JP2004162056A - Moisture-permeable waterproof film and moisture-permeable waterproof composite material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moisture-permeable waterproof film exellent in moisture permeability and film strength and a moisture-permeable waterproof composite material using the film. <P>SOLUTION: The moisture-permeable waterproof film comprises a hydrophobic resin and a hydrophilic resin; these resins are phase separated in a cross section of the thickness direction. The moisture-permeable waterproof composite material is prepared by laminating the film to a substrate. <P>COPYRIGHT: (C)2004,JPO

Description

  TECHNICAL FIELD The present invention relates to a moisture-permeable waterproof film having both excellent moisture permeability and membrane strength. More specifically, the present invention combines outdoor wear such as fishing and mountaineering clothing, ski-related wear, windbreaker, athletic wear, golf wear, tennis wear, rainwear, casual coat, outdoor workwear, gloves by combining with textiles and the like. Suitable for use in the field of clothing such as shoes and shoes, and also in the field of non-clothing such as building materials such as wall materials and roof tiles and living-related materials such as base materials for dehumidifiers in combination with a film alone or in combination with a substrate according to the application. And a moisture-permeable waterproof film.

  Conventionally, in order to obtain a moisture-permeable waterproof film using a solvent-based resin, it has been necessary to introduce a very large number of hydrophilic portions that affect moisture permeability in designing the solvent-based resin (see, for example, Patent Document 1). ).

  In recent years, it has become desirable to shift the resin from a solvent type to an aqueous type in consideration of the environment, and in the field of paints and resins for artificial leather, etc., flexible and high film strength aqueous emulsion resins have been developed. (See, for example, Patent Document 2). However, since these resins hardly exhibit moisture permeability, the transition to water-based resins for moisture-permeable waterproof films that are worthy of practical use has been delayed.

  There are two techniques for making the resin water-based: forced emulsification of a solvent-based resin with an emulsifier or the like, and self-emulsification with a resin into which an internal emulsifier is introduced.

  A film using a resin in which a solvent-based resin is forcibly emulsified has moisture permeability and film strength that can withstand practical use in both film strength, but the emulsifier bleeds on the film surface during film formation, lowering the waterproofness, It is not preferable because a problem such as stickiness occurs.

  On the other hand, a film using a self-emulsified resin has no problems such as a decrease in waterproofness due to bleeding of an emulsifier and a sticky surface on a film using a resin using a forcedly emulsified resin, and is preferable as a moisture-permeable waterproof film. . However, it is difficult to obtain a film having a practically sufficient film performance in both moisture permeability and film strength. That is, 1. In the case of an aqueous resin by self-emulsification, the molecular weight is increased in water by chain elongation of the resin, but the molecular weight cannot be increased as much as the chain elongation in a solvent, so that the film strength is weakened. The main reason for the resin having a self-emulsifiable amount of hydrophilic segments is that it is difficult to achieve both film strength and moisture permeability by balancing the hydrophobic segments and the hydrophilic segments.

As described above, it has been difficult to obtain a moisture-permeable waterproof film that simultaneously satisfies moisture permeability and film strength using a self-emulsifiable aqueous resin.
JP-A-10-1764 JP 2002-179759 A

  The present invention has been made in view of the above circumstances, and has as its object to provide a moisture-permeable waterproof film having high moisture permeability and membrane strength using an aqueous resin, and a moisture-permeable waterproof composite material using the same.

  The present invention has the following configuration in order to solve the above-mentioned problem.

  That is, the moisture-permeable waterproof film of the present invention contains a hydrophobic resin and a hydrophilic resin that are phase-separated in a cross section in the thickness direction.

  Further, the moisture-permeable waterproof composite of the present invention is obtained by laminating the moisture-permeable waterproof film on a substrate.

  According to the present invention, it is possible to obtain a moisture-permeable waterproof film having both moisture permeability and membrane strength, and a moisture-permeable waterproof composite material using the same.

  The moisture-permeable waterproof film of the present invention contains a hydrophobic resin and a hydrophilic resin.

  Here, the hydrophobic resin refers to a resin having a linear swelling ratio of water absorption of 0% or more and less than 1% when formed into a film. The hydrophilic resin refers to a resin that is soluble in water when formed into a film, or a resin that has a linear swelling ratio of water absorption of 1% or more and 400% or less when formed into a film. The linear swelling ratio of water absorption is determined by immersing a resin film having a thickness of 50 μm, which is marked at a fixed interval, in water at 25 ° C. and increasing the marking interval after 24 hours.

  In the present invention, the hydrophobic resin and the hydrophilic resin are mixed to form a film, and the mixed state is not necessarily uniform and one resin may not be uniformly dispersed in the other resin, The dispersion may be uneven.

  The moisture-permeable waterproof film of the present invention has a portion where the hydrophobic resin and the hydrophilic resin are phase-separated in the cut surface in the thickness direction of the film. The presence of the part where the hydrophilic resin and the hydrophobic resin are phase-separated allows high moisture permeability to be exhibited.

  The term “phase separation” as used herein refers to a state in which a hydrophobic resin and a hydrophilic resin are in contact with each other via an interface. The phase separation structure is not particularly limited, and may be, for example, a regular structure such as a lamella, a cylinder, or a sea-island structure.These regular structures are randomly dispersed, or the hydrophobic resin and the hydrophilic resin are regularly arranged. It may be in a state of non-uniform dispersion without any structural parts.

  The part where the hydrophilic resin and the hydrophobic resin are phase-separated can be confirmed by observing the cross section in the thickness direction of the moisture-permeable waterproof film using an optical microscope. At that time, if necessary, the sample may be stained with a dye or the like so that the phase-separated portion can be easily confirmed.

  In the cross section in the thickness direction of the film, the area of the hydrophilic portion occupies 30% or more and less than 100%, more preferably 40% or more and less than 100% of the area of the entire cross section with respect to the interface, and thus, has excellent moisture permeability. It is preferable from the viewpoint of obtaining the effect.

Film of the present invention, for example, in a film having a thickness of 50 [mu] m, moisture permeability according to JIS L-1099 potassium acetate method shows excellent moisture permeability of 30,000g / m ² · 24h or more 300,000g / m ² · 24h or less And the film strength is 5 MPa or more and 50 MPa or less.

  In the present invention, one of the hydrophobic resin and the hydrophilic resin preferably has a structure capable of self-emulsification. It is also preferable that both the hydrophobic resin and the hydrophilic resin have a structure capable of self-emulsification. The term “self-emulsification of a resin” as used herein means that the resin can be emulsified in water without adding an emulsifier or the like, or becomes soluble in water.

  The self-emulsifying molecular structure improves the affinity between a polymer chain and water, and is obtained by, for example, introducing a hydrophilic group into a resin. Examples of the hydrophilic group include an ionic dissociation group (for example, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a sulfonate group, a carbamoylsulfonate group, a quaternary amino group or a quaternary ammonium salt), a nonionic group [ For example, a polyoxyalkylene group (for example, a polyoxyethylene group and the like), an epoxy group and the like] can be exemplified. Among these hydrophilic groups, an anionic group (a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a sulfonate group, a carbamoyl sulfonate group) and a nonionic group (a polyoxyethylene group) are preferable, and an anionic group is particularly preferable. Groups (carboxyl groups or salts thereof, sulfonic acid groups or salts thereof) are preferred.

  As the hydrophilic resin used in the present invention, polyester-based, acrylic-based, polyurethane-based, polyether-based, polyamide-based, and silicone-based resins can be used, but the molecular design is easy, and the performance of the obtained resin is high. Thus, a polyurethane resin is preferred.

  The polyurethane-based resin is not particularly limited, and polyether-based, polyester-based, polycarbonate-based, polyamide-based, silicone-based, and fluorine-based resins can be used.

  Examples of the hydrophilic resin used in the present invention include those which have a molecular structure exhibiting the following hydrophilicity and can retain water between polymer chains and swell. Ionic dissociation group (for example, carboxyl group or salt thereof, sulfonic acid group or salt thereof, sulfonate group, carbamoylsulfonate group, quaternary amino group or quaternary ammonium salt), nonionic group [for example, polyoxyalkylene group Resins having (for example, a polyoxyethylene group or the like), an epoxy group or the like], a hydroxyl group (for example, an alcohol or a saccharide), a silanol group, an amino group, an amide group (for example, a peptide, a protein, or a nylon) can be given. . Among these, a structure having a nonionic group, a hydroxyl group, a silanol group, and an amide group is preferred from the viewpoint of the resistance to deterioration of the resin, and more specifically, a structure having a polyoxyethylene group, a peptide, a protein, a tertiary amine, and nylon. More preferred.

  Such a structure can be stained with osmium oxide (VIII). In addition, what can be stained with osmium oxide (VIII) has a portion that can react with osmium oxide (VIII) or a portion that can coordinate, and therefore, besides the above-described structure, for example, tryptophan, cystine, and methionine. And structures such as sulfide bonds.

  The hydrophobic resin used in the present invention does not have the above-mentioned molecular structure expressing hydrophilicity, or has the above-described molecular structure expressing hydrophilicity, but retains water between polymer chains. A resin that cannot be formed and has a linear swelling ratio of water absorption of 0% or more and less than 1% is exemplified.

  As the hydrophobic resin used in the present invention, polyester-based, acrylic-based, polyurethane-based, polyether-based, polyamide-based, and silicone-based resins can be used, but the molecular design is easy, and the performance of the obtained resin is high. Thus, a polyurethane resin is preferred.

  The polyurethane-based resin is not particularly limited, and polyether-based, polyester-based, polycarbonate-based, polyamide-based, silicone-based, and fluorine-based resins can be used.

  Next, a method for producing the moisture-permeable waterproof film of the present invention will be described.

  For the production of the moisture-permeable waterproof film of the present invention, a blend resin comprising a water-emulsion-based hydrophobic resin and a water-emulsion-based hydrophilic resin, or a water-emulsion-based hydrophobic resin and a water-soluble hydrophilic resin A resin liquid mainly composed of a resin blend is used.

  The water emulsion is preferably one in which a resin is emulsified and dispersed in water and has a particle diameter of 1 nm or more and 500 nm or less and is stably present. As the water-soluble hydrophilic resin, a resin in which a polymer constituting the resin is uniformly dispersed and dissolved in water is preferable.

  There is no limitation on the method of blending the resins, and for example, the method can be performed using a stirrer, a homogenizer, or the like.

  Further, a crosslinking agent or the like may be appropriately added to the resin liquid for the purpose of improving the film strength.

  Furthermore, in the case of improving the film forming property, a water-soluble solvent such as N, N-dimethylformamide, N-methyl-2-pyrrolidone or the like may be appropriately added to the resin solution.

  When coloring the film, an inorganic pigment or an organic pigment may be appropriately added to the resin liquid before use.

  In the case of improving the slip property of the film surface, inorganic particles such as silica, titanium oxide and alumina, and organic particles such as polyurethane and acrylic may be appropriately added and used.

  When the film structure is a porous film, a water-soluble substance such as starch and calcium chloride may be appropriately added.

  Next, a film is obtained by casting or coating the resin solution on the substrate and applying heat in an oven or a tenter to form a dry film.

  The heat treatment conditions are preferably at 50 ° C. to 150 ° C. for 0.5 minutes to 20 minutes since low temperature drying requires a long time and high temperature drying tends to deteriorate the resin.

  The substrate on which the resin liquid is applied is not particularly limited, but a substrate having smoothness and excellent releasability is preferable. For example, polyester, polyamide, synthetic fibers made of polymers such as polyacrylic, and fibers such as natural fibers such as cotton, wool, and silk, or a fiber structure such as a woven fabric, knitted fabric, or nonwoven fabric made of a blend thereof, and a film , Paper, wood, glass, metal and the like.

  Depending on the final use, a composite material having moisture permeability and waterproofness can be obtained with the film provided on the substrate. As the base material, a material similar to the above-mentioned substrate can be used depending on the purpose, but a material excellent in adhesiveness between the film and the base material is particularly preferable. The composite material, specifically, outdoor wear such as fishing and mountaineering clothing, ski-related wear, windbreaker, athletic wear, golf wear, tennis wear, rainwear, casual coat, outdoor work clothes, by combining with fiber material, It can be used as clothing such as gloves and shoes. Further, it can be used as a building material such as a wall material or a roof tile, a life-related material such as a dehumidifier base material, or the like, in combination with a base material according to the use.

  Examples of a method of providing a film on a substrate include a method of casting, coating and applying heat with an oven or a tenter, and a method of laminating the film and the substrate by bonding.

  When bonding, the moisture-permeable waterproof film may be directly bonded to the substrate, or may be bonded via an adhesive or the like.

  When the film is directly adhered to the substrate, it can be performed using a hot roll or the like.

  In the case of bonding using an adhesive, an adhesive is applied in advance to both the film and the base material, or only one of them, and is adhered by pressure bonding, and the adhesive is solidified by heat treatment.

  The type of the adhesive includes a wet lamination method, a dry lamination method, a hot melt lamination method, and the like, but is not limited to these methods.

  When applying the adhesive, the entire surface may be adhered or the surface may be partially adhered, but from the viewpoint of texture and moisture permeability, partial adhesion is preferred.

  The method of applying the adhesive in the case of partial bonding includes dot coating using a gravure roll, spray coating, and the like, but is not limited to these methods.

  The resulting moisture-permeable waterproof composite of the present invention can be subjected to post-treatment. The post-treatment can be arbitrarily performed depending on the field of use, and examples thereof include a water-repellent treatment, a softening treatment, an antistatic treatment, a flameproofing treatment, and a hard finishing treatment.

Further, it is preferable that the moisture permeability by JIS L-1099 potassium acetate method moisture-permeable waterproof composite (B-1 method) is not more than 500g ^/ m 2 · 24h or more 100,000g ^/ m 2 · 24h. Further, the water resistance of the moisture permeable waterproof composite material according to JIS L-1092 high water pressure method is preferably 0.005 MPa or more and 5 MPa or less.

  The performance of the moisture-permeable and waterproof composite material is such that the area of the hydrophilic portion accounts for 30% or more and less than 100%, more preferably 40% or more and less than 100% of the area of the entire cross section in the cross section in the thickness direction of the film. Is expressed by combining with a base material.

  Hereinafter, the moisture-permeable waterproof film of the present invention and the moisture-permeable waterproof composite material using the same will be described in more detail with reference to Examples along with a method for producing the same.

  The moisture-permeable waterproof film of the present invention, the method for evaluating the moisture-permeable waterproof composite material using the same, and the base material are described below.

[Linear swelling ratio of water absorption]
A 50 μm-thick resin film marked on the coating at 10 cm intervals was immersed in water at 25 ° C., and the average rate of increase of the marking interval after 24 hours was defined as the linear swelling rate.

[Moisture permeability]
Using a film having a thickness of 50 μm or a composite material, the measurement was performed according to the JIS L-1099 potassium acetate method.

[water resistant]
The composite material was measured according to JIS L-1092 high water pressure method.

[Film strength]
The film in a dry state was measured using “Tensilon UTM-100III” manufactured by Orientec under the following conditions.

Sample shape: 8cm × 1cm × 50μm (length × width × thickness, measurement part is 5cm × 1cm × 50μm)
Crosshead speed: 300mm / min
[Observation of cross section of film and area ratio of hydrophilic portion]
The film is cut with a microtome in the thickness direction (sample thickness 5 μm), and the cross section is observed at 400 × using a transmission optical microscope BX60 manufactured by OLYMPUS. The cross section is photographed using an OLYMPUS digital camera DP10, and the darkest and lightest parts are enlarged by digital processing on a personal computer and printed with an OLYMPUS digital color printer P-330. Measure with And the L ^* of the most dark portion in the cross section photograph 0 to 30, and most after the light-colored portion L ^* was determined to be 85 or more and 100 or less, Crop photo of the entire film cross-section, the film The weight ratio of the entire portion where L ^* was 0 or more to 30 or less with respect to the weight of the entire cross section was calculated. This was performed on five cross-sectional photographs of the film sample, and the average value was defined as the area ratio.

[Base material]
The following nylon taffeta was used after being treated with a 4% aqueous dispersion of AG925 (trade name, manufactured by Asahi Glass Co., Ltd.), which is a fluorine-based water and oil repellent.

Nylon taffeta Thread use 77 decitex-68 filament yarn of nylon 6 (vertical yarn and weft yarn)
Weaving density Vertical: 45.7 lines / cm, Horizontal: 34.6 lines / cm
Weight 72g / m ²
[Example 1]
Hydrophobic resin "Permarine UA-310" (trade name, manufactured by Sanyo Chemical Industries, Ltd.), which is a polycarbonate-based polyurethane, and 50 parts of undiluted solution and hydrophilic resin "Sunfresh ST-500MPS", which is spherical acrylic acid fine particles (Sanyo Chemical Industries, Ltd. Co., Ltd., 20 parts were mixed, cast on release paper, and heat-treated in an oven at 120 ° C. for 10 minutes to produce a moisture-permeable waterproof film (film thickness 50 μm) of the present invention.

  The film sample was dyed using a basic dye “Kayacryl Black NL” (trade name, manufactured by Nippon Kayaku Co., Ltd.) by treatment at 100 ° C. for 60 minutes, and the cross-sectional structure of the film was observed.

As shown in Table 1, the area ratio of the hydrophilic portion to the entire cross section of the film was 46%, the moisture permeability was 32,000 g / m ² · 24 h, and the film strength was 14 MPa. It was a moisture-permeable waterproof film with high moisture permeability and membrane strength.

[Example 2]
Example 1 was the same as Example 1 except that a resin solution obtained by mixing 50 parts of a stock solution of a hydrophobic resin “Vinibulan 2778” (trade name, manufactured by Nissin Chemical Industry Co., Ltd.) and 25 parts of egg white as a hydrophilic resin was used. Similarly, a moisture-permeable waterproof film (film thickness 50 μm) of the present invention was produced.

A weighing bottle containing 10 cc of a 10 wt% aqueous solution of osmium (VIII) oxide and a film sample are placed in a closed container (volume: 8000 cm ³ ), and the whole closed container is subjected to gas phase treatment in an oven at 60 ° C. for 8 hours for dyeing. The cross-sectional structure of the film was observed.

As shown in Table 1, the area ratio of the hydrophilic portion (dark portion) to the entire cross section of the film was 48%, the moisture permeability was 36,000 g / m ² · 24 h, and the film strength was 33 MPa. It was a moisture-permeable waterproof film with high moisture permeability and membrane strength.

[Example 3]
Acrylic emulsion hydrophobic resin "ViniBlan 2778" (trade name, manufactured by Nissin Chemical Co., Ltd.) 50 parts of undiluted solution and hydrophilic resin "AQ nylon", water-soluble nylon, (trade name, manufactured by Toray Industries, Inc.) 50 Part, 20 parts of "Sumitec Resin M-3" (trade name, manufactured by Sumitomo Chemical Co., Ltd.) which is a melamine-based crosslinking agent, and "Sumitex Accelerator ACX" (trade name, manufactured by Sumitomo Chemical Co., Ltd.) which is a catalyst 2) A moisture-permeable waterproof film (film thickness: 50 μm) of the present invention was prepared in the same manner as in Example 1 except that a resin solution in which 2 parts were mixed was used.

  Observation of the film cross-sectional structure was performed in the same manner as in Example 2.

As shown in Table 1, the area ratio of the hydrophilic portion (dark portion) to the entire cross section of the film was 38%, the moisture permeability was 82,000 g / m ² · 24 h, and the film strength was 13 MPa. It was a moisture-permeable waterproof film with high moisture permeability and membrane strength.

[Example 4]
Hydrophobic resin "Permarin UA-310" which is a polycarbonate-based polyurethane (trade name, manufactured by Sanyo Chemical Industries, Ltd.) 50 parts of undiluted solution and hydrophilic resin "AQ nylon" which is a water-soluble nylon (trade name, manufactured by Toray Industries, Inc.) 50 parts, 20 parts of "Sumitec Resin M-3" (trade name, manufactured by Sumitomo Chemical Co., Ltd.) which is a melamine-based cross-linking agent, "Sumitex Accelerator ACX" (trade name, manufactured by Sumitomo Chemical Co., Ltd.) which is a catalyst Name) A resin liquid mixed with 2 parts was cast on release paper and heat-treated in an oven at 140 ° C. for 2 minutes to produce a moisture-permeable waterproof film (film thickness 50 μm) of the present invention.

  Observation of the film cross-sectional structure was performed in the same manner as in Example 2.

As shown in Table 1, the area ratio of the hydrophilic portion (dark portion) to the entire cross section of the film was 56%, the moisture permeability was 120,000 g / m ² · 24 h, and the film strength was 12 MPa. It was a moisture-permeable waterproof film with high moisture permeability and membrane strength.

[Example 5]
Hydrophobic resin "Vinibulan 2778" (trade name, manufactured by Nissin Chemical Industry Co., Ltd.) which is an acrylic emulsion 50 parts of a stock solution and a 15% by weight aqueous solution 167 of a polyether polyurethane which is a hydrophilic resin having a water swellability of 65% A moisture-permeable waterproof film (thickness: 50 μm) of the present invention was produced in the same manner as in Example 4 except that a resin solution in which parts were mixed was used.

  Observation of the film cross-sectional structure was performed in the same manner as in Example 2.

As shown in Table 1, the area ratio of the hydrophilic portion (dark portion) to the entire cross section of the film was 64%, the moisture permeability was 98,000 g / m ² · 24 h, and the film strength was 16 MPa. It was a moisture-permeable waterproof film with high moisture permeability and membrane strength.

[Example 6]
25 parts by weight of a stock solution of a hydrophobic resin "Permarine UA-310" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) and a 15% by weight aqueous solution of a polyether-based polyurethane which is a hydrophilic resin having a water swelling of 65% A moisture-permeable waterproof film (film thickness: 50 μm) of the present invention was produced in the same manner as in Example 4 except that a resin solution mixed with 66.7 parts was used.

  Observation of the film cross-sectional structure was performed in the same manner as in Example 2. One example of the optical micrograph is shown in FIG.

As shown in Table 1, the area ratio of the hydrophilic portion (dark portion) to the entire cross section of the film was 94%, the moisture permeability was 140,000 g / m ² · 24 h, and the film strength was 18 MPa. It was a moisture-permeable waterproof film with high moisture permeability and membrane strength.

[Example 7]
Hydrophobic resin "Permarin UA-310" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) which is a polycarbonate-based polyurethane, and 50 parts of a stock solution and hydrophilic resin "Sunfresh ST-500MPS", which is spherical acrylic acid fine particles (Sanyo Chemical Industries, Ltd.) Example 2 except that a resin solution obtained by mixing 9.9 parts of a block isocyanate “Elastron BN69” (trade name of Daiichi Kogyo Seiyaku Co., Ltd.) with a block dissociation temperature of 120 ° C. was 20 parts. In the same manner as in Example 1, a moisture-permeable waterproof film (film thickness 50 μm) of the present invention was produced.

  Observation of the film cross-sectional structure was performed in the same manner as in Example 1.

As shown in Table 1, the area ratio of the hydrophilic portion to the entire cross section of the film was 50%, the moisture permeability was 28,000 g / m ² · 24 h, and the film strength was 19 MPa. It was a moisture-permeable waterproof film with high moisture permeability and membrane strength.

Example 8
25 parts by weight of a stock solution of a hydrophobic resin "Permarin UA-310" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) and a 15% by weight aqueous solution of a polyether-based polyurethane which is a hydrophilic resin having a water swellability of 65% Same as Example 4 except that a resin solution obtained by mixing 4.9 parts of a blocked isocyanate “Elastron BN69” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) having a block dissociation temperature of 120 ° C. and 66.7 parts was used. The moisture-permeable waterproof film (film thickness 50 μm) of the present invention was produced.

  Observation of the film cross-sectional structure was performed in the same manner as in Example 2.

As shown in Table 1, the area ratio of the hydrophilic portion (dark portion) to the entire cross section of the film was 92%, the moisture permeability was 110,000 g / m ² · 24 h, and the film strength was 24 MPa. It was a moisture permeable waterproof film with high moisture permeability and membrane strength.

[Comparative Example 1]
A hydrophobic resin "Permarin UA-310" (trade name, manufactured by Sanyo Chemical Industries, Ltd.), which is a polycarbonate-based polyurethane, was prepared in the same manner as in Example 1 except that the stock solution was used as the resin solution. (Film thickness 50 μm)
Observation of the film cross-sectional structure was performed in the same manner as in Example 2.

As shown in Table 1, the area ratio of the hydrophilic portion (dark portion) to the entire cross section of the film was 0%, the moisture permeability was 0 g / m ² · 24 h, and the film strength was 27 MPa. The film was not wet.

[Comparative Example 2]
A resin was prepared in the same manner as in Example 1 except that a 15% by weight aqueous solution of a polyether-based polyurethane which was a hydrophilic resin having a water swellability of 65% was used as a resin solution. (Film thickness 50 μm)
Observation of the film cross-sectional structure was performed in the same manner as in Example 2.

As shown in Table 1, the area ratio of the hydrophilic portion (dark portion) to the entire cross section of the film is 100%, the moisture permeability is 220,000 g / m ² · 24 h, the film strength is 0.79 MPa, and the moisture permeability is Although high, the film strength was low.

[Example 9]
The film obtained in Example 7 was overlaid on a nylon taffeta and bonded, and passed through a heat roll having a linear pressure between a metal roll and a rubber roll of 9 kg / cm and a metal roll temperature of 150 ° C. to bond the nylon taffeta and the film. Thus, a moisture-permeable waterproof composite material of the present invention was produced.

As shown in Table 2, it was a moisture permeable waterproof composite material having a high moisture permeability of 14,000 g / m ² · 24 h and a water pressure of 0.29 MPa, and both high moisture permeability and high water resistance.

[Example 10]
A moisture-permeable waterproof composite material of the present invention was produced in the same manner as in Example 10, except that the film obtained in Example 9 was used.

As shown in Table 2, the moisture-permeable waterproof composite material was 15,000 g / m ² · 24 h and had a water pressure resistance of 0.56 MPa, and had both high moisture permeability and high water resistance.

[Example 11]
An aqueous adhesive “Boncoat ES141” (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) is applied to a nylon taffeta with a 50 mesh gravure roll, and after predrying, the film is crimped on the film obtained in Example 7 at 120 ° C. And then aged at room temperature for 24 hours or more to produce a moisture-permeable waterproof composite of the present invention.

As shown in Table 2, it was a moisture-permeable and waterproof composite material having a moisture permeability of 16,000 g / m ² · 24 h, a water pressure of 0.27 MPa, and both high moisture permeability and water pressure resistance.

[Example 12]
A moisture-permeable waterproof composite material of the present invention was produced in the same manner as in Example 13 except that the film obtained in Example 9 was used.

As shown in Table 2, the moisture-permeable waterproof composite material had a high moisture permeability of 19,000 g / m ² · 24 h and a water pressure of 0.31 MPa, and had both high moisture permeability and high water resistance.

[Comparative Example 3]
A composite material for comparison was produced in the same manner as in Example 8, except that the film obtained in Comparative Example 2 was used.

As shown in Table 2, the moisture permeability was 27,000 g / m ² · 24 h, the water pressure resistance was 0.001 MPa, and the composite material had high moisture permeability but low water resistance.

FIG. 1 is an optical microscope photograph cross-sectional view illustrating a cross-sectional portion in the thickness direction of the moisture-permeable waterproof film of the present invention.

Explanation of reference numerals

1: hydrophilic resin part 2: hydrophobic resin part

Claims (8)

A moisture-permeable waterproof film comprising a hydrophobic resin and a hydrophilic resin phase-separated in a cross section in a thickness direction. The moisture-permeable waterproof film according to claim 1, wherein the hydrophobic resin and / or the hydrophilic resin have a structure capable of self-emulsification. The moisture permeable waterproof film according to claim 1 or 2, wherein the hydrophobic resin and / or the hydrophilic resin is polyurethane. The moisture-permeable waterproof film according to any one of claims 1 to 3, wherein the hydrophilic resin is dyeable with osmium (VIII) oxide. A moisture-permeable waterproof composite material obtained by laminating the moisture-permeable waterproof film according to claim 1 on a substrate. A garment using the moisture-permeable waterproof composite according to claim 5. A building material using the moisture-permeable waterproof film according to any one of claims 1 to 4 or the moisture-permeable waterproof composite according to claim 5. A life-related material comprising the moisture-permeable waterproof film according to claim 1 or the moisture-permeable waterproof composite according to claim 5.