JP4760040B2 - Moisture permeable waterproof film and moisture permeable waterproof composite material - Google Patents

Description

  The present invention relates to a moisture permeable waterproof film and a moisture permeable waterproof composite material that can be manufactured in a low environmental load process by using a polymer that has excellent moisture permeability, waterproofness and material durability, and can be water-based. It is about. More specifically, the present invention is combined with woven or knitted fabric, non-woven fabric, paper, porous film, existing moisture permeable waterproof material, porous board, etc., and outdoor wear such as fishing and mountaineering clothing, ski related wear, windbreaker. , Athletic wear, golf wear, tennis wear, rainwear, casual coat, outdoor work clothes, clothing such as gloves and shoes, clothing materials, wallpaper, roofing waterproof sheets, building materials such as tiles, film base materials for dehumidifiers, etc. The present invention relates to a moisture permeable waterproof film and a moisture permeable waterproof composite material that can be suitably used in the non-clothing field such as electrical equipment members.

  Conventionally, in order to obtain a moisture permeable waterproof film and a moisture permeable waterproof composite material excellent in moisture permeability and waterproofness, a hydrophilic portion is introduced into the polymer chain, or a highly moisture permeable hydrophilic property in a low moisture permeable resin. A method of blending resins has been employed, and in any case, various studies have been made by modifying polymers in solvent-based resins and polymer blending (see Patent Document 1 and Patent Document 2).

In recent years, VOC (Volatile Organic Compounds) regulations have been implemented in consideration of the global environment, and water-based organic solvents, which are resin solvents, are desired. Some applications of water-based resins in moisture-permeable and waterproof composites are also being considered. (See Patent Document 3 and Patent Document 4). However, there is still no technology that can achieve both moisture permeability and waterproofness as in the case of using a solvent-based resin, and no current technology has been found that has a performance that can withstand practical use. Moreover, there is no technology that has material durability in addition to practical performance. That is, in the case of a water-based resin, a method of introducing a hydrophilic portion into a polymer chain like a solvent-based resin, or blending a highly moisture-permeable hydrophilic resin with a low moisture-permeable resin, Since the film strength is remarkably lowered, it is extremely difficult to achieve both material performance and material durability.
Japanese Patent Laid-Open No. 7-9631 (Japanese Patent No. 3212418) Japanese Patent Laid-Open No. 7-3148 (Japanese Patent No. 3272467) JP-A-1-97272 JP-A-1-97274 (Patent No. 2592465)

  Therefore, in view of the above-described present situation, the present invention provides a moisture permeable waterproofing that can be manufactured by a low environmental load process by using a polymer that has excellent moisture permeability, waterproofness, material durability, and water-based properties. It aims at providing a film and a moisture-permeable waterproof composite material.

  In order to solve the above-described problems, the present invention has the following configuration.

That is, the moisture-permeable waterproof film of the present invention comprises a resin layer containing two or more resins containing bishydroxyalkyl fatty acid and alkylene glycol as polymerization components, and the bishydroxyalkyl fatty acid is 0.08 mmol / g and 0.5 mmol / g or less, at least one of the alkylene glycols is polyethylene glycol, and the polyethylene glycol is contained in an amount of 20 μm or more and 60 wt% or less with respect to the resin solid content, and the average film thickness is 20 μm. The moisture permeability according to JIS L-1099, potassium acetate method (B-1 method) is 3 × 10 ³ g / m ² · 24 h or more and 200 × 10 ³ g / m ² · 24 h or less. It is a moisture waterproof film.
According to a preferred embodiment of the moisture permeable waterproof film of the present invention, the alkylene glycol is an alkylene glycol having 3 to 12 repeating units of alkylene units, and both of the two types of resins are It is a polyurethane resin.

According to a preferred embodiment of the moisture-permeable waterproof film of the present invention, the moisture-resistant waterproof film has a water pressure resistance of 0.1 MPa or more and 1.0 MPa or less according to JIS L-1092, the water pressure resistance method. The dispersion diameter of the resin is 2 μm or less.
The moisture-permeable and waterproof composite material of the present invention has the moisture-permeable and waterproof film provided on at least one surface of the substrate, and has a moisture permeability of 1 according to JIS L-1099, potassium acetate method (B-1 method). It is a moisture-permeable and waterproof composite material of not less than × 10 ³ g / m ² · 24 h and not more than 50 × 10 ³ g / m ² · 24 h.
Moreover, according to the preferable aspect of the moisture-permeable waterproof composite material of this invention, the water-resistant pressure retention after 24 hours washing of a moisture-permeable waterproof composite material is 80% or more and 100% or less.

  According to the present invention, it is possible to obtain a moisture-permeable and waterproof composite material that can be manufactured by a low environmental load process by using a resin that is excellent in moisture permeability, waterproofness, material durability, and water-based. Can do. Furthermore, further improvement in performance can be achieved by controlling the dispersion state of the resins in the film.

  In the present invention, a resin layer containing two or more kinds of resins containing bishydroxyalkyl fatty acid and alkylene glycol as polymerization components is used.

  The resin layer containing two or more types of resins containing bishydroxyalkyl fatty acid and alkylene glycol as polymerization components refers to a resin layer composed of two or more different types of polymers containing these polymerization components.

  The bishydroxyalkyl fatty acid used in the present invention is a compound in which two hydroxyalkyl groups are bonded to the main chain of the alkyl fatty acid. Specific examples of the bishydroxyalkyl fatty acid include 2,2-bishydroxymethylpropionic acid and 2,2-bishydroxymethylbutanoic acid, but the carbon number of the hydroxyalkyl group part is the same, but the carbon of the alkyl fatty acid part. Compounds with increased numbers, and compounds with the same number of carbon atoms in the alkyl fatty acid moiety, such as 2,2-bishydroxyethylpropionic acid and 2,2-bishydroxypropylpropionic acid, but with an increased number of carbon atoms in the hydroxyalkyl group However, the present invention is not limited to these.

  In the present invention, the bishydroxyalkyl fatty acid contained in the resin layer is 0.08 mmol / g or more and 0.5 mmol / g or less with respect to the resin solid content. From the viewpoint of improving the blendability of the resins, the content of each of the two or more resins is preferably 0.16 mmol / g or more and 0.33 mmol / g or less, and the difference in content between the two or more resins is 0. 0.08 mmol or less is preferable.

The amount of bishydroxyalkyl fatty acid mentioned here is included in the polymer constituting the resin as a polymerization component, and the amount contained in the polymer is within this range, thereby improving the blendability between the resins and the film strength. Therefore, both moisture permeability and water resistance can be achieved.
Further, the amount of bishydroxyalkyl fatty acid can be represented by an acid value (mgKOH / g) when titrated with potassium hydroxide. In terms of the acid value, in the case of the present invention, it is 5 or more and 30 or less. From the viewpoint of improving the blendability of the resins, the two acid values are preferably in the range of 10 to 20, and the difference between the acid values of the two or more resins is preferably 5 or less.

  Alkylene glycol is a compound in which both ends of an alkyl chain are hydroxyl groups, specifically, ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc. Examples of such compounds include, but are not limited to, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol and polyhexamethylene glycol.

  Further, the alkylene glycol may be included as a part of the polyester diol or the polycarbonate diol.

In the present invention, it is preferable that the polyalkylene glycol is contained in an amount of 40 wt% or more and 80 wt% or less with respect to the solid content of the resin from the viewpoint of achieving both function expression and film strength.
The introduction site of the alkylene glycol is not limited to the main chain or side chain of the polymer, but it is preferably contained in the main chain from the viewpoint of effect expression. By containing alkylene glycol in this range in the polymer component constituting the resin, it becomes possible to soften the film by lowering the Tg and to increase the moisture permeability by improving the mobility of the polymer.

  From the viewpoint of achieving both high moisture permeability and film strength, a polyalkylene glycol having a number average molecular weight of 500 or more and 3000 or less is preferable, and the number average molecular weight is preferably 800 or more and 2500 or less.

  In the present invention, at least one of the alkylene glycols is polyethylene glycol, and it is important that the polyethylene glycol is contained in an amount of 20 wt% to 60 wt% with respect to the weight of the resin layer. When at least one of the alkylene glycols is polyethylene glycol, the moisture permeability of the coating can be dramatically improved. The moisture permeability improves if the polyethylene glycol content is high, but the content is preferably 30 to 50 wt% from the viewpoint of film strength and durability. From the viewpoint of achieving both high moisture permeability and film strength, the number average molecular weight of polyethylene glycol is preferably 800 or more and 2500 or less. From the viewpoint of improving moisture permeability, it is preferable that polyethylene glycol is contained in all of the resins constituting the film, but it may not be preferable from the viewpoint of film strength. By making only a specific resin highly hydrophilic, other resins to be blended can be made into a highly hydrophobic resin with stronger membrane strength, and both the moisture permeability and membrane strength can be balanced as the overall performance balance of the film. It becomes easy.

  Examples of the resin used in the present invention include polymers typified by polyurethane-based, polyester-based, polyamide-based, acrylic-based, silicone-based, and the like, or copolymers composed of two or more of these polymers. However, it is not limited to these.

The moisture-permeable waterproof film of the present invention has a moisture permeability of 3 × 10 ³ g / m ² · 24 h or more, 200 × 10 ³ g / 200 JIS L-1099 at a film thickness of 20 μm, potassium acetate method (B-1 method). m ² · 24h or less. The moisture permeability is preferably 8 × 10 ³ g / m ² · 24 h or more and 200 × 10 ³ g / m ² · 24 h or less.
By controlling the moisture permeability within this range by the above-described polymer configuration, the film can be developed for various uses when it is a single film or a laminate. The moisture permeability can be adjusted by adjusting the content of polyalkylene glycol, particularly polyethylene glycol. In order to reduce the moisture permeability, the amount of polyethylene glycol is decreased, and in order to increase the moisture permeability, the content of polyethylene glycol may be increased.
Structure of waterproof breathable film is not particularly limited, non-porous film alone, a porous membrane alone, but such as a multilayer film of the laminated film and non-porous film / porous film of the same kind film each other like limited thereto It is not a thing.

The film thickness referred to here is the thickness of the film itself, and in the case of being laminated on a support or a substrate, it means a value obtained by subtracting the thickness of the support or the substrate from the laminate. Thickness is calculated | required by the method of directly measuring a film, a laminated body, etc. with a peacock, the method of observing a cross section by SEM.
The moisture permeability at a film thickness of 20 μm means, for example, that the moisture permeability of a film having a thickness of 50 μm is 3 × 10 ³ g / m ² · 24 h by the above-described method, and the moisture permeability of a film having a thickness of 10 μm is 100 × 10. ^{In the case of 3} g / m ² · 24 h, the moisture permeability at a film thickness of 20 μm referred to in the present invention is
The former is (3 × 10 ³ g / m ² · 24 h) ÷ (50 μm / 20 μm) = 1.2 × 10 ³ g / m ² · 24 h, and the latter is (20 μm / 10 μm) × (100 × 10 ³ g / m ² · 24h) = 50 × 10 ³ g / m ² · 24h.
The film thickness of the moisture permeable waterproof film of the present invention may be adjusted to a thickness suitable for the application, and is not particularly limited. However, from the viewpoint of film strength and film formability, 3 μm to 300 μm, preferably 10 μm to 100 μm. It is.

  In the present invention, the polyalkylene glycol is preferably a polyalkylene glycol having 3 to 12 carbon atoms in the alkylene unit. When the number of carbon atoms of the alkylene glycol constituting the polymer is within this range, blendability with a polymer containing polyethylene glycol having high hydrophilicity can be further improved, and polyalkylene glycol having higher hydrophobicity should be used. It can also contribute to improving the film strength. The number average molecular weight of the polyalkylene glycol is preferably 800 or more and 2500 or less, and the number of carbon atoms is preferably 4 to 6 from the viewpoint of achieving both film strength and moisture permeability. Among these, the polyalkylene glycol is polytetramethylene glycol. Or hexamethylene glycol is preferable.

  Furthermore, in the present invention, it is preferable that the two kinds of resins are both polyurethane resins. Excellent texture in the case of a resin film alone, texture in the case of lamination on a substrate, excellent stretchability, and excellent conformability between films even when films with different film thicknesses are laminated. This is because the adhesion between the films is excellent.

  The polyurethane-based resin contains a copolymer obtained by reacting polyisocyanate and polyol as a main component. In the case of a water-based resin, a bond such as a urea bond is introduced during chain extension by a diamine, which may result in a polyurethane urea, but may contain a urea moiety.

  As the isocyanate component, aromatic polyisocyanate, aliphatic polyisocyanate alone or a mixture thereof can be used.

Examples of the isocyanate component include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate.
Moreover, as a polyol component, polyether type polyol, polyester type polyol, polycarbonate type polyol, etc. can be used. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyhexamethylene glycol. Polyester polyols include diols such as ethylene glycol and propylene glycol, adipic acid, sebacic acid, terephthalic acid, and isophthalic acid. Aromatic polycarbonates, aliphatic polycarbonates and the like synthesized by the phosgene method, transesterification method, etc. can be used as polycarbonate-based polyols, such as reaction products with dibasic acids and ring-opening polymers such as caprolactone. In addition, ether / ester systems, amide systems, silicone systems, fluorine systems, various copolymer systems, and the like can be used as appropriate, but the present invention is not limited to these.

  As the polyisocyanate, 4,4′-diphenylmethane diisocyanate and 4,4′-methylenebis (cyclohexyl isocyanate) are preferable from the viewpoint of the strength, solvent resistance, and light resistance of the resin film. From the viewpoint of strength and hydrolysis resistance, polytetramethylene glycol, polyhexamethylene glycol, and polyhexamethylene carbonate are preferable, and from the viewpoint of moisture permeability, a polyurethane resin mainly composed of polyethylene glycol is preferable.

  Moreover, in this invention, it is preferable that the water-proof pressure by a water-permeable waterproof film of JISL-1092 and a water-pressure-proof method is 0.1 MPa or more and 1.0 MPa or less. In addition to the moisture permeability described above, it also has water resistance, so that it can be developed for more applications.

Furthermore, in the moisture permeable waterproof film of the present invention, a higher performance moisture permeable waterproof film can be obtained by setting the dispersion diameter of the resin to 2 μm or less in the observation of the film cross section. That is, the moisture permeable waterproof film of the present invention can exhibit very high performance even when the resin dispersion diameter is large, but the present inventors can further improve the film performance by controlling the dispersibility of the resin. I found it.
In the present invention, the film cross section is a cross section in the thickness direction of the film, and the section refers to a thin piece cut in the length or width direction. “Observation” here means that the surface of the thin piece is observed in the direction perpendicular to the cross section of the film (the length or width direction of the thin piece).
The dispersion diameter of the resin being 2 μm or less means that the size of the resin mass observed in the surface observation is 2 μm or less. The smaller the dispersion diameter, that is, the closer to 0 μm which is a compatible state, the higher performance can be expressed. Dispersion diameter of resin substantially compatible to that 0μm or more, 2 [mu] m or less, preferably 0μm or more, under 0.5μm or less.
The dispersion diameter here can be measured by observing the cross section of the film with an optical microscope, SEM (scanning electron microscope), TEM (transmission electron microscope) or the like. For example, the cross section in the direction perpendicular to the thickness direction of the film cross section selected arbitrarily at five locations is observed with a SEM at a magnification capable of observing the dispersion diameter of the resin lump in the range of 500 to 20000 magnification. An average value of the maximum diameter Y in the vertical direction and the maximum diameter X in the horizontal direction may be set as the dispersion diameter. If it is difficult to observe the resin mass, the resin portion may be dyed and observed with a dye, osmium oxide or the like.
The moisture-permeable and waterproof composite material of the present invention is formed by providing the moisture-permeable and waterproof film on at least one surface of a base material, and the moisture permeability by L-1099, potassium acetate method (B-1 method) is 1 × 10. It is a moisture permeable and waterproof composite material of ³ g / m ² · 24 h or more and 50 × 10 ³ g / m ² · 24 h or less. Furthermore, the moisture permeability is preferably 8 × 10 ³ g / m ² · 24 h or more, more preferably 50 × 10 ³ g / m ² · 24 h or less , in terms of comfort and the range of material application. There is . The moisture permeability of the moisture permeable and waterproof composite material depends on the moisture permeability of the base material itself, but as described above, it is controlled by the moisture permeability of the film itself by adjusting the polymer recipe, the film thickness adjustment, the film adhesion method, etc. be able to.
When the moisture permeable waterproof film is provided on at least one surface of the substrate, the moisture permeable waterproof film of the present invention is laminated on at least one surface of the substrate and covers a part or all of one surface of the substrate. Say. Here, the coating is preferably a continuous coating with a continuous layer, but may be a discontinuous layer depending on the purpose of use.

  Examples of the base material include woven and knitted fabrics made of fibers, non-woven fabrics, paper, porous films, existing moisture-permeable and waterproof materials, and sheet-like materials such as porous boards, but the present invention is not limited thereto. is not.

  When coating a substrate with a moisture permeable waterproof film, a method of forming a film by casting or coating a resin solution prepared for the moisture permeable waterproof film on the substrate, or preparing a moisture permeable waterproof film in advance. The moisture-permeable and waterproof composite material of the present invention can be obtained by a method of laminating it on a substrate.

  When the film structure of the moisture permeable waterproof film is a porous film, a method of making the film thickness a discontinuous layer, a method of selectively aggregating by adding a water-soluble solvent, etc., an elution component in the coating liquid A porous film can be formed by a method suitable for the purpose, such as a method of adding a water-soluble substance or the like and eluting the film after film formation.

  In the case of coating, generally, coating formulations such as knife over roll coating, direct roll coating, reverse roll coating and gravure coating are used, and the coating amount is appropriately set on the substrate so as to obtain a desired film thickness. You just apply.

  As for the heat treatment conditions, the low temperature drying requires a long time and there is a risk that crosslinking and the like may be insufficient, and the high temperature drying may cause resin deterioration. The treatment time is preferably 0.5 minutes to 10 minutes.

  In order to improve the adhesiveness between the resin constituting the moisture permeable waterproof film and the substrate, various methods can be utilized. A method of roughening the surface of the substrate, a method of undercoating or primer treatment, and the like can be appropriately used depending on the purpose, but the present invention is not limited to these. In the case of undercoat or primer treatment, if a crosslinking agent such as blocked isocyanate is added to the treatment agent, cross-linking is formed between the resin layer and the substrate even after the coating liquid is laminated on the substrate. The sex is further improved.

  Further, when the resin layer is prepared in advance and laminated, the resin liquid may be formed on the release support and then laminated on the base material using an adhesive or the like. The mold release support means a taffeta fabric, film, paper, or the like that has a smooth surface and a low affinity for the resin film that the surface forms on the support. Usually, release paper or film coated with a release agent such as silicone resin, release paper laminated with polypropylene, and the like are preferably used.

  In order to apply a resin liquid onto a release support and form a film, generally, a coating formulation such as knife over roll coating, direct roll coating, reverse roll coating, and gravure coating is used to obtain a desired film thickness. The coating amount may be appropriately set on the mold release support so that the film is coated, dried, and formed into a film.

  In order to make the resin into a continuous layer, a knife coating method is suitable. By repeatedly applying and forming a film on the resin layer formed into a film, a laminated resin layer can be formed.

The moisture permeable waterproof composite material having the moisture permeability and waterproof property of the present invention can be obtained by selecting a substrate according to the final application purpose and providing a resin layer on the substrate.
When the resin layer is colored, an inorganic pigment or an organic pigment can be appropriately added to the resin liquid.

  When improving the lubricity of the surface of the resin layer, inorganic particles such as silica, titanium oxide and alumina, a method of directly adding organic particles such as polyurethane and acrylic into the film, inorganic particles such as silica, titanium oxide and alumina In addition, a method of applying a resin containing organic particles such as polyurethane and acrylic in a dot shape on the film surface to form an unevenness and reducing the scratched area can be appropriately used.

  Furthermore, it is preferable that the moisture-permeable waterproof composite material of the present invention has a water pressure resistance retention rate after washing for 24 hours of 80% or more and 100% or less. As described above, by providing the above-mentioned moisture permeability and water resistance as well as a water pressure resistance retention rate, it can be developed for more applications.

  In order to improve the water pressure retention rate, it is preferable that the resin layer has two or more different crosslinked structures. When the resin layer has a cross-linked structure, the resin polymer constituting the resin layer has a cross-linkable terminal functional group, and when the polymers are cross-linked, a cross-linking agent having a cross-linkable terminal functional group is used. It means a case where polymers are cross-linked by intervening. Having two or more types of cross-linked structures means that there are two or more types of cross-linked structures.

  Examples of the terminal functional group having crosslinkability include an isocyanate group, an epoxy group, a silanol group, a methylol group, and an oxazoline group, but the present invention is not limited thereto.

  Examples of the cross-linked terminal corresponding to the cross-linking terminal group include a hydroxyl group, an amino group, and a carboxyl group in addition to the same terminal, but the present invention is not limited thereto.

From the viewpoint of film strength, the terminal functional group having crosslinkability preferably has a structure capable of crosslinking with other polymers. For example, if the terminal of the polymer is a structure such as a hydroxyl group, an amino group, or a carboxyl group, a polyisocyanate compound can be suitably used. In particular, 4,4′-diphenylmethane diisocyanate or 4,4′-diphenylmethane diisocyanate can be used to improve the film strength. A polyisocyanate compound containing 4'-methylenebis (cyclohexyl isocyanate) as a main component can be preferably used. Among these, a block type aqueous polyisocyanate compound in which a functional group capable of reacting with a terminal functional group having crosslinkability is blocked is preferably used.
From the viewpoint of film forming properties, the dissociation temperature of the block is preferably 80 to 180 ° C, more preferably 100 to 140 ° C.

  From the viewpoint of improving the adhesion to the base material, the crosslinkable terminal functional group can preferably use a structure capable of cross-linking with the polymer and the base material. Among them, a compound having a methylol group, for example, a methylolated melamine-based cross-linking agent. Can be suitably used.

  The addition amount of the crosslinking agent may be determined based on the total performance (moisture permeability, water resistance, durability, etc.) required for the moisture permeable waterproof composite material, but is generally 0.1 to 10 wt. % Addition is preferred. Moreover, as a terminal functional group which has the crosslinkability which a polymer has, a silanol group etc. are preferable from a viewpoint of heat resistance, a weather resistance, and a soft improvement.

  From these facts, high moisture permeability, high water resistance, and high water pressure retention when made into a composite material are improved water permeability due to high hydrophilicity of the polymer and hydrophobic polymer with high film strength. In combination with the functional complementation and optimal cross-linking method.

  Next, the manufacturing method of the moisture-permeable waterproof film and moisture-permeable waterproof composite material of this invention is demonstrated.

  In the present invention, when the resin layer obtained by removing the solvent of the coating liquid containing the resin for the moisture permeable waterproof film is provided on the substrate, the organic solvent contained in the coating liquid is added to the resin solid content weight. On the other hand, the content is preferably 0% by weight or more and 10% by weight or less, and is preferably coated on a substrate, formed into a film, and laminated.

  In the coating liquid used in the present invention, the content of the organic solvent is 0% by weight or more and 10% by weight or less, preferably 0% by weight or more and 3% by weight or less, based on the resin solid content weight. By regulating the amount of organic solvent, the amount of organic solvent discharged during film formation can be greatly reduced compared to the processing of conventional solvent-based resins, and the burden on the environment is reduced.

  The organic solvent here is a solvent or compatibilizer that dissolves the resin, is contained in the coating liquid as a film-forming aid, etc., and is an aromatic compound such as toluene, benzene, xylene, isopropanol, acetone, Examples include, but are not limited to, aliphatic compounds such as methyl ethyl ketone, N, N-dimethylformamide, and N-methyl-2-pyrrolidone.

The content of the organic solvent contained in the resin solution includes the resin solid content weight contained in the resin solution, the weight of the organic solvent contained in the resin solution quantified by gas chromatography, etc., and the resin coating amount, It can be calculated from the weight of the organic solvent generated up to the same coating amount.

  The main component of the solvent other than the organic solvent is preferably water. By setting the water to 25 wt% or more and 1900 wt% or less with respect to the resin solid content weight, a good coating solution can be prepared while the content of the organic solvent is 0 wt% or more and 10 wt% or less.

  From the above, a water-based resin can be suitably used for the resin used in the present invention.

  As the water-based resin here, a compulsory emulsification resin obtained by forcibly emulsifying a polymer having no emulsification property or water solubility using a surfactant or the like, a self emulsification resin obtained by emulsifying and dispersing a polymer having self emulsification property, Examples thereof include water-soluble resins in which a water-soluble polymer is dissolved.

  In this invention, the film which consists of resin which satisfy | fills the structure of the above-mentioned this invention among these resins is utilized.

  In the present invention, from the viewpoint of moisture permeability, water resistance, and film strength, it is preferable that at least one resin is a self-emulsifying resin or a water-soluble resin that contains little surfactant or the like, and more preferably self-emulsifying property. Resins in which the resins are blended with each other, water-soluble resins, or a self-emulsifiable resin and a water-soluble resin can be suitably used.

  Self-emulsifying means that the resin is in a dispersed state having a particle size at the resin liquid stage. Water-soluble means that the resin does not have a particle size and is in a dissolved state at the stage of the resin liquid.

  Specifically, the presence / absence of the particle size can be measured as an average particle size by a light scattering method using a helium-neon light source. In the case of a self-emulsifying resin, the particle size is 10 nm or more and 200 nm or less. The particle diameter is preferably 40 nm or more and 100 nm or less. Similarly, in the case of a water-soluble resin, the particle diameter means a particle diameter of 10 nm or more and 200 nm or less, and the water-soluble resin means that a particle having such particle size is not detected.

  In order to satisfy the constitution of the present invention and the resin itself is self-emulsifying or water-soluble, for example, in the molecular structure, an ionic dissociation group which is a hydrophilic group (for example, carboxyl group or a salt thereof, sulfonic acid group or Salt, sulfonate group, carbamoyl sulfonate group, quaternary amino group or quaternary ammonium salt), nonionic group [eg, polyoxyalkylene group (eg, polyoxymethylene, polyoxyethylene group, etc.), epoxy group, etc. ] May be introduced, but the present invention is not limited to these.

  As the hydrophilic group, as described above, an anionic group which is an ionic dissociation group is preferable, and among them, a carboxyl group or a salt thereof is preferable.

From the viewpoint of film forming property, the carboxyl group is preferably a salt neutralized with an organic amine compound such as triethylamine. In the present invention, the dihydroxyalkyl fatty acid of the polymer is previously neutralized with triethylamine or the like to form an aqueous system. The resin solution obtained can be suitably used.
Moreover, in this invention, the dispersibility of the resin lump in a moisture-permeable waterproof film can be improved with the following methods. For example, in a water-based resin or the like, a highly dispersed state can be maintained even after film formation by optimizing the charge state of the resin solution to create a highly dispersed state at the resin solution stage. Specifically, by adding a lower alkyl fatty acid such as acetic acid or propionic acid to the resin liquid and adjusting the pH, the dispersibility of the resins at the resin liquid stage can be enhanced. Regarding the dispersibility, it can be considered that the dispersibility is increased if the transmissivity is improved by measuring the light transmissivity of the resin liquid.
The moisture-permeable and waterproof film of the present invention can be suitably used for building materials such as wall materials and roof tiles, life-related material members such as dehumidifier base materials, etc. by using the film alone or in combination with the base material according to the application. Moreover, as a moisture permeable and waterproof composite material by combining with a base material such as fiber material, outdoor wear such as fishing and mountaineering clothing, ski related wear, windbreaker, athletic wear, golf wear, tennis wear, rain wear, casual coat, It is suitably used for outdoor work clothes, clothing such as gloves and shoes, and clothing materials.

  Hereinafter, the moisture-permeable waterproof film and moisture-permeable waterproof composite material of the present invention will be specifically described with reference to examples. In addition, the base fabric used for this invention and the evaluation method are as follows.

[Base material]
(1) Use of nylon taffeta thread 77 decitex-68 filament (vertical, horizontal)
Weaving density 116 × 88 / cm
Weight per unit: 72g / m ²
(2) Polyester taffeta thread use 84 dtex-72 filament (vertical, horizontal)
Weaving density 110 × 37 / cm
150 g / m ²
(3) Nylon nonwoven fabric fineness 11 dtex / filament basis weight 110 g / m ²
(4) Polyethylene porous net weight 29g / m ²
Thickness 0.12mm
Water repellent treatment (AG925 (Asahi Glass Co., Ltd.), which is a fluorine-based water and oil repellent agent, in the base materials of the above (1) to (3) and the above (5) to (6), which does not pass through after the resin liquid is applied. Product name) treated with 4% aqueous dispersion) and used so that the water repellency is 3 or more after 20 home washings. In addition, about the base material of said (2), the prescription which added 2 parts of water-soluble block isocyanate type crosslinking agents with respect to water repellent solid content was used.

[Moisture permeability]
Measured according to JIS L-1099 potassium acetate method (B-1 method).

[water resistant]
It measured according to JIS L-1092 high water pressure method. In the case of the film alone, the film was mounted and measured by the same method so that water pressure was applied to the film surface in a state of being combined with the support.
[Water pressure retention]
Washing machine MAYTAG CLOTHE WASHER (model: LAT9206AAE)
Bath ratio 1:50
The water pressure resistance after 24 hours of continuous washing in a water-washed state without adding a surfactant was measured, and the percentage (%) with respect to the water pressure resistance when not washed was defined as the retention rate. However, for those with a water pressure pressure exceeding 0.3 MPa, the retention rate was calculated with 0.3 MPa as the upper limit.

[Resin dispersion diameter measurement]
The film was hung in a stainless steel sealed container (volume: 8000 cm ³ ), 10 cc of a 10 wt% aqueous solution of osmium oxide (VIII) was placed, and dyeing was performed in the gas phase at a temperature of 60 ° C. for 8 hours. A thin piece of a dyed film was prepared and magnified 10,000 times with a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.), and a reflected electron image was observed and used as a photographic image. The average value of the maximum diameter Y in the vertical direction and the maximum diameter X in the horizontal direction of the resin mass observed arbitrarily in the image was calculated as the dispersion diameter.
[ Reference Example 1]
4,4'-methylenebis (cyclohexyl isocyanate) was used as the polyisocyanate component, 2,2-bishydroxymethylpropionic acid as the bishydroxyalkyl fatty acid was 0.248 mmol / g based on the resin solids, and the number average as the polyalkylene glycol component A water-soluble resin composed mainly of a water-soluble polyurethane containing a silanol group as a terminal functional group having crosslinkability, synthesized from polyethylene glycol having a molecular weight of 1000 so as to be 67.2 wt% based on the resin solid content, and a polyisocyanate component 4,4'-methylenebis (cyclohexyl isocyanate), 2,2-bishydroxymethylbutanoic acid as bishydroxyalkyl fatty acid, 0.295 mmol / g based on resin solids, and number average content as alkylene glycol component Using “Resamine D2060” (trade name, registered trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.) whose main component is a self-emulsifying polyurethane synthesized using polytetramethylene glycol in an amount of 2000, each solid content Were mixed so as to have an equal weight to prepare a blend resin having a solid content of 27 wt%. The bishydroxyalkyl fatty acid contained in the blend resin solids was 0.256 mmol / g, and the polyethylene glycol was 33.6 wt%.

  “Sumitex Resin M-3”, a melamine-based crosslinking agent having a methylol group at the reactive end, as a crosslinking agent for the solid content of the blend resin (trade name, registered trademark 2 wt%, manufactured by Sumitomo Chemitex Co., Ltd.) 5.6 wt% of “BN-69” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a blocked isocyanate-based crosslinking agent having an isocyanate group at the reactive end, is added as a lubricant for the resin layer surface. Then, 10 wt% of porous silica having an average particle size of 2.7 μm was added to the solid content of the blend resin, stirred with a mixer, defoamed, and used as a coating solution.

The adjusted coating solution was coated on a polyester film with a roll-on-knife system with a clearance of 0.1 mm. After coating, it is dried for 2 minutes at a temperature of 140 ° C. using a hot air dryer, further heat-treated at a temperature of 160 ° C. for 2 minutes, after film formation, peeled from the polyester film, and aged at room temperature for 48 hours. A moisture permeable waterproof film was obtained. The film thickness was 20 μm. Table 1 shows the composition and the like, and Table 3 shows the results. Table 2 shows the composition of the moisture-permeable and waterproof composite material of the present invention, and Table 4 shows the results.
[Reference Example 2]
4,4'-methylenebis (cyclohexyl isocyanate) was used as the polyisocyanate component, 2,2-bishydroxymethylpropionic acid as the bishydroxyalkyl fatty acid was 0.248 mmol / g based on the resin solids, and the number average as the polyalkylene glycol component A water-soluble resin composed mainly of a water-soluble polyurethane containing a silanol group as a terminal functional group having crosslinkability, synthesized from polyethylene glycol having a molecular weight of 1000 to 67.2 wt% based on the resin solid content, and a polyisocyanate component 4,4'-methylenebis (cyclohexyl isocyanate), 2,2-bishydroxymethylbutanoic acid as a bishydroxyalkyl fatty acid, 0.295 mmol / g based on the resin solids, and a number average molecular weight of 20 as an alkylene glycol component A polytetramethylene glycol of 00 and a resin whose main component is self-emulsifiable polyurethane synthesized using water-added xylylenediamine as a chain extender, and mixed so that each solid content becomes equal weight. A blend resin of 27 wt% was prepared. The bishydroxyalkyl fatty acid contained in the blend resin solid content was 0.256 mmol / g, and the polyethylene glycol was 33.6 wt%.
2 wt% of "Sumitex Resin M-3" (trade name, registered trademark) manufactured by Sumitomo Chemitex Co., Ltd., which is a melamine-based cross-linking agent having a methylol group at the reactive end, as a cross-linking agent for the solid content of the blend resin. 5.6 wt% of “BN-69” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a blocked isocyanate-based crosslinking agent having an isocyanate group at the reactive end, is further added as a lubricant for the resin layer surface. Then, 10 wt% of porous silica having an average particle size of 2.7 μm was added to the solid content of the blend resin, stirred with a mixer, defoamed, and used as a coating solution. The adjusted coating solution was coated on a polyester film by a roll-on knife method with a clearance of 0.1 mm. After coating, it is dried at 140 ° C. for 2 minutes using a hot air dryer, further heat-treated at 160 ° C. for 2 minutes, after film formation, peeled off from the polyester film, and aged at room temperature for 48 hours. Got. The film thickness was 20 μm. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable waterproof film has high moisture permeability and water resistance, and since it is a water-based resin, it is a moisture permeable waterproof material that emits less organic solvent and has a lower environmental impact than conventional processes. It was a film.
[Reference Example 3]
Except not adding a crosslinking agent, it produced similarly to the reference example 1, and obtained the moisture-permeable waterproof film of this invention. The film thickness was 20 μm. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable waterproof film has high moisture permeability and water resistance, and since it is a water-based resin, it is a moisture permeable waterproof material that emits less organic solvent and has a lower environmental impact than conventional processes. It was a film.
[Reference Example 4]
The resin solid content of the coating liquid of Reference Example 1 was 8 wt%, cast on a polyester film, dried for 2 minutes at a temperature of 140 ° C. using a hot air dryer, and further heat-treated at a temperature of 160 ° C. for 2 minutes. After film formation, the film was peeled from the polyester film and aged at room temperature for 48 hours to obtain a moisture-permeable waterproof film of the present invention. The film thickness was 20 μm. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable waterproof film has high moisture permeability and water resistance, and since it is a water-based resin, it is a moisture permeable waterproof material that emits less organic solvent and has a lower environmental impact than conventional processes. It was a film.
[Reference Example 5]
“Resamine D2060” (trade name, registered trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.) is a melamine-based crosslinker having a methylol group at the reactive end as a crosslinker. -3 "(trade name, registered trademark) manufactured by Sumitomo Chemitex Co., Ltd., 2 wt%, as a lubricant for the resin layer surface, 15 wt% of porous silica having an average particle size of 2.7 μm is added to the solid content of the blend resin, After stirring and defoaming with a mixer, a coating solution was obtained. Using a 0.8 mm dot 60 ° staggered gravure roll, dot coating is performed on the film surface of the composite material of Reference Example 1, and drying is performed at a temperature of 120 ° C. for 1 minute using a hot air dryer. A wet waterproof film was obtained. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable waterproof film has high moisture permeability and water resistance, and since it is a water-based resin, it is a moisture permeable waterproof material that emits less organic solvent and has a lower environmental impact than conventional processes. It was a film. Moreover, it was a film with high surface smoothness by the unevenness | corrugation of the film surface.
[Reference Example 6]
4,4'-methylenebis (cyclohexyl isocyanate) was used as the polyisocyanate component, 2,2-bishydroxymethylpropionic acid as the bishydroxyalkyl fatty acid was 0.213 mmol / g based on the resin solids, and hexamethylene glycol as the alkylene glycol component Each of a resin containing a self-emulsifiable polyurethane synthesized using polyhexamethylene carbonate having a number average molecular weight of 1000 and water-added xylylenediamine as a chain extender and the water-soluble polyurethane resin of Reference Example 1 as solids. A blend resin having a solid content of 27.8 wt% was prepared by mixing so that the wt% of the mixture was 30:70. Except having used this resin, it produced similarly to the reference example 5, and obtained the moisture-permeable waterproof film of this invention. The bishydroxyalkyl fatty acid contained in the blend resin solids was 0.224 mmol / g, and the polyethylene glycol was 47.0 wt%. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable waterproof film has high moisture permeability and water resistance, and since it is a water-based resin, it is a moisture permeable waterproof material that emits less organic solvent and has a lower environmental impact than conventional processes. It was a film.
[Reference Example 7]
Water-soluble blend of polyurethane-based resin “Permarin UA-310” (trade name, registered trademark) manufactured by Sanyo Chemical Industries, Ltd., containing 0.179 mmol / g of bishydroxyalkyl fatty acid with respect to resin solids A moisture permeable waterproof film of the present invention was obtained in the same manner as in Reference Example 1 except that the resins were blended in the same wt%. The bishydroxyalkyl fatty acid contained in the blend resin solids was 0.213 mmol / g, and the polyethylene glycol was 33.6 wt%. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture-permeable and waterproof film is a water-based resin having high moisture permeability, water resistance and water pressure retention, and therefore has a low environmental impact and less organic solvent emissions than conventional processes. It was a moisture permeable waterproof film.
[Reference Example 8]
A moisture permeable and waterproof composite material of the present invention was obtained in the same manner as in Reference Example 1 except that the clearance was 0.15 mm and laminated on nylon taffeta. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable and waterproof composite material has high moisture permeability, water resistance and water pressure retention, and is a water-based resin. It was a breathable waterproof composite.
[Reference Example 9]
Except having used the polyester taffeta, it produced similarly to the reference example 8, and obtained the moisture-permeable waterproof composite material of this invention. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable and waterproof composite material has high moisture permeability, water resistance and water pressure retention, and is a water-based resin. There was a breathable waterproof composite.
[Reference Example 10]
Except having used the nylon nonwoven fabric, it produced similarly to the reference example 8, and obtained the moisture-permeable waterproof composite material of this invention. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable and waterproof composite material has high moisture permeability, water resistance and water pressure retention, and is a water-based resin. It was a breathable waterproof composite.
[Reference Example 11]
A moisture-permeable and waterproof composite material of the present invention was obtained in the same manner as in Reference Example 8 except that a polyethylene porous net “DELNETP-620W” (trade name, registered trademark, manufactured by Sanki Co., Ltd.) was used. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture permeable and waterproof composite material has both high moisture permeability and water resistance, and is a water-based resin. It was a waterproof composite.
[Reference Example 12]
A moisture permeable waterproof composite material of the present invention was obtained in the same manner as in Reference Example 8 except that the clearance was 0 mm by the floating knife method and coating was performed. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture-permeable and waterproof composite material is a water-based resin that has high moisture permeability and high water pressure resistance retention, and therefore has a low environmental impact with less organic solvent emissions than conventional processes. It was a moisture permeable waterproof composite.
[Reference Example 13]
After blending so that the solid contents of the self-emulsifying resin and the water-soluble resin used in Reference Example 1 are 30:70 (wt%: wt%), “Takenate WD725” (Mitsui Takeda Chemical), which is a water-soluble polyisocyanate 20 wt% of the product name (registered trademark) manufactured by Co., Ltd. was added to the solid content of the blend resin, and the mixture was stirred and defoamed with a mixer to obtain an adhesive.

The film formed in Reference Example 1 was coated using a 150 mesh gravure roll so that the coating amount was 8 g / m ^2, and preliminarily dried at a temperature of 80 ° C. for 1 minute using a hot air dryer. Laminated with nylon taffeta that has not been subjected to water repellent treatment, thermocompression bonding is performed at a temperature of 120 ° C. and a linear pressure of 2 kg / cm using a hot roll press machine. After thermocompression bonding, the release film is peeled off from the substrate, The moisture-permeable waterproof composite material of the present invention was obtained by aging at room temperature for 48 hours. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture-permeable and waterproof composite material is a water-based resin with high moisture permeability, water resistance and water pressure retention, and therefore has a low environmental load with less organic solvent emissions than conventional processes. It was a breathable waterproof composite.
[ Reference Example 14]
As a base material, moisture permeability by JIS L-1099, potassium acetate method (B-1 method) is 1.4 × 10 ³ g / m ² · 24 h, JIS L-1092, water pressure resistance by water pressure method is 0.23 MPa. A moisture-permeable and waterproof composite material of the present invention was produced in the same manner as in Reference Example 8 except that a moisture-permeable and waterproof material based on a certain solvent-based wet polyurethane porous membrane and a nylon taffeta was used. Table 1 shows the composition and the like, and Table 3 shows the results. As shown in Table 3, the obtained moisture-permeable and waterproof composite material has high moisture permeability, water resistance and water pressure resistance retention, but is partly a solvent-based process. It was a composite material.
[ Reference Example 15]
As a substrate, JIS L-1099, moisture permeability by potassium acetate method (B-1 method) is 1.2 × 10 ³ g / m ² · 24 h, JIS L-1092, water pressure resistance by water pressure method is 0.07 MPa. the polyurethane porous film made from a certain aqueous resin prepared by elution method, present the polyurethane porous film as a functional film, except for using the moisture-permeable waterproof material which nylon taffeta and base fabric, in the same manner as in reference example 8 A moisture permeable waterproof composite material of the invention was prepared. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite material is a water-based resin having high moisture permeability, water resistance and water pressure retention, and therefore has a low environmental load with less organic solvent emissions than conventional processes. It was a breathable waterproof composite.
[ Reference Example 16]
As a crosslinking agent, “BN-69” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a blocked isocyanate-based crosslinking agent, “Epocross WS700” (produced by Nippon Shokubai Co., Ltd.), which is an oxazoline-based crosslinking agent having an oxazoline group. A moisture-permeable and waterproof composite material of the present invention was produced in the same manner as in Reference Example 8 except that 2 wt% of the trade name (registered trademark) was added. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite material is a water-based resin having high moisture permeability, water resistance and water pressure retention, and therefore has a low environmental load with less organic solvent emissions than conventional processes. It was a breathable waterproof composite.
[ Reference Example 17]
As a cross-linking agent, “Smitex Resin M-3” (trade name, registered trademark of Sumitomo Chemitex Co., Ltd.), which is a melamine-based cross-linking agent having a methylol group, is “Denacol 313” which is an epoxy-based cross-linking agent having an epoxy group. A moisture-permeable and waterproof composite material of the present invention was produced in the same manner as in Reference Example 8 except that 2 wt% of Nagase ChemteX Corporation trade name, registered trademark) was added. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite material is a water-based resin having high moisture permeability, water resistance and water pressure retention, and therefore has a low environmental load with less organic solvent emissions than conventional processes. It was a breathable waterproof composite.
[ Reference Example 18]
The self-emulsifying resin polyester resin "Vylonal MD-1985" (manufactured by Toyobo Co., trade name, registered trademark) and, to prepare a coating liquid was equal weight solids and water-soluble polyurethane, Reference Example 5 Similarly, a moisture-permeable and waterproof composite material of the present invention was produced. The bishydroxyalkyl fatty acid contained in the blend resin solids was 0.151 mmol / g, and the polyethylene glycol was 33.6 wt%. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite material is a water-based resin having high moisture permeability, water resistance and water pressure retention, and therefore has a low environmental load with less organic solvent emissions than conventional processes. It was a breathable waterproof film.
[ Reference Example 19]
The self-emulsifying resin and silicone resin "BY22-826" (Toray Dow Corning Silicone Co., Ltd. trade name), to adjust the coating liquid was equal weight solids and water-soluble polyurethane, the same manner as in Reference Example 5 It was manufactured a moisture-permeable waterproof composite of the present invention. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite material is a water-based resin having high moisture permeability, water resistance and water pressure retention, and therefore has a low environmental load with less organic solvent emissions than conventional processes. It was a breathable waterproof composite.
[ Reference Example 20]
Self-emulsifying resin and acrylic resin "Bon Coat 350" (Dainippon Ink Co., trade name, registered trademark) and, to adjust the coating liquid was equal weight solids and water-soluble polyurethane, as in Reference Example 5 Similarly, a moisture-permeable and waterproof composite material of the present invention was produced. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite material is a water-based resin having high moisture permeability, water resistance and water pressure retention, and therefore has a low environmental load with less organic solvent emissions than conventional processes. It was a breathable waterproof composite.
[Reference Example 21]
A coating solution was prepared in the same manner as in Reference Example 1 except that the water-soluble polyurethane of Reference Example 1 was used alone, and a moisture-permeable waterproof composite material of the present invention was produced in the same manner as in Reference Example 8. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture permeable waterproof composite material is a moisture permeable waterproof composite material that has high moisture permeability and is low in environmental load because it is a water-based resin and emits less organic solvent. It was.
[ Reference Example 22]
A coating solution was prepared in the same manner as in Reference Example 1 except that porous silica was not added, and a film was formed in the same manner as in Reference Example 1 to obtain a moisture-permeable waterproof film of the present invention. The film thickness was 20 μm. As shown in FIG. 1, the dispersion diameter of the resin was larger than 2 μm, and the film had low dispersibility. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite material has high moisture permeability and water resistance, and is a water-based resin. It was a film.
[Example 23]
Acetic acid was added to the resin solution of Reference Example 1, as well as to pH6.2 from pH 7.8, except that no addition of porous silica, similarly prepare a coating solution as in Reference Example 1, Reference Example 1 A film was formed in the same manner to obtain a moisture permeable waterproof film of the present invention. The film thickness was 20 μm. As shown in FIG. 2, the dispersion diameter of the resin was smaller than 2 μm, and the film was highly dispersible. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture permeable waterproof film has high moisture permeability and water resistance, and since it is a water-based resin, it is a moisture permeable waterproof material that emits less organic solvent and has a lower environmental impact than conventional processes. It was a film.
[Example 24]
Except having used the coating liquid of Example 23, it produced similarly to the reference example 8, and obtained the moisture-permeable waterproof composite material of this invention. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite material has high moisture permeability and water resistance, and since it is a water-based resin, it emits less organic solvent and has a low environmental load. It was a waterproof composite.
[ Reference Example 25]
A coating solution was prepared in the same manner as in Reference Example 6 except that porous silica was not added, and a film was formed in the same manner as in Reference Example 6 to obtain a moisture-permeable waterproof film of the present invention. The film thickness was 20 μm. As shown in FIG. 3, the dispersion diameter of the resin was larger than 2 μm, and the film had low dispersibility. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture permeable waterproof film has high moisture permeability and water resistance, and since it is a water-based resin, it is a moisture permeable waterproof material that emits less organic solvent and has a lower environmental impact than conventional processes. It was a film.
[Example 26]
Acetic acid was added to the resin liquid of Reference Example 6 to adjust the pH from 7.8 to 6.2, and the coating liquid was adjusted in the same manner as Reference Example 6 except that porous silica was not added. A film was formed in the same manner to obtain a moisture permeable waterproof film of the present invention. The film thickness was 20 μm. As shown in FIG. 4, the dispersion diameter of the resin was smaller than 2 μm, and the film was highly dispersible. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture permeable waterproof film has high moisture permeability and water resistance, and since it is a water-based resin, it is a moisture permeable waterproof material that emits less organic solvent and has a lower environmental impact than conventional processes. It was a film.
[Example 27]
Except having used the coating liquid of Example 26, it produced similarly to the reference example 8, and obtained the moisture-permeable waterproof composite material of this invention. Table 2 shows the composition and the like, and Table 4 shows the results. As shown in Table 4, the obtained moisture-permeable and waterproof composite agent has high moisture permeability and water resistance, and since it is a water-based resin, it has a low environmental load and less moisture permeability compared to conventional processes. It was a waterproof composite.
[Comparative Example 1]
A composite material was obtained in the same manner as in Reference Example 5 except that “Samprene HMP17A” (trade name, registered trademark, manufactured by Sanyo Chemical Industries, Ltd.) was used alone. As shown in Table 4, it was a composite material with a large environmental load.

  According to the present invention, it is possible to obtain a moisture-permeable and waterproof composite material that can be manufactured by a low environmental load process by using a resin that is excellent in moisture permeability, waterproofness, material durability, and water-based. Can do. Furthermore, further improvement in performance can be achieved by controlling the dispersion state of the resins in the film.

FIG. 1 is a scanning electron micrograph illustrating a normal resin dispersion state of a cross section of a moisture permeable waterproof film of the present invention ( Reference Example 22). FIG. 2 is a scanning electron micrograph illustrating the state of resin dispersion in the cross section of the moisture-permeable waterproof film of the present invention (Example 23). FIG. 3 is a scanning electron micrograph illustrating the resin dispersion state of the cross section of the moisture permeable waterproof film of the present invention ( Reference Example 25). FIG. 4 is a scanning electron micrograph showing the resin dispersion state of the cross section of the moisture-permeable waterproof film of the present invention (Example 26).

1: Water-soluble resin part (white part)
2: Self-emulsifying resin part (black part)

Claims (5)

It consists of a resin layer containing two or more kinds of resins containing bishydroxyalkyl fatty acid and alkylene glycol as polymerization components, and the bishydroxyalkyl fatty acid is contained in an amount of 0.08 mmol / g or more and 0.5 mmol / g or less based on the resin solid content. In addition, at least one of the alkylene glycols is polyethylene glycol, and the polyethylene glycol is contained in an amount of 20 wt% or more and 60 wt% or less with respect to the resin solid content, and JIS L-1099 having an average film thickness of 20 μm, the potassium acetate method (B −1 method) has a moisture permeability of 3 × 10 ³ g / m ² · 24 h or more and 200 × 10 ³ g / m ² · 24 h or less, and further has a water pressure resistance of 0.1 MPa according to JIS L-1092 and the water pressure method. Above, 1.0 MPa or less, and in the observation of the film cross section, the resin Moisture-permeable waterproof film that Chi径 is characterized in that it is 2μm or less. The moisture-permeable waterproof film according to claim 1, wherein the alkylene glycol is an alkylene glycol having 3 to 12 carbon atoms in the repeating unit of the alkylene portion. The moisture permeable waterproof film according to claim 1 or 2, wherein both of the two types of resins are polyurethane resins. The moisture-permeable waterproof film according to any one of claims 1 to 3 is provided on at least one side of a substrate, and has a moisture permeability of 1 × 10 ³ g according to JISL-1099, potassium acetate method (B-1 method). The moisture-permeable and waterproof composite material is not less than / m ² · 24 h and not more than 50 × 10 ³ g / m ² · 24 h. The moisture-permeable waterproof composite material according to claim 4, wherein the water pressure retention after 24 hours of washing is 80% or more and 100% or less.