JP2002030576A - Moisture-permeable and waterproof material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture-permeable and waterproof material optimized in the balance between the moisture absorbability/releasability of the material as a whole and that of the coat thereon, having higher moisture permeation performance as a result of continually raising moisture releasability out of the garment, and furnished with waterproof performance as well, and to provide a method for producing such a material. SOLUTION: This moisture-permeable and waterproof material is such that one side of a fibrous structural material is provided with at least one continuous moisture-absorbing/releasing layer; wherein the difference between the moisture absorption at 30 deg.C and 90%RH and that at 20 deg.C and 65%RH is 6-15% for the moisture-absorbing/releasing layer(s) singly, the difference between the moisture absorption at 30 deg.C and 90%RH and that at 20 deg.C and 65%RH is 1-6% for this material, and the percent linear swelling of the material on absorbing water is 10-25%.

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 and waterproof material having excellent moisture-permeability by imparting high moisture-absorbing and desorbing properties and also having a waterproof property.

[0002]

2. Description of the Related Art Hitherto, in order to further improve the comfort of a moisture-permeable waterproof material, various studies have been made on improving the moisture permeability.

In the case of using a porous layer, the pore size,
The moisture permeability is improved by controlling the porosity, and in the case of using a non-porous layer, the moisture permeability is improved by polymer phase separation and introduction of a hydrophilic segment.

[0004] In recent years, many materials that focus on hydrophilic nonporous membranes have been studied.
Many materials have high moisture permeability and low dew condensation when they come into direct contact with liquid sweat.

[0005] However, in the improvement of moisture permeability by making the nonporous membrane hydrophilic, a decrease in water resistance and a decrease in film strength due to the high hydrophilicity are observed. Thus, although the moisture permeability of the membrane alone is high, it is required when a material is used. At present, sufficient performance has not been obtained and a comprehensive design has not yet been made.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention focuses on the balance between the moisture absorption / desorption properties of the entire material and the moisture absorption / desorption properties of the coating film, and constantly enhances the moisture absorption / desorption property outside the clothes.
It is an object of the present invention to provide a moisture-permeable waterproof material having excellent moisture-permeability and also having waterproof performance.

[0007]

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

Specifically, in a material having at least one moisture absorbing / releasing layer provided on one surface of a fiber structure, the moisture absorbing / releasing layer alone has a moisture absorption rate at 30 ° C. of 90% RH and a moisture absorption rate of 20 ° C. 65% RH.
The difference between the moisture absorption rate at 30 ° C. and 90% RH and the difference between the moisture absorption rate at 30 ° C. and 90% RH and the moisture absorption rate at 20 ° C. and 65% RH are 1 or more and 6 or less, A moisture-permeable and waterproof material characterized in that the moisture absorption / release layer alone has a greater moisture absorption than the material.

[0009]

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

The moisture-permeable and waterproof material of the present invention comprises at least one moisture-absorbing layer provided on one surface of a fiber structure.

[0011] The provision of at least one moisture absorbing / releasing layer on one surface of the fiber structure means that the resin layer capable of highly absorbing moisture and releasing the absorbed moisture on the fiber structure is a fiber. It means that it is bonded to the structure.

The term "adhesion" as used herein means that the coating itself is directly adhered to the fibrous structure or adhered via an adhesive.

Further, it is preferable that the moisture absorption / release layer is provided continuously on the fiber structure.

The resin layer used for the moisture absorbing / releasing layer is composed of a resin alone containing a polyurethane-based, polyester-based, polyamide-based, silicone-based polymer, or the like as a main component, or a mixture of these resins. It can be suitably used from the viewpoint of.

Among them, a polyurethane resin containing a hydrophilic polyol such as polyethylene glycol or polypropylene glycol can be preferably used in order to exhibit a high degree of moisture absorption and release, and the content of the hydrophilic polyol is 10% by weight or more and 50% by weight or less. Are preferred.

Particularly, from the viewpoint of film strength, a polyurethane in which a diol composed of an aliphatic carbonate is introduced into the main chain is preferable. Further, it is preferable that the hydrophilic polyol is mainly contained in the side chain rather than the main chain.

In the present invention, the difference between the moisture absorption of the material at 30 ° C. and 90% RH and the moisture absorption at 20 ° C. and 65% RH is 2 or more and 6 or less.

30 ° C., 90% RH means an atmosphere at a temperature of 30 ° C. and a relative humidity of 90%.

The moisture absorption is a ratio calculated from the amount of moisture absorption when left in the atmosphere for a certain period of time.

In the present invention, at 30 ° C.
The difference between the moisture absorption rate at 0% RH and the moisture absorption rate at 20 ° C. and 65% RH is 6 or more and 15 or less;
The difference between the moisture absorption at 20 ° C. and 65% RH is 1
It is important that the number is 6 or less.

It is important that the moisture absorption / desorption layer has a higher moisture absorption than the material.

As described above, by setting the moisture absorption / desorption property of the moisture absorption / desorption layer alone to be higher than the moisture absorption / desorption property of the material, the movement of moisture in the entire material is always performed from the moisture absorption / desorption layer side to the fiber structure side, that is, clothing. The driving force works from the inside to the outside of the garment, allowing for more comfortable material design.

In the material of the present invention, as described above, the moisture absorption and desorption layers alone at 30 ° C. and 90% RH and the moisture absorption at 20 ° C. and 65% RH are used from the viewpoint of high moisture permeability and imparting comfort. It is preferable that the difference from the ratio is 6 or more and 15 or less,
The difference between the moisture absorption rate at 30 ° C. and 90% RH and the moisture absorption rate at 20 ° C. and 65% RH is to correlate with the comfort when assuming actual wearing.

Further, the range of the difference in the moisture absorption rate of the moisture absorbing / releasing layer is preferably 6 or more from the viewpoints of suppressing a decrease in film physical properties due to hydrophilicity and suppressing an increase in weight due to moisture absorption of the material itself. It is preferably 15 or less from the viewpoint of suppressing a decrease in film physical properties due to hydrophilicity.

The range of the difference between the moisture absorption rates of the raw materials is as follows from the viewpoint of moving the moisture in the whole raw material from the moisture absorbing / releasing layer side to the fiber structure side.
It is preferable that it is 1 or more and 6 or less, and it is preferable that it is 1/3 or less of the difference in moisture absorption of the moisture absorption / release layer alone.

The linear swelling ratio of the moisture absorption / release layer of the present invention when absorbing water alone is preferably 10% or more and 25% or less.

Due to the high swelling property when absorbing water, high moisture absorption / desorption properties can be exhibited even when the swelling of the moisture absorption / desorption layer itself is suppressed due to adhesion to the fiber structure.

The linear swelling ratio of the moisture absorbing / releasing layer alone is preferably 10% or more from the viewpoint of high moisture permeability and imparting comfort, and from the viewpoint of exhibiting water resistance and suppressing deterioration of film properties due to hydrophilicity. % Is preferable.

The present invention may have a structure in which at least one moisture absorbing / releasing layer is provided on a porous layer laminated on a fiber structure.

The material in which the porous layer is laminated on the fibrous structure means that the porous resin layer is adhered on the fibrous structure.

As used herein, the porous resin layer includes a porous layer formed by immersing a resin in a poor solvent and wet-solidifying it, a porous film formed by stretching a fused fine particle film, and the like. In particular, the porous layer is preferably made of a polyurethane resin that has been wet-coagulated.

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

The material of the present invention is produced by applying a moisture-absorbing / desorbing resin solution to a fibrous structure, heat-treating and forming a film.

The moisture absorbing / releasing resin solution is a resin which can form a moisture absorbing / releasing layer dissolved and emulsified in an organic solvent, water or the like.

The coating on the fibrous structure is generally performed by using a coating formulation such as knife over roll coating, direct roll coating, reverse roll coating, gravure coating or the like to obtain a desired film thickness. That means.

Heat treatment and film formation means that an organic solvent, water, etc., in which a resin is dissolved and emulsified, are heated at 50 ° C. to 150 ° C.
Drying under conditions of 0.5 to 10 minutes to form a film. In particular, a knife coating method can be suitably used in order to make the moisture absorbing / releasing layer a continuous layer.

At the time of film formation, a crosslinking agent such as a polyisocyanate compound or a polyepoxy compound may be appropriately used in order to improve adhesion, solvent resistance and film strength.

In the case of coloring the resin layer, it is possible to appropriately add an inorganic or organic pigment to the resin layer, and in the case of changing the surface touch, silicon dioxide particles or the like by a known method.

The present material can also be produced by coating a moisture absorbing / releasing resin solution in advance, coating an adhesive layer thereon, and laminating with a fiber structure.

Pre-coating the moisture-absorbing / desorbing resin solution means that:
This means that only a film is prepared in advance by applying a moisture absorbing / releasing resin on a release support such as a release paper or a film coated with a silicone resin, or a release paper laminated with polypropylene, and then performing a heat treatment.

Applying an adhesive layer thereon means applying an adhesive on the film-formed moisture absorbing / releasing layer. For the coating, a coating formula such as knife over roll coating, direct roll coating, reverse roll coating, gravure coating, or the like can be used, and the coating may be performed so as to have a desired film thickness and coverage. Adhesives having high moisture absorption and release properties are also preferable from the viewpoint of the expression of moisture permeability, and those composed of a resin alone containing a polyurethane-based, polyester-based, polyamide-based, or silicone-based polymer alone, or a mixture thereof. Can be suitably used from the viewpoint of texture and stretchability.

As for the coverage by the adhesive, there is no problem even if the entire surface of the coating is 100% as long as the adhesive has high moisture permeability. However, from the viewpoint of compatibility between moisture permeability and water resistance, the coverage is generally 40 to 80%. It is preferable that

Laminating with a fiber structure means laminating and bonding an adhesive layer and a fiber structure. The bonding method may be selected depending on the characteristics of the adhesive such as a wet lamination method and a dry lamination method. After bonding, the material of the present invention can be obtained by peeling it from the release support.

With such a configuration, the function of the present invention is to use the moisture absorption / release properties of the material itself and the difference in moisture absorption / release between the inside and outside of the garment of the material, so that the driving force is always applied to the outside of the garment. It is a material that can achieve both high waterproofness and moisture permeability.

Due to such action, the material of the present invention can be used for outdoor work clothes, gloves, shoes, etc., in addition to outdoor wear such as fishing and mountaineering clothes, ski-related wear, windbreaker, athletic wear, golf wear rainwear, casual coat and the like. It can also be used for example.

[0046]

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 Threading 77 texitex-68 filament (vertical, horizontal) Weave density 116 × 88 / inch Basis weight 72 g / m ² [Porous material] (1) Porous material Fabric use Nylon taffeta Thread use 77 texitex-68 filament (vertical, horizontal) Weave density 116 × 88 yarns / inch Basis weight 72 g / m ² B. Porous layer Wet polyurethane layer C.I. Performance moisture permeability 12,000g / m ² · 24hr Water resistant 0.05 MPa [hygroscopic] (1) 4 hours moisture absorption material upon standing at 20 ° C. 65% RH atmosphere (hereinafter, will leave MRL) and 30 ° C. 90% R
The material's moisture absorption when left for 4 hours in an H atmosphere (hereinafter, M
RH) and calculated by the following equation.

Moisture absorption rate = (weight of material when absorbing moisture−weight of material when absolutely dry) × 100 / weight of material when absolutely dry ΔMR = MRH-MRL Equipment used: (1) Moisture absorption: constant temperature and humidity chamber manufactured by ADVANTEC (AGX-325) (2) Absolute drying: 110 ° C. × time in heat oven [linear swelling ratio] (1) A coating having a thickness of 0.05 mm was prepared by a casting method, and marking was performed on the coating at intervals of 10 cm in length and width.

(2) After immersion in water at 23 ° C. for 24 hours, vertical and horizontal marking intervals were measured, and the average of the elongation was defined as the linear swelling ratio.

Linear swelling ratio = (marking interval after water immersion−
10) × 100/10 *: The vertical and horizontal linear swelling ratios were summed and divided by 2. [Moisture Permeability] (1) Measured according to JIS L 1099 potassium acetate method. [Hydraulic pressure resistance] (1) Measured according to JIS L 1092 high water pressure method. [Example 1] A polyether-based polyurethane resin in which isocyanate is 4,4'-diphenylmethane diisocyanate and polyethylene glycol is contained in a soft segment (MRL = 4.3%, MRH = 12.9%, ΔMR =
8.6, linear swelling ratio = 21%) was dissolved in a mixed solvent of dimethylformamide and methyl ethyl ketone, and 30% by weight.
Was prepared. Further, a trimer of hexamethylene diisocyanate having a cyanuric skeleton was added as a crosslinking agent in an amount of 1 part based on the weight of the solution to prepare a coating solution.

A nylon taffeta treated with a 4% aqueous dispersion of a fluorine-based water / oil repellent AG710 (Asahi Glass Co., Ltd.) was applied with a knife coater at a clearance of 100 μm, dried at 120 ° C. for 2 minutes, and formed into a film. Was.

After bonding, the release support was peeled off and the sample
The material of the present invention was produced by aging at room temperature for an hour.

As shown in Table 1, the ΔMR of the material is 3.
8, moisture permeability 21,000g / m ² · 24hr and water pressure is 0.3M
It was a moisture-permeable and waterproof material having Pa and a high degree of moisture permeability and waterproofness, as well as high film surface strength against scratching and peeling and no reduction in water pressure resistance. [Example 2] A polyether-based polyurethane resin in which the isocyanate is 4,4'-diphenylmethane diisocyanate and the polyethylene glycol is contained in the soft segment (MRL = 4.3%, MRH = 12.9%, ΔMR =
8.6, linear swelling ratio = 21%) in a mixed solvent of dimethylformamide and methyl ethyl ketone, and 23% by weight
Was prepared. Using a knife coater, apply on a release paper with a clearance of 100 μm, dry at 120 ° C. for 2 minutes,
A film was formed.

A polyether-based polyurethane resin in which the isocyanate is 4,4'-methylenebis (cyclohexyl isocyanate) and the soft segment contains polyethylene glycol (MRL = 5.5%, MRH = 1
5.6%, ΔMR = 11.1, linear swelling ratio = 30%) dissolved in a mixed solvent of dimethylformamide, methyl ethyl ketone and toluene to give 23% by weight, and a hexamethylene having a cyanuric skeleton as a crosslinking agent. Six parts of the trimer of diisocyanate was added to the solution weight to obtain an adhesive.

Using a knife coater, the solution was applied on the release resin layer formed on the release support with a clearance of 140 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
Aging was performed at room temperature for a period of time, and then only the fluorine-based water and oil repellent, AG710 (Asahi Glass Co., Ltd.) 4%
The material of the present invention was prepared by treating with an aqueous dispersion.

As shown in Table 1, the ΔMR of the material is 5.
1, moisture permeability 23,000g / m ² · 24hr and water pressure is 0.3M
It was a breathable and waterproof material with Pa and high moisture permeability and waterproofness. Example 3 A moisture-permeable and waterproof material was used in the same manner as in Example 2 except that the resin layer of Example 2 was laminated and bonded with an adhesive layer applied in a dotted manner so that the coverage of the resin layer with the adhesive was 60%. Was prepared.

As shown in Table 1, the ΔMR of the material is 4.
2, moisture permeability 28,000g / m ² · 24hr and water pressure is 0.2M
It was a breathable and waterproof material with Pa and high moisture permeability and waterproofness. Example 4 Polyether-based polyurethane resin in which the isocyanate is 4,4′-diphenylmethane diisocyanate and the polyethylene glycol is contained in the soft segment (MRL = 4.3%, MRH = 12.9%, ΔMR =
8.6, linear swelling ratio = 21%) was dissolved in a mixed solvent of dimethylformamide and methyl ethyl ketone, and 20% by weight
Was prepared.

Using a knife coater, the material was applied on the porous material with a clearance of 50 μm, dried at 120 ° C. for 2 minutes, and formed into a film to prepare the material of the present invention.

As shown in Table 1, the ΔMR of the material is 2.
2, moisture permeability 11,000g / m ² · 24hr and water pressure is 0.2M
It was a breathable and waterproof material with Pa and high moisture permeability and waterproofness. [Example 5] A polyether-based polyurethane resin in which the isocyanate is 4,4'-diphenylmethane diisocyanate and polyethylene glycol is contained in the soft segment (MRL = 4.3%, MRH = 12.9%, ΔMR =
8.6, linear swelling ratio = 21%) in a mixed solvent of dimethylformamide and methyl ethyl ketone, and 23% by weight
Was prepared. Using a gravure coater, the composition was applied on release paper to a dry film thickness of 5 μm, dried at 120 ° C. for 2 minutes, and formed into a film.

A polyether polyurethane resin having an isocyanate of 4,4'-methylenebis (cyclohexyl isocyanate) and containing polyethylene glycol in a soft segment (MRL = 5.5%, MRH = 1)
5.6%, ΔMR = 11.1, linear swelling ratio = 30%) dissolved in a mixed solvent of dimethylformamide, methyl ethyl ketone and toluene to give 23% by weight, and a hexamethylene having a cyanuric skeleton as a crosslinking agent. Six parts of the trimer of diisocyanate was added to the solution weight to obtain an adhesive.

The solution was applied on the resin layer formed on the release support using a gravure coater to a dry film thickness of 5 μm, and dried at 120 ° C. for 1 minute to form a film.

The porous material was placed on the adhesive layer, and the porous layer and the adhesive layer were bonded 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
Aging was performed at room temperature for a time to prepare a material of the present invention.

As shown in Table 1, the ΔMR of the material is 2.
5, moisture permeability 16,000g / m ² · 24hr and water pressure 0.2
It was a moisture-permeable and waterproof material with high moisture permeability and waterproofness of 5 MPa. [Example 6] A polyether-based polyurethane resin (M) in which the isocyanate is 4,4'-methylenebis (cyclohexyl isocyanate), the aliphatic segment contains an aliphatic polycarbonate and polyethylene glycol 400, and the side chain contains polyethylene glycol 1000
RL = 6.1%, MRH = 17.3%, ΔMR = 11.0
(2, linear swelling ratio = 24%) was dissolved in a mixed solvent of dimethylformamide, methyl ethyl ketone and toluene to give 30% by weight.

As shown in Table 1, the ΔMR of the material is 2.
8, moisture permeability 18,000g / m ² · 24hr and water pressure 0.2
It was a moisture-permeable and waterproof material with high moisture permeability and waterproofness of 5 MPa. [Comparative Example 1] A polyether-based polyurethane resin in which the isocyanate is xylylene diisocyanate and polytetramethylene glycol is contained in the soft segment (MRL = 1.3%, MRH = 1.8%, ΔMR =
0.5, linear swelling ratio = 2%) was dissolved in a mixed solvent of dimethylformamide and methyl ethyl ketone to prepare a 23% by weight solution. Further, a trimer of hexamethylene diisocyanate having a cyanuric skeleton was added as a crosslinking agent in an amount of 1 part based on the weight of the solution to prepare a coating solution.

A nylon taffeta treated with a 4% aqueous dispersion of a fluorine-based water / oil repellent AG710 (Asahi Glass Co., Ltd.) was applied with a knife coater at a clearance of 100 μm, dried at 120 ° C. for 2 minutes, and formed into a film. Was.

After bonding, the release support was peeled off and the sample
The material of the present invention was produced by aging at room temperature for an hour.

As shown in Table 1, the ΔMR of the material is 0.
9, moisture permeability 2,100g / m ² · 24hr, water pressure is 0.3MPa
It was a material with high waterproofness but low moisture permeability and poor comfort. Comparative Example 2 A polyether-based polyurethane resin (MRL) in which the isocyanate is xylylene diisocyanate and the soft segment contains polytetramethylene glycol
= 1.3%, MRH = 1.8%, ΔMR = 0.5, linear swelling ratio = 2%) was dissolved in a mixed solvent of dimethylformamide and methyl ethyl ketone to prepare a 23% by weight solution. Further, a trimer of hexamethylene diisocyanate having a cyanuric skeleton was added as a crosslinking agent in an amount of 1 part based on the weight of the solution to prepare a coating solution.

Using a knife coater, the porous material was applied with a clearance of 50 μm, dried at 120 ° C. for 2 minutes, and formed into a film.

After bonding, the release support was peeled off and the sample
The material of the present invention was produced by aging at room temperature for an hour.

As shown in Table 1, the ΔMR of the material is 0.
9, moisture permeability 1,900g / m ² · 24hr, water pressure is 0.3MPa
It was a material with high waterproofness but low moisture permeability and poor comfort.

[0074]

[Table 1]

[0075]

According to the present invention, the balance between the moisture absorption / desorption properties of the entire material and the moisture absorption / desorption properties of the coating film is optimized, and the moisture absorption / desorption property outside the clothes is constantly increased, so that a more excellent moisture permeability can be obtained. In addition, it is possible to provide a moisture-permeable waterproof material having waterproof performance.

Claims (3)

[Claims] 1. A material comprising at least one continuous moisture absorbing / releasing layer provided on one surface of a fiber structure, wherein the moisture absorbing / releasing layer alone has a moisture absorption rate at 30 ° C. 90% RH and a temperature of 20 ° C. 65%. RH
The difference from the moisture absorption rate of the material is 6 or more and 15 or less.
The difference between the moisture absorption rate at 0 ° C. 90% RH and the moisture absorption rate at 20 ° C. 65% RH is 1 or more and 6 or less, and the moisture absorption rate of the moisture absorption / release layer alone is larger than that of the material. Moisture permeable waterproof material. 2. The water swelling layer alone has a linear swelling ratio of 10% when absorbing water.
The moisture-permeable waterproof material according to claim 1, wherein the content is at least 25%. 3. The moisture permeable and waterproof material according to claim 1, wherein at least one moisture absorbing / releasing layer is provided on the porous layer laminated on the fiber structure.