JPWO2020080084A1 - Breathable waterproof fabric and textile products using it - Google Patents

Abstract

At least one surface of the fiber cloth contains a porous waterproof layer containing a urethane resin and an abrasion protection layer formed on the entire surface or a part of the surface of the waterproof layer, and the urethane resin is an ester-based and / or polycarbonate-based urethane resin. A moisture-permeable and waterproof fabric characterized by the above, and a textile product using the same are provided.

Description

The present invention is a moisture-permeable and waterproof fabric, particularly a moisture-permeable and waterproof fabric having a resin film, and the moisture-permeable and waterproof fabric in which the resin film can be used on the front side of clothes and bags and fibers using the same. It is about the product.

Waterproof fabrics are used in various materials such as clothes such as a pair of feathers, ski wear, and windbreakers, as well as tents and shoe materials to prevent the ingress of water such as rain.
In the waterproof fabric, a porous or non-porous resin film having waterproof properties is laminated on one side or both sides of the fiber fabric or between two fiber fabrics. Further, in addition to waterproofness, there is also known a structure in which a resin film having moisture permeability that allows moisture in clothes to pass through and suppresses stuffiness and sweat dew condensation in clothes is laminated on a fiber cloth. (Patent Document 1, Patent Document 2, Patent Document 3)
When a moisture-permeable and waterproof fabric having a resin film on one side of the fiber cloth is generally used for clothes and the like, the resin film is used on the body side (that is, the back side of the clothes and the like).

On the other hand, synthetic leather is made by laminating porous or non-porous resin films colored in black, white, red, blue, etc., including transparent leather on one or both sides of the fiber fabric. It is used in fashion clothing as a substitute for leather products so that the resin film is on the front side of clothes such as coats, bags, shoes, etc. Since the resin film does not allow water to permeate, it is used not only as a fashion material as a substitute for leather but also as a waterproof and windproof material for baseball ground jumpers, gloves, shoes, bags, etc. It is known that it has excellent wear strength, and it is used in various textile products.

JP-A-55-80583 Japanese Unexamined Patent Publication No. 7-9631 Japanese Unexamined Patent Publication No. 2008-307813

In recent fashion trends, there is a demand for a material having a resin film on the front side of clothes and the like and having moisture permeability and waterproofness.
When the resin film is on the front side of clothes or the like, the design of clothes or the like can be enhanced by coloring the resin film with a dye or pigment or printing a design on the surface of the resin film.

However, such a resin film having moisture permeability and waterproof property has a problem that the resin film is vulnerable to abrasion and a problem that the resin film swells when it comes into contact with water and the appearance quality deteriorates. Improvement was required to use such a resin film on the front side of the.
Further, when synthetic leather is used as a waterproof material, it has waterproof property and does not swell even when it gets wet with water, but it has almost no moisture permeability, and improvement of moisture permeability is required.
Therefore, in the present invention, it is a moisture-permeable and waterproof fabric having a resin film, and the resin film can be used as the front side of textile products such as clothes, shoes and bags, and is also excellent in moisture permeability and waterproofness. It is an object of the present invention to provide a moisture-permeable and waterproof fabric and a textile product using the same.

As a result of diligent studies to solve the above problems, the present inventors have laminated a porous waterproof layer containing a hydrophobic urethane resin on a cloth, and further, a wear protection layer on the entire surface or a part of the surface of the waterproof layer. By providing the material, the material has excellent moisture permeability and waterproofness, has sufficient wear resistance to use the resin film surface on the front side of clothes, etc., and has a function of not causing water swelling. We have found and completed the present invention.

That is, the moisture-permeable and waterproof fabric according to the present invention includes a porous waterproof layer containing a urethane resin and an abrasion protection layer formed on the entire surface or a part of the surface of the waterproof layer on at least one surface of the fiber fabric. The urethane resin is an ester-based and / or polycarbonate-based urethane resin.

Further, the moisture-permeable and waterproof fabric according to the present invention has a water pressure resistance of 2000 mmH ₂ O or more, and has a moisture permeability based on JIS L1099: 2012 A-1 method and a moisture permeability based on the B-1 method, both of which are 3500 g / g. m is preferably ^2/24 hr or more.

Further, the wear ring: No. It is preferable that no holes are confirmed in the waterproof layer after 500 tests in a test according to the JIS L1096: 2010 abrasion strength C method (Teva type method) using CS-17 and a load of 4.9 N.

Further, the thickness of the wear protection layer is preferably 6 μm or less.

Further, it is preferable that the wear protection layer contains a silicone resin or a silicone-modified resin.

Further, it is preferable that the wear protection layer contains a polycarbonate urethane resin.

Further, it is preferable that the waterproof layer contains inorganic particles. Further, it is more preferable that the inorganic particles are selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide and combinations thereof.

Further, the textile product according to the present invention is a textile product using at least a part of any of the above-mentioned moisture-permeable and waterproof fabrics.

The moisture-permeable and waterproof fabric of the present invention is obtained by laminating a porous waterproof layer containing a hydrophobic urethane resin on the fabric and further providing a wear protection layer on the entire surface or a part of the waterproof layer. Although it is waterproof, it has moisture permeability, is excellent in abrasion resistance, and can suppress deterioration of appearance quality due to water swelling even when the resin film comes into contact with water.
Therefore, if the moisture-permeable and waterproof fabric of the present invention is used, clothes and shoes having a resin film surface on the front side, which suppresses rain and the like from entering clothes and the like, suppresses stuffiness, and is resistant to wear. , Bags and other textile products can be provided.

<Moisture permeable and waterproof fabric>
The moisture-permeable and waterproof fabric according to the present invention includes a porous waterproof layer containing a urethane resin and an abrasion protection layer formed on the entire surface or a part of the surface of the waterproof layer on at least one surface of the fiber fabric, and the urethane. The resin is an ester-based and / or polycarbonate-based urethane resin.

Useful fiber materials constituting the fiber fabric in the present embodiment include polyester, nylon, acrylic, polyurethane, rayon such as acetate, cupra, and viscose, and in addition to these, polylactic acid. , Aromatic polyamide, chemical fibers such as polyimide or polyphenylene sulfide, natural fibers such as cotton, linen, silk or wool, or blends, blends, weaves or knits of these materials can be used, especially limited. It is not something that is done. Transfer to the resin film surface From the viewpoint of sublimation fastness, cotton, wool, cupra, rayon, and nylon are preferable. Nylon is particularly preferable.

Further, the fibers constituting the fiber fabric may be either long fibers or short fibers. Further, the yarn using this fiber may be any of raw silk, twisted yarn, and processed yarn. The processed yarn is also not particularly limited, and is not particularly limited, and is false twisted yarn (Woolly processed yarn, DTY, improved false twisted yarn, etc.), pressed yarn, shaped yarn, scraped yarn, Taslan yarn, yarn. Long-difference aligned processed yarns, composite processed yarns, fluff processed yarns, entangled focusing yarns, entangled mixed yarns, and the like can be used.

The cross-sectional shape of the fiber is also not particularly limited, and examples thereof include a round shape, a triangular shape, a star shape, a flat shape, a C shape, a hollow shape, a well shape, and a dock bone.

The fiber fabric used in the present embodiment may be in any form such as a woven fabric, a knitted fabric, or a non-woven fabric, and even a woven fabric in which tear strength and seam strength are likely to decrease can be used.

Further, these fiber fabrics may or may not be colored in advance. When pre-coloring the textile fabric, a disperse dye, a cationic dye, an acidic dye, a direct dye, a reactive dye, a vat dye, a dye such as a sulfide dye, a fluorescent whitening agent, or a pigment is used. Can be colored. Further, various treatments usually performed at the time of coloring may be performed, such as a fixing treatment using synthetic tannin or the like, which is carried out when nylon is dyed with an acid dye. The material used for coloring the fiber cloth is not particularly limited to these materials, and an appropriate material may be selected according to the material of each fiber cloth.

Further, the coloring method includes methods such as dyeing, dyeing, and printing, and is not particularly limited.

In addition, as long as the fiber fabric does not deviate from the intended purpose, water repellent treatment, calendar processing, flame retardant processing, antistatic processing, antibacterial deodorant processing, antibacterial processing, ultraviolet shielding processing, light resistance improving processing, or It may be subjected to water absorption processing, moisture absorption processing, or the like.
In particular, when the moisture-permeable and waterproof fabric of the present embodiment is used to make a reversible garment in which the front surface is turned inside out and used, the fiber fabric preferably has water repellency.
Further, when used for an application in which a large amount of sweat or dew condensation is generated, it is preferable to use a fiber cloth having water absorption or hygroscopicity. In particular, when using it as clothing, etc., when lining or batting is not used and it is desired to suppress stickiness on the skin, the surface of the fiber fabric on the body side is made water repellent and the surface on the resin film side is hydrophilic. You may use the made fiber cloth.

The porous waterproof layer containing the urethane resin in the present embodiment contains a hydrophobic ester-based and / or polycarbonate-based urethane resin, and is composed of, for example, only the ester-based and / or polycarbonate-based urethane resin. May be done. Although not particularly limited, the content of the ester-based and / or polycarbonate-based urethane resin in the waterproof layer is, for example, 60% or more, 70% or more, 80% or more, 90% or more, or 100% by mass ratio. May be good. Among the urethane resins, for example, by using a water-swellable ether-based urethane resin, an ether-ester-based urethane resin, or the like, even if the waterproof layer is not porous but has no pores, the moisture permeability of the waterproof fabric obtained can be obtained. It is possible to improve. However, when such a water-swellable urethane resin is used, there is a risk that the appearance quality may be deteriorated due to water swelling when the obtained resin film comes into contact with water. In contrast, according to the breathable waterproof fabric according to the present embodiment, a hydrophobic ester-based and / or polycarbonate-based urethane resin is used in the waterproof layer to make it porous. While improving the moisture permeability, it is possible to reliably suppress the deterioration of the appearance quality due to water swelling even when the obtained resin film comes into contact with water. Further, when carrying out the step of coagulating the urethane resin described later in a coagulation liquid containing water as a main component, there is an advantage that the coagulation property is excellent if a hydrophobic urethane resin is used.

In addition, from the viewpoint of reducing the burden on the global environment, dicarboxylic acids such as succinic acid and sebacic acid made from vegetable fats and oils and waste materials, and 1,3-propanediol obtained by fermentation of sugars made from corn etc. A biourethane resin synthesized by partially using a plant-derived component such as a diol such as 1,4-butanediol and a derivative thereof may be used.

In addition, ester-based and / or polycarbonate-based urethane resins have better wear resistance than materials such as polytetrafluoroethylene (PTFE), and thus the thickness of the wear protection layer, which will be described later, can be made thinner. There are advantages. For example, since a material such as PTFE is inferior in wear resistance, even if a wear protection layer is provided on the material, problems such as peeling or tearing may occur due to the wear action from above the wear protection layer. .. In order to prevent such a defect from occurring, for example, it is necessary to make the wear protection layer thicker. However, in this case, there is a risk that the moisture permeability of the entire moisture-permeable and waterproof fabric will decrease. In contrast, ester-based and / or polycarbonate-based urethane resins can improve moisture permeability by making them porous, but have a certain degree of wear resistance even when made porous. Therefore, by using an ester-based and / or polycarbonate-based urethane resin for the waterproof layer, the wear protection layer formed on the ester-based urethane resin can be made relatively thin. Therefore, the ester-based and / or polycarbonate-based urethane resin is very advantageous not only from the viewpoint of suppressing deterioration of the appearance quality due to water swelling but also from the viewpoint of improving the moisture permeability of the entire moisture-permeable and waterproof fabric. ..

The porous waterproof layer containing the urethane resin described above is a film that can impart waterproofness to the fiber fabric because it is hydrophobic while having moisture permeability, and the size, shape, and distribution state of the pores thereof. Is not particularly limited. Generally, from the viewpoint of moisture permeability and waterproofness, the waterproof layer has pores having a pore diameter of about 1 μm or less on the surface of the porous membrane, and an empty space having a pore diameter of about 10 to 50 μm inside the porous membrane. It is preferable that the porous membrane has pores, has pores having a pore diameter of about 1 μm or less on the wall surface of the pores, and has a structure in which the pores communicate with each other by these pores.

Examples of the method for forming the porous waterproof layer containing the urethane resin include stretching, needle punching, laser perforation, mechanical foaming, chemical foaming, and wet coagulation method. From the viewpoint of ease of processing and cost, urethane is used. A wet coagulation method in which the resin is applied to the fiber cloth and then immersed in a coagulation liquid containing water as a main component to coagulate the urethane resin is preferable.

When a porous waterproof layer containing a urethane resin is laminated on a fiber cloth by a wet coagulation method, the urethane resin and N, N-dimethylformamide (DMF), N, N are contained in the urethane resin solution applied to the fiber cloth. A water-soluble polar organic solvent mainly composed of -dimethylacetamide, N-methylpyrrolidone, etc. is preferably used.
Further, a colorant such as a pigment, a polyisocyanate-based cross-linking agent, a catalyst, an antioxidant, an ultraviolet absorber, or the like may be added to the urethane resin solution.

Then, by applying this urethane resin solution to the fiber cloth using a knife coater, a bar coater, a comma coater or the like, a fiber cloth coated with the urethane resin solution can be obtained.
Next, the fiber cloth coated with the urethane resin solution is immersed in water or a coagulating liquid containing about 5 to 20% of a water-soluble polar organic solvent such as DMF as a main component to coagulate the urethane resin. .. The solidification temperature is preferably in the range of 10 to 50 ° C. from the viewpoint of appropriately adjusting the pore diameter of the pores formed in the resin film.

Next, the urethane resin is desolvated. Water is preferable as the cleaning liquid for desolvation, and the desolvation temperature is preferably 10 to 80 ° C.
By removing the solvent and then drying the fabric at 90 to 150 ° C., a moisture-permeable waterproof fabric in which a porous waterproof layer containing urethane resin or only urethane resin is formed can be obtained. After that, if necessary, water repellent treatment, antistatic treatment, antibacterial deodorant treatment, antibacterial treatment, ultraviolet shielding treatment, and the like may be performed.

When a porous waterproof layer containing a urethane resin is produced by a wet solidification method, it is preferable that the urethane resin to be coated contains inorganic particles for the purpose of improving the moisture permeability of the resin film. The inorganic particles have the effect of promoting the replacement of water with a solvent such as DMF contained in the urethane resin when the urethane resin coated on the fiber cloth is immersed in a coagulation liquid containing water as a main component to coagulate. be. As a result, the formation of a porous structure is promoted and the moisture permeability is improved.

Inorganic particles are often agglomerated, so in order to uniformly disperse and mix them in urethane resin, a solvent such as DMF, a resin as a vehicle, a dispersant, etc. are blended and easily dispersed by a disperser or the like. It is preferable to use a pretreated product.

The content of the inorganic particles is preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the urethane resin that is the base of the porous membrane. More preferably, it is 1 to 50 parts by mass. If the content is below the above range, the effect of adding the inorganic particles is unlikely to appear, and if the content exceeds the above range, the porosity may become too high and the water pressure resistance may decrease.

Further, it is more preferable that the inorganic particles are selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide and combinations thereof. If an acidic liquid with a pH of less than 4.0 or an alkaline liquid with a pH of more than 7.0 adheres to human skin, the balance of acidity of the skin may be lost, which may cause skin stress or rough skin. For example, when the film surface is turned inside, the moisture such as sweat adhering to the film surface of the waterproof layer exhibits a pH of 4.0 to 7.0, which is gentle on human skin when wet. On the other hand, when calcium carbonate or the like is used as the inorganic particles, the pH of the water adhering to the waterproof layer may become weakly alkaline, which is not particularly preferable in the application of providing the waterproof layer inside clothes or the like.

The thickness of the porous waterproof layer containing the urethane resin is preferably about 10 to 100 μm. If the thickness of the waterproof layer is less than 10 μm, the waterproof property may decrease. When the thickness of the waterproof layer exceeds 100 μm, the texture of the obtained breathable waterproof fabric becomes hard. Although not particularly limited, the thickness of the waterproof layer may be, for example, 15 μm or more, 20 μm or more, or 30 μm or more, and may be 80 μm or less, 70 μm or less, or 60 μm or less.

The porous waterproof layer containing the urethane resin in the present embodiment is further provided with a wear protection layer on the entire surface or a part thereof. The abrasion protection layer plays a role of improving the abrasion resistance of the porous waterproof layer containing urethane resin.

Since the moisture-permeable and waterproof fabric according to the present embodiment uses a porous waterproof layer, good moisture permeability is good even when the thickness of the abrasion protection layer is relatively thick, for example, 7 μm or more. It is possible to maintain. However, in order to improve the moisture permeability more remarkably, the thickness of the wear protection layer is preferably 6 μm or less. It is more preferably 5 μm or less, even more preferably 4.5 μm or less, and most preferably 4 μm or less. Further, from the viewpoint of wear resistance, the lower limit is preferably 0.1 μm or more. The thickness of the wear protection layer may be 0.5 μm or more or 1 μm or more. On the other hand, if the thickness of the abrasion protection layer becomes too thin, the abrasion protection layer becomes unclear by observation with a scanning electron microscope described later because it is mixed with the unevenness of the entire moisture-permeable and waterproof fabric, and the abrasion protection layer becomes unclear. It may be difficult to determine the thickness. However, in such a case, the wear protection layer is calculated on the assumption that the wear protection layer forms a film having a uniform thickness based on the amount of resin consumed during processing, the processing area, and the resin density. When the thickness is 0.1 μm or more, the wear resistance of the wear protection layer is easily exhibited, which is preferable.
If the wear protection layer contains granules or the like and the granules or the like protrude from the wear protection layer, the protruding portion shall not be regarded as the thickness of the wear protection layer.

The abrasion protection layer is not particularly limited as long as it is hydrophobic and improves the abrasion resistance of the waterproof layer. Specific examples thereof include (meth) acrylic resin, (meth) acrylic urethane resin, urethane resin, epoxy resin, melamine resin, fluororesin, and silicone resin. It is preferable that the polycarbonate urethane resin is contained from the viewpoint that the texture of the fabric is not impaired, the weather resistance is good, and the abrasion resistance is further improved. Further, from the viewpoint of improving surface slipperiness, it is preferable to contain a silicone resin or a silicone-modified resin, and it is particularly preferable to include a silicone-modified urethane resin. Regarding the silicone resin contained in the wear protection layer and the silicone segment in the silicone-modified resin, the mass ratio is preferably 10% or more, preferably 20% or more, with respect to all the components forming the wear protection layer. On the other hand, the water-swellable material cannot be said to have a wear protection function because its resistance to wear is lowered by absorbing water, and therefore, the wear protection layer according to the present invention can be formed. Can not.

Further, by using a urethane resin containing a water repellent such as a fluorine-based water repellent, a silicone-based water repellent, or a hydrocarbon-based water repellent as the wear protection layer, the hydrophobicity is enhanced and the obtained waterproof layer can be obtained. It is also possible to enhance the function of suppressing deterioration of appearance quality due to water swelling.

The wear protection layer may be provided on the entire surface of the porous waterproof layer containing the urethane resin, or may have a dot shape, a linear shape, a grid shape, or the like, and is not particularly limited. The wear protection layer preferably covers 50% or more of the waterproof layer, and more preferably covers the entire surface with almost no gap.

The wear protection layer includes pigments, antistatic agents, antibacterial agents, ultraviolet absorbers, infrared absorbers, deodorants, antioxidants, hygroscopic agents, moisture-absorbing heat-generating materials, and flame retardants, as long as the object of the present invention is not deviated. , Water repellent, cross-linking agent, and fillers such as inorganic particles and organic particles for the purpose of increasing the strength, waterproofness, and moisture permeability of the resin film, and for changing the tactile sensation when the resin film comes into contact with the skin. Etc. may be included.

According to the moisture-permeable and waterproof fabric according to the present embodiment having the above configuration, the waterproofness of the moisture-permeable and waterproof fabric can be remarkably improved, for example, 2000 mmH ₂ O or more, preferably 3000 mmH ₂ O or more. , More preferably, it is possible to achieve a water pressure resistance of _{4000 mmH 2 O or more.} If the water pressure resistance of the moisture permeable and waterproof fabric _{is less than 2000 mmH 2} O, it may not be able to fully fulfill its original role as a waterproof layer. In such a case, the covering article gets wet with water. There is a risk that it will end up. The upper limit of the water pressure resistance is not particularly limited, but may be, for example, 100,000 mmH ₂ O or less, 80,000 mmH ₂ O or less, 60,000 mmH ₂ O or less, or 50,000 mmH ₂ O or less.

Further, according to the moisture-permeable and waterproof fabric according to the present embodiment having the above configuration, the moisture permeability of the moisture-permeable and waterproof fabric can be remarkably improved. for moisture permeability based on moisture permeability and B-1 method based on the calcium chloride method) (potassium acetate method), both 3500g / m ² / 24hr or more, preferably 4500g / m ² / 24hr or more, more preferably 5000 g / m ² It is possible to achieve a moisture permeability of / 24 hr or more. If the moisture permeability based on the A-1 method of moisture-permeable waterproof fabric 3500g / m ² / 24hr or more, moisture in the clothes due to insensible perspiration is discharged smoothly, sufficient function to suppress the unpleasant stuffiness feeling It is demonstrated in. Further, if the moisture permeability of the moisture permeable waterproof fabric based on the B-1 method is 3500g / m ² / 24hr or more, to prevent condensation in the garment by sweating, function to suppress a feeling of uncomfortable sticky sufficiently exhibited Will be done. Incidentally, the A-1 method and moisture permeability upper limit based on the B-1 method is not particularly limited, for example, 80000g / m ² / 24hr or less, 60000g / m ² / 24hr or less, 50000g / m ² / 24hr hereinafter, or 40000g / m ² / 24hr may be less. The water pressure resistance and moisture permeability of the moisture permeable and waterproof fabric in the above range are the materials used for the fiber fabric, the waterproof layer, and the abrasion protection layer described above and their characteristics (for example, the thickness, the degree of hydrophobicity and the pores). This can be achieved by appropriately selecting and / or controlling the pore size, etc.).

Further, according to the moisture-permeable and waterproof fabric according to the present embodiment having the above configuration, the wear resistance of the moisture-permeable and waterproof fabric can be remarkably improved, for example, with respect to the moisture-permeable and waterproof fabric. Wear wheel: No. In a test based on JIS L1096: 2010 wear strength C method (Teva type method) using CS-17 and load: 4.9N, the number of frictions between holes in the resin film, especially the waterproof layer, was 500 or more. It is possible to achieve the wear resistance of. Generally, if the number of frictions in this test is 500 or more, a moisture-permeable and waterproof fabric can be used for general clothes such as coats and jumpers. From the viewpoint of having more excellent abrasion resistance and using the moisture-permeable and waterproof fabric of the present embodiment in shoes, bags and the like, 1000 times or more is preferable, and 1500 times or more is particularly preferable. The larger the number of frictions in the above test, the better, and the upper limit value is not specified, but in general, the upper limit value may be 20000 times or less, 15000 times or less, or 10000 times or less. The number of frictions in the above range shall be achieved, among other things, by appropriately selecting and / or controlling the materials used for the waterproof layer and the wear protection layer described above and their properties (eg, thickness and pore size, etc.). Is possible.

<Textile products using moisture-permeable and waterproof fabric>
The textile product using the moisture-permeable and waterproof fabric in the present embodiment is one in which the moisture-permeable and waterproof fabric is used for at least a part, preferably the moisture-permeable and waterproof fabric is used for at least a part of the front side thereof. For example, we can provide clothes such as windbreakers, coats, jackets, yackes, anoraks, ski wear, snowboard wear, a pair of feathers, work clothes, hats, gloves, tents, sleeping bags, mattress covers, shoes, bags, and the like.

Since the textile product using the moisture-permeable and waterproof fabric in the present embodiment uses the moisture-permeable and waterproof fabric, it has moisture permeability, excellent wear resistance, and is waterproof. Even when the resin film comes into contact with water, deterioration of appearance quality due to water swelling can be suppressed.
Therefore, if the moisture-permeable and waterproof fabric of the present invention is used, clothes and shoes having a resin film surface on the front side, which suppresses rain and the like from entering clothes and the like, suppresses stuffiness, and is resistant to wear. , Bags and other textile products can be provided.

Hereinafter, examples of the moisture-permeable and waterproof fabric according to the present embodiment will be described, but the present invention is not limited to these examples. The measurement and evaluation of various physical properties in each of the evaluation items A to G in the following Examples and Comparative Examples were carried out by the following methods. Further, "%" and "part" in Examples and Comparative Examples are "mass%" and "parts by mass".
[A: Water pressure resistance]
The water pressure resistance was measured by a method according to JIS L1092: 2009 water resistance test B method (high water pressure method). The measured values were _{converted into mmH 2} O units and displayed.
If the test piece is stretched by applying water pressure, a nylon taffeta (the total density of warp and weft threads per 2.54 cm is about 210) is placed on the test piece and the tester is used. It was attached to and measured.
[B: Moisture permeability]
Regarding the moisture permeability, both the moisture permeability based on the JIS L1099-2012 A-1 method (calcium chloride method) and the moisture permeability based on the JIS L1099-2012 B-1 method (potassium acetate method) were measured.
The water contact surface was a fiber cloth surface, and the moisture permeability of each was converted into the moisture permeability per 24 hours.
[C: Abrasion resistance]
The wear resistance was tested according to JIS L1096: 2010 wear strength C method (Teva type method), and the number of times until the waterproof layer was punctured (whether the resin film surface was punctured every 100 times). Was confirmed, and the evaluation was made by measuring the number of times immediately before the hole was confirmed). The case where no hole was confirmed in the waterproof layer after 500 tests was regarded as a pass.
The wear ring used at the time of measurement is No. The load was CS-17 and the load was 4.90N.
[D: Thickness of wear protection layer]
Using a scanning electron microscope (SEMEDX Type H type: Hitachi Science Systems Co., Ltd.), observe the cross section of the moisture-permeable and waterproof fabric at 1000 to 4500 times, and measure the thickness of the wear protection layer at any 5 points. , The average value of them was calculated and determined as the thickness of the wear protection layer.
[E: pH of moisture permeable and waterproof fabric]
The pH of the moisture permeable and waterproof fabric was measured by the JIS L1096: 2010 A method.

[F: Water swelling]
Water swelling was evaluated by dropping 2 g of water on the resin film surface of a 10 cm square sample, spreading it, allowing it to stand for 5 minutes, and then confirming the appearance.
[G: Actual wear test]
A breathable waterproof cloth cut to 10 cm x 10 cm is sewn on the shoulder of the test jacket so that the film surface is on the front side, and a rucksack adjusted to a total of 5 kg with a weight is carried on the back, and a staircase of 18 cm per step. It went up and down in total of 1800 steps while going back and forth. The appearance of the sewn test piece after the test was evaluated for actual wear resistance in the following three stages. ◎ and 〇 were accepted.
◎: No change ○: Twisting occurs but no holes are opened ×: Holes are opened

(Example 1)
<Fiber fabric>
Nylon taffeta (fiber thickness: warp 83 decitex / 72 filaments, weft 83 decitex / 72 filaments. Fiber density: warp 114 / 2.54 cm, weft 92 / 2.54 cm) was dyed in a navy color with an acid dye.
Next, this nylon taffeta is subjected to water repellent treatment using a 5% aqueous solution of the fluorine-based water repellent Asahigard AG-E081 (manufactured by AGC Co., Ltd.), and then at 170 ° C., pressure (linear pressure) 128 kgf / cm. The one processed by the calendar in 1 was used as the fiber cloth.

<Porous waterproof layer containing urethane resin by stretching method>
To 100 parts of polycarbonate urethane resin Chrisbon NY-331 (manufactured by DIC Corporation), 1 part of calcium carbonate and 1 part of stearic acid having an average particle size of 2 μm were added and kneaded with a laboplast mill. The obtained mixed solution was applied onto a paper pattern and then dried with hot air at 120 ° C. to form a film having a thickness of 50 μm. The film obtained by peeling the release paper was stretched with a roll stretching machine under the conditions of a stretching speed of 6 m / min and a stretching rate of 300% to obtain a porous waterproof film.
Next, using a gravure coater, a moisture-curable hot-melt type urethane resin adhesive Tyforce NH-320 (manufactured by DIC Corporation) was heated to 110 ° C. to melt it, and the adhesive was applied to the surface of the waterproof film in dots. ..
Next, the surface to which the adhesive of the waterproof film was applied and the calendar-treated surface of the fiber fabric were overlapped so as to face each other, and heat-pressed at 100 ° C. using a nip roll. After heat-pressing, it was aged at 70 ° C. for 72 hours to obtain a moisture-permeable waterproof cloth in which a porous waterproof layer containing a urethane resin formed by a stretching method was laminated on the fiber cloth.

<Giving a wear protection layer>
Next, a solution obtained by diluting 100 parts of silicone-modified polycarbonate-based urethane resin Chrisbon NY-373 (manufactured by DIC Corporation) with 60 parts of toluene is gravured on the entire surface of the waterproof layer of the moisture-permeable waterproof fabric in which the waterproof layer is laminated. After coating with a coater, it was dried with hot air at 120 ° C. to obtain a moisture-permeable waterproof cloth having a wear protection layer provided on the surface of the waterproof layer. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 1.

(Comparative Example 1)
<Porous waterproof layer containing PTFE by stretching method>
Moisture-curing hot-melt type urethane resin adhesive Typorex NH-320 (manufactured by DIC Co., Ltd.) using a gravure coater on a 30 μm-thick PTFE film Tetratex (manufactured by Nippon Donaldson Co., Ltd.) that has been made porous by the stretching method. ) Was heated to 110 ° C. to melt it, and the film was applied to the surface of the PTFE film in dots.
Next, the adhesive-coated surface of the PTFE film and the calendar-treated surface of the fiber fabric described in Example 1 were overlapped so as to face each other, and heat-pressed at 100 ° C. using a nip roll. After heat-bonding, it was aged at 70 ° C. for 72 hours to obtain a moisture-permeable and waterproof fabric on which a porous waterproof layer containing PTFE formed by a stretching method was laminated.

Next, by the method described in Example 1, a abrasion protection layer was applied to the surface of the waterproof layer, and a moisture-permeable waterproof fabric provided with the abrasion protection layer on the surface of the waterproof layer was obtained. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 1.

(Comparative Example 2)
<Non-porous waterproof layer containing urethane resin by dry laminating method>
After applying a solution of 100 parts of ester urethane resin Chrisbon S-125 (manufactured by DIC Corporation) diluted with 50 parts of 2-butanone (MEK) on the release paper, it is dried with hot air at 120 ° C. to make urethane with a thickness of 13 μm. A resin film was formed.
Next, 100 parts of ester urethane resin adhesive Chrisbon 4070 (manufactured by DIC Co., Ltd.), 12 parts of polyisocyanate solution Coronate L (manufactured by Toso Co., Ltd.), and 0.2 part of N-methyldiethanolamine were prepared and diluted with 60 parts of toluene. The stirred solvent was applied onto the waterproof film and then dried with hot air at 90 ° C. to impart an adhesive layer to the waterproof film.
Next, the adhesive layer of the film was superposed so that the calendar-treated surfaces of the fiber fabric described in Example 1 faced each other, and heat-pressed at 120 ° C. using a nip roll. After heat-bonding and aging at 60 ° C. for 24 hours, the release paper was peeled off to obtain a moisture-permeable waterproof fabric on which a non-porous waterproof layer containing a urethane resin formed by a dry laminating method was laminated.

Next, by the method described in Example 1, a abrasion protection layer was applied to the surface of the waterproof layer, and a moisture-permeable waterproof fabric provided with the abrasion protection layer on the surface of the waterproof layer was obtained. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 1.

(Comparative Example 3)
A solution obtained by diluting 100 parts of ether-based urethane resin Chrisbon S-525 (manufactured by DIC Corporation) with 50 parts of MEK was applied on a release paper, and then dried with hot air at 120 ° C. to form a urethane resin film having a thickness of 13 μm. ..
Next, 100 parts of ether / ester urethane resin adhesive Chrisbon TA-150 (manufactured by DIC Co., Ltd.), 12 parts of polyisocyanate solution Coronate L (manufactured by Toso Co., Ltd.), and 0.2 part of N-methyldiethanolamine were prepared, and toluene was prepared. A solvent diluted in 60 parts and stirred was applied onto a film formed on a release paper, and then dried with hot air at 90 ° C. to give an adhesive layer to the film.
Next, the adhesive layer of the film was superposed so that the calendar-treated surfaces of the fiber fabric described in Example 1 faced each other, and heat-pressed at 120 ° C. using a nip roll. After heat-bonding and aging at 60 ° C. for 24 hours, the release paper was peeled off to obtain a moisture-permeable waterproof fabric on which a non-porous waterproof layer containing a urethane resin formed by a dry laminating method was laminated.

Next, by the method described in Example 1, a abrasion protection layer was applied to the surface of the waterproof layer, and a moisture-permeable waterproof fabric provided with the abrasion protection layer on the surface of the waterproof layer was obtained. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 1.

(Comparative Example 4)
<Porous waterproof layer containing urethane resin by wet solidification method>
A solution obtained by diluting 100 parts of ester urethane resin Chrisbon MP-858 (manufactured by DIC Corporation) with 40 parts of DMF was applied to the calendar-treated surface of the fiber cloth described in Example 1, and then immersed in water at 20 ° C. for 5 minutes. The urethane resin was coagulated and further immersed in warm water at 40 ° C. for 5 minutes of desolvation. Further, the fiber cloth was dried with hot air at 120 ° C. to obtain a moisture-permeable waterproof cloth in which a porous waterproof layer containing a urethane resin formed by a wet coagulation method having a thickness of 40 μm was laminated on the fiber cloth. .. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 1.

(Example 2)
100 parts of ester-based urethane resin Chrisbon MP-858 (manufactured by DIC Corporation) and 20 parts of titanium dioxide-based pigment Resamine CUT-934T (manufactured by Dainichi Seika Kogyo Co., Ltd.) on the calendar-treated surface of the fiber cloth described in Example 1. Was prepared, diluted with 40 parts of DMF and stirred, and then immersed in water at 20 ° C. for 5 minutes to solidify the urethane resin, and further immersed in warm water at 40 ° C. for 5 minutes to remove the solvent. Further, the fiber cloth was dried with hot air at 120 ° C. to obtain a moisture-permeable waterproof cloth in which a porous waterproof layer containing a urethane resin formed by a wet coagulation method having a thickness of 40 μm was laminated on the fiber cloth. ..

Next, by the method described in Example 1, a abrasion protection layer was applied to the surface of the waterproof layer, and a moisture-permeable waterproof fabric provided with the abrasion protection layer on the surface of the waterproof layer was obtained. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 2.

(Example 3)
By the method described in Example 2, a waterproof layer was laminated on the fiber cloth to obtain a moisture-permeable waterproof cloth in which a porous waterproof layer containing a urethane resin was laminated.

Next, a solution obtained by diluting 100 parts of silicone-modified polycarbonate-based urethane resin Chrisbon NY-373 (manufactured by DIC Corporation) with 60 parts of toluene is applied to the entire surface of the waterproof layer of the moisture-permeable waterproof cloth in which the waterproof layer is laminated. After coating with a coater, it was dried with hot air at 120 ° C. to obtain a moisture-permeable waterproof cloth having a wear protection layer provided on the surface of the waterproof layer. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 2.

(Example 4)
By the method described in Example 2, a waterproof layer was laminated on the fiber cloth to obtain a moisture-permeable waterproof cloth in which a porous waterproof layer containing a urethane resin was laminated.

Next, a solution obtained by diluting 100 parts of silicone-modified ester-based urethane resin Luxkin U2960-2 (manufactured by Seiko Kasei Co., Ltd.) with 60 parts of toluene was added to the entire surface of the waterproof layer of the moisture-permeable waterproof cloth in which the above waterproof layer was laminated. After coating with a gravure coater, it was dried with hot air at 120 ° C. to obtain a moisture-permeable waterproof cloth in which a wear protection layer was provided on the surface of the waterproof layer. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 2.

(Example 5)
By the method described in Comparative Example 4, a waterproof layer was laminated on the fiber cloth, and a moisture-permeable waterproof cloth in which a porous waterproof layer containing a urethane resin was laminated was obtained.
Next, by the method described in Example 1, a abrasion protection layer was applied to the surface of the waterproof layer, and a moisture-permeable waterproof fabric provided with the abrasion protection layer on the surface of the waterproof layer was obtained. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 2.

(Example 6)
100 parts of ester urethane resin Chrisbon MP-858 (manufactured by DIC Corporation) and 20 parts of calcium carbonate pigment Dilac filler F-14 (manufactured by DIC Corporation) are blended on the calendar-treated surface of the fiber cloth described in Example 1. After applying the solution diluted with 40 parts of DMF and stirred, the solution was immersed in water at 20 ° C. for 5 minutes to solidify the urethane resin, and further immersed in warm water at 40 ° C. for 5 minutes to remove the solvent. Further, the fiber cloth was dried with hot air at 120 ° C. to obtain a moisture-permeable waterproof cloth in which a porous waterproof layer containing a urethane resin formed by a wet coagulation method having a thickness of 40 μm was laminated on the fiber cloth. ..

Next, by the method described in Example 1, a abrasion protection layer was applied to the surface of the waterproof layer, and a moisture-permeable waterproof fabric provided with the abrasion protection layer on the surface of the waterproof layer was obtained. The performance of the obtained moisture-permeable and waterproof fabric is shown in Table 2.

With reference to Tables 1 and 2, in the moisture-permeable waterproof fabric of Comparative Example 1 in which the waterproof layer is made of PTFE, the PTFE itself is inferior in abrasion resistance. The waterproof layer was damaged by the abrasion action from above the layer, and as a result, sufficient wear resistance was not obtained. In Comparative Example 2, since the waterproof layer was non-porous, the moisture permeability based on both the A-1 method and the B-1 method was low, and sufficient moisture permeability could not be obtained. In Comparative Example 3, although the waterproof layer was non-porous, the moisture permeability was somewhat improved as compared with Comparative Example 2 because the waterproof layer was composed of a water-swellable ether urethane resin. However, in Comparative Example 3, since the waterproof layer was made of a water-swellable ether urethane resin, water swelling was observed and deterioration of the appearance quality was observed. In Comparative Example 4, since the wear protection layer was not provided, holes were confirmed in the waterproof layer after 200 tests in a test according to JIS L1096: 2010 wear strength C method (Teva type method), and actual wear was observed. The test also failed, with the lowest wear resistance performance.

In contrast, in the moisture permeable and waterproof fabrics of all the examples according to the present invention, the waterproof layer is further made porous by being composed of a hydrophobic ester-based and / or polycarbonate-based urethane resin, and on the waterproof layer. by providing the wear protection layer, high without loss of appearance quality due to water swelling waterproof and achieve moisture permeability of 2000mmH ₂ O or more at the lowest embodiments specifically water pressure resistance and 3500g / m ² / 24hr The moisture permeability based on the above A-1 method and B-1 method was achieved, and further excellent wear resistance could be achieved. Especially, the thickness of the wear protection layer is 7 [mu] m, even moisture permeable waterproof fabric of relatively thick Example 3 as compared with other examples, 3500g / m ² / 24hr or more A-1 method and B-1 We were able to achieve legal moisture permeability. On the other hand, in the moisture-permeable waterproof fabric of Example 2 having the same configuration as that of Example 3 except that the thickness of the abrasion protection layer is reduced, the thickness of the abrasion protection layer is reduced to 6 μm or less to provide sufficient waterproofing. It can be seen that the moisture permeability can be significantly improved while maintaining the properties and abrasion resistance.

Further, in Example 4 in which the wear protection layer was made of an ester-based urethane resin, holes were confirmed in the waterproof layer after 900 tests in a test according to JIS L1096: 2010 wear strength C method (Teva type method). On the other hand, in other examples in which the wear protection layer was made of a polycarbonate-based urethane resin, no holes were confirmed in the waterproof layer even after 2000 tests. Further, as compared with the moisture-permeable waterproof fabric of Example 5 in which the waterproof layer does not contain inorganic particles, the moisture-permeable fabric of Example 2 has the same configuration as that of Example 5 except that the waterproof layer contains inorganic particles. It can be seen that the moisture permeability of the waterproof fabric is greatly improved. In addition, the moisture-permeable and waterproof fabric of Example 6 using calcium carbonate as the inorganic particles was able to achieve excellent moisture permeability, but showed a weakly alkaline pH value. On the other hand, in Examples 2 and 4 in which titanium dioxide was used as the inorganic particles, the pH was controlled to 4.0 to 7.0, which is gentle on human skin, while remarkably improving the moisture permeability by using the inorganic particles. I was able to.

In the moisture-permeable waterproof fabric obtained as described above, a porous waterproof layer containing a hydrophobic urethane resin is laminated on the fabric, and a wear protection layer is provided on the entire surface or a part of the waterproof layer. Therefore, while having waterproofness, it has moisture permeability, is excellent in abrasion resistance, and can suppress deterioration of appearance quality due to water swelling even when the resin film comes into contact with water.
Therefore, by using the moisture-permeable and waterproof fabric of the present invention, clothes having a resin film surface used on the surface, which suppresses rain or the like from entering clothes, suppresses stuffiness, and is resistant to wear, We can provide textile products such as shoes and bags.

Claims (9)

At least one surface of the fiber cloth contains a porous waterproof layer containing a urethane resin and an abrasion protection layer formed on the entire surface or a part of the surface of the waterproof layer, and the urethane resin is an ester-based and / or polycarbonate-based urethane resin. A moisture-permeable and waterproof fabric characterized by being. According moisture permeability based on based on the 2012 A-1 method moisture permeability and B-1 method is characterized in that it is both 3500g / m ² / 24hr or more: water pressure resistance is at 2000mmH ₂ O or more, and JIS L1099 Item 2. The moisture-permeable and waterproof fabric according to Item 1. Abrasion wheel: No. It is a test based on JIS L1096: 2010 abrasion strength C method (Teva type method) using CS-17 and load: 4.9N, and it is characterized in that no holes are confirmed in the waterproof layer after 500 tests. The moisture-permeable and waterproof fabric according to claim 1 or 2. The moisture-permeable and waterproof fabric according to any one of claims 1 to 3, wherein the thickness of the abrasion protection layer is 6 μm or less. The moisture-permeable and waterproof fabric according to any one of claims 1 to 4, wherein the wear protection layer contains a silicone resin or a silicone-modified resin. The moisture-permeable and waterproof fabric according to any one of claims 1 to 4, wherein the wear protection layer contains a polycarbonate-based urethane resin. The moisture-permeable and waterproof fabric according to any one of claims 1 to 6, wherein the waterproof layer contains inorganic particles. The moisture-permeable and waterproof fabric according to claim 7, wherein the inorganic particles are selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide and a combination thereof. A textile product using at least a part of the moisture-permeable and waterproof fabric according to any one of claims 1 to 8.