JP2000280392A - Adhesive moisture permeable waterproof film and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject film having high-degree moisture permeability and waterproofness capable of imparting both of high moisture permeability and water resistance to a base material only by bonding the film to the base material and also having adhesiveness and a method for producing the same. SOLUTION: An adhesive moisture permeable waterproof film consists of at least one continuous water swellable resin layer and an adhesive layer. In this case, the water swellable resin layer is not provided with pores with a pore size of 400 nm or more in a state not swollen by water and the adhesive layer contains a crosslinking agent capable of liberating a reactive terminal by thermal dissociation and the moisture permeability of the film is 30,000 g/m2.24 hr or more and the water pressure necessary for water permeation thereof is 2.0 kgf/cm2 or more. This film is obtained by coating a release support with a water swellable resin soln. to form a continuous layer and coating this layer with an adhesive soln. containing a crosslinking agent capable of liberating a reactive terminal by thermal dissociation to form a coating film at temp. lower than the thermal dissociation temp. of the crosslinking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-permeable waterproof film having an adhesive property. More specifically, the present invention relates to an adhesive moisture-permeable waterproof film that can achieve both high moisture permeability and water resistance simply by bonding to a substrate, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a moisture-permeable and waterproof material, particularly a material in which a microporous layer has a moisture-permeable and water-resistant layer, has been problematic in that its water resistance is low due to its porosity.

In order to solve such problems, a method of controlling the pore size of the microporous layer, a method of laminating a nonporous layer on the microporous layer by a dry film forming method, and a method of converting the microporous layer itself to a hydrophilic nonporous layer A method has been proposed to replace it.

However, these methods can impart the durability of water resistance, but still have various problems such as sacrificing moisture permeability or water resistance.

Specifically, the method of controlling the pore size of the microporous layer has a problem that the pore size is limited and the durability of the non-porous layer is poor.

In the method of laminating a non-porous layer on a microporous layer by a dry film-forming method, when a film is laminated by a solvent-based coating method, the solvent re-dissolves the microporous and forms a non-porous layer. The problem is that water permeability can be imparted but moisture permeability is significantly reduced.

[0007] In the case of laminating a non-porous layer which has been dry-formed in advance on a microporous layer, there is a problem that the use of a conventional adhesive significantly reduces moisture permeability.

In the method in which the microporous layer itself is replaced with a hydrophilic nonporous layer, water resistance and durability can be imparted. However, the adhesive is applied in a dot form to reduce the area covered by the adhesive. As a result, a new problem has arisen such that the water pressure resistance itself is reduced in order to suppress a decrease in moisture permeability as a material.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and provides an adhesive moisture-permeable waterproof film excellent in adhesiveness and capable of achieving both high moisture permeability and water resistance by simply adhering to a substrate, and production thereof. It is intended to provide a method.

[0010]

The adhesive moisture-permeable waterproof film of the present invention has the following structure to solve the above-mentioned problems.

That is, a film comprising at least one continuous water-swellable resin layer and an adhesive layer, wherein the water-swellable resin layer has a thickness of 400 nm when not swollen with water.
Not having the above pores, the adhesive layer contains a crosslinking agent capable of releasing a reactive terminal by thermal dissociation, and the film has a moisture permeability of 30,000 g / m ² · 24 hr or more, which is necessary for water permeability. An adhesive moisture-permeable waterproof film having a water pressure of 2.0 kgf / cm ² or more.

In one embodiment of the method for producing the adhesive moisture-permeable waterproof film of the present invention, a water-swellable resin solution is applied on a release support to form a film, a continuous layer is formed, and a heat A method for producing an adhesive moisture-permeable waterproof film, comprising applying an adhesive layer solution containing a crosslinking agent capable of releasing a reactive terminal by dissociation, and forming a film at a temperature lower than the thermal dissociation temperature of the crosslinking agent. It is.

Another aspect of the method for producing the adhesive moisture-permeable waterproof film of the present invention is to mix a crosslinking agent capable of releasing a reactive terminal by thermal dissociation into a water-swellable resin solution, And producing a film at a temperature lower than the thermal dissociation temperature of the crosslinking agent.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The film of the present invention is a film comprising at least one continuous water-swellable resin layer and an adhesive layer,
When the water-swellable resin layer is not swollen with water, it does not have pores of 400 nm or more.

[0016] At least one continuous water-swellable resin layer means that the resin layer is two-dimensionally continuous, has no discontinuous and discontinuous portions, and has holes such as pinholes, defects that are communicated from front to back. It means that the layer swells by absorbing moisture and water, but has low water permeability and can exhibit water resistance even in a single layer.

The water-swellable resin layer means a resin layer having a linear swelling ratio of 1% or more when only the resin layer is immersed in water. In order to exhibit sufficient moisture permeability, a resin layer having a linear swelling ratio of 5% or more, more preferably 10% or more, can be preferably used.

The water-swellable resin layer used in the present invention does not have pores of 400 nm or more when not swelled with water. That is, the resin layer itself does not have microporous portions that appear opaque in the visible light region, such as a polyurethane film produced by a wet film-forming method.
There is no hole of 0 nm or more.

The adhesive layer is a layer for adhering the water-swellable resin layer to the substrate, and contains a crosslinking agent capable of releasing a reactive terminal by thermal dissociation.

The release of the reactive terminal by thermal dissociation means that the substance that blocks the cross-linking site of the cross-linking agent and significantly reduces the reactivity of the reactive terminal capable of forming a cross-linking reaction is placed in an atmosphere at a certain temperature. Means that the block is released and the terminal having high reactivity is released.

When the reactive terminal is released at a certain temperature, the crosslinking of the adhesive layer does not proceed in an atmosphere up to a certain temperature, so that the adhesiveness of the film can be maintained for a long time. In addition, when a certain temperature is reached, the reactive terminal of the crosslinking agent is released, and crosslinking within the adhesive layer and a crosslinking reaction with the base material occur to enable adhesion.

The film of the present invention has a moisture permeability of 30,0.
00g / m ²・ 24hr or more, water pressure required for permeation is 2.0kgf / cm ²
That is all. The moisture permeability of the film alone is 30,000 g /
If it is lower than m ² · 24 hr, the reduction in moisture permeability during bonding will increase. On the other hand, if the water pressure required for water permeability is lower than 2.0 kgf / cm ² , the water resistance cannot be improved at the time of bonding.

The main component of the water-swellable resin layer in the present invention is a polyurethane resin, and the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of isocyanate constituting the polyurethane resin is 5 or more and less than 30. Is preferred.

When the main component is a polyurethane resin,
When a film is bonded to a substrate such as a cloth, a coating material, or a laminate material to be bonded, the film has excellent stretchability, a small change in texture, and even when films having different thicknesses are laminated, the film This is preferable because the followability is extremely excellent and the adhesion between the films is kept high.

The polyurethane resin mentioned here includes a copolymer obtained by reacting a polyisocyanate and a polyol.

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

For example, tolylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, 4,4'-
Methylene bis (cyclohexyl isocyanate), hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate and the like can be used.

As the polyol component, polyether polyol, polyester polyol and the like can be used. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. Polyester polyols include reaction products of diols such as ethylene glycol and propylene glycol with dibasic acids such as adipic acid and sebacic acid, and caprolactone. Ring-opening polymers and the like. In addition, an ether / ester type, an amide type, a carbonate type, a silicone-modified type alone or a mixture thereof can be used as appropriate.

The polyisocyanate is preferably 4,4'-diphenylmethane diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate) from the viewpoint of the development of tensile strength of the resin, and the polyurethane is preferably a polyurethane resin containing polyethylene glycol as the main component from the viewpoint of moisture permeability. It is.

In the present invention, the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of isocyanate constituting polyurethane is preferably 5 or more and less than 30 from the viewpoint of achieving both excellent moisture permeability and waterproofness. .

By using such a resin, 0.1.
003 mm to 0.06 mm film thickness, preferably 0.005 mm
When the resin layer is a continuous layer in the thickness range of mm to 0.03, and the material has water permeability of 30,000 g / m ² · 24 hr or more even if there are no large holes, the resin layer is water-permeable. The required water pressure is 2.0 kgf / cm ² or more, which makes it possible to achieve both moisture permeability and water resistance.

The main component of the adhesive layer is a polyurethane resin, and the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of isocyanates constituting the polyurethane is preferably 20 or more and less than 30.

When the main component is polyurethane, it is preferable because the adhesiveness to the water-swellable resin layer and the adhesive surface to the substrate are excellent and the adhesiveness is kept high.

When the ratio of the number of polyethylene glycols to the number of isocyanates in the polyurethane resin is 20 or more and less than 30, the soft segment ratio is high, so that a soft resin layer can be obtained, and the softening point can be lowered to improve the meltability. In addition, it is preferable to maintain high moisture permeability as a film even after crosslinking with a crosslinking agent.

Here, it is preferable that the thermal dissociation temperature at which the reactive end of the crosslinking agent contained in the adhesive layer is released is higher than the softening point of the main component polymer of the adhesive layer.

When the thermal dissociation temperature is higher than the softening point of the polymer, the polymer is brought into a molten state, and the reactive terminal is released only after the polymer has sufficiently adhered to the base material, whereby cross-linking between the polymers and the polymer and the base material are completed. This is because the cross-linking with is sufficient.

The relationship between the softening point of the main component polymer and the thermal dissociation temperature of the crosslinking agent is preferably (softening point + 10 ° C.) or more, more preferably (softening point + 20 ° C.) or more. If the temperature difference between the thermal dissociation temperature and the softening point is too small, softening and cross-linking of the resin occur at the same time, so that sufficient adhesiveness may not be obtained.

Considering the thermal dissociation temperature of the cross-linking agent, if it is necessary to improve the meltability of the adhesive layer, the addition of a polyhydric alcohol serving as a soft segment and the addition of an aliphatic epoxy compound as appropriate may be used. You may.

The reactive terminal released by thermal dissociation is preferably an isocyanate group. Isocyanate groups are excellent in reactivity, can be bonded to various functional groups such as hydroxyl group and amino group, and can easily block isocyanate groups that are reactive terminals, and have various thermal dissociation characteristics tailored to the base material This is because a crosslinking agent can be synthesized.

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

For example, tolylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, 4,4'-
Methylene bis (cyclohexyl isocyanate), hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, or the like, or a combination thereof with a polyol can also be used as a terminal isocyanate urethane prepolymer.

As the blocking agent, the isocyanate terminal of the above-mentioned isocyanate component is converted to bisulfite, ε-
Lactams such as caprolactam, ethyl acetoacetate,
Active methylene compounds such as acetylacetone, oximes such as acetoxime and cyclohexanone oxime,
Secondary aromatic amines such as N-methylaniline, aromatic mercaptans such as hydrocyanic acid and β-thionaphthol, aliphatic mercaptans such as ethyl mercaptan, and lower alcohols such as phenol, methanol and ethanol are used according to thermal dissociation temperature. Is done.

Next, the usage of the film of the present invention will be described. (1) The adhesive layer is a continuous layer and has no pores of 400 nm or more in a state not swelled with water, and is entirely laminated on the water-swellable resin layer. The layer is a discontinuous layer, has no pores of 400 nm or more in a state not swelled with water, and is partially laminated on the water-swellable resin layer. (3) The adhesive layer is continuous (4) The adhesive layer is a discontinuous layer and a porous layer, and is partially laminated on the water-swellable resin layer. There are four forms of use.

The form (1) is a state in which a continuous water-swellable resin layer is provided, and a continuous nonporous adhesive layer is laminated thereon. Since the adhesive layer is entirely laminated, it can be preferably used when high adhesiveness is required.

The form (2) is a state in which a continuous water-swellable resin layer is provided, and a non-porous adhesive layer is laminated on the continuous water-swellable resin layer. Since the adhesive layer is partially laminated, it can be preferably used when flexibility is required.

The form (3) is a state in which a continuous water-swellable resin layer is provided, and a continuous porous adhesive layer is laminated thereon. Since it is entirely laminated with a porous layer, it can be preferably used when moisture permeability and adhesiveness are required.

The mode (4) refers to a state in which a continuous water-swellable resin layer is provided, and a dot-like porous adhesive layer is laminated thereon. Since the adhesive layer is partially laminated and a porous layer, it can be preferably used when flexibility and adhesiveness are required.

In the present invention, the water-swellable resin layer itself may be an adhesive layer. In this case, it becomes a continuous one-layer adhesive film containing the crosslinking agent in the water-swellable resin layer itself. It is provided between the substrates to be bonded, and can be preferably used when lamination bonding is required.

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

The film of the present invention is formed by coating a water-swellable resin solution on a release support to form a continuous layer, on which a crosslinking agent capable of releasing a reactive terminal by thermal dissociation. Is produced by applying a solution of an adhesive layer containing, and forming a film at a temperature lower than the thermal dissociation temperature of the crosslinking agent.

The release support used in the present invention means a support having a smooth surface and a low affinity for a resin film formed on the support, such as a taffeta fabric, film, or paper. . Usually, a release paper or film coated with a silicone resin, a polypropylene film and a release paper laminated with the film are preferably used.

The term “resin solution” as used in the present invention refers to a resin solution obtained by dissolving a resin component in a mixed solvent of a volatile organic solvent, a forced emulsified dispersion obtained by forcibly emulsifying the resin component in water with a surfactant, or the like. It refers to a self-emulsifying dispersion or an aqueous resin solution that has been made self-emulsifying or soluble in water by polymer modification of components.

These resin solutions may be applied onto a mold release support, and the solid content may be solidified by eliminating the solvent in which the resin is dissolved to form a film.

In order to coat a resin on a release support and form a film, generally, knife over roll coating,
Using a coating formulation such as direct roll coating, reverse roll coating, gravure coating, or rotary screen, the coating amount is appropriately set on the release support so that a desired film thickness is obtained, and the coating is performed at a temperature of 5 ° C.
Drying at 0 ° C to 180 ° C for 0.5 to 10 minutes,
It can be formed by coating.

In the case of coloring the water-swellable resin layer or the like, an inorganic or organic pigment or the like is appropriately added to the resin solution by a known method. It is also possible to form a film.

The film of the present invention can be produced by applying an adhesive layer solution containing a crosslinking agent which releases a reactive terminal by thermal dissociation and forming a film at a temperature lower than the thermal dissociation temperature of the crosslinking agent.

The adhesive layer may be formed on the previously formed water-swellable resin layer by applying a solvent, dissolving the solvent in which the adhesive layer resin is dissolved, and solidifying the solid content.

The coating method of the adhesive layer is appropriately selected depending on the use form of the film. In the case of laminating the adhesive layer over the entire surface, coating-film formation may be generally performed using a coating formulation such as knife over roll coating, direct roll coating, and reverse roll coating.

When the adhesive layer is partially laminated, it may be formed by coating using a coating formulation such as gravure coating or rotary screen.

When the adhesive layer is a porous layer, the resin solvent is replaced with a poor solvent after coating the adhesive layer by the above-described method.
Porosity may be obtained by a method such as porosity by a wet film forming method of coagulation, porosity by a dry film forming method of selectively evaporating an elution solvent, or porosity by a dry film forming method of gas foaming.

At this time, it is important that the film forming temperature of the adhesive layer is lower than the thermal dissociation temperature of the crosslinking agent. Regarding the relationship between the film forming temperature and the thermal dissociation temperature, the film forming temperature is preferably (thermal dissociation temperature −10 ° C.) or less, more preferably (thermal dissociation temperature −20 ° C.) or less. If the temperature difference between the film forming temperature and the thermal dissociation temperature is too small, a cross-linking reaction occurs simultaneously with the formation of the adhesive layer, so that sufficient adhesiveness may not be obtained.

The present film is obtained by mixing a crosslinking agent capable of releasing a reactive terminal by thermal dissociation with a water-swellable resin solution,
It can also be produced by coating on a release support and forming a film at a temperature lower than the thermal dissociation temperature of the crosslinking agent.

In this case, a water-swellable resin solution containing a crosslinking agent capable of releasing a reactive terminal by thermal dissociation is applied onto a release support, and a film is formed at a temperature lower than the thermal dissociation temperature of the crosslinking agent. What is necessary is just to form a continuous layer, and what is necessary is just to utilize the above-mentioned method suitably for the method of coating-film formation.

At this time, it is important that the film forming temperature of the water-swellable resin layer is lower than the thermal dissociation temperature of the crosslinking agent. The relationship between the film forming temperature and the thermal dissociation temperature is as follows.
0 ° C.) or lower, and (thermal dissociation temperature −20).
C) or lower. If the temperature difference between the film forming temperature and the thermal dissociation temperature is too small, a cross-linking reaction occurs simultaneously with the formation of the adhesive layer, and it is not preferable because sufficient adhesiveness may not be obtained.

As described above, the main component of the water-swellable resin layer of the film of the present invention is a polyurethane resin, and the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of isocyanate constituting the polyurethane resin is 5%. It is preferably at least 30 and less than 30.

Specifically, a resin solution in which a polyurethane resin having a ratio of 5 or more and less than 30 is dissolved in a mixed solvent of a polar organic solvent such as dimethylformamide and a volatile organic solvent such as methyl ethyl ketone in an amount of 5 to 60% by weight. It can be used in the form of a forced emulsified dispersion which is forcibly emulsified in water with a surfactant or the like, a self-emulsified dispersion which is made to have self-emulsifiability or solubility in water by polymer modification, or an aqueous resin solution.

It is preferable that the main component of the adhesive layer is polyurethane having a ratio of the number of ethylene glycol constituting the polyethylene glycol in the polyol to the number of isocyanates of 20 or more and less than 30.

Specifically, a resin solution obtained by dissolving a polyurethane resin having a ratio of 5 to less than 30 in a mixed solvent of a polar organic solvent such as dimethylformamide and a volatile organic solvent such as methyl ethyl ketone in an amount of 5 to 60% by weight. It can be used in the form of a forced emulsified dispersion which is forcibly emulsified in water with a surfactant or the like, a self-emulsified dispersion which is made to have self-emulsifiability or solubility in water by polymer modification, or an aqueous resin solution.

In the present invention, the reactive terminal released by thermal dissociation is preferably an isocyanate group.

As the compound having an isocyanate group, a polyisocyanate having a reactive terminal blocked can be used.

The amount of the block type polyisocyanate to be added depends on the isocyanate terminal amount, but is preferably 0.3% by weight or more based on the solid content of the main component polymer in the adhesive layer in view of the balance between moisture permeability and adhesiveness after adhesion. % By weight, more preferably 1% by weight to 10% by weight.

As described above, high moisture permeability is achieved by comprising a continuous film layer having high water permeability and high water permeability having water swelling properties and an adhesive layer exhibiting crosslinking and adhesion by heat treatment. And high water resistance can be obtained.

The film of the present invention can be improved in material performance simply by being attached to a substrate. In addition to fishing, climbing clothing and other outdoor wear, ski-related wear, windbreakers, athletic wear, golf wear rainwear, casual coat, etc.
Improvement of moisture-permeable and waterproof materials that can be used for outdoor work clothes, gloves, shoes, etc., and fabrics made of synthetic fibers such as polyester, polyamide, and acrylic, and fibers such as natural fibers such as cotton, wool, and silk. , A knitted fabric, a non-woven fabric, or the like to impart a moisture-permeable and waterproof function.

[0074]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

The evaluation in the examples was performed by the following method. [Moisture permeability] Measured according to JIS L1099 potassium acetate method. [Hydraulic pressure] Measured according to JIS L1092 high water pressure method. However, in order to suppress rupture due to membrane elongation, the water pressure at the time when water was leaked through the taffeta was covered with the polyester taffeta, and the water pressure was used as the water pressure.

<Polyester Taffeta> Threading 75 denier-72 filaments (vertical, horizontal) Weaving density 110 × 95 yarns / inch Weight 150 g / m ² [Adhesiveness] A film was formed, and after 24 hours, a main component of the adhesive layer was formed. Roll temperature above the softening point of the polymer, linear pressure 1.2
Thermal lamination was performed at kg / cm. After lamination, the laminate was treated in an atmosphere at a temperature equal to or higher than the thermal dissociation temperature of the cross-linking agent for 2 minutes to adhere to the nylon taffeta. Then 2
After immersion in water at 3 ° C. for 24 hours, the wet peel strength was measured, and a value of 150 g / cm or more was regarded as high adhesiveness.

<Wet Peel Strength> １５０150 g / cm or more １００ 100 g / cm or more and less than 150 g / cm △ 50 g / cm or more and less than 100 g / cm × less than 50 g / cm <Nylon Taffeta> Threading 70 D / N-68 filament (vertical, Horizontal) Weave density 116 × 88 yarns / inch Weight 72 g / m ² Example 1 The isocyanate is 4,4′-diphenylmethane diisocyanate, and the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number is 8.4. Dissolve a certain water-swellable polyurethane resin in a mixed solvent of dimethylformamide and methyl ethyl ketone,
A 23% by weight solution was prepared.

Using a knife coater, a coat of 0.08 mm was applied to release paper on which a polypropylene film was laminated, and dried at 120 ° C. for 2 minutes to form a film.

A water-swellable polyurethane resin in which the isocyanate is 4,4'-methylenebis (cyclohexyl isocyanate) and the ratio of the number of ethylene glycol constituting the polyethylene glycol in the polyol to the number is 25 is obtained by mixing dimethylformamide and methyl ethyl ketone. It was dissolved in a solvent to prepare a 23% by weight solution.

To the solution was added 4,4'-diphenylmethane diisocyanate whose isocyanate group was blocked with methyl ethyl ketoxime so as to be 10% by weight based on the weight of the resin to prepare an adhesive layer solution.

This adhesive layer solution was applied over the entire surface of the water-swellable resin layer formed on the release paper using a knife coater with a clearance of 0.1 mm, and dried at 110 ° C. for 1 minute to form a film. Then, a film was prepared.

As shown in Table 1, the moisture permeability was 48,000.
It was an adhesive moisture-permeable and waterproof film having high moisture permeability and waterproofness at a g / m ² · 24 hr and a water permeability of 3.0 kgf / cm ^2, and having high adhesiveness.

Example 2 An adhesive layer solution was coated on a water-swellable resin layer with a dot diameter of 0.2 m.
m, dot pitch: 0.3 mm, dot depth: 0.1 mm, dot arrangement: a film was produced in the same manner as in Example 1 except that the coating was partially applied with a 60 ° staggered roll.

As shown in Table 1, the moisture permeability was 72,000.
It was an adhesive moisture-permeable and waterproof film having high moisture permeability and waterproofness at a g / m ² · 24 hr and a water permeability of 3.0 kgf / cm ^2, and having high adhesiveness.

Example 3 In the adhesive layer solution, 2%
A film was produced in the same manner as in Example 1 except that 2'-azobisisobutyronitrile was added.

As shown in Table 1, the moisture permeability was 56,000.
g / m ² · 24 hr, water pressure resistance of 3.0 kgf / cm ² , a highly moisture-permeable and waterproof film having high moisture permeability and high adhesiveness.

Example 4 The release support was changed to a polypropylene film, and a water-swellable resin layer was formed under the same conditions as in Example 1. The adhesive layer solution in which the solvent was replaced with dimethylformamide was completely coated on the water-swellable resin layer with a knife coater with a clearance of 0.1 mm, and then immersed in water at 25 ° C for 5 minutes to form a film by wet coagulation. A film was produced.

As shown in Table 1, the moisture permeability was 50,000.
g / m ² · 24 hr, water pressure resistance of 3.0 kgf / cm ² , a highly moisture-permeable and waterproof film having high moisture permeability and high adhesiveness.

Example 5 An adhesive layer solution was applied onto a water-swellable resin layer with a dot diameter of 0.2 m.
m, dot pitch: 0.3 mm, dot depth: 0.1 mm, dot arrangement: a film was produced in the same manner as in Example 3 except that the coating was partially applied with a 60 ° staggered roll.

As shown in Table 1, the moisture permeability was 83,000.
It was an adhesive moisture-permeable and waterproof film having high moisture permeability and waterproofness at a g / m ² · 24 hr and a water permeability of 3.0 kgf / cm ^2, and having high adhesiveness.

Example 6 A water-swellable polyurethane resin in which the isocyanate is 4,4'-diphenylmethane diisocyanate and the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of the isocyanate is 8.4 was prepared by using dimethylformamide and methyl ethyl ketone. Dissolved in a mixed solvent of
A 23% by weight solution was prepared.

To the solution was added 4,4'-diphenylmethane diisocyanate having an isocyanate group blocked with ε-caprolactam so as to be 10% by weight based on the resin weight to prepare an adhesive layer solution.

A knife coater was used to coat a release film on which a polypropylene film was laminated with a clearance of 0.15 mm, dried at 120 ° C. for 2 minutes, and formed into a film to prepare a film.

As shown in Table 1, this film has a high moisture permeability and a waterproof property of 80,000 g / m ² · 24 hr and a water pressure resistance of 3.0 kgf / cm ² , and at the same time has high adhesiveness. It was an adhesive moisture-permeable waterproof film having the following.

Example 7 A water-swellable polyurethane resin in which the isocyanate is 4,4'-methylenebis (cyclohexyl isocyanate) and the ratio of the number of ethylene glycol constituting the polyethylene glycol in the polyol to the number of the water is 25 was dimethylformamide and methyl ethyl ketone. Was dissolved in a mixed solvent of to prepare a 23% by weight solution.

To the solution was added 4,4'-diphenylmethane diisocyanate whose isocyanate group was blocked with methyl ethyl ketoxime so as to be 10% by weight based on the weight of the resin to prepare an adhesive layer solution.

Using a knife coater, a polypropylene film was coated on release paper with a clearance of 0.15 mm, dried at 120 ° C. for 2 minutes, and formed into a film to produce a film.

As shown in Table 1, this film has a high moisture permeability and a high water vapor transmission property of 96,000 g / m ² · 24 hr and a water pressure resistance of 3.0 kgf / cm ² , and at the same time has high adhesiveness. It was an adhesive moisture-permeable waterproof film having the following.

Example 8 A film was produced in the same manner as in Example 1, except that glycerin was added as a melt improver for the adhesive layer in an amount of 20% by weight based on the weight of the resin.

As shown in Table 1, this film has a high moisture permeability of 96,000 g / m ² · 24 hr, a water pressure resistance of 2.0 kgf / cm ² , a high degree of moisture permeability and waterproofness, and a high adhesiveness. It was an adhesive moisture-permeable waterproof film having the following.

Example 9 A film was produced in the same manner as in Example 1 except that glycerin was added as a melting improver for the adhesive layer and glycerol polyglycidyl ether was added as an adhesion improver at 10% by weight based on the weight of the resin. .

As shown in Table 1, this film has a high moisture permeability of 88,000 g / m ² · 24 hr and a water pressure resistance of 3.0 kgf / cm ^2, and has high moisture permeability and waterproofness, and at the same time, high adhesiveness. It was an adhesive moisture-permeable waterproof film having the following.

Comparative Example 1 A hydrophobic polyurethane resin in which the isocyanate is 4,4'-diphenylmethane diisocyanate and the ratio of the number of ethylene glycol constituting the polyethylene glycol in the polyol to the number is 0 is used instead of the water-swellable resin. A film was produced in the same manner as in Example 1 except that the film was made.

As shown in Table 1, the water permeation pressure was 6.0 kgf / cm.
^While having high water resistance exceeding ² , it has high adhesiveness, but because it is a hydrophobic polyurethane, moisture permeability is 3,
The film was as low as 2,000 g / m ² · 24 hr.

Comparative Example 2 A film was produced in the same manner as in Example 1, except that the isocyanate was not blocked with methyl ethyl ketoxime.

As shown in Table 1, the moisture permeability was 32,000.
g / m ²・ 24hr Water permeability is 4.0kgf / cm ^2, which has high moisture permeability and waterproofness. The film was inactivated and had low adhesion.

[0107]

[Table 1]

[0108]

According to the present invention, a continuous film layer having high moisture permeability and high water permeability having a water swelling property and an adhesive layer exhibiting crosslinking and adhesive properties by heat treatment are provided. A film that can achieve both high moisture permeability and high water resistance can be obtained.

By utilizing these effects, it is possible to improve the material performance simply by attaching the film of the present invention. In addition to outdoor wear such as fishing and mountaineering clothing, ski-related wear, windbreaker, athletic wear, golf wear rainwear, casual coat, etc., as well as outdoor work clothes, gloves, shoes, etc. Is a polyester,
Fabrics, knits, and fibers made of polyamide, synthetic fibers such as acrylics, and natural fibers such as cotton, wool, and silk.
It is also possible to provide a moisture-permeable and waterproof function by attaching the film to a nonwoven fabric or the like.

Continued on the front page F-term (reference) 4F100 AK01A AK01B AK01G AK51A BA02 CA02 DC27B DC27G DJ10B DJ10G EH46 EH462 GB72 JA04B JA04G JB07 JB10A JD04 JL11 JL11B JL11G YY00 YY00A 4J03 DC03 DF03 DB03 DG01 HC12 HC22 HC23 HC61 HC64 HD01 HD02 HD03 HD04 HD07 HD12 HD13 QB04 QB19 QC03 RA03 RA09 4L033 AC07 AC11 BA09 BA69 BA99 CA50 CA51

Claims (15)

[Claims] 1. A film comprising at least one continuous water-swellable resin layer and an adhesive layer, wherein said water-swellable resin layer does not have pores of 400 nm or more when not swelled with water. The adhesive layer contains a crosslinking agent capable of releasing a reactive terminal by thermal dissociation, the film has a moisture permeability of 30,000 g / m ² · 24 hr or more, and a water pressure required for water permeability of 2.
An adhesive moisture-permeable waterproof film having a weight of 0 kgf / cm ² or more. 2. The main component of the water-swellable resin layer is a polyurethane resin, and the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of isocyanates constituting the polyurethane resin is 5 or more and less than 30. The adhesive moisture-permeable waterproof film according to claim 1, characterized in that: 3. The adhesive layer according to claim 1, wherein a main component of the adhesive layer is a polyurethane resin, and a ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of isocyanate constituting the polyurethane is 20 or more and less than 30. The adhesive moisture-permeable waterproof film according to claim 1. 4. The adhesive according to claim 1, wherein the thermal dissociation temperature at which the reactive terminal of the crosslinking agent is released is higher than the softening point of the main component polymer of the adhesive layer. Water-permeable moisture-permeable film. 5. The adhesive moisture-permeable waterproof film according to claim 1, wherein the reactive terminal is an isocyanate group. 6. The method according to claim 1, wherein said adhesive layer is a continuous layer, has no pores of 400 nm or more when not swelled with water, and is entirely laminated on the water-swellable resin layer. The adhesive moisture-permeable waterproof film according to claim 1. 7. The adhesive layer is a discontinuous layer, has no pores of 400 nm or more in a state not swelled with water, and is partially laminated on a water-swellable resin layer. The adhesive moisture-permeable waterproof film according to any one of claims 1 to 5, wherein 8. The adhesive moisture-permeable material according to claim 1, wherein said adhesive layer is a continuous layer and a porous layer, and is entirely laminated on the water-swellable resin layer. Waterproof film. 9. The adhesive transparent layer according to claim 1, wherein the adhesive layer is a discontinuous layer and a porous layer, and is partially laminated on the water-swellable resin layer. Moist waterproof film. 10. The adhesive moisture-permeable waterproof film according to claim 1, wherein the water-swellable resin layer itself is also an adhesive layer. 11. An adhesive containing a cross-linking agent capable of releasing a reactive terminal by thermal dissociation to form a continuous layer by coating a water-swellable resin solution on a release support. A method for producing an adhesive moisture-permeable waterproof film, comprising applying a layer solution and forming a film at a temperature lower than the thermal dissociation temperature of the crosslinking agent. 12. A cross-linking agent capable of releasing a reactive terminal by thermal dissociation is mixed with a water-swellable resin solution, coated on a release support, and formed into a film at a temperature lower than the thermal dissociation temperature of the cross-linking agent. A method for producing an adhesive moisture-permeable waterproof film. 13. The water-swellable resin layer is mainly composed of a polyurethane resin, and the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of isocyanates constituting the polyurethane resin is 5 or more and less than 30. The method for producing an adhesive moisture-permeable waterproof film according to claim 11 or 12, wherein: 14. A main component of the adhesive layer is a polyurethane resin, and the ratio of the number of ethylene glycol constituting polyethylene glycol in the polyol to the number of isocyanates constituting the polyurethane is 20 or more and less than 30. A method for producing the adhesive moisture-permeable waterproof film according to any one of claims 11 to 13. 15. The method for producing an adhesive moisture-permeable waterproof film according to claim 11, wherein said reactive terminal is an isocyanate group.