WO2013157156A1 - 多層シート、それを備える保温用構造物及び多層シートの製造方法 - Google Patents
多層シート、それを備える保温用構造物及び多層シートの製造方法 Download PDFInfo
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- WO2013157156A1 WO2013157156A1 PCT/JP2012/071785 JP2012071785W WO2013157156A1 WO 2013157156 A1 WO2013157156 A1 WO 2013157156A1 JP 2012071785 W JP2012071785 W JP 2012071785W WO 2013157156 A1 WO2013157156 A1 WO 2013157156A1
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- moisture
- permeable
- resin
- multilayer sheet
- powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G9/00—Bed-covers; Counterpanes; Travelling rugs; Sleeping rugs; Sleeping bags; Pillows
- A47G9/02—Bed linen; Blankets; Counterpanes
- A47G9/0207—Blankets; Duvets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/026—Knitted fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
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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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0068—Polymeric granules, particles or powder, e.g. core-shell particles, microcapsules
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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
- D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
- B32B2262/062—Cellulose fibres, e.g. cotton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/06—Vegetal particles
- B32B2264/062—Cellulose particles, e.g. cotton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/105—Metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/304—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
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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
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/02—Natural macromolecular compounds or derivatives thereof
- D06N2203/024—Polysaccharides or derivatives thereof
- D06N2203/026—Cellulose or derivatives thereof
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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
- D06N2205/00—Condition, form or state of the materials
- D06N2205/10—Particulate form, e.g. powder, granule
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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
- D06N2209/06—Properties of the materials having thermal properties
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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
- D06N2209/12—Permeability or impermeability properties
- D06N2209/121—Permeability to gases, adsorption
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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
Definitions
- the present invention relates to a multilayer sheet excellent in heat retention utilizing moisture absorption heat generation, a method for producing the same, and a structure for heat insulation such as bedding and cold clothing, which includes the multilayer sheet as all or part of the constituent requirements.
- Patent Document 1 discloses a stretchable and moisture-permeable base material (specifically, a knitted fabric, a woven fabric, a nonwoven fabric, paper, or a plastic sheet), an aluminum powder or a fine aluminum foil piece applied to one side of the base material.
- a heat-insulating sheet-like material comprising a resin layer in which is dispersed and a thermoplastic resin sheet covering the surface of the resin layer. This heat-insulating sheet-like material is used by being affixed to the body or housed in a housing part formed in clothing, and is not planned to be used for washing.
- Patent Document 2 discloses a metal-containing fabric having a metal thin film layer such as aluminum and a colorant-containing layer on at least one surface of the fabric, and the metal thin film layer and the colorant-containing layer are yarns constituting the fabric surface. And a metal-containing fabric that has an air permeability of 125 cc / cm 2 / sec or more at 125 Pa. The feature of this fabric is that it is excellent in thermal characteristics and also in design, flexibility and breathability. However, when this fabric is washed, aluminum is dissolved as aluminum hydroxide.
- Patent Documents 3 and 4 describe that polycarboxylic acid-treated cellulose fibers obtained by treating cellulose fibers with polycarboxylic acid exhibit hygroscopic exothermic properties.
- the polycarboxylic acid adhered to the cellulose fiber is dissolved by washing, that is, lacks washing resistance. Therefore, heat treatment, soaping treatment (Patent Document 3), curing treatment, acid treatment (Patent Document 4), and the like have been tried to impart washing resistance. It cannot be said that washability is imparted.
- Patent Document 3 also describes that the amount of heat generated from untreated cellulose fibers is insufficient for the human body to feel the warmth when worn, and this causes cold feeling when wearing cotton products.
- Patent Document 5 also describes that cellulose fibers are not excellent in heat retaining properties like wool, so that it is a drawback to feel cold when touching the skin.
- Patent Document 6 discloses an invention of an outer garment obtained by coating a windproof waterproof resin containing a substance having absorption / release properties as a particulate additive on the back surface of a fabric.
- the particulate additive include collagen fiber, sponge, chitin, cellulose, gelatin, wool and silk.
- Patent Document 7 discloses an invention for a novel water-repellent treatment composition for clothing characterized by containing at least 5 to 500 parts by weight of feather fine powder with respect to 100 parts by weight of the solid content of the resin composition. Is disclosed.
- Patent Document 8 discloses a synthetic resin surface layer containing an organic filler such as cellulose powder, cork powder, and wood powder.
- Patent Document 9 discloses an invention of a heat storage fiber structure characterized in that a heat storage capsule in which a heat storage substance is contained in a microcapsule is fixed to the fiber structure with a resin binder.
- Patent Document 9 may contain natural organic fine powders such as collagen powder, silk powder, wool powder, cellulose powder, chitin powder, and soybean powder for the purpose of imparting moisture absorption / release properties to the heat storage fiber structure. There is a statement to that effect.
- Patent Document 10 includes an invention of a coating composition for a fiber material, which contains an aqueous solution of a low molecular weight polypeptide produced by hydrolyzing silk fibroin and an aqueous binder that cures at 120 ° C. or lower. Is disclosed. Patent Document 10 has a description that this composition may be mixed with far-infrared radiation ceramics such as an aluminum alone or a composite or an oxide.
- An object of the present invention is to apply a technique different from the conventional technique, specifically, a multilayer sheet having excellent heat retention using a granular material exhibiting hygroscopic heat generation and a method for producing the same And it is providing the structure for heat insulation provided with such a sheet
- the present inventor surprisingly has a specific water-insoluble hygroscopic exothermic property on at least one surface of a moisture-permeable substrate such as a cloth or a polymer film.
- a moisture-permeable substrate such as a cloth or a polymer film.
- the present invention includes a moisture permeable substrate layer and a moisture permeable resin layer formed on at least one surface of the moisture permeable substrate layer.
- the moisture-permeable resin may be a resin adhering to the moisture-permeable substrate, a hydrolyzate of a water-insoluble hygroscopic exothermic granular material derived from a plant, and / or
- the amount of the resin adhering to the moisture-permeable base material is 20 to 80% by mass and the amount of the water-insoluble moisture-absorbing exothermic granular material is the total amount of the moisture-permeable resin.
- the present invention relates to a multilayer sheet characterized by being 80 to 20% by mass. In applications where flexibility is required, the moisture-permeable resin layer is preferably formed only on one surface of the moisture-permeable substrate layer.
- the amount of the water-insoluble hygroscopic exothermic granular material may be 5 to 100 g / m 2 .
- the water-insoluble hygroscopic exothermic granular material is preferably a cellulose hydrolyzate powder, particularly a pulp / cellulose hydrolyzate powder.
- the water-insoluble hygroscopic exothermic granular material is also preferably a protein hydrolyzate powder derived from animals.
- the resin that adheres to the moisture permeable substrate is preferably an acrylic resin.
- the moisture-permeable resin is a composition obtained by adding a water-insoluble hygroscopic exothermic granular material to an acrylic binder containing an acrylic monomer (that is, a precursor of an acrylic resin) as a main component. It may be formed by using a composition in which a water-insoluble hygroscopic exothermic granular material is added to an adhesive mainly composed of an acrylic resin. Also good.
- the moisture permeable polymer film (I) is present on the surface of one or both moisture permeable resin layers. Or a knitted fabric, a woven fabric or a moisture-permeable nonwoven fabric is present.
- Moisture permeability of the moisture-permeable polymeric film (I) is preferably 400g / m 2/24 hours or more.
- the moisture-permeable polymer film (I) is preferably a moisture-permeable polyurethane film, particularly a waterproof / breathable polyurethane film.
- the multilayer sheet of the present invention has a moisture-permeable polymer film (I) on the surface of one or both moisture-permeable resin layers, one or both of the moisture-permeable polymer films (I) Further, a knitted fabric, a woven fabric, or a moisture-permeable nonwoven fabric may be present on the outer side of the fabric through a moisture-permeable adhesive layer.
- the multilayer sheet of the present invention includes an embodiment in which the moisture-permeable resin further contains aluminum powder, and the amount thereof is 40% by mass or less in the total amount of the moisture-permeable resin.
- the moisture-permeable resin further contains aluminum powder, and the amount thereof is 40% by mass or less in the total amount of the moisture-permeable resin.
- a waterproof / breathable polymer film (I) is disposed on both sides of the aluminum powder-containing moisture-permeable resin layer.
- the aluminum powder-containing moisture-permeable resin layer and the waterproof / breathable polymer film (I) may not be in direct contact with each other. That is, another layer may exist between the aluminum powder-containing moisture-permeable resin layer and the waterproof / breathable polymer film (I).
- the present invention also relates to a heat insulation structure including the multilayer sheet according to any one of the above aspects.
- the present invention relates to a moisture-permeable substrate, a resin adhering to the moisture-permeable substrate or a precursor of such a resin, a hydrolyzate of a water-insoluble hygroscopic exothermic granular material derived from a plant, and And / or applying a composition comprising a hydrolyzate of animal origin in an amount of 10 to 200 g / m 2 and curing the resin or precursor of such resin that adheres to the moisture permeable substrate.
- the present invention also relates to a method for producing a multilayer sheet, characterized in that the hygroscopic exothermic particles are contained in an amount of 80 to 20% by mass.
- the step of applying the composition is preferably performed by mechanical coating.
- the coating amount is preferably 10 to 50 g / m 2 .
- a multilayer sheet exhibiting sufficient warmth to exhibit a hygroscopic exothermic effect by the hygroscopic exothermic granular material, and a structure for keeping warm such as bedding having the multilayer sheet as all or part of the constituent requirements Things are provided.
- the multilayer sheet and the heat retaining structure of the present invention are excellent in washing resistance, a product life similar to that of conventional bedding and the like is realized.
- the heat retaining performance is further enhanced.
- a moisture-permeable base material contains a raising knitted fabric, heat retention performance improves. If the raised knitted fabric is made of microfiber, the heat retaining performance is further enhanced.
- the present invention contributes to resource saving.
- FIG. 1 is a schematic cross-sectional view showing an example of the multilayer sheet of the present invention.
- the multilayer sheet 100 of the present invention includes a layer 1 of a moisture-permeable substrate and a layer 3 of a moisture-permeable resin formed on one surface of the layer 1 of the moisture-permeable substrate.
- FIG. 2 is a schematic cross-sectional view showing another example of the multilayer sheet of the present invention.
- the multilayer sheet 200 of the present invention includes a moisture-permeable substrate layer 1 and moisture-permeable resin layers 3x and 3y formed on both surfaces of the moisture-permeable substrate layer 1.
- the moisture permeable resin layers 3, 3 x, and 3 y include a resin 31 that adheres to the moisture permeable substrate and a cellulose hydrolyzate powder 33.
- the boundary between the moisture-permeable base material layer 1 and the moisture-permeable resin layers 3, 3x, and 3y is drawn in a straight line, but the boundary may be ambiguous.
- the moisture-permeable resin containing the resin 31 that adheres to the moisture-permeable substrate and the cellulose hydrolyzate powder 33 is outside the layer 1 of the moisture-permeable substrate (that is, the layer 3 of the moisture-permeable resin in FIGS. 1 and 2). , 3x, 3y) as well as inside the layer 1 of the moisture-permeable substrate.
- the moisture-permeable resin layers 3, 3 x, 3 y are not only present on the surface of the moisture-permeable substrate layer 1, but also moisture-permeable.
- the entire layer 1 of the moisture-permeable base material enters the base material when forming the layers 3, 3x, 3y of the moisture-permeable resin.
- Such an embodiment is also encompassed by the present invention.
- FIG. 3 is a schematic cross-sectional view showing still another example of the multilayer sheet of the present invention.
- the multilayer sheet 300 of the present invention includes a moisture-permeable substrate layer 1, a moisture-permeable resin layer 3 formed on one surface thereof, and a moisture-permeable polymer formed on the surface of the moisture-permeable resin layer 3. -Film (I) 5 is provided.
- FIG. 4 is a schematic cross-sectional view showing still another example of the multilayer sheet of the present invention.
- the multilayer sheet 400 of the present invention includes a moisture permeable substrate layer 1, moisture permeable resin layers 3 x and 3 y formed on both surfaces thereof, and a moisture permeable resin layer 3 x formed on the surface of the moisture permeable resin layer 3 x.
- the multilayer sheet 400 has two moisture-permeable resin layers 3x and 3y, and only one of the layers 3x is an example in which the surface is covered with the moisture-permeable polymer film (I) 5.
- a sheet in which a knitted fabric, a woven fabric, or a moisture-permeable nonwoven fabric is arranged is also a multilayer sheet of the present invention.
- FIG. 5 is a schematic cross-sectional view showing still another example of the multilayer sheet of the present invention.
- the multilayer sheet 500 of the present invention includes a layer 1 of a moisture permeable substrate, a layer 3 of a moisture permeable resin formed on one surface thereof, and a moisture permeable polymer layer 3 present on the surface of the layer 3 of the moisture permeable resin.
- the other moisture permeable resin layer may also be provided on the other surface of the moisture permeable substrate layer 1, in which case the moisture permeable polymer film (on the surface of the other moisture permeable resin layer ( And a knitted fabric, a woven fabric or a moisture permeable non-woven fabric bonded through a layer of a moisture permeable adhesive on the outside of the moisture permeable polymer film (I). Also good.
- FIG. 6 is a schematic cross-sectional view showing still another example of the multilayer sheet of the present invention.
- the layer 1 of the moisture permeable substrate includes a knitted fabric, a woven fabric or a moisture permeable nonwoven fabric 1a disposed on the outside, a moisture permeable polymer film (II) 1b disposed on the inside, and these It consists of a layer 1c of a moisture-permeable adhesive for adhering.
- On the surface of the moisture permeable polymer film (II) 1b there is formed a moisture permeable resin layer 3 including a resin 31 that adheres to the moisture permeable substrate, a cellulose hydrolyzate powder 33, and an aluminum powder 35.
- a moisture permeable polymer film (I) 5 On the surface of the moisture permeable resin layer 3 is a moisture permeable polymer film (I) 5.
- a knitted fabric, a woven fabric or a moisture-permeable nonwoven fabric may be provided.
- a knitted fabric, a woven fabric, or a moisture-permeable nonwoven fabric bonded through a layer of a moisture-permeable adhesive may be provided outside the moisture-permeable polymer film (I) 5.
- the other moisture-permeable resin layer may also be provided on the other surface of the moisture-permeable base material layer 1, that is, on the surface of the knitted fabric, woven fabric or moisture-permeable nonwoven fabric 1a.
- the surface of the moisture-permeable resin layer may be covered with a moisture-permeable polymer film (I), and further, on the outer side of the moisture-permeable polymer film (I), through a layer of moisture-permeable adhesive.
- Adhered knitted fabrics, woven fabrics or moisture-permeable nonwoven fabrics may be present.
- the heat insulation structure of the present invention can be used, for example, as a bedding such as a blanket, a mattress, a mattress pad, a quilt and a futon cover, or as a cold clothing such as a poncho, or as a disaster prevention sheet or sleeping bag.
- the multilayer sheet of the present invention constitutes part or all of the structural requirements of the heat retaining structure as a material of the heat retaining structure.
- the moisture permeable substrate constituting the layer 1 of the moisture permeable substrate is a material capable of transmitting moisture, that is, water vapor, specifically, a knitted fabric, a woven fabric, a moisture permeable nonwoven fabric, a moisture permeable polymer film (hereinafter referred to as a moisture permeable polymer film).
- a moisture permeable polymer film sometimes referred to as “moisture permeable polymer film (II)”.
- Knitted fabrics and woven fabrics exhibit high air permeability, but when air permeability is high, they are also excellent in moisture permeability. Therefore, the knitted fabric and the woven fabric are not specifically defined as “moisture permeable”, but are naturally moisture permeable and have a high degree of moisture permeation.
- the material of the yarn constituting the knitted fabric or woven fabric is not particularly limited. Natural fibers, semi-synthetic fibers, or synthetic fibers may be used. From the viewpoint of warmth, a raised knitted fabric using micro fibers is particularly preferable.
- the moisture-permeable nonwoven fabric is not particularly limited as long as it is moisture-permeable.
- a spunbond nonwoven fabric, a thermal bond nonwoven fabric, a melt blown nonwoven fabric, a spunlace nonwoven fabric, or a spun needle nonwoven fabric may be used.
- the material of the fiber which comprises a nonwoven fabric is not limited,
- the polyolefin resin, such as polyethylene and a polypropylene, a polyester resin, and a polyamide-type resin are mentioned as the example, for example.
- the moisture-permeable polymer film (II) is not particularly limited as long as it is moisture-permeable.
- polymers that are the main materials for polymers and films include polyolefin resins such as polyethylene and polypropylene, polyester resins, polyether resins, polyurethane resins, polyamide resins, polyvinyl alcohol resins, and polycarbonate resins. It is done.
- various additives that are usually used in this technical field such as a plasticizer, a heat stabilizer, a colorant, a flame retardant, an ultraviolet absorber, an antistatic agent, and a lubricant are used for the polymer film.
- Polymer films based on polymers are usually moisture permeable, except for special ones.
- Polyurethane resin is preferred as the polymer, which is the main material of the polymer film, because it is excellent in flexibility and can achieve high moisture permeability, and can have both waterproofness and moisture permeability.
- a plastic polyurethane resin is particularly preferable.
- the polyurethane-based resin may be a polyester-based polyurethane or a polyether-based polyurethane, and may have a polyoxyethylene portion as a soft segment. As the proportion of the polyoxyethylene moiety in the polyurethane molecule increases, the moisture permeability of the polymer film increases. Therefore, it is preferable to design the chemical structure of the polyurethane molecule so that the desired moisture permeability is expressed. Even when waterproofness is required, the chemical structure of the polyurethane molecule may be designed so that such properties are expressed.
- the layer 1 of the moisture permeable substrate may be a single layer or a multilayer.
- a multilayer as an example of the structure, as shown in FIG. 6, a knitted fabric, a woven fabric or a moisture-permeable nonwoven fabric 1a, a moisture-permeable polymer film (II) 1b, and a moisture-permeable adhesive that bonds them together
- the mode that it consists of layer 1c of this is mentioned.
- the material of the knitted fabric, woven fabric, moisture-permeable nonwoven fabric, and moisture-permeable polymer film (II) is as described above.
- the adhesive constituting the moisture-permeable adhesive layer 1c is capable of adhering the knitted fabric, woven fabric or moisture-permeable nonwoven fabric to the moisture-permeable polymer film (II), and the formed adhesive layer 1c is moisture-permeable. As long as it becomes, it will not specifically limit. It may be a solvent type, an emulsion type, a hot melt type, an ultraviolet ray or electron beam curing type, a two-component reaction curing type, or a self-crosslinking type.
- the polymer layer, which is the main component of the adhesive, or the polymer layer formed by polymerizing the monomer, which is the main component of the adhesive is usually moisture permeable except for special ones.
- Moisture permeability of the moisture-permeable base material is not particularly limited, is preferably 400g / m 2/24 hours or more, 700 g / m 2 / more preferably 24 hours or more, and more preferably 800 g / m 2/24 hours or more.
- the upper limit of the moisture permeability of the moisture permeable substrate is 5,000 g / m.
- the moisture permeable substrate contains the moisture permeable polymer film (II)
- the upper limit of the moisture permeability of the moisture permeable substrate JIS K7129 (Method A); Lissy method; 40 ° C .; 90% RH) is 2, preferably 000 g / m 2 / is 24 hours or less, still more preferably not more than 1,000 g / m 2/24 hours.
- the thickness of the moisture-permeable base material is preferably 100 to 400 g / m 2 , and more preferably 130 to 250 g / m 2 for a knitted fabric.
- the thickness is preferably 100 to 300 g / m 2 , and more preferably 120 to 200 g / m 2 .
- the thickness is preferably 10 to 100 ⁇ m, and more preferably 15 to 50 ⁇ m.
- each layer is usually thinner than the thickness of a single layer, and the thickness of the moisture-permeable adhesive layer 1c is the amount of adhesive composition applied in the case of mechanical coating. 10 to 50 g / m 2 is preferable, and 15 to 30 g / m 2 is more preferable.
- the moisture-permeable resin layer 3 is a layer formed by curing an adhesive or a binder, and is derived from the adhesive or the binder, and is hydrolyzed from a resin that adheres to a moisture-permeable substrate and from a plant or animal. And a water-insoluble hygroscopic exothermic granular material. Adhesive and binder are adhered to the moisture permeable substrate, and when the layer 5 of the moisture permeable polymer film (I) is present, the resin layer is also adhered to the moisture permeable polymer film (I). As long as is permeable to moisture, there is no particular limitation.
- the polymer layer which is the main component of the adhesive or binder, or the polymer layer formed by polymerizing the monomer, which is the main component of the adhesive or binder, is usually moisture permeable except for special ones. is there.
- the adhesive or binder may be a solvent type, an emulsion type, a hot melt type, an ultraviolet or electron beam curing type, a two-component reaction curing type, or a self-crosslinking type.
- a two-component reactive curing type the water-insoluble moisture-absorbing exothermic granular material and one liquid agent are usually mixed and then the other liquid agent is mixed.
- curing means that the polymer, which is a solid content of the adhesive, is solidified by evaporating the solvent (including water-based one).
- the adhesive component hardens due to a decrease in temperature.
- the adhesive component (resin or polymer precursor is irradiated by ultraviolet ray or electron beam irradiation).
- a two-component reactive curing type it means that the components of the two types of liquid agent react with each other and cure.
- Examples of the resin constituting the moisture permeable resin and adhering to the moisture permeable substrate include acrylic, urethane, vinyl acetate, starch, ethylene-vinyl acetate copolymer, and acrylic-vinyl acetate copolymer. Can be mentioned. Of these, acrylic resins are preferred. Adhesives that provide acrylic resins include poly (acrylic ester) as an adhesive component (solvent type, one-component type, emulsion type), and acrylic ester monomers that are precursors of acrylic resins (Emulsion type, aqueous solution, solvent type).
- Acrylic acid ester monomers are polymerized by polymerization of monomers by self-crosslinking by irradiation with ultraviolet rays or electron beams (above, one-component type) or by reaction between components (two-component type). It becomes.
- the moisture-permeable resin may have flexibility depending on the properties of the resin that adheres to the moisture-permeable base material, which is the main component, or on the properties of a plasticizer used as a subcomponent. preferable.
- the “water-insoluble hygroscopic exothermic granular material, which is a hydrolyzate derived from a plant and / or a hydrolyzate derived from an animal” constituting the moisture-permeable resin is as follows: (1) Water-insoluble: The property is usually considered to be insoluble in water. This includes cases where it is insoluble or extremely insoluble in water. (2) Hygroscopic exothermic property: It can absorb water vapor and, as a result, generate heat. (3) Granule: In this specification, the definition of “powder” includes granules such as granules and fine granules, coarse powder, fine powder, ultrafine powder, and usually powder. Included are the designated powders. The shape is not particularly limited.
- hydrolyzate of water-insoluble hygroscopic exothermic granular material derived from plants is cellulose hydrolyzate powder.
- a mineral acid is allowed to act on the raw material cellulose, a part of the glucoside bond is hydrolyzed.
- the degree of polymerization of glucose, and thus the average molecular weight is smaller than that before hydrolysis.
- the number of functional groups (specifically, OH groups) per weight increases due to hydrolysis.
- raw material cellulose wood pulp, non-wood pulp, lint, linter, explosion pulp, deinked pulp, waste paper pulp, cellulose produced by microorganisms, celluloses such as cotton cellulose, lignocelluloses such as wood powder and coconut shell powder And regenerated cellulose such as rayon, cupra, lyocell, and acetylcellulose.
- cellulose powder produced by hydrolyzing pulp / cellulose especially wood pulp / cellulose.
- a cellulose powder derived from cotton produced by hydrolyzing lint or linter may be used.
- the cellulose powder produced by hydrolysis preferably has an apparent specific gravity of 0.08 to 0.36 g / cm 3 , and more preferably 0.09 to 0.30 g / cm 3 .
- the average particle size is preferably 10 to 60 ⁇ m, more preferably 30 to 50 ⁇ m, and particularly preferably 32 to 45 ⁇ m.
- “animal” includes not only mammals but also birds.
- Examples of water-insoluble hygroscopic exothermic granular materials derived from animals include animal hair such as wool, cashmere and mohair, feathers of waterfowl such as geese and domestic duck, silk thread, collagen fibers and the like.
- the main component of animal hair is keratin protein, and the main component of silk is fibroin protein. It is preferable that animal hair has been defatted. This is because if animal hair is covered with a fat or oil such as lanolin, it may be difficult for animal hair to adhere to the moisture-permeable base material, or moisture absorption and heat generation performance may be inferior.
- the protein material hydrolyzate powder as described above is produced by subjecting the animal hair, feathers, threads, fibers, etc., to hydrolysis and mechanical treatment (classification and / or grinding). Hydrolysis reduces the average molecular weight and increases the number of functional groups (specifically, COOH groups and NH 2 groups) per weight. In addition, even if it is a hydrolyzate of protein material, the water-soluble thing constitutes the moisture-permeable resin "hydrolyzate of water-insoluble hygroscopic exothermic granular material derived from animals" is not.
- the average particle size of the hydrolyzate powder derived from animals is preferably 10 to 60 ⁇ m, and more preferably 20 to 50 ⁇ m.
- the apparent specific gravity is preferably 0.2 to 0.7 g / cm 3 , and more preferably 0.3 to 0.5 g / cm 3 .
- cellulose hydrolyzate powder and animal hair hydrolyzate powder are pulverized to a smaller size and then subjected to granulation to give granules or fine granules which are water-insoluble in the present invention. It can be used as a hygroscopic exothermic powder.
- the moisture permeable resin may further contain an aluminum powder.
- the moisture-permeable resin contains a water-insoluble moisture-absorbing exothermic granular material such as a cellulose hydrolyzate powder and an aluminum powder, the heat retention performance is enhanced by these synergistic effects.
- the aluminum powder includes atomized powder (sprayed powder), dry pulverized powder (flake powder), and wet pulverized powder (aluminum paste), and any of them may be used in the present invention. From the viewpoint of safety, aluminum paste is preferable.
- the average particle diameter of the aluminum powder is preferably 10 to 150 ⁇ m, and more preferably 20 to 100 ⁇ m.
- the amount of the resin adhered to the moisture-permeable substrate is 20 to 80% by mass, preferably 25 to 75% by mass, more preferably 30 to 70% by mass, and plant And / or a hydrolyzate derived from an animal, wherein the amount of the water-insoluble hygroscopic exothermic powder is 80 to 20% by mass, preferably 75 to 25% by mass, and more preferably 70. Thru
- the “total amount of moisture-permeable resin” is mainly the amount of resin derived from the solid content when a solvent-type adhesive is used, for example. The amount of solvent is not included.
- the quantity when using together aluminum powder, it is preferable that the quantity is 40 mass% or less in a moisture-permeable resin whole quantity, and it is more preferable that it is 30 mass% or less.
- the hydrolyzate derived from plants and / or animals and other than the water-insoluble hygroscopic exothermic granular material for example, when using a solid component such as aluminum powder, the permeation in the total amount of the moisture-permeable resin.
- the amount of the resin that adheres to the wet substrate is 20 to 80% by mass, preferably 25 to 75% by mass, and more preferably 30 to 70% by mass.
- the solid component is firmly fixed by the resin that adheres to the moisture-permeable substrate, and the moisture-permeable group in the moisture-permeable substrate and the moisture-permeable resin If the moisture-permeable polymer film (I) or the like is present on the surface of the moisture-permeable resin that does not face the moisture-permeable substrate, as described later, the moisture-permeable polymer film (I ) Etc. and the resin that adheres to the moisture permeable substrate) is also firmly adhered. Moreover, sufficient moisture absorption exothermic effect is exhibited by using the hydrolyzate of the thing derived from a plant and / or an animal in this quantity, and a water-insoluble hygroscopic exothermic granular material.
- the water-insoluble hygroscopic exothermic granular material which is a hydrolyzate of the plant and / or animal-derived material contained in the moisture-permeable resin, is shown in the amount per 1 m 2 of the multilayer sheet of the present invention (permeability).
- permeability the amount per 1 m 2 of the multilayer sheet of the present invention.
- the total of the two layers is preferably 5 to 100 g, more preferably 5 to 70 g, and particularly preferably 5 to 50 g. 8 to 50 g is most preferable.
- the total amount thereof is preferably 5 to 100 g / m 2 , more preferably 5 to 70 g / m 2 , particularly preferably 5 to 50 g / m 2 , and 8 to 50 g. Most preferred.
- the amount of “hydrolyzate of water-insoluble hygroscopic exothermic granular material derived from plants” is preferably 5 to 30 g / m 2 , and preferably 5 to 25 g / m 2 . More preferably, the weight is 8 to 25 g.
- the amount of “hydrolyzate of water-insoluble hygroscopic exothermic granular material derived from animals” is preferably 5 to 70 g / m 2 , and preferably 5 to 50 g / m 2. More preferred is 8 to 50 g.
- the amount of aluminum powder is preferably 3 to 30 g / m 2 , and more preferably 5 to 25 g / m 2 .
- the moisture permeable resin layer 3 is formed on at least one surface of the moisture permeable substrate layer 1, but the moisture permeable resin is formed on the surface of the moisture permeable substrate layer 1. In addition, it may also be present in the layer 1 of the moisture permeable substrate.
- the moisture permeable substrate is a knitted fabric or a woven fabric
- a composition for forming the layer 3 of the moisture permeable resin is applied on the surface thereof, a part of the applied composition is inside the knitted fabric or the woven fabric. To penetrate.
- the moisture permeable resin layer 3 is formed by means of drying or the like, there is a moisture permeable resin that has penetrated during application, even inside the knitted fabric or woven fabric and in the vicinity of the surface. Further, when the layer 3 of the moisture permeable resin is formed by immersing the knitted fabric or the woven fabric in the composition for the moisture permeable resin and then drying the composition, the surface of the knitted fabric or the woven fabric Not only that, there is a permeated moisture-permeable resin up to the inside.
- An embodiment in which the moisture-permeable substrate layer 1 and the moisture-permeable resin layer 3 have such a relationship is also included in the multilayer sheet of the present invention.
- the thickness of the moisture permeable resin layer 3 on the surface of the moisture permeable base material layer 1 is not particularly limited.
- the coating amount of the composition for forming the moisture permeable resin layer 3 is as follows. It is preferably 10 to 60 g / m 2 , more preferably 20 to 50 g / m 2 , and particularly preferably 30 to 40 g / m 2 .
- the coating amount is about 100 to 200 g / m 2 .
- the moisture-permeable polymer film (I) 5 covering one surface of the moisture-permeable resin layer 3 is not particularly limited as long as it is a moisture-permeable polymer film.
- the polymer that is the main material of the moisture permeable polymer film (I) include polyolefin resins such as polyethylene and polypropylene, polyester resins, polyether resins, polyurethane resins, polyamide resins, polyvinyl alcohol resins, Polycarbonate resin is mentioned.
- various additives that are usually used in this technical field such as a plasticizer, a heat stabilizer, a colorant, a flame retardant, an ultraviolet absorber, an antistatic agent, and a lubricant are used for the polymer film.
- Polymer films based on polymers are usually moisture permeable, except for special ones.
- the polyurethane-based resin may be a polyester-based urethane resin or a polyether-based urethane resin, and may have a polyoxyethylene portion as a soft segment. As the proportion of the polyoxyethylene moiety in the polyurethane molecule increases, the moisture permeability of the polymer film increases. Therefore, it is preferable to design the chemical structure of the polyurethane molecule so that the desired moisture permeability is expressed. Even when waterproofness is required, the chemical structure of the polyurethane molecule may be designed so that such properties are expressed.
- Moisture permeability of the moisture-permeable polymeric film (I) is preferably at 400g / m 2/24 hours or more, 700 g / m 2 / more preferably at least 24 hours, and particularly preferably 800 g / m 2/24 hours or more.
- the upper limit is preferably not more than 5,000g / m 2/24 hours, more preferably not more than 2,000g / m 2/24 hours.
- the thickness is preferably 10 to 100 ⁇ m, more preferably 15 to 50 ⁇ m, from the viewpoint of moisture permeability and strength. As the thickness of the moisture-permeable polymer film (I) decreases, the moisture permeability increases, but if it is too thin, the strength may be insufficient.
- a knitted fabric, a woven fabric or a moisture-permeable nonwoven fabric may be used in place of the moisture-permeable polymer film (I) to cover one surface of the layer 3 of the moisture-permeable resin.
- a knitted fabric, a woven fabric, and a moisture-permeable nonwoven fabric these description in a moisture-permeable base material is used.
- the multilayer sheet of the present invention may be one in which a knitted fabric, a woven fabric or a moisture permeable nonwoven fabric 7a is present outside the moisture permeable polymer film (I) 5 via a layer 7b of a moisture permeable adhesive.
- the adhesive constituting the moisture-permeable adhesive layer 7b can bond the knitted fabric, the woven fabric or the moisture-permeable nonwoven fabric and the moisture-permeable polymer film (I), and the formed adhesive layer is moisture-permeable.
- the polymer layer, which is the main component of the adhesive, or the polymer layer formed by polymerizing the monomer, which is the main component of the adhesive is usually moisture permeable except for special ones.
- the adhesive may be a solvent type, an emulsion type, a hot melt type, an ultraviolet ray or electron beam curing type, a two-component reaction curing type, or a self-crosslinking type.
- the thickness of the moisture-permeable adhesive layer 7b is not particularly limited, but in the case of mechanical coating, the adhesive application amount is preferably 10 to 60 g / m 2 , and more preferably 20 to 50 g / m 2. 30 to 40 g / m 2 is particularly preferable. In addition, in the case of hand coating, it cannot be applied thinly like mechanical coating, and the coating amount is about 100 to 200 g / m 2 . About the material, thickness, etc. of a knitted fabric, a woven fabric, or a moisture-permeable nonwoven fabric, the description described in the description column of a moisture-permeable base material is used.
- the moisture permeability of the knitted fabric, woven fabric or moisture-permeable nonwoven layer 7a and moisture-permeable adhesive layer 7b is also particularly effective as long as they exhibit moisture permeability.
- knitted, as a complex with a layer 7b of woven or breathable nonwoven 7a and breathable adhesives are preferred, 700g / m 2/24 hours is at 400g / m 2/24 hours or more it is more preferable, and particularly preferably 800g / m 2/24 hours or more.
- the method for producing the multilayer sheet of the present invention is not particularly limited, and is a moisture-permeable substrate, a resin that adheres to the moisture-permeable substrate or a precursor of such a resin, and a water-insoluble hygroscopic exothermic granular material.
- a method including a step of forming a moisture-permeable resin by curing a precursor of such a resin is preferable. More preferably, the step of applying the composition is performed by mechanical coating, and the coating amount is 10 to 50 g / m 2 .
- the multilayer sheet of the present invention is preferably produced as follows.
- Multilayer sheet comprising layer 1 of moisture-permeable substrate and layer 3 of moisture-permeable resin Composition for forming layer 3 of moisture-permeable resin on one surface of moisture-permeable substrate (for example, cellulose hydrolysis)
- a powder containing water-insoluble moisture-absorbing exothermic particles such as a powder of a product, or a powder containing a cellulose hydrolyzate powder and an aluminum powder is applied at an appropriate thickness. Drying, monomer polymerization, and the like are performed so that the moisture-permeable resin layer 3 is formed.
- the moisture permeable resin layer 3 applied on one surface of the moisture permeable substrate layer 1 is formed.
- the composition is also applied to the other surface with an appropriate thickness, and thereafter, drying, polymerization of the monomer, and the like are performed.
- the moisture permeable substrate is immersed in a composition for forming the layer 3 of the moisture permeable resin, taken out, dried, and the like.
- Composition for forming layer 3 of moisture-permeable resin on one side of knitted fabric, woven fabric, moisture-permeable nonwoven fabric or moisture-permeable polymer film for example, water-insoluble moisture-absorbing exothermic powder such as cellulose hydrolyzate powder
- the surface of the applied composition is covered with a moisture-permeable polymer film (I).
- the monomer in the composition for forming the moisture-permeable resin layer 3 is polymerized by irradiating ultraviolet rays or electron beams from the outside of the polymer film (I).
- an adhesive for the layer 1c of the moisture permeable adhesive is applied in an appropriate thickness.
- the surface of the applied adhesive is then covered with a moisture permeable polymer film (II).
- the monomer in the adhesive is polymerized by irradiating ultraviolet rays or an electron beam from the outside of the polymer film (II).
- a moisture-permeable base material is manufactured.
- Composition for forming layer 3 of moisture-permeable resin on the surface of moisture-permeable polymer film (II) of moisture-permeable substrate for example, water-insoluble moisture-absorbing exothermic powder such as cellulose hydrolysate powder
- moisture-permeable substrate for example, water-insoluble moisture-absorbing exothermic powder such as cellulose hydrolysate powder
- a substance containing a body or a substance containing a cellulose hydrolyzate powder and an aluminum powder is applied at an appropriate thickness.
- the surface of the applied composition is covered with a moisture-permeable polymer film (I).
- the monomer in the composition for forming the moisture-permeable resin layer 3 is polymerized by irradiating ultraviolet rays or electron beams from the outside of the polymer film (I).
- a composition for forming the moisture-permeable resin layer 3 may be applied on one side of the moisture-permeable polymer film (I), and the surface of the applied composition may be covered with a moisture-permeable substrate. At this time, the moisture-permeable polymer film (II) in the moisture-permeable substrate is directed to the applied composition side.
- a knitted fabric, a woven fabric or a moisture-permeable nonwoven fabric 7a is present on the outside of the moisture-permeable polymer film (I) via a layer 7b of a moisture-permeable adhesive, in the column (2) or (3)
- a composite of a moisture permeable substrate, a moisture permeable resin and a moisture permeable polymer film (I) is produced by the described method.
- an adhesive for the layer 7b of the moisture-permeable adhesive is applied.
- the surface of the applied adhesive is covered with a knitted fabric, a woven fabric, or a moisture-permeable nonwoven fabric 7a.
- An adhesive for the layer 7b of the moisture-permeable adhesive may be applied on one side of the knitted fabric, woven fabric or moisture-permeable nonwoven fabric 7a, and the surface of the applied adhesive may be covered with the composite.
- a multilayer sheet in which the moisture permeable resin layer 3 is present on both sides of the moisture permeable base material layer 1 and both surfaces of the moisture permeable resin layer 3 are covered with a knitted fabric, a woven fabric or a moisture permeable nonwoven fabric.
- a composition for forming the layer 3 of the moisture-permeable resin is applied at an appropriate thickness.
- the surface of the applied composition is covered with a knitted fabric, a woven fabric or a moisture-permeable nonwoven fabric. Drying, monomer polymerization, and the like are performed so that the moisture-permeable resin layer 3 is formed.
- the composition for forming the layer 3 of a moisture-permeable resin is apply
- the surface of the applied composition is covered with a knitted fabric, a woven fabric or a moisture-permeable nonwoven fabric. Drying, monomer polymerization, and the like are performed so that the moisture-permeable resin layer 3 is formed.
- the heat insulation structure of the present invention is provided with the multilayer sheet of the present invention in its entirety or in part.
- all of the blanket, mattress, knee lap, poncho and disaster prevention sheet which are the heat insulation structure of the present invention, may be composed of the multilayer sheet of the present invention.
- the structure for heat insulation of this invention is a laying pad
- the multilayer sheet of this invention can be used as a surface material and / or a lining.
- the heat insulation structure of the present invention is a futon cover or a sleeping bag, the whole may be constituted by the multilayer sheet of the present invention, or a part thereof (for example, if the shape is a bag shape) 1 ⁇ 2 (only one surface) may be constituted by the multilayer sheet of the present invention.
- thermoplastic polyurethane film Measurement of moisture permeability of thermoplastic polyurethane film The moisture permeability of three types of thermoplastic polyurethane films having different thicknesses was measured by the Lissy method (JIS K7129 (Method A)) under the following conditions. .
- Example 2 Measurement of Temperature Change due to Moisture Absorption and Heat Generation of Cellulose Hydrolyzate Powder Heat generation (temperature change) due to moisture absorption was measured over time for two types of cellulose hydrolyzate powders.
- Constant temperature and humidity chamber HUMIDIC CHAMBER IG-42M manufactured by Yamato Scientific Co., Ltd.
- Thermometer Yokogawa Meter &Instruments' ⁇ R1800 automatic temperature recorder Measuring conditions: 23 ° C, 90% RH
- Example 3 Measurement of temperature change due to hygroscopic heat generation of multilayer sheet
- the moisture permeable substrate is a thermoplastic polyurethane film or polyester / cotton blended fabric
- the moisture permeable resin is an acrylic resin containing cellulose hydrolyzate powder
- the moisture permeable polymer film (I) is a thermoplastic polyurethane.
- composition prepared in (ii) is applied at 200 g / m 2 on one surface of the moisture-permeable substrate.
- the surface of the coated composition is covered with a thermoplastic polyurethane film.
- the composite prepared in (iv) is dried at 40 ° C. for 12 hours, cut into 30 cm ⁇ 24 cm, and used as a measurement sample.
- the amount of the cellulose hydrolyzate powder in the produced multilayer sheet (that is, after drying) was about 20.6 g / m 2 .
- Constant temperature and humidity chamber HUMIDIC CHAMBER IG-42M manufactured by Yamato Scientific Co., Ltd.
- Thermometer Yokogawa Meter &Instruments' ⁇ R1800 automatic temperature recorder Measuring conditions: 23 ° C, 90% RH
- Example 4 Measurement of temperature change due to hygroscopic heat generation of multilayer sheet (part 2)
- the moisture permeable substrate is a polyester / cotton blended fabric
- the moisture permeable resin is a mixture of the following acrylic resin and cellulose hydrolyzate powder and aluminum powder
- a moisture permeable polymer film A multilayer sheet in which I) is a thermoplastic polyurethane film was prepared, and the temperature was measured over time.
- the aluminum content of the aluminum paste is 75% by mass, and the balance is mainly fatty acid (20% by mass) and solvent (5% by mass).
- the average particle size of the aluminum powder is about 80 ⁇ m.
- composition for forming moisture-permeable resin layer (a) Mixture of cellulose hydrolyzate powder (composition for sample a) Weigh 15 g of cellulose hydrolyzate powder, add 30 g of toluene and blend in with toluene. 100 g of an acrylic resin adhesive is measured, and a powder of cellulose hydrolyzate containing toluene is added thereto and stirred well to obtain a composition.
- the moisture-permeable resin formed from the composition includes 52 to 55% by mass of a resin that adheres to the base material and 48 to 45% by mass of cellulose hydrolyzate powder.
- composition for sample b Mixture of aluminum powder (composition for sample b) Weigh 100 g of acrylic resin adhesive, add 15 g of aluminum paste to this, and stir well to obtain a composition.
- the moisture-permeable resin formed from this composition contains 53 to 56% by mass of a resin that adheres to the base material, 37 to 34% by mass of aluminum powder, and the remaining fatty acid.
- C A mixture of cellulose hydrolyzate powder and aluminum powder (composition for sample c) Weigh 15 g of cellulose hydrolyzate powder, add 30 g of toluene and blend in with toluene. Weigh 100 g of acrylic resin adhesive, add toluene hydrolyzed powder of cellulose and 15 g of aluminum paste, and stir well to obtain a composition.
- the moisture-permeable resin formed from this composition is a resin that adheres to 35 to 38% by weight of a substrate, 33 to 32% by weight of a cellulose hydrolyzate powder, 25 to 24% by weight of an aluminum powder, And the remaining fatty acid.
- sample a Cellulose hydrolyzate powder about 20.0 g / m 2
- sample b Aluminum powder
- sample c Cellulose hydrolyzate powder about 18.7 g / m 2 + aluminum powder about 18.7 g / m 2
- Constant temperature and humidity chamber HUMIDIC CHAMBER IG-42M manufactured by Yamato Scientific Co., Ltd.
- Thermometer Yokogawa Meter &Instruments' ⁇ R1800 automatic temperature recorder Measuring conditions: 23 ° C, 90% RH
- Example 5 Measurement of Wash Resistance of Multilayer Sheet
- the moisture permeable substrate is a polyester / cotton blended fabric and a thermoplastic polyurethane film
- the moisture permeable resin is an acrylic resin containing cellulose hydrolyzate powder
- Example 1 Material of multilayer sheet
- a polyurethane film bonded with acrylic binder XE-3773 (toluene (solvent) content, solid content 16 to 18%) made by Toupe, which is an acrylic resin adhesive.
- Moisture permeable resin Composition for forming layer Acrylic binder XE-3773 (containing toluene (solvent), solid content 16 to 18%) made by Toupe, which is an acrylic resin adhesive, is a cellulose hydrolyzate powder.
- Multilayer sheet manufacturing method One surface of a polyester / cotton blend fabric is coated with an acrylic resin adhesive at 100 g / m 2 , and the surface of the coated adhesive is 12 ⁇ m thick. Cover with thermoplastic polyurethane film.
- (Ii) Weigh 15 g of cellulose hydrolyzate powder, add 30 g of toluene and blend in with toluene.
- (Iii) Weigh 100 g of acrylic resin adhesive, add the powder of toluene-containing cellulose hydrolyzate prepared in (ii), and stir well to form a moisture permeable resin layer.
- composition prepared in (iii) is applied at 100 g / m 2 on the surface of the moisture-permeable substrate thermoplastic polyurethane film prepared in (i).
- the surface of the coated composition is covered with a 15 ⁇ m thick thermoplastic polyurethane film.
- the composite prepared in (v) is dried at 40 ° C. for 12 hours to obtain a measurement sample.
- the amount of the cellulose hydrolyzate powder in the produced multilayer sheet was about 10.3 g / m 2 .
- Test method Washing resistance was tested according to JIS 0217 103 method at Kaken Test Center. The test conditions are as shown in Table 5.
- Table 6 shows the results. As is apparent from Table 6, it was revealed that the multilayer sheet of the present invention did not peel off even after 30 washings and was excellent in washing resistance.
- Example 6 Measurement of temperature when using a bedding made of a structure for heat insulation (part 1)
- Bedcloth of the present invention (1-1) Material
- (a) Moisture permeable substrate Mouton-like knitted fabric manufactured with polyester microfiber, basis weight 200 g / m 2
- the aluminum content of the aluminum paste is 75% by mass, and the balance is mainly fatty acid (20% by mass) and solvent (5% by mass).
- the average particle size of the aluminum powder is about 80 ⁇ m.
- the moisture-permeable resin formed from this composition comprises 23.3 to 25.5% by mass of a resin that adheres to a moisture-permeable substrate, 44.8 to 43.5% by mass of a cellulose hydrolyzate powder, Consists of 25.2 to 24.5% by weight of aluminum powder and the balance fatty acid.
- C Moisture permeable polymer film 15 ⁇ m-thick thermoplastic polyurethane film used in Example 1
- a composition for forming a moisture-permeable resin layer is applied on one surface of a mouton-like knitted fabric in an amount of 20 g / m 2 .
- the surface of the coated composition is covered with a thermoplastic polyurethane film.
- the composite prepared in (ii) is dried at 40 ° C. for 12 hours.
- the amount of the cellulose hydrolyzate powder of the manufactured bedcloth was about 9.8 g / m 2
- the amount of the aluminum powder was about 7.3 g / m 2 .
- Comforter cover of the present invention (2-1) Manufacturing method
- the mat of the present invention is arranged so that the surface of the mouton knitted fabric is the outside (the polyurethane film is the inner surface of the comforter cover and faces the comforter).
- Comforter Side land 100% cotton (40 x 40/230)
- Middle material 90% down + 10% small feather, 1.2kg
- the test subject lies on his / her bed on his / her back, hangs a comforter, and maintains a certain posture.
- a sensor portion (a rod-like portion having a diameter of 2 mm) of the temperature measuring device is placed under the right buttock of the subject, and the temperature is measured between the human and the bedding (see FIG. 10).
- Example 7 Measurement of temperature change due to hygroscopic heat generation of multilayer sheet (part 3)
- the moisture-permeable substrate was a polyester / cotton blended fabric and the moisture-permeable resin was an acrylic resin containing a cellulose hydrolyzate powder was measured, and the temperature change due to moisture-absorbing heat generation was measured.
- Material used (a) Moisture permeable substrate Polyester / cotton blended fabric (65% polyester, 45% cotton, 45 ⁇ 45/110 ⁇ 76) for both sample and blank (B) Composition for forming a layer of moisture-permeable resin
- composition prepared in (ii) is applied at 200 g / m 2 on one surface of the moisture-permeable substrate.
- the obtained composite is naturally dried overnight, and then dried at 40 ° C. for 2 hours.
- the amount of the cellulose hydrolyzate powder of the produced multilayer sheet (ie after drying) was about 33.3 g / m 2 .
- Example 8 Measurement of hygroscopic heat generation and evaluation of washing resistance of multilayer sheet
- the moisture-permeable base material is a polyester nonwoven fabric
- the moisture-permeable resin is an acrylic resin containing powder of cellulose hydrolyzate
- moisture-permeable property A multilayer sheet in which the polymer film was a thermoplastic polyurethane film was prepared, and the temperature change due to moisture absorption heat generation was measured.
- Samples I, II, III (2) Manufacturing method of multilayer sheet (samples I, II, III) (i) Sample I: 3 g of cellulose hydrolyzate powder is weighed, 6 g of toluene is added, and the mixture is conditioned with toluene. Sample II: Weigh 5 g of cellulose hydrolyzate powder, add 10 g of toluene and blend in with toluene. Sample III Weigh 8 g of cellulose hydrolyzate powder, add 16 g of toluene and blend in with toluene. Sample IV: 35 g of cellulose hydrolyzate powder is weighed, 70 g of toluene is added, and the mixture is conditioned with toluene.
- Sample V Weigh 45 g of cellulose hydrolyzate powder, add 90 g of toluene and blend in with toluene.
- Sample VI Weigh 75 g of cellulose hydrolyzate powder, add 150 g of toluene and blend in with toluene.
- composition for measuring 100 g of acrylic resin adhesive adding one of the powders of cellulose hydrolyzate containing toluene prepared in (i), stirring well, and forming a layer of moisture-permeable resin
- the moisture-permeable resin formed from the composition contains a resin that adheres to the moisture-permeable substrate and a cellulose hydrolyzate powder in the following proportions.
- Results Table 11 shows the results. As is apparent from Table 11, when the amount of the cellulose hydrolyzate powder is small (Sample I), the maximum temperature reached by heat generation is low, and the time until the maximum temperature is reached is long. On the other hand, if the amount of cellulose hydrolyzate powder is too large (sample VI), the washing resistance is poor.
- Example 9 Measurement of temperature change due to hygroscopic heat generation of multilayer sheet (part 4)
- the moisture-permeable substrate is a polyester / cotton blended fabric
- the moisture-permeable resin is an acrylic resin containing cellulose hydrolyzate powder
- the moisture-permeable polymer film (I) is a thermoplastic polyurethane film
- composition prepared in (ii) is coated at 100 g / m 2 on one surface of a polyester / cotton blend fabric.
- the surface of the coated composition is covered with a thermoplastic polyurethane film.
- the composite prepared in (iv) is dried at 40 ° C. for 12 hours, cut into 30 cm ⁇ 24 cm, and used as a measurement sample.
- the amount of the cellulose hydrolyzate powder in the produced multilayer sheet was about 14.3 g / m 2 .
- Constant temperature and humidity chamber HUMIDIC CHAMBER IG-42M manufactured by Yamato Scientific Co., Ltd.
- Thermometer Yokogawa Meter &Instruments' ⁇ R1800 automatic temperature recorder Measuring conditions: 23 ° C, 90% RH
- Example 10 Measurement of temperature change due to hygroscopic heat generation of wool hydrolyzate powder and cellulose hydrolyzate powder
- the heat generation (temperature change) due to moisture absorption over time was measured. Measured.
- Constant temperature and humidity chamber HUMIDIC CHAMBER IG-42M manufactured by Yamato Scientific Co., Ltd.
- Thermometer Yokogawa Meter & Instruments ⁇ R1800 Automatic Temperature Recorder Measurement conditions: 30 ° C, 90% RH
- Example 11 Measurement of temperature change due to hygroscopic heat generation of multilayer sheet (part 5) A multilayer sheet in which the moisture-permeable base material is polyester / cotton blended fabric, the moisture-permeable resin is an acrylic resin containing powder of cotton hydrolyzate, and the multilayer sheet is an acrylic resin containing powder of wool hydrolyzate. And temperature change due to hygroscopic heat generation was measured.
- composition prepared in (ii) is applied at 200 g / m 2 on one surface of the moisture-permeable substrate.
- the obtained composite is naturally dried overnight, and then dried at 40 ° C. for 2 hours.
- the amount of the produced cotton hydrolyzate powder or wool hydrolyzate powder was about 33.3 g / m 2 .
- Example 12 Measurement of temperature when using a bedding made of a structure for heat insulation (part 2) The bedding which is the structure for heat insulation of this invention was produced, and the temperature at the time of sleeping using it was measured with time.
- Bedding which is a structure for heat insulation subjected to a temperature measurement test
- Material (1-1) Moisture permeable substrate 15 ⁇ m-thick thermoplastic polyurethane film used in Example 1
- the moisture-permeable resin formed from the composition a is a resin that adheres to 69.9% by mass of a moisture-permeable substrate, 20.1% by mass of a wool hydrolyzate powder, and 10.0% by mass of cellulose.
- the moisture-permeable resin formed from this composition b comprises 70.3% by mass of a resin that adheres to a moisture-permeable substrate, 10.1% by mass of a wool hydrolyzate powder, and 10.1% by mass of cellulose. It consists of powder of hydrolyzate, 7.6 mass% aluminum powder, and the remaining fatty acid.
- composition a is applied on one surface of the thermoplastic polyurethane film, and the coated surface is covered with a mouton knitted fabric.
- the composite prepared in (i) is dried at 40 ° C. for 12 hours.
- composition b is coated on the other surface of the thermoplastic polyurethane film, and the coated surface is covered with a silky knitted fabric.
- the amount of the powder of the wool hydrolyzate of the produced bedding is 3.42 g / m 2
- the amount of the powder of cellulose hydrolyzate is 2.28 g / m 2
- the amount of the aluminum powder is 0. It was 855 g / m 2 .
- the subject maintains a fixed posture during the test.
- a sensor portion a rod-like portion having a diameter of 2 mm
- the temperature measuring device is placed under the right buttock of the subject, and the temperature is measured between the human and the bedding (see FIG. 10).
- Example 13 Measurement of temperature change due to hygroscopic heat generation of multilayer sheet (Part 6)
- a multilayer sheet (comparative sample) which is an acrylic resin containing cellulose powder in which the moisture-permeable base material is a polyester / cotton blended fabric and the moisture-permeable resin is not hydrolyzed, was measured for temperature change due to moisture-absorbing heat generation.
- Non-decomposed cellulose powder made by Izumi Senko Co., Ltd .; apparent specific gravity: 0.4 g / cm 3 ; average particle size: about 60 ⁇ m
- composition prepared in (ii) is applied at 200 g / m 2 on one surface of the moisture-permeable substrate.
- the obtained composite is naturally dried overnight, and then dried at 40 ° C. for 2 hours.
- the amount of the cellulose powder (not hydrolyzed) in the produced multilayer sheet (that is, after drying) was about 33.3 g / m 2 .
- the multilayer sheet of the present invention having a layer of moisture-permeable resin containing powder of cellulose hydrolyzate has a maximum temperature higher than that of the blank, and A higher temperature than the blank was maintained until the end of the test, but the comparative multilayer sheet with a layer of moisture permeable resin containing unhydrolyzed cellulose powder was cooler than the blank throughout the test.
- a hydrolyzed cellulose powder to be added to the moisture-permeable resin a temperature increase effect due to moisture absorption heat generation can be obtained.
- Moisture permeable substrate Polyester / cotton blended fabric (65% polyester, 45% cotton, 45 ⁇ 45/110 ⁇ 76)
- composition prepared in (ii) is applied at 200 g / m 2 on one surface of the moisture-permeable substrate.
- the obtained composite is naturally dried all day and night, then dried at 40 ° C. for 2 hours, cut into 30 cm ⁇ 24 cm, and used as a measurement sample.
- the amount of the wool powder of the manufactured multilayer sheet was about 20 g / m 2 .
- Constant temperature and humidity chamber HUMIDIC CHAMBER IG-42M manufactured by Yamato Scientific Co., Ltd.
- Thermometer Yokogawa Meter & Instruments ⁇ R1800 Automatic Temperature Recorder Measurement conditions: 30 ° C, 90% RH
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Description
(1)非水溶性: 通常、その性質が水に不溶であるとされていること。水に溶けないか、極めて溶け難い場合も含む。
(2)吸湿発熱性: 水蒸気を吸収することができ、その結果として発熱すること。
(3)粉粒体: 本明細書においては、「粉粒体」の定義には、顆粒や細粒等の粒体と、粗粉体、微粉体、超微粉体、及び通常は粉末と呼称されている粉体が含まれる。その形状は、特に限定されない。経済性の観点から、粉末が好ましい。
(4)植物に由来するもの: 植物に由来する、上記(1)乃至(3)を充足する物質の主成分の化学組成の例として、セルロースが挙げられる。
(5)動物に由来するもの: 動物に由来する、上記(1)乃至(3)を充足する物質の主成分の化学組成の例として、ケラチン、フィブロイン、コラーゲン等の硬蛋白質が挙げられる。
「加水分解物」の意味及び「非水溶性の吸湿発熱性粉粒体」の具体例については、次に説明する。
(1)透湿性基材の層1と透湿性樹脂の層3からなる多層シート
透湿性基材の一方の表面上に、透湿性樹脂の層3を形成するための組成物(例えばセルロース加水分解物の粉末等の非水溶性の吸湿発熱性粉粒体を含むもの、又は、セルロース加水分解物の粉末等とアルミニウム粉末とを含むもの)を適切な厚さで塗布する。透湿性樹脂の層3が形成されるように、乾燥、モノマーの重合等を行う。透湿性基材の層1の両面上に透湿性樹脂の層3を形成する場合には、透湿性基材の層1の一方の表面上に塗布した透湿性樹脂の層3を形成するための組成物が乾いた後(あるいはモノマーが重合した後)、他方の表面上にも、当該組成物を適切な厚さで塗布し、その後、乾燥、モノマーの重合等を行う。或いは、透湿性基材を、透湿性樹脂の層3を形成するための組成物に浸漬し、取り出し、乾燥等を行う。
編物、織布、透湿性不織布又は透湿性ポリマー・フィルムの片面上に、透湿性樹脂の層3を形成するための組成物(例えばセルロース加水分解物の粉末等の非水溶性の吸湿発熱性粉粒体を含むもの、又は、セルロース加水分解物の粉末等とアルミニウム粉末とを含むもの)を適切な厚さで塗布する。次いで、塗布された組成物の表面を透湿性ポリマー・フィルム(I)で覆う。必要であれば、ポリマー・フィルム(I)の外側から、紫外線又は電子線を照射し、透湿性樹脂の層3を形成するための組成物中のモノマーを重合させる。
編物、織布又は透湿性不織布の片面上に、透湿性接着剤の層1c用の接着剤を適切な厚さで塗布する。次いで、塗布された接着剤の表面を透湿性ポリマー・フィルム(II)で覆う。必要であれば、ポリマー・フィルム(II)の外側から、紫外線又は電子線を照射し、接着剤中のモノマーを重合させる。このようにして、透湿性基材を製造する。
(2)又は(3)欄に記載した方法で、透湿性基材、透湿性樹脂及び透湿性ポリマー・フィルム(I)の複合体を製造する。この複合体の透湿性ポリマー・フィルム(I)の表面上に、透湿性接着剤の層7b用の接着剤を塗布する。次いで、塗布された接着剤の表面を、編物、織布又は透湿性不織布で7a覆う。編物、織布又は透湿性不織布7aの片面上に透湿性接着剤の層7b用の接着剤を塗布し、塗布された接着剤の表面を、前記複合体で覆ってもよい。
透湿性基材の層1の一方の表面上に、透湿性樹脂の層3を形成するための組成物を適切な厚さで塗布する。次いで、塗布された組成物の表面を編物、織布又は透湿性不織布で覆う。透湿性樹脂の層3が形成されるように、乾燥、モノマーの重合等を行う。透湿性基材の層1の他方の表面上に、透湿性樹脂の層3を形成するための組成物を適切な厚さで塗布する。次いで、塗布された組成物の表面を編物、織布又は透湿性不織布で覆う。透湿性樹脂の層3が形成されるように、乾燥、モノマーの重合等を行う。
[実施例1] 熱可塑性ポリウレタン・フィルムの透湿度の測定
厚さの異なる熱可塑性ポリウレタン・フィルム3種について、リッシー法(JIS K7129(A法))にて、以下の条件で透湿度を測定した。
リッシー社製Vapor Permeation Tester L80-4000
(2)測定条件
40℃、90%RH
(3)結果
結果を表1に示す。
2種類のセルロース加水分解物の粉末について、吸湿による発熱(温度変化)を経時的に測定した。
(a)日本製紙ケミカル社製W-100GK: セルロース加水分解物の粉末、比重=0.3~0.4g/cm3、見掛け比重=0.20~0.30g/cm3、平均粒子径=約37μm
(b)日本製紙ケミカル社製W-50GK: セルロース加水分解物の粉末、見掛け比重=0.15~0.20g/cm3、平均粒子径=約45μm
(c)ブランク: ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)、40cm×40cm
恒温恒湿器: ヤマト科学社製HUMIDIC CHAMBER IG-42M
温度測定器: 横河メータ&インスツルメント社製 μR1800自動温度記録計
測定条件: 23℃、90%RH
(i)セルロース加水分解物の粉末9gを計り取り、直径100mmのシャーレに入れ、均等にならす。
(ii-1)セルロース加水分解物の粉末内に温度測定器の測定部位(センサー)が埋まるように、温度測定器を固定する。
(ii-2)ブランクの織物は、その一辺の長さが1/4となるように交互に折り曲げ、その大きさが10cm×10cmである16層構造物とし、その16層構造物の厚み方向の真ん中(上から8層目の下面且つ下から8層目の上面)に温度測定器を挟み込む。
(iii)シャーレ及び織物を23℃、90%RHに設定された恒温恒湿器内に入れ、経時的に温度を測定する。
結果を表2及び図7に示す。表2及び図7から明らかなように、ブランク(ポリエステル・綿混紡織物のみ)と比べ、セルロース加水分解物の粉末は、吸湿発熱によって温度が上昇し、試験開始から1時間後においても、ブランクよりも高い温度を示した。
透湿性基材が熱可塑性ポリウレタン・フィルム又はポリエステル・綿混紡織物であり、透湿性樹脂がセルロース加水分解物の粉末入りアクリル系樹脂であり、そして、透湿性ポリマー・フィルム(I)が熱可塑性ポリウレタン・フィルムである多層シートを作製し、経時的に温度を測定した。
(a)透湿性基材
試料1: 実施例1で使用した15μm厚の熱可塑性ポリウレタン・フィルム
試料2: ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)
ブランク: 試料2と同じ
(b)透湿性樹脂の層を形成するための組成物
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)に、セルロース加水分解物の粉末である日本製紙ケミカル社製W-100GKを混合したもの
(c)透湿性ポリマー・フィルム(I)
実施例1で使用した15μm厚の熱可塑性ポリウレタン・フィルム
(i)セルロース加水分解物の粉末15gを計り、トルエン30gを加えてトルエンで馴染ませる。
(ii)アクリル系樹脂接着剤100gを計り、これに(i)で調製したトルエン入りセルロース加水分解物の粉末を加え、よく撹拌し、透湿性樹脂の層を形成するための組成物とする。この組成物から形成される透湿性樹脂は、52乃至55質量%の透湿性基材に接着する樹脂と、48乃至45質量%のセルロース加水分解物の粉末とを含む。
(iii)(ii)で調製された組成物を、透湿性基材の一方の表面上に、200g/m2で塗工する。
(iv)塗工された組成物の表面を熱可塑性ポリウレタン・フィルムで覆う。
(v)(iv)で調製された複合体を、40℃にて12時間乾燥させ、30cm×24cmに切り出して測定用試料とする。
なお、製造された多層シート(即ち、乾燥後)(試料1,2)のセルロース加水分解物の粉末の量は、約20.6g/m2であった。
恒温恒湿器: ヤマト科学社製HUMIDIC CHAMBER IG-42M
温度測定器: 横河メータ&インスツルメント社製 μR1800自動温度記録計
測定条件: 23℃、90%RH
試料1,2及びブランク(ポリエステル・綿混紡織物のみ)の各々を、その一辺の長さが1/4となるように交互に折り曲げ、その大きさが7.5cm×6cmである16層構造物とする。この16層構造物の厚み方向の真ん中(上から8層目の下面且つ下から8層目の上面)に温度測定器を挟み込み、23℃、90%RHに設定された恒温恒湿器内に入れ、経時的に温度を測定する。
結果を表3及び図8に示す。表3及び図8から明らかなように、ブランク(ポリエステル・綿混紡織物のみ)と比べ、本発明の多層シートである試料1及び2は、吸湿発熱によって温度が上昇し、試験開始から1時間後においても、ブランクよりも高い温度に保持されていた。
透湿性基材がポリエステル・綿混紡織物であり、透湿性樹脂が下記のアクリル系樹脂にセルロース加水分解物の粉末とアルミニウム粉末とを混合してなるものであり、そして、透湿性ポリマー・フィルム(I)が熱可塑性ポリウレタン・フィルムである多層シートを作製し、経時的に温度を測定した。
(a)透湿性基材
ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)
(b)透湿性樹脂の層を形成するための組成物
基剤は、アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)である。基剤のみ(ブランク)、セルロース加水分解物の粉末である日本製紙ケミカル社製W-100GKを混合したもの(試料a用の組成物)、アルミニウムペーストである林化学工業社製アルミペーストA2を混合したもの(試料b用の組成物)、及びセルロース加水分解物の粉末とアルミニウムペーストの両者を混合したもの(試料c用の組成物)を使用した。なお、アルミニウムペーストのアルミニウム含有率は75質量%であり、残部は主として脂肪酸(20質量%)及び溶剤(5質量%)である。また、アルミニウム粉末の平均粒子径は約80μmである。
(c)透湿性ポリマー・フィルム
実施例1で使用した15μm厚の熱可塑性ポリウレタン・フィルム
(a)セルロース加水分解物の粉末を混合したもの(試料a用の組成物)
セルロース加水分解物の粉末15gを計り、トルエン30gを加えてトルエンで馴染ませる。アクリル系樹脂接着剤100gを計り、これにトルエン入りセルロース加水分解物の粉末を加え、よく撹拌し、組成物とする。この組成物から形成される透湿性樹脂は、52乃至55質量%の基材に接着する樹脂と、48乃至45質量%のセルロース加水分解物の粉末とを含む。
(b)アルミニウム粉末を混合したもの(試料b用の組成物)
アクリル系樹脂接着剤100gを計り、これに、アルミニウムペースト15gを加え、よく撹拌し、組成物とする。この組成物から形成される透湿性樹脂は、53乃至56質量%の基材に接着する樹脂と、37乃至34質量%のアルミニウム粉末と、残部の脂肪酸とを含む。
(c)セルロース加水分解物の粉末とアルミニウム粉末の両者を混合したもの(試料c用の組成物)
セルロース加水分解物の粉末15gを計り、トルエン30gを加えてトルエンで馴染ませる。アクリル系樹脂接着剤100gを計り、これに、トルエン入りセルロース加水分解物の粉末と、アルミニウムペースト15gを加え、よく撹拌し、組成物とする。この組成物から形成される透湿性樹脂は、35乃至38質量%の基材に接着する樹脂と、33乃至32質量%のセルロース加水分解物の粉末と、25乃至24質量%のアルミニウム粉末と、残部の脂肪酸とを含む。
(i)透湿性樹脂の層を形成するための組成物を、ポリエステル・綿混紡織物の一方の表面上に、200g/m2で塗工する。
(ii)塗工された組成物の表面を熱可塑性ポリウレタン・フィルムで覆う。
(iii)(ii)で調製された複合体を、40℃にて12時間乾燥させ、30cm×24cmに切り出して測定用試料とする。
(試料a) セルロース加水分解物の粉末 約20.0g/m2
(試料b) アルミニウム粉末 約19.5g/m2
(試料c) セルロース加水分解物の粉末 約18.7g/m2+アルミニウム粉末 約18.7g/m2
恒温恒湿器: ヤマト科学社製HUMIDIC CHAMBER IG-42M
温度測定器: 横河メータ&インスツルメント社製 μR1800自動温度記録計
測定条件: 23℃、90%RH
試料の各々を、その一辺の長さが1/4となるように交互に折り曲げ、その大きさが7.5cm×6cmである16層構造物とする。この16層構造物の厚み方向の真ん中(上から8層目の下面且つ下から8層目の上面)に温度測定器を挟み込み、23℃、90%RHに設定された恒温恒湿器内に入れ、経時的に温度を測定する。
結果を表4及び図9に示す。表4及び図9から明らかなように、ブランク(透湿性樹脂の層を形成するための組成物として、アクリル系樹脂接着剤のみを使用したもの)と比べ、本発明の多層シートである試料a及びcは、吸湿発熱によって温度が上昇し、試験開始から1時間後においても、ブランクよりも高い温度に保持されていた。また、反射熱による保温性能が知られているアルミニウム粉末が使用された試料bと比べると、試料aはより短時間で最高温度に到達し、この点において、セルロース加水分解物の粉末の使用に優位性があることが確認された。試料cは、試料a及びbよりも高い温度を示した。
透湿性基材がポリエステル・綿混紡織物及び熱可塑性ポリウレタン・フィルムであり、透湿性樹脂がセルロース加水分解物の粉末入りアクリル系樹脂であり、そして、透湿性ポリマー・フィルムが熱可塑性ポリウレタン・フィルムである多層シートを作製し、耐洗濯性を試験した。
(a)透湿性基材
ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)と、実施例1で使用した12μm厚の熱可塑性ポリウレタン・フィルムとを、アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)で接着させたもの
(b)透湿性樹脂の層を形成するための組成物
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)に、セルロース加水分解物の粉末である日本製紙ケミカル社製W-100GKを混合したもの
(c)透湿性ポリマー・フィルム
実施例1で使用した15μm厚の熱可塑性ポリウレタン・フィルム
(i)ポリエステル・綿混紡織物の一方の表面に、アクリル系樹脂接着剤を100g/m2で塗工し、塗工された接着剤の表面を、12μm厚の熱可塑性ポリウレタン・フィルムで覆う。
(ii)セルロース加水分解物の粉末15gを計り、トルエン30gを加えてトルエンで馴染ませる。
(iii)アクリル系樹脂接着剤100gを計り、これに(ii)で調製したトルエン入りセルロース加水分解物の粉末を加え、よく撹拌し、透湿性樹脂の層を形成するための組成物とする。
(iv)(iii)で調製された組成物を、(i)で調製した透湿性基材の熱可塑性ポリウレタン・フィルムの表面上に、100g/m2で塗工する。
(v)塗工された組成物の表面を15μm厚の熱可塑性ポリウレタン・フィルムで覆う。
(vi)(v)で調製された複合体を、40℃にて12時間乾燥させ、測定用試料とする。
なお、製造された多層シート(即ち、乾燥後)のセルロース加水分解物の粉末の量は、約10.3g/m2であった。
一般財団法人カケンテストセンターにて、JIS 0217 103法で耐洗濯性を試験した。試験条件は、表5に示すとおりである。
結果を表6に示す。表6から明らかなように、本発明の多層シートは、洗濯回数30回でも剥がれ等は発生せず、耐洗濯性に優れることが明らかとなった。
本発明の保温用構造物である敷布及び掛布団カバーを作製し、それらを使用して就寝した場合の温度を経時的に測定した。
(1)本発明の敷布
(1-1)材料
(a)透湿性基材
ポリエステル製マイクロ・ファイバーで製造されたムートン調編物、目付け=200g/m2
(b)透湿性樹脂の層を形成するための組成物
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)(有姿:65質量%)に、セルロース加水分解物の粉末である日本製紙ケミカル社製W-100GKを20質量%、アルミニウムペーストである林化学工業社製アルミペーストA2を15質量%の割合で混合したもの。なお、アルミニウムペーストのアルミニウム含有率は75質量%であり、残部は主として脂肪酸(20質量%)及び溶剤(5質量%)である。また、アルミニウム粉末の平均粒子径は約80μmである。この組成物から形成される透湿性樹脂は、23.3乃至25.5質量%の透湿性基材に接着する樹脂と、44.8乃至43.5質量%のセルロース加水分解物の粉末と、25.2乃至24.5質量%のアルミニウム粉末と、残部の脂肪酸とからなる。
(c)透湿性ポリマー・フィルム
実施例1で使用した15μm厚の熱可塑性ポリウレタン・フィルム
(i)ムートン調編物の一方の表面上に、透湿性樹脂の層を形成するための組成物を20g/m2の量で塗工する。
(ii)塗工された組成物の表面を熱可塑性ポリウレタン・フィルムで覆う。
(iii)(ii)で調製された複合体を、40℃にて12時間乾燥させる。
なお、製造された敷布のセルロース加水分解物の粉末の量は、約9.8g/m2であり、アルミニウム粉末の量は、約7.3g/m2であった。
ムートン調編物の面が人体側となるように、本発明の敷布で敷布団の表面を覆う。
(2-1)製造方法
本発明の敷布と、ポリエステル製マイクロ・ファイバーで製造されたフリース編物(目付け=150g/m2)とを縫い合わせる。この際、本発明の敷布は、ムートン調編物の面が外側(ポリウレタン・フィルムが、掛布団カバーの内面であって布団と向き合う側)となるように配置する。
掛布団カバーに掛布団を入れ、フリース編物の面が外気側(ムートン調編物の面が人体側)となるように、敷布の上に掛布団を置く。
ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)製の敷布及び掛布団カバー
(4-1)敷布団
側地: ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)製
中綿: ポリエステル100%、3kg
側地: 綿100%(40×40/230本)
中材: ダウン90%+スモールフェザー10%、1.2kg
(1)寝具の使用状況
表7に示す状況で寝具を使用して就寝し、温度を経時的に測定した。
楠本化成社製環境シュミレータ
HIOK製温度測定器 LR8500
10℃、50%RH。なお、実測値は、温度は9.9乃至10.4℃、湿度は47.1乃至50.7%RHであった。
被験者は、敷布の上に仰向けに横たわり、掛布団を掛けて、一定の姿勢を保つ。温度測定器のセンサー部分(直径2mmの棒状部分)を、被験者の右臀部下に配置し、ヒトと寝具との間において温度を測定する(図10参照)。
結果を表8及び図11に示す。表8及び図11から明らかなように、本発明の保温構造物製寝具を使用すると、ヒトと寝具との間の温度が、ブランクに比べて高くなった。また、敷布と掛布団カバーの両者に本発明の保温構造物を使用(試験2)すると、敷布のみの場合(試験1)に比べて、さらに温度が高くなった。
透湿性基材がポリエステル・綿混紡織物であり、透湿性樹脂がセルロース加水分解物の粉末入りアクリル系樹脂である多層シートを作製し、吸湿発熱による温度変化を測定した。
(a)透湿性基材
試料及びブランク共に、ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)
(b)透湿性樹脂の層を形成するための組成物
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)に、セルロース加水分解物の粉末である日本製紙ケミカル社製W-100GKを混合したもの
(i)セルロース加水分解物の粉末60gを計り、トルエン60gを加えてトルエンで馴染ませる。
(ii)アクリル系樹脂接着剤240gを計り、これに(i)で調製したトルエン入りセルロース加水分解物の粉末を加え、よく撹拌し、透湿性樹脂の層を形成するための組成物とする。この組成物から形成される透湿性樹脂は、42乃至39質量%の透湿性基材に接着する樹脂と、58乃至61質量%のセルロース加水分解物の粉末とを含む。
(iii)(ii)で調製された組成物を、透湿性基材の一方の表面上に、200g/m2で塗工する。
(iv)得られた複合物を一昼夜自然乾燥し、その後、40℃にて2時間乾燥させる。
なお、製造された多層シート(即ち、乾燥後)のセルロース加水分解物の粉末の量は、約33.3g/m2であった。
一般財団法人カケンテストセンターの吸湿発熱B法(改良法)
http://www.kaken.or.jp/research/2002/theme2002-08.html参照
(3-1)測定条件
測定時間: 30分間
試験室温度: 20±2℃
湿度: 初期は40%RH、加湿時(測定時)は90%RH
測定面: 試験試料の表面(透湿性樹脂の側)
洗濯処理: 未処理
(i)試験試料が入った反応容器に乾燥空気を供給し、反応容器内を40%RHとする。
(ii)恒湿(40%RH)となって2時間が経過したら、飽和水蒸気の供給を開始する。
(iii)飽和水蒸気の供給が始まったら、試料の表面(透湿性樹脂の側)の温度を経時的に測定する。
結果を表9、表10及び図12に示す。これらのデータから明らかなように、本発明の多層シートは、セルロース加水分解物の粉末が吸湿発熱作用を示したため、ブランクに比べ、上昇温度が1.0℃高かった。
透湿性基材がポリエステル製不織布であり、透湿性樹脂がセルロース加水分解物の粉末入りアクリル系樹脂であり、そして、透湿性ポリマー・フィルムが熱可塑性ポリウレタン・フィルムである多層シートを作製し、吸湿発熱による温度変化を測定した。
(a)透湿性基材
試料及びブランク共に、ポリエステル製スパンニードル不織布(厚さ=80g/m2;透湿度=3,280g/m2/24時間(JIS K7129(A法);リッシー法;40℃;90%RH))
(b)透湿性樹脂の層を形成するための組成物
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)に、セルロース加水分解物の粉末である日本製紙ケミカル社製W-100GKを混合したもの
(c)透湿性ポリマー・フィルム
実施例1で使用した15μm厚の熱可塑性ポリウレタン・フィルム
(i)試料I: セルロース加水分解物の粉末3gを計り、トルエン6gを加えてトルエンで馴染ませる。
試料II: セルロース加水分解物の粉末5gを計り、トルエン10gを加えてトルエンで馴染ませる。
試料III セルロース加水分解物の粉末8gを計り、トルエン16gを加えてトルエンで馴染ませる。
試料IV: セルロース加水分解物の粉末35gを計り、トルエン70gを加えてトルエンで馴染ま せる。
試料V: セルロース加水分解物の粉末45gを計り、トルエン90gを加えてトルエンで馴染ませる。
試料VI: セルロース加水分解物の粉末75gを計り、トルエン150gを加えてトルエンで馴染ませる。
試料I: 樹脂=85.7乃至84.2質量%; セルロース加水分解物の粉末=14.3乃至15.8質量%
試料II: 樹脂=78.3乃至76.2質量%; セルロース加水分解物の粉末=21.7乃至23.8質量%
試料III: 樹脂=69.2乃至66.7質量%; セルロース加水分解物の粉末=30.8乃至33.3質量%
試料IV: 樹脂=34.0乃至31.4質量%; セルロース加水分解物の粉末=66.0乃至68.6質量%
試料V: 樹脂=28.6乃至26.3質量%; セルロース加水分解物の粉末=71.4乃至73.7質量%
試料VI: 樹脂=19.4乃至17.6質量%; セルロース加水分解物の粉末=80.6乃至82.4質量%
(iv)塗工された組成物の表面を透湿性ポリマー・フィルムで覆う。
(v)(iv)で調製された複合体を、40℃にて12時間乾燥させる。
試料I乃至Vを、30cm×24cmに切り出した。これらの試料を用い、実施例3と同様の条件及び方法で測定した。
試料I乃至Vを、20cm×20cmに切り出した。これらの試料を、家庭用小型洗濯機で、液体洗濯用洗剤にて洗濯(洗濯=5分;脱水=1分;濯ぎ=5分;脱水=1分;濯ぎ=5分;脱水=1分)し、室内(25℃)に干した。これを30回繰り返した。
結果を表11に示す。表11から明らかなように、セルロース加水分解物の粉末の量が少ない(試料I)と、発熱によって到達する最高温度が低く、且つ、最高温度に到達する間での時間が長い。一方、セルロース加水分解物の粉末の量が多すぎる(試料VI)と、耐洗濯性に劣る。
透湿性基材がポリエステル・綿混紡織物であり、透湿性樹脂がセルロース加水分解物の粉末入りアクリル系樹脂であり、そして、透湿性ポリマー・フィルム(I)が熱可塑性ポリウレタン・フィルムである多層シートを作製し、経時的に温度を測定した。
(a)透湿性基材
ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)
(b)透湿性樹脂の層を形成するための組成物
水性エマルジョンタイプのアクリル系接着剤である中部サイデン社製バンスターX1417B10(連続相:水;固形分濃度=45乃至50%)に、セルロース加水分解物の粉末である日本製紙ケミカル社製W-100GKを混合したもの
(c)透湿性ポリマー・フィルム
実施例1で使用した15μm厚の熱可塑性ポリウレタン・フィルム
ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)、30cm×24cm
(i)セルロース加水分解物の粉末20gを計り、水40gを加えて水で馴染ませる。
(ii)水性エマルジョンタイプのアクリル系接着剤80gを計り、これに(i)で調製した水入りセルロース加水分解物の粉末を加え、よく撹拌し、透湿性樹脂の層を形成するための組成物とする。この組成物から形成される透湿性樹脂は、64.3乃至66.7質量%の透湿性基材に接着する樹脂と、35.7乃至33.3質量%のセルロース加水分解物の粉末とを含む。
(iii)(ii)で調製された組成物を、ポリエステル・綿混紡織物の一方の表面上に、100g/m2で塗工する。
(iv)塗工された組成物の表面を熱可塑性ポリウレタン・フィルムで覆う。
(v)(iv)で調製された複合体を、40℃にて12時間乾燥させ、30cm×24cmに切り出して測定用試料とする。
なお、製造された多層シート(即ち、乾燥後)のセルロース加水分解物の粉末の量は、約14.3g/m2であった。
恒温恒湿器: ヤマト科学社製HUMIDIC CHAMBER IG-42M
温度測定器: 横河メータ&インスツルメント社製 μR1800自動温度記録計
測定条件: 23℃、90%RH
試料とブランクの各々を、その一辺の長さが1/4となるように交互に折り曲げ、その大きさが7.5cm×6cmである16層構造物とする。この16層構造物の厚み方向の真ん中(上から8層目の下面且つ下から8層目の上面)に温度測定器を挟み込み、23℃、90%RHに設定された恒温恒湿器内に入れ、経時的に温度を測定する。
結果を表12及び図13に示す。表12及び図13から明らかなように、ブランク(ポリエステル・綿混紡織物のみ)と比べ、本発明の多層シートである試料は、吸湿発熱によって温度が上昇し、試験開始から約10分後にはブランクよりも1.5℃高い最高温度に到達し、試験開始から1時間後においても、ブランクよりも高い温度に保持されていた。
羊毛加水分解物の粉末及びセルロース加水分解物の粉末について、吸湿による発熱(温度変化)を経時的に測定した。
(a)イズミ染工社製の羊毛(脱脂化炭処理及び加水分解処理がなされたもの)を粉砕した粉末、見掛け比重=0.44g/cm3、平均粒子径=約40μm
(b)日本製紙ケミカル社製W-100GK: セルロース加水分解物の粉末、比重=0.3~0.4g/cm3、見掛け比重=0.20~0.30g/cm3、平均粒子径=約37μm
恒温恒湿器: ヤマト科学社製HUMIDIC CHAMBER IG-42M
温度測定器: 横河メータ&インスツルメント社製 μR1800自動温度記録計
測定条件: 30℃、90%RH
(i)粉末150gを計り取り、直径100mmのシャーレに入れ、均等にならす。
(ii)粉末内に温度測定器の測定部位(センサー)が埋まるように、温度測定器を固定する。
(iii)シャーレを30℃、90%RHに設定された恒温恒湿器内に入れ、経時的に温度を測定する。
結果を表13及び図14に示す。表13及び図14から明らかなように、セルロース加水分解物の粉末と比べ、羊毛加水分解物の粉末は、さらに高い吸湿発熱性を示した。
透湿性基材がポリエステル・綿混紡織物であり、透湿性樹脂が木綿加水分解物の粉末入りアクリル系樹脂である多層シートと透湿性樹脂が羊毛加水分解物の粉末入りアクリル系樹脂である多層シートとを作製し、吸湿発熱による温度変化を測定した。
(a)透湿性基材
試料及びブランク共に、ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)
(b-1)木綿加水分解物の粉末入り組成物
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)に、イズミ染工社製の加水分解処理木綿粉末(平均粒子径:約40μm)を混合したもの
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)に、実施例10で使用したイズミ染工社製の羊毛を粉砕した粉末(すなわち、脱脂化炭処理及び加水分解処理がなされた羊毛の粉末)を混合したもの
(i)木綿加水分解物の粉末又は羊毛加水分解物の粉末60gを計り、トルエン60gを加えてトルエンで馴染ませる。
(ii)アクリル系樹脂接着剤240gを計り、これに(i)で調製したトルエン入り木綿加水分解物の粉末又は羊毛加水分解物の粉末を加え、よく撹拌し、透湿性樹脂の層を形成するための組成物とする。この組成物から形成される透湿性樹脂は、42乃至39質量%の透湿性基材に接着する樹脂と、58乃至61質量%の木綿加水分解物の粉末又は羊毛加水分解物の粉末とを含む。
(iii)(ii)で調製された組成物を、透湿性基材の一方の表面上に、200g/m2で塗工する。
(iv)得られた複合物を一昼夜自然乾燥し、その後、40℃にて2時間乾燥させる。
なお、製造された多層シート(即ち、乾燥後)の木綿加水分解物の粉末又は羊毛加水分解物の粉末の量は、約33.3g/m2であった。
一般財団法人カケンテストセンターの吸湿発熱B法(改良法)
http://www.kaken.or.jp/research/2002/theme2002-08.html参照
(3-1)測定条件
測定時間: 30分間
試験室温度: 20±2℃
湿度: 初期は40%RH、加湿時(測定時)は90%RH
測定面: 試験試料の表面(透湿性樹脂の側)
洗濯処理: 未処理
(i)試験試料が入った反応容器に乾燥空気を供給し、反応容器内を40%RHとする。
(ii)恒湿(40%RH)となって2時間が経過したら、飽和水蒸気の供給を開始する。
(iii)飽和水蒸気の供給が始まったら、試料の表面(透湿性樹脂の側)の温度を経時的に測定する。
結果を表14、表15及び図15に示す。ブランクは、試験開始後すぐ(約3分後)に最高温度に達し、その後急速に温度が低下した。木綿加水分解物の粉末を含む本発明の多層シートは、最高温度に達するまでにやや時間を要し(約5分)、最高温度はブランクの場合よりもやや低かったが、最高温度に達した後は、試験終了(30分間)まで、ブランクよりは約0.5℃高い温度が保持された。羊毛加水分解物の粉末を含む本発明の多層シートは、最高温度に達するまでにやや時間を要し(約5分)、最高温度はブランクの場合とほぼ同様であったが、発熱が試験終了(30分間)まで持続した。即ち、本発明の多層シートでは、長時間にわたる発熱が期待できる。
本発明の保温用構造物である寝具を作製し、それを使用して就寝した場合の温度を経時的に測定した。
(1)材料
(1-1)透湿性基材
実施例1で使用した15μm厚の熱可塑性ポリウレタン・フィルム
(1-2-1)組成物a
塗工面積1m2あたり、アクリル系樹脂接着剤であるトウペ社製アクリル・バインダー(トルエン(溶剤)含有、固形分濃度=15%)53g、羊毛加水分解物の粉末(実施例10で使用したものと同じ)2.28g、セルロース加水分解物の粉末(日本製紙ケミカル社製W-100GK)1.14gを用意し、これらを混合して組成物aを調製する。この組成物aから形成される透湿性樹脂は、69.9質量%の透湿性基材に接着する樹脂と、20.1質量%の羊毛加水分解物の粉末と、10.0質量%のセルロース加水分解物の粉末とを含む。
(1-2-2)組成物b
塗工面積1m2あたり、アクリル系樹脂接着剤であるトウペ社製アクリル・バインダー(トルエン(溶剤)含有、固形分濃度=15%)53g、羊毛加水分解物の粉末(実施例10で使用したものと同じ)1.14g、セルロース加水分解物の粉末(日本製紙ケミカル社製W-100GK)1.14g、アルミニウムペースト(林化学工業社製アルミペーストA2)1.14gを用意し、これらを混合して組成物bを調製する。なお、アルミニウムペーストのアルミニウム含有率は75質量%であり、残部は主として脂肪酸(20質量%)及び溶剤(5質量%)である。また、アルミニウム粉末の平均粒子径は約80μmである。この組成物bから形成される透湿性樹脂は、70.3質量%の透湿性基材に接着する樹脂と、10.1質量%の羊毛加水分解物の粉末と、10.1質量%のセルロース加水分解物の粉末と、7.6質量%のアルミニウム粉末と、残部の脂肪酸とからなる。
ポリエステルマイクロファイバー製ムートン調起毛編物
(1-4)組成物bによって形成された透湿性樹脂の外側に配される材料
ポリエステルマイクロファイバー製シルキー調起毛編物
(i)熱可塑性ポリウレタン・フィルムの一方の表面上に、組成物aを塗工し、塗工面をムートン調編物で覆う。
(ii)(i)で調製された複合体を、40℃にて12時間乾燥させる。
(iii)熱可塑性ポリウレタン・フィルムの他方の表面上に、組成物bを塗工し、塗工面をシルキー調編物で覆う。
なお、製造された寝具の羊毛加水分解物の粉末の量は3.42g/m2であり、セルロース加水分解物の粉末の量は2.28g/m2であり、アルミニウム粉末の量は0.855g/m2であった。
(1)寝具の使用状況
敷布団の上に、1.で作製した寝具を、ムートン調起毛編物側が上面となるように敷き、その上に被験者(42才、男性、56kg)が横たわった。被験者に、1.で作製した寝具をムートン調起毛編物側が人体側となるようにして掛け、その上に掛布団をかけた。
ブランク試験も、同じ被験者で行った。敷布団の上に1.で作製した寝具の代わりにポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)製の敷布を敷き、その上に被験者が横たわった。被験者に、ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)製の掛布団カバーで覆われた掛布団を掛けた。
楠本化成社製環境シュミレータ
HIOK製温度測定器 LR8500
9℃、50%RH。なお、実測値は、温度は9.9乃至10.2℃であった。
被験者は、試験の間、一定の姿勢を保つ。温度測定器のセンサー部分(直径2mmの棒状部分)を、被験者の右臀部下に配置し、ヒトと寝具との間において温度を測定する(図10参照)。
結果を表16及び図16に示す。表16及び図16から明らかなように、本発明の保温構造物製寝具を使用すると、試験開始から約5分経過後には、ヒトと寝具との間の温度がブランクに比べて高くなった。試験開始から2時間後においても、本発明の保温構造物製寝具を使用した方が、温度が高かった。
透湿性基材がポリエステル・綿混紡織物であり、透湿性樹脂が加水分解されていないセルロース粉末入りアクリル系樹脂である多層シート(比較例試料)を作製し、吸湿発熱による温度変化を測定した。
(a)透湿性基材
比較例試料及びブランク共に、ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)に、加水分解されていないセルロース粉末(イズミ染工社製;見掛け比重:0.4g/cm3;平均粒子径:約60μm)を混合したもの
(i)加水分解されていないセルロース粉末60gを計り、トルエン60gを加えてトルエンで馴染ませる。
(ii)アクリル系樹脂接着剤240gを計り、これに(i)で調製したトルエン入りセルロース粉末(加水分解されていないもの)を加え、よく撹拌し、透湿性樹脂の層を形成するための組成物とする。この組成物から形成される透湿性樹脂は、42乃至39質量%の透湿性基材に接着する樹脂と、58乃至61質量%のセルロース粉末(加水分解されていないもの)とを含む。
(iii)(ii)で調製された組成物を、透湿性基材の一方の表面上に、200g/m2で塗工する。
(iv)得られた複合物を一昼夜自然乾燥し、その後、40℃にて2時間乾燥させる。
なお、製造された多層シート(即ち、乾燥後)のセルロース粉末(加水分解されていないもの)の量は、約33.3g/m2であった。
一般財団法人カケンテストセンターの吸湿発熱B法(改良法)
http://www.kaken.or.jp/research/2002/theme2002-08.html参照
(3-1)測定条件
測定時間: 30分間
試験室温度: 20±2℃
湿度: 初期は40%RH、加湿時(測定時)は90%RH
測定面: 比較例の多層シートは、透湿性樹脂の側
洗濯処理: 未処理
(i)ブランク試料であるポリエステル・綿混紡織物又は比較例の多層シートが入った反応容器に乾燥空気を供給し、反応容器内を40%RHとする。
(ii)恒湿(40%RH)となって2時間が経過したら、飽和水蒸気の供給を開始する。
(iii)飽和水蒸気の供給が始まったら、試料の表面(比較例の多層シートについては透湿性樹脂の側)の温度を経時的に測定する。
結果を表17、表18及び図17に示す。ブランク(ポリエステル・綿混紡織物のみ)は、試験開始後すぐ(約3分後)に最高温度に達し、その後急速に温度が低下した。比較例の多層シートは、最高温度に達するまでの時間がブランクよりも長く(約4分)、最高温度はブランクの場合よりも1.3℃も低かった。
透湿性基材がポリエステル・綿混紡織物であり、透湿性樹脂が、加水分解されていない又は加水分解された羊毛粉末入りアクリル系樹脂である多層シートを作製し、経時的に温度を測定した。
(a)透湿性基材: ポリエステル・綿混紡織物(ポリエステル65%、綿45%、45×45/110×76本)
(b)透湿性樹脂の層を形成するための組成物
アクリル系樹脂接着剤であるトウペ社製アクリル・バインダーXE-3773(トルエン(溶剤)含有、固形分濃度=16乃至18%)に、脱脂化炭処理がなされているが、加水分解処理がなされていない羊毛粉末(見掛け比重:0.7g/cm3;平均粒子径:約80μm)又は脱脂化炭処理及び加水分解処理がなされた羊毛粉末(実施例10で使用したものと同じ)を混合したもの
(i)加水分解処理がなされていない又は加水分解処理がなされた羊毛粉末30gを計り、トルエン30gを加えてトルエンで馴染ませる。
(ii)アクリル系樹脂接着剤240gを計り、これに(i)で調製したトルエン入り羊毛粉末を加え、よく撹拌し、透湿性樹脂の層を形成するための組成物とする。この組成物から形成される透湿性樹脂は、56乃至59質量%の透湿性基材に接着する樹脂と、44乃至41質量%の羊毛粉末とを含む。
(iii)(ii)で調製された組成物を、透湿性基材の一方の表面上に、200g/m2で塗工する。
(iv)得られた複合物を一昼夜自然乾燥し、その後、40℃にて2時間乾燥させ、30cm×24cmに切り出して測定用試料とする。
なお、製造された多層シート(即ち、乾燥後)の羊毛粉末の量は、約20g/m2であった。
恒温恒湿器: ヤマト科学社製HUMIDIC CHAMBER IG-42M
温度測定器: 横河メータ&インスツルメント社製 μR1800自動温度記録計
測定条件: 30℃、90%RH
測定用試料の各々を、その一辺の長さが1/4となるように交互に折り曲げ、その大きさが7.5cm×6cmである16層構造物とする。この16層構造物の厚み方向の真ん中(上から8層目の下面且つ下から8層目の上面)に温度測定器を挟み込み、30℃、90%RHに設定された恒温恒湿器内に入れ、経時的に温度を測定する。
結果を表19及び図18に示す。表19及び図18から明らかなように、加水分解処理がなされていない羊毛粉末を含む樹脂層が形成された多層シート(比較例)と比べ、加水分解処理がなされた羊毛粉末を含む樹脂層が形成された多層シート(発明例)は、吸湿発熱によって温度がより高く上昇した。具体的には、試験開始から約10分後には、比較例よりも1.0℃高い最高温度に到達し、試験開始から40分後においても、比較例よりも高い温度に保持されていた。
1a 編物、織布又は不織布
1b 透湿性ポリマー・フィルム(II)
1c 透湿性接着剤の層
3,3x,3y 透湿性樹脂の層
5 透湿性ポリマー・フィルム(I)
7a 編物、織布又は不織布
7b 透湿性接着剤の層
31 透湿性基材に接着する樹脂
33 セルロース加水分解物の粉末
35 アルミニウム粉末
100,200,300,400,500,600 多層シート
Claims (14)
- 透湿性基材の層と、その透湿性基材の層の少なくとも一方の表面上に形成された透湿性樹脂の層とを備え、透湿性樹脂は、透湿性基材の層の内部にも存在していてもよく、透湿性樹脂は、透湿性基材に接着する樹脂と、非水溶性の吸湿発熱性粉粒体であって植物に由来するものの加水分解物及び/又は動物に由来するものの加水分解物とを含み、透湿性樹脂全量中、透湿性基材に接着する樹脂の量は20乃至80質量%であり且つ非水溶性の吸湿発熱性粉粒体の量は80乃至20質量%であることを特徴とする多層シート。
- 非水溶性の吸湿発熱性粉粒体の量が、5乃至100g/m2である、請求項1に記載の多層シート
- 非水溶性の吸湿発熱性粉粒体が、セルロース加水分解物の粉末である、請求項1又は2に記載の多層シート。
- 非水溶性の吸湿発熱性粉粒体が、動物に由来する蛋白質の加水分解物の粉末である、請求項1又は2に記載の多層シート。
- 透湿性基材に接着する樹脂がアクリル系樹脂である、請求項1乃至4のいずれか一項に記載の多層シート。
- さらに、一方又は両方の透湿性樹脂の層の表面上に透湿性ポリマー・フィルム(I)が存在する、請求項1乃至5のいずれか一項に記載の多層シート。
- 透湿性ポリマー・フィルム(I)の透湿度(JIS K7129(A法);リッシー法)が400g/m2/24時間以上である、請求項6に記載の多層シート。
- 透湿性ポリマー・フィルム(I)が透湿性ポリウレタン・フィルムである、請求項6又は7に記載の多層シート。
- 一方又は両方の透湿性ポリマー・フィルム(I)の外側に、更に、透湿性接着剤の層を介して、編物、織布又は透湿性不織布が存在する、請求項6乃至8のいずれか一項に記載の多層シート。
- さらに、一方又は両方の透湿性樹脂の層の表面上に、編物、織布又は透湿性不織布が存在する、請求項1乃至5のいずれか一項に記載の多層シート。
- 透湿性樹脂が、更にアルミニウム粉末を含有し、その量は、透湿性樹脂全量中において40質量%以下である、請求項1乃至10のいずれか一項に記載の多層シート。
- 請求項1乃至11のいずれか一項に記載の多層シートを備えることを特徴とする保温用構造物。
- 透湿性基材に、透湿性基材に接着する樹脂又はそのような樹脂の前駆体と、非水溶性の吸湿発熱性粉粒体であって植物に由来するものの加水分解物及び/又は動物に由来するものの加水分解物とを含む組成物を、10乃至200g/m2の量で塗布する工程と、透湿性基材に接着する樹脂又はそのような樹脂の前駆体を硬化させることによって透湿性樹脂を形成する工程とを含み、ここで、形成された透湿性樹脂は、その全量中、透湿性基材に接着する樹脂を20乃至80質量%の量で含み且つ非水溶性の吸湿発熱性粉粒体を80乃至20質量%の量で含むものであることを特徴とする多層シートの製造方法。
- 前記組成物を塗布する工程を機械塗工によって実施し、その塗布量が10乃至50g/m2である、請求項13に記載の多層シートの製造方法。
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201280002384.XA CN103492177A (zh) | 2012-04-18 | 2012-08-29 | 多层片、具有该多层片的保温用结构物和多层片的制造方法 |
| RU2013102964A RU2013102964A (ru) | 2012-04-18 | 2012-08-29 | Многослойный лист, содержащая его термическая структура и способ получения многослойного листа |
| KR1020137003496A KR20150007916A (ko) | 2012-04-18 | 2012-08-29 | 다층 시트, 이를 포함하는 보온용 구조물 및 다층 시트의 제조 방법 |
| EP12803500.3A EP2684692A4 (en) | 2012-04-18 | 2012-08-29 | MULTI-LAYER SHEET, HEAT RETENTION STRUCTURE HAVING THE SAME, AND METHOD FOR PRODUCING MULTI-LAYER SHEET |
| US13/812,023 US20130276772A1 (en) | 2012-04-18 | 2012-08-29 | Multi-layered sheet, thermal structure comprising it, and process for producing multi-layered sheet |
| TW102113515A TW201350062A (zh) | 2012-04-18 | 2013-04-16 | 多層片材、具備其之保溫用構造物及多層片材之製造方法 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPPCT/JP2012/060395 | 2012-04-18 | ||
| PCT/JP2012/060395 WO2013157085A1 (ja) | 2012-04-18 | 2012-04-18 | 多層シート及びそれを備える保温用構造物 |
| PCT/JP2012/064377 WO2013157151A1 (ja) | 2012-04-18 | 2012-06-04 | 多層シート、それを備える保温用構造物及び多層シートの製造方法 |
| JPPCT/JP2012/064377 | 2012-06-04 |
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| WO2013157156A1 true WO2013157156A1 (ja) | 2013-10-24 |
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| PCT/JP2012/060395 Ceased WO2013157085A1 (ja) | 2012-04-18 | 2012-04-18 | 多層シート及びそれを備える保温用構造物 |
| PCT/JP2012/064377 Ceased WO2013157151A1 (ja) | 2012-04-18 | 2012-06-04 | 多層シート、それを備える保温用構造物及び多層シートの製造方法 |
| PCT/JP2012/071785 Ceased WO2013157156A1 (ja) | 2012-04-18 | 2012-08-29 | 多層シート、それを備える保温用構造物及び多層シートの製造方法 |
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| PCT/JP2012/060395 Ceased WO2013157085A1 (ja) | 2012-04-18 | 2012-04-18 | 多層シート及びそれを備える保温用構造物 |
| PCT/JP2012/064377 Ceased WO2013157151A1 (ja) | 2012-04-18 | 2012-06-04 | 多層シート、それを備える保温用構造物及び多層シートの製造方法 |
Country Status (6)
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|---|---|
| EP (1) | EP2684692A4 (ja) |
| KR (1) | KR20150007916A (ja) |
| CN (1) | CN103492177A (ja) |
| RU (1) | RU2013102964A (ja) |
| TW (1) | TW201350062A (ja) |
| WO (3) | WO2013157085A1 (ja) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017080938A (ja) * | 2015-10-24 | 2017-05-18 | 株式会社エムズコーポレーション | 積層繊維構造体とその製造方法 |
| JP2017124552A (ja) * | 2016-01-14 | 2017-07-20 | セーレン株式会社 | 調湿性カバー材及びその製造方法 |
| US10307984B2 (en) | 2014-03-31 | 2019-06-04 | Ceraloc Innovation Ab | Composite boards and panels |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3034109B1 (fr) * | 2015-03-27 | 2017-03-24 | Ferrari Serge Sas | Textile enduit anti condensation |
| TWI673408B (zh) * | 2017-12-20 | 2019-10-01 | Taiwan Textile Research Institute | 吸溼發熱劑及其製備方法 |
| TR2023005264A2 (tr) * | 2023-05-11 | 2023-05-22 | Pelsan Tekstil Ueruenleri Sanayi Ve Ticaret Anonim Sirketi | Bebek örtüsü üreti̇m yöntemi̇ |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10307984B2 (en) | 2014-03-31 | 2019-06-04 | Ceraloc Innovation Ab | Composite boards and panels |
| US10967608B2 (en) | 2014-03-31 | 2021-04-06 | Ceraloc Innovation Ab | Composite boards and panels |
| US11541630B2 (en) | 2014-03-31 | 2023-01-03 | Ceraloc Innovation Ab | Composite boards and panels |
| JP2017080938A (ja) * | 2015-10-24 | 2017-05-18 | 株式会社エムズコーポレーション | 積層繊維構造体とその製造方法 |
| JP2017124552A (ja) * | 2016-01-14 | 2017-07-20 | セーレン株式会社 | 調湿性カバー材及びその製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201350062A (zh) | 2013-12-16 |
| WO2013157085A1 (ja) | 2013-10-24 |
| WO2013157151A1 (ja) | 2013-10-24 |
| RU2013102964A (ru) | 2016-06-10 |
| CN103492177A (zh) | 2014-01-01 |
| EP2684692A1 (en) | 2014-01-15 |
| EP2684692A4 (en) | 2015-11-04 |
| KR20150007916A (ko) | 2015-01-21 |
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