊維長51mmにカットしてステープルとし、カードおよびクロスラッパーを通して繊維ウェブを形成し、ニードルパンチ処理により、不織布とした。このようにして得られた不織布を、98℃の温度の湯中に2分間浸漬させて収縮させ、100℃の温度で5分間乾燥させ、繊維質基材用不織布とした。
上記の繊維質基材用不織布を95℃の温度に加熱した濃度10g/Lの水酸化ナトリウム水溶液に浸漬して30分間処理を行い、海島型複合繊維の海成分を除去した脱海シートを得た。脱海シート表面の平均単繊維直径は3μmであった。
ケン化度99%、重合度1400のPVA(日本合成化学株式会社製NM-14)を固形分10質量%の水溶液に調製し、PVA液を得た。
上記の脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
ポリオールにポリヘキサメチレンカーボネートを適用し、イソシアネートにジシクロヘキシルメタンジイソシアネートを適用したポリカーボネート系自己乳化型ポリウレタン液の固形分100質量部に対して、感熱凝固剤として過硫酸アンモニウム(APS)2質量部を加え、水によって全体を固形分20質量%に調製し、水分散型ポリウレタン液を得た。感熱凝固温度は72℃であった。
上記のPVAを付与した脱海シートに、上記のポリウレタン液を含浸させ、100℃の温度の湿熱雰囲気下で5分間処理後、乾燥温度120℃の温度で5分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
上記のポリウレタンを付与したシートを、95℃に加熱した水中に浸漬して10分処理を行い、付与したPVAを除去したシートを得た。
上記のPVA除去シートを厚さ方向に半裁し、半裁面と反対の表面を240メッシュのエンドレスサンドペーパーを用いた研削によって起毛処理した後、サーキュラー染色機を用いて分散染料により染色し還元洗浄を行い、シート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用平織物)
タテ糸、ヨコ糸ともに84dtex/36フィラメントのポリエチレンテレフタレート繊維を用い、タテ密度123本/2.54cm、ヨコ密度98本/2.54cmの繊維質基材用平織物を製織した。
実施例1-1と同様のPVA液を用いた。
上記の織物に、実施例1-1と同様の上記PVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、織物の繊維質量に対するPVA質量が20質量%のPVA付与シートを得た。
実施例1-1と同様のポリウレタン液を用いた。
上記のPVAを付与した織物に、上記のポリウレタン液を含浸させ、100℃の温度の湿熱雰囲気下で5分間処理後、乾燥温度120℃の温度で5分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の繊維質量に対するポリウレタンの付着量が10質量%となるようにポリウレタンを付与したシートを得た。
上記のポリウレタンを付与したシートを、95℃に加熱した水中に浸漬して10分処理を行い、付与したPVAを除去したシートを得た。
上記のPVAを除去したシートの表面を320メッシュのエンドレスサンドペーパーを用いた研削によって起毛処理した後、サーキュラー染色機を用いて分散染料により染色し還元洗浄を行い、シート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例1-1と同様の繊維質基材用不織布を用いた。
実施例1-1と同様にして、上記の繊維質基材用不織布から脱海シートを得た。
ケン化度99%、重合度1100のPVA(日本合成化学株式会社製NM-11)を固形分10質量%の水溶液に調製し、PVA液を得た。
脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が15質量%のPVA付与シートを得た。
実施例1-1と同様の水分散型ポリウレタン液を用いた。
実施例1-1と同様にして、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例1-1と同様にして、付与したPVAを除去したシートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例1-1と同様の繊維質基材用不織布を用いた。
実施例1-1と同様にして、上記の繊維質基材用不織布から脱海シートを得た。
ケン化度99%、重合度2600のPVA(日本合成化学株式会社製NH-26)を固形分10質量%の水溶液に調製し、PVA液を得た。
脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が5質量%のPVA付与シートを得た。
実施例1-1と同様の水分散型ポリウレタン液を用いた。
実施例1-1と同様にして、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例1-1と同様にして、付与したPVAを除去したシートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
[実施例1-5]
(繊維質基材用不織布)
海成分として、5-スルホイソフタル酸ナトリウムを8mol%共重合したポリエチレンテレフタレートを用い、島成分として、ポリエチレンテレフタレートを用い、海成分20質量%、島成分80質量%の複合比率で、島数16島/1フィラメント、平均単繊維直径30μmの海島型複合繊維を得た。得られた海島型複合繊維を、繊維長51mmにカットしてステープルとし、カードおよびクロスラッパーを通して繊維ウェブを形成し、ニードルパンチ処理により不織布とした。このようにして得られた不織布を98℃の温度の湯中に2分間浸漬させて収縮させ、100℃の温度で5分間乾燥させ、繊維質基材用不織布とした。
上記の繊維質基材用不織布を実施例1-1と同様にして処理を行い、海島型複合繊維の海成分を除去した脱海シートを得た。脱海シート表面の平均単繊維直径は、4.4μmであった。
実施例1-1と同様のPVA液を用いた。
実施例1-1と同様にして、PVA付与シートを得た。
実施例1-1と同様の水分散型ポリウレタン液を用いた。
実施例1-1と同様にして、ポリウレタン付与シートを得た。
実施例1-1と同様にして、PVA除去シートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例1-1と同様の繊維質基材用不織布を用いた。
実施例1-1と同様にして、上記の繊維質基材用不織布から脱海シートを得た。
実施例1-1と同様のPVA液を用いた。
実施例1-1と同様のPVA液を用い、含浸後の絞りを調節してPVAの付着量を変更した以外は実施例1と同様にして、脱海シートの繊維質量に対するPVAの付着量が20質量%のPVA付与シートを得た。
実施例1-1と同様の水分散型ポリウレタン液を用いた。
実施例1-1と同様にして、ポリウレタン付与シートを得た。
実施例1-1と同様にして、PVA除去シートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
海成分として、5-スルホイソフタル酸ナトリウムを8mol%共重合したポリエチレンテレフタレートを用い、島成分として、ポリエチレンテレフタレートを用い、海成分20質量%、島成分80質量%の複合比率で、島数16島/1フィラメント、平均単繊維直径30μmの海島型複合繊維を得た。得られた海島型複合繊維を、繊維長51mmにカットしてステープルとし、カードおよびクロスラッパーを通して繊維ウェブを形成し、ウェブの両面に、PETの84dtex-72フィラメント、撚り数2000T/mの強撚糸使いの平織物を積層し、ニードルパンチ処理により不織布とした。このようにして得られた不織布を98℃の温度の湯中に2分間浸漬させて収縮させ、100℃の温度で5分間乾燥させ、繊維質基材用不織布とした。
上記の繊維質基材用不織布を実施例1-1と同様にして処理を行い、海島型複合繊維の海成分を除去した脱海シートを得た。脱海シート表面の平均単繊維直径は、4.4μmであった。
実施例1-1と同様のPVA液を用いた。
実施例1-1と同様にして、PVA付与シートを得た。
実施例1-1と同様の水分散型ポリウレタン液を用いた。
実施例1-1と同様にして、ポリウレタン付与シートを得た。
実施例1-1と同様にして、PVA除去シートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例1-1と同様の繊維質基材用不織布を用いた。
実施例1-1と同様にして、上記の繊維質基材用不織布から脱海シートを得た。
ケン化度99%、重合度1000のPVA(クラレ株式会社製PVA110)を固形分10質量%の水溶液に調製し、PVA液を得た。
脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が15質量%のPVA付与シートを得た。
実施例1-1と同様の水分散ポリウレタン液を用いた。
実施例1-1と同様にして、不織布の繊維質重量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例1-1と同様にして、付与したPVAを除去したシートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例1-1と同様の繊維質基材用不織布を用いた。
実施例1-1と同様にして、上記の繊維質基材用不織布から脱海シートを得た。
ケン化度99%、重合度1400のPVA(日本合成化学株式会社製NM-14)を固形分10質量%の水溶液に調製し、PVA液を得た。
脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
ポリオールにポリヘキサメチレンカーボネートを適用し、イソシアネートにジシクロヘキシルメタンジイソシアネートを適用したポリカーボネート系自己乳化型ポリウレタン液の固形分100質量部に対して、増粘剤(サンノプコ株式会社製SNシックナー612)を10質量部を加え、水によって全体をポリウレタン固形分20質量%に調製し、水分散型ポリウレタン液を得た。
上記のPVAを付与した脱海シートに、上記のポリウレタン液を含浸させ、乾燥温度120℃の温度で8分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例1-1と同様にして、付与したPVAを除去したシートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例1-1と同様の繊維質基材用不織布を用いた。
実施例1-1と同様にして、上記の繊維質基材用不織布から脱海シートを得た。
ケン化度87%、重合度500のPVA(日本合成化学株式会社製GL-05)を固形分10質量%の水溶液に調製してPVA液を得た。
上記の脱海シートを用いて実施例1-1と同様にして、脱海シートの繊維質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
実施例1-1と同様の水分散型ポリウレタン液を用いた。
実施例1-1と同様にして、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例1-1と同様にして、付与したPVAを除去したシートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物は、PVAが水分散型ポリウレタン液に一部溶解したことによって均一な付与状態とならず、表面外観は繊維の分散状態が悪く、立毛の緻密感がない不良であり、風合いは硬いものであった。
(繊維質基材用不織布)
実施例1-1と同様の繊維質基材用不織布を用いた。
実施例1-1と同様にして、上記の繊維質基材用不織布から脱海シートを得た。
ケン化度99%、重合度500のPVA(日本合成化学株式会社製NL-05)を固形分10質量%の水溶液に調製してPVA液を得た。
上記の脱海シートを用いて、実施例1-1と同様にして、脱海シートの繊維質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
実施例1-1と同様の水分散型ポリウレタン液を用いた。
実施例1-1と同様にして、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例1-1と同様にして、付与したPVAを除去したシートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物は、PVAが水分散型ポリウレタン液に一部溶解したことによって均一な付与状態とならず、表面外観は繊維の分散状態が悪く、立毛の緻密感がない不良であり、風合いは硬いものであった。
(繊維質基材用不織布)
実施例1-1と同様の繊維質基材用不織布を用いた。
実施例1-1と同様にして、上記の繊維質基材用不織布から脱海シートを得た。
実施例1-1と同様のPVA液を用いた。
含浸後の絞りを調節してPVAの付着量を変更した以外は実施例1-1と同様にして、脱海シートの繊維質量に対するPVAの付着量が55質量%のPVA付与シートを得た。
実施例1-1と同様の水分散型ポリウレタン液を用いた。
実施例1-1と同様にして、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例1-1と同様にして、付与したPVAを除去したシートを得た。
実施例1-1と同様にしてシート状物を得た。得られたシート状物は、風合いは柔軟であったが、PVAが多すぎたためにポリウレタンによる繊維の把持が不十分で、表面外観は立毛が長すぎて不良となり、また耐摩耗性は悪いものであった。
PVA液の調製、PVAの付与・除去を行わない以外は実施例1-1と同様にしてシート状物を得た。得られたシート状物の風合いは硬くなった。また、表面外観は立毛がなく、不良であった。
(繊維質基材用不織布)
海成分として、5-スルホイソフタル酸ナトリウムを8mol%共重合したポリエチレンテレフタレートを用い、島成分として、ポリエチレンテレフタレートを用い、海成分45質量%、島成分55質量%の複合比率で、島数36島/1フィラメント、平均単繊維直径17μmの海島型複合繊維を得た。得られた海島型複合繊維を繊維長51mmにカットしてステープルとし、カードおよびクロスラッパーを通して繊維ウェブを形成し、ニードルパンチ処理により、不織布とした。このようにして得られた不織布を、98℃の温度の湯中に2分間浸漬させて収縮させ、100℃の温度で5分間乾燥させ、繊維質基材用不織布とした。
ケン化度99%、重合度1400のPVA(日本合成化学株式会社製NM-14)を固形分10質量%の水溶液に調製し、PVA液を得た。
上記の繊維質基材用不織布に上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、繊維質基材用不織布の海島繊維の島成分質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
ポリオールにポリヘキサメチレンカーボネートを適用し、イソシアネートにジシクロヘキシルメタンジイソシアネートを適用したポリカーボネート系自己乳化型ポリウレタン液の固形分100質量部に対して、感熱凝固剤として過硫酸アンモニウム(APS)2質量部を加え、水によって全体を固形分20質量%に調製し、水分散型ポリウレタン液を得た。感熱凝固温度は、72℃であった。
上記のPVAを付与したシートに、上記のポリウレタン液を含浸させ、100℃の温度の湿熱雰囲気下で5分間処理後、乾燥温度120℃の温度で5分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の島成分質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
上記のポリウレタンを付与したシートを、95℃に加熱した水中に浸漬して10分処理を行い、付与したPVAを除去したシートを得た。
上記のPVAを除去したシートを95℃の温度に加熱した濃度10g/Lの水酸化ナトリウム水溶液に浸漬して30分間処理を行い、海島型複合繊維の海成分を除去した脱海シートを得た。脱海シート表面の平均単繊維直径は、3μmであった。
上記の脱海シートを厚さ方向に半裁し、半裁面と反対の表面を240メッシュのエンドレスサンドペーパーを用いた研削によって起毛処理した後、サーキュラー染色機を用いて分散染料により染色し還元洗浄を行い、シート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
海成分として、5-スルホイソフタル酸ナトリウムを8mol%共重合したポリエチレンテレフタレートを用い、島成分として、ポリエチレンテレフタレートを用い、海成分20質量%、島成分80質量%の複合比率で、島数16島/1フィラメント、平均単繊維直径30μmの海島型複合繊維を得た。得られた海島型複合繊維を、繊維長51mmにカットしてステープルとし、カードおよびクロスラッパーを通して繊維ウェブを形成し、ニードルパンチ処理により不織布とした。このようにして得られた不織布を98℃の温度の湯中に2分間浸漬させて収縮させ、100℃の温度で5分間乾燥させ、繊維質基材用不織布とした。
実施例2-1と同様のPVA液を用いた。
実施例2-1と同様にして、PVA付与シートを得た。
実施例2-1と同様の水分散型ポリウレタン液を用いた。
実施例2-1と同様にして、ポリウレタン付与シートを得た。
実施例2-1と同様にして、PVA除去シートを得た。
上記のPVAを除去したシートに対して、実施例2-1と同様にして繊維極細化処理を行い、海島型複合繊維の海成分を除去した脱海シートを得た。脱海シート表面の平均単繊維直径は、4.4μmであった。
実施例2-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例2-1と同様の繊維質基材用不織布を用いた。
実施例2-1と同様のPVA液を用いた。
実施例2-1と同様のPVA液を用い、含浸後の絞りを調節してPVAの付着量を変更した以外は実施例2-1と同様にして、繊維質基材用不織布の海島繊維の島成分質量に対するPVAの付着量が20質量%のPVA付与シートを得た。
実施例2-1と同様の水分散型ポリウレタン液を用いた。
実施例2-1と同様にして、ポリウレタン付与シートを得た。
実施例2-1と同様にして、PVA除去シートを得た。
実施例2-1と同様にして、脱海シートを得た。
実施例2-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例2-1と同様の繊維質基材用不織布を用いた。
ケン化度99%、重合度1100のPVA(日本合成化学株式会社製NM-11)を固形分10質量%の水溶液に調製し、PVA液を得た。
上記の繊維質基材用不織布に上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、繊維質基材用不織布の海島繊維の島成分質量に対するPVAの付着量が15質量%のPVA付与シートを得た。
実施例2-1と同様の水分散型ポリウレタン液を用いた。
実施例2-1と同様にして、ポリウレタン付与シートを得た。
実施例2-1と同様にして、PVA除去シートを得た。
実施例2-1と同様にして、脱海シートを得た。
実施例2-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例2-1と同様の繊維質基材用不織布を用いた。
ケン化度99%、重合度2600のPVA(日本合成化学株式会社製NH-26)を固形分10質量%の水溶液に調製し、PVA液を得た。
上記の繊維質基材用不織布に上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、繊維質基材用不織布の海島繊維の島成分質量に対するPVAの付着量が5質量%のPVA付与シートを得た。
実施例2-1と同様の水分散型ポリウレタン液を用いた。
実施例2-1と同様にして、ポリウレタン付与シートを得た。
実施例2-1と同様にして、PVA除去シートを得た。
実施例2-1と同様にして、脱海シートを得た。
実施例2-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例2-1と同様の繊維質基材用不織布を用いた。
実施例2-1と同様のPVA液を用いた。
上記の繊維質基材用不織布に実施例2-1で得た上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、繊維質基材用不織布の島成分質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
実施例2-1と同様の水分散型ポリウレタン液を用いた。
上記のPVAを付与した繊維質基材用不織布に、上記のポリウレタン液を含浸させ、100℃の温度の湿熱雰囲気下で5分間処理後、乾燥温度120℃の温度で5分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の島成分質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
上記のポリウレタンを付与したシートを、95℃の温度に加熱した濃度10g/Lの水酸化ナトリウム水溶液に浸漬して40分間処理を行い、PVAの除去、そして海島型複合繊維の海成分を除去した脱海シートを得た。脱海シート表面の平均単繊維直径は3μmであった。ここで、PVAの除去と脱海とは同時に行われる。
実施例2-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例2-1と同様の繊維質基材用不織布を用いた。
実施例2-1と同様のPVA液を用いた。
実施例2-1と同様にして、PVA付与シートを得た。
ポリオールにポリヘキサメチレンカーボネートを適用し、イソシアネートにジシクロヘキシルメタンジイソシアネートを適用したポリカーボネート系自己乳化型ポリウレタン液の固形分100質量部に対して、増粘剤(サンノプコ株式会社製SNシックナー612)を10質量部を加え、水によって全体をポリウレタン固形分20質量%に調製し、水分散型ポリウレタン液を得た。
上記のPVAを付与した脱海シートに、上記のポリウレタン液を含浸させ、乾燥温度120℃の温度で8分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例2-1と同様にして、PVA除去シートを得た。
上記のPVAを除去したシートに対して、実施例2-1と同様にして繊維極細化処理を行い、海島型複合繊維の海成分を除去した脱海シートを得た。脱海シート表面の平均単繊維直径は、3μmであった。
実施例2-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例2-1と同様の繊維質基材用不織布を用いた。
ケン化度87%、重合度500のPVA(日本合成化学株式会社製GL-05)を固形分10質量%の水溶液に調製してPVA液を得た。
上記のPVA液を用いた以外は実施例2-1と同様にしてPVA付与シートを得た。
実施例2-1と同様の水分散型ポリウレタン液を用いた。
実施例2-1と同様にして、ポリウレタン付与シートを得た。
実施例2-1と同様にして、PVA除去シートを得た。
実施例2-1と同様にして、脱海シートを得た。
実施例2-1と同様にしてシート状物を得た。得られたシート状物は、PVAが水分散型ポリウレタン液に一部溶解したことによって均一な付与状態とならず、表面外観は繊維の分散状態が悪く、立毛の緻密感がない不良であり、風合いは硬いものであった。
(繊維質基材用不織布)
実施例2-1と同様の繊維質基材用不織布を用いた。
ケン化度99%、重合度500のPVA(日本合成化学株式会社製NL-05)を固形分10質量%の水溶液に調製してPVA液を得た。
上記のPVA液を用いた以外は実施例2-1と同様にしてPVA付与シートを得た。
実施例2-1と同様の水分散型ポリウレタン液を用いた。
実施例2-1と同様にして、ポリウレタン付与シートを得た。
実施例2-1と同様にして、PVA除去シートを得た。
実施例2-1と同様にして、脱海シートを得た。
実施例2-1と同様にしてシート状物を得た。得られたシート状物は、PVAが水分散型ポリウレタン液に一部溶解したことによって均一な付与状態とならず、表面外観は繊維の分散状態が悪く、立毛の緻密感がない不良であり、風合いは硬いものであった。
(繊維質基材用不織布)
実施例2-1と同様の繊維質基材用不織布を用いた。
実施例2-1と同様のPVA液を用いた。
実施例2-1と同様のPVA液を用い、含浸後の絞りを調節してPVAの付着量を変更した以外は実施例2-1と同様にして、繊維質基材用不織布の海島繊維の島成分質量に対するPVAの付着量が55質量%のPVA付与シートを得た。
実施例2-1と同様の水分散型ポリウレタン液を用いた。
実施例2-1と同様にして、ポリウレタン付与シートを得た。
実施例2-1と同様にして、PVA除去シートを得た。
実施例2-1と同様にして、脱海シートを得た。
実施例2-1と同様にしてシート状物を得た。得られたシート状物は、風合いは柔軟であったが、PVAが多すぎたためにポリウレタンによる繊維の把持が不十分で、表面外観は立毛が長すぎて不良となり、また耐摩耗性は悪いものであった。
PVA液の調製、PVAの付与・除去を行わない以外は実施2-1と同様にしてシート状物を得た。得られたシート状物の風合いは硬くなった。また、表面外観は立毛がなく、不良であった。
(繊維質基材用不織布)
海成分として、5-スルホイソフタル酸ナトリウムを8mol%共重合したポリエチレンテレフタレートを用い、島成分として、ポリエチレンテレフタレートを用い、海成分45質量%、島成分55質量%の複合比率で、島数36島/1フィラメント、平均単繊維直径17μmの海島型複合繊維を得た。得られた海島型複合繊維を繊維長51mmにカットしてステープルとし、カードおよびクロスラッパーを通して繊維ウェブを形成し、ニードルパンチ処理により、不織布とした。このようにして得られた不織布を、98℃の温度の湯中に2分間浸漬させて収縮させ、100℃の温度で5分間乾燥させ、繊維質基材用不織布とした。
ポリオールにポリテトラメチレングリコールを適用し、イソシアネートにジシクロヘキシルメタンジイソシアネートを適用したポリエーテル系強制乳化型ポリウレタン液の固形分100質量部に対して、感熱凝固剤として硫酸マグネシウム2質量部を加え、水によって全体を固形分20質量%に調製し、水分散型ポリウレタン液を得た。感熱凝固温度は、64℃であった。
上記の繊維質基材用不織布に、上記の1段目ポリウレタン液を含浸させ、100℃の温度の湿熱雰囲気下で5分間処理後、乾燥温度120℃の温度で5分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の島成分質量に対する1段目ポリウレタンの付着量が3質量%となるように1段目ポリウレタン付与シートを得た。
上記のポリウレタン付与シートを95℃の温度に加熱した濃度10g/Lの水酸化ナトリウム水溶液に浸漬して30分間処理を行い、海島型複合繊維の海成分を除去した脱海シートを得た。脱海シート表面の平均単繊維直径は、3μmであった。
ケン化度99%、重合度1400のPVA(日本合成化学株式会社製NM-14)を固形分10質量%の水溶液に調製し、PVA液を得た。
上記の脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
ポリオールにポリヘキサメチレンカーボネートを適用し、イソシアネートにジシクロヘキシルメタンジイソシアネートを適用したポリカーボネート系自己乳化型ポリウレタン液の固形分100質量部に対して、感熱凝固剤として過硫酸アンモニウム(APS)2質量部を加え、水によって全体を固形分20質量%に調製し、水分散型ポリウレタン液を得た。感熱凝固温度は、72℃であった。
上記のPVAを付与した脱海シートに、上記の2段目ポリウレタン液を含浸させ、100℃の温度の湿熱雰囲気下で5分間処理後、乾燥温度120℃の温度で5分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の繊維質量に対する2段目ポリウレタンの付着量が30質量%となるように2段目ポリウレタンを付与したシートを得た。
上記の2段目ポリウレタンを付与したシートを、95℃に加熱した水中に浸漬して10分処理を行い、PVA除去シートを得た。
上記のPVAを除去したシートを厚さ方向に半裁し、半裁面と反対の表面を240メッシュのエンドレスサンドペーパーを用いた研削によって起毛処理した後、サーキュラー染色機を用いて分散染料により染色し還元洗浄を行い、シート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
海成分として、5-スルホイソフタル酸ナトリウムを8mol%共重合したポリエチレンテレフタレートを用い、島成分として、ポリエチレンテレフタレートを用い、海成分20質量%、島成分80質量%の複合比率で、島数16島/1フィラメント、平均単繊維直径30μmの海島型複合繊維を得た。得られた海島型複合繊維を、繊維長51mmにカットしてステープルとし、カードおよびクロスラッパーを通して繊維ウェブを形成し、ニードルパンチ処理により不織布とした。このようにして得られた不織布を98℃の温度の湯中に2分間浸漬させて収縮させ、100℃の温度で5分間乾燥させ、繊維質基材用不織布とした。
実施例3-1と同様の1段目ポリウレタンを用いた。
実施例3-1と同様にして1段目ポリウレタン付与シートを得た。
実施例3-1と同様にして脱海シートを得た。脱海シート表面の平均単繊維直径は、4.4μmであった。
実施例3-1と同様のPVA液を用いた。
実施例3-1と同様にしてPVA付与シートを得た。
実施例3-1と同様の2段目ポリウレタン液を用いた。
実施例3-1と同様にして2段目ポリウレタン付与シートを得た。
実施例3-1と同様にしてPVA除去シートを得た。
実施例3-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例3-1と同様の繊維質基材用不織布を用いた。
実施例3-1と同様の1段目ポリウレタン液を用いた。
実施例3-1と同様にして1段目ポリウレタン付与シートを得た。
実施例3-1と同様にして脱海シートを得た。
ケン化度99%、重合度1100のPVA(日本合成化学株式会社製NM-11)を固形分10質量%の水溶液に調製し、PVA液を得た。
上記の脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が15質量%のPVA付与シートを得た。
実施例3-1と同様の2段目ポリウレタン液を用いた。
実施例3-1と同様にして、2段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、PVA除去シートを得た。
実施例3-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例3-1と同様の繊維質基材用不織布を用いた。
実施例3-1と同様の1段目ポリウレタン液を用いた。
実施例3-1と同様にして、1段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、脱海シートを得た。
ケン化度99%、重合度2600のPVA(日本合成化学株式会社製NH-26)を固形分10質量%の水溶液に調製し、PVA液を得た。
上記の脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が5質量%のPVA付与シートを得た。
実施例3-1と同様の2段目ポリウレタン液を用いた。
実施例3-1と同様にして、2段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、PVA除去シートを得た。
実施例3-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例3-1と同様の繊維質基材用不織布を用いた。
実施例3-1と同様の1段目ポリウレタン液を用いた。
実施例3-1と同様にして1段目ポリウレタン付与シートを得た。
実施例3-1と同様にして脱海シートを得た。
実施例3-1と同様のPVA液を用いた。
実施例3-1と同様にしてPVA付与シートを得た。
ポリオールにポリヘキサメチレンカーボネートを適用し、イソシアネートにジシクロヘキシルメタンジイソシアネートを適用したポリカーボネート系自己乳化型ポリウレタン液の固形分100質量部に対して、増粘剤(サンノプコ株式会社製SNシックナー612)を10質量部を加え、水によって全体をポリウレタン固形分20質量%に調製し、水分散型ポリウレタン液を得た。
上記のPVAを付与した脱海シートに、上記のポリウレタン液を含浸させ、乾燥温度120℃の温度で8分間熱風乾燥させ、さらに150℃の温度で2分間乾熱処理を行うことにより、不織布の繊維質量に対するポリウレタンの付着量が30質量%となるようにポリウレタンを付与したシートを得た。
実施例3-1と同様にして、PVA除去シートを得た。
実施例3-1と同様にしてシート状物を得た。得られたシート状物の表面外観は良好で、柔軟な風合いを有し、耐摩耗性も良好であった。
(繊維質基材用不織布)
実施例3-1と同様の繊維質基材用不織布を用いた。
実施例3-1と同様の1段目ポリウレタンを用いた。
実施例3-1と同様にして、1段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、脱海シートを得た。
ケン化度87%、重合度500のPVA(日本合成化学株式会社製GL-05)を固形分10質量%の水溶液に調製してPVA液を得た。
上記の脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
実施例3-1と同様の2段目ポリウレタン液を用いた。
実施例3-1と同様にして、2段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、PVA除去シートを得た。
実施例3-1と同様にしてシート状物を得た。得られたシート状物は、PVAが水分散型ポリウレタン液に一部溶解したことによって均一な付与状態とならず、表面外観は繊維の分散状態が悪く、立毛の緻密感がない不良であり、風合いは硬いものであった。
(繊維質基材用不織布)
実施例3-1と同様の繊維質基材用不織布を用いた。
実施例3-1と同様の1段目ポリウレタンを用いた。
実施例3-1と同様にして、1段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、脱海シートを得た。
ケン化度99%、重合度500のPVA(日本合成化学株式会社製NL-05)を固形分10質量%の水溶液に調製してPVA液を得た。
上記の脱海シートに上記のPVA液を含浸させ、140℃の温度で10分間加熱乾燥を行い、脱海シートの繊維質量に対するPVAの付着量が10質量%のPVA付与シートを得た。
実施例3-1と同様の2段目ポリウレタン液を用いた。
実施例3-1と同様にして、2段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、PVA除去シートを得た。
実施例3-1と同様にしてシート状物を得た。得られたシート状物は、PVAが水分散型ポリウレタン液に一部溶解したことによって均一な付与状態とならず、表面外観は繊維の分散状態が悪く、立毛の緻密感がない不良であり、風合いは硬いものであった。
(繊維質基材用不織布)
実施例3-1と同様の繊維質基材用不織布を用いた。
実施例3-1と同様の1段目ポリウレタンを用いた。
実施例3-1と同様にして、1段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、脱海シートを得た。
実施例3-1と同様のPVA液を用いた。
実施例3-1と同様のPVA液を用い、含浸後の絞りを調節してPVAの付着量を変更した以外は実施例3-1と同様にして、脱海シートの繊維質量に対するPVAの付着量が55質量%のPVA付与シートを得た。
実施例3-1と同様の2段目ポリウレタン液を用いた。
実施例3-1と同様にして、2段目ポリウレタン付与シートを得た。
実施例3-1と同様にして、PVA除去シートを得た。
実施例3-1と同様にしてシート状物を得た。得られたシート状物は、風合いは柔軟であったが、PVAが多すぎたためにポリウレタンによる繊維の把持が不十分で、表面外観は立毛が長すぎて不良となり、また耐摩耗性は悪いものであった。
PVA液の調製、PVAの付与・除去を行わない以外は実施例3-1と同様にしてシート状物を得た。得られたシート状物の風合いは硬くなった。また、表面外観は立毛がなく、不良であった。
Claims (9)
- 次のa、b、cの工程をこの順に行うことを特徴とするシート状物の製造方法。
a.繊維質基材にケン化度が98%以上、かつ重合度が800~3500であるポリビニルアルコールを繊維質基材に含まれる繊維質量に対し0.1~50質量%付与する工程、
b.該ポリビニルアルコールが付与された繊維質基材に水分散型ポリウレタンを付与する工程、
c.該水分散型ポリウレタンを付与した繊維質基材から、ポリビニルアルコールを除去する工程。 - 前記工程a、b、cの繊維質基材が平均単繊維直径0.3~7μmの極細繊維または極細繊維発現型繊維を主構成成分とし、前記繊維質基材が極細繊維を主構成成分とする場合において、前記ポリビニルアルコールを付与する前に極細繊維発現型繊維から前記極細繊維を発現させる工程を行い、前記繊維質基材が極細繊維発現型繊維を主構成成分とする場合において、前記ポリビニルアルコールを除去した後に、または前記水分散型ポリウレタンを付与した後に前記ポリビニルアルコールを除去するのと同時に、前記極細繊維発現型繊維から極細繊維を発現させる工程を行うことを特徴とする請求項1記載のシート状物の製造方法。
- 極細繊維を発現する工程がアルカリ水溶液で処理する工程であることを特徴とする請求項2記載のシート状物の製造方法。
- 前記工程a、b、cの段階における繊維質基材が平均単繊維直径0.3~7μmの極細繊維を主構成成分とし、前記工程aの前に、極細繊維発現型繊維を主構成成分とする繊維質基材から極細繊維を発現させる工程を経ることを特徴とする請求項1~3のいずれか記載のシート状物の製造方法。
- 前記工程a、b、cの段階における繊維質基材が平均単繊維直径0.3~7μmの極細繊維を主構成成分とし、前記工程aの前に極細繊維発現型繊維を主構成成分とする繊維質基材に水分散型ポリウレタンを付与し、前記水分散型ポリウレタンを付与した繊維質基材から前記極細繊維を発現させた後に、前記工程aを経ることを特徴とする請求項1~3のいずれか記載のシート状物の製造方法。
- 前記工程a、b、cの段階における繊維質基材が極細繊維発現型繊維を主構成成分とし、前記工程cの後もしくは同時に、前記極細繊維発現型繊維を主構成成分とする繊維質基材から、平均単繊維直径が0.3~7μmの極細繊維を発現させる工程を経ることを特徴とする1~3のいずれか記載のシート状物の製造方法。
- 前記ポリビニルアルコールの抗張力が400~800kg/cm2であることを特徴とする請求項1~6のいずれか記載のシート状物の製造方法。
- 繊維質基材が、平均単繊維直径0.3~7μmの極細繊維または極細繊維発現型繊維と織物および/または編物とが絡合一体化してなることを特徴とする請求項1~7のいずれか記載のシート状物の製造方法。
- 請求項1~8のいずれか記載の製造方法により得られるシート状物であって、密度が
0.2~0.7g/cm3であることを特徴とするシート状物。
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CN201380047851.5A CN104619909B (zh) | 2012-09-14 | 2013-09-13 | 片状物的制造方法及利用该制造方法得到的片状物 |
KR1020157008233A KR102131678B1 (ko) | 2012-09-14 | 2013-09-13 | 시트상물의 제조 방법 및 이 제조 방법으로부터 얻어지는 시트상물 |
US14/427,744 US10301770B2 (en) | 2012-09-14 | 2013-09-13 | Process for producing sheet-shaped material and sheet-shaped material obtained by said process |
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WO2019244862A1 (ja) * | 2018-06-20 | 2019-12-26 | 東レ株式会社 | シート状物の製造方法 |
WO2021125029A1 (ja) * | 2019-12-20 | 2021-06-24 | 東レ株式会社 | シート状物およびその製造方法 |
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CN107794774B (zh) * | 2017-11-03 | 2019-05-03 | 江苏尚科聚合新材料有限公司 | 一种高耐磨人工皮革及其制备方法 |
JP2019099970A (ja) * | 2017-12-07 | 2019-06-24 | セーレン株式会社 | ヌバック調布帛、及びヌバック調布帛の製造方法 |
KR102062215B1 (ko) * | 2018-05-29 | 2020-01-03 | 삼덕통상 주식회사 | 닥나무 펄프를 포함하는 신발 부재 |
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JPWO2016031694A1 (ja) * | 2014-08-28 | 2017-06-08 | 東レ株式会社 | シート状物およびその製造方法 |
WO2019244862A1 (ja) * | 2018-06-20 | 2019-12-26 | 東レ株式会社 | シート状物の製造方法 |
JPWO2019244862A1 (ja) * | 2018-06-20 | 2021-07-08 | 東レ株式会社 | シート状物の製造方法 |
JP7163959B2 (ja) | 2018-06-20 | 2022-11-01 | 東レ株式会社 | シート状物の製造方法 |
WO2021125029A1 (ja) * | 2019-12-20 | 2021-06-24 | 東レ株式会社 | シート状物およびその製造方法 |
JP6904494B1 (ja) * | 2019-12-20 | 2021-07-14 | 東レ株式会社 | シート状物およびその製造方法 |
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CN104619909B (zh) | 2017-09-22 |
EP2896741B1 (en) | 2019-08-07 |
EP2896741A4 (en) | 2016-06-08 |
EP2896741A1 (en) | 2015-07-22 |
US10301770B2 (en) | 2019-05-28 |
TWI583847B (zh) | 2017-05-21 |
KR102131678B1 (ko) | 2020-07-08 |
JPWO2014042241A1 (ja) | 2016-08-18 |
US20150233050A1 (en) | 2015-08-20 |
KR20150058268A (ko) | 2015-05-28 |
JP5880721B2 (ja) | 2016-03-09 |
TW201425685A (zh) | 2014-07-01 |
CN104619909A (zh) | 2015-05-13 |
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