JP2003041482A - Moisture-permeable and water-proof material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture-permeable and water-proof material, capable of utilizing good points of both of a porous layer and a nonporous layer and always enhancing moisture-release property to the outside of clothes and having excellent moisture-permeable performance and water-proof performance by changing a resin layer to the porous layer when perspiration is low and changing the resin layer to the nonporous layer when perspiration is high. SOLUTION: This moisture-permeable and water-proof material has one or more resin layers at least on one side of a fiber structure and contains fine particles having stimulus responsive property in the resin layer and has spaces formed by partial release of a closely bonded part between the resin layer and the fine particles around these fine particles. These fine particles cause a volume change by outside stimulation such as humidity or temperature.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a moisture-permeable waterproof material. More specifically, the present invention provides a gas sweat,
The present invention relates to a moisture-permeable waterproof material having excellent moisture permeability of liquid sweat and having a soft texture.

[0002]

2. Description of the Related Art Conventionally, there are mainly two types of structure of a resin layer that exhibits moisture permeability of a moisture permeable and waterproof material, that is, a porous layer and a non-porous layer. In order to further improve the comfort of the material, Regarding the resin layer structure of (1), improvement of the moisture permeability of gas perspiration and the moisture permeability of liquid perspiration has been studied. For example, attempts have been made to control the pore size and porosity in the porous layer, and to make the non-porous layer highly hydrophilic by introducing hydrophilic segments.

However, the porous layer has an advantage over the non-porous layer in moisture vapor permeation. However, in order to improve the moisture vapor permeability of liquid perspiration, it is necessary to make it hydrophilic, so that it becomes hydrophilic. Then, there is a drawback that a problem of waterproofness is likely to occur. Further, the non-porous layer has an advantage over the porous layer in moisture permeation of liquid sweat, but it is necessary to make it highly hydrophilic and thin in order to increase the moisture permeability of gas perspiration. Becoming
When the film is made thin, there are drawbacks such as a decrease in water resistance and a decrease in film strength. And, in the method of laminating the porous layer and the non-porous layer, the moisture permeability of the gas perspiration is decreased due to the increase of the film thickness, and thus it is very difficult to optimize the performance of the material and the resin layer structure at present. is there.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned situation, the present invention therefore changes the resin layer to a porous layer when the sweat rate is low and to a non-porous layer when the sweat rate is high, so that both the porous layer and the non-porous layer are changed. It is an object of the present invention to provide a moisture-permeable and waterproof material which has improved moisture-releasing ability to the outside by taking advantage of its advantages, has more excellent moisture-permeable performance, and also has waterproof performance.

[0005]

The moisture-permeable waterproof material of the present invention has the following constitution in order to solve the above-mentioned problems. That is, the moisture-permeable waterproof material of the present invention is characterized in that in the material having at least one resin layer on at least one surface of the fiber structure, the resin layer contains fine particles having stimulus responsiveness. It is a breathable waterproof material.

The fine particles used in the moisture-permeable waterproof material of the present invention preferably have voids formed around the fine particles having stimulus responsiveness by partially peeling the resin layer and the close contact portion of the fine particles. Moreover, it is preferable that the particles are particles that change in volume by an external stimulus. The external stimulus is preferably fine particles that cause a volume change due to humidity stimulus and / or temperature stimulus. Water-swellable polyurethane is preferably used as the resin forming the resin layer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The moisture-permeable waterproof material of the present invention will be described in detail below.

The moisture-permeable waterproof material of the present invention comprises one or more resin layers provided on at least one side of a fiber structure. The fact that one or more resin layers are provided on at least one side of the fiber structure means a state in which the resin layer is bonded onto the fiber structure. The term "adhesion" as used herein means that the resin layer itself is adhered to the fiber structure directly and / or via an adhesive or another resin layer.

The resin constituting the resin layer used in the present invention is preferably a water-swellable resin from the viewpoint of improving moisture permeability. Examples of the water-swellable resin include resins having polyurethane, polyester, polyamide, silicone and the like as a main component, or a mixture thereof. Among these, polyurethane resins and silicone resins are preferable from the viewpoint of weather resistance and hydrolysis resistance, and polyurethane resins that are easier in molecular design for highly exhibiting moisture absorption and desorption are particularly preferably used.

The polyurethane resin preferably used in the present invention means a resin whose main component is a copolymer obtained by reacting polyisocyanate and polyol. Examples of the polyisocyanate component include bifunctional diisocyanates such as aromatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates, and trifunctional or higher polyisocyanates, which are used alone or in combination of two or more. can do.

As the aromatic diisocyanate,
For example, m- or p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (ND
I), 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof (MD
I), 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate and the like can be exemplified.

Examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI). ), Ω, ω'-diisocyanate-1,4-diethylbenzene and the like.

Examples of the alicyclic diisocyanate include 1,3-cyclopentene diisocyanate and 1,4
-Cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-
3,5,5-Trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4 '
-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate or mixtures thereof (hydrogenated MD
I), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hydrogenated XDI)
Etc. can be illustrated.

Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (H
DI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2 , 6-diisocyanate methyl caprate and the like can be exemplified.

Of these polyisocyanate components,
Examples of aromatic diisocyanates include TDI and M
DI, NDI and the like are preferable, as the araliphatic diisocyanate, for example, XDI and TMXDI are preferable, and as the alicyclic diisocyanate, for example, IPD
I, hydrogenated XDI, hydrogenated MDI and the like are preferable, and as the aliphatic diisocyanate, HDI and the like are preferably used. As the polyisocyanate, those blocked with phenol, oxime or the like may be used.

As the polyol component, polyether polyol or polyester polyol can be used. As the polyether polyol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like can be used. As the polyester polyol, ethylene glycol, propylene glycol or the like can be used. Examples thereof include a reaction product of a diol and a dibasic acid such as adipic acid and sebacic acid, and a ring-opening polymer such as caprolactone. Others, ether / ester type, amide type,
A carbonate type can also be used as appropriate. These polyol components can be used alone or in combination of two or more.

The polyurethane resin used in the present invention is
It may be in the form of the organic solvent solution or aqueous solution,
It may be in the form of an aqueous dispersion of polyurethane resin.
The aqueous dispersion can be prepared by emulsifying and dispersing the polyurethane prepolymer and extending the chain with a chain extender such as a diamine component.

When the polyurethane prepolymer does not have a hydrophilic group, an aqueous dispersion can be usually prepared by emulsifying the polyurethane prepolymer with an emulsifier and chain-elongating it with a chain extender.

As the emulsifier, for example, polyvinyl alcohol, cellulose derivative such as carboxymethyl cellulose, water-soluble polymeric protective colloid such as gelatin and dextrin; polyoxyethylene C8-20 alkylphenyl ether such as polyoxyethylene nonylphenyl ether, Nonionic surfactant such as polyoxyethylene-oxypropylene block copolymer; C8-20 alkyl sulfate alkali metal salt such as sodium lauryl sulfate, C such as sodium dodecylbenzenesulfonate
Anionic surfactants such as 8-20 alkylbenzene sulfonic acid alkali metal salts and the like can be mentioned.

When the polyurethane prepolymer has a hydrophilic group, for example, a hydrophilic compound is used as at least a part of the diol component to react with an isocyanate compound to introduce the hydrophilic group into the polyurethane prepolymer.
An aqueous dispersion can be prepared by dispersing this polyurethane prepolymer in water and chain-extending it using a chain extender such as a diamine component. As the hydrophilic group, an ionic dissociative group (eg, carboxyl group, sulfonic acid group, sulfonate group, carbamoyl sulfonate group, 4
Primary amino groups or quaternary ammonium salts), nonionic groups [eg, polyoxyalkylene groups (eg, polyoxyethylene groups), epoxy groups, etc.] and the like.
Among these hydrophilic groups, anionic groups (carboxyl group, sulfonic acid group, sulfonate group, carbamoyl sulfonate group), nonionic groups (polyoxyethylene group), especially anionic groups (carboxyl group, sulfonic acid group) Is preferred. In order to dissolve or disperse the prepolymer having an anionic hydrophilic group such as a carboxyl group or a sulfonic acid group, it is preferable to neutralize the anionic group with a neutralizing agent and then extend the chain.

The hydrophilic compound has a group reactive with an isocyanate group and a hydrophilic group in the molecule. Examples of the reactive group with respect to the isocyanate group include a hydroxyl group, an amino group and a mercapto group. As the hydrophilic compound, for example, dihydroxycarboxylic acid (for example,
Dihydroxy C2-10 carboxylic acid such as 2,2-dimethylolpropionic acid, 2,2-dimethylol butyric acid and 2,2-dimethylol valeric acid, dihydroxy C4-10 polycarboxylic acid such as dioxymaleic acid, 2,6 -Dihydroxyaromatic carboxylic acid such as dihydroxybenzoic acid), diaminocarboxylic acid (for example, diaminoaromatic carboxylic acid such as 3,4-diaminobenzoic acid), acid anhydride (for example, maleic anhydride, phthalic anhydride) Acid, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, etc.) and compounds having a reactive group for isocyanate groups (dihydroxy compounds such as diols, diamines, etc.)
A compound having a carboxyl group such as a reaction product with or an oligoester polyol obtained by copolymerizing a compound having these carboxyl groups; oxysulfonic acid (for example, 2-oxyethanesulfonic acid, phenolsulfonic acid, etc.) , Sulfocarboxylic acid (eg, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, etc.),
Amino group-containing sulfonic acid (eg, sulfanilic acid,
1,3-phenylenediamine-4,6-disulfonic acid,
2,4-diaminotoluene-5-sulfonic acid, etc.) or a compound having a sulfonic acid group, or an oligoester polyol obtained by copolymerizing a compound having these sulfonic acid groups; containing a reactive group for an isocyanate group Examples thereof include polyoxy C2-4 alkylene compounds, and oligoester ether polyols obtained by copolymerizing these polyoxyalkylene compounds. These hydrophilic compounds may be used alone or in combination of two or more.

Since the composition of the polyurethane resin used in the present invention needs to have both moisture permeability and film strength, the content of the hydrophilic polyol is preferably 5% by weight or more and 70% by weight or less, more preferably 10% by weight. % Or more and 50% by weight or less and a polyurethane in which a diol composed of an aliphatic polycarbonate is introduced into the main chain is preferably used. Further, when the polyurethane resin is a water-dispersible polyurethane, it is preferable that the hydrophilic polyol has a structure mainly containing in the side chain rather than the main chain.

The water-swellable polyurethane used in the present invention has a linear swelling ratio of the resin when absorbing water, a moisture absorption ratio (hereinafter referred to as MRL) of the material when left to stand in an atmosphere of 20 ° C. and 65% RH for 4 hours, and a temperature of 30 ° C. The moisture absorptivity (hereinafter referred to as MRH) of the material when left for 4 hours in a% RH atmosphere is measured, and the moisture absorptivity difference (hereinafter referred to as ΔMR) is evaluated. If both are too low, the moisture permeability is not sufficiently exhibited, and if too high, the required film strength cannot be maintained.
% Or more and 70% or less, and ΔMR is preferably 6.0 or more and 15.0 or less, and more preferably the linear swelling rate is 20% or more and 60%.
Hereinafter, ΔMR is 6.5 or more and 13.0 or less. Also,
In order to achieve both moisture permeability and film strength of the polyurethane resin, the polyurethane resin may be blended with another resin before use.

The film thickness of the resin layer formed of the above-mentioned resin is preferably 1 to 100 μm, but if it is too thin, durability problems occur, and if it is too thick, the texture of the material is impaired. It is preferably 20 to 50 μm and more preferably.

Next, the stimulus-responsive fine particles used in the present invention will be described. Examples of the stimulus in the stimulus-responsive fine particles contained in the resin layer include temperature, humidity, light and the like.

In the present invention, the fact that the stimulus-responsive fine particles are contained in the resin layer means a state in which the stimulus-responsive fine particles have even a portion in direct contact with the resin. This includes not only the inside of the resin layer but also the state in which fine particles are present on the surface of the resin layer. In this case, the surface of the resin layer means the surface of the resin layer on the coating film side.

The stimulus-responsiveness of the stimulus-responsive fine particles used in the present invention means that the fine particles cause a reversible volume change by the above-mentioned stimulus. The term “volume change” as used herein means that the particle size changes due to contraction and expansion of the fine particles. The volume change amount is preferably 5 or more and 150 or less in terms of the volume ratio of the volume of the fine particles to the volume of the fine particles to the volume of the fine particles when it expands, but from the viewpoint of void formation and performance expression described later and the restriction of the thickness and particle diameter of the resin layer, which will be described later. , 7 or more and 120 or less are particularly preferable, and 10 or more and 100 or less are more preferable.

The fine particles in the stimuli-responsive fine particles are
Indicates a particle or powder in a state where the volume is contracted. The average particle size is preferably 0.01 to 10 μm, but 0.02 to 5 μm from the relationship between the particle size at the time of volume expansion and the thickness of the resin layer.
μm is particularly preferable, and 0.03 to 3 μm is further preferable.

As such a stimulus-responsive fine particle, for example, a fine particle responsive to temperature is LCST.
A crosslinked polymer having a (lower critical solution temperature), IPNs (interpenetrating network structure) in which two-component polymer compounds are hydrogen-bonded to each other are preferable. The crosslinked polymer has a property of shrinking at high temperature, and specific examples thereof include poly (N-alkyl-substituted acrylamide) such as poly (N-isopropylacrylamide) and poly (N-).
Alkyl-substituted methacrylamide) crosslinked body, N-alkyl-substituted acrylamide and N-alkyl-substituted methacrylamide crosslinked body of copolymer of acrylic acid and methacrylic acid or a metal salt thereof or an alkyl ester thereof, acrylamide and methacrylamide, and methylcellulose And a cross-linked product of an alkyl-substituted cellulose derivative such as hydroxyethyl cellulose. IPNs have the property of swelling at high temperatures, and specific examples include IPNs of a crosslinked body composed of polyacrylamide and polymethacrylamide and a crosslinked body composed of polyacrylic acid and polymethacrylic acid, and partial metal chlorides thereof. Examples include, but are not limited to, IPNs and partial metal chlorides thereof, which are crosslinked products of copolymers containing polyacrylamide and polymethacrylamide as main components and crosslinked products of polyacrylic acid and polymethacrylic acid. .

Examples of the fine particles which respond to humidity include water-absorbing polymer compounds. Specifically, examples of the water-absorbing polymer compound include a graft polymer of fibroin and acrylic acid, a graft polymer of starch / acrylic acid salt, a crosslinked carboxymethyl cellulose, a vinyl alcohol / acrylic acid salt copolymer, and polyacrylonitrile. Hydrolyzate, cross-linked acrylate / acrylamide copolymer, acrylate polymer, modified polyvinyl alcohol,
Examples thereof include isobutylene / maleic anhydride copolymer, but are not limited thereto.

Examples of the fine particles that respond to light include high molecular compounds having a molecular structure that ionically dissociates by light, such as triarylmethane derivatives and spirobenzopyran derivatives. Specific examples thereof include, but are not limited to, a crosslinked product of a copolymer of vinyl-substituted triarylmethane leuco derivative and acrylamide or methacrylamide.

In the present invention, each stimuli-responsive fine particle may be used alone, or a plurality of fine particles may be used in combination.

In the present invention, the stimuli-responsive fine particles in the membrane are
As described above, the volume is changed by being stimulated. At that time, when the fine particles move from the expanded state to the contracted state, voids are generated between the resin and the fine particles, so that the resin layer structure becomes a porous layer, which is advantageous for moisture vapor permeability. Further, when the fine particles move from the contracted state to the expanded state, the voids disappear, so that the resin layer structure becomes a non-porous layer, which is advantageous for the moisture permeability of liquid water.

The term "void" as used herein refers to a space of closed cells formed by the partial peeling of the resin and the fine particles in contact with each other. Further, moisture vapor transmission means that water vapor is absorbed by the resin layer and released as water vapor, and moisture vapor transmission of liquid water means that liquid water is absorbed by the resin layer and released as water vapor. Say. The size of the voids is calculated from the volume change of the fine particles and the particle size described above, and is preferably 1.7 × 10 ⁻²³ m ³ or more and 6.2 × 10 ⁻¹³ m ³ or less, and more preferably,
2.0 × 10 ⁻²² m ³ or more and 6.2 × 10 ⁻¹⁴ m ³ or less, more preferably 1.0 × 10 ⁻²¹ m ³ or more and 1.1 × 10 ⁻¹⁴
m ³ or less.

The amount of the stimuli-responsive fine particles added to the resin for exhibiting such performance is preferably 0.05% by weight or more and 5% by weight or less, but if it is too small, the performance is not exhibited, and if it is too large, the film is not formed. It is more preferable to be 0.1% by weight or more and 3% by weight or less because a communication hole is generated therein and the water resistance is reduced.

Examples of the fiber structure in the present invention include those in the form of fabrics such as woven and knitted fabrics and non-woven fabrics mainly composed of synthetic fibers such as polyester fibers, polyamide fibers and acrylic fibers.

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

The moisture-permeable waterproof material of the present invention is obtained by applying a water-swellable resin solution containing stimulus-responsive fine particles on a fiber structure or on a porous layer laminated on the fiber structure, followed by heat treatment and film formation. It is manufactured by

The water-swellable resin solution containing stimulus-responsive fine particles is a solution in which the stimulus-responsive fine particles are uniformly dispersed in a solution obtained by dissolving and emulsifying the water-swellable resin in an organic solvent, water and the like. . The material in which the porous layer is laminated on the fibrous structure means that the porous resin layer is bonded onto the fibrous structure.

Examples of the porous resin layer here include a porous layer obtained by immersing a resin in a poor solvent and wet coagulating it, and a porous film formed by stretching a fused fine particle film. Of these, the porous layer is preferably made of a polyurethane resin which is wet-coagulated. In addition, the term "adhesion" means that the porous layer is directly adhered to the fiber structure or adhered via an adhesive.

The term "coating on a fiber structure" generally means coating with a coating formulation such as knife over roll coating, direct roll coating, reverse roll coating, gravure coating and the like. Among them, the knife coating method is preferable in order to form the resin film as a continuous layer.

Heat treatment and film formation means that the water-swellable resin solution containing the stimulus-responsive fine particles is heated to 50 to 150 ° C.
Is to be dried to form a film under the condition of 0.5 to 10 minutes. At the time of forming a film, a crosslinking agent such as a polyisocyanate compound, a polyepoxy compound, and a melamine compound may be used together in order to improve adhesion, solvent resistance and film strength.

In the case of coloring the resin layer, an inorganic pigment or an organic pigment may be added to the resin layer, and in the case of changing the surface touch, silicon dioxide particles may be appropriately added by a known method. is there.

The moisture-permeable waterproof material of the present invention can also be produced by forming a film of a water-swellable resin solution in advance, coating an adhesive layer on the solution, and laminating it with a fiber structure.

Pre-coating the water-swellable resin solution means that
It means that a water-swelling resin is applied on a release support such as a release paper or film coated with a silicone resin or a release paper laminated with polypropylene and heat-treated to prepare only a film in advance.

To apply an adhesive layer thereon means to apply an adhesive agent onto the resin layer which has been formed into a film. For coating,
A coating formulation such as knife over roll coating, direct roll coating, reverse roll coating, and gravure coating can be used, and coating may be performed so as to obtain a desired film thickness and coverage. From the viewpoint of moisture permeability, it is preferable that the adhesive also has a high moisture absorption and desorption property, and is composed of a resin containing polyurethane-based, polyester-based, polyamide-based, silicone-based polymer or the like as a main component, or a mixture thereof. Can be suitably used from the viewpoint of texture and stretchability.

With respect to the coverage with an adhesive, if it is a highly moisture-permeable adhesive, there is no problem with 100% coating on the entire surface, but from the viewpoint of both moisture permeability and water resistance, the coverage is generally 40-80%. It is preferable to set it as a rate.

To adhere to the fibrous structure means to laminate and bond the adhesive layer and the fibrous structure. The bonding method may be selected according to the characteristics of the adhesive, such as a wet laminating method and a dry laminating method. After adhesion, the material of the present invention can be obtained by peeling from the release support.

From the above structure, the operation of the present invention is 1
One resin layer changes to a porous layer when low sweating and a non-porous layer when high sweating, making use of the advantages of both porous and non-porous layers to constantly improve the moisture release to the outside of the clothes, and more excellent moisture permeability In addition to having the above, it becomes a moisture-permeable waterproof material that also has waterproof performance.

Due to such an action, the moisture-permeable waterproof material of the present invention is used for outdoor wear such as fishing and mountain climbing clothes,
In addition to ski-related wear, windbreaker, athletic wear, golf wear, rainwear, casual coats, etc., it can be suitably used for outdoor work clothes, gloves and shoes.

[0051]

EXAMPLES The present invention will be described in more detail below with reference to examples. The fiber structure (base cloth) used in the present invention and the evaluation method are shown below.

[Base fabric] (1) Nylon taffeta Using yarn 77 decitex-68 filament (longitudinal, horizontal) Weave density 116 × 88 filaments / inch Unit weight 72 g / m ² [Porous material] A. Use of fabric Nylon taffeta Use of yarn 77 decitex-68 filament (vertical, horizontal) Weave density 116 × 88 / inch Eye weight 72 g / m ² B. Porous layer Wet polyurethane layer C. Performance Moisture permeability A-1 method 9,800 g / m ² · 24 hr B-1 method 12,000 g / m ² · 24 hr Water resistance 0.05 MPa [Hygroscopicity] (1) When left in 20 ° C 65% RH atmosphere for 4 hours The moisture absorption rate (MRL) of the material and the moisture absorption rate (MRH) of the material when left to stand in an atmosphere of 30 ° C. and 90% RH for 4 hours were calculated by the following formulas, and the moisture absorption rate difference (ΔMR) was determined. Moisture absorption rate = (material weight when absorbing moisture-material weight when absolutely dry) x 1
00 / Material weight when absolutely dried △ MR = MRH-MRL Equipment used: (1) Moisture absorption: Constant temperature and humidity chamber (AG) manufactured by ADVANTEC
X-325) (2) Absolute drying: hot oven 110 ° C. × time [linear swelling ratio] (1) A 0.05 mm-thick coating film was prepared by a casting method, and marking was performed on the coating film at intervals of 10 cm in length and width.

(2) After being immersed in water at 23 ° C. for 24 hours, the vertical and horizontal marking intervals were measured, and the average of the elongation rates was taken as the linear swelling rate. Linear swelling ratio = (marking interval after immersion in water-10) x 10
0/10 *: The vertical and horizontal linear swelling ratios were summed and divided by 2.

[Moisture Permeability] (1) Moisture Permeability of Water Vapor Measured according to JIS L 1099 calcium chloride method.

(2) Moisture permeability of liquid water It was measured according to JIS L 1099 potassium acetate method.

[Water pressure resistance] (1) Measured according to JIS L 1092 high water pressure method.

[Example 1] Isocyanate was 4,4'-
Diphenylmethane diisocyanate, a polyether polyurethane resin containing polyethylene glycol 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 to prepare a 30% by weight solution. Furthermore, a trimer of hexamethylene diisocyanate having a cyanuric skeleton as a cross-linking agent is used in an amount of 1 part based on the weight of the solution, and a poly (N-isopropylacrylamide) cross-linking body as a stimulus-responsive fine particle ("Thermogel 250" manufactured by Kojin Co., Ltd.). (Trade name) was freeze-pulverized, and 0.3 parts of the fine particles having an average particle diameter of 2 μm were added to the solution weight by removing the coarse particles to prepare a coating solution.
Nylon taffeta treated with 4% aqueous dispersion of AG925 (trade name, manufactured by Asahi Glass Co., Ltd.), which is a fluorine-based water and oil repellent, was coated with a knife coater at a clearance of 100 μm.
It was dried at 120 ° C. for 2 minutes and formed into a film to prepare the moisture-permeable waterproof material of the present invention. As shown in Table 1, the vapor permeability of water vapor is 7,300 g / m ² · 24 hr, and the moisture permeability of liquid water is 22,000.
It had a high moisture permeability of 0g / m ² · 24hr and a water pressure resistance of 0.31MPa, and at the same time, it was a highly moisture-permeable and waterproof material.

Example 2 Isocyanate was 4,4'-
Methylene bis (cyclohexyl isocyanate), a polyether polyurethane resin containing polyethylene glycol and a hydrophilic group as a part thereof in the soft segment (MRL = 4.1%, MRH = 12.3%, ΔMR
= 8.2%, linear swelling ratio = 19%) and finely dispersed in water 3
A 0 wt% solution was prepared. Further, 1 part by weight of a solution of a trimer of hexamethylene diisocyanate having a cyanuric skeleton blocked with oxime as a crosslinking agent,
Crosslinked poly (N-isopropylacrylamide) as stimulus-responsive fine particles ("Thermogel 250" manufactured by Kojin Co., Ltd.)
(Trade name) was freeze-pulverized, and 0.3 parts by weight of the solution weight of fine particles having an average particle diameter of 2 μm excluding coarse particles were added to obtain a coating liquid. Nylon taffeta treated with 4% aqueous dispersion of AG925 (trade name of Asahi Glass Co., Ltd.), which is a fluorine-based water and oil repellent, is applied with a knife coater at a clearance of 100 μm, dried at 120 ° C. for 2 minutes, and at 150 ° C. for 1 minute. A film was formed by curing to prepare the moisture-permeable waterproof material of the present invention.
As shown in Table 1, water vapor permeability is 7,000 g / m ² · 2
4hr, moisture permeability of liquid water is 21,000g / m ² · 24hr, and water pressure resistance is 0.30MPa.
It was a highly breathable waterproof material.

Example 3 Isocyanate was 4,4'-
Diphenylmethane diisocyanate, a polyether polyurethane resin containing polyethylene glycol 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 to prepare a 30% by weight solution. Furthermore, 1 part by weight of a solution of a hexamethylene diisocyanate trimer having a cyanuric skeleton as a cross-linking agent, and a polyacrylate cross-linking body as a stimulus-responsive fine particle (manufactured by Sumitomo Seika KK)
AQUAKEEP (trade name) was freeze-pulverized, and 0.3 parts of fine particles having an average particle size of 3 μm were added to the solution weight to remove the granules to prepare a coating solution. As shown in Table 1, the moisture vapor permeability of water vapor is 8, 1
00g / m ² · 24 hr, liquid water vapor permeability is 21,0
It had a high moisture permeability of 00 g / m ² · 24 hr and a water pressure resistance of 0.30 MPa, and at the same time, it was a moisture permeable and waterproof material having high waterproofness.

[Example 4] Isocyanate was 4,4'-
It is methylene bis (cyclohexyl isocyanate) and has a hydrophilic polyol content of 4 including polyethylene glycol and a hydrophilic group as a part thereof in the soft segment.
0% by weight of polyether polyurethane resin (A) (M
RL = 4.5%, MRH = 15.1%, ΔMR = 10.
6%, linear swelling ratio = 50%) and isocyanate is 4,4
Polyether polyurethane resin (B) (MRL = 3.1), which is ???-methylenebis (cyclohexyl isocyanate) and whose soft segment is a polycarbonate containing polyethylene glycol and a hydrophilic group as a part thereof.
%, MRH = 9.8%, ΔMR = 6.7%, elongation at break = 600%) (A) 70 parts (B) 30 parts resin finely dispersed in water, % Solution was prepared. Furthermore, 1 part by weight of a solution of hexamethylene diisocyanate having a cyanuric skeleton blocked with oxime as a cross-linking agent based on the solution weight, and poly (N-isopropylacrylamide) cross-linked product as stimulus-responsive fine particles (Kohjin Co., Ltd.). "Thermogel 250" (trade name) manufactured by the present invention was freeze-pulverized, and 0.3 parts of fine particles having an average particle diameter of 2 µm were added to the solution weight by removing the granules to obtain a coating solution. The film formation was performed in the same manner as in Example 2. As shown in Table 1, moisture vapor permeability is 9,100 g / m ² · 24 hr, liquid water vapor permeability is 23,000 g / m ² · 24 hr, and water pressure resistance is 0.3.
It was a moisture-permeable and waterproof material having a high waterproofness as well as having a high moisture permeability of 1 MPa.

Example 5 Isocyanate is 4,4'-
Diphenylmethane diisocyanate, a polyether polyurethane resin containing polyethylene glycol 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 methylethylketone to prepare a 23% by weight solution. Further, a poly (N-isopropylacrylamide) cross-linked product ("Thermogel 250" trade name manufactured by Kojin Co., Ltd.) was freeze-pulverized as stimuli-responsive fine particles, and fine particles having an average particle size of 2 μm were removed to remove the coarse particles to obtain a solution weight. On the other hand, 0.3 part was added to obtain a coating liquid. Clearance 10 on the release paper using a knife coater
It was applied at 0 μm and dried at 120 ° C. for 2 minutes to form a film. Further, the isocyanate is 4,4′-methylenebis (cyclohexyl isocyanate) and the polyether segment polyurethane resin containing polyethylene glycol in the soft segment (MRL = 5.5%, MRH = 15.
Hexamethylene diisocyanate having a cyanuric skeleton as a cross-linking agent was prepared by dissolving 6%, ΔMR = 11.1%, linear swelling ratio = 30%) in a mixed solvent of dimethylformamide, methyl ethyl ketone and toluene to 23% by weight. The trimer of 6 parts was added to the solution weight to prepare an adhesive. This solution was applied onto the resin layer formed on the release support with a knife coater at a clearance of 140 μm, and 1
It was dried at 20 ° C. for 1 minute to form a film. Nylon taffeta was placed on the adhesive layer, and the nylon taffeta and the resin layer were bonded together 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 adhesion, the release support was peeled off and the sample was aged for 48 hours at room temperature, and then only the base fabric surface side was a fluorine-based water and oil repellent, AG925 (trade name of Asahi Glass Co., Ltd.) 4% aqueous dispersion. The material of the present invention was produced by treating with. As shown in Table 1, the moisture vapor permeability is 6,700 g / m ² · 24h.
r, moisture permeability of liquid water is 23,000g / m ² · 24h
It was a moisture-permeable and waterproof material having a high water-proof property while having a high water vapor pressure resistance of 0.30 MPa.

[Comparative Example 1] Isocyanate was 4,4'-
Diphenylmethane diisocyanate, a polyether polyurethane resin containing polyethylene glycol 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 methylethylketone to prepare a 30% by weight solution. Furthermore, 1 part of a trimer of hexamethylene diisocyanate having a cyanuric skeleton as a cross-linking agent was added to the weight of the solution to prepare a coating solution. The film formation was performed in the same manner as in Example 1. As shown in Table 1, the moisture vapor permeability is 5,000 g / m ² · 24 hr,
Liquid water vapor permeability is 21,000g / m ² · 24hr,
Since the water pressure resistance was 0.30 MPa and the resin layer was non-porous, the moisture permeability of liquid water was high, but the moisture permeability of water vapor was low.

[Comparative Example 2] Isocyanate was 4,4'-
Diphenylmethane diisocyanate, a polyether polyurethane resin containing polyethylene glycol in the soft segment (MRL = 4.3%, MRH = 12.
9%, ΔMR = 8.6%, linear swelling ratio = 21%) was dissolved in dimethylformamide to prepare a 30% by weight solution. Furthermore, a trimer of hexamethylene diisocyanate having a cyanuric skeleton is used as a cross-linking agent in an amount of 1 relative to the weight of the solution.
Part was added to obtain a coating liquid. AG, a fluorine-based water and oil repellent
Nylon taffeta treated with 4% aqueous dispersion of 925 (trade name of Asahi Glass Co., Ltd.) was coated with a knife coater at a clearance of 100 μm. Then, put the cloth in water at 15 ℃
Wet film formation was carried out by dipping for a minute to prepare a comparative material. As shown in Table 1, the moisture vapor permeability is 8,300 g.
/ M ² · 24 hr, liquid water vapor permeability 9,800g /
Since the resin layer is porous with m ² · 24 hours and a water pressure resistance of 0.21 MPa, the water vapor permeability is high, but the liquid water permeability and water resistance are low.

[Comparative Example 3] Isocyanate was 4,4'-
Diphenylmethane diisocyanate, a polyether polyurethane resin containing polyethylene glycol 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 methylethylketone to prepare a 30% by weight solution. Furthermore, a trimer of hexamethylene diisocyanate having a cyanuric skeleton as a cross-linking agent was added in an amount of 1 part based on the weight of the solution to prepare a coating solution.
Further, as fine particles, spherical cellulose having an average particle size of 10 μm (trade name of “Viscopearl Mini” manufactured by Rengo Co., Ltd.) was freeze-ground, and coarse particles were removed to make the average particle size 2 μm, and 1 part was added to the weight of the solution. It was used as a coating liquid. The film formation was performed by the same method as in Example 1. As shown in Table 1,
Water vapor permeability is 7,000g / m ² · 24hr, liquid water vapor permeability is 9,200g / m ² · 24hr, and water resistance is 0.30MPa. There was no change in the pore layer and the porous layer, and it became a material with particularly low moisture permeability of liquid water.

[0065]

[Table 1]

[0066]

According to the present invention, the resin layer changes to a porous layer when the sweat rate is low and changes to a non-porous layer when the sweat rate is high, so that the advantages of both the porous layer and the non-porous layer are utilized, and the resin layer is always released to the outside of clothes. It is possible to obtain a moisture permeable and waterproof material having improved moisture permeability and excellent moisture permeability as well as waterproof performance.

Claims (8)

[Claims] 1. A moisture-permeable waterproof material, wherein a material having one or more resin layers on at least one surface of a fibrous structure, wherein the resin layer contains fine particles having stimulus responsiveness. 2. The moisture-permeable waterproof material according to claim 1, characterized in that, around the fine particles having a stimulus responsiveness, there is a void formed by partially peeling a resin layer and a contact portion of the fine particles. . 3. The moisture-permeable waterproof material according to claim 1, wherein the stimuli-responsive fine particles cause a volume change by an external stimulus. 4. The transparent particle according to claim 1, wherein the stimuli-responsive fine particles are fine particles that cause a volume change by a humidity stimulus and / or fine particles that cause a volume change by a temperature stimulus. Wet and waterproof material. 5. The volume change amount of the fine particles is 5 or more and 150 as a volume ratio of the expanded volume to the contracted volume of the fine particles.
It is the following, The moisture-permeable waterproof material in any one of Claims 1-4. 6. The average particle diameter of the fine particles is 0.01 to 10 μm.
The moisture-permeable waterproof material according to any one of claims 1 to 5, wherein 7. The moisture-permeable waterproof material according to claim 1, wherein the resin layer changes into a porous layer when the sweat rate is low and a non-porous layer when the sweat rate is high. 8. The moisture-permeable waterproof material according to claim 1, wherein the resin forming the resin layer is water-swellable polyurethane.