JP2010163729A - Moisture-permeable and water-proof fabric and process for the production of same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moisture-permeable and water-proof fabric, the water pressure resistance of which rarely lowers even after has been washed repeatedly. <P>SOLUTION: The moisture-permeable and water-proof fabric is a laminate composed of a fabric and a microporous film laid on the back side of a surface fabric having a front side of camouflaged pattern, the microporous film comprising a polyurethane resin as the main component. Further, the microporous film contains 15 to 45 mass% of silica fine powder, 1 to 9 mass% of a fluorine-containing water repellent, 0.1 to 2 mass% of an oil-soluble fluorine-containing surfactant. The moisture-permeable and water-proof fabric can be produced by applying a resin composition for the formation of microporous film onto the back side of a surface fabric, and dipping the resulting fabric in an aqueous solution containing N,N-dimethylformamide in an amount of 5 to 30 mass% to solidify the resin composition and thus form a microporous film, the resin composition being a solution or dispersion in N,N-dimethylformamide which is prepared by dissolving or dispersing, in N,N-dimethylformamide, a polyurethane resin as the main component, 15 to 45 mass% of silica fine powder, 1 to 9 mass% of a fluorine-containing water repellent, 0.1 to 2 mass% of an oil-soluble fluorine-containing surfactant. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a camouflage fabric having a camouflage pattern which is difficult to visually recognize by visible light to near infrared rays, and is particularly permeable to moisture and waterproof camouflage fabric having excellent moisture permeability and waterproof performance and its production. It is about the method.

  Camouflage fabric has been useful as a material for combat clothes worn by the military or the like, or as a material for tents or the like equipped by the military or the like. Since military forces often work in heavy rain, high waterproof performance is required for combat clothes to be worn. Moreover, since a large amount of perspiration is caused by the work, high permeation performance is required in order to release the perspiration to the outside.

  Such a moisture-permeable waterproof camouflage fabric is generally obtained by applying a resin composition for forming a microporous film mainly composed of polyurethane resin on the back surface of a surface with a camouflage pattern, and then immersing it in water. Is produced by wet coagulation and forming a microporous film on the back surface of the outer material. For example, in Patent Document 1, a resin composition for forming a microporous film containing a polyurethane resin and silica fine powder is applied to the back surface of a surface material on which a camouflage pattern has been applied, and then immersed in water. It describes that a moisture-permeable and waterproof camouflage fabric is produced by wet coagulation. The moisture permeable waterproof camouflage fabric obtained by such a method has a high moisture permeability and is therefore excellent in moisture permeability, and since it has a high water pressure resistance, it is excellent in waterproof performance and is preferable. Is.

JP 2000-265308 A

  However, the conventional moisture-permeable waterproof camouflage fabric as described in Patent Document 1 initially has a high water pressure resistance, but when washing is repeated, the water pressure resistance decreases and the desired waterproof performance is lost. There was a drawback of end. In particular, battle clothes made of camouflage fabric are very dirty and repeat washing many times. Therefore, such a defect is often regarded as a problem. An object of the present invention is to provide a moisture-permeable and waterproof camouflage fabric in which the water pressure resistance is unlikely to decrease even after repeated washing.

  In order to solve the above-mentioned problems, the present invention mixes a fluorine-based water repellent and an oil-soluble fluorine-based surfactant in a resin composition for forming a microporous film, and the fluorine film is obtained in the resulting microporous film. A water-based water repellent and a fluorine-based surfactant are contained so that the water pressure resistance is not easily lowered even after repeated washing. That is, the present invention relates to a moisture permeable waterproof camouflage fabric in which a microporous film mainly composed of a polyurethane resin is laminated on the back surface of a surface material having a camouflage pattern on the surface. Moisture permeable waterproof camouflage fabric characterized by containing 15 to 45% by weight of powder, 1 to 9% by weight of a fluorine-based water repellent and 0.1 to 2% by weight of an oil-soluble fluorine-based surfactant and its It relates to a manufacturing method.

  As the fabric for the outer material used in the present invention, fabrics such as knitted fabrics and nonwoven fabrics conventionally used for combat clothes and the like are used. In general, a woven fabric mainly composed of polyamide synthetic fiber yarn represented by nylon 6 and nylon 66 is used. This is because it is excellent in strength and is not easily damaged. The woven fabric structure is preferably a ripstop structure excellent in tearing. Further, as the thick yarn used in the ripstop structure, it is preferable to use a polyester synthetic fiber yarn represented by aramid fiber yarn or polyethylene terephthalate from the viewpoint of strength.

  The outer material has a camouflage pattern on its surface. A conventionally known camouflage pattern is adopted. Specifically, a camouflage pattern that is difficult to see even during near-infrared exploration at night is preferable, and the reflectance of light from the visible light region of 600 nm to the near-infrared region of 1200 nm is in the range of 2% to 65%. Is preferred. In particular, the camouflage pattern is preferably a conventionally known divided camouflage pattern. At least three kinds of colors are divided and printed, and the light reflectance at 600 to 1200 nm of each color is 2% or more and 65% or less. It is preferable that the reflectance is within the range and has a different reflectance. Furthermore, it is preferable that the reflectances be as uniform as possible within a range of 2% to 65%.

  As a color used for printing the divided camouflage pattern, it is preferable to use three or four colors from light green, dark green, brown and black. This is because the divided camouflage pattern composed of these colors has a large camouflage effect even in the daytime. Light green has a light reflectance of 600 to 1200 nm of about 10 to 55%, dark green is about 6 to 45%, brown is about 6 to 30%, and black is about 3 to 9%. is there. When the wavelength is 800 nm or more, even if the reflectance is close by the reflectance of each color, the difference is about 10 to 20%. Therefore, each of these colors has a high camouflage effect even in the near infrared region. As a method of printing each of these colors, after dyeing one color on the entire surface, it is possible to print another color on a predetermined location, or to print a predetermined color on each location without staining the entire surface. A color may be printed. In order to realize these colors, the following dyes or pigments may be mixed. That is, CI Acid Blue 2,40,58,113,120,171,232,296, CI Acid Green 28,109, CI Acid Brown 289,298, CI Acid Black 58,112,132,170,194,222, CI Acid Orange 149, CI Acid Yellow 127, CI Acid Red 266, carbon black and other dyes or pigments may be mixed to create.

  In addition, when it is difficult to adjust the near-infrared reflectance only with dyes or pigments constituting each color, an infrared-absorbing dye that easily absorbs near-infrared rays may be mixed. Examples of infrared absorbing dyes that can be used include polymethine dyes, phthalocyanine dyes, dithiol dyes, naphthoquinone / anthraquinone dyes, triphenylmethane dyes, aminium / diimmonium dyes, mercaptonaphthol metal complex dyes, and the like. . Carbon black can easily absorb all wavelengths in the near infrared region and can be used as appropriate.

  When pigments or pigments are used, it is preferable to use a binder in combination with the camouflage pattern. That is, a printing solution containing a binder is applied to the surface material in a predetermined pattern and dried to print a camouflage pattern. This is because the camouflage pattern can be firmly printed on the outer material by the binder. As the binder, conventionally known resins such as acrylic resins, polyurethane resins, polyester resins, polyamide resins and the like are used. Since this binder is applied to the surface of the surface material, it is preferable to adjust the binder so that the moisture permeability does not decrease.

  The outer surface is preferably water-repellent. That is, it is preferable to immerse the surface material in a conventionally known water repellent emulsion or apply it to at least the back surface of the surface material to perform water repellent processing. As the water repellent emulsion, a conventionally known fluorine water repellent emulsion, silicone water repellent emulsion, paraffin water repellent emulsion or the like can be used. In the present invention, it is preferable to use a fluorinated water repellent emulsion, and among them, perfluorooctanoic acid remains in the fluorinated water repellent or perfluorooctane over time from the fluorinated water repellent. It is preferable to use one that does not easily generate an acid. This is because perfluorooctanoic acid is difficult to decompose and remains in the environment, which is undesirable for the global environment. A typical example of such a fluorine-based water repellent is one obtained by polymerizing an acrylate compound having a C 1-6 perfluoroalkyl group in the side chain. Specifically, “Asahi Guard AG-E061” manufactured by Asahi Glass Co., Ltd., “Unidyne TG-5521” manufactured by Daikin Industries, Ltd., “NK Guard SCH-02” manufactured by Nikka Chemical Co., Ltd., “NUVA manufactured by Clariant Japan Co., Ltd. N2114 LIQ "and the like.

  A conventionally well-known method can also be employ | adopted as a method of water-repellent | finishing a surface material. Specifically, means such as a padding method, a coating method, a gravure coating method, and a spray method can be employed. For example, in the padding method, after immersing the surface material in a water repellent emulsion, it is squeezed with a mangle, adjusted to a predetermined application amount, dried at a temperature of 80 to 150 ° C., and then at a temperature of 150 to 180 ° C. for 30 seconds to 2 minutes. Cure. As a result, a surface with water repellent finish on both sides is obtained. In the gravure coating method, a water repellent emulsion is attached only to the back surface of the outer surface using a high mesh gravure roll, and thereafter drying and curing are performed in the same manner. As a result, a surface material having a water repellent finish only on the back surface is obtained. Moreover, after drying and curing, it is preferable to crush the back surface of the outer surface using a calendar processing machine equipped with a mirror surface roll. This is to prevent the resin composition for forming a microporous film, which is later applied to the back surface of the surface material, from penetrating deeply into the surface material.

  The amount of the water repellent applied in the surface is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass in terms of solid content. When the applied amount is less than 0.1% by mass, it is difficult to impart sufficient water repellency to the outer surface. On the other hand, when the applied amount exceeds 3% by mass, the texture of the resulting moisture-permeable waterproof camouflage fabric is hard to be cured. Adhesiveness with the porous membrane may be reduced, or the moisture permeability of the microporous membrane may be adversely affected.

  In the water repellent emulsion, a triazine compound, an isocyanate compound or the like may be mixed for the purpose of improving the water repellency durability. In these, an isocyanate compound is suitable from an environmental viewpoint. From the viewpoint of processing stability of the water repellent emulsion, a thermal dissociation type blocked isocyanate compound in which an isocyanate group is blocked with acetoxime, phenol, caprolactam or the like is more preferable.

  The microporous film mainly composed of polyurethane resin laminated on the back surface of the outer surface is obtained by wet coagulation of the following resin composition for forming a microporous film. That is, the resin composition for forming a microporous film mainly comprises a polyurethane resin, 15 to 45% by mass of silica fine powder, 1 to 9% by mass of a fluorine-based water repellent and 0.1% of an oil-soluble fluorine-based surfactant. It is a liquid containing ˜2% by mass.

  As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component and a polyol component may be employed. As the polyisocyanate component, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and the like are used alone or in combination. Specifically, a polyisocyanate having 3 or more functional groups is used as the main component, such as tolylene-2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6-hexane diisocyanate or 1,4-cyclohexane diisocyanate. May be used. On the other hand, polyether polyol, polyester polyol, or the like is used as the polyol component. As the polyether polyol, polyethylene glycol, polypropylene glycol, polytetraethylene glycol or the like is used. As the polyester polyol, a reaction product of a diol such as ethylene glycol or propylene glycol and a dibasic acid such as adipic acid or sebacic acid, or a ring-opening polymer such as caprolactone can be used. Alternatively, a polymer of the prepolymer can also be used.

  The polyurethane resin is preferably contained in an amount of 50% by mass or more in the solid content of the resin composition for forming a microporous film. When the polyurethane resin content is reduced, the content of silica fine powder and the like is relatively increased, and the microporous membrane tends to become brittle. Of course, if the microporous membrane does not become brittle, it may be slightly less than 50% by mass.

  As the fine silica powder, conventionally known fine powders made of silicon dioxide can be used. Generally, fine powder made of silicon dioxide having a primary particle diameter of about 7 to 40 nm is used. When the primary particle diameter exceeds 40 nm, the diameter of the pores formed in the microporous film increases, and the water pressure resistance tends to decrease. In the present invention, fumed silica fine powder is preferably used as the fine silica powder, which is composed of amorphous glassy spherical primary particles having no pores. Specifically, hydrophilic fumed silica fine powder or hydrophobic fumed silica fine powder is used. In the present invention, it is particularly preferable to use hydrophobic fumed silica fine powder. Such silica fine powders are commercially available, for example, hydrophilic fumed silica such as “AEROSIL 90”, “AEROSIL 130”, “AEROSIL 150”, “AEROSIL 200”, “AEROSIL 300” manufactured by Nippon Aerosil Co., Ltd. Fine powder, “AEROSIL R104”, “AEROSIL R106”, “AEROSIL R202”, “AEROSIL R805”, “AEROSIL RX200”, “AEROSIL RX300”, “AEROSIL R972”, “AEROSIL R974”, “AEROSIL R976”, “AEROSIL” Hydrophobic fumed silica fine powders such as “R7200”, “AEROSIL R8200”, and “AEROSIL R9200” are used. Moreover, “AEROSIL COK84” which is a fine powder obtained by mixing fumed silica and fumed aluminum oxide can be used as the fine silica powder.

  Silica fine powder is contained in an amount of 15 to 45% by mass in the solid content of the resin composition for forming a microporous film. Since the present invention relates to a camouflage fabric, it is required to be less stuffy, and when the content of the silica fine powder is less than 15% by mass, moisture permeability is lowered and stuffiness tends to occur, such being undesirable. On the other hand, when the content of the silica fine powder exceeds 45% by mass, the formed microporous membrane becomes brittle, the water pressure resistance is lowered and the washing durability is also lowered. Silica fine powder is contained in a relatively large amount in the resin composition for forming a microporous film, but is preferably contained in a uniformly dispersed state. In order to uniformly disperse the silica fine powder, it is previously mixed with a polyurethane resin by using a mixer such as a three-roll mill machine, a kneader machine or a sand mill machine, and then a resin composition for forming a microporous film. Is preferably prepared.

  A conventionally well-known thing is used as a fluorine-type water repellent. In the present invention, the fluorine-based water repellent is used because it is possible to obtain a resin composition for forming a microporous film that is easy to mix with a fluorine-based surfactant, easy to prepare, and easy to apply. In the present invention, among the fluorine-based water repellents, it is preferable to use those in which perfluorooctanoic acid remains or from which perfluorooctanoic acid is difficult to be formed over time. This is because perfluorooctanoic acid is difficult to decompose and remains in the environment, which is undesirable for the global environment. Such a fluorine-based water repellent is obtained by polymerizing an acrylate compound having a C 1-6 perfluoroalkyl group in the side chain. Specifically, “Asahi Guard AG-E061” manufactured by Asahi Glass Co., Ltd., “Unidyne TG-5521” manufactured by Daikin Industries, Ltd., “NK Guard SCH-02” manufactured by Nikka Chemical Co., Ltd., “NUVA manufactured by Clariant Japan Co., Ltd. N2114 LIQ "and the like.

  The fluorine-based water repellent is contained in an amount of 1 to 9% by mass in the solid content of the resin composition for forming a microporous film. When the content of the fluorine-based water repellent is less than 1% by mass, the detergent is easily adsorbed into the micropores in the microporous membrane when washing is repeated, which is not preferable. That is, if the detergent is adsorbed in the micropores, it is not preferable because water is easily attracted and washing durability (washing durability of water pressure resistance) is lowered. Moreover, when content of a fluorine-type water repellent exceeds 9 mass%, stability of the resin composition for microporous film formation will worsen, it will become difficult to apply | coat, and it will become difficult to form a uniform microporous film. As a result, spots are formed in the microporous membrane, and both the water pressure resistance and the washing durability are deteriorated.

  As the oil-soluble fluorosurfactant, a surfactant having a hydrophobic group composed of a perfluoroalkyl group and a hydrophilic group such as a polyoxyalkylene group, a sulfonic acid group or a carboxylic acid group and having a surfactant activity is adopted. Is done. Here, oil-soluble means that 50% by mass or more dissolves or is compatible with toluene. That is, when 50 parts by mass of a fluorosurfactant is mixed and stirred with respect to 100 parts by mass of toluene, phase separation does not occur even after 1 hour. In the present invention, the reason why the oil-soluble fluorosurfactant is used is that the solvent of the microporous film-forming resin composition is an organic solvent, so that the fluorosurfactant is uniformly dissolved or dispersed therein. It is. This is because the fluorine-based water repellent is uniformly present in the microporous film by the surface activity of the fluorine-based surfactant. As the oil-soluble fluorosurfactant, “SURFLON S-651”, “SURFLON S-611”, “SURFLON S-386”, “SURFLON S-243” and the like manufactured by AGC Seimi Chemical Co., Ltd. are used.

  In the present invention, it is particularly preferable to use an oil-soluble and water-soluble fluorine surfactant. Since water is also present in the microporous film-forming resin composition, the fluorosurfactant is more soluble or even more soluble in the microporous film-forming resin composition if it is oil-soluble and water-soluble. This is because they are dispersed. Here, the term “water-soluble” means that 50% by mass or more dissolves or is compatible with water, as in the case of oil solubility. That is, when 50 parts by mass of a fluorosurfactant is mixed and stirred with respect to 100 parts by mass of water, phase separation does not occur even after 1 hour. Examples of the oil-soluble and water-soluble fluorosurfactant include “SURFLON S-386” and “SURFLON S-243” manufactured by AGC Seimi Chemical Co., Ltd.

  In the present invention, a fluorine-based surfactant that is water-soluble but not oil-soluble, or a fluorine-based surfactant that is neither water-soluble nor oil-soluble can be used. For example, as the former fluorosurfactant, “SURFLON S-241”, “SURFLON S-221”, “SURFLON S-211”, etc., manufactured by AGC Seimi Chemical Co., Ltd. exist. Activators cannot be used. In addition, as the latter fluorosurfactant, there is “SURFLON S-420” manufactured by AGC Seimi Chemical Co., Ltd., but such a fluorosurfactant cannot be used.

  Typical examples of the chemical structure of the fluorosurfactant used in the present invention include a perfluoroalkyl group having 1 to 6 carbon atoms as a hydrophobic group and a polyoxyalkylene such as a polyoxyethylene group or a polyoxypropylene group as a hydrophilic group. It has a group. For example, an oligomer obtained by polymerizing an acrylate compound having a polyoxyethylene group or a polyoxypropylene group together with a perfluoroalkyl group having 1 to 6 carbon atoms in the side chain is used. Moreover, what added the oligomer which superposed | polymerized the acrylate compound which has a C1-C6 perfluoroalkyl group in a side chain to the compound which has a polyoxyethylene group or a polyoxypropylene group is used. Here, the reason why the perfluoroalkyl group having 1 to 6 carbon atoms is used as the hydrophobic group is the same as described in the explanation of the fluorine-based water repellent. That is, it is because perfluorooctanoic acid that has an adverse effect on the global environment remains in the fluorosurfactant or is hardly generated from the fluorosurfactant over time.

  The oil-soluble fluorosurfactant is contained in an amount of 0.1 to 2% by mass in the solid content of the resin composition for forming a microporous film. When the content of the fluorosurfactant is less than 0.1% by mass, the stability and coating properties of the resin composition for forming a microporous film are deteriorated, and the water pressure resistance of the formed microporous film is reduced. Since washing durability also falls, it is not preferable. On the other hand, when the content of the fluorosurfactant exceeds 2% by mass, the water repellency of the formed microporous film is lowered, the water pressure resistance is lowered, and the washing durability is also lowered.

  The resin composition for forming a microporous film contains a crosslinkable isocyanate compound as a third component in addition to the polyurethane resin, silica fine powder, fluorine-based water repellent and oil-soluble fluorine-based surfactant. It is preferable. This is because the polyurethane resin forming the microporous film is cross-linked to improve the strength of the microporous film and to improve the adhesive force between the microporous film and the back surface. The crosslinkable isocyanate compound is preferably contained in an amount of about 1 to 10% by mass in the solid content of the resin composition for forming a microporous film. When the content of the crosslinkable isocyanate compound is less than 1% by mass, it is difficult to improve the strength of the microporous membrane and to improve the adhesion between the microporous membrane and the back surface of the outer surface. Moreover, when content of a crosslinkable isocyanate compound exceeds 10 mass%, the tendency for the texture of a microporous film to become hard will arise.

  As the crosslinkable isocyanate compound, tolylene 2,4-diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or the like is used. Triisocyanates obtained by addition reaction of 3 mol of these diisocyanates with 1 mol of a compound containing active hydrogen are also used. In addition, as a compound containing active hydrogen, a trimethylol propane, glycerol, etc. can be used, for example. Of the crosslinkable isocyanate compounds, the use of blocked isocyanate is particularly advantageous in terms of stability and pot life of the resin composition for forming a microporous film. As the blocked isocyanate, a type that dissociates by heat treatment is preferable, and specifically, those obtained by forming an additional block with phenol, lactam, methyl ketoxime, or the like are preferable.

  Furthermore, as the third component, a resin other than the polyurethane resin may be contained in a small amount, for example, about 20% by mass or less in the solid content. Examples of such a resin include polymers or copolymers such as polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acid, and polycarbonate. Also, those obtained by modifying these polymers or copolymers with fluorine, silicon or the like can be used. In addition, various functional materials such as various additives such as pigments and fillers, antibacterial agents, deodorants, and flame retardants may be contained as the third component.

  In the resin composition for forming a microporous film, a known organic solvent is used to uniformly dissolve or disperse the polyurethane resin, silica fine powder, fluorine-based water repellent and oil-soluble fluorine-based surfactant. . In particular, it is preferable to use N, N-dimethylformamide, which is a parent solvent for polyurethane resins. The content of the organic solvent is also a conventionally known ratio and is about 70 to 85% by mass.

  A microporous film is formed by applying the resin composition for forming a microporous film on the back surface of the outer surface by a known means such as a comma coater or a knife coater and then immersing the resin composition in a wet coagulation liquid. As the wet coagulation liquid, water or an aqueous solution containing 5 to 30% by mass of N, N-dimethylformamide is used. The temperature of the coagulation liquid is preferably about 5 to 35 ° C., and the coagulation time is about 30 seconds to 5 minutes. After the resin composition for forming a microporous film is coagulated with a wet coagulation liquid and a microporous film is obtained, in order to remove N, N-dimethylformamide, it is washed with hot water at a temperature of 35 to 80 ° C. for 1 to 10 minutes. To do. And after water washing, the moisture-permeable waterproof camouflage fabric in which the microporous film was formed is obtained by drying for 1 to 10 minutes at the temperature of 50-150 degreeC. The thickness of the microporous membrane is a matter that can be appropriately set, but is generally about 10 to 50 μm. When the thickness of the microporous membrane is reduced, the water pressure resistance tends to decrease, and when the thickness is increased, the texture tends to decrease.

  In the present invention, a nonporous film may be further laminated on the surface of the microporous film. Of course, a moisture-permeable non-porous film is adopted as the non-porous film. However, when the non-porous film is laminated, the water pressure resistance is further improved. As the non-porous film, since the microporous film is mainly composed of a polyurethane resin, it is preferable to use a polyurethane resin film having good adhesion to the microporous film. In order to form the nonporous film, the resin composition for forming a nonporous film may be applied to the surface of the microporous film and dried. Moreover, after apply | coating the resin composition for nonporous film formation to surface of mold release base materials, such as a release paper, and drying and obtaining a nonporous film, this may be laminated | stacked on the microporous film surface. As the resin composition for forming a nonporous film, generally, a polyurethane resin dissolved in an organic solvent is used. As the organic solvent, when the nonporous film-forming resin composition is directly applied to the surface of the microporous film, it is preferable to use a solvent having a low content of N, N-dimethylformamide or not containing it at all. preferable. This is because N, N-dimethylformamide hits the parent solvent of the polyurethane resin, and if the organic solvent is contained in a large amount, the surface layer of the microporous film may be eroded. In the case of adopting a method in which a nonporous film-forming resin composition is applied to the surface of the release substrate, and once the nonporous film is formed, it is bonded to the microporous film by thermocompression bonding or an adhesive. In this case, it is not necessary to pay attention to the content of N, N-dimethylformamide in the organic solvent, and it may be carried out in consideration of drying property, pressure bonding property, and the like.

  The viscosity of the nonporous film-forming resin composition is preferably about 100 to 10,000 mPa · s (25 ° C.) so that it can be easily applied. Moreover, it is preferable that solid content of the resin composition for non-porous film formation is about 10-30 mass%. A conventionally known method may be employed as a means for forming the nonporous film by applying the nonporous film forming resin composition. For example, using a knife coater, comma coater, reverse coater or high mesh / low depth gravure roll, the resin composition for nonporous film formation is applied to the surface of the microporous film or the release substrate, and then dried. A nonporous film may be formed.

  The thickness of the nonporous film is preferably about 0.5 to 12 μm. When the thickness of the non-porous film is less than 0.5 μm, there is a tendency that the intended improvement in water pressure resistance is insufficient. When the thickness of the nonporous film exceeds 12 μm, the moisture permeability generally decreases although it depends on the moisture permeability of the nonporous film itself.

  In the present invention, from the viewpoint of simplification of sewing and prevention of stickiness when wearing a lot of sweat, it is common to bond a lining to the surface of the microporous membrane or the nonporous membrane using an adhesive. That is, a microporous film or a nonporous film and a backing may be bonded via an adhesive. The moisture permeable and waterproof fabric thus obtained has a form in which the outer layer / microporous membrane / adhesive / lining or the outer layer / microporous membrane / nonporous membrane / adhesive / lining are laminated in this order. Yes.

  The lining is polyamide synthetic fiber or polyester synthetic fiber having a fineness of 15 to 78 dtex, or a polyamide synthetic fiber / cotton having the same fineness class as described above in consideration of cost, texture, lightness, and seam tape adhesion. Or a woven or knitted fabric made of a mixed fiber of polyester-based synthetic fiber / cotton or a nonwoven fabric is preferred. Among them, a knitted fabric or non-woven fabric made of polyamide long fibers or polyester long fibers having a fineness of 15 to 44 dtex is advantageous in terms of ease of seam tape adhesion to the sewing portion, waterproof performance of the sealing portion, and durability thereof. Therefore, it is more preferable. The seam tape is an adhesive tape that is bonded to the seam of the sewing product for the purpose of waterproofing.

  What is necessary is just to employ | adopt a conventionally well-known thing as an adhesive agent for bonding a lining. For example, natural rubber, synthetic rubber such as nitrile rubber or chloroprene rubber, vinyl acetate resin, acrylic resin, polyamide resin, polyester resin, ethylene-vinyl acetate copolymer resin, polyurethane resin, etc. alone or Used as a mixture. As the type of adhesive, it is preferable to use a curable adhesive from the viewpoint of adhesion durability. Curing adhesives include so-called crosslinkable polyurethane resins, polyester resins, polyamide resins, polyethylene-vinyl acetate copolymer resins having reactive groups such as hydroxyl groups, isocyanate groups, amino groups or carboxyl groups. It is self-crosslinked or is cured by crosslinking with a crosslinking agent such as an isocyanate compound or an epoxy compound. Among these, polyurethane-based resins are preferable because they are rich in flexibility and excellent in moisture permeability.

  Further, the properties of the adhesive may be any of an emulsion type, a solvent type and a hot melt type. In the case of an emulsion-type or solvent-type adhesive, the viscosity is set to about 500 to 5000 mPa · s, and it is applied to the entire surface of the microporous film surface, the nonporous film surface or the backing surface by a coating means such as a gravure roll or a comma coater. Apply partially. After coating, the microporous film or nonporous film and the backing may be bonded by pressure bonding or thermocompression bonding with a laminating machine. In the case of a hot-melt type adhesive, a temperature of about 80 to 180 ° C. is applied to the hot-melt type adhesive and melted, and then the entire surface is applied to the surface of the microporous film, the nonporous film or the backing surface. Or apply partially. And what is necessary is just to carry out the pressure bonding of a microporous film or a non-porous film | membrane, and a backing with a laminating machine, cooling as needed.

  As described above, the adhesive is applied to the entire surface or a part of the surface of the microporous film or the like. It is preferable to apply partially from the viewpoint of moisture permeability and texture. For example, it is preferably applied uniformly over the entire surface of the microporous membrane or the like in the form of a dot, line, checkered pattern, turtle shell pattern or the like. The area occupied by the adhesive is preferably about 10 to 80%. When the area occupied by the adhesive is less than 10%, the adhesive force becomes insufficient even if the thickness of the adhesive is increased, and the lining tends to be easily peeled off. In addition, when the area occupied by the adhesive exceeds 80%, the adhesive force tends to be sufficient, but the moisture permeation performance may be lowered. However, if a moisture-permeable polyurethane adhesive is used as the adhesive, the occupied area of the adhesive may exceed 80%. The thickness of the applied adhesive may be about 5 to 100 μm, although it depends on the area occupied by the adhesive, the unevenness of the lining and the span feeling. If the thickness of the adhesive is less than 5 μm, the adhesive strength with the backing tends to be insufficient. When the thickness of the adhesive exceeds 100 μm, the moisture permeability of the moisture permeable waterproof camouflage fabric tends to be lowered, or the texture tends to harden.

  As described above, the moisture permeable waterproof camouflage fabric according to the present invention includes the fabric body / microporous membrane, the fabric body / microporous membrane / nonporous membrane, the fabric body / microporous membrane / adhesive / lining, and the fabric body. There are various layers laminated in the order of / microporous membrane / nonporous membrane / adhesive / lining. The moisture permeable waterproof camouflage fabric may be subjected to water repellent treatment in order to further improve the water pressure resistance. The method of water repellent finishing is rarely performed by crushing, but can basically be performed in the same manner as the method of water repellent finishing of the surface. In addition, various pattern printing may be given to the microporous film, the nonporous film, or the back surface. Such pattern printing is useful when the moisture-permeable waterproof camouflage fabric is used as a material for fashion camouflage clothing, not as a material for combat clothing.

  The moisture permeable waterproof camouflage fabric according to the present invention is excellent in water pressure resistance, moisture permeability and washing durability, and as a material for combat clothes adopted by the military, as well as materials for military equipment such as tents. It can be used. Furthermore, it can also be used as a material for fashion camouflage clothing.

  The moisture permeable waterproof camouflage fabric according to the present invention is formed by laminating a microporous film mainly composed of a polyurethane resin on the back surface of a surface having a camouflage pattern on the surface, and the microporous film is made of silica. Using a resin composition for forming a microporous film comprising 15 to 45% by mass of fine powder, 1 to 9% by mass of a fluorine-based water repellent and 0.1 to 2% by mass of an oil-soluble fluorosurfactant. It is formed. For this reason, due to the presence of fine silica powder, a large number of micropores with small pore diameters are formed, and since a fluorine-based water repellent and an oil-soluble fluorine-based surfactant are used in combination, even the fine pore details can be fluorinated. A water-repellent agent is uniformly applied. In addition, when washing is repeated on a moisture-permeable waterproof camouflage fabric, the detergent remains in the micropores, but the action of the oil-soluble fluorosurfactant is not clear, but the detergent is easily detached by washing with water. To do. Therefore, although the moisture permeable waterproof camouflage fabric according to the present invention is excellent in the initial water pressure resistance and moisture permeability, the initial water pressure resistance is hardly lowered even when washing is repeated, and there is an effect that the washing durability is excellent. .

It is the graph showing the light reflectance of light green, dark green, brown, and black regarding the camouflage pattern of the moisture-permeable waterproof camouflage fabric surface obtained in Example 1 of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example. According to the present invention, when a microporous film is formed by adding a predetermined amount of silica fine powder, a fluorine-based water repellent and an oil-soluble fluorine-based surfactant in a resin composition for forming a microporous film, the durability to washing is improved. It should be interpreted as being based on the knowledge that an excellent moisture permeable waterproof camouflage fabric can be obtained.

Example 1
[Preparation of the dress material]
Nylon 6 multifilament 122dtex / 24f is used for both warp and weft, and a ripstop taffeta with a warp density of 80 / 2.54cm, a weft density of 76 / 2.54cm, and a lattice spacing of 9mm in both longitudinal and weft directions. Weaved. This ripstop taffeta is refined by a normal method, and then the taffeta surface is divided into a large number of areas, printed using the following four colors of printing solution so that the colors do not overlap, and then at 120 ° C. for 5 The camouflage pattern was applied to the taffeta surface after drying for a minute. Then, after heat-steaming at 102 ° C. for 20 minutes with a high-temperature steamer, heat treatment was further performed at 150 ° C. for 1 minute. And after water washing, it wash | cleaned for 10 minutes at 60 degreeC with the aqueous solution which consists of surfactant 1g / L and soda ash 1g / L. Then, after processing for 5 minutes at 60 degreeC with the aqueous solution which consists of the fixing agent 2g / L for nylons, and acetic acid 0.3g / L, it washed with water and dried and obtained the surface material in which the camouflage pattern was given to the surface.

<Light green printing solution>
Acid Yellow 127 0.3 parts by weight Acid Red 266 0.1 parts by weight Acid Blue 120 0.2 parts by weight Carbon black fine particles 0.04 parts by weight Guar gum (15% by weight aqueous solution) 30 parts by weight Urea 5 parts by weight Ethylene glycol 1 part by weight Part Butyl cellosolve 1 part by mass Ester-based urethane resin 8 parts by mass (“RYUDYE-W Binder UF-770” manufactured by DIC Corporation)
0.8 parts by mass of blocked isocyanate crosslinking agent (“RYUDYE-W FIXER 185” manufactured by DIC Corporation)
47.8 parts by weight of water

<Dark green printing solution>
Acid Yellow 127 1.5 parts by weight Acid Red 266 0.2 parts by weight Acid Blue 120 0.5 parts by weight Carbon black fine particles 0.1 parts by weight Guar gum (15% by weight aqueous solution) 30 parts by weight Urea 5 parts by weight Ethylene glycol 1 part by weight Part Butyl cellosolve 1 part by mass Ester-based urethane resin 10 parts by mass (“RYUDYE-W Binder UF-770” manufactured by DIC Corporation)
1 part by mass of blocked isocyanate crosslinking agent (“RYUDYE-W FIXER 185” manufactured by DIC Corporation)
50 parts by weight of water

<Brown printing liquid>
Acid Yellow 127 1.7 parts by weight Acid Red 266 1.0 part by weight Acid Blue 120 0.2 part by weight Carbon black fine particles 0.3 part by weight Guar gum (15% by weight aqueous solution) 30 parts by weight Urea 5 parts by weight Ethylene glycol 1 part by weight Part Butyl cellosolve 1 part by mass Ester-based urethane resin 10 parts by mass (“RYUDYE-W Binder UF-770” manufactured by DIC Corporation)
1 part by mass of blocked isocyanate crosslinking agent (“RYUDYE-W FIXER 185” manufactured by DIC Corporation)
50 parts by weight of water

<Black printing liquid>
Acid Black 194 8.0 parts by weight Carbon black fine particles 3.5 parts by weight Guar gum (15% by weight aqueous solution) 30 parts by weight Urea 5 parts by weight Ethylene glycol 1 part by weight Butyl cellosolve 1 part by weight Ester urethane resin 10 parts by weight (DIC Corporation) "RYUDYE-W Binder UF-770")
1 part by mass of blocked isocyanate crosslinking agent (“RYUDYE-W FIXER 185” manufactured by DIC Corporation)
44 parts by weight of water

  Subsequently, a 5% aqueous dispersion of a fluorine-based water repellent emulsion ("Asahi Guard GS10" manufactured by Asahi Glass Co., Ltd.) was applied to the outer surface by the padding method (pickup rate 40%), dried, and then 170 ° C x A 40 second heat treatment was performed. Subsequently, using a pair of calender rolls, one of which is a mirror roll, calendering was performed under the conditions of a temperature of 175 ° C., a pressure of 300 kPa, and a speed of 25 m / min so that the back surface of the outer coat was in contact with the mirror roll. As a result, the outer surface of the material was crushed and the entire surface was water-repellent.

[Preparation of resin composition for forming microporous film]
First, 30 parts by mass of an ester type polyurethane resin solution (“Lackskin 1740-29B” manufactured by Seiko Kasei Co., Ltd., solid content 28% by mass) using N, N-dimethylformamide as a solvent, hydrophobic fumed that is a fine silica powder 10 parts by mass of silica (“AEROSIL R-972” manufactured by Nippon Aerosil Co., Ltd., primary particle size 16 nm, N, N-dimethylformamide adsorption amount 260 mL / 100 g) and 10 parts by mass of N, N-dimethylformamide After kneading, uniform kneading was performed using a three-roll mill to prepare 50 parts by weight of a colorless and transparent resin solution A.

  Next, after 0.2 part by mass of an oil-soluble and water-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.) is dissolved in 42 parts by mass of N, N-dimethylformamide 6 parts by mass of a fluorine-based water repellent emulsion (“NUVA N2114 LIQ” manufactured by Clariant Japan Co., Ltd., solid content: 31% by mass) was mixed and dispersed to prepare 48.2 parts by mass of a resin solution B.

  Then, 50 parts by mass of the resin solution A, 48.2 parts by mass of the resin solution B, and an ester-type polyurethane resin solution using “N, N-dimethylformamide” as a solvent (“Lackskin 1740-29B” manufactured by Seiko Kasei Co., Ltd.), solid content 28 50 parts by mass), 2 parts by mass of a crosslinkable isocyanate compound (“Rezamin X” manufactured by Dainichi Seika Kogyo Co., Ltd.), a colorant (“DILAC GREEN L-5799K” manufactured by DIC Corporation), and a pigment content of about 20 masses. %) 8 parts by mass were mixed, and the mixture was stirred and mixed using a disper type stirrer while vacuum degassing to prepare a resin composition for forming a microporous film. This resin composition for forming a microporous film had a solid content concentration of 24% by mass and a viscosity of 11000 mPa · s / 25 ° C. Therefore, in the solid content, the silica fine powder (hydrophobic fumed silica) is contained by 28% by mass, the fluorine-based water repellent is contained by 5% by mass, and the fluorine-based surfactant is 0.6% by mass. It will be contained.

[Preparing the lining]
Using a nylon filament 22 dtex / 7 filament, a 28-gauge tricot fabric was knitted and scoured by a conventional method to prepare a lining.

[Manufacture of moisture-permeable and waterproof fabrics]
The resin composition for forming a microporous film was applied to the back surface of the outer surface (the surface on which the mirror roll contacted) with a comma coater at an application amount of 110 g / m ² . Thereafter, the polyurethane resin was coagulated by immersing in a coagulation bath made of an aqueous N, N-dimethylformamide solution (20 ° C.) having a concentration of 15% by mass for 2 minutes. Then, it was washed with hot water at 50 ° C. for 5 minutes, the surface was squeezed with mangle, and then dried at 130 ° C. for 2 minutes to form a microporous film mainly composed of polyurethane resin. Then, the setting process for 1 minute was performed at 170 degreeC, and the microporous film was formed in the surface back surface. The thickness of the obtained microporous membrane was about 30 μm, and many micropores mainly having a pore diameter of 1 μm or less were formed throughout.

Using a gravure roll (20 mesh) engraved with a dot pattern on the surface of the formed microporous membrane, a moisture-curable polyurethane resin hot melt adhesive ("Takemelt MA3229" manufactured by Mitsui Takeda Chemical Co., Ltd.) is applied. The coating was performed at 10 g / m ² . And the said lining was laminated | stacked on the application surface, and it crimped | bonded by the pressure of 300 kPa. Thereafter, aging was performed at room temperature for 3 days to obtain a moisture permeable waterproof camouflage fabric. The light reflectance of the obtained camouflage fabric is shown in FIG. According to the figure, the reflectivity varies stepwise for all colors, and in particular, the reflectivity varies with a substantially uniform difference in the wavelength region of 800 to 1200 nm. As a result, an excellent camouflage effect is exhibited. I understand that.

Example 2
[Preparation of non-porous film-forming resin composition]
The resin composition for nonporous film formation shown below was prepared. This non-porous film-forming resin composition had a solid content of 13% by weight and a viscosity of 2000 mPa · s / 25 ° C. In addition, N, N-dimethylformamide was hardly contained in the solvent of the resin composition for forming a nonporous film, and the content thereof was less than 1% by mass.
[Resin composition for non-porous film formation]
100 parts by mass of non-yellowing polyurethane resin ("Haimuren Y301-3" manufactured by Dainichi Seika Kogyo Co., Ltd.)
Isopropyl alcohol 20 parts by mass Toluene 40 parts by mass

The nonporous film-forming resin composition was applied to the surface of the microporous film obtained in Example 1 using a knife coater so that the solid content was 15 g / m ² . Then, a non-porous film having a thickness of about 2 μm was formed by drying at 120 ° C. for 2 minutes. Then, the adhesive agent was apply | coated to the nonporous film surface by the same method as Example 1, the lining was bonded, and the moisture-permeable waterproof camouflage fabric was obtained.

Comparative Example 1
[Preparation of resin composition for forming microporous film]
15 parts by weight of a colorless and transparent resin solution A prepared in Example 1, an ester type polyurethane resin solution using N, N-dimethylformamide as a solvent (“Lackskin 1740-29B” manufactured by Seiko Kasei Co., Ltd., solid content: 28% by mass) A resin composition for forming a microporous film was prepared by mixing 85 parts by mass and 35 parts by mass of N, N-dimethylformamide and stirring and adjusting the mixture using a disper type stirrer while vacuum degassing. This resin composition for forming a microporous film had a solid content concentration of 22% by mass and a viscosity of 11000 mPa · s / 25 ° C. Therefore, 10 mass% of silica fine powder (hydrophobic fumed silica) is contained in the solid content, and neither the fluorine-based water repellent nor the fluorine-based surfactant is contained.

[Manufacture of moisture-permeable and waterproof fabrics]
A moisture permeable and waterproof camouflage fabric was obtained in the same manner as in Example 1, except that the resin composition for forming a microporous film was used instead of the resin composition for forming a microporous film used in Example 1. The thickness of the microporous membrane existing between the outer material and the lining material was about 60 μm, and many holes mainly having a hole diameter of about 10 to 40 μm were formed throughout.

Comparative Example 2
[Preparation of resin composition for forming microporous film]
Mixing 100 parts by weight of the colorless and transparent resin solution A prepared in Example 1 and 40 parts by weight of N, N-dimethylformamide, and using a disper-type stirrer with vacuum degassing, the mixture is stirred to form a microporous film. A resin composition was prepared. This resin composition for forming a microporous film had a solid content concentration of 26% by mass and a viscosity of 11000 mPa · s / 25 ° C. Therefore, in the solid content, the silica fine powder (hydrophobic fumed silica) is contained in an amount of 54% by mass, and neither the fluorine-based water repellent nor the fluorine-based surfactant is contained.

[Manufacture of moisture-permeable and waterproof fabrics]
A moisture permeable and waterproof camouflage fabric was obtained in the same manner as in Example 1, except that the resin composition for forming a microporous film was used instead of the resin composition for forming a microporous film used in Example 1. The thickness of the microporous membrane existing between the outer material and the lining was about 30 μm, and many micropores mainly having a pore diameter of 1 μm or less were formed throughout.

Comparative Example 3
[Preparation of resin composition for forming microporous film]
Except for changing the amount of the fluorine-based water repellent emulsion used in Example 1 ("Asahi Guard AG710" manufactured by Asahi Glass Co., Ltd., solid content 19% by mass) from 5 parts by mass to 20 parts by mass, A resin composition for forming a microporous film was prepared by the same method. This resin composition for forming a microporous film had a solid content concentration of 23% by mass and a viscosity of 11000 mPa · s / 25 ° C. Therefore, in the solid content, 25% by mass of silica fine powder (hydrophobic fumed silica) is contained, 15% by mass of fluorinated water repellent is contained, and 0.5% by mass of fluorinated surfactant is contained. It is contained.

[Manufacture of moisture-permeable and waterproof fabrics]
A moisture permeable and waterproof camouflage fabric was obtained in the same manner as in Example 1, except that the resin composition for forming a microporous film was used instead of the resin composition for forming a microporous film used in Example 1. The thickness of the microporous membrane existing between the outer material and the lining was about 30 μm, and many micropores mainly having a pore diameter of 1 μm or less were formed throughout.

Comparative Example 4
[Preparation of resin composition for forming microporous film]
The amount of the oil-soluble and water-soluble fluorosurfactant used in Example 1 (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.) is changed from 0.2 parts by mass to 1 part by mass, A resin composition for forming a microporous film was prepared in the same manner as in Example 1. This resin composition for forming a microporous film had a solid content concentration of 23% by mass and a viscosity of 11000 mPa · s / 25 ° C. Therefore, in the solid content, silica fine powder (hydrophobic fumed silica) is contained by 27% by mass, fluorine-based water repellent is contained by 4% by mass, and fluorine-based surfactant is contained by 3% by mass. It is what.

[Manufacture of moisture-permeable and waterproof fabrics]
A moisture permeable and waterproof camouflage fabric was obtained in the same manner as in Example 1, except that the resin composition for forming a microporous film was used instead of the resin composition for forming a microporous film used in Example 1. The thickness of the microporous membrane existing between the outer material and the lining was about 30 μm, and many micropores mainly having a pore diameter of 1 μm or less were formed throughout.

With respect to the moisture-permeable and waterproof camouflage fabrics obtained in Examples 1 and 2 and Comparative Examples 1 to 4, water resistance, washing durability and moisture permeability were measured by the following methods. The results are shown in Table 1.
(1) Water pressure resistance (kPa)
It measured according to JIS L-1092 (high water pressure method).
(2) Washing durability (%)
After the washing according to JIS L-0217 (Method 103) was repeated 100 times, the water pressure resistance (B) of the moisture permeable waterproof fabric was measured, and after washing against the water pressure resistance (A) before washing according to the following formula The water pressure resistance (B) retention rate was calculated, and this value was defined as the washing durability (%) of the moisture-permeable and waterproof fabric.
Washing durability (%) = (B / A) × 100
(3) Moisture permeability (g / m ² · 24 hrs)
It measured according to JIS L-1099 A-1 method (calcium chloride method).

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Water pressure
━━━━━━━━━━━━━━
Before washing After washing 100 times Washing durability Moisture permeability ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 227 173 76 10145
Example 2 450 405 90 8796
───────────────────────────────────
Comparative Example 1 145 75 52 7650
Comparative Example 2 212 96 45 8373
Comparative Example 3 108 60 56 9879
Comparative Example 4 122 41 34 9660
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

  When Examples 1 and 2 and Comparative Examples 1 to 4 are compared, the moisture-permeable waterproof camouflage fabric according to the Examples has higher water pressure resistance and good washing durability than those according to the Comparative Examples. I understand that. The reason for this is considered as follows. The moisture permeable waterproof camouflage fabric obtained by the method according to Comparative Example 1 has a relatively large pore formed in the microporous membrane because the amount of silica fine powder used is small. Inferior in durability. The moisture permeable and waterproof fabric obtained by the method according to Comparative Example 2 uses too much silica fine powder, so that the formed microporous membrane becomes brittle. Therefore, the water pressure resistance is low and the washing durability is improved. Inferior. The moisture-permeable and waterproof fabric obtained by the method according to Comparative Example 3 has too much fluorine-based water repellent contained in the resin composition for forming a microporous film, so that there is no problem when the microporous film is formed. Arise. As a result, since the microporous film is not formed uniformly, the water pressure resistance is low and the washing durability is poor. The moisture-permeable and waterproof fabric obtained by the method according to Comparative Example 4 has a low water pressure resistance and a high washing durability because the amount of the oil-soluble fluorosurfactant contained in the microporous membrane is too large. Inferior. That is, when a predetermined amount of fine silica powder, a fluorine-based water repellent, and an oil-soluble fluorine-based surfactant are present in the microporous membrane, a high water pressure resistance can be obtained and washing durability is improved. .

  Next, the following examples and comparative examples demonstrate that a moisture-permeable waterproof fabric with good washing durability cannot be obtained unless an oil-soluble fluorosurfactant is used.

Example 11
[Preparation of the dress material]
A plain structure woven fabric having a warp density of 115 / 2.54 cm and a weft density of 95 / 2.54 cm was woven using nylon 6 multifilament 78 dtex / 68f for both the warp and the weft. The obtained plain tissue fabric was scoured and then dyed with 1.0% omf of an acid dye (“Kayanol Blue N2G” manufactured by Nippon Kayaku Co., Ltd.) to obtain a dyed fabric. Thereafter, a 5% aqueous dispersion of a fluorine-based water repellent emulsion ("Asahi Guard GS10" manufactured by Asahi Glass Co., Ltd.) was applied to the dyed fabric by the padding method (pickup rate 40%), dried, and then 170 ° C x A 40 second heat treatment was performed. Subsequently, using a pair of calender rolls, one of which is a mirror roll, calendering is performed under the conditions of a temperature of 170 ° C., a pressure of 300 kPa, and a speed of 30 m / min so that the back surface of the outer coat is in contact with the mirror roll. Got.

[Preparation of resin composition for forming microporous film]
First, 50 parts by mass of the colorless and transparent resin solution A used in Example 1 was prepared. Next, 0.2 parts by mass of an oil-soluble and water-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.) is dissolved in 40 parts by mass of N, N-dimethylformamide. 7 parts by mass of a fluorine-based water repellent emulsion (“NUVA N2114 LIQ” manufactured by Clariant Japan Co., Ltd., solid content: 31% by mass) was mixed and dispersed to prepare 47.2 parts by mass of a resin solution B.

  Then, 50 parts by mass of resin solution A, 47.2 parts by mass of resin solution B, and an ester type polyurethane resin solution using N, N-dimethylformamide as a solvent (“Lackskin 1740-29B” manufactured by Seiko Kasei Co., Ltd., solid content 28 (Mass%) 50 parts by mass and 2 parts by mass of a crosslinkable isocyanate compound ("Rezamin X" manufactured by Dainichi Seika Kogyo Co., Ltd.) are mixed with stirring using a disper type stirrer while vacuum degassing, A resin composition for forming a microporous film was prepared. This resin composition for forming a microporous film had a solid content concentration of 24% by mass and a viscosity of 10,000 mPa · s / 25 ° C. Therefore, in the solid content, the silica fine powder (hydrophobic fumed silica) is contained by 28% by mass, the fluorine-based water repellent is contained by 6% by mass, and the fluorine-based surfactant is 0.6% by mass. It will be contained.

[Manufacture of moisture permeable waterproof fabric]
The resin composition for forming a microporous film was applied to the back surface of the outer surface (the surface on which the mirror roll contacted) with a comma coater at an application amount of 90 g / m ² . Thereafter, the polyurethane resin was coagulated by immersing in a coagulation bath made of an aqueous N, N-dimethylformamide solution (20 ° C.) having a concentration of 15% by mass for 2 minutes. Then, it was washed with hot water at 50 ° C. for 5 minutes, the surface was squeezed with mangle, and then dried at 130 ° C. for 2 minutes to form a microporous film mainly composed of polyurethane resin. Thereafter, a set process was performed at 170 ° C. for 1 minute to obtain a moisture permeable waterproof fabric. The thickness of the obtained microporous membrane was about 25 μm, and many micropores mainly having a pore diameter of 1 μm or less were formed throughout.

Example 12
Instead of using 0.2 part by mass of an oil-soluble and water-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.), 0.5 parts by mass is mixed and dispersed. Otherwise, a waterproof moisture-permeable fabric was obtained in the same manner as in Example 11. Therefore, the resin composition for forming a microporous film used here had a solid content concentration of 24% by mass and a viscosity of 10,000 mPa · s / 25 ° C. Further, in the solid content, 28% by mass of silica fine powder (hydrophobic fumed silica) is contained, 6% by mass of fluorinated water repellent is contained, and 1.4% by mass of fluorinated surfactant. It will be contained.

Example 13
Instead of 0.2 parts by mass of an oil-soluble and water-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.), an oil-soluble fluorosurfactant (manufactured by AGC Seimi Chemical Co., Ltd. “ SURFLON S-611 "(This is not water-soluble.) A waterproof moisture-permeable fabric was obtained in the same manner as in Example 11 except that 0.2 parts by mass was used for mixing and dispersing. Therefore, the resin composition for forming a microporous film used here had a solid content concentration of 24% by mass and a viscosity of 10,000 mPa · s / 25 ° C. Further, in the solid content, the silica fine powder (hydrophobic fumed silica) is contained by 28% by mass, the fluorine-based water repellent is contained by 6% by mass, and the fluorine-based surfactant is 0.6% by mass. It will be contained.

Example 14
Instead of 0.2 parts by mass of an oil-soluble and water-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.), an oil-soluble fluorosurfactant (manufactured by AGC Seimi Chemical Co., Ltd. “ SURFLON S-651 "(This is not water-soluble.) A waterproof moisture-permeable fabric was obtained by the same method as in Example 11 except that 0.2 parts by mass was used for mixing and dispersing. Therefore, the resin composition for forming a microporous film used here had a solid content concentration of 24% by mass and a viscosity of 10,000 mPa · s / 25 ° C. Further, in the solid content, the silica fine powder (hydrophobic fumed silica) is contained by 28% by mass, the fluorine-based water repellent is contained by 6% by mass, and the fluorine-based surfactant is 0.6% by mass. It will be contained.

Example 15
Oil-soluble and water-soluble fluorosurfactant ("SURFLON S-386" manufactured by AGC Seimi Chemical Co., Ltd.) instead of 0.2 parts by mass Oil-soluble and water-soluble fluorosurfactant (AGC Seimi Chemical Co., Ltd.) A waterproof and moisture-permeable fabric was obtained in the same manner as in Example 11, except that 0.2 part by mass of “SURFLON S-243” manufactured by the company was used. Therefore, the resin composition for forming a microporous film used here had a solid content concentration of 24% by mass and a viscosity of 10,000 mPa · s / 25 ° C. Further, in the solid content, the silica fine powder (hydrophobic fumed silica) is contained by 28% by mass, the fluorine-based water repellent is contained by 6% by mass, and the fluorine-based surfactant is 0.6% by mass. It will be contained.

Comparative Example 11
Instead of 0.2 parts by mass of an oil-soluble and water-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.), a water-soluble fluorosurfactant (manufactured by AGC Seimi Chemical Co., Ltd. “ SURFLON S-241 ". Solid content concentration of 30% by mass. This is not oil-soluble.) A waterproof and moisture-permeable fabric is obtained by the same method as in Example 11 except that 0.6 parts by mass is mixed and dispersed. It was. Therefore, the resin composition for forming a microporous film used here had a solid content concentration of 24% by mass and a viscosity of 10,000 mPa · s / 25 ° C. Further, in the solid content, the silica fine powder (hydrophobic fumed silica) is contained by 28% by mass, the fluorine-based water repellent is contained by 6% by mass, and the fluorine-based surfactant is 0.6% by mass. It will be contained.

Comparative Example 12
Instead of 0.2 parts by mass of an oil-soluble and water-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.), a water-soluble fluorosurfactant (manufactured by AGC Seimi Chemical Co., Ltd. “ SURFLON S-241 ". Solid content concentration of 30% by mass. This is not oil-soluble.) A waterproof and moisture-permeable fabric is obtained by the same method as in Example 11 except that 1.5 parts by mass is mixed and dispersed. It was. Therefore, the resin composition for forming a microporous film used here had a solid content concentration of 24% by mass and a viscosity of 10,000 mPa · s / 25 ° C. Further, in the solid content, 28% by mass of silica fine powder (hydrophobic fumed silica) is contained, 6% by mass of fluorinated water repellent is contained, and 1.4% by mass of fluorinated surfactant. It will be contained.

Comparative Example 13
Instead of 0.2 parts by mass of an oil-soluble and water-soluble fluorosurfactant (“SURFLON S-386” manufactured by AGC Seimi Chemical Co., Ltd.), a water-soluble fluorosurfactant (manufactured by AGC Seimi Chemical Co., Ltd. “ SURFLON S-221 ". Solid content concentration of 30% by mass. This is not oil-soluble.) A waterproof and moisture-permeable fabric is obtained by the same method as in Example 11 except that 0.6 parts by mass is mixed and dispersed. It was. Therefore, the resin composition for forming a microporous film used here had a solid content concentration of 24% by mass and a viscosity of 10,000 mPa · s / 25 ° C. Further, in the solid content, the silica fine powder (hydrophobic fumed silica) is contained by 28% by mass, the fluorine-based water repellent is contained by 6% by mass, and the fluorine-based surfactant is 0.6% by mass. It will be contained.

  With respect to the moisture-permeable and waterproof fabrics obtained in Examples 11 to 15 and Comparative Examples 11 to 13, the water pressure resistance, washing durability, and moisture permeability were measured by the same method as that employed in Example 1. The results are shown in Table 2.

[Table 2]
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Water pressure
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Before washing After washing 100 times Washing durability Moisture permeability ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 11 192 136 71 11892
Example 12 180 133 74 11824
Example 13 162 115 71 11790
Example 14 152 93 61 12707
Example 15 118 78 66 12129
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Comparative Example 11 82 43 52 11391
Comparative Example 12 76 37 49 11832
Comparative Example 13 92 44 48 12206
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  When Examples 11 to 15 and Comparative Examples 11 to 13 are compared, the moisture-permeable and waterproof fabric according to the Examples has a high water pressure resistance and good washing durability as compared with those according to the Comparative Examples. I understand. The reason for this is considered as follows. All of the moisture-permeable waterproof fabrics obtained by the methods according to Comparative Examples 11 to 13 do not contain an oil-soluble fluorosurfactant in the microporous membrane, and are not oil-soluble but water-soluble fluorine-based fabrics. Since the surfactant is contained, the water pressure resistance is low and the washing durability is poor. That is, when a predetermined amount of oil-soluble fluorosurfactant, fine silica powder, and fluorophobic water repellent is present in the microporous membrane, the washing durability of the resulting moisture-permeable waterproof fabric is improved. To do.

Claims (12)

  In a moisture permeable waterproof camouflage fabric in which a microporous membrane mainly composed of a polyurethane resin is laminated on the back surface of the outer surface having a camouflage pattern on the surface, the microporous membrane has a silica fine powder of 15 to 45 mass%. Further, a moisture-permeable waterproof camouflage fabric containing 1 to 9% by mass of a fluorine-based water repellent and 0.1 to 2% by mass of an oil-soluble fluorine-based surfactant.   The camouflage pattern is printed by dividing at least three kinds of colors, and the light reflectance at 600 to 1200 nm of each color is in the range of 2% to 65%, and different reflectances. The moisture-permeable waterproof camouflage fabric according to claim 1.   The moisture permeable waterproof camouflage according to claim 1, wherein the fluorosurfactant has a hydrophobic group composed of a perfluoroalkyl group having 1 to 6 carbon atoms and a hydrophilic group composed of a polyoxyethylene group or a polyoxypropylene group. Fabric.   The moisture permeable waterproof camouflage fabric according to claim 1, wherein the silica fine powder is fumed silica fine powder.   The moisture-permeable and waterproof camouflage fabric according to claim 1, wherein the fluorine-based water repellent is obtained by polymerizing an acrylate compound having a perfluoroalkyl group having 1 to 6 carbon atoms in the side chain.   The moisture permeable waterproof camouflage fabric according to claim 1, wherein at least the back surface of the outer material is water repellent.   The moisture-permeable waterproof camouflage fabric according to claim 1, wherein a non-porous membrane mainly comprising a polyurethane resin is laminated on the surface of the microporous membrane.   The moisture permeable waterproof camouflage fabric according to claim 1, wherein the microporous membrane and the lining are bonded via an adhesive.   The moisture permeable waterproof camouflage fabric according to claim 8, wherein the non-porous membrane and the lining are bonded through an adhesive.   On the back surface of the outer surface with a camouflage pattern on the surface, polyurethane resin is the main component, silica fine powder 15 to 45 mass%, fluorine-based water repellent 1 to 9 mass%, and oil-soluble fluorine-based surfactant. After applying a resin composition for forming a microporous film in which 1-2% by mass is dissolved or dispersed in N, N-dimethylformamide, it is immersed in an aqueous solution containing 5-30% by mass of N, N-dimethylformamide. A method for producing a moisture-permeable and waterproof camouflage fabric, wherein the microporous film is formed by solidifying the resin composition for forming a microporous film.   A method for producing a moisture-permeable and waterproof camouflage fabric, wherein a microporous membrane is formed by the method according to claim 10 and then the microporous membrane and a backing are bonded with an adhesive.   A microporous film is formed by the method according to claim 10, and then a nonporous film mainly comprising a polyurethane resin is formed on the surface of the microporous film, and then the nonporous film and the backing are bonded with an adhesive. A method of manufacturing a moisture permeable waterproof camouflage fabric.

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