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WO2014061182A1 - Moisture-permeable waterproof sheet and method for manufacturing same - Google Patents

Moisture-permeable waterproof sheet and method for manufacturing same Download PDF

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Publication number
WO2014061182A1
WO2014061182A1 PCT/JP2013/004877 JP2013004877W WO2014061182A1 WO 2014061182 A1 WO2014061182 A1 WO 2014061182A1 JP 2013004877 W JP2013004877 W JP 2013004877W WO 2014061182 A1 WO2014061182 A1 WO 2014061182A1
Authority
WO
WIPO (PCT)
Prior art keywords
moisture
porous
permeable waterproof
waterproof sheet
polyurethane
Prior art date
Application number
PCT/JP2013/004877
Other languages
French (fr)
Japanese (ja)
Inventor
林　豊
正勝 西原
Original Assignee
小松精練株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 小松精練株式会社 filed Critical 小松精練株式会社
Priority to JP2014541909A priority Critical patent/JP6262660B2/en
Publication of WO2014061182A1 publication Critical patent/WO2014061182A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Definitions

  • the present invention relates to a moisture-permeable waterproof sheet and a manufacturing method thereof.
  • Moisture, ski wear, windbreakers, tents, shoe materials, gloves, etc. use moisture-permeable waterproof fabrics that allow moisture such as sweat released from the body to pass through but prevent rain and other water from entering. Yes.
  • a moisture permeable waterproof fabric As a moisture permeable waterproof fabric, a fiber fabric laminated with a porous film is known.
  • a moisture-permeable waterproof fabric using a porous membrane has not only moisture permeability and waterproofness but also air permeability. For this reason, if it wears the goose etc. which were manufactured with such a moisture-permeable waterproof fabric, it can work under a comfortable environment even in the rain.
  • the moisture-permeable waterproof fabric using the porous membrane has a problem that the water resistance is lowered and the waterproof property is deteriorated when the washing treatment is performed because the surface of the porous membrane is open. . This is because the surfactant contained in the detergent used during the washing process remains in the porous membrane, making it easier to draw water.
  • the phenomenon that the water pressure resistance is reduced occurs not only during the washing process but also when a hydrophilic component is contained in sweat or dirt components.
  • Patent Document 1 proposes a technique for preventing a decrease in water pressure resistance by a nonporous layer.
  • the present invention has been made to solve such problems, and is a moisture-permeable waterproof sheet using a porous membrane, which suppresses a decrease in water pressure resistance due to washing treatment while having air permeability.
  • An object is to provide a moisture-permeable waterproof sheet.
  • a moisture-permeable waterproof sheet according to the present invention is a porous material containing polyurethane on at least one surface of a porous film having a plurality of pores whose surfaces are open and / or in the porous film. A layer is formed.
  • the air permeability is preferably 0.005 cm 3 / cm 2 ⁇ s or more and 1 cm 3 / cm 2 ⁇ s or less.
  • the water pressure resistance after 10 washing processes is 5000 mm or more.
  • the porous film is preferably a porous polytetrafluoroethylene film.
  • a water repellent is attached to the surface of the porous layer.
  • the method for producing a moisture-permeable waterproof sheet according to the present invention is characterized by laminating a porous film having a plurality of pores whose surfaces are open and a polyurethane solution.
  • the porous film is preferably a porous polytetrafluoroethylene film.
  • the polyurethane solution is preferably a polyurethane emulsion of a W / O type emulsion.
  • the present invention it is possible to obtain a moisture-permeable waterproof sheet that has air permeability and can suppress a decrease in water pressure resistance due to washing treatment or the like. Therefore, by using this moisture-permeable tarpaulin for windbreakers, goose, coats, jackets, ski wear, snowboard wear, jackets, tents, gloves, shoes, sleeping bags, bags, filters, etc. It is possible to provide a textile product that can suppress dripping and suppress water pressure drop even when washing is performed while suppressing intrusion and exhibit excellent waterproofness.
  • the moisture-permeable waterproof sheet according to the embodiment of the present invention is provided on at least one surface of a porous film whose surface is open (hereinafter, also referred to as “open porous film” or simply “porous film”). And / or a porous layer containing polyurethane (hereinafter, also simply referred to as “porous layer”) formed in the porous film. Furthermore, the moisture-permeable waterproof sheet in the present embodiment has an air permeability of 0.005 cm 3 / cm 2 ⁇ s or more and 1 cm 3 / cm 2 ⁇ s or less, and has a water pressure retention rate of 10 after 10 washing treatments. % Or more is preferable.
  • the opened porous membrane means a porous membrane having a plurality of micropores whose surfaces are infinitely open. In this embodiment, these micropores communicate with each other. It has the ability to pass moisture from one surface of the porous membrane to the other while having air permeability while suppressing the intrusion of rain and the like. A liquid or sweat containing a detergent can enter the pores of the porous membrane.
  • the size of the pores formed in the porous membrane is not particularly limited, and examples include pores having a pore diameter of about 0.01 ⁇ m to 30 ⁇ m.
  • porous film having an open surface a porous polytetrafluoroethylene film (hereinafter also referred to as “PTFE film”) having the structure as described above, a porous polyurethane film, and a porous polyester film Examples thereof include, but are not limited to, a porous polyethylene film or a porous polypropylene film.
  • PTFE film porous polytetrafluoroethylene film
  • a PTFE membrane which is excellent in waterproof property at the initial stage (before washing treatment or before wearing clothes).
  • the PTFE membrane is handled by Nippon Gore Co., Ltd. or Nippon Donaldson Co., Ltd., and is called PTFE or e-PTFE (expanded PTFE), and has a thickness of about 10 ⁇ m to 300 ⁇ m.
  • a moisture-permeable waterproof sheet for clothes such as a windbreaker or a feather
  • the porous layer containing polyurethane is a surface of a porous film having an open surface and / or a porous layer formed using polyurethane in the porous film.
  • the pore diameter of the pores formed in the porous layer is about 0.001 ⁇ m to 30 ⁇ m.
  • the pores of the porous layer formed in the porous membrane are the pores formed in the porous layer portion where the porous membrane does not exist Compared with, the pore diameter tends to be smaller due to the influence of the pores of the porous membrane.
  • the pores in the porous membrane may be clogged with polyurethane for forming the porous layer.
  • the porous layer in the porous membrane is also porous, at least some of the pores are clogged. They communicate with each other. As a result, the moisture-permeable waterproof sheet obtained is kept breathable.
  • the thickness of the porous layer is preferably about 5 to 100 ⁇ m. More preferably, it is 10 ⁇ m or more, and more preferably 50 ⁇ m or less. When the thickness of the porous layer is less than 5 ⁇ m, the effect of suppressing the decrease in the water pressure resistance due to the washing treatment may not be sufficiently exhibited. On the other hand, when the thickness of the porous layer exceeds 100 ⁇ m, the effect of suppressing the decrease in the water pressure resistance is not improved so much and the texture may be cured.
  • the thickness of the porous layer refers to the sum of the thickness of the porous layer on the porous membrane surface and the thickness of the porous layer in the porous membrane.
  • the formation of a porous layer containing polyurethane on at least one surface of the porous membrane having an open surface and / or in the porous membrane suppresses a decrease in water pressure resistance even after washing treatment.
  • a moisture-permeable waterproof sheet that can exhibit excellent waterproof properties can be obtained. This effect is exhibited particularly when a PTFE membrane is used as the porous membrane.
  • a porous film containing polyurethane in at least a part of the porous film is particularly preferable.
  • an ether-based, ester-based, ester-ether-based, or polycarbonate-based polyurethane can be used, and is not particularly limited. However, from the viewpoint of moisture permeability, it is hydrophilic. From the viewpoint of film strength (scratch resistance, scratch resistance), a hydrophobic polyurethane is preferable. These polyurethanes may be used in combination of a plurality of types.
  • a water repellent is attached to the surface of the porous layer.
  • a water repellent agent is added to the polyurethane solution forming the porous layer, or after forming the porous layer, a padding method, a gravure method or a spray method is applied to the surface of the porous layer.
  • a water repellent may be applied by the above. More preferably, a porous layer is formed by adding a water repellent to a polyurethane solution for forming a porous layer, and further, a padding method, a gravure method or a spray method is formed on the surface of the formed porous layer.
  • a water repellent agent may be applied. That is, it is advisable to add a water repellent to the polyurethane solution and to carry out a post-water repellent treatment. Thereby, the quality of a moisture-permeable waterproof sheet can be stabilized.
  • a fluorine-based, silicone-based, or paraffin-based water repellent can be used, and is not particularly limited, but it is preferable to use a fluorine-based one from the viewpoint of durability.
  • the polyurethane constituting the porous layer one having a silicone segment or a fluorine segment in the main chain or side chain may be used.
  • the water pressure retention after the tenth washing treatment of the moisture-permeable waterproof sheet in the present embodiment is 10% or more, more preferably 20%, and further preferably 30%.
  • the water pressure resistance retention rate is a percentage obtained by dividing the water pressure resistance after the washing process 10 times by the water pressure before the washing process (initial), and is obtained by the following formula.
  • Water pressure retention rate (%) water pressure after washing process 10 times ⁇ water pressure before washing process (initial) x 100
  • washing processing is performed according to JIS L0217 103 method. Specifically, when washing is performed in a washing solution containing a detergent for 25 minutes and then rinsed twice for 10 minutes while water is poured twice, this operation is repeated twice and dried. As a treatment, it was assumed that it was hung and dried only once at the end.
  • a synthetic detergent for washing uses Attack High Activity Bio-EX manufactured by Kao Co., Ltd. at 1 g / l
  • a washing machine is a national fully automatic electric washing machine NA manufactured by the former Matsushita Electric Industrial Co., Ltd. (currently Panasonic Corporation). -F50Y2 was used. Note that heat treatment such as dry iron finishing was not performed after drying.
  • the water pressure resistance of the moisture-permeable waterproof sheet means that measured according to JIS L1092-1998 water resistance test method B (high water pressure method).
  • nylon taffeta the total density of warp yarns and weft yarns per 2.54 cm is about 210) is piled on the test piece. Attach to a testing machine and measure.
  • the water pressure resistance of the moisture-permeable waterproof sheet before washing is preferably 10,000 mm or more. Moreover, it is preferable that the water pressure resistance of the moisture-permeable waterproof sheet after 10 times of washing treatment is 5000 mm or more. Further, the water pressure resistance after the 10th washing treatment is preferably 10,000 mm or more. When the water pressure resistance after the 10-times washing treatment of the moisture-permeable waterproof sheet is 10000 mm or more, the infiltration of rain is prevented even in the case of severe wind and rain.
  • the upper limit of the water pressure resistance after 10 washing treatments is not particularly limited, but if the water pressure resistance is too high, the texture of the moisture-permeable waterproof sheet may be cured, so the upper limit is about 100,000 mm.
  • the moisture-permeable waterproof sheet in the present embodiment has an air permeability of 0.005 cm 3 / cm 2 ⁇ s or more. If the air permeability is 0.005 cm 3 / cm 2 ⁇ s or more, moisture and the like in the clothes can be released to the outside, so that stuffiness can be suppressed and comfort can be maintained. From the viewpoint of further suppressing the stuffiness, the air permeability is preferably 0.01 cm 3 / cm 2 ⁇ s or more, and more preferably 0.05 cm 3 / cm 2 ⁇ s or more.
  • the upper limit of the air permeability is not particularly limited, but the air permeability is preferably 1 cm 3 / cm 2 ⁇ s or less. If it is a moisture-permeable waterproof sheet with an air permeability of 1 cm 3 / cm 2 ⁇ s or less, the effect of suppressing stuffiness is excellent while maintaining waterproofness.
  • the air permeability can be measured according to JIS L1096 A method (fragile method).
  • the moisture permeability of the moisture permeable waterproof sheet in the present embodiment is not particularly limited, but the moisture permeability (calcium chloride method) measured according to JIS L1099-1993 A-1 method is 5000 to 20000 g. / M 2 ⁇ 24 hours is preferable. If the moisture permeability is less than 5000 g / m 2 ⁇ 24 hours, there is a risk of stuffiness when wearing clothes or the like obtained from a moisture-permeable waterproof fabric. Further, if the moisture permeability exceeds 20000 g / m 2 ⁇ 24 hours or more, there is a possibility that sufficient waterproofness cannot be obtained.
  • the moisture permeability of the moisture permeable waterproof sheet is measured according to JIS L1099-1993 B-1 method or B-2 method
  • the moisture permeability is 5000 to 200000 g / m 2 ⁇ 24 hours. It is preferable.
  • the B-2 method is used when the water pressure resistance decreases and the measurement by the B-1 method leaks water.
  • the moisture-permeable waterproof sheet in the present embodiment may have a fiber fabric laminated on one or both sides of the moisture-permeable waterproof sheet. That is, the fiber fabric is preferably laminated on one side or both sides of the porous membrane or the porous layer.
  • the fiber fabric may be any fiber such as polyester, nylon, polyurethane, acrylic, rayon, acetate, polylactic acid, soy protein, silk, wool, cotton, hemp, or other chemical fibers or natural fibers.
  • these fibers may be mixed, mixed, woven or knitted.
  • you may have what forms, such as a woven fabric, a knitted fabric, or a nonwoven fabric.
  • Lamination of a porous membrane or a porous layer and a fiber fabric is a point where an adhesive (binder) or the like is dotted on at least one of the porous membrane, the porous layer, and the fiber fabric without departing from the gist of the present invention.
  • They may be provided as a linear shape or a lattice shape and laminated by bonding.
  • the adhesive is not particularly limited, and as the adhesive, for example, urethane, epoxy, melamine, nylon, polyester, or acrylic adhesives can be used.
  • the adhesive may be either a one-component type or a two-component type, and may be a hot-melt type urethane resin including a moisture curable type.
  • dyeing, printing, water-repellent, anti-static, water-absorbing, SR, antibacterial, deodorant, antibacterial, deodorant, UV shielding, flameproofing, or calendaring for fiber fabrics Etc. may be given.
  • the porous layer is colored by adding a colorant such as a pigment, or the surface of the porous film or porous layer.
  • a colorant such as a pigment
  • polyurethane or acrylic resin containing a colorant such as a pigment may be applied in a pattern such as a dot, lattice, geometric pattern or floral pattern.
  • pigments, organic particles, inorganic particles, antibacterial agents, heat storage agents, flame retardants, etc. are contained in the porous layer for the purpose of improving water pressure resistance, improving touch or imparting antibacterial properties
  • Other polyurethanes or acrylic resins that partially contain pigments, organic particles, inorganic particles, antibacterial agents, heat storage agents, flame retardants, etc. on the surface of the porous layer do not depart from the gist of the present invention. You may make it adhere in the range.
  • the moisture-permeable waterproof sheet in this Embodiment is not limited to what is manufactured with the following manufacturing method.
  • the opened porous membrane and porous layer are the same as those described above.
  • the method for producing a moisture-permeable waterproof sheet includes a step of laminating a polyurethane solution on a porous film having an open surface.
  • a method of laminating the polyurethane solution a method of directly laminating the polyurethane solution on the porous film using a knife coater, a bar coater, a comma coater, a kiss coater, a gravure coater, a die coater or the like can be cited.
  • the polyurethane solution used in this production method is for forming a porous layer, it further includes a porosification step of making the polyurethane solution porous by foaming the polyurethane solution or the like.
  • a porosification step By foaming the polyurethane solution, a porous layer containing porous polyurethane can be formed.
  • the timing of performing such a porosification step is before laminating the polyurethane solution on the porous membrane, after laminating the polyurethane solution on the porous membrane, and on the porous membrane. Any of the simultaneous formation of the polyurethane solution may be used.
  • the polyurethane solution is foamed by mixing with air using a high pressure foaming machine, and the foamed polyurethane solution is used with the coater as described above.
  • a method mechanical foaming method in which a porous layer is formed by directly applying and laminating on a porous film and then performing heat treatment.
  • a porous layer is formed on the porous film by generating carbon dioxide by the reaction of water and isocyanate.
  • a film forming method chemical foaming method
  • a polyurethane emulsion of a W / O emulsion is used as a polyurethane solution, and the polyurethane solution is directly applied on the porous membrane, laminated, and then heat-treated, whereby toluene contained in the W / O emulsion
  • a method of forming a porous layer on the porous film by volatilizing an organic solvent having a lower boiling point than water such as methyl ethyl ketone, coagulating polyurethane with the remaining water, and then evaporating the water.
  • the polyurethane solution for wet coagulation using dimethylformamide or the like having a high affinity for water as a polyurethane solution
  • the polyurethane solution is applied and laminated on the porous film, and then immersed in water.
  • a method wet coagulation method in which a porous layer is formed on a porous membrane by replacing dimethylformamide and water.
  • a method of forming a porous layer on the porous film may be used.
  • a method of applying the polyurethane solution directly to the porous film is not used, but a knife coater, bar coater, comma coater, kiss coater, gravure coater is used on a release paper or a release film.
  • a method of laminating the polyurethane solution on the porous film by applying a polyurethane solution using a die coater or the like and superposing the porous film on the applied polyurethane solution may be used.
  • the porous process may be performed by applying the method when the polyurethane solution is applied on the porous film, for example, W / O type on the release paper.
  • a porous layer containing polyurethane can be formed on one side of the porous membrane and in the porous membrane by applying a polyurethane emulsion of emulsion, laminating the porous membrane on it, and heat-treating it. .
  • the heat treatment temperature for forming or forming the porous layer varies depending on the type of polyurethane and the foaming method, but the heat treatment may be performed at about 60 to 200 ° C. for about 1 second to 1 hour.
  • the method for forming the porous layer is not limited to the above, and a compound other than water is used as the foaming agent, the porous layer is formed by combining the above methods, or the above-described method.
  • the porous layer may be formed by other known methods.
  • a low boiling point organic solvent is volatilized first, so that it is 10 ° C. to 40 ° C. to 110 ° C., more preferably 50 to 90 ° C.
  • the manufacturing method in the present embodiment is such that, from the viewpoint of the adhesive strength between the porous film and the porous layer, the porous layer and the porous film are formed with an adhesive or the like after the porous layer is formed alone.
  • a polyurethane solution is laminated on the porous membrane. That is, the porous layer is formed on the porous film by laminating the polyurethane solution on the porous film.
  • the polyurethane solution is impregnated into the porous film, and a porous layer containing polyurethane is formed in the porous film.
  • a polyurethane solution is applied onto a release paper or release film using a knife coater, bar coater, comma coater, kiss coater, gravure coater or die coater. It is preferable to use a method of laminating a porous film on the applied polyurethane solution.
  • a PTFE membrane is used as the porous membrane, it is preferable to apply a polyurethane solution on a release paper or a release film, and laminate the porous membrane on the applied polyurethane solution.
  • the porous film is not particularly limited, but the polyurethane solution is directly applied to the porous film.
  • the porous membrane is preferably bonded to a fiber cloth or the like in advance. Thereby, even when tension is applied, it is possible to prevent the porous film from extending or the length in the width direction from being shortened.
  • the polyurethane solution may be a polyurethane emulsion of W / O type emulsion or a polyurethane solution for wet coagulation containing a solvent having a high affinity for water such as dimethylformamide.
  • a polyurethane solution of a W / O emulsion is particularly preferably used as the polyurethane solution.
  • the polyurethane emulsion of the W / O type emulsion contains an organic solvent having a boiling point lower than that of water.
  • an organic solvent having a certain degree of mutual solubility with water is preferably used.
  • Examples of the organic solvent that can be used in the polyurethane emulsion of the W / O emulsion include methyl ethyl ketone (MEK), methyl-N-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, Methyl acetate or ethyl acetate is preferably used, and acetone, cyclohexanone, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene (TOL), xylene, dimethylformamide (DMF), dimethyl sulfoxide, perchlorethylene, Methyl cellosolve, butyl cellosolve, cellosolve acetate or the like can also be used.
  • MEK methyl ethyl ketone
  • organic solvents may be used as a mixture. Also, among these organic solvents, those that have no limit on mutual solubility with water, or those that do not dissolve at all, should be used as a mixture with other organic solvents with a limit on the mutual solubility with water. Is preferred.
  • the polyurethane in the polyurethane emulsion of the W / O type emulsion may be completely dissolved in an organic solvent or may be partially precipitated.
  • DIC Corporation's XOLTEX PX550, PX-309, PX-300, PX-100F, etc.
  • Dainichi Seika Kogyo Co., Ltd. X-3040, X-3041, X-3050, X-3062, ATX-1, ATX-10, etc.
  • the polyurethane solution contains pigments for coloring, or organic particles such as silk powder, gelatin powder and eggshell membrane powder for imparting moisture absorption, moisture permeability and waterproofing.
  • Inorganic particles such as silicon oxide, aluminum oxide, and calcium carbonate, porous particles such as porous silica for countermeasures against contamination of resin films by disperse dyes, or silver zeolite and pyridine series for imparting antibacterial properties
  • deodorants, antistatic agents, ultraviolet absorbers, antioxidants, flame retardants, infrared absorbers, and the like may be added.
  • a water repellent to the polyurethane solution from the viewpoint of improving water repellency, waterproofing and suppressing water pressure drop after washing.
  • a cross-linking agent is added to improve the strength of the porous layer, and a wetting improver and a thickener are added to adjust the impregnation of the resin into the porous membrane.
  • an antifoaming agent may be added.
  • the crosslinking agent include an isocyanate crosslinking agent, an aziridine crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, and an oxazoline crosslinking agent.
  • the lamination is performed by bonding the porous membrane and the fiber fabric using an adhesive before or after the polyurethane solution is applied onto the porous membrane. do it.
  • laminating stacking a fiber cloth on a porous layer, after forming a porous layer, what is necessary is just to bond a porous layer and a fiber cloth using an adhesive agent.
  • the adhesive is preferably applied in the form of dots, lines or lattices, and covers all the contact surfaces between the fiber fabric and the porous membrane. It is advisable to apply an adhesive partially so that there is no such problem. Further, the entire contact surface between the fiber fabric and the porous membrane may be covered with an adhesive, but in this case, it is preferable to use a porous adhesive to ensure air permeability.
  • urethane, epoxy, melamine, nylon, polyester, or acrylic adhesives can be used as the adhesive.
  • the adhesive may be either a one-component type or a two-component type, and may be a hot-melt type urethane resin including a moisture curable type.
  • the fiber fabric may be laminated on both surfaces (the surface on which the porous membrane and the porous layer are formed) of the obtained moisture-permeable waterproof sheet, or the surface of the porous membrane and the porous layer It may be laminated
  • a pattern for improving water pressure resistance, touch improvement, and design improvement is provided without departing from the object of the present invention.
  • the acrylic resin may be attached using a gravure coater or a screen printing machine.
  • a solution containing a water repellent, an antibacterial agent, a flame retardant, an SR agent, a deodorant, an antistatic agent, a water absorbing agent or an ultraviolet absorber You may give to the said moisture-permeable waterproof sheet by the spray method or the gravure method.
  • the moisture-permeable waterproof sheet according to the present invention will be further described with reference to examples, but the present invention is not limited to these examples.
  • the “part” described below means “part by mass”, “%” means mass%, and the blending ratio means mass ratio.
  • various physical property values and the like in the following examples were measured and evaluated by the following methods.
  • the moisture permeability by the calcium chloride method was measured by the JIS L1099-993A-1 method. Further, the moisture permeability by the potassium acetate method was measured by the JIS L1099-1993B-1 method.
  • both the calcium chloride method and the calcium acetate method were converted to moisture permeation per 24 hours.
  • the method B-2 was used when water resistance dropped and water leaked.
  • ⁇ B water pressure resistance> The water pressure resistance was measured by a method according to JIS L1092-1998 water resistance test (hydrostatic pressure method) A method (low water pressure method) and B method (high water pressure method). The unit was converted to the unit of the low water pressure method so that it can be easily compared with the low water pressure method and the high water pressure method.
  • a nylon taffeta (the total density of warp yarns and weft yarns per 2.54 cm is about 210) is piled on the test piece. Attached to the measurement.
  • washing processes were performed according to JIS L0217 103 method. That is, when washing is performed in a washing solution containing a detergent for 25 minutes and then rinsing twice while water is poured for 10 minutes, this operation is repeated twice, and the final drying process is performed twice. It was assumed that it was hung and dried only once.
  • a synthetic detergent for washing uses Attack High Activity Bio-EX manufactured by Kao Co., Ltd. at 1 g / l, and a washing machine is a national fully automatic electric washing machine NA manufactured by the former Matsushita Electric Industrial Co., Ltd. (currently Panasonic Corporation). -F50Y2 was used. Note that heat treatment such as dry iron finishing was not performed after drying.
  • the water pressure retention rate is a percentage obtained by dividing the water pressure resistance after the washing process 10 times by the water pressure before the washing process (initial), and was obtained by the following formula.
  • Water pressure retention rate (%) water pressure after washing process 10 times / water pressure before washing process (initial) ⁇ 100
  • the air permeability was measured according to JIS L1096 A method (Fragile type method).
  • a temperature rise difference was obtained as an index representing heat retention.
  • the difference in temperature rises between two test pieces (the moisture-permeable waterproof sheet of Example 3 and the infrared ray in Example 3) at a distance of 15 cm from PRF-500 WB / D for daylight color of a photographic reflex lamp manufactured by Panasonic Corporation.
  • a moisture-permeable waterproof sheet (comparative sample) manufactured by the same method except that no absorbent was added was installed, and the porous layer surface was irradiated with light.
  • thermometer (EMISION THERMOMETER MODEL 530 04: horizontal) Kawase Seisakusho) was used to measure the temperature of the porous layer surface of the moisture-permeable waterproof sheet of Example 3 when the temperature of the porous layer surface of the comparative sample reached 40 ° C. It was.
  • Temperature rise difference (° C) temperature of moisture-permeable waterproof sheet of Example 3-temperature of comparative sample (40 ° C)
  • Example 1 In Example 1, a PTFE membrane (made by Nippon Donaldson Co., Ltd., TX2201) was used as the open porous membrane.
  • the following polyurethane solution was applied on the full-dal release paper EV130TPD (manufactured by Lintec Co., Ltd.) using a comma coater with a slit thickness of 0.07 mm, and then the wet polyurethane solution applied on the release paper was A white PTFE membrane was laminated on top.
  • the release paper, the polyurethane resin solution, and the PTFE membrane are laminated in this order.
  • a porous layer was formed on the PTFE membrane by passing through each chamber at a speed that would make the residence time 30 seconds and performing heat treatment.
  • Example 2 The same laminate of release paper, porous layer and PTFE membrane produced in the same manner as in Example 1 was allowed to stand for 24 hours, and the following adhesive resin solution was dotted on the PTFE membrane using a gravure coater. And dried at 120 ° C.
  • Adhesive resin solution ⁇ Two-component polyurethane resin (HI-MUREN Y134-45 (manufactured by Dainichi Seika Kogyo Co., Ltd.), solid content 60%) 100 parts ⁇ Toluene 30 parts ⁇ MEK 40 parts ⁇ Isocyanate (Coronate HL (Nippon Polyurethane Industry Co., Ltd.) ) Made)) 9 parts ⁇ Amine catalyst (HI-299 (Daiichi Seika Kogyo Co., Ltd.)) 0.5 parts
  • polyester taffeta was used as the fiber fabric to be the base fabric, and the polyester taffeta was placed on the surface of the PTFE film to which the adhesive was applied. After nipping with a nip roll, heat treatment was performed at 150 ° C. for 30 seconds.
  • the warp yarn and the weft yarn are both 83 dtex / 72 filament, the density is 180 warp / 2.54 cm, warp 90 / 2.54 cm, and the disperse dye is used.
  • the release paper was peeled off to obtain a moisture-permeable waterproof sheet.
  • Example 1 A moisture-permeable waterproof sheet was obtained in the same manner as in Example 2 except that the porous layer was not provided.
  • Example 3 Also in Example 3, a PTFE membrane (Nippon Donaldson Co., Ltd., TX2201) was used as the open porous membrane.
  • the following polyurethane solution was applied on the full-dal release paper EV130TPD (manufactured by Lintec Co., Ltd.) using a comma coater with a slit thickness of 0.07 mm, and then the wet polyurethane solution applied on the release paper was A PTFE membrane was laminated on top.
  • the release paper, the polyurethane resin solution, and the PTFE membrane are laminated in this order.
  • a porous layer was formed on the PTFE membrane by passing through each chamber at a speed that would make the residence time 30 seconds and performing heat treatment.
  • a moisture-curing hot-melt urethane resin tie hose NH300 (manufactured by DIC Corporation) was heated to 100 ° C., melted, and applied onto the PTFE film in a dotted manner using a gravure coater.
  • polyester taffeta was used as the fiber fabric to be the base fabric, and the polyester taffeta was placed on the surface of the PTFE film to which the adhesive was applied, and nipped with a nip roll heated to 100 ° C.
  • polyester taffeta both warp and weft are 83 dtex / 72 filaments, the density is 180 / 2.54 cm, 90 / 2.54 cm, and they are dyed blue with disperse dye. What was calendered at 170 ° C. was used.
  • the water-repellent agent is applied to the surface of the pores of the porous layer by applying the following water-repellent agent solution by the padding method to the fiber fabric, PTFE membrane, and porous layer laminated in this order. Then, after heat treatment at 120 ° C. for 30 seconds, finishing set was performed together with heat treatment at 150 ° C. for 30 seconds to obtain a moisture-permeable waterproof sheet.
  • the moisture-permeable waterproof sheet obtained by laminating nylon tricot as a lining to the porous layer surface of the moisture-permeable waterproof sheet of Example 3 using the above adhesive solution prepares a separate lining at the time of sewing. There is no need, and the load during sewing can be reduced.
  • Example 2 A moisture-permeable waterproof sheet was obtained in the same manner as in Example 3 except that the porous layer was not provided.
  • Example 3 using the same moisture-curable hot-melt urethane resin tie hose NH300 (manufactured by DIC Corporation) as in Example 3, it was applied on the PTFE membrane in a dotted manner in the same manner as in Example 3.
  • nylon twill was used as the fiber fabric, and the nylon twill was placed on the surface to which the adhesive of the PTFE film was applied and nipped with a nip roll heated to 100 ° C.
  • the warp yarn is 77 dtex / 34 filament
  • the horizontal yarn is 92 dtex / 74 filament
  • the density is vertical 124 yarns / 2.54 cm
  • a dyed red color with an acid dye and calendered at 170 ° C. was used.
  • the release paper was peeled off to obtain a moisture permeable waterproof sheet in which a fiber fabric, a PTFE membrane, and a porous layer were laminated in this order.
  • Example 3 post-water-repellent treatment was performed, but in Example 4, post-water-repellent treatment was not performed.
  • the water repellent treatment is performed on the nylon twill in the same manner as in Example 2 before the PTFE membrane and the porous layer are bonded together.
  • Example 5 A moisture-permeable waterproof sheet was obtained in the same manner as in Example 4 except that the fluorine-based water repellent (ASSISTOR SD27M) was removed from the polyurethane solution.
  • ASSISTOR SD27M fluorine-based water repellent
  • Table 1 below shows the measurement results of various physical properties and the like for each of the moisture-permeable waterproof sheets of Examples 1 to 5 and Comparative Examples 1 and 2 obtained as described above.
  • Example 1 for comparison with Example 1, only PTFE membrane (only PTFE membrane in Comparative Example 1) was washed 10 times, and the water pressure resistance was about 400 mm to 900 mm. Met.
  • the moisture-permeable tarpaulin according to the present invention can be widely used for various textile products such as windbreakers, goose, jumpers, coats, jackets, ski wear, snowboard wear, jackets, tents, shoes, sleeping bags, bags or gloves. it can.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Provided is a moisture-permeable waterproof sheet capable of inhibiting a reduction of water pressure resistance due washing or the like while having air permeability. The moisture-permeable waterproof sheet according to the present invention has a porous layer containing polyurethane formed on at least one surface and/or inside a porous film having a plurality of pores opened in the surface. Moreover, the moisture-permeable waterproof sheet preferably has an air permeability of 0.005 cm3/cm2 ⋅ s to 1 cm3/cm2 ⋅ s, inclusive, and water pressure resistance retention of 10% or more after 10 wash cycles.

Description

透湿性防水シートおよびその製造方法Moisture permeable waterproof sheet and method for producing the same
　本発明は、透湿性防水シートおよびその製造方法に関するものである。 The present invention relates to a moisture-permeable waterproof sheet and a manufacturing method thereof.
　合羽やスキーウエア、ウインドブレーカーをはじめ、テント、靴材、手袋などでは、身体から放出される汗などの湿気は通過させるが、雨などの水の浸入を防止する透湿性防水布帛が使用されている。 Moisture, ski wear, windbreakers, tents, shoe materials, gloves, etc. use moisture-permeable waterproof fabrics that allow moisture such as sweat released from the body to pass through but prevent rain and other water from entering. Yes.
　透湿性防水布帛には、繊維布帛に多孔質膜を積層したものが知られている。多孔質膜を用いた透湿性防水布帛は、透湿性や防水性を有するだけではなく通気性を有している。このため、このような透湿性防水布帛で製造された合羽などを着用すれば、雨の中でも快適な環境のもと作業が可能である。 As a moisture permeable waterproof fabric, a fiber fabric laminated with a porous film is known. A moisture-permeable waterproof fabric using a porous membrane has not only moisture permeability and waterproofness but also air permeability. For this reason, if it wears the goose etc. which were manufactured with such a moisture-permeable waterproof fabric, it can work under a comfortable environment even in the rain.
　しかしながら、多孔質膜を用いた透湿性防水布帛は、多孔質膜の表面が開放されているので、洗濯処理などを行うと耐水圧が低下し、防水性が悪化するといった問題を有していた。これは、洗濯処理時に用いられた洗剤に含まれる界面活性剤が多孔質膜内に残留し、水を引き込みやすくするためである。この耐水圧が低下する現象は、洗濯処理時に限らず、汗や汚れ成分などの中に親水性成分が含まれている場合にも発生する。 However, the moisture-permeable waterproof fabric using the porous membrane has a problem that the water resistance is lowered and the waterproof property is deteriorated when the washing treatment is performed because the surface of the porous membrane is open. . This is because the surfactant contained in the detergent used during the washing process remains in the porous membrane, making it easier to draw water. The phenomenon that the water pressure resistance is reduced occurs not only during the washing process but also when a hydrophilic component is contained in sweat or dirt components.
　そこで、多孔質膜の表面や多孔質膜中に透湿性を有する無孔質層を形成することによって、多孔質膜内への界面活性剤の浸入を抑制して耐水圧の低下を抑制するとともに、万が一、多孔質膜内に界面活性剤が残留した場合においても無孔質層により耐水圧の低下を防ぐ技術が提案されている（特許文献１）。 Therefore, by forming a non-porous layer having moisture permeability on the surface of the porous membrane or in the porous membrane, the penetration of the surfactant into the porous membrane is suppressed and the decrease in the water pressure resistance is suppressed. In the unlikely event that a surfactant remains in the porous membrane, a technique for preventing a decrease in water pressure resistance by a nonporous layer has been proposed (Patent Document 1).
特開２００３－３２６６６１号公報JP 2003-326661 A
　しかしながら、多孔質膜に無孔質層を形成したものは、洗濯処理等による耐水圧の低下を抑制することはできるものの、多孔質膜の特徴である通気性が著しく低下するという問題がある。 However, although a non-porous layer formed on a porous membrane can suppress a decrease in water pressure resistance due to washing treatment or the like, there is a problem that the air permeability, which is a characteristic of the porous membrane, is significantly reduced.
　本発明は、このような問題を解決するためになされたものであり、多孔質膜を用いた透湿性防水シートであって、通気性を有していながら洗濯処理等による耐水圧の低下を抑制できる透湿性防水シートを提供することを課題とする。 The present invention has been made to solve such problems, and is a moisture-permeable waterproof sheet using a porous membrane, which suppresses a decrease in water pressure resistance due to washing treatment while having air permeability. An object is to provide a moisture-permeable waterproof sheet.
　上記課題を解決するために、本発明に係る透湿性防水シートは、表面が開放された複数の孔を有する多孔質膜の少なくとも片面上および／または当該多孔質膜中に、ポリウレタンを含む多孔質層が形成されていることを特徴とする。 In order to solve the above-mentioned problems, a moisture-permeable waterproof sheet according to the present invention is a porous material containing polyurethane on at least one surface of a porous film having a plurality of pores whose surfaces are open and / or in the porous film. A layer is formed.
　また、本発明に係る透湿性防水シートにおいて、通気度が０．００５ｃｍ３／ｃｍ２・ｓ以上、１ｃｍ３／ｃｍ２・ｓ以下であることが好ましい。 In the moisture-permeable waterproof sheet according to the present invention, the air permeability is preferably 0.005 cm 3 / cm 2 · s or more and 1 cm 3 / cm 2 · s or less.
　また、本発明に係る透湿性防水シートにおいて、１０回洗濯処理後の耐水圧が５０００ｍｍ以上であることが好ましい。 Moreover, in the moisture-permeable waterproof sheet according to the present invention, it is preferable that the water pressure resistance after 10 washing processes is 5000 mm or more.
　また、本発明に係る透湿性防水シートにおいて、前記多孔質膜は、多孔質ポリテトラフルオロエチレン膜であることが好ましい。 In the moisture-permeable waterproof sheet according to the present invention, the porous film is preferably a porous polytetrafluoroethylene film.
　また、本発明に係る透湿性防水シートにおいて、前記多孔質層の表面に撥水剤が付着されていることが好ましい。 In the moisture-permeable waterproof sheet according to the present invention, it is preferable that a water repellent is attached to the surface of the porous layer.
　また、本発明に係る透湿性防水シートの製造方法は、表面が開放された複数の孔を有する多孔質膜とポリウレタン溶液とを積層することを特徴とする。 The method for producing a moisture-permeable waterproof sheet according to the present invention is characterized by laminating a porous film having a plurality of pores whose surfaces are open and a polyurethane solution.
　また、本発明に係る透湿性防水シートの製造方法において、前記多孔質膜は、多孔質ポリテトラフルオロエチレン膜であることが好ましい。 In the method for producing a moisture-permeable waterproof sheet according to the present invention, the porous film is preferably a porous polytetrafluoroethylene film.
　また、本発明に係る透湿性防水シートの製造方法において、前記ポリウレタン溶液は、Ｗ／Ｏ型エマルジョンのポリウレタン乳濁液であることが好ましい。 In the method for producing a moisture-permeable waterproof sheet according to the present invention, the polyurethane solution is preferably a polyurethane emulsion of a W / O type emulsion.
　本発明によれば、通気性を有していながら洗濯処理等による耐水圧の低下を抑制することができる透湿性防水シートを得ることができる。したがって、この透湿性防水シートを、ウインドブレーカー、合羽、コート、ジャケット、スキーウエア、スノーボードウエア、ヤッケ、テント、手袋、靴、寝袋、鞄またはフィルター等に用いることにより、衣服内等への水の浸入を抑えながら、ムレを抑え、洗濯処理を行っても耐水圧の低下が抑制され、優れた防水性を発揮できる繊維製品を提供することができる。 According to the present invention, it is possible to obtain a moisture-permeable waterproof sheet that has air permeability and can suppress a decrease in water pressure resistance due to washing treatment or the like. Therefore, by using this moisture-permeable tarpaulin for windbreakers, goose, coats, jackets, ski wear, snowboard wear, jackets, tents, gloves, shoes, sleeping bags, bags, filters, etc. It is possible to provide a textile product that can suppress dripping and suppress water pressure drop even when washing is performed while suppressing intrusion and exhibit excellent waterproofness.
　以下に本発明の好ましい実施の形態について説明するが、本発明はこれらの態様のみに限定されるものではなく、本発明の精神と実施の範囲において多くの変形が可能であることを理解されたい。 Preferred embodiments of the present invention will be described below, but it should be understood that the present invention is not limited only to these embodiments, and that many modifications can be made within the spirit and scope of the present invention. .
　［透湿性防水シート］
　本発明の実施の形態に係る透湿性防水シートは、表面が開放された多孔質膜（以下、「開放された多孔質膜」、あるいは単に「多孔質膜」ということもある）の少なくとも片面上および／または当該多孔質膜中に、ポリウレタンを含む多孔質層（以下、単に「多孔質層」ともいう）が形成されたものである。さらに、本実施の形態における透湿性防水シートは、通気度が０．００５ｃｍ３／ｃｍ２・ｓ以上、１ｃｍ３／ｃｍ２・ｓ以下であり、１０回洗濯処理後の耐水圧保持率が１０％以上であることが好ましい。 [Moisture permeable waterproof sheet]
The moisture-permeable waterproof sheet according to the embodiment of the present invention is provided on at least one surface of a porous film whose surface is open (hereinafter, also referred to as “open porous film” or simply “porous film”). And / or a porous layer containing polyurethane (hereinafter, also simply referred to as “porous layer”) formed in the porous film. Furthermore, the moisture-permeable waterproof sheet in the present embodiment has an air permeability of 0.005 cm 3 / cm 2 · s or more and 1 cm 3 / cm 2 · s or less, and has a water pressure retention rate of 10 after 10 washing treatments. % Or more is preferable.
　本実施の形態において、開放された多孔質膜とは、膜の表面が無数に開放された複数の微細孔を有する多孔質膜のことをいい、本実施の形態では、これらの微細孔が連通したものであって、雨などの浸入を抑制しながら、通気性を有し、気体状の汗などの湿気を多孔質膜の一方の面から他方の面に通過させることができる性能を有するとともに、洗剤を含む液体や汗が多孔質膜の孔内に浸入可能なものである。 In the present embodiment, the opened porous membrane means a porous membrane having a plurality of micropores whose surfaces are infinitely open. In this embodiment, these micropores communicate with each other. It has the ability to pass moisture from one surface of the porous membrane to the other while having air permeability while suppressing the intrusion of rain and the like. A liquid or sweat containing a detergent can enter the pores of the porous membrane.
　多孔質膜に形成される孔の大きさは特に限定されるものではないが、例えば、孔径で０．０１μｍ～３０μｍ程度のものを挙げることができる。 The size of the pores formed in the porous membrane is not particularly limited, and examples include pores having a pore diameter of about 0.01 μm to 30 μm.
　より具体的には、表面が開放された多孔質膜として、前記のような構造を有する多孔質ポリテトラフルオロエチレン膜（以下、「ＰＴＦＥ膜」ともいう）、多孔質ポリウレタン膜、多孔質ポリエステル膜、多孔質ポリエチレン膜、または多孔質ポリプロピレン膜などを挙げることができるが、特にこれらに限定されるものではない。 More specifically, as a porous film having an open surface, a porous polytetrafluoroethylene film (hereinafter also referred to as “PTFE film”) having the structure as described above, a porous polyurethane film, and a porous polyester film Examples thereof include, but are not limited to, a porous polyethylene film or a porous polypropylene film.
　このうち、多孔質膜としては、初期（洗濯処理前や衣服着用前）の防水性に優れるＰＴＦＥ膜を用いることが好ましい。ＰＴＦＥ膜は、日本ゴア株式会社または日本ドナルドソン株式会社などで取り扱われており、ＰＴＦＥやｅ－ＰＴＦＥ（ｅｘｐａｎｄｅｄ　ＰＴＦＥ）と称され、厚さは１０μｍ～３００μｍ程度のものが市販されている。なお、透湿性防水シートをウインドブレーカーや合羽等の衣服に用いる場合、衣料用の防水性、透湿性、工程通過性または風合いなどの観点から、厚みが２０μｍ以上１００μｍ以下のＰＴＦＥ膜を用いることが好ましい。 Among these, as the porous membrane, it is preferable to use a PTFE membrane which is excellent in waterproof property at the initial stage (before washing treatment or before wearing clothes). The PTFE membrane is handled by Nippon Gore Co., Ltd. or Nippon Donaldson Co., Ltd., and is called PTFE or e-PTFE (expanded PTFE), and has a thickness of about 10 μm to 300 μm. In addition, when using a moisture-permeable waterproof sheet for clothes such as a windbreaker or a feather, it is preferable to use a PTFE film having a thickness of 20 μm or more and 100 μm or less from the viewpoint of waterproofness, moisture permeability, processability or texture for clothing. preferable.
　また、本実施の形態において、ポリウレタンを含む多孔質層とは、表面が開放された多孔質膜の表面および／または当該多孔質膜中に、ポリウレタンを用いて形成された多孔質の層のことをいう。多孔質層に形成される孔の孔径は、０．００１μｍ～３０μｍ程度である。多孔質膜中に形成される多孔質層の孔（すなわち、多孔質膜の中の孔の中にポリウレタンで形成される孔）は、多孔質膜が存在しない多孔質層部分に形成される孔に比べ、多孔質膜の孔の影響を受け、その孔径は小さくなる傾向にある。 In the present embodiment, the porous layer containing polyurethane is a surface of a porous film having an open surface and / or a porous layer formed using polyurethane in the porous film. Say. The pore diameter of the pores formed in the porous layer is about 0.001 μm to 30 μm. The pores of the porous layer formed in the porous membrane (that is, the pores formed of polyurethane in the pores in the porous membrane) are the pores formed in the porous layer portion where the porous membrane does not exist Compared with, the pore diameter tends to be smaller due to the influence of the pores of the porous membrane.
　また、多孔質膜中の孔は、多孔質層を形成するためのポリウレタンで閉塞されることもあるが、多孔質膜中の多孔質層も多孔質であるため、少なくとも一部は閉塞しておらず連通している。これにより、得られる透湿性防水シートは、通気性が保たれたものとなっている。 In addition, the pores in the porous membrane may be clogged with polyurethane for forming the porous layer. However, since the porous layer in the porous membrane is also porous, at least some of the pores are clogged. They communicate with each other. As a result, the moisture-permeable waterproof sheet obtained is kept breathable.
　また、多孔質層の厚みは、５～１００μｍ程度であることが好ましい。より好ましくは１０μｍ以上であり、５０μｍ以下がより好ましい。多孔質層の厚みが５μｍ未満の場合は、洗濯処理による耐水圧の低下を抑制する効果が十分発揮できないおそれがある。一方、多孔質層の厚みが１００μｍを超える場合は、耐水圧の低下を抑制する効果がさほど向上せず、また、風合いも硬化するおそれがある。なお、多孔質層の厚みとは、多孔質膜面上の多孔質層の厚みと、多孔質膜中の多孔質層の厚みとを合計したものをいう。 The thickness of the porous layer is preferably about 5 to 100 μm. More preferably, it is 10 μm or more, and more preferably 50 μm or less. When the thickness of the porous layer is less than 5 μm, the effect of suppressing the decrease in the water pressure resistance due to the washing treatment may not be sufficiently exhibited. On the other hand, when the thickness of the porous layer exceeds 100 μm, the effect of suppressing the decrease in the water pressure resistance is not improved so much and the texture may be cured. The thickness of the porous layer refers to the sum of the thickness of the porous layer on the porous membrane surface and the thickness of the porous layer in the porous membrane.
　以上のように、表面が開放された多孔質膜の少なくとも片面上および／または多孔質膜中に、ポリウレタンを含む多孔質層を形成することにより、洗濯処理後においても耐水圧の低下が抑制され、優れた防水性を発揮できる透湿性防水シートを得ることができる。この効果は、特に多孔質膜としてＰＴＦＥ膜を用いたときにより発揮される。 As described above, the formation of a porous layer containing polyurethane on at least one surface of the porous membrane having an open surface and / or in the porous membrane suppresses a decrease in water pressure resistance even after washing treatment. Thus, a moisture-permeable waterproof sheet that can exhibit excellent waterproof properties can be obtained. This effect is exhibited particularly when a PTFE membrane is used as the porous membrane.
　また、本実施の形態における透湿性防水シートについては、衣服等として用いた際の揉みや摩耗時に対する耐久性を付与するとの観点からは、多孔質膜中の少なくとも一部にポリウレタンを含む多孔質層が形成されている形態が特に好ましい。 Further, for the moisture-permeable waterproof sheet in the present embodiment, from the viewpoint of imparting durability against stagnation and wear when used as clothes, etc., a porous film containing polyurethane in at least a part of the porous film The form in which the layer is formed is particularly preferable.
　多孔質層を構成するポリウレタンとしては、エーテル系、エステル系、エステル－エーテル系またはポリカーボネート系等のポリウレタンを用いることができ、特に限定されるものではないが、透湿性の観点からは、親水性のポリウレタンであることが好ましく、膜強度（耐揉性、耐擦過性）の観点からは、疎水性のポリウレタンであることが好ましい。また、これらのポリウレタンは、複数の種類を配合して用いてもよい。 As the polyurethane constituting the porous layer, an ether-based, ester-based, ester-ether-based, or polycarbonate-based polyurethane can be used, and is not particularly limited. However, from the viewpoint of moisture permeability, it is hydrophilic. From the viewpoint of film strength (scratch resistance, scratch resistance), a hydrophobic polyurethane is preferable. These polyurethanes may be used in combination of a plurality of types.
　また、洗濯処理による耐水圧の低下を抑制するとの観点からは、多孔質層の表面に撥水剤が付着しているとよい。撥水剤を付着する方法としては、多孔質層を形成するポリウレタン溶液に撥水剤を添加したり、多孔質層を形成した後に、多孔質層の表面にパディング法、グラビア法またはスプレー法などによって撥水剤を付与してもよい。より好ましくは、多孔質層を形成するためのポリウレタン溶液に撥水剤を添加したもので多孔質層を形成し、さらに、形成された多孔質層の表面に、パディング法、グラビア法またはスプレー法などによって撥水剤を付与するとよい。つまり、ポリウレタン溶液に撥水剤を内添しておくとともに、さらに、後撥水処理を行うとよい。これにより、透湿性防水シートの品質を安定させることができる。撥水剤としては、フッ素系、シリコーン系またはパラフィン系等の撥水剤を用いることができ、特に限定されるものではないが、耐久性の観点からはフッ素系のものを用いることが好ましい。 Further, from the viewpoint of suppressing a decrease in water pressure resistance due to the washing treatment, it is preferable that a water repellent is attached to the surface of the porous layer. As a method of attaching the water repellent agent, a water repellent agent is added to the polyurethane solution forming the porous layer, or after forming the porous layer, a padding method, a gravure method or a spray method is applied to the surface of the porous layer. A water repellent may be applied by the above. More preferably, a porous layer is formed by adding a water repellent to a polyurethane solution for forming a porous layer, and further, a padding method, a gravure method or a spray method is formed on the surface of the formed porous layer. A water repellent agent may be applied. That is, it is advisable to add a water repellent to the polyurethane solution and to carry out a post-water repellent treatment. Thereby, the quality of a moisture-permeable waterproof sheet can be stabilized. As the water repellent, a fluorine-based, silicone-based, or paraffin-based water repellent can be used, and is not particularly limited, but it is preferable to use a fluorine-based one from the viewpoint of durability.
　また、多孔質層を構成するポリウレタンとして、主鎖や側鎖にシリコーンセグメントやフッ素セグメントを有するものを用いてもよい。 Further, as the polyurethane constituting the porous layer, one having a silicone segment or a fluorine segment in the main chain or side chain may be used.
　なお、ＰＴＦＥ膜に対して、ポリウレタンを含む多孔質層を形成せずに撥水剤を付与しても、洗濯処理による耐水圧の低下を抑制する効果はほとんど見受けられないが、多孔質膜の表面および／または多孔質膜中にポリウレタンを含む多孔質層を形成した透湿性防水シートについては、多孔質層に撥水剤を付与することによって、洗濯処理による耐水圧の低下を大きく抑制することができる。 Note that even if a water repellent is applied to the PTFE membrane without forming a porous layer containing polyurethane, there is hardly any effect of suppressing a decrease in water pressure resistance due to washing treatment. For moisture permeable waterproof sheets with a porous layer containing polyurethane on the surface and / or porous membrane, a water repellent is added to the porous layer to greatly suppress the decrease in water pressure resistance due to washing treatment. Can do.
　また、本実施の形態における透湿性防水シートの１０回洗濯処理後の耐水圧保持率は、１０％以上であり、より好ましくは２０％、さらに好ましくは３０％である。 Further, the water pressure retention after the tenth washing treatment of the moisture-permeable waterproof sheet in the present embodiment is 10% or more, more preferably 20%, and further preferably 30%.
　ここで、耐水圧保持率とは、洗濯処理を１０回行った後の耐水圧を、洗濯処理前（初期）の耐水圧で除したものの百分率のことであり、下記式で求められる。 Here, the water pressure resistance retention rate is a percentage obtained by dividing the water pressure resistance after the washing process 10 times by the water pressure before the washing process (initial), and is obtained by the following formula.
　耐水圧保持率（％）＝洗濯処理を１０回行った後の耐水圧÷洗濯処理前（初期）の耐水圧×１００ Water pressure retention rate (%) = water pressure after washing process 10 times ÷ water pressure before washing process (initial) x 100
　なお、１０回洗濯処理とは、ＪＩＳ　Ｌ０２１７　１０３法に準じて行われる。具体的には、２５分間洗剤を含む洗濯液中で洗濯を行い、その後１０分間注水を行いながらのすすぎを２回行ったものを洗濯５回としたときに、この操作を２回繰り返し、乾燥処理として最後に１回のみ吊り干し乾燥を行ったものとした。この場合、洗濯用合成洗剤は花王株式会社製のアタック高活性バイオＥＸを１ｇ／ｌで使用し、洗濯機は旧松下電気産業株式会社製（現パナソニック株式会社）のナショナル全自動電気洗濯機ＮＡ－Ｆ５０Ｙ２を用いた。なお、乾燥後、ドライアイロン仕上げなどの熱処理は行わないものとした。 In addition, 10 times of washing processing is performed according to JIS L0217 103 method. Specifically, when washing is performed in a washing solution containing a detergent for 25 minutes and then rinsed twice for 10 minutes while water is poured twice, this operation is repeated twice and dried. As a treatment, it was assumed that it was hung and dried only once at the end. In this case, a synthetic detergent for washing uses Attack High Activity Bio-EX manufactured by Kao Co., Ltd. at 1 g / l, and a washing machine is a national fully automatic electric washing machine NA manufactured by the former Matsushita Electric Industrial Co., Ltd. (currently Panasonic Corporation). -F50Y2 was used. Note that heat treatment such as dry iron finishing was not performed after drying.
　また、透湿性防水シートの耐水圧とは、ＪＩＳ　Ｌ１０９２－１９９８耐水度試験Ｂ法（高水圧法）に準じて測定したものをいう。なお、試験中に水圧をかけることにより試験片が伸びる場合には、試験片の上にナイロンタフタ（２．５４ｃｍ当りのタテ糸とヨコ糸の密度の合計が２１０本程度のもの）を重ねて、試験機に取り付けて測定を行う。 In addition, the water pressure resistance of the moisture-permeable waterproof sheet means that measured according to JIS L1092-1998 water resistance test method B (high water pressure method). When the test piece is stretched by applying water pressure during the test, nylon taffeta (the total density of warp yarns and weft yarns per 2.54 cm is about 210) is piled on the test piece. Attach to a testing machine and measure.
　透湿性防水シートの洗濯処理前の耐水圧は１００００ｍｍ以上であるとよい。また、透湿性防水シートの１０回洗濯処理後の耐水圧は５０００ｍｍ以上であることが好ましい。さらに、１０回洗濯処理後の耐水圧についても１００００ｍｍ以上であるとよい。透湿性防水シートの１０回洗濯処理後の耐水圧が１００００ｍｍ以上であると、激しい風雨などの場合においても雨の浸入を防止する。 The water pressure resistance of the moisture-permeable waterproof sheet before washing is preferably 10,000 mm or more. Moreover, it is preferable that the water pressure resistance of the moisture-permeable waterproof sheet after 10 times of washing treatment is 5000 mm or more. Further, the water pressure resistance after the 10th washing treatment is preferably 10,000 mm or more. When the water pressure resistance after the 10-times washing treatment of the moisture-permeable waterproof sheet is 10000 mm or more, the infiltration of rain is prevented even in the case of severe wind and rain.
　１０回洗濯処理後の耐水圧の上限は特に限定されるものではないが、耐水圧が高すぎると透湿性防水シートの風合いが硬化してしまうおそれがあるため、１０００００ｍｍ程度が上限である。 The upper limit of the water pressure resistance after 10 washing treatments is not particularly limited, but if the water pressure resistance is too high, the texture of the moisture-permeable waterproof sheet may be cured, so the upper limit is about 100,000 mm.
　また、本実施の形態における透湿性防水シートは、通気度が０．００５ｃｍ３／ｃｍ２・ｓ以上である。通気度が０．００５ｃｍ３／ｃｍ２・ｓ以上であれば、衣服内の湿気等を外部に放出することができるので、ムレを抑制し快適性を維持できる。よりムレを抑制するとの観点からは、通気度は、０．０１ｃｍ３／ｃｍ２・ｓ以上が好ましく、０．０５ｃｍ３／ｃｍ２・ｓ以上がさらに好ましい。 Further, the moisture-permeable waterproof sheet in the present embodiment has an air permeability of 0.005 cm 3 / cm 2 · s or more. If the air permeability is 0.005 cm 3 / cm 2 · s or more, moisture and the like in the clothes can be released to the outside, so that stuffiness can be suppressed and comfort can be maintained. From the viewpoint of further suppressing the stuffiness, the air permeability is preferably 0.01 cm 3 / cm 2 · s or more, and more preferably 0.05 cm 3 / cm 2 · s or more.
　また、通気度の上限は、特に限定するもではないが、通気度は、１ｃｍ３／ｃｍ２・ｓ以下とすることが好ましい。通気度が１ｃｍ３／ｃｍ２・ｓ以下の透湿性防水シートであれば、防水性を維持しながら、ムレを抑制する効果に優れる。 The upper limit of the air permeability is not particularly limited, but the air permeability is preferably 1 cm 3 / cm 2 · s or less. If it is a moisture-permeable waterproof sheet with an air permeability of 1 cm 3 / cm 2 · s or less, the effect of suppressing stuffiness is excellent while maintaining waterproofness.
　なお、通気度の測定は、ＪＩＳ　Ｌ１０９６　Ａ法（フラジール形法）に準じて測定することができる。 The air permeability can be measured according to JIS L1096 A method (fragile method).
　なお、本実施の形態における透湿性防水シートの透湿性とは、特に限定されるものではないが、ＪＩＳ　Ｌ１０９９－１９９３　Ａ－１法に準じて測定した透湿度（塩化カルシウム法）が５０００～２００００ｇ／ｍ２・２４時間であることが好ましい。透湿度が５０００ｇ／ｍ２・２４時間未満であると、透湿性防水布帛から得られる衣服等を着用した場合にムレるおそれがある。また、透湿度が２００００ｇ／ｍ２・２４時間以上を超えると、十分な防水性が得られないおそれがある。 The moisture permeability of the moisture permeable waterproof sheet in the present embodiment is not particularly limited, but the moisture permeability (calcium chloride method) measured according to JIS L1099-1993 A-1 method is 5000 to 20000 g. / M 2 · 24 hours is preferable. If the moisture permeability is less than 5000 g / m 2 · 24 hours, there is a risk of stuffiness when wearing clothes or the like obtained from a moisture-permeable waterproof fabric. Further, if the moisture permeability exceeds 20000 g / m 2 · 24 hours or more, there is a possibility that sufficient waterproofness cannot be obtained.
　また、透湿性防水シートの透湿度を、ＪＩＳ　Ｌ１０９９－１９９３　Ｂ－１法またはＢ－２法に準じて測定する場合、透湿度（酢酸カリウム法）は５０００～２０００００ｇ／ｍ２・２４時間であることが好ましい。なお、Ｂ－２法は、耐水圧が低下し、Ｂ－１法による測定では漏水する場合に用いる。 Further, when the moisture permeability of the moisture permeable waterproof sheet is measured according to JIS L1099-1993 B-1 method or B-2 method, the moisture permeability (potassium acetate method) is 5000 to 200000 g / m 2 · 24 hours. It is preferable. Note that the B-2 method is used when the water pressure resistance decreases and the measurement by the B-1 method leaks water.
　また、本実施の形態における透湿性防水シートは、当該透湿性防水シートの片面または両面に繊維布帛が積層されているとよい。すなわち、多孔質膜や多孔質層の片面または両面に繊維布帛が積層されているとよい。 In addition, the moisture-permeable waterproof sheet in the present embodiment may have a fiber fabric laminated on one or both sides of the moisture-permeable waterproof sheet. That is, the fiber fabric is preferably laminated on one side or both sides of the porous membrane or the porous layer.
　この場合、繊維布帛とは、ポリエステル、ナイロン、ポリウレタン、アクリル、レーヨン、アセテート、ポリ乳酸、大豆蛋白、絹、羊毛、綿または麻などの化学繊維や天然繊維等、いかなる繊維であってもよく、また、これらの繊維は、混繊、混紡、交織または交編等がなされているものであってもよい。また、繊維布帛の形態としては、織物、編物または不織布等、いかなる形態を有するものであってもよい。 In this case, the fiber fabric may be any fiber such as polyester, nylon, polyurethane, acrylic, rayon, acetate, polylactic acid, soy protein, silk, wool, cotton, hemp, or other chemical fibers or natural fibers. In addition, these fibers may be mixed, mixed, woven or knitted. Moreover, as a form of a fiber fabric, you may have what forms, such as a woven fabric, a knitted fabric, or a nonwoven fabric.
　多孔質膜や多孔質層と繊維布帛との積層は、本発明の主旨を逸脱しない範囲で、多孔質膜、多孔質層および繊維布帛の少なくともいずれかに、接着剤（バインダー）などを点状、線状または格子状などとして付与し、貼り合せることにより積層すればよい。この場合、接着剤も特に限定されるものではなく、接着剤としては、例えば、ウレタン系、エポキシ系、メラミン系、ナイロン系、ポリエステル系またはアクリル系などの接着剤を用いることができる。また、接着剤は、１液型および２液型のいずれであってもよく、また、湿気硬化型などを含むホットメルトタイプのウレタン樹脂であってもよい。 Lamination of a porous membrane or a porous layer and a fiber fabric is a point where an adhesive (binder) or the like is dotted on at least one of the porous membrane, the porous layer, and the fiber fabric without departing from the gist of the present invention. They may be provided as a linear shape or a lattice shape and laminated by bonding. In this case, the adhesive is not particularly limited, and as the adhesive, for example, urethane, epoxy, melamine, nylon, polyester, or acrylic adhesives can be used. The adhesive may be either a one-component type or a two-component type, and may be a hot-melt type urethane resin including a moisture curable type.
　また、繊維布帛に対して、染色加工、捺染加工、撥水加工、制電加工、吸水加工、ＳＲ加工、抗菌防臭加工、制菌加工、消臭加工、紫外線遮蔽加工、防炎加工またはカレンダー加工などを施してもよい。 Also, dyeing, printing, water-repellent, anti-static, water-absorbing, SR, antibacterial, deodorant, antibacterial, deodorant, UV shielding, flameproofing, or calendaring for fiber fabrics Etc. may be given.
　また、繊維布帛が積層されない多孔質膜や多孔質層の表面に、意匠性を付与するため、多孔質層に顔料等の着色剤を含有させ着色したり、多孔質膜や多孔質層の表面に顔料等の着色剤を含むポリウレタンやアクリル樹脂などを、点状、格子状、幾何柄または花柄などの柄模様で付与してもよい。 In addition, in order to impart designability to the surface of the porous film or porous layer on which the fiber fabric is not laminated, the porous layer is colored by adding a colorant such as a pigment, or the surface of the porous film or porous layer. Further, polyurethane or acrylic resin containing a colorant such as a pigment may be applied in a pattern such as a dot, lattice, geometric pattern or floral pattern.
　また、耐水圧の向上、タッチの改良または抗菌性の付与などを目的として、多孔質層に顔料、有機粒子、無機粒子、抗菌剤、蓄熱剤または難燃剤などを含有させたり、多孔質膜や多孔質層の表面に、点状や線状など部分的に顔料、有機粒子、無機粒子、抗菌剤、蓄熱剤または難燃剤などを含む他のポリウレタンやアクリル樹脂などを本発明の主旨を逸脱しない範囲で付着させてもよい。 In addition, pigments, organic particles, inorganic particles, antibacterial agents, heat storage agents, flame retardants, etc. are contained in the porous layer for the purpose of improving water pressure resistance, improving touch or imparting antibacterial properties, Other polyurethanes or acrylic resins that partially contain pigments, organic particles, inorganic particles, antibacterial agents, heat storage agents, flame retardants, etc. on the surface of the porous layer do not depart from the gist of the present invention. You may make it adhere in the range.
　以下に、本実施の形態における透湿性防水シートの好ましい製造方法について説明を行う。なお、本実施の形態における透湿性防水シートは、下記の製造方法で製造されるものに限定されない。また、開放された多孔質膜および多孔質層等は、前記で述べたものと同一である。 Hereinafter, a preferable manufacturing method of the moisture-permeable waterproof sheet in the present embodiment will be described. In addition, the moisture-permeable waterproof sheet in this Embodiment is not limited to what is manufactured with the following manufacturing method. The opened porous membrane and porous layer are the same as those described above.
　透湿性防水シートの製造方法は、表面が開放された多孔質膜の上に、ポリウレタン溶液を積層する工程を含むものである。 The method for producing a moisture-permeable waterproof sheet includes a step of laminating a polyurethane solution on a porous film having an open surface.
　ポリウレタン溶液の積層方法としては、ナイフコータ、バーコータ、コンマコータ、キスコータ、グラビアコータまたはダイコータなどを用いて、ポリウレタン溶液を多孔質膜上に直接塗布し、積層する方法が挙げられる。 As a method of laminating the polyurethane solution, a method of directly laminating the polyurethane solution on the porous film using a knife coater, a bar coater, a comma coater, a kiss coater, a gravure coater, a die coater or the like can be cited.
　また、本製造方法で用いられるポリウレタン溶液は、多孔質層を形成するためのものであるので、さらに、ポリウレタン溶液を発泡等させることによりポリウレタン溶液を多孔質化する多孔質化工程を含む。ポリウレタン溶液を発泡させることによって、多孔質化されたポリウレタンを含む多孔質層を形成することができる。このような多孔質化工程（発泡工程）を行うタイミングは、多孔質膜の上にポリウレタン溶液を積層する前、多孔質膜の上にポリウレタン溶液を積層した後、および、多孔質膜の上にポリウレタン溶液を積層すると同時のいずれであってもよい。 Further, since the polyurethane solution used in this production method is for forming a porous layer, it further includes a porosification step of making the polyurethane solution porous by foaming the polyurethane solution or the like. By foaming the polyurethane solution, a porous layer containing porous polyurethane can be formed. The timing of performing such a porosification step (foaming step) is before laminating the polyurethane solution on the porous membrane, after laminating the polyurethane solution on the porous membrane, and on the porous membrane. Any of the simultaneous formation of the polyurethane solution may be used.
　例えば、ポリウレタン溶液を多孔質膜に積層する前に発泡させる方法としては、高圧発泡機などを用いて、ポリウレタン溶液を空気とともにミキシングして発泡させ、発泡したポリウレタン溶液を上記のようなコータを用いて多孔質膜上に直接塗布し、積層させ、その後、熱処理を行うことで多孔質層を形成する方法（機械発泡法）がある。 For example, as a method of foaming before laminating the polyurethane solution on the porous membrane, the polyurethane solution is foamed by mixing with air using a high pressure foaming machine, and the foamed polyurethane solution is used with the coater as described above. There is a method (mechanical foaming method) in which a porous layer is formed by directly applying and laminating on a porous film and then performing heat treatment.
　また、ポリウレタン溶液を多孔質膜に積層した後に発泡させる方法としては、ポリウレタン溶液の中に熱膨張性のマイクロカプセルを添加しておき、ポリウレタン溶液を多孔質膜上に直接塗布し、積層した後、熱処理を行うことでマイクロカプセルを膨張（発泡）させて多孔質層を形成する方法がある。 In addition, as a method of foaming after laminating the polyurethane solution on the porous membrane, after adding thermally expandable microcapsules in the polyurethane solution, and directly coating and laminating the polyurethane solution on the porous membrane There is a method of forming a porous layer by expanding (foaming) microcapsules by performing heat treatment.
　また、ポリウレタン溶液を多孔質膜に積層すると同時に発泡させる方法としては、以下の方法がある。 Further, as a method of foaming at the same time as laminating the polyurethane solution on the porous membrane, there are the following methods.
　例えば、ポリウレタン溶液として未反応のイソシアネート基を含有させたものを用いるとともに発泡剤として水や水蒸気を用いて、水とイソシアネートとの反応により炭酸ガスを発生させることにより多孔質膜に多孔質層を成膜する方法（ケミカル発泡法）がある。 For example, using a polyurethane solution containing an unreacted isocyanate group and using water or water vapor as a foaming agent, a porous layer is formed on the porous film by generating carbon dioxide by the reaction of water and isocyanate. There is a film forming method (chemical foaming method).
　あるいは、ポリウレタン溶液としてＷ／Ｏ型エマルジョンのポリウレタン乳濁液を用いて、当該ポリウレタン溶液を多孔質膜上に直接塗布し、積層した後、熱処理することにより、Ｗ／Ｏ型エマルジョンに含まれるトルエンやメチルエチルケトンなどの水よりも低沸点の有機溶剤を揮発させ、残留する水によりポリウレタンを凝固させ、その後水も蒸発させることによって多孔質膜に多孔質層を成膜する方法もある。 Alternatively, a polyurethane emulsion of a W / O emulsion is used as a polyurethane solution, and the polyurethane solution is directly applied on the porous membrane, laminated, and then heat-treated, whereby toluene contained in the W / O emulsion There is also a method of forming a porous layer on the porous film by volatilizing an organic solvent having a lower boiling point than water such as methyl ethyl ketone, coagulating polyurethane with the remaining water, and then evaporating the water.
　あるいは、ポリウレタン溶液として溶媒に水と親和性の高いジメチルホルムアミドなどを用いた湿式凝固用のポリウレタン溶液を用いて、当該ポリウレタン溶液を多孔質膜上に塗布し積層した後、水中に浸漬することにより、ジメチルホルムアミドと水とが置き換わることで多孔質膜に多孔質層を形成する方法（湿式凝固法）もある。 Alternatively, by using a polyurethane solution for wet coagulation using dimethylformamide or the like having a high affinity for water as a polyurethane solution, the polyurethane solution is applied and laminated on the porous film, and then immersed in water. There is also a method (wet coagulation method) in which a porous layer is formed on a porous membrane by replacing dimethylformamide and water.
　また、水溶性成分を添加したポリウレタン溶液を塗布し、熱処理により成膜し、あるいは水中で凝固させ成膜した後、水中で洗浄処理し、成膜された膜から水溶性成分を除去することで、多孔質膜に多孔質層を形成する方法などを用いてもよい。 In addition, by applying a polyurethane solution to which water-soluble components have been added, forming a film by heat treatment, or coagulating in water to form a film, washing in water, and removing the water-soluble component from the formed film Alternatively, a method of forming a porous layer on the porous film may be used.
　また、多孔質膜とポリウレタン溶液とを積層する場合、ポリウレタン溶液を直接多孔質膜に塗布する方法を用いるのではなく、離型紙や離型フィルム上に、ナイフコータ、バーコータ、コンマコータ、キスコータ、グラビアコータまたはダイコータなどを用いてポリウレタン溶液を塗布し、塗布されたポリウレタン溶液の上に多孔質膜を重ね合わせることで、多孔質膜にポリウレタン溶液を積層する方法を用いてもよい。 In addition, when laminating a porous film and a polyurethane solution, a method of applying the polyurethane solution directly to the porous film is not used, but a knife coater, bar coater, comma coater, kiss coater, gravure coater is used on a release paper or a release film. Alternatively, a method of laminating the polyurethane solution on the porous film by applying a polyurethane solution using a die coater or the like and superposing the porous film on the applied polyurethane solution may be used.
　なお、ポリウレタン溶液に多孔質膜を積層する方法においても、多孔質化工程は、ポリウレタン溶液を多孔質膜上に塗布したときの方法を応用すればよく、例えば、離型紙上にＷ／Ｏ型エマルジョンのポリウレタン乳濁液を塗布し、その上に多孔質膜を積層し、熱処理することにより、多孔質膜の片面上および多孔質膜中に、ポリウレタンを含む多孔質層を形成することができる。 In addition, in the method of laminating the porous film on the polyurethane solution, the porous process may be performed by applying the method when the polyurethane solution is applied on the porous film, for example, W / O type on the release paper. A porous layer containing polyurethane can be formed on one side of the porous membrane and in the porous membrane by applying a polyurethane emulsion of emulsion, laminating the porous membrane on it, and heat-treating it. .
　多孔質層を形成または成膜するための熱処理温度は、ポリウレタンの種類や発泡法により異なるが、６０～２００℃程度で１秒～１時間程度の熱処理を行えばよい。 The heat treatment temperature for forming or forming the porous layer varies depending on the type of polyurethane and the foaming method, but the heat treatment may be performed at about 60 to 200 ° C. for about 1 second to 1 hour.
　なお、多孔質層を形成する方法は上記に限定されるものではなく、発泡剤として水以外の化合物を用いたり、上記の方法を組み合わせて多孔質層を形成したり、また、上記に記載のない他の公知の方法で多孔質層を形成してもよい。 In addition, the method for forming the porous layer is not limited to the above, and a compound other than water is used as the foaming agent, the porous layer is formed by combining the above methods, or the above-described method. The porous layer may be formed by other known methods.
　また、Ｗ／Ｏ型エマルジョンのポリウレタン乳濁液を用いる場合には、低沸点の有機溶剤を先に揮発させておくために、４０℃～１１０℃、より好ましくは５０～９０℃にて、１０秒～１０分程度にて予め熱処理し、その後、多孔質層を形成（成膜）するために、１００℃～２００℃にて１５秒～１０分程度の熱処理を行うとよい。 When a polyurethane emulsion of W / O type emulsion is used, a low boiling point organic solvent is volatilized first, so that it is 10 ° C. to 40 ° C. to 110 ° C., more preferably 50 to 90 ° C. In order to form (deposit) a porous layer, it is preferable to perform heat treatment at 100 ° C. to 200 ° C. for about 15 seconds to 10 minutes.
　なお、本実施の形態における製造方法は、多孔質膜と多孔質層との接着強度の観点から、多孔質層を単独で成膜した後に、接着剤等にて当該多孔質層と多孔質膜とを積層するのではなく、多孔質層を形成するためにポリウレタン溶液を多孔質膜上に積層するものである。つまり、ポリウレタン溶液を多孔質膜に積層することで多孔質膜に多孔質層を形成するものである。このような製造方法を用いることにより、合羽等に用いて洗濯処理を行ったり、着用により揉まれたりした場合においても、多孔質膜と多孔質層とが剥がれることを抑制できる透湿性防水シートを得ることができる。 Note that the manufacturing method in the present embodiment is such that, from the viewpoint of the adhesive strength between the porous film and the porous layer, the porous layer and the porous film are formed with an adhesive or the like after the porous layer is formed alone. In order to form a porous layer, a polyurethane solution is laminated on the porous membrane. That is, the porous layer is formed on the porous film by laminating the polyurethane solution on the porous film. By using such a production method, a moisture-permeable waterproof sheet that can prevent the porous membrane and the porous layer from peeling off even when washing processing is performed using the wings or when it is rubbed by wearing. Obtainable.
　より好ましくは、ポリウレタン溶液の少なくとも一部が多孔質膜に含浸し、多孔質膜中にポリウレタンを含む多孔質層が形成されていることがよい。 More preferably, at least a part of the polyurethane solution is impregnated into the porous film, and a porous layer containing polyurethane is formed in the porous film.
　また、安定した防水性、透湿性または接着強度を得るとの観点からは、離型紙や離型フィルム上に、ナイフコータ、バーコータ、コンマコータ、キスコータ、グラビアコータまたはダイコータなどを用いてポリウレタン溶液を塗布し、塗布されたポリウレタン溶液の上に多孔質膜を重ね合わせて積層する方法を用いることが好ましい。特に、多孔質膜としてＰＴＦＥ膜を用いた場合には、離型紙や離型フィルム上にポリウレタン溶液を塗布し、塗布されたポリウレタン溶液の上に多孔質膜を重ね合わせて積層する方法がよい。 In addition, from the viewpoint of obtaining stable waterproofness, moisture permeability, or adhesive strength, a polyurethane solution is applied onto a release paper or release film using a knife coater, bar coater, comma coater, kiss coater, gravure coater or die coater. It is preferable to use a method of laminating a porous film on the applied polyurethane solution. In particular, when a PTFE membrane is used as the porous membrane, it is preferable to apply a polyurethane solution on a release paper or a release film, and laminate the porous membrane on the applied polyurethane solution.
　また、離型紙上等にポリウレタン溶液を塗布し、塗布されたポリウレタン溶液の上に多孔質膜を積層する場合には、多孔質膜について特に限定はされないが、多孔質膜に直接ポリウレタン溶液を塗布する際に張力がかかることにより伸びてしまう多孔質膜を用いる場合には、多孔質膜を繊維布帛等にあらかじめ貼り合せておくことが好ましい。これにより、張力がかかった場合においても多孔質膜が伸びたり幅方向の長さが短くなったりすることを抑制できる。 In addition, when a polyurethane solution is applied on release paper or the like and a porous film is laminated on the applied polyurethane solution, the porous film is not particularly limited, but the polyurethane solution is directly applied to the porous film. In the case of using a porous membrane that stretches when tension is applied, the porous membrane is preferably bonded to a fiber cloth or the like in advance. Thereby, even when tension is applied, it is possible to prevent the porous film from extending or the length in the width direction from being shortened.
　また、安定した通気度を維持するとの観点からは、ポリウレタン溶液はＷ／Ｏ型エマルジョンのポリウレタン乳濁液、または、ジメチルホルムアミド等の水と親和性の高い溶媒を含む湿式凝固用のポリウレタン溶液が好ましく用いられる。また、加工の安定性や生産工程中における風合いやタッチの観点からは、ポリウレタン溶液として、特にＷ／Ｏ型エマルジョンのポリウレタン溶液が好ましく用いられる。 From the viewpoint of maintaining a stable air permeability, the polyurethane solution may be a polyurethane emulsion of W / O type emulsion or a polyurethane solution for wet coagulation containing a solvent having a high affinity for water such as dimethylformamide. Preferably used. From the viewpoint of processing stability, texture and touch during the production process, a polyurethane solution of a W / O emulsion is particularly preferably used as the polyurethane solution.
　Ｗ／Ｏ型エマルジョンのポリウレタン乳濁液には、水よりも沸点が低い有機溶剤が含まれていることが好ましい。この場合、有機溶剤としては、水とある程度の相互溶解性があるものが好ましく用いられる。 It is preferable that the polyurethane emulsion of the W / O type emulsion contains an organic solvent having a boiling point lower than that of water. In this case, an organic solvent having a certain degree of mutual solubility with water is preferably used.
　Ｗ／Ｏ型エマルジョンのポリウレタン乳濁液に用いることのできる有機溶剤としては、例えば、メチルエチルケトン（ＭＥＫ）、メチル－Ｎ－プロピルケトン、メチルイソブチルケトン、ジエチルケトン、ギ酸メチル、ギ酸エチル、ギ酸プロピル、酢酸メチルまたは酢酸エチルを用いることが好ましく、また、アセトン、シクロヘキサノン、テトラヒドロフラン、ジオキサン、メタノール、エタノール、イソプロピルアルコール、ブタノール、トルエン（ＴＯＬ）、キシレン、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド、パークロルエチレン、メチルセルソルブ、ブチルセルソルブまたはセルソルブアセテート等も用いることもできる。これらの有機溶剤は混合して用いてもよい。また、これらの有機溶剤のうち、水との相互溶解度に限界のないもの、あるいは全く溶解しないものは、他の有機溶剤との混合物とし、水との相互溶解度に限界を持たせて使用することが好ましい。 Examples of the organic solvent that can be used in the polyurethane emulsion of the W / O emulsion include methyl ethyl ketone (MEK), methyl-N-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, Methyl acetate or ethyl acetate is preferably used, and acetone, cyclohexanone, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene (TOL), xylene, dimethylformamide (DMF), dimethyl sulfoxide, perchlorethylene, Methyl cellosolve, butyl cellosolve, cellosolve acetate or the like can also be used. These organic solvents may be used as a mixture. Also, among these organic solvents, those that have no limit on mutual solubility with water, or those that do not dissolve at all, should be used as a mixture with other organic solvents with a limit on the mutual solubility with water. Is preferred.
　なお、Ｗ／Ｏ型エマルジョンのポリウレタン乳濁液中のポリウレタンは、有機溶剤中に全てが溶解したものであってもよいし、一部が析出したものであってもよい。ポリウレタンが析出しているものを用いる場合には、多孔質層の品位や防水性の観点から粒子径が大きいものは除去して使用するとよい。具体的には、多孔質層の厚みにもよるが、２０μｍ以上、より好ましくは１０μｍ以上の粒子径のものは除去するとよい。 The polyurethane in the polyurethane emulsion of the W / O type emulsion may be completely dissolved in an organic solvent or may be partially precipitated. In the case of using a polyurethane-precipitated one, it is preferable to remove the one having a large particle size from the viewpoint of the quality of the porous layer and the waterproof property. Specifically, although depending on the thickness of the porous layer, particles having a particle diameter of 20 μm or more, more preferably 10 μm or more may be removed.
　また、Ｗ／Ｏ型エマルジョンのポリウレタン溶液としては、ＤＩＣ株式会社のＸＯＬＴＥＸ（ＰＸ５５０、ＰＸ―３０９、ＰＸ－３００、ＰＸ－１００Ｆなど）、または、大日精化工業株式会社のハイムレン（Ｘ－３０３８、Ｘ－３０４０、Ｘ－３０４１、Ｘ－３０５０、Ｘ－３０６２、ＡＴＸ－１、ＡＴＸ－１０など）の商品が挙げられる。 In addition, as a polyurethane solution of W / O type emulsion, DIC Corporation's XOLTEX (PX550, PX-309, PX-300, PX-100F, etc.) or Dainichi Seika Kogyo Co., Ltd. X-3040, X-3041, X-3050, X-3062, ATX-1, ATX-10, etc.).
　また、ポリウレタン溶液には、ポリウレタン以外に、着色のための顔料、あるいは吸湿性などを付与するためのシルクパウダー、ゼラチンパウダーや卵殻膜パウダーなどの有機粒子、透湿性や防水性を向上させるための酸化ケイ素、酸化アルミニウム、炭酸カルシウムなどの無機粒子、分散染料による樹脂膜の汚染対策のための多孔質状のシリカなどの多孔性粒子、または、抗菌性付与のための銀ゼオライトやピリジン系などの抗菌剤をはじめ、消臭剤、帯電防止剤、紫外線吸収剤、酸化防止剤、難燃剤または赤外線吸収剤等を添加してもよい。 In addition to polyurethane, the polyurethane solution contains pigments for coloring, or organic particles such as silk powder, gelatin powder and eggshell membrane powder for imparting moisture absorption, moisture permeability and waterproofing. Inorganic particles such as silicon oxide, aluminum oxide, and calcium carbonate, porous particles such as porous silica for countermeasures against contamination of resin films by disperse dyes, or silver zeolite and pyridine series for imparting antibacterial properties In addition to antibacterial agents, deodorants, antistatic agents, ultraviolet absorbers, antioxidants, flame retardants, infrared absorbers, and the like may be added.
　また、撥水性向上、防水性向上および洗濯処理後の耐水圧性低下抑制の観点より、ポリウレタン溶液には、撥水剤を添加することが好ましい。 In addition, it is preferable to add a water repellent to the polyurethane solution from the viewpoint of improving water repellency, waterproofing and suppressing water pressure drop after washing.
　また、ポリウレタン溶液の中には、多孔質層の強度を向上させために架橋剤を添加したり、多孔質膜内への樹脂の含浸を調整するために濡れ向上剤や増粘剤を添加したり、また、消泡剤など添加してもよい。架橋剤としては、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、カルボジイミド系架橋剤またはオキサゾリン系架橋剤などが挙げられる。 In addition, in the polyurethane solution, a cross-linking agent is added to improve the strength of the porous layer, and a wetting improver and a thickener are added to adjust the impregnation of the resin into the porous membrane. Or an antifoaming agent may be added. Examples of the crosslinking agent include an isocyanate crosslinking agent, an aziridine crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, and an oxazoline crosslinking agent.
　また、透湿性防水シートとして繊維布帛を積層した構成とする場合には、ポリウレタン溶液を多孔質膜上に塗布する前または後に接着剤を用いて多孔質膜と繊維布帛とを貼り合せることにより積層すればよい。また、多孔質層上に繊維布帛を積層する場合には、多孔質層を形成した後、接着剤を用いて多孔質層と繊維布帛とを貼り合せればよい。 Further, when the fiber fabric is laminated as the moisture-permeable waterproof sheet, the lamination is performed by bonding the porous membrane and the fiber fabric using an adhesive before or after the polyurethane solution is applied onto the porous membrane. do it. Moreover, when laminating | stacking a fiber cloth on a porous layer, after forming a porous layer, what is necessary is just to bond a porous layer and a fiber cloth using an adhesive agent.
　透湿性防水シートの通気性を維持するために、接着剤は、点状、線状または格子状などに付与されることが好ましく、繊維布帛と多孔質膜との接触面のすべてを覆ってしまわないように部分的に接着剤を塗布するとよい。また、繊維布帛と多孔質膜との接触面の全面を接着剤で覆ってもよいが、この場合、接着剤も多孔質状のものを用い、通気性を確保することが好ましい。 In order to maintain the breathability of the moisture permeable waterproof sheet, the adhesive is preferably applied in the form of dots, lines or lattices, and covers all the contact surfaces between the fiber fabric and the porous membrane. It is advisable to apply an adhesive partially so that there is no such problem. Further, the entire contact surface between the fiber fabric and the porous membrane may be covered with an adhesive, but in this case, it is preferable to use a porous adhesive to ensure air permeability.
　接着剤としては、上述のように、ウレタン系、エポキシ系、メラミン系、ナイロン系、ポリエステル系またはアクリル系などの接着剤を用いることができる。また、接着剤は、１液型および２液型のいずれであってもよく、また、湿気硬化型などを含むホットメルトタイプのウレタン樹脂であってもよい。 As described above, urethane, epoxy, melamine, nylon, polyester, or acrylic adhesives can be used as the adhesive. The adhesive may be either a one-component type or a two-component type, and may be a hot-melt type urethane resin including a moisture curable type.
　また、繊維布帛は、得られる透湿性防水シートの両面（多孔質膜の表面および多孔質層が形成された面）に積層されていてもよいし、また、多孔質膜の表面および多孔質層が形成された面のいずれか一方の面のみに積層されていてもよい。 In addition, the fiber fabric may be laminated on both surfaces (the surface on which the porous membrane and the porous layer are formed) of the obtained moisture-permeable waterproof sheet, or the surface of the porous membrane and the porous layer It may be laminated | stacked only on either one surface of the surface in which was formed.
　また、透湿性防水シートの繊維布帛が積層されていない面に、上記と同様に本発明の目的を逸脱しない範囲で、耐水圧の向上、タッチの改良、意匠性の向上のための柄の付与、または、機能性の付与を目的として、ウレタン樹脂膜の片面に点状や線状など部分的に顔料、有機粒子、無機粒子、抗菌剤、蓄熱剤または防炎剤などを含む他のポリウレタンやアクリル樹脂を、グラビアコータやスクリーン捺染機を用いて付着させてもよい。 Further, on the surface of the moisture permeable waterproof sheet on which the fiber fabric is not laminated, a pattern for improving water pressure resistance, touch improvement, and design improvement is provided without departing from the object of the present invention. Or, for the purpose of imparting functionality, other polyurethanes containing pigments, organic particles, inorganic particles, antibacterial agents, heat storage agents, flame retardants, etc. partially on one side of the urethane resin film, such as dotted or linear The acrylic resin may be attached using a gravure coater or a screen printing machine.
　また、透湿性防水シートを得た後、必要に応じ、撥水剤、抗菌剤、難燃剤、ＳＲ剤、消臭剤、帯電防止剤、吸水剤または紫外線吸収剤など含む溶液を、パディング法、スプレー法またはグラビア法などにより、当該透湿性防水シートに付与してもよい。 Further, after obtaining a moisture-permeable waterproof sheet, if necessary, a solution containing a water repellent, an antibacterial agent, a flame retardant, an SR agent, a deodorant, an antistatic agent, a water absorbing agent or an ultraviolet absorber, You may give to the said moisture-permeable waterproof sheet by the spray method or the gravure method.
　以下、実施例により本発明に係る透湿性防水シートの説明を更に行うが、本発明はこれらの実施例によりなんら限定されるものではない。なお、以下に記載される「部」とは、「質量部」のことであり、「％」とは質量％のことであり、配合比とは質量比のことである。また、以下の例における各種物性値等の測定および評価は次の方法で行った。 Hereinafter, the moisture-permeable waterproof sheet according to the present invention will be further described with reference to examples, but the present invention is not limited to these examples. The “part” described below means “part by mass”, “%” means mass%, and the blending ratio means mass ratio. In addition, various physical property values and the like in the following examples were measured and evaluated by the following methods.
　＜Ａ　透湿度＞
　塩化カルシウム法による透湿度は、ＪＩＳ　Ｌ１０９９－１９９３Ａ－１法にて測定した。また、酢酸カリウム法による透湿度は、ＪＩＳ　Ｌ１０９９－１９９３Ｂ－１法にて測定した。 <A moisture permeability>
The moisture permeability by the calcium chloride method was measured by the JIS L1099-993A-1 method. Further, the moisture permeability by the potassium acetate method was measured by the JIS L1099-1993B-1 method.
　なお、塩化カルシウム法、酢酸カルシウム法ともに、２４時間当りの透湿量に換算した。また、Ｂ－２法は、耐水圧が低下し、漏水する場合に用いた。 In addition, both the calcium chloride method and the calcium acetate method were converted to moisture permeation per 24 hours. The method B-2 was used when water resistance dropped and water leaked.
　＜Ｂ　耐水圧＞
　耐水圧は、ＪＩＳ　Ｌ１０９２－１９９８耐水度試験（静水圧法）Ａ法（低水圧法）およびＢ法（高水圧法）に準じた方法で測定した。なお、単位は、低水圧法、高水圧法とも比較しやすいように、低水圧法の単位に換算した。 <B water pressure resistance>
The water pressure resistance was measured by a method according to JIS L1092-1998 water resistance test (hydrostatic pressure method) A method (low water pressure method) and B method (high water pressure method). The unit was converted to the unit of the low water pressure method so that it can be easily compared with the low water pressure method and the high water pressure method.
　また、水圧をかけることにより試験片が伸びる場合には、試験片の上にナイロンタフタ（２．５４ｃｍ当りのタテ糸とヨコ糸の密度の合計が２１０本程度のもの）を重ねて、試験機に取り付けて測定を行った。 In addition, when the test piece is stretched by applying water pressure, a nylon taffeta (the total density of warp yarns and weft yarns per 2.54 cm is about 210) is piled on the test piece. Attached to the measurement.
　１０回洗濯処理は、ＪＩＳ　Ｌ０２１７　１０３法に準じて行った。すなわち、２５分間洗剤を含む洗濯液中で洗濯を行い、その後１０分間注水を行いながらのすすぎを２回行ったものを洗濯５回としたときに、この操作を２回繰り返し、乾燥処理として最後に１回のみ吊り干し乾燥を行ったものとした。この場合、洗濯用合成洗剤は花王株式会社製のアタック高活性バイオＥＸを１ｇ／ｌで使用し、洗濯機は旧松下電気産業株式会社製（現パナソニック株式会社）のナショナル全自動電気洗濯機ＮＡ－Ｆ５０Ｙ２を用いた。なお、乾燥後、ドライアイロン仕上げなどの熱処理は行わないものとした。 -10 washing processes were performed according to JIS L0217 103 method. That is, when washing is performed in a washing solution containing a detergent for 25 minutes and then rinsing twice while water is poured for 10 minutes, this operation is repeated twice, and the final drying process is performed twice. It was assumed that it was hung and dried only once. In this case, a synthetic detergent for washing uses Attack High Activity Bio-EX manufactured by Kao Co., Ltd. at 1 g / l, and a washing machine is a national fully automatic electric washing machine NA manufactured by the former Matsushita Electric Industrial Co., Ltd. (currently Panasonic Corporation). -F50Y2 was used. Note that heat treatment such as dry iron finishing was not performed after drying.
　＜Ｃ　耐水圧保持率＞
　耐水圧保持率は、洗濯処理を１０回行った後の耐水圧を、洗濯処理前（初期）の耐水圧で除したものの百分率であり、下記式で求めた。 <C water pressure retention rate>
The water pressure retention rate is a percentage obtained by dividing the water pressure resistance after the washing process 10 times by the water pressure before the washing process (initial), and was obtained by the following formula.
　耐水圧保持率（％）＝洗濯処理を１０回行った後の耐水圧／洗濯処理前（初期）の耐水圧×１００ Water pressure retention rate (%) = water pressure after washing process 10 times / water pressure before washing process (initial) × 100
　＜Ｄ　通気度＞
　通気度は、ＪＩＳ　Ｌ１０９６　Ａ法（フラジール形法）に準じて測定を行った。 <D air permeability>
The air permeability was measured according to JIS L1096 A method (Fragile type method).
　＜Ｅ　風合い＞
　風合いは、手でさわって判断を行った。 <E texture>
The texture was touched and judged.
　＜Ｆ　温度上昇差＞
　本実施例では、保温性を表す指標として温度上昇差を求めた。温度上昇差は、パナソニック（株）製写真用レフランプのデイライトカラ－用ＰＲＦ－５００ＷＢ／Ｄから１５ｃｍの距離に２枚の試験片（実施例３の透湿性防水シートと、実施例３において赤外線吸収剤を添加しなかった以外は同一の方法で製造した透湿性防水シート（比較試料））を設置して多孔質層面に光を照射し、非接触型温度計（ＥＭＩＳＳＩＯＮ　ＴＨＥＲＭＯＭＥＴＥＲ　ＭＯＤＥＬ　５３０　０４：横河製作所製）を用いて、比較試料の多孔質層面の温度が４０℃になった時の実施例３の透湿性防水シートの多孔質層面の温度を測定して下記式により温度上昇差を求めた。 <F Temperature rise difference>
In this example, a temperature rise difference was obtained as an index representing heat retention. The difference in temperature rises between two test pieces (the moisture-permeable waterproof sheet of Example 3 and the infrared ray in Example 3) at a distance of 15 cm from PRF-500 WB / D for daylight color of a photographic reflex lamp manufactured by Panasonic Corporation. A moisture-permeable waterproof sheet (comparative sample) manufactured by the same method except that no absorbent was added was installed, and the porous layer surface was irradiated with light. A non-contact type thermometer (EMISION THERMOMETER MODEL 530 04: horizontal) Kawase Seisakusho) was used to measure the temperature of the porous layer surface of the moisture-permeable waterproof sheet of Example 3 when the temperature of the porous layer surface of the comparative sample reached 40 ° C. It was.
　温度上昇差（℃）＝実施例３の透湿性防水シートの温度－比較試料の温度（４０℃） Temperature rise difference (° C) = temperature of moisture-permeable waterproof sheet of Example 3-temperature of comparative sample (40 ° C)
　（実施例１）
　実施例１では、開放された多孔質膜として、ＰＴＦＥ膜（日本ドナルドソン（株）製、ＴＸ２２０１）を用いた。 (Example 1)
In Example 1, a PTFE membrane (made by Nippon Donaldson Co., Ltd., TX2201) was used as the open porous membrane.
　まず、フルダル離型紙ＥＶ１３０ＴＰＤ（リンテック（株）製）上に下記のポリウレタン溶液をコンマコータを用いてスリットの厚み０．０７ｍｍで全面塗布し、引き続き、離型紙上に塗布された湿潤状態のポリウレタン溶液の上に白色のＰＴＦＥ膜を積層した。 First, the following polyurethane solution was applied on the full-dal release paper EV130TPD (manufactured by Lintec Co., Ltd.) using a comma coater with a slit thickness of 0.07 mm, and then the wet polyurethane solution applied on the release paper was A white PTFE membrane was laminated on top.
　［ポリウレタン溶液］
　・Ｗ／Ｏ型エマルジョンのポリウレタン乳濁液（ＸＯＬＴＥＸ　ＰＸ５５０（ＤＩＣ（株）製）、固形分２９～３３％。溶剤：ＭＥＫ：水＝９５：５）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１００部
　・配合有機溶剤（ＭＥＫ／ＴＯＬ（１：１））　　　　　　　　　６０部
　・フッ素系撥水剤（ＡＳＳＩＳＴＯＲ　ＳＤ２７Ｍ（ＤＩＣ（株）製））　　　　　　　　　　　　　　　　　　　　　　　　　　 　　   　　１部
　・水／ＭＥＫ（９：１）　　　　　　　　　　　　　　　　　　　７５部
　・顔料（ＤＩＬＡＣ　Ｂｌａｃｋ　ＨＳ９５３０（ＤＩＣ（株）製））　　　　　　　　　　　　　　　　　　　　　　　　　   　　　　　５部 [Polyurethane solution]
・ W / O emulsion polyurethane emulsion (XOLTEX PX550 (manufactured by DIC Corporation), solid content 29-33%. Solvent: MEK: water = 95: 5) 100 parts ・ Compounded organic solvent (MEK / TOL ( 1: 1)) 60 parts ・ Fluorine-based water repellent (ASSISTOR SD27M (made by DIC Corporation)) 1 part ・ Water / MEK (9: 1) 75 parts ・ Pigment (DIRAC Black HS9530 (made by DIC Corporation)) 5 parts
　次に、第１室６０℃、第２室８０℃、第３室１００℃、第４室１２０℃に設定した乾燥機に、離型紙、ポリウレタン樹脂溶液、ＰＴＦＥ膜の順に積層されたものを、各部屋での滞留時間が３０秒になるような速度で通過させ、熱処理を行うことでＰＴＦＥ膜上に多孔質層を形成した。 Next, in the dryer set to the first chamber 60 ° C., the second chamber 80 ° C., the third chamber 100 ° C., and the fourth chamber 120 ° C., the release paper, the polyurethane resin solution, and the PTFE membrane are laminated in this order. A porous layer was formed on the PTFE membrane by passing through each chamber at a speed that would make the residence time 30 seconds and performing heat treatment.
　次に、室温にて２４時間放置した後、離型紙を剥離した。これにより、多孔質層がグレーに着色された透湿性防水シートを得た。 Next, after leaving at room temperature for 24 hours, the release paper was peeled off. Thereby, a moisture-permeable waterproof sheet in which the porous layer was colored gray was obtained.
　（実施例２）
　実施例１と同様に製造した、離型紙、多孔質層、ＰＴＦＥ膜の順番に積層されたものを２４時間放置し、グラビアコータを用いてＰＴＦＥ膜の上に下記の接着剤樹脂溶液を点状に塗布し、１２０℃で乾燥した。 (Example 2)
The same laminate of release paper, porous layer and PTFE membrane produced in the same manner as in Example 1 was allowed to stand for 24 hours, and the following adhesive resin solution was dotted on the PTFE membrane using a gravure coater. And dried at 120 ° C.
　［接着剤樹脂溶液］
　・２液型ポリウレタン樹脂（ＨＩ－ＭＵＲＥＮ　Ｙ１３４－４５（大日精化工業（株）製）、固形分６０％）　　　　　　　　　　　　　　１００部
　・トルエン　　　　　　　　　　　　　　　　　　　　　　　　　３０部
　・ＭＥＫ　　　　　　　　　　　　　　　　　　　　　　　　　　４０部
　・イソシアネート（コロネートＨＬ（日本ポリウレタン工業（株）製））　　　　　　　　　　　　　　　　　　　　　　　　　　　  　　　　９部
　・アミン系触媒（ＨＩ－２９９（大日精化工業（株）））　　　０．５部 [Adhesive resin solution]
・ Two-component polyurethane resin (HI-MUREN Y134-45 (manufactured by Dainichi Seika Kogyo Co., Ltd.), solid content 60%) 100 parts ・ Toluene 30 parts ・ MEK 40 parts ・ Isocyanate (Coronate HL (Nippon Polyurethane Industry Co., Ltd.) ) Made)) 9 parts ・ Amine catalyst (HI-299 (Daiichi Seika Kogyo Co., Ltd.)) 0.5 parts
　次に、基布となる繊維布帛としてポリエステルタフタを用い、ＰＴＦＥ膜の接着剤が付与された面に当該ポリエステルタフタを載せ、ニップロールでニップした後、１５０℃で３０秒間の熱処理を行った。 Next, polyester taffeta was used as the fiber fabric to be the base fabric, and the polyester taffeta was placed on the surface of the PTFE film to which the adhesive was applied. After nipping with a nip roll, heat treatment was performed at 150 ° C. for 30 seconds.
　なお、このとき用いたポリエステルタフタとしては、タテ糸およびヨコ糸がともに８３デシテックス／７２フィラメントで、密度がタテ１８０本／２．５４ｃｍ、ヨコ９０本／２．５４ｃｍであり、また、分散染料で青色に染色し、フッ素系撥水剤アサヒガードＡＧ７１０（旭硝子（株）製）の５％水溶液を用いてパディング法にて撥水加工し、撥水加工後、１７０℃にてカレンダー加工したものを用いた。 As the polyester taffeta used at this time, the warp yarn and the weft yarn are both 83 dtex / 72 filament, the density is 180 warp / 2.54 cm, warp 90 / 2.54 cm, and the disperse dye is used. What was dyed blue, water-repellent processed by padding using a 5% aqueous solution of fluorinated water repellent Asahi Guard AG710 (Asahi Glass Co., Ltd.), calendered at 170 ° C. after water-repellent processing Using.
　次に、７０℃にて４８時間のエージングを行った後、離型紙を剥離し、透湿性防水シートを得た。 Next, after aging at 70 ° C. for 48 hours, the release paper was peeled off to obtain a moisture-permeable waterproof sheet.
　（比較例１）
　多孔質層を設けなかった以外は、実施例２と同様の方法によって透湿性防水シートを得た。 (Comparative Example 1)
A moisture-permeable waterproof sheet was obtained in the same manner as in Example 2 except that the porous layer was not provided.
　（実施例３）
　実施例３でも、開放された多孔質膜として、ＰＴＦＥ膜（日本ドナルドソン（株）、ＴＸ２２０１）を用いた。 (Example 3)
Also in Example 3, a PTFE membrane (Nippon Donaldson Co., Ltd., TX2201) was used as the open porous membrane.
　まず、フルダル離型紙ＥＶ１３０ＴＰＤ（リンテック（株）製）上に下記のポリウレタン溶液をコンマコータを用いてスリットの厚み０．０７ｍｍで全面塗布し、引き続き、離型紙上に塗布された湿潤状態のポリウレタン溶液の上にＰＴＦＥ膜を積層した。 First, the following polyurethane solution was applied on the full-dal release paper EV130TPD (manufactured by Lintec Co., Ltd.) using a comma coater with a slit thickness of 0.07 mm, and then the wet polyurethane solution applied on the release paper was A PTFE membrane was laminated on top.
　［ポリウレタン溶液］
　・Ｗ／Ｏ型エマルジョンのポリウレタン乳濁液（ＸＯＬＴＥＸ　ＰＸ５５０（ＤＩＣ（株）製）、固形分２９～３３％。溶剤：ＭＥＫ：水＝９５：５）　　　　　　　　　　　　　　　　　　　　　　　　　　　１００質量部
　・ＭＥＫ／ＴＯＬ（１：１）の配合有機溶剤　　　　　　　　６０質量部
　・イソシアネート系架橋剤（ＸＯＬＴＥＸ　ＣＬ－１５（ＤＩＣ（株）製））　　　　　　　　　　　　　　　　　　　　　　　　　　　　３質量部
　・水／ＭＥＫ（９：１）　　　　　　　　　　　　　　　　　６０質量部
　・赤外線吸収剤（セルナックスＣＸＺ３３０Ｈ（日産化学工業（株）製））　　　　　　　　　　　　　　　　　　　　　　　　　　　　　５質量部 [Polyurethane solution]
・ W / O emulsion polyurethane emulsion (XOLTEX PX550 (manufactured by DIC Corporation), solid content 29-33%. Solvent: MEK: water = 95: 5) 100 parts by mass. MEK / TOL (1: 1 ) Organic solvent 60 parts by weight-Isocyanate-based crosslinking agent (XOLTEX CL-15 (manufactured by DIC Corporation)) 3 parts by weight-Water / MEK (9: 1) 60 parts by weight-Infrared absorber (CELUX CXZ330H ( Nissan Chemical Industries, Ltd.)) 5 parts by mass
　次に、第１室６０℃、第２室８０℃、第３室１００℃、第４室１２０℃に設定した乾燥機に、離型紙、ポリウレタン樹脂溶液、ＰＴＦＥ膜の順に積層されたものを、各部屋での滞留時間が３０秒になるような速度で通過させ、熱処理を行うことでＰＴＦＥ膜上に多孔質層を形成した。 Next, in the dryer set to the first chamber 60 ° C., the second chamber 80 ° C., the third chamber 100 ° C., and the fourth chamber 120 ° C., the release paper, the polyurethane resin solution, and the PTFE membrane are laminated in this order. A porous layer was formed on the PTFE membrane by passing through each chamber at a speed that would make the residence time 30 seconds and performing heat treatment.
　次に、湿気硬化型ホットメルトタイプウレタン樹脂タイホースＮＨ３００（ＤＩＣ（株）製）を１００℃に加熱し、溶融させて、グラビアコータを用いて点状にＰＴＦＥ膜の上に付与した。 Next, a moisture-curing hot-melt urethane resin tie hose NH300 (manufactured by DIC Corporation) was heated to 100 ° C., melted, and applied onto the PTFE film in a dotted manner using a gravure coater.
　次に、基布となる繊維布帛としてポリエステルタフタを用い、ＰＴＦＥ膜の接着剤が付与された面に当該ポリエステルタフタを載せ、１００℃に加熱されたニップロールでニップした。 Next, polyester taffeta was used as the fiber fabric to be the base fabric, and the polyester taffeta was placed on the surface of the PTFE film to which the adhesive was applied, and nipped with a nip roll heated to 100 ° C.
　なお、ポリエステルタフタとしては、タテ糸およびヨコ糸がともに８３デシテックス／７２フィラメントで、密度がタテ１８０本／２．５４ｃｍ、ヨコ９０本／２．５４ｃｍであり、また、分散染料で青色に染色し、１７０℃にてカレンダー加工したものを用いた。 As polyester taffeta, both warp and weft are 83 dtex / 72 filaments, the density is 180 / 2.54 cm, 90 / 2.54 cm, and they are dyed blue with disperse dye. What was calendered at 170 ° C. was used.
　次に、７０℃にて４８時間のエージングを行った後、離型紙を剥離した。 Next, after aging at 70 ° C. for 48 hours, the release paper was peeled off.
　次に、繊維布帛、ＰＴＦＥ膜、多孔質層の順に積層されたものに対して、パディング法にて下記の撥水剤溶液を塗布することで撥水剤を多孔質層の孔の表面に付与し、１２０℃、３０秒の熱処理の後、１５０℃、３０秒の熱処理とともに仕上げセットを行い、透湿性防水シートを得た。 Next, the water-repellent agent is applied to the surface of the pores of the porous layer by applying the following water-repellent agent solution by the padding method to the fiber fabric, PTFE membrane, and porous layer laminated in this order. Then, after heat treatment at 120 ° C. for 30 seconds, finishing set was performed together with heat treatment at 150 ° C. for 30 seconds to obtain a moisture-permeable waterproof sheet.
　［撥水剤溶液］
　・フッ素系撥水剤（アサヒガードＡＧ－Ｅ０６１（旭硝子（株）製）、固形分２０％）            　　　　　　　　　              ５．０質量％
　・イソシアネート系架橋剤（アクアネート１００（日本ポリウレタン工業（株）製）、固形分１００％）　　　　　　　　　　　　　　０．２質量％
　・水　　　　　　　　　　　　　　　　　　　　　　　　９４．８質量％ [Water repellent solution]
・ Fluorine-based water repellent (Asahi Guard AG-E061 (Asahi Glass Co., Ltd.), solid content 20%) 5.0% by mass
・ Isocyanate-based crosslinking agent (Aquanate 100 (manufactured by Nippon Polyurethane Industry Co., Ltd.), solid content 100%) 0.2% by mass
・ Water 94.8% by mass
　なお、実施例３の透湿性防水シートの多孔質層面に、裏地としてナイロン製のトリコットを上記接着剤溶液を用いて貼り合せることで得られた透湿性防水シートは、縫製時に別途裏地を準備する必要もなく、縫製時の負荷をも軽減することができる。 In addition, the moisture-permeable waterproof sheet obtained by laminating nylon tricot as a lining to the porous layer surface of the moisture-permeable waterproof sheet of Example 3 using the above adhesive solution prepares a separate lining at the time of sewing. There is no need, and the load during sewing can be reduced.
　（比較例２）
　多孔質層を設けなかった以外は、実施例３と同様の方法によって透湿性防水シートを得た。 (Comparative Example 2)
A moisture-permeable waterproof sheet was obtained in the same manner as in Example 3 except that the porous layer was not provided.
　（実施例４）
　実施例１で用いたＷ／Ｏ型エマルジョン樹脂のポリウレタン乳濁液を、ＸＯＬＴＥＸ　ＰＸ５５０からＨＩ－ＭＵＲＥＮ　Ｘ－３０４０（エーテル系ポリウレタン。大日精化工業（株）製、固形分３０％。溶剤：ＭＥＫ：水＝９４：６）に代えるとともに、実施例１で用いた顔料を、ＤＩＬＡＣ　Ｂｌａｃｋ　ＨＳ９５３０（ＤＩＣ（株）製）からＤＩＬＡＣ　Ｗｈｉｔｅ　ＨＳ９５３０（ＤＩＣ（株）製）に代えた以外は、実施例１と同様の方法によってＰＴＦＥ膜上に白色の多孔質層を形成した。 Example 4
The polyurethane emulsion of the W / O emulsion resin used in Example 1 was converted from XOLTEX PX550 to HI-MUREN X-3040 (ether polyurethane, manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 30%. Solvent: MEK : Water = 94: 6) and the pigment used in Example 1 was changed to DICAC White HS9530 (manufactured by DIC Corporation) instead of DILA Black HS9530 (manufactured by DIC Corporation). A white porous layer was formed on the PTFE membrane by the same method as described above.
　次に、実施例３と同じ湿気硬化型ホットメルトタイプウレタン樹脂タイホースＮＨ３００（ＤＩＣ（株）製）を用いて、実施例３と同様に、点状にＰＴＦＥ膜の上に付与した。 Next, using the same moisture-curable hot-melt urethane resin tie hose NH300 (manufactured by DIC Corporation) as in Example 3, it was applied on the PTFE membrane in a dotted manner in the same manner as in Example 3.
　次に、繊維布帛としてナイロンツイルを用い、ＰＴＦＥ膜の接着剤が付与された面に当該ナイロンツイルを載せ、１００℃に加熱されたニップロールでニップした。 Next, nylon twill was used as the fiber fabric, and the nylon twill was placed on the surface to which the adhesive of the PTFE film was applied and nipped with a nip roll heated to 100 ° C.
　なお、このとき用いたナイロンツイルとしては、タテ糸が７７デシテックス／３４フィラメント、ヨコ糸が９２デシテックス／７４フィラメント、密度がタテ１２４本／２．５４ｃｍ、ヨコ６５本／２．５４ｃｍであり、また、酸性染料で赤色に染色し、１７０℃にてカレンダー加工したものを用いた。 As for the nylon twill used at this time, the warp yarn is 77 dtex / 34 filament, the horizontal yarn is 92 dtex / 74 filament, the density is vertical 124 yarns / 2.54 cm, and horizontal yarn 65 yarns / 2.54 cm. A dyed red color with an acid dye and calendered at 170 ° C. was used.
　その後、７０℃にて４８時間のエージングを行った後、離型紙を剥離し、繊維布帛、ＰＴＦＥ膜、多孔質層の順に積層された透湿性防水シートを得た。 Then, after aging at 70 ° C. for 48 hours, the release paper was peeled off to obtain a moisture permeable waterproof sheet in which a fiber fabric, a PTFE membrane, and a porous layer were laminated in this order.
　なお、実施例３では、後撥水処理を行っているが、実施例４では後撥水処理を行っていない。撥水処理は、ＰＴＦＥ膜と多孔質層とを貼り合わせる前に、実施例２と同様にしてナイロンツイルに行っている。 In Example 3, post-water-repellent treatment was performed, but in Example 4, post-water-repellent treatment was not performed. The water repellent treatment is performed on the nylon twill in the same manner as in Example 2 before the PTFE membrane and the porous layer are bonded together.
　（実施例５）
　ポリウレタン溶液からフッ素系撥水剤（ＡＳＳＩＳＴＯＲ　ＳＤ２７Ｍ）を除いた以外は、実施例４と同様の方法によって透湿性防水シートを得た。 (Example 5)
A moisture-permeable waterproof sheet was obtained in the same manner as in Example 4 except that the fluorine-based water repellent (ASSISTOR SD27M) was removed from the polyurethane solution.
　以上のようにして得られた実施例１～実施例５および比較例１、２の各透湿性防水シートについて、各種物性値等の測定結果を以下の表１に示す。なお、表１には示していないが、実施例１との比較のために、ＰＴＦＥ膜のみ（比較例１におけるＰＴＦＥ膜のみ）について１０回洗濯処理を行ったところ、耐水圧は４００ｍｍ～９００ｍｍ程度であった。 Table 1 below shows the measurement results of various physical properties and the like for each of the moisture-permeable waterproof sheets of Examples 1 to 5 and Comparative Examples 1 and 2 obtained as described above. Although not shown in Table 1, for comparison with Example 1, only PTFE membrane (only PTFE membrane in Comparative Example 1) was washed 10 times, and the water pressure resistance was about 400 mm to 900 mm. Met.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例１～５の透湿性防水シートによれば、比較例１、２のものと比べて、通気度を著しく低下させることなく、洗濯処理による耐水圧の低下を抑制できることが分かる。 As shown in Table 1, according to the moisture-permeable waterproof sheets of Examples 1 to 5, compared with those of Comparative Examples 1 and 2, the decrease in the water pressure resistance due to washing treatment is suppressed without significantly reducing the air permeability. I understand that I can do it.
　また、実施例１～５の透湿性防水シートの断面および表面を、走査型電子顕微鏡（ＳＥＭＥＤＸ　Ｔｙｐｅ　Ｈ形：（株）日立サイエンスシステムズ）を用いて５００倍～３０００倍で観察したところ、多孔質層には直径１～１０μｍ程度の多数の孔が確認された。 Further, the cross section and the surface of the moisture-permeable waterproof sheets of Examples 1 to 5 were observed at 500 to 3000 times using a scanning electron microscope (SEMEDX Type H type: Hitachi Science Systems, Ltd.). A large number of pores having a diameter of about 1 to 10 μm were confirmed in the layer.
　本発明に係る透湿性防水シートは、ウインドブレーカー、合羽、ジャンパー、コート、ジャケット、スキーウエア、スノーボードウエア、ヤッケ、テント、靴、寝袋、鞄または手袋等の種々の繊維製品に広く利用することができる。 The moisture-permeable tarpaulin according to the present invention can be widely used for various textile products such as windbreakers, goose, jumpers, coats, jackets, ski wear, snowboard wear, jackets, tents, shoes, sleeping bags, bags or gloves. it can.

Claims (8)

  1. 　表面が開放された複数の孔を有する多孔質膜の少なくとも片面上および／または当該多孔質膜中に、ポリウレタンを含む多孔質層が形成されていることを特徴とする透湿性防水シート。 A moisture-permeable waterproof sheet, wherein a porous layer containing polyurethane is formed on at least one surface of a porous film having a plurality of pores whose surfaces are open and / or in the porous film.
  2. 　通気度が０．００５ｃｍ３／ｃｍ２・ｓ以上、１ｃｍ３／ｃｍ２・ｓ以下であることを特徴とする請求項１に記載の透湿性防水シート。 2. The moisture-permeable waterproof sheet according to claim 1, wherein the air permeability is 0.005 cm 3 / cm 2 · s or more and 1 cm 3 / cm 2 · s or less.
  3. 　１０回洗濯処理後の耐水圧が５０００ｍｍ以上であることを特徴とする請求項１または２に記載の透湿性防水シート。 The moisture-permeable waterproof sheet according to claim 1 or 2, wherein the water pressure resistance after 10 washing treatments is 5000 mm or more.
  4. 　前記多孔質膜が、多孔質ポリテトラフルオロエチレン膜であることを特徴とする請求項１～３のいずれか１項に記載の透湿性防水シート。 The moisture-permeable waterproof sheet according to any one of claims 1 to 3, wherein the porous film is a porous polytetrafluoroethylene film.
  5. 　前記多孔質層の表面に撥水剤が付着されていることを特徴とする請求項１～４のいずれか１項に記載の透湿性防水シート。 The moisture-permeable waterproof sheet according to any one of claims 1 to 4, wherein a water repellent is attached to the surface of the porous layer.
  6. 　表面が開放された複数の孔を有する多孔質膜とポリウレタン溶液とを積層することを特徴とする透湿性防水シートの製造方法。 A method for producing a moisture-permeable waterproof sheet, comprising laminating a porous film having a plurality of pores with open surfaces and a polyurethane solution.
  7. 　前記多孔質膜は、多孔質ポリテトラフルオロエチレン膜であることを特徴とする請求項６に記載の透湿性防水シートの製造方法。 The method for producing a moisture-permeable waterproof sheet according to claim 6, wherein the porous film is a porous polytetrafluoroethylene film.
  8. 　前記ポリウレタン溶液は、Ｗ／Ｏ型エマルジョンのポリウレタン乳濁液であることを特徴とする請求項６または７に記載の透湿性防水シートの製造方法。 The method for producing a moisture-permeable waterproof sheet according to claim 6 or 7, wherein the polyurethane solution is a polyurethane emulsion of a W / O type emulsion.
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JP2019210584A (en) * 2018-06-08 2019-12-12 儀城企業有限公司 Composite film material and compound type spinning product
CN114714694A (en) * 2022-03-08 2022-07-08 湖北卓乐医疗用品有限公司 Waterproof breathable operating coat material, preparation method thereof and operating coat
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KR20190040089A (en) * 2014-09-12 2019-04-16 컬럼비아 스포츠웨어 노스 아메리카, 인크. Fabric having a waterproof barrier
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JP2019210584A (en) * 2018-06-08 2019-12-12 儀城企業有限公司 Composite film material and compound type spinning product
CN114714694A (en) * 2022-03-08 2022-07-08 湖北卓乐医疗用品有限公司 Waterproof breathable operating coat material, preparation method thereof and operating coat
CN114714694B (en) * 2022-03-08 2023-08-11 湖北卓乐医疗用品有限公司 Waterproof breathable surgical gown material, preparation method thereof and surgical gown
WO2023234386A1 (en) * 2022-06-02 2023-12-07 株式会社イノアックコーポレーション Foamed sheet for collecting fine particles and bedding

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