KR102298944B1 - Waterproof fabric and textile product employing same - Google Patents

Abstract

Provided is a waterproof fabric comprising a resin film that can suppress hardening of the touch and suppress a decrease in waterproofness even in an extremely low-temperature environment of -40°C or less. A waterproof fabric comprising a fiber fabric laminated on at least one side of a urethane resin film having a glass transition point of less than -30°C, wherein the urethane resin film is mainly made of an ether-based urethane resin.

Description

Waterproof fabric and textile products using the same

The present invention relates to waterproof fabrics. In particular, it relates to a waterproof fabric that can be used even in a low-temperature environment.

Waterproof fabrics are used in a variety of things, from raincoats, ski wear, and windbreakers, to tents and shoe materials to prevent water ingress from rain.

The waterproof fabric has a waterproof resin film laminated on one side or both sides of the textile fabric, and is not only waterproof, but also has moisture permeability to allow moisture in clothes to pass through, and to suppress sweat or moisture loss in clothes. It is known that the structure is laminated on the . (Patent Document 1, Patent Document 2)

Such waterproof fabrics are used in various environments, and in winter sports such as ski wear, they are used in an environment of about -15°C to 5°C, and in midsummer work clothes, they are sometimes used in an environment of about 30-50°C. In addition, it is also used in an environment of about -40 ℃ in the freezer, in the Antarctic or the Arctic, and in the high-altitude mountains.

Among these various environments, especially when used in a low-temperature environment, we are concerned about hardening of a waterproof fabric.

As waterproof clothing used in a low-temperature environment, it is known that an air-buffering material has a porous polytetrafluoroethylene membrane having moisture permeability and waterproofness inside the body facing the body. (Patent Document 3)

However, the hardening of a waterproof fabric in a low-temperature environment, or the fall of waterproofness are not examined about, and this technique is related with the transfer material and batting.

Japanese Patent Laid-Open No. 55-80583 Japanese Patent Laid-Open No. 11-124774 Japanese Patent Laid-Open No. 8-302506

In a waterproof fabric having a resin film, it has been found that although the resin itself is cured in a low-temperature environment of about -40°C, the waterproofness of the waterproof fabric may also decrease. This is because the resin film of waterproof fabrics used for clothes, etc. loses its flexibility under low-temperature environments and hardens, and the resin film is damaged by movement of the wearer wearing the clothes, and the water attached to the waterproof fabric freezes and is waterproofed by the generated ice. If the fabric is hardened and worn as clothes or the like in that state, the generated ice cracks, and the resin film is damaged at the corners and the like, and it is speculated that the cause is that the waterproofness is lowered.

In addition, waterproof fabric is used as the outer fabric of textile products such as clothes, and having a textile fabric on the inner side (body side) of the textile product is difficult to be affected by low temperatures because the textile fabric is inside the clothes, and low temperature Although it was thought that problems, such as hardening of a touch, did not arise also in an environment, there exists a possibility that a touch may harden in the low-temperature environment of about -40 degreeC.

Therefore, in the present invention, in the waterproof fabric comprising a resin film, even under an extreme low temperature environment of -40 ° C. or less, to provide a waterproof fabric capable of suppressing the hardening of the feel of the waterproof fabric and suppressing the decrease in waterproofness is aimed at

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors came to this invention as a result of earnest examination.

That is, this invention has the following structures (1)-(7).

(1) A waterproof fabric comprising a fiber fabric laminated on at least one side of a urethane resin film having a glass transition point of less than -30 ° C.

The waterproof fabric, characterized in that the urethane resin film is mainly composed of an ether-based urethane resin.

(2) The waterproof fabric according to the above (1), wherein the waterproof fabric is used as an outer fabric for textile products.

(3) The waterproof fabric according to the above (1) or (2), characterized in that the amount of water picked up of the textile fabric used inside the textile product is 100 g/m 2 or less when it is used as a textile product.

(4) The waterproof fabric according to any one of (1) to (3), wherein the urethane resin film is a porous film.

(5) The waterproof fabric according to any one of (1) to (4), wherein the urethane resin film is adhered to the textile fabric through an adhesive.

(6) The waterproof fabric according to the above (5), wherein the adhesive is an ether-based urethane resin.

(7) The fiber fabric according to the above (5) or (6), characterized in that the glass transition point of the urethane resin used for the adhesive is less than -30°C.

(8) A textile product using the waterproof fabric according to any one of (1) to (7) as an outer fabric.

The waterproof fabric of the present invention can provide a waterproof fabric capable of suppressing hardening of the tactile feel of the waterproof fabric and maintaining waterproofness even in a low-temperature environment.

When the waterproof fabric of the present invention is used in textile products such as windbreaker, coat, jacket, jacket, anorak, ski wear, snowboard wear, raincoat, work clothes, tent, sleeping bag, hat, shoes, low temperature Even in an environment, hardening of the feel of a textile can be suppressed and the fall of waterproofness can be suppressed.

The waterproof fabric of the present invention is a waterproof fabric in which a fiber fabric is laminated on at least one side of a urethane resin film having a glass transition point (Tg) of less than -30°C, and the urethane resin film is mainly made of an ether-based urethane resin.

Moreover, it is preferable if a waterproof fabric is used as the outer material of textile products, such as clothes. The waterproof fabric of the present invention is used as an outer fabric for textile products such as clothes, and thus, unlike conventionally known waterproof fabrics, even in a low-temperature environment of -20°C, -30°C, -40°C or less, or about -50°C. While suppressing the hardening of the tactile feel of the waterproof fabric, it is possible to exhibit the effect of suppressing a decrease in waterproofness.

In particular, in the present invention, the waterproof fabric is used as the outer fabric of textile products such as clothes, and with respect to having the textile fabric on the inner side (body side) of the textile product, particularly, the hardening of the feel is suppressed, and the decrease in waterproofness can be suppressed. can

The lower limit which can exhibit such an effect of the waterproof fabric of this invention is about -70 degreeC. When using for textile products used in the environment of -70 degreeC or less, you may use the waterproofing fabric of this invention as an intermediate|middle layer between the lining of textile products, or an outer and lining.

<Urethane resin film>

Tg of the urethane resin film of this invention is less than -30 degreeC. From a viewpoint of suppressing hardening of the touch of a waterproof fabric even under a lower temperature environment, Preferably -40 degreeC or less is good. More preferably, -50°C or less is good.

In the present invention, Tg is measured by differential scanning calorimetry (DSC).

In addition, the said urethane resin film consists mainly of an ether type urethane resin. Mainly means that among the urethane resins forming the urethane resin film, 50% or more by mass ratio consists of an ether-based urethane resin.

As an ether-type urethane resin, what used polyether polyol for the polyol used as a raw material of a urethane resin may be said, and what used polyether ester polyol or these modified bodies may be sufficient. Preferably, it is preferable to use a polyether polyol that does not contain an ester in the polyol.

Moreover, as long as it does not deviate from the objective of this invention, what mix|blended the ether type urethane resin and the ester type urethane resin may be sufficient as a urethane resin film. However, the blending ratio of the ester-based urethane resin is less than 50% by mass in the urethane resin film.

Moreover, when using the thing which has moisture permeability as a urethane resin film, it is preferable to use the oxyethylene group containing polymeric diol as a polyol.

The urethane resin film may contain a pigment, an antistatic agent, an antibacterial agent, an ultraviolet absorber, an infrared absorber, a deodorant, an antioxidant, a desiccant, a moisture absorption heat generating material, a flame retardant, and the like.

The shape of the urethane resin film may be either a non-porous film or a porous film. In the case of a porous membrane, it may be formed by the wet method, or may be formed by the dry foaming method. Moreover, what laminated|stacked a plurality of non-porous membranes, a thing which laminated|stacked a plurality of porous membranes, or a combination of a porous membrane and a non-porous membrane may be sufficient.

From the viewpoint of suppressing tactile curing in a low-temperature environment of the waterproof fabric, the urethane resin film is preferably nonporous. In the case of a nonporous urethane resin film, even when exposed to a low-temperature environment in a state in which water is contained in the resin film, hardening of the tactile feel is unlikely to occur.

In addition, the urethane resin film is preferably porous from the viewpoint of suppressing a decrease in the waterproofness of the waterproof fabric in a low-temperature environment. In the case of a porous urethane resin film, even when it is exposed to a low-temperature environment, it is hard to generate|occur|produce the fall of waterproofness.

More specifically, even in a low-temperature environment, if you wear clothes to perform work or sports, gaseous sweat is emitted from the human body. While the sweat is passing through the porous membrane, it liquefies into water by a low-temperature environment, and further solidifies into ice, filling the pores of the porous membrane. As a result, the pores, which are the passageways for gaseous sweat, are clogged and moisture permeability is lowered, and condensation in clothes is promoted by gaseous sweat that has lost its way, and ice is generated in or on the surface of the porous urethane resin film. There is a possibility that the feel is hardened and the resin film is damaged by the ice, thereby lowering the waterproofness.

Moreover, as long as it does not deviate from the objective of this invention, what laminated|stacked the urethane resin film on the porous polytetrafluoroethylene film|membrane, and the fiber cloth may be laminated|stacked. In this case, for the above reasons, it is preferable that the pores of the porous polytetrafluoroethylene are filled with a urethane resin so that the entire film is made nonporous.

As for the thickness of a urethane resin film, 1-200 micrometers is preferable.

When the urethane resin film is nonporous, it is good that it is about 3-100 micrometers, More preferably, it is 3-80 micrometers, More preferably, it is 5-50 micrometers. When the thickness of the non-porous membrane is less than 1 µm, there is a fear that sufficient waterproof performance cannot be exhibited, and when it exceeds 200 µm, the feel of the resulting waterproof fabric becomes hard.

When a urethane resin film is porous, it is good that it is about 10-150 micrometers, More preferably, it is 20-100 micrometers. If it is less than 10 micrometers, there exists a possibility that sufficient waterproofness cannot be exhibited. In particular, when used in a low-temperature environment, 15 µm or more may be sufficient from the viewpoint of maintaining waterproofness. Moreover, when it exceeds 150 micrometers, there exists a possibility that the feel of a waterproof fabric may become hard.

In addition, the lamination|stacking of a urethane resin film and a textile fabric may be laminated|stacked using an adhesive agent. The adhesive may be laminated by bonding the urethane resin film and the fiber fabric by interposing the urethane resin film and the fiber fabric in a dotted, linear, lattice, or full-surface form. From a waterproof viewpoint, it is preferable that the adhesive agent is interposed in the full-surface solid phase. In addition, from the viewpoint of suppressing the formation of ice between the fiber fabric and the urethane resin film, it is sufficient if the waterproof fabric having an adhesive is configured as a full surface between the urethane resin film and the fiber fabric.

As the adhesive, an isocyanate-based, epoxy-based, oxazoline-based or the like can be used, but an isocyanate-based adhesive, particularly a urethane-based adhesive, may be used.

In addition, in the case of laminating a urethane resin film and a textile fabric by interposing an adhesive in the entire surface, an ether-based urethane resin is preferable, and particularly preferably, an ether-based urethane having a Tg of less than -30°C as in the urethane resin film. Resins are preferred. More preferably, Tg is -40°C or less, and still more preferably -50°C or less.

If the Tg of the adhesive is an ether-based urethane resin of less than -30°C, curing of the waterproof fabric in a low-temperature environment is suppressed, and a decrease in waterproofness is also suppressed.

The adhesive may be either a one-component type or a two-component type, or may be a moisture curing hot melt type adhesive.

<Textile fabric>

The material of the textile fabric useful for the waterproof fabric of the present invention is a chemical fiber such as polyester, nylon, acrylic, polyurethane, acetate, rayon, polylactic acid, aramid, and polyimide, and natural fibers such as cotton, hemp, silk, and wool. These blends, blends, and textiles may be used, but are not particularly limited. In addition, any form, such as a woven fabric, a knitted fabric, and a nonwoven fabric, may be sufficient as these.

In particular, the waterproof fabric of the present invention is used as the outer fabric of textile products such as clothes, and when it is made into textile products such as clothes, the water pickup rate of the textile fabric used on the outside (opposite side to the body) of the textile product is 10 % is preferred, less than 5% is more preferred, less than 3% is still more preferred, and less than 1% is even more preferred. The lower limit is preferably 0%.

By making the pick-up rate of water less than 10%, the impregnation of water into the textile fabric is suppressed, and the occurrence of ice in the textile fabric in a low-temperature environment of 0° C. or less is suppressed, thereby suppressing hardening of the feel and deterioration of waterproofness. When used in an environment below 0°C, it may be thought that liquid water does not have a chance to adhere to the outside of clothing. Liquid water adheres to textile fabrics, and the water freezes due to repeated entry and exit into and out of a warm office or tent, or between a cold freezer and a hot outside (in some cases it is raining). There are concerns.

It is preferable to use a hydrophobic material, such as polyester or wool, as a textile fabric whose water pick-up is less than 10%. In addition, by providing a water repellent such as fluorine-based, silicone-based, paraffin-based to the textile fabric, it is preferable to make the water pickup rate of the textile fabric less than 10%. More preferably, it is good that polyester, nylon, aramid, polyimide, and wool were subjected to water-repellent treatment. Especially preferably, the polyester to which the said water repellent agent was provided is good.

Moreover, from a viewpoint of making the pickup of the water of a textile fabric into less than 10 %, 3rd grade or more of water repellency of a textile fabric is preferable, 4th grade or more is more preferable, 5th grade is still more preferable.

In addition, from the viewpoint of suppressing the hardening of the touch in a lower temperature environment, or from the viewpoint of suppressing the decrease in waterproofness, the waterproof fabric of the present invention is used as an outer material of textile products such as clothes, It is preferable that it is 100 g/m<2> or less of the pick-up amount of the said textile fabric used for the inner side (body side) of a textile product. More preferably, 70 g/m 2 or less, still more preferably 50 g/m 2 or less, and still more preferably 30 g/m 2 or less.

When a textile fabric in which the pickup amount of water exceeds 100 g/m 2 is used, a large amount of unsatisfied sweat is contained in the textile fabric, and there is a fear that the water resulting from the sweat freezes in a low-temperature environment to harden the textile fabric. Further, if work or exercise is continued with the ice produced at this time adhering, there is a risk that the resin film may be damaged at the corners of the ice and the waterproofness may be lowered.

That is, under a low-temperature environment of less than -30 ° C, even inside textile products such as clothes, sweat from the human body becomes dehydrated (liquefied) from the gaseous state near the outer fabric side of the clothes, and the liquefied water freezes, so that the waterproof fabric There is a risk that ice adheres to the inside of the hood and hardens to the touch, or the resin film at the corners of the ice may be damaged by operation in a state where the ice is adhered, thereby reducing the waterproofness.

The fiber fabric used on the inside of the textile product is similar to the textile fabric used on the outside of the textile product, by providing a water repellent such as a fluorine-based, silicone-based, paraffin-based water repellent to the textile fabric, the pickup amount of the textile fabric is reduced, and the body You may suppress that sweat generated from the back forms inside the textile product and freezes.

Conversely, within the range of 100 g/m2 or less of the pickup amount of water above, using textile fabrics or textile materials with absorbency or hygroscopicity to reduce the humidity in clothes, or to absorb sweat or lack of sweat in the textile fabric in the gas phase By rapidly diffusing liquid sweat on the textile fabric, it suppresses the formation of ice, which is thick enough to damage the urethane resin film, or utilizes the heat effect caused by moisture absorption. good to do In addition, as the fiber fabric having water absorption or hygroscopicity, one having water absorption or hygroscopicity in the fiber itself may be used, or a hydrophilic compound or a hygroscopic compound or the like may be added to the fiber, and water absorption or hygroscopicity may be imparted to the fiber fabric. Moreover, you may use the textile fabric which has hygroscopicity and repellency.

In addition, the pick-up rate and amount of water are, after measuring the mass of the mass (A) of the dried fiber fabric, immerse the fiber fabric in water for about 10 seconds, and immediately weave with a mangle twice. , The mass (B) of the textile fabric after weaving with the second mangle was calculated|required, and it calculated|required by following formula (1) and Formula (2).

Pickup rate (%) = (B(g)-A(g))/A(g) x 100... (One)

Pickup amount (g/m2) = (B(g)-A(g))/A(g) x mass per unit area of fiber fabric (g/m2)... (2)

Further, the textile fabric may be subjected to antistatic processing, antibacterial and deodorizing processing, bactericidal processing, ultraviolet shielding processing, infrared absorbing processing, infrared reflecting agent, etc. starting with dyeing and printing.

The waterproofness of the waterproof fabric of the present invention is good if the water pressure resistance is 1000 mm or more. From a waterproof viewpoint, 3000 mm or more of water pressure resistance is preferable, More preferably, it is 5000 mm or more, More preferably, it is 10000 mm or more, More preferably, 20000 mm or more is good.

Here, the water pressure resistance refers to a value measured by a method according to JIS L1092-2009 water resistance test (hydrostatic method) 　 A method (low water pressure method) or B method (high water pressure method). In addition, when the test piece was elongated by applying water pressure, a nylon taffeta (the thing in which the sum of the density of vertical and cross yarn per 2.54 cm is about 210) was overlapped on the test piece, and it installed in the tester and measured. In addition, the measurement by method B is converted into mm of method A in order to make comparison with method A easy.

Moreover, it is good also considering leaving it to stand for 10 minutes in the environment of -50 degreeC, and the water pressure resistance after rubbing is 1000 mm or more. If the water pressure can be maintained by leaving it for 10 minutes in an environment of -50 ° C and rubbing it, the decrease in waterproofness can be suppressed even when working or playing sports by wearing clothes made using waterproof fabrics in a low-temperature environment. have. From the viewpoint of waterproofness, preferably, the water pressure resistance after rubbing is preferably 3000 mm or more, more preferably 5000 mm or more, still more preferably 10000 mm or more, still more preferably 20000 mm or more.

In addition, after leaving it to stand for 10 minutes in the environment of -50 degreeC, and rubbing, the following two methods evaluated.

(1) Put a 20 cm long x 20 cm wide sample in an environmental test tank (PSL-4SPH, manufactured by Tabai Spec Co., Ltd.) set at a temperature of -50 ° C, leave it for 10 minutes, fold the sample in half, and remove the glove Hold the sample so that the distance between the hand and the hand is about 5 cm with the gloved hand, and rub it up and down 20 times in the environmental test chamber. Thereafter, the sample is taken out from the environmental test tank and left to stand at room temperature for 24 hours, and then the water pressure resistance is measured by the method according to the above JIS L1092-2009 A method (low water pressure method) or B method (high water pressure method).

(2) After immersing the test sample in water for 5 minutes before putting it into the environmental test tank, the same environmental test tank as in (1) above except that the water droplets adhering to the surface of the sample were lightly wiped off with a towel. and measure the water pressure. In addition, when a sample floats when made to immerse in water, a 100-g weight was put on the sample, and it was made to immerse the whole sample in water.

Moreover, the waterproof fabric of this invention may be a moisture-permeable waterproof fabric which also has moisture permeability. Moisture permeability is measured by the calcium chloride method JIS L1099-2012 A-1 method and the potassium acetate method JIS L1099-2012 B-1 method, and the water vapor transmission rate according to the calcium chloride method is 2000 g/m 2 ·24 hrs or more and/or the potassium acetate method It is good if the moisture permeability according to the above is 2000 g/m 2 ·24 hrs or more. More preferably, the moisture permeability according to the calcium chloride method is 5000 g/m 2 ·24 hrs or more and/or the water vapor transmission rate according to the potassium acetate method is 5000 g/m 2 ·24 hrs or more. More preferably, the moisture permeability according to the calcium chloride method is 10000 g/m 2 ·24 hrs or more and/or the water vapor transmission rate according to the potassium acetate method is 10000 g/m 2 ·24 hrs or more.

As for the upper limit, the water vapor transmission rate by the calcium chloride method is about 20000 g/m<2>*24 hrs, and the water vapor transmission rate by the potassium acetate method is about 50000 g/m<2>*24 hrs. When the upper limit is exceeded, the waterproofness is insufficient or moisture absorbed into the urethane resin film is frozen under low temperature, and there is a fear that the tactile feel of the waterproof fabric may be hardened or the urethane resin film may be lost.

In addition, the water vapor transmission rate is converted into the water vapor transmission rate per 24 hours for both the calcium chloride method and the calcium acetate method.

In addition, the waterproof fabric of the present invention may be one in which a fiber fabric is laminated on at least one surface of the urethane resin film, but may be used as an outer fabric when it is made into a textile product such as clothes, and the inner side of the textile product (body side) It is desirable to have a textile fabric in the By having the above preferable textile fabric on the inner side (body side) of the textile product, it is possible to suppress a decrease in waterproofness due to freezing of water in a low-temperature environment.

In addition, when there is no textile fabric on the outside (opposite side of the body) of clothes or the like, even when water adheres to the surface of the outer side of the waterproof fabric, it easily falls off from the surface of the waterproof fabric, suppressing the hardening of the feel, It is preferable from a viewpoint of suppression of the fall of waterproofness.

In addition, when it is made into textile products such as clothes, it is used as an outer material, and if the textile fabric is provided on the outside (opposite side of the body) of the textile product, the loss of the urethane resin film due to physical abrasion or the like is suppressed, and the low temperature environment It is possible to suppress a decrease in waterproofness caused by freezing of water in the

Especially preferably, it is preferable that the fiber fabric is laminated|stacked on both surfaces of a urethane resin film. By laminating the above textile fabric on both sides of the urethane resin film, the loss of the urethane resin film is prevented, and at the same time, the hardening of the feel of the waterproof fabric in a lower temperature environment, and the decrease in the waterproofness of the waterproof fabric due to freezing of water. can

When a fiber fabric is laminated|stacked on both surfaces of a urethane resin film, the same fiber fabric may be sufficient as the fiber fabric laminated|stacked on each surface, and a different fiber fabric may be sufficient as it. Preferably, it is preferable to use the textile fabric suitable for the said preferable conditions of what is used for the inside of clothes (textile product), and what is used for the outside of clothes (textile product), respectively.

In addition, when the fiber fabric is laminated on only one side of the urethane resin film, pigments, spherical particles, scaly particles, amorphous particles, infrared absorbers, ultraviolet absorbers, charging A resin containing an inhibitor, a water repellent, an antibacterial agent, a moisture absorbent, etc. is given in an arbitrary shape such as dots, linear, lattice, geometric, etc. good.

<Textiles>

Next, the textile products using the waterproof fabric of this invention as outer fabrics, such as clothes, are demonstrated. In addition, this invention is not limited to the textile product demonstrated below. In addition, in the following description, some descriptions of previously described parts will be omitted.

The textile product of the present invention refers to a textile product manufactured by using the waterproof fabric of the present invention for at least a part as an outer material and performing secondary processing such as sewing or fusion bonding. Specific examples include, but are not limited to, windbreakers, coats, jackets, jackets, anoraks, ski wear, snowboard wear, raincoats, work clothes, tents, sleeping bags, hats, and shoes. .

In the textile product of the present invention, a lining made of another fabric may be used, or a batting layer such as feathers or cotton may be provided between the outer and inner linings. Further, a fabric having a structure similar to that of the waterproof fabric of the present invention may be used as the outer fabric, the lining, and the batting.

In the textile product of the present invention, as for the waterproof fabric of the present invention used for outer fabric, even if a textile fabric is used for the outer side of the textile product (outer side to the body, etc.), and a fiber cloth is used for the inner side (body side) of the textile product. also good In addition, when the outer side is made of a resin film without using a textile fabric for the outer side, it is good that it is formed using a urethane resin excellent in abrasion resistance. When the outer side is a fiber fabric, it is preferable that the fiber fabric has water repellency, and in particular, a fiber fabric that satisfies the preferable conditions when using the fiber fabric as the outer side may be used.

In addition, when using a textile fabric for the inner side (body side) of a textile product, what is necessary is just to use the textile fabric which satisfy|fills the preferable conditions at the time of using said textile fabric as an inner side. In this invention, especially with respect to the waterproof fabric which has a textile fabric inside (body side), hardening of a touch is suppressed and the effect of suppressing the fall of waterproofness is exhibited.

Moreover, the textile product manufactured using what laminated|stacked the textile fabric on both surfaces of the urethane resin film may be sufficient.

Next, according to one preferred manufacturing method of the present invention, the present invention will be described in more detail with an example of a waterproof fabric in which a fiber fabric is laminated on both sides of a urethane resin film. In addition, this invention is not limited to what can be obtained by the manufacturing method demonstrated below. In addition, in the following description, some descriptions of previously described parts will be omitted.

<Method for producing waterproof fabric>

First, a resin solution of the ether-based urethane resin is applied on a release paper, dried at 50 to 130° C., and heat-treated at 120 to 170° C. as necessary to form a nonporous urethane resin film.

At this time, a porous urethane resin film can also be formed by a well-known foaming technique, for example, mixing air with the urethane resin to be applied, or adding a foaming agent in a urethane resin.

After forming the urethane resin film, a resin solution containing an adhesive is applied on the obtained urethane resin film, dried at 50 to 130 ° C. (nip) Alternatively, it can be nipped using a heating roll, joined, and manufactured according to the dry lamination method.

In addition, it can be manufactured according to the wet lamination method by bonding the textile fabric 1 without drying the resin solution containing the adhesive.

Textile fabric 1 may be subjected to scouring, dyeing, printing, antistatic processing, water repellent processing, antibacterial and deodorizing processing, bactericidal processing, ultraviolet shielding processing, calendering, etc. as needed. What is necessary is just to give water-repellent processing when using the textile fabric 1 for the outer side (the side opposite to a body) of textile products, such as clothes, when the obtained waterproof fabric is used as the outer material of a textile product. In addition, when using the textile fabric 1 as the inner side (body side) of clothes etc., what is necessary is just to give a hydrophilic process, moisture absorption process, or water repellency process.

The resin solution of the urethane resin applied to the release paper is preferably selected from the above ether-based urethane resin and an organic solvent such as dimethylformamide (hereinafter referred to as DMF), toluene, or methyl ethyl ketone as the solvent. Moreover, you may mix|blend an ester type urethane resin in the range which does not deviate from the objective of a part of this invention.

In the urethane resin solution, a colorant such as a pigment, a polyisocyanate-based crosslinking agent, a catalyst, an antioxidant, an ultraviolet absorber, a moisture absorbent, a flame retardant, a deodorant, etc. may also be added in the same manner as above.

The resin solution of this urethane resin is apply|coated on the release paper using a knife coater, a bar coater, a comber coater, etc.

In addition, the application of the adhesive on the nonporous urethane resin film obtained on the release paper is performed by applying a resin solution containing the adhesive described above using a knife coater, a bar coater, a comber coater, a gravure coater, etc. , Apply the adhesive over the entire surface of the beta phase.

The resin solution containing the adhesive may be dissolved in an organic solvent such as dimethylformamide (hereinafter, DMF), toluene, or methyl ethyl ketone, or if it is a hot-melt resin, it may be dissolved by heating.

In the resin solution containing the adhesive, a crosslinking agent, a catalyst, an antioxidant, an ultraviolet absorber, a moisture absorbent, a flame retardant, a deodorant, and the like may also be added.

In addition, after the non-porous membrane is laminated on the textile fabric 1 through an adhesive, if necessary, aging is performed at 50 to 100° C. for 12 to 72 hours, and the release paper is peeled off.

Next, a resin solution containing an adhesive is applied to the surface of the non-porous urethane resin on which the fiber fabric 1 is not laminated. After drying at 50 ~ 130 ℃ as described above, it can be manufactured according to the dry lamination method by bonding with the textile fabric 2 .

In addition, it can be manufactured according to the wet lamination method by bonding the fiber fabric without drying the resin solution containing the adhesive.

After that, as above, after laminating the non-porous membrane to the fiber fabric 2 through an adhesive, if necessary, aging at 50 to 100 ° C. for 12 to 72 hours to obtain a waterproof fabric in which the fiber fabric is laminated on both sides of the urethane resin film can

The textile fabric 2 may be subjected to scouring, dyeing and printing, starting with scouring, dyeing, and printing, as needed, in the textile fabric 2, antistatic processing, water repellency processing, antibacterial deodorization processing, bactericidal processing, ultraviolet shielding processing, calendering processing, and the like. What is necessary is just to give water-repellent processing when using the textile fabric 1 for the outer side of textile products, such as clothes, when the obtained waterproof fabric is used as outer fabric of textile products. In addition, when using the textile fabric 1 as the inner side of clothes etc., what is necessary is just to give a hydrophilic process, moisture absorption process, and/or water repellency process.

For waterproof fabrics in which fiber fabrics are laminated on both sides of an aged urethane resin film as needed, after laminating the fiber fabric on the urethane resin film, starting dyeing and printing, antistatic processing, water repellency processing, antibacterial deodorization processing, bactericidal processing, UV shielding You may perform processing, calendering, etc. as needed.

Moreover, when water-repellent processing is not previously given to the textile fabric used for the outer side of textile products, such as clothes, after laminating|stacking on a urethane resin film, what is necessary is just to give water-repellent processing. In addition, if the textile fabric used as the inner side of clothes is not previously subjected to hydrophilic processing, moisture absorption processing, or water repellency processing, it may be laminated on a urethane resin film and then subjected to hydrophilic processing, moisture absorption processing, or water repellency processing. .

Example

Hereinafter, the present invention will be further described by way of Examples, but the present invention is not limited by these Examples. In addition, "part" in an example is a mass part.

The evaluation in the following examples was performed according to the following method.

A　Pick-up rate and amount

After measuring the mass (A) of the dried textile fabric, the water pickup rate and pickup amount are immersed in water for about 10 seconds, immediately weaving the mangle twice, and woven the second mangle. The mass (B) of the later fiber fabric was calculated|required by following formula (1) and formula (2). In addition, the mass per unit area means the mass per unit area in the standard state of JIS L1096-2010 　 A method (JIS method).

Pickup rate (%) = (B(g)-A(g))/A(g) x 100... (One)

Pickup amount (g/m2) = (B(g)-A(g))/A(g) x mass per unit area (g/m2)... (2)

In addition, for the mangle, the material of the rubber part nitrile-butadiene rubber (NBR), hardness 80 degree, winding thickness 12.5 cm, diameter 150 mm, and the thing of 1750 kpa (17.9 kg/cm<2>) surface pressure were used.

B　Moisture permeability

It measured by the calcium chloride method 　 JIS 　 L1099-2012 　 A-1 method.

It measured by the potassium acetate method 　 JIS 　 L1099-2012 　 B-1 method.

In addition, any water vapor transmission rate was converted into the water vapor transmission rate per 24 hours.

C　Water pressure resistance

It was measured by the method according to JIS　L1092-2009　Water resistance test (hydrostatic method)　A method (low water pressure method) or B method (high water pressure method).

When the test piece was elongated by applying water pressure, a nylon taffeta (the sum of the density of vertical and cross yarns per 2.54 cm of about 210) was stacked on the test piece, installed in a testing machine, and measurement was performed.

C-1: Water pressure resistance 1 after rubbing in an environment of -50°C

Put a 20 cm long x 20 cm wide sample in an environmental test tank (PSL-4 SPH manufactured by Tabai Spec Co., Ltd.) set at a temperature of -50 ℃ and leave it open for 10 minutes, then fold the sample in half, With a gloved hand, the sample was held so that the distance between the hand and the hand was about 5 cm, and the sample was rubbed up and down 20 times in the environmental test chamber. After that, the sample is taken out from the environmental test tank and left at room temperature for 24 hours, and then the water pressure resistance is measured by the method according to the above JIS L1092-2009 A method (low water pressure method) or B method (high water pressure method).

C-2: Water pressure resistance 2 after rubbing in an environment of -50 °C

Before putting the test sample into an environmental test tank set at -50 ° C, it was immersed in water for 5 minutes and then pre-treated to remove water droplets adhering to the surface of the sample with a towel. The water resistance was measured. In addition, when a sample floats when made to immerse in water, a 100-g weight was put on the sample, and it was made to immerse the whole sample in water.

D　Tactile

After leaving the sample to stand for 10 minutes under the conditions of C-1 and C-2, the tactile feel was evaluated by touching the glove with one hand in an environmental test tank. Compared with normal temperature, the case equal to (circle), the thing which hardened slightly was evaluated (triangle|delta), and the thing which hardened|cured to the extent considered difficult to use as clothes was evaluated as x.

D　Water repellency

The water repellency of the textile fabric 1 was measured according to the JIS 　 L1092-2009 　 spray test.

(Example 1)

A polyester plain fabric (warp 84 decitex/72 filament, weft warp 84 decitex/72 filament, mass per unit area 120 g/m2) was dyed black with a disperse dye, and fluorine-based water repellent agent Asahigard What was water-repellent processed using 3% aqueous solution of AG-E081 (made by Asahi Glass Co., Ltd.) was used as textile fabric 1. When this textile fabric 1 is used as clothes, it is used as an outer material on the side opposite to a body (outside). In addition, the pick-up rate of Fiber Fabric 1 was less than 1%.

Next, the following resin solution was applied on a release paper with a slit of 0.07 mm using a comber coater, and dried at 120° C. to obtain a 13 μm-thick, nonporous urethane resin film.

Resin solution (for production of non-porous urethane resin film)

100 parts of ether-based polyurethane resin (solid content: 30%; Tg: -50 °C)

Methyl ethyl ketone 　　　　　　　　　　　　　　　 60 parts

8 copies of white pigment

Next, the following resin solution for adhesive was applied in a beta phase to the entire surface of the nonporous urethane resin film with a slit of 0.08 mm using a comber coater. Next, it dried at 120 degreeC for 2 minutes.

Resin solution (for adhesive)

Ether-based polyurethane resin (solid content 45%; Tg: -50 °C)　 100 parts

50 parts of toluene

9 parts of isocyanate-based crosslinking agent

1 copy of organotin-based catalyst

On this adhesive surface, the fiber fabric 1 is polymerized and bonded by thermal compression (dry lamination).

In addition, peel the release paper, and apply the same resin solution for adhesive as above to the surface of the non-porous urethane resin film on which the fiber fabric 1 is not laminated with a slit of 0.08 mm using a comber coater, and apply on the entire surface of the non-porous film in a beta phase. did. Next, it dried at 120 degreeC for 2 minutes.

Textile fabric 2 (half tree coat made of nylon; 18 decitex/7 filament; dyed gray with acid dye; mass per unit area of 36 g/m2; After polymerization and bonding the fiber fabric 2 by thermocompression (dry lamination), it was aged at 70°C for 48 hours.

Next, the finishing set was performed at 150° C. for 30 seconds to obtain a waterproof fabric in which the fiber fabric was laminated on both sides of the urethane resin film. In addition, when the textile fabric 2 is used as the outer material of clothes, it is used for the body side (inside of clothes).

Table 1 shows the physical properties of the obtained waterproof fabric.

Comparative Example 1

On one side of the textile fabric 1 similar to Example 1, the following resin solution was applied with a slit of 0.10 mm using a comber coater, immersed in water to solidify, solvent-removed, washed with water, dried, and porous with a thickness of 50 µm A urethane resin film was formed. Thereafter, drying was performed at 150° C. for 30 seconds to obtain a waterproof fabric in which a fiber fabric was laminated on one side of a porous urethane resin film. Similar to Example 1, this textile fabric 1 is used for the side opposite to the body (outside of the clothes) when used as the outer fabric for clothes.

Resin solution (for production of porous urethane resin film)

100 parts of ester-based polyurethane resin (solid content: 25%; Tg: -15 °C)

50 copies of methyl ethyl ketone

8 copies of white pigment

Next, the fiber fabric 2 similar to Example 1 was laminated|stacked similarly to Example 1 on the porous urethane resin film surface on which the fiber fabric 1 is not laminated|stacked, and the waterproof fabric was obtained. In addition, when the textile fabric 2 is used as the outer material of clothes, it is used for the body side (inside of clothes).

Table 1 shows the physical properties of the obtained waterproof fabric.

Comparative Example 2

As the textile fabric 2, a polyester fabric having a pickup amount of 104 g/m 2 (83 decitex/72 filaments; mass per unit area of 155 g/m 2 ) was used. In addition, when the textile fabric 2 is used as the outer material of clothes, it is used for the body side (inside of clothes).

A waterproof fabric was obtained in the same manner as in Example 1 except that the above was used as the textile fabric 2.

Table 1 shows the physical properties of the obtained waterproof fabric.

Example 2

As the textile fabric 1, the polyester plain fabric used in Example 1 was subjected to water-repellent treatment using a 3% aqueous solution of NT-X620 (manufactured by NANO-TEX, USA) as a water repellent agent. The pick-up rate of Fiber Fabric 1 was 1.8%. A waterproof fabric was obtained in the same manner as in Example 1 except that the above was used as the textile fabric 1. Table 1 shows the physical properties of the obtained waterproof fabric.

Example 3

As textile fabric 1, polyester twill (warp 84 decitex/72 filaments; weft warp 167 decitex/36 filaments; mass per unit area 200 g/m2) was dyed yellow with a disperse dye, and a fluorine-based water repellent agent Asahigard AG-E081 What was water-repellent processed using the 3% aqueous solution of (Asahi Glass Co., Ltd. product) was used. When this textile fabric 1 is used as clothes, it is used for the outer side (outside) of a body as an outer material. In addition, the pick-up rate of Fiber Fabric 1 was less than 1%.

As the textile fabric 2, a polyester fabric having a pickup amount of 24 g/m 2 (22 decitex/24 filaments; mass per unit area of 50 g/m 2 ) was used. In addition, when the textile fabric 2 is used as the outer material of clothes, it is used for the body side (inside of clothes).

A waterproof fabric was obtained in the same manner as in Example 1, except that the above was used as the textile fabric 1 and the textile fabric 2.

Table 1 shows the physical properties of the obtained waterproof fabric.

Example 4

As textile fabric 1, nylon ripstop taffeta (warp 26 decitex/20 filaments; weft warp 26 decitex/20 filaments; mass per unit area 80 g/m2) is dyed red with an acid dye, and fluorine-based water repellent agent Asahigard AG -E081 (manufactured by Asahi Glass Co., Ltd.) was water-repellent treated using a 3% aqueous solution. When this textile fabric 1 is used as clothes, it is used as an outer material on the side opposite to a body (outside). In addition, the pick-up rate of Fiber Fabric 1 was less than 1%.

As the textile fabric 2, a nylon half-tricoat having a pickup amount of 7 g/m 2 (mass per unit area of 10 g/m 2; dyed gray with an acid dye) was used. In addition, when the textile fabric 2 is used as the outer material of clothes, it is used for the body side (inside of clothes).

A waterproof fabric was obtained in the same manner as in Example 1, except that the above was used as the textile fabric 1 and the textile fabric 2.

Table 1 shows the physical properties of the obtained waterproof fabric.

From the results of Examples, Examples 1 to 4 using a urethane resin film obtained using an ether-based urethane resin having a glass transition point of less than -30 ° C., do not harden the feel even in an environment of -50 ° C. As textile products such as clothes was available

In contrast, in Comparative Example 1 using an ester-based urethane resin having a glass transition point of -30°C or higher, the feel was remarkably hardened in an environment of -50°C, and it was not usable as textile products such as clothes.

Further, in Examples 1 to 4 in which the pickup of water of the textile fabric used on the inner side (body side) of the textile product as a garment is less than 100 g/m2, under an environment of -50 ° C., fibers such as clothes having a somewhat hardened feel It was available as a product.

On the other hand, in the comparative example 2 in which the pickup amount of water exceeds 100 g/m<2>, touch hardened|cured remarkably, and it was not able to utilize as textile products, such as clothes. In addition, when the water pressure was measured by returning it to room temperature, the waterproofness was significantly reduced.

Claims (9)

A waterproof fabric comprising a fiber fabric laminated on at least one side of a urethane resin film having a glass transition point of less than -30 ° C.
The urethane resin film is made of an ether-based urethane resin of 50% or more by mass,
When it is set as a textile product, the water pickup amount of the said textile textile used inside the said textile product is 50 g/m<^2> or less, The waterproof fabric characterized by the above-mentioned.
According to claim 1,
The waterproof fabric, characterized in that the glass transition point is -50 ℃ or less.
3. The method of claim 1 or 2,
A waterproof fabric having moisture permeability and having a water vapor transmission rate of 2000 g/m 2 ·24 hrs or more according to the calcium chloride method and/or a water vapor transmission rate of 2000 g/m 2 ·24 hrs or more according to the potassium acetate method.
3. The method of claim 1 or 2,
A waterproof fabric, characterized in that the waterproof fabric is used as an outer material of a textile product.
3. The method of claim 1 or 2,
The waterproof fabric, characterized in that the urethane resin film is a non-porous film.
3. The method of claim 1 or 2,
The waterproof fabric, characterized in that the urethane resin film is adhered to the textile fabric through an adhesive.
7. The method of claim 6,
The adhesive is a waterproof fabric, characterized in that the ether-based urethane resin.
7. The method of claim 6,
Waterproof fabric, characterized in that the glass transition point of the urethane resin used in the adhesive is less than -30 ℃.
A textile product using the waterproof fabric according to claim 1 or 2 as an outer material.