JPH11207879A - Moisture permeable and waterproofing stock and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a moisture permeable and waterproofing a stock, which has a high filmy surface strength simultaneous with the high grade moisture permeability and waterproofness. SOLUTION: In this moisture permeable and water proofing stock, at least one water growing resin layer is provided so as to bond on one whole surface of a fibrous structure. At least one continuous resin layer is laminated onto a release substrate under the condition that its bonding layer becomes its uppermost layer and then turned into a film so as to contact-band the fibrous structure to the bonding layer. After bonding, the release substrate is removed. Thus, the enlargement of the developing usage in especially laminated stock becomes possible.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a moisture-permeable and waterproof material. More specifically, the present invention relates to a moisture-permeable waterproof material having high moisture-permeable performance and high waterproof performance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in a moisture-permeable and waterproof material, particularly a laminate type material in which a film is adhered, a method using an adhesive has been used to bond the film and the fabric.

[0003] Specifically, an adhesive is applied to a coating or a cloth, the coating and the cloth are pressed, and the adhesive is solidified to bond the two. However, in such a method, moisture permeability is low. Since the coating surface is covered with a low adhesive, there is a serious problem that the moisture permeability as a material is greatly reduced.

[0004] In order to solve such a problem, it is effective to use a method in which the adhesive is applied in a point-like form and the coating area of the film is reduced by the adhesive, thereby suppressing a decrease in moisture permeability as a material. It was a means.

[0005] However, in such a method, although the decrease in moisture permeability is suppressed due to the point-like adhesion, the coating is adhered to the cloth in a point-like manner, so that the film has a particularly high moisture permeability and water swellability. The coating has a new problem in that the coating has low water pressure resistance, and because of the point-like bonding, the unbonded coating is vulnerable to scratching or peeling.

[0006] From these facts, at present, there is no laminate material that can express moisture permeability, water resistance, and film surface strength in a well-balanced manner.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, an object of the present invention is to provide a moisture-permeable and waterproof material which is excellent in moisture permeability and water resistance and has excellent membrane surface strength, and a method for producing the same. It is assumed that.

[0008]

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

That is, it is a moisture-permeable and waterproof material in which at least one continuous water-swellable resin layer is provided on one surface of the fiber structure so as to adhere to the entire surface of the fiber structure.

[0010] The method for producing a moisture-permeable and waterproof material of the present invention has the following configuration to solve the above-mentioned problems.

That is, at least one continuous resin layer was laminated on the release support so that the adhesive layer was the uppermost layer, a film was formed, and a fibrous structure was bonded to the adhesive layer by pressure bonding. Thereafter, the method is a method for producing a moisture-permeable and waterproof material in which the release support is peeled off.

[0012]

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

[0013] The moisture-permeable waterproof material of the present invention comprises at least one continuous water-swellable resin layer provided on one surface of the fibrous structure so as to adhere to the entire fibrous structure.

In the present invention, at least one continuous water-swellable resin layer is provided on one surface of the fibrous structure, and this resin layer is a film which can swell by absorbing water on the fibrous structure. .

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. 5% to exhibit sufficient moisture permeability
As described above, a resin layer having a linear swelling ratio of 10% or more is more preferably used.

The fact that the fiber structure is adhered to the entire surface means that the fiber structure is taken as a surface instead of being adhered by a point-like adhesive layer as in the prior art. It means that the fiber structure surface is continuously covered and adhered to the resin layer surface. In other words, a structure that can exhibit water resistance even when only one resin layer is provided. The term “continuous resin layer” means that the resin film is two-dimensionally continuous in a range where the resin film is adhered to the fibrous structure, and has no discontinuous and discontinuous portions.

In the present invention, the resin layer preferably does not have pores of 400 nm or more when swelling in non-water. That is, this is because the resin layer itself does not have micropores that appear opaque in the visible light region, such as a polyurethane film produced by a wet film forming method,
It means a state in which there is no hole of not less than nm.

When the resin layer is a single layer, the layer itself is a continuous surface which is entirely adhered to the fibrous structure, and since there is no large hole, even a single layer of water swelling has high waterproofness. Can be expressed. The resin layer provided on the fiber structure is not limited to one layer, but may be a laminate of two or more resin layers. One of the layers is a layer (adhesion layer) that is entirely adhered to the fiber structure. In the present invention, the main component of the resin layer is preferably a polyurethane resin. Excellent texture and stretchability when the resin layer is bonded to the fiber structure, and even when layers with different thicknesses are laminated, the ability to follow each other is extremely excellent. Is also excellent in adhesiveness.

The polyurethane resin 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. Further, 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, ether / ester type, amide type, and carbonate type can also be appropriately used.

The polyisocyanate is preferably 4,4'-diphenylmethane diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate) from the viewpoint of the tensile strength of the resin, and the polyol 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 the polyethylene glycol in the polyol to the number of isocyanates constituting the polyurethane is preferably 5 or more and less than 30 from the viewpoint of achieving both excellent moisture permeability and waterproofness. .

By using a resin having the above constitutional requirements, a film having a thickness of 5 μm to 60 μm, preferably 1 μm to 60 μm.
In the range of 0 μm to 40 μm in thickness, the resin layer is a continuous layer. Even if there are no large pores, the material has a moisture permeability of 10,000 g / m ² · 24 hr or more and a water pressure of 2.
This makes it possible to achieve both 0 kgf / cm ^{2 and} higher performance.

In the present invention, the main component of the resin layer (adhesive layer) completely adhered to the fiber structure 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 determined. It is preferable that the ratio is 20 or more and less than 30.

In the present invention, all the resin layers provided on the fiber structure are continuous layers, and the adhesive layer also forms a continuous layer and is entirely adhered to the fiber structure. Therefore, the moisture permeability of the adhesive layer is very low. High is preferred.

Therefore, it is preferable to use a resin mainly composed of a polyurethane resin having a ratio of the number of polyethylene glycols to the number of isocyanates of 20 to less than 30 in the adhesive layer. Since the fiber structure is present on one side, swelling of the coating is suppressed, but excellent moisture permeability can be exhibited.

In the present invention, the adhesive layer in the resin layer is preferably a reaction product of a mixed resin of polyurethane and polyglycidyl ether and / or polyisocyanate.

When the reaction product of the mixed resin with polyglycidyl ether and / or polyisocyanate is used as the adhesive layer, it becomes a cross-linking agent between the polyurethane resins to increase the film strength and, at the same time, has a cross-linked structure with the fiber structure. Thereby, the adhesiveness is improved, and the waterproofness can be improved.

The polyglycidyl ether referred to here is an ether compound having two or more epoxy groups.
Sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylpropane polyglycidyl Ether, neopentyl glycerol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol glycidyl ether, polytetramethylene glycol diglycidyl ether, and the like can be used.

From the viewpoint of suppressing a decrease in moisture permeability after crosslinking, hydrophilic polyglycidyl ether is more preferable, and glycerol-based polyglycidyl ether can be preferably used.

As the polyisocyanate, any of an aromatic polyisocyanate and an aliphatic polyisocyanate can be used.
4'-diphenylmethane diisocyanate, 4,4'-
Dimers and trimers such as methylene bis (cyclohexyl isocyanate), hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate, and trimers modified by trimethylpropane can be used as appropriate.

From the viewpoint that the adhesive layer is in contact with the fibrous structure due to the fact that the adhesive layer is in contact with the fibrous structure, aliphatic polyisocyanates of a non-yellow type are more preferable, and dimers and trimers of hexamethylene diisocyanate, modified by trimethylpropane. Trimers are preferably used.

The fibrous structure in the present invention is a woven fabric made of synthetic fibers such as polyester, polyamide and acrylic and fibers such as natural fibers such as cotton, wool and silk.
It refers to a form such as a knit or a non-woven fabric, but is not limited thereto.

Next, a method of manufacturing a laminated material according to the present invention will be described.

The material of the present invention is formed by laminating and forming one or more continuous resin layers on a release support so that the adhesive layer is the uppermost layer, and pressing and adhering to a fibrous structure. It is manufactured by peeling from a mold support.

The release support used in the present invention refers to a material such as taffeta fabric, film, paper, etc., which has a smooth surface and a low affinity for a resin film formed on the support. Normally, release paper or film coated with a silicone resin, release paper laminated with polypropylene, or the like is preferably used. Laminating one or more continuous resin layers so that the adhesive layer is the uppermost layer, and forming a film,
In applying a resin layer on the release support and forming a film,
When the resin layer is a single layer, the layer itself serves as an adhesive layer and a resin layer. When a plurality of resin layers are laminated, the resin layers are sequentially applied so that the resin layer to be finally applied and formed becomes an adhesive layer. Means to be laminated.

In order to apply 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, or gravure coating, the coating amount is appropriately set on the release support so as to have a desired film thickness, and the coating is performed at a temperature of 50 ° C to 150 ° C. .
It can be formed by drying and forming a film under the conditions of 5 to 10 minutes.

Since the resin is a continuous layer, a knife coating method is preferable. If the resin is repeatedly formed and applied on the formed resin layer, the laminated resin layer can be formed.

At the time of coating, an isocyanate compound or the like may be appropriately used as a cross-linking agent in the resin solution for the purpose of improving solvent resistance and film strength.

When the resin layer is colored,
In the case of changing the surface touch, an inorganic or organic pigment or the like can be appropriately added to the resin layer by a known method.

Next, the fibrous structure is superimposed on the adhesive layer provided on the uppermost layer on the release support produced by the method described above, and pressure is applied to the resin layer and the fibrous structure via the adhesive layer. Then, the fibrous structure to which the resin layer is bonded is peeled off from the release support.

In the present invention, pressure is applied to press down and adhere to each other. In the present invention, pressure is applied between rolls, and the fiber structure laminated with the release support and the resin passes between the rolls. It is adhered by doing. At this time, by applying a desired pressure between the rolls and, at the same time, heating the rolls, it is possible to further improve the pressure-bonding property.

Next, the moisture-permeable waterproof material of the present invention can be obtained by peeling the release support from the fibrous structure to which the release support and the resin layer are bonded.

After peeling, if necessary, high cross-linking by aging and curing, and water-repellent treatment of the surface of the fiber structure can be appropriately performed by a known method.

As described above, the ratio of the number of ethylene glycols constituting the polyethylene glycol in the polyol to the number of isocyanates is 5 to 30.
Preferably, the polyurethane is less than.

Specifically, a resin solution in which a polyurethane resin having this 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 10 to 60% by weight. Is coated on a release support to form a film.

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

More specifically, a resin solution in which polyurethane having a ratio of 20 to 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 10 to 60% by weight is used. It is applied on the uppermost layer of the resin layer to form a film.

Further, the adhesive layer is preferably a reaction product of a mixed resin of polyurethane and polyglycidyl ether and / or polyisocyanate.

Specifically, polyglycidyl ether or polyisocyanate alone is used alone in a polyurethane resin solution dissolved in a mixed solvent of a polar organic solvent such as dimethylformamide or the like and a volatile organic solvent such as methyl ethyl ketone or the like in an amount of 10 to 60% by weight. Or a mixed resin solution containing a mixture thereof is applied to the uppermost layer of the resin layer to form a film.

The amount of polyglycidyl ether added to the solid content of the polyurethane is preferably 1% by weight or more and less than 30% by weight, and the amount of polyisocyanate added is 3% by weight or more and less than 40% by weight from the viewpoint of moisture permeability and adhesion. preferable.

With such a constitution, the function of the present invention is to obtain a film surface strength which cannot be obtained by point-like bonding, since the continuous coating layer having water swelling and having high moisture permeability is entirely adhered to the fiber structure. At the same time, since the swelling of the membrane itself is suppressed, it is a material that can achieve both high waterproofness and moisture permeability.

By using such an action, the material of the present invention can be used for outdoor workwear such as fishing, mountaineering clothing and other outdoor wear, ski-related wear, windbreaker, athletic wear, golf wear rainwear, casual coat, and the like. , Gloves, shoes, etc.

[0055]

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

The base fabric used in the present invention and the evaluation method are described below.

[Base cloth] (1) Nylon taffeta Thread use 70 denier-68 filament (vertical, horizontal) Weave density 116 × 88 / inch  Weight 72g / m^Two (2) Polyester taffeta Threading 75 denier-72 filaments (vertical, horizontal) Weave density 110 × 95 / inch Weight 150g / m^Two [Moisture permeability] According to JIS L 1099 potassium acetate method
Measured.

[Water resistance] Measured according to JIS L 1092 high water pressure method.

[Film surface strength 1] A stainless steel paper knife was attached to the friction part of the Gakushin type friction fastness measuring device.
The water pressure was measured after the film surface was reciprocated once with a load of 200 g.

[Film surface strength 2] A cloth gum tape (Nichiban rayon cloth tape) is adhered to the sample film surface and peeled off at a stretch. The water pressure resistance after peeling was measured.

[Example 1] 4,4'-isocyanate
A water-swellable polyurethane resin which is diphenylmethane diisocyanate and the ratio of the number of ethylene glycol constituting the polyethylene glycol in the polyol to the number is 8.4 is dissolved in a mixed solvent of dimethylformamide and methyl ethyl ketone, and a 23% by weight solution is dissolved. Prepared.

Using a knife coater, apply on the release support with a clearance of 200 μm and dry at 120 ° C. for 2 minutes.
A film was formed.

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.

Polyglycerol glycidyl ether (epoxy equivalent: 141) was added to the above solution in an amount of 20% by weight based on the weight of the resin, and isocyanurate bond, a trimer of hexamethylene diisocyanate, was added in an amount of 10% by weight based on the weight of the resin. Hexamethylene diisocyanate was added to prepare an adhesive layer solution.

Using a knife coater, this solution was applied to a resin layer formed on a release support, using a knife coater to give a clearance of 200 μm.
m and dried at 120 ° C. for 1 minute to form a film.

Nylon taffeta was superimposed on the adhesive layer, and the nylon taffeta and the resin layer were adhered by passing through a hot roll having a linear pressure between the metal roll and the rubber roll of 9 kg / cm and a metal roll temperature of 130 ° C.

After bonding, the release support was peeled off and the sample
Aged at room temperature for hours.

After aging, curing was performed at 160 ° C. for 2 minutes to produce a material of the present invention.

As shown in Table 1, the moisture permeability was 23,000.
At the same time g / m ² · 24hr and water pressure comprises a waterproof and 3.0 kgf / cm ² Advanced breathable, scratching, even film surface has high strength against peeling, moisture-permeable waterproof pressure drop is no It was a waterproof material.

Example 2 A moisture-permeable and waterproof material was produced in the same manner as in Example 1 except that a polyester fabric was used as the base fabric.

As shown in Table 1, the moisture permeability was 32,000.
At the same time g / m ² · 24hr and water pressure comprises a waterproof and 3.0 kgf / cm ² Advanced breathable, scratching, even film surface has high strength against peeling, moisture-permeable waterproof pressure drop is no It was a waterproof material.

Example 3 A moisture-permeable and waterproof material was produced in the same manner as in Example 1 except that only the adhesive layer of Example 1 was used.

As shown in Table 1, the moisture permeability was 26,000.
At the same time g / m ² · 24hr and water pressure comprises a waterproof and 3.0 kgf / cm ² Advanced breathable, scratching, even film surface has high strength against peeling, moisture-permeable waterproof pressure drop is no It was a waterproof material.

Example 4 A mixture of hexamethylene diisocyanate without adding glycerol glycidyl ether was prepared.
Example 1 except that the monomer was added in an amount of 20 parts based on the weight of the resin.
A moisture permeable waterproof material was produced in the same manner as described above.

As shown in Table 1, the moisture permeability was 20,000.
At the same time g / m ² · 24hr and water pressure comprises a waterproof and 3.0 kgf / cm ² Advanced breathable, scratching, even film surface has high strength against peeling, moisture-permeable waterproof pressure drop is no It was a waterproof material.

[Comparative Example 1] The same method as in Example 1 was used except that the resin layer of Example 1 was laminated and bonded with an adhesive layer applied in a dotted pattern so that the coverage of the resin layer with the adhesive layer was 40%. A wet waterproof material was produced.

As shown in Table 1, the moisture permeability was 34,000.
g / m ² · 24hr and water pressure comprises a waterproof and 2.0 kgf / cm ² Advanced moisture permeability, but since it is a point-like adhesive, scratching, a low resistant material with respect to flaking of the film surface there were.

[0078]

[Table 1]

[0079]

According to the present invention, it is possible to obtain a moisture-permeable waterproof material having high moisture permeability and waterproofness, and at the same time, a high film surface strength. Becomes

Claims (9)

[Claims] 1. A moisture-permeable and waterproof material characterized in that at least one continuous water-swellable resin layer is provided on one surface of the fiber structure so as to be adhered to the entire surface of the fiber structure. 2. The method according to claim 1, wherein said resin layer is 400 n
2. The moisture-permeable and waterproof material according to claim 1, wherein the material does not have a hole of not less than m. 3. A method according to claim 1, wherein the main component of the 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 moisture-permeable waterproof material according to claim 1 or 2, wherein 4. A polyurethane resin is the main component of the resin layer entirely bonded to the fiber structure, 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 to 30. Less than 3
The moisture-permeable waterproof material according to any of the above. 5. The resin layer according to claim 1, wherein the resin layer entirely adhered to the fiber structure comprises a reaction product of a mixed resin of polyurethane and polyglycidyl ether and / or polyisocyanate. Moisture permeable waterproof material. 6. A film is formed by laminating at least one continuous resin layer on a release support so that an adhesive layer is an uppermost layer.
A method for producing a moisture-permeable and waterproof material, comprising: pressing a fibrous structure onto the adhesive layer, bonding the fibrous structure to the adhesive layer, and releasing the release support. 7. The moisture-permeable and waterproof material according to claim 6, wherein the main component of the resin layer is a polyurethane having a ratio of the number of ethylene glycol constituting the polyethylene glycol in the polyol to the number of isocyanates of 5 to less than 30. Material manufacturing method. 8. The transparent material according to claim 6, wherein a main component of the adhesive layer is a polyurethane having a ratio of the number of ethylene glycol constituting the polyethylene glycol in the polyol to the number of isocyanates of from 20 to less than 30. Manufacturing method of wet waterproof material. 9. The method for producing a moisture-permeable and waterproof material according to claim 6, wherein said adhesive layer comprises a reaction product of a mixed resin of polyurethane and polyglycidyl ether and / or polyisocyanate. .