JP2000096452A - Production of laminated fabric having high moisture permeability and high waterproofness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a laminated fabric having high moisture permeability and high waterproofness, scarcely releasing a mold release base fabric from the produced resin film in a wet film product ion process. SOLUTION: A synthetic polymer solution consisting mainly of a polyurethane resin is coated on the surface of a mold release base fabric to produce a two-layered laminate. The solvent of the synthetic polymer solution is N,N-dimethylformamide, and inorganic particles having an average particle diameter of <=1 μm and an N,N- dimethylformamide adsorption of >=200 ml/100 g is contained in the synthetic polymer solution in an amount of >=1 wt.%. The produced two-layered laminate is introduced into water and subsequently wound up in the water, or the two-layered laminate is floated in a state folded in the longitudinal direction and carried to the next process. A tension is thus positively not given to the two-layered laminate. The removal of the solvent is approximately completed to coagulate the polyurethane resin, thus producing the resin film. The produced resin film is non-wholly uniformly coated with a polyurethane-based adhesive, adhered to a fiber fabric and subsequently subjected to the release of the mold release base fabric, thus producing the moisture- permeable and waterproof fabric which comprises the laminate formed in the order of the fiber fabric/resin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminated fabric having excellent moisture permeability and waterproofness, which is used for various types of clothing such as raincoats, top coats, mountain climbing suits, and the like.

[0002]

2. Description of the Related Art A highly moisture-permeable and highly waterproof fabric having both high moisture permeability and high waterproofness has a function of releasing water vapor caused by sweating from the body out of clothes and a function of preventing rain from entering into clothes. Have Such highly moisture permeable and highly waterproof fabrics are used as materials for sports clothing and winter clothing, and among them, are often used as clothing materials for sports and outdoor activities in which the amount of sweat caused by exercise is relatively large. In particular, it is an indispensable clothing material in the fields of skiing, athletic, and mountain climbing.

[0003] Such high moisture permeable and high waterproof fabrics include high-density woven fabrics in which yarns are woven at high density, polyurethane resins, polyamino acid resins, polyester resins, polyamide resins, polytetrafluoroethylene resins, and the like. A laminated fabric obtained by laminating a resin film made of a synthetic polymer described above on the surface of a fiber fabric by means such as coating or laminating is well known. Among these, a laminated fabric in which a microporous polyurethane-based resin film is bonded to the surface of a fiber fabric is particularly preferable because it has excellent moisture permeability and waterproofness.

A laminated fabric obtained by laminating a microporous polyurethane-based resin film to a fiber fabric has been conventionally produced by the following method. That is, the polyurethane resin is N, N
-A synthetic polymer solution dissolved in a solvent such as dimethylformamide is applied to the surface of the fiber fabric, and then introduced into a water bath while transporting the solution; the solvent is eluted in water to coagulate the polyurethane resin; It is manufactured by a method of forming a porous polyurethane resin film (so-called direct coating method). By this method, a laminated fabric having both a certain degree of moisture permeability and waterproofness can be obtained, but it has been difficult to obtain a fabric having both high moisture permeability and high waterproofness.

[0005] For this reason, the present inventors have proposed that a synthetic polymer solution mainly composed of a polyurethane resin contains N, N-solvent.
Using dimethylformamide containing 1% by weight or more of an inorganic fine powder having an average particle diameter of 1 μm or less and an N, N-dimethylformamide adsorption amount of 200 ml / 100 g or more, laminated by the direct coating method described above. It was proposed to obtain a fabric (Japanese Unexamined Patent Publication No. 6-272).
Example described in Japanese Patent Publication No. 168). In this method, N, N-dimethylformamide as a solvent is adsorbed on the surface of the inorganic fine powder, and as a result, the concentration of the solvent is increased around the inorganic fine powder, and the polyurethane resin is coagulated in that state. Accordingly, the concentration of the solvent is high but the concentration of the polyurethane resin is low around the inorganic fine powder, and the fine pores are easily formed around the inorganic fine powder, and the laminated fabric has both high moisture permeability and high waterproofness. Can be obtained. However, depending on the type of the fiber cloth to which the synthetic polymer solution is applied, the synthetic polymer solution may penetrate into the fiber cloth, and the feeling of the obtained laminated cloth may be reduced.

Accordingly, the present inventors have attempted to obtain a laminated fabric by a so-called transfer method as described below. That is, a polyurethane resin is dissolved in a solvent, N, N-dimethylformamide, and has an average particle diameter of 1 μm or less, and is N, N-dimethylformamide.
The amount of dimethylformamide adsorbed is 200 ml /
After applying a synthetic polymer solution containing 100% or more of inorganic fine powder of 1% by weight or more to the surface of the release base fabric, the solution is introduced into a water bath while being transported, and the solvent is eluted in water to form a polyurethane resin. To form a microporous polyurethane resin film. Then, while further being conveyed, immersion in a water bath and mangle squeezing are repeated a plurality of times to remove the solvent and wash with water. After passing through such a wet film forming process, drying is performed to remove moisture, and then an adhesive is partially applied to the surface of the polyurethane resin film, and the fiber cloth is bonded to the polyurethane resin film via the adhesive. I do. Then, an attempt was made to obtain a highly moisture-permeable and highly waterproof laminated fabric in which a microporous polyurethane-based resin film was bonded to a fiber fabric by peeling the releasable base fabric from the polyurethane resin film.

[0007]

However, in such a production method, after the polyurethane resin is coagulated in a water bath, the polyurethane resin film is separated from the releasable fabric during repeated removal of the solvent and washing with water. In some cases, they peeled off. This is because such a wet film forming process is performed while transporting a laminate composed of the releasable fabric and the polyurethane resin film, and therefore, tension is applied to the releasable fabric and the polyurethane resin film. It is believed that there is. That is, the releasable fabric and the polyurethane resin film have different extensibility and the like due to a tension load, and the difference in their behavior causes
It is considered that both are separated.

[0008] In order to prevent the separation of the releasable fabric from the polyurethane resin film, for example, it is conceivable to lower the degree of releasability of the releasable fabric. However, when the releasability is reduced, when the releasable fabric and the polyurethane resin film are separated in a later step, it becomes difficult to separate the polyurethane resin film, which causes a new defect such as a breakage of the polyurethane resin film. In addition, when the releasability is lowered, the water pressure resistance, moisture permeability, and feel of the obtained polyurethane resin film are sometimes reduced. Although the reason for this is not clear, it is considered that the polyurethane resin film digs into the surface of the release fabric.

Accordingly, the present invention provides a method for manufacturing by employing a specific method in which a tension is not applied as much as possible during a wet film forming process after coagulation of a polyurethane resin in a water bath until desolvation is substantially completed. An object of the present invention is to provide a highly moisture-permeable and highly waterproof laminated fabric which is difficult to peel off a release fabric and a polyurethane resin film on the way, and is excellent in water pressure resistance, moisture permeability and texture.

[0010]

That is, according to the present invention, a two-layer laminate obtained by applying a synthetic polymer solution mainly composed of a polyurethane resin to the surface of a releasable base fabric is introduced into water. The solvent in the polymer solution is eluted into the water to coagulate the polyurethane resin, and after a wet film forming step of forming a resin film mainly composed of the polyurethane resin on the surface of the releasing base fabric, The method of producing a highly moisture-permeable and highly waterproof laminated fabric by transferring the resin film to a fiber fabric, wherein N, N-dimethylformamide is used as a solvent in the synthetic polymer solution, and N, N having an average particle size of 1 μm or less is used. To the next step, using the two-layer laminate introduced into the water in the wet film-forming step while using the one containing at least 1% by weight of an inorganic fine powder having an adsorption amount of dimethylformamide of 200 ml / 100 g or more; With no loaded with active tension for feeding, to a method for producing a high moisture-permeable high waterproof laminated fabric, characterized in that to produce the resin film. Hereinafter, the present invention will be described in the order of steps.

[First Step] First, in the present invention, a releasable base fabric is prepared. The release base fabric is obtained by adding a release agent to a known cloth. Specifically, woven fabrics made of synthetic fibers such as polyamide synthetic fibers represented by nylon 6, nylon 66, polyester synthetic fibers represented by polyethylene terephthalate, polyacrylonitrile synthetic fibers, and polyvinyl alcohol synthetic fibers. A release agent such as a paraffinic water repellent, a fluorine water repellent, or a polysiloxane water repellent is applied to a base fabric such as a knitted fabric by a known method such as a padding method or a spray method. In particular, a releasable base fabric obtained by adding a release agent to a woven fabric made of a polyester-based synthetic fiber is preferable because it has excellent dimensional stability and heat resistance and is inexpensive.

An inorganic fine powder having a solvent of N, N-dimethylformamide having an average particle diameter of 1 μm or less and having an adsorbed amount of N, N-dimethylformamide of 200 ml / 100 g or more is coated on the surface of the releasable base fabric. A two-layer laminate is obtained by applying a synthetic polymer solution containing at least 1% by weight and mainly composed of a polyurethane resin. In the synthetic polymer solution,
50-100% by weight of polyurethane resin as resin component
It is preferable that it is contained to a certain degree. Resin components other than polyurethane resin include polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acid,
Polycarbonate or the like or a copolymer thereof may be contained in a range of less than 50% by weight, and of course, a polymer modified with fluorine, silicone, or the like may be included.

A polyurethane resin is a polymer obtained by reacting an isocyanate component and a polyol component. As the isocyanate component, an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic diisocyanate or the like is used alone or as a mixture. Specifically, trilene-2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,4-cyclohexane diisocyanate, or the like is used as a main component, and if necessary, trifunctional or more functional isocyanate is used. May be used. On the other hand, as the polyol component, polyether polyol, polyester polyol, or the like is used. As a polyether polyol,
For example, polyethylene glycol, polypropylene glycol, polytetraethylene glycol and the like are used. As the polyester polyol, for example, a diol such as ethylene glycol or propylene glycol,
Reaction products with dibasic acids such as adipic acid and sebacic acid,
Alternatively, a ring-opening polymer such as caprolactone can be used, and of course, a polymer of an oxyacid monomer or a prepolymer thereof can also be used.

As the solvent in the synthetic polymer solution, N, N
Using dimethylformamide (DMF); this is,
This is because it is a polar organic solvent that easily dissolves the polyurethane resin, and the inorganic fine powder used in the present invention has a property of easily adsorbing a large amount of N, N-dimethylformamide.

The inorganic fine powder dispersed in the synthetic polymer solution has an average particle diameter of 1 μm or less, and preferably has an average particle diameter of 0.1 μm or less. If the average particle size exceeds 1 μm, relatively large pores may be formed at the location where the inorganic fine powder is present, and the waterproof property may be reduced. The average particle size referred to here is the median size, and it goes without saying that it is the size of the primary particles of the inorganic fine powder. Further, the inorganic fine powder is preferably substantially non-porous. If there are pores connected to the inside of the inorganic fine powder, N, N-dimethylformamide is absorbed at this portion, and N, N on the surface of the inorganic fine powder is absorbed.
There is a tendency that the concentration of N-dimethylformamide does not increase.

The inorganic fine powder must have an adsorption amount of N, N-dimethylformamide of 200 ml / 100 g or more, and in particular, 250 ml / 100 g.
It is preferably 100 g or more. If the amount of N, N-dimethylformamide adsorbed is less than 200 ml / 100 g, the concentration of the polyurethane resin on the surface of the inorganic fine powder is not so low, and a laminated fabric having high moisture permeability cannot be obtained. Here, the adsorption amount of N, N-dimethylformamide is measured by the following method. That is, 5 g of inorganic fine powder is placed on a glass plate,
Each time one drop of N, N-dimethylformamide was added, the kneading operation using a stainless steel spatula was repeated, and the N, N-dimethyl which was required immediately before softening with one drop of N, N-dimethylformamide was obtained. Means the volume of formamide (unit: milliliter)
N, instead of oil, boiled sesame described in SK-5101K
It uses N-dimethylformamide. Specific examples of the inorganic fine powder having an average particle diameter of 1 μm or less and an N, N-dimethylformamide adsorption amount of 200 ml / 100 g or more include anhydrous silicon dioxide fine powder and dialuminum trioxide fine powder as described above. Can be used.

The content of the inorganic fine powder in the synthetic polymer solution needs to be 1% by weight or more, particularly preferably 3% by weight or more. Content of inorganic fine powder is 1
If the content is less than 10% by weight, the proportion of the inorganic fine powder in the polyurethane resin film becomes too small, and a laminated fabric having high moisture permeability cannot be obtained.

As a method of applying the synthetic polymer solution to the surface of the release base fabric, it may be applied by a usual coating method using a knife coater, a comma coater, a reverse coater or the like. Further, the amount of application is arbitrary, but generally, the dry weight of the obtained resin film is preferably 10 g / m ² or more, and more preferably 15 g / m ² or more.

As described above, the two-layer laminate obtained by applying the synthetic polymer solution to the surface of the release base fabric is introduced into water. Specifically, the two-layer laminate may be immersed in a water bath at 5 to 60 ° C. Then, the solvent in the applied synthetic polymer solution is eluted into the water bath, the polyurethane resin and other polymers dissolved or dispersed in the synthetic polymer solution are solidified, and the microporous resin film is formed. Generate. And
In order to completely solidify the resin film, the solvent is further removed in a water bath and, if necessary, washed with water. In general, the step of forming a microporous resin film by such a method is called a wet film forming step. In the present invention, in this wet film forming step, an active process for transporting to the next step is performed. The method is characterized in that the resin film is formed without applying a specific tension. That is, conventionally, in this wet film forming process, the tension for transporting in the machine direction, that is, the tension for transporting to the next process is applied to the two-layer laminate (therefore, the two-layer laminate has its longitudinal direction applied). This is characterized in that the wet film forming step is performed without applying such a positive tension. As described above, in the wet film forming process, the solidified resin film and the releasable base fabric are less likely to be separated unless an aggressive tension is applied for transporting to the next process.

Specific examples of the above-mentioned wet film forming step performed without applying a positive tension for transporting to the next step include the following. For example, there is an embodiment in which the two-layer laminate is introduced into water, and then the two-layer laminate is wound in the water. That is, in this mode, a certain amount of tension is applied by winding, but this is not a tension for transporting to the next step, so that winding can be performed with a low tension. With this level of tension, the solidified resin film and the releasable base fabric are less likely to peel off. In such an embodiment, when the two-layer laminate is introduced into water, the applied synthetic polymer solution solidifies to some extent, and then the solidification proceeds even after winding. In this embodiment, the meaning of introducing the two-layer laminate into water and winding the same in water means that the entire two-layer laminate is wound in contact with water. Therefore, the two-layer laminate may be introduced into a water bath and rolled up, and the whole rolled up roll may be immersed in water, or a part of the roll may be immersed in water and the roll may rotate. And the whole may always be in contact with water. Further, a mode in which water is sprayed on the two-layer laminate by a shower or the like is also included in the content of introducing the two-layer laminate into water. Therefore, the form in which water is sprayed on the two-layer laminate by a shower or the like and the two-layer laminate is wound up in that state is included in the content of introducing the two-layer laminate into water and winding the same in water. is there.

In another aspect, a J-box,
Even when a scouring and bleaching device such as an L-box is used, the wet film forming step can be performed without applying a positive tension for transporting to the next step. J-box or L
-In the case of using a box, the two-layer laminate is conveyed to the next step, but the tension is hardly applied in the longitudinal direction in a certain area, and the two-layer laminate is folded in the longitudinal direction. (Because almost no tension is applied in the longitudinal direction, the two-layer laminate stays in the longitudinal direction and becomes folded.) Then, since it is transported to the next step, it is floating in the machine direction in a folded state. Since this play is mainly pushed out of the previous step, it moves as if it is being conveyed to the next step, and is not being conveyed under a positive tension. In this embodiment, the two-layer laminate may be introduced into a J-box or an L-box, and the two-layer laminate may be introduced into water in this box. The meaning of introduction into water is
As in the above case, this means contact with water.

Further, as another embodiment, an embodiment in which the two-layer laminate is shaken down in a water tank filled with water can be used. Since the two-layer laminate is simply shaken off, no tension is applied for transporting to the next step. Further, an embodiment using a Jigga dyeing machine can also be used.
In this embodiment, a two-layer laminate is wound alternately between two rolls disposed in water. The two-layer laminate is loaded with tension by winding, but it is not a high tension for transporting to the next step, so that the solidified resin film and the releasable base fabric are not easily separated.

According to the above method, the solvent of the synthetic polymer solution applied to the surface of the release base fabric elutes in water and solidifies,
A microporous resin film mainly composed of a polyurethane resin is generated. The elution of the solvent (desolvation) is generally completed in the process of introducing the two-layer laminate into water and removing it from the water. However, the desolvation may not be completely completed in this step, and in this case, the two-layer laminate taken out from the water is completely desolvated using an arbitrary apparatus such as a Jigga dyeing machine. Is also good. After the completion of the solvent removal, it may be dried by a known method. Of course, before drying
If necessary, it may be washed with water.

[Second Step] After that, the resin film provided on the surface of the releasing base cloth is transferred to a fiber cloth, whereby the highly moisture-permeable and waterproof laminated cloth according to the present invention can be obtained. As a transfer unit, any conventionally used method is adopted.
For example, after applying an adhesive to a resin film, it may be bonded to a fiber cloth, or after applying an adhesive to the fiber cloth,
This may be bonded to a resin film. In the present invention, it is preferable to employ the following method as a specific means for transferring.

First, a polyurethane-based adhesive is uniformly applied over the entire surface of the resin film formed on the surface of the release base fabric. Here, the reason that the polyurethane-based adhesive is used is that it has excellent adhesiveness to a resin film mainly composed of a polyurethane resin. Further, to apply uniformly on the non-entire surface means that there are applied portions and non-applied portions, and these exist uniformly over the entire surface. Specifically, scattered spots, linearly spaced lines,
It means that it is applied in a form such as a checkered pattern or a turtle pattern. The occupied area of the polyurethane adhesive (the total area of the portion where the adhesive is applied) is preferably 20 to 60%, more preferably 25 to 50%, based on the surface area of the resin film. If the occupied area is less than 20%, the adhesiveness between the resin film and the fiber fabric becomes insufficient, and the two tend to be easily separated. When the occupied area exceeds 60%, the area occupied by the polyurethane adhesive having poor moisture permeability increases, and the moisture permeability tends to decrease as a whole. In addition, the presence of the adhesive also tends to reduce the overall texture.

The polyurethane adhesive may be applied in any form, but is generally applied in a solution form. As a solution type polyurethane adhesive,
A solution mainly containing a reaction product of an isocyanate compound and a polyol compound and / or a solution mainly containing a mixture of an isocyanate compound and a polyol compound are used. Further, in this solution, another resin may be contained for improving the adhesiveness. For example, if the fiber cloth to which the resin film is transferred is a polyamide fiber cloth, if a dimer acid-based polyamide resin or a general polyamide hot melt resin is contained, the adhesiveness between the fiber cloth and the adhesive is improved. It is preferred because it improves. When the fiber cloth is a polyester fiber cloth, it is preferable to include a polyester hot melt resin or the like, since the adhesiveness between the fiber cloth and the adhesive is improved. As a specific method of applying the polyurethane adhesive in the form of a solution to the surface of the resin film, a known gravure coater, a rotary screen, a flat screen, or the like may be used to form a scattered spot, a line provided at equal intervals, or the like. A uniform pattern is applied over the entire surface in a desired pattern such as a checkered pattern or a turtle pattern, and then 50 to 150
What is necessary is just to dry at the temperature of ° C for 0.5 to 5 minutes.

Thereafter, a fiber cloth is laminated on the surface of the resin film coated with the polyurethane adhesive. Any fiber fabric can be used. For example, polyamide-based synthetic fibers represented by nylon 6, nylon 66, polyester-based synthetic fibers represented by polyethylene terephthalate, polyacrylonitrile-based synthetic fibers, polyvinyl alcohol-based synthetic fibers, semi-synthetic fibers such as triacetate, cotton, etc. A woven fabric, a knitted fabric, a non-woven fabric, or the like made of natural fibers alone or as a mixture can be used.
Since the polyurethane-based adhesive generally exhibits tackiness, the resin film and the fiber cloth can be bonded together by laminating the fiber cloths and then pressing or thermocompressing while applying heat as desired. As described above, it is possible to obtain a highly moisture-permeable and highly waterproof laminated fabric having a three-layer structure, which is laminated and bonded in the order of the releasable base fabric / polyurethane resin film / fiber fabric. In the present invention, as it is, that is, without peeling the releasable base fabric from the resin film, it is also possible to obtain a highly moisture-permeable and high-waterproof laminated fabric, but the third and subsequent steps of peeling the releasable base fabric are performed. Through the process, a highly moisture-permeable and highly waterproof laminated fabric can be obtained.

[Third Step] The resin film and the fiber cloth are bonded together via a polyurethane-based adhesive. Since the resin film has a releasable base cloth attached to it, When the base fabric is peeled off from the resin film, a highly moisture-permeable and waterproof laminated fabric obtained by laminating the fiber fabric and the resin film is obtained. In addition, after peeling the releasable base fabric, a water-repellent treatment may be applied to the fiber fabric surface and / or the resin film surface, if necessary, for the purpose of improving the water pressure resistance. For example, a known water repellent such as a paraffin-based water repellent, a polysiloxane-based water repellent, or a fluorine-based water repellent can be used to perform a water repellent treatment by a known method such as a padding method or a spray method. .

[Fourth Step (Part 1)] Also, after the release base fabric is peeled off, a resin thin film mainly composed of polyurethane resin may be formed on the resin film surface for the purpose of improving the water pressure resistance. good. Specifically, a synthetic polymer solution mainly composed of a polyurethane resin may be applied to the surface of the resin film and dried. As a synthetic polymer solution, a polar organic solvent such as N, N-dimethylformamide is not used much as a solvent,
For example, it is preferable to use a less polar solvent such as toluene, methyl ethyl ketone, and ethyl acetate. If a large amount of the polar organic solvent is used, the surface of the microporous resin film generated in the wet film forming process may be dissolved in the polar organic solvent, and the microporous may be broken to form a nonporous resin film. When the resin film becomes nonporous, the moisture permeability tends to decrease.

As a method of applying a synthetic polymer solution mainly composed of a polyurethane resin to the surface of the resin film, the same coating method as described above is employed, and dry coating is performed. In the dry coating, as in the above-mentioned wet film forming process, after coating, the coating is not introduced into water but dried as it is. Therefore, a nonporous resin thin film is obtained instead of a microporous resin film as described above. Since such a nonporous resin thin film has a large thickness, the moisture permeability obtained with a microporous resin film may be impaired. Therefore, the thickness of the nonporous resin thin film is preferably such that the water pressure is improved and the moisture permeability is not impaired, and the dry weight is preferably about 1 to 15 g / m ² . The thickness of the resin thin film is 1 g / m ^{2 by} dry weight.
When it is less than the above range, the water pressure tends to hardly improve. If the dry weight exceeds 15 g / m ² , the moisture permeability tends to be impaired.

[Fourth Step (No. 2)] In the present invention, after the releasable cloth is peeled off, in order to protect the resin film or change the appearance as required, Further, a fiber cloth may be bonded. Specifically, after a polyurethane adhesive is uniformly applied on the entire surface of the resin film, the fiber cloth may be bonded via the polyurethane adhesive. This makes it possible to obtain a high-moisture-permeable, high-waterproof laminated fabric having a three-layer structure laminated and laminated in the order of fiber fabric / resin film / fiber fabric. Further, after a polyurethane adhesive is uniformly applied to the entire surface of the resin thin film obtained in the fourth step (part 1), the fiber cloth may be bonded via the polyurethane adhesive. This makes it possible to obtain a high-moisture-permeable, high-waterproof laminated fabric having a four-layer structure laminated and bonded in the order of fiber fabric / resin film / resin thin film / fiber fabric. Note that the method of bonding the fiber cloth to the resin film or the resin thin film surface may be performed in the same manner as the method adopted in the second step.

[0032]

EXAMPLES The present invention will be described more specifically with reference to the following examples. The measurement and evaluation of each performance of the highly moisture-permeable and highly waterproof laminated fabric in the examples were performed by the following methods. (1) Water pressure resistance: JIS L-1092 (high water pressure method) (2) Moisture permeability: JIS L-1099 (A-1 method) (3) Texture: The handling was evaluated relative to the texture in the following four stages. ◎ ・ ・ Very soft ○ ・ ・ Soft △ ・ ・ Slightly hard × ・ ・ Hard

Example 1 Polyester multifilament 75 denier / 72 filament was used for both the warp and the weft, and the warp density was 1
After weaving a plain woven fabric having a density of 00 yarns / inch and a weft density of 80 yarns / inch, scouring is carried out by a usual method, and padding is performed with an aqueous dispersion having the composition shown in the following formula 1 (drawing ratio 35%).
After drying, a heat treatment was performed at 170 ° C. for 1 minute, and then calendering was performed at a temperature of 170 ° C., a pressure of 30 kgf / cm ² , and a speed of 30 m / min to obtain a releasable base fabric. [Prescription 1] 10% by weight of Asahigard AG970 (fluorine-based water-repellent emulsion manufactured by Asahi Glass Co., Ltd.) KM740 2% by weight (emulsion type silicone release agent manufactured by Shin-Etsu Chemical Co., Ltd.) 1 weight of Sumitex Resin M-3 % (Melamine resin manufactured by Sumitomo Chemical Co., Ltd.) Sumitex Accelerator ACX 0.1% by weight (Organic amine salt catalyst manufactured by Sumitomo Chemical Co., Ltd.) Isopropyl alcohol 1% by weight Water remaining weight%

Next, a synthetic polymer solution having a solid content concentration of 27% by weight and a viscosity of 11,000 mPa · s (25 ° C.) having the composition shown in the following prescription 2 was applied to the above-mentioned releasable group using a knife over roll coater. On the calender side of the cloth, apply 150
g / m ² , the two-layer laminate was immediately introduced into water at 15 ° C., wound up in a state where everything was immersed, and allowed to stand for 5 minutes in that state to completely coagulate the polyurethane resin. Desolvation (de-DMF) was almost completed. Thereafter, the film was wound on a roll completely immersed in an overflowing normal-temperature water bath to completely remove the solvent, and then dried. As described above, a microporous resin film mainly composed of a polyurethane resin was formed on the surface of the releasable base fabric. The resin film contained 13% by weight of inorganic fine powder (fine powder of silicon dioxide). [Prescription 2] 100 parts by weight of rack skin 1740-29B (ester-type polyurethane resin manufactured by Seiko Chemical Co., Ltd.) 1 part by weight of Rezamin X (isocyanate compound manufactured by Dainichi Seika Kogyo Co., Ltd.) 35 parts by weight of N, N-dimethylformamide 5 parts by weight of Aerosil R-972 (manufactured by Nippon Aerosil Co., Ltd., fine powder of hydrophobic silicon dioxide having an average particle size of 0.016 μm and an adsorption amount of N, N-dimethylformamide of 350 ml / 100 g)

Next, a 25-mesh, 180 μm-depth, circular dot shape (dot width 0.7 mm, dot interval 0.35
mm, a gravure roll having an adhesive occupying area of about 40%) and applying a polyurethane adhesive solution having a composition shown in the following formulation 3 and having a solid content of 37% by weight to the above-mentioned microporous resin film surface. 60 g / m ² , apply evenly over the entire non-
Dry at 0 ° C. for 2 minutes. [Formulation 3] 100 parts by weight of UD108 (ester-type polyurethane adhesive manufactured by Seiko Chemical Co., Ltd.) 7 parts by weight of Coronate HL (isocyanate compound manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.5 part by weight of UY-5 (Seiko Chemical Co., Ltd.) 20% by weight methyl ethyl ketone

Then, immediately, the following fiber cloth was laminated on the resin film surface and pressed at a pressure of 3 kgf / cm ² . The fiber fabric used was a nylon multifilament 70 denier / 68 filament for both the warp and the weft,
A plain woven fabric having a warp density of 120 yarns / inch and a weft yarn density of 95 yarns / inch is woven, scoured and dyed by a usual method (Kyanol Navy Blue, manufactured by Nippon Kayaku Co., Ltd.).
R 3% owf) and obtained as a dress material.

After the pressure bonding, aging was carried out by leaving the room for 3 days in a room (normal temperature), and then the releasable base fabric was peeled off. Then, Asahi Guard LS is used in the usual way.
-317 (a fluorinated water repellent emulsion manufactured by Asahi Glass Co., Ltd.) padding with 5% by weight aqueous dispersion (squeezing ratio 40
%) And dried at 130 ° C. for 1 minute, and then heat-treated at 170 ° C. for 40 seconds to obtain a highly moisture-permeable and waterproof laminated fabric.

Comparative Example 1 The two-layer laminate was heated at 15 ° C. without being wound in water.
Dipping in water for 1 minute to solidify the resin, transporting the two-layer laminate in the machine direction, performing mangle squeezing multiple times, and removing the solvent and washing with water at normal temperature. An attempt was made to produce a highly moisture-permeable and highly waterproof laminated fabric by the same method as in Example 1 except that the following method was adopted. However, in the solvent removal and water washing steps, the releasable base fabric and the resin film were separated, and a highly moisture-permeable and highly waterproof laminated fabric could not be obtained.

Reference Example 1 In Example 1, Aerosil R-97 used in Formulation 2 was used.
Except for omitting 2, a moisture-permeable waterproof laminated fabric was obtained in the same manner as in Example 1.

Reference Example 2 In Example 1, Aerosil R-97 used in Formulation 2 was used.
2 in place of Crystallite VX-X (manufactured by Shiraishi Calcium Co., Ltd., silicon dioxide fine powder having an average particle size of 1.8 μm and an N, N-dimethylformamide adsorption amount of 60 ml / 100 g), A moisture-permeable waterproof laminated fabric was obtained in the same manner as in Example 1. This resin film contained 13% by weight of crystallite VX-X fine powder.

Comparative Example 2 The fiber cloth (plain woven fabric using nylon multifilament 70 denier / 68 filament for both the warp and the weft) used in Example 1 was replaced with Asahigard LS-317 (manufactured by Asahi Glass Co., Ltd., fluorine-based). (Water-repellent emulsion) padding with a 5% by weight aqueous dispersion (40% squeezing rate)
After drying at 1 ° C. for 1 minute, heat treatment was performed at 170 ° C. for 40 seconds, and then calendering was performed at a temperature of 170 ° C., a pressure of 30 kgf / cm ² , and a speed of 30 m / min to obtain a fiber cloth.

Next, it was shown in Formulation 2 used in Example 1.
Synthetic polymer solution using knife over roll coater
The amount of application is 150 g on the calender surface of the fiber base cloth.
/ M ^TwoTo obtain a laminated fabric. And then
Laminated fabric is immersed in water at 15 ° C for 1 minute to solidify resin
And transport the laminated fabric in the machine direction,
While removing the solvent at room temperature and washing with water.
Fiber by the direct coating method
Moisture permeable waterproof coat with polyurethane resin film laminated on fabric
A printing fabric was obtained.

The high moisture permeable high waterproof laminated fabric obtained by the method according to Example 1 and the moisture permeable waterproof laminated fabric and the moisture permeable waterproof coated fabric obtained by the methods according to Reference Examples 1 and 2 and Comparative Example 2 were used. Each performance was measured, and the results are shown in Table 1.

[Table 1] As is clear from the results in Table 1, the highly moisture-permeable and highly waterproof laminated fabric obtained by the method according to Example 1 is the same as the highly moisture-permeable and waterproof laminated fabric obtained by the method according to Reference Examples 1 and 2 and Comparative Example 2. It can be seen that all of the water pressure resistance, the moisture permeability and the texture are improved in a better balance than the moisture permeable waterproof coated fabric.

Example 2 On the calender surface of the releasable base fabric used in Example 1, a composition having the composition shown in Formula 4 below, having a solid content of 26% by weight and a viscosity of 110
The coating amount of the synthetic polymer solution of 00 mPa · s (25 ° C.) was applied using a knife over roll coater to 140 g / m ^2.
Is immediately introduced into water at 15 ° C., wound up in a state where everything is immersed, and left for 5 minutes in that state to completely coagulate and desolventize the polyurethane resin (desolvation). DMF) was almost completed. Thereafter, the film was wound on a roll completely immersed in an overflowing normal-temperature water bath to completely remove the solvent, and then dried. As described above, a microporous resin film mainly composed of a polyurethane resin was formed on the surface of the releasable base fabric. The resin film contained 9% by weight of an inorganic fine powder (a fine powder of dialuminum trioxide). [Prescription 4] 100 parts by weight of rack skin 1740-29B (ester-type polyurethane resin manufactured by Seiko Chemical Co., Ltd.) 1 part by weight of resamine X (isocyanate compound manufactured by Dainichi Seika Kogyo Co., Ltd.) 35 parts by weight of N, N-dimethylformamide Alumina AKP-G015 3 parts by weight (manufactured by Sumitomo Chemical Co., Ltd., average particle size 0.03 μm,
Hydrophobic dialuminum trioxide fine powder with N, N-dimethylformamide adsorption amount of 310 ml / 100 g)

Thereafter, using the polyurethane adhesive solution of Formula 3 used in Example 1 and the fiber cloth used in Example 1, a highly moisture-permeable and waterproof laminated fabric was obtained in the same manner as in Example 1. Was.

Reference Example 3 In Example 2, the alumina AKP-G used in Formulation 4 was used.
Instead of using 015, 3 parts by weight of alumina A-42-6 (manufactured by Showa Denko KK, fine powder of dialuminum trioxide having an average particle diameter of 5 μm and an N, N-dimethylformamide adsorption amount of 32 ml / 100 g) was used. A moisture-permeable waterproof laminated fabric was obtained in the same manner as in Example 2. This resin film contained 9% by weight of alumina A-42-6 fine powder.

The performance of the highly moisture-permeable and waterproof laminated fabric obtained by the method of Example 2 and the performance of the moisture-permeable waterproof laminated fabric obtained by the method of Reference Example 3 were measured, and the results are shown in Table 2. Indicated.

[Table 2] As is clear from the results in Table 2, the moisture-permeable and waterproof laminated fabric obtained by the method according to Example 2 has a higher moisture permeability than the moisture-permeable waterproof laminated fabric obtained by the method according to Reference Example 3. It can be seen that it has been significantly improved.

Example 3 A polyurethane resin having a composition shown in Formula 5 below and having a solid content of 25% by weight and a viscosity of 2500 mPa · s was applied to the resin film surface of the highly moisture-permeable and highly waterproof laminated fabric obtained by the method according to Example 1. Was applied using a floating knife coater at an application amount of 12 g / m ² ,
Drying for minutes was performed. As a result, a resin thin film mainly composed of a polyurethane resin is formed on the resin film surface of the highly moisture-permeable and highly waterproof laminated fabric, and a fiber fabric / a resin film mainly composed of a polyurethane resin / a resin thin film mainly composed of a polyurethane resin is formed. A laminated fabric laminated in order was obtained. [Formulation 5] 100 parts by weight of LUXSKIN U2514-1 (non-yellowing type polyurethane resin manufactured by Seiko Chemical Co., Ltd.) 5 parts by weight of isopropyl alcohol 15 parts by weight of toluene

Comparative Example 3 The procedure of Example 3 was repeated, except that the moisture-permeable waterproof coated fabric obtained by the method of Comparative Example 2 was used instead of the high-moisture-permeable and waterproof laminated fabric obtained by the method of Example 1. In the same manner as described above, a coated fabric was obtained in which fiber fabric / resin film mainly composed of polyurethane resin / resin thin film mainly composed of polyurethane resin were laminated in this order.

The performance of each of the laminated fabric obtained by the method of Example 3 and the coated fabric obtained by the method of Comparative Example 3 was measured. The results are shown in Table 3.

[Table 3] As is clear from the results in Table 3, the laminated fabric obtained by the method according to Example 3 had a very soft texture as compared with the coated fabric obtained by the method according to Comparative Example 3. I understand.

Example 4 The polyurethane adhesive solution of Formulation 3 used in Example 1 was applied to the resin film surface of the highly moisture-permeable and waterproof waterproof laminated fabric obtained by the method according to Example 1 in the same manner as in Example 1. And dried in the same manner. Then, immediately, the following fiber cloth was laminated on the resin film surface, and pressed under a pressure of 3 kgf / cm ² . The fiber fabric used was obtained by knitting a 28-gauge tricot fabric using nylon filament 20 denier / 7 filaments, performing scouring by a usual method, and using it as a backing. Then, after the pressure bonding, aging was performed by being left in a room (room temperature) for 3 days. The obtained laminated fabric was laminated in the order of fiber fabric (outer fabric) / resin film mainly composed of polyurethane resin / fiber fabric (lining).

Comparative Example 4 The procedure of Example 4 was repeated, except that the moisture-permeable and waterproof coated fabric obtained by the method of Comparative Example 2 was used instead of the highly moisture-permeable and waterproof laminated fabric obtained by the method of Example 1. By the same method as that described above, a coated fabric was obtained in which fiber fabric (outer fabric) / resin film mainly composed of polyurethane resin / fiber fabric (lining) was laminated in this order.

Each performance of the laminated fabric obtained by the method according to Example 4 and the coated fabric obtained by the method according to Comparative Example 4 was measured, and the results are shown in Table 4.

[Table 4] As is clear from the results in Table 4, the laminated fabric obtained by the method according to Example 4 had a very soft texture as compared with the coated fabric obtained by the method according to Comparative Example 4. I understand.

Example 5 The polyurethane adhesive solution of Formulation 3 used in Example 1 was applied to the resin thin film surface of the laminated fabric obtained by the method according to Example 3 by the same method as in Example 1. Dried. Then, the fiber fabric as a lining used in Example 4 was immediately laminated on the resin thin film surface, and thereafter, a laminated fabric was obtained in the same manner as in Example 4. This laminated fabric was laminated in the following order: fiber fabric (outer fabric) / resin film mainly composed of polyurethane resin / resin thin film mainly composed of polyurethane resin / fiber fabric (lining).

Comparative Example 5 Instead of the laminated fabric obtained by the method according to Example 3,
A fiber fabric (outer fabric) / a resin film mainly composed of a polyurethane resin / a resin thin film mainly composed of a polyurethane resin / Thus, a coated fabric laminated in the order of fiber fabric (lining) was obtained.

The performance of each of the laminated fabric obtained by the method of Example 5 and the coated fabric obtained by the method of Comparative Example 5 was measured. The results are shown in Table 5.

[Table 5] As is clear from the results in Table 5, the laminated fabric obtained by the method according to Example 5 has a very soft texture compared to the coated fabric obtained by the method according to Comparative Example 5. I understand.

[0057]

The method for producing a highly moisture-permeable and highly waterproof laminated fabric according to the present invention is characterized in that the solvent is N, N-dimethylformamide, the average particle size is 1 μm or less, and the amount of N, N-dimethylformamide adsorbed. A two-layer laminate obtained by applying a synthetic polymer solution mainly composed of a polyurethane resin containing at least 1% by weight of an inorganic fine powder of 200 ml / 100 g or more to the surface of a release base fabric is introduced into water, In the wet film forming step of desolvating and solidifying the polyurethane resin, the two-layer laminate introduced in water is not subjected to a positive tension for transporting to the next step, and a polyurethane resin film is formed. Has features. Therefore, the wet film formation can be completed without applying an excessive tension to the two-layer laminate, so that in the wet film formation step, the resin film mainly composed of the polyurethane resin and the releasable base fabric are not easily separated. . Accordingly, there is little trouble due to such peeling, and the effect of efficiently manufacturing a highly moisture-permeable and waterproof laminated fabric can be achieved.

Further, since the releasable base fabric and the resin film are hardly peeled off, an arbitrary releasable base fabric can be adopted. In particular, if a release fabric having a low knitting density is used, the rate of solvent removal from the release fabric side can be increased, and the specific inorganic fine powder is contained in the synthetic polymer solution. In combination with the above, moisture permeability can be increased. In addition, if the moisture permeability can be increased, the thickness of the resin film can be set to be large, and the waterproofness can be further improved. Furthermore, in the present invention, since a so-called transfer method is employed, a soft texture can be given to the obtained laminated fabric. Therefore, there is also an effect that a highly moisture-permeable and highly waterproof laminated fabric having high softness and high waterproofness and high moisture permeability can be easily obtained.

Continuing on the front page F-term (reference) 3B005 EB09 FA06 FC09Z FC20Z GA17 4F055 BA12 CA06 CA14 FA15 FA27 FA40 GA40 4F100 AA00B AA20 AK17 AK36 AK51 AK51B AK52 BA02 BA10A BA10B CA19 CA23 CB02 DE01B DG11 EC03 EG11 EC012 GB12 EC012 ECG JL09 4L033 AB04 AC07 AC11 CA17 CA22 CA50 CA59

Claims (7)

[Claims] 1. A two-layer laminate obtained by applying a synthetic polymer solution mainly composed of a polyurethane resin to the surface of a release base fabric,
Introduced into water, the solvent in the synthetic polymer solution is eluted into the water to coagulate the polyurethane resin and form a resin film mainly composed of the polyurethane resin on the surface of the release base fabric. In a method for producing a highly moisture-permeable and highly waterproof laminated fabric by transferring the resin film to a fiber fabric after a film forming step, the synthetic polymer solution may contain N, N-dimethylformamide as a solvent, In addition to using 1% by weight or more of an inorganic fine powder having a diameter of 1 μm or less and adsorbing N, N-dimethylformamide of 200 ml / 100 g or more, the two layers introduced into the water in the wet film forming step are used. A method for producing a highly moisture-permeable and highly waterproof laminated fabric, wherein the resin film is formed without applying a positive tension to the laminate to transport the laminate to the next step. 2. A state in which a two-layer laminate introduced into water in a wet film-forming step is wound in the water so that positive tension for transferring the two-layer laminate to the next step is not applied. The method for producing a highly moisture-permeable and highly waterproof laminated fabric according to claim 1. 3. In the wet film forming step, the two-layer laminate introduced into water is floated in a state of being folded in the longitudinal direction, so that the two-layer laminate is positively transported to the next step. The method for producing a highly moisture-permeable and highly waterproof laminated fabric according to claim 1, wherein no tension is applied. 4. The method according to claim 1, wherein the solvent is N, N-dimethylformamide, and contains 1% by weight or more of an inorganic fine powder having an average particle diameter of 1 μm or less and an adsorption amount of N, N-dimethylformamide of 200 ml / 100 g or more. A two-layer laminate formed by applying a synthetic polymer solution mainly composed of a polyurethane resin to the surface of the release base fabric is introduced into water, wet-formed and rolled up in water, and the desolvation is completed. A first step of forming a resin film mainly composed of the polyurethane resin on the surface of the release base fabric, after uniformly applying a polyurethane-based adhesive to the entire surface of the resin film, A method for producing a highly moisture-permeable and highly waterproof laminated fabric, comprising: a second step of laminating a fiber cloth by peeling the base fabric from the resin film, if desired. 5. After the third step, a resin containing a polyurethane resin as a main component is applied to the surface of the resin film from which the release fabric has been peeled, by applying a synthetic polymer solution containing a polyurethane resin as a main component and then drying the solution. The method according to claim 4, further comprising a fourth step of forming a thin film. 6. The highly moisture-permeable and highly waterproof laminated fabric according to claim 5, wherein a polyurethane adhesive is uniformly applied to the entire surface of the resin thin film on a non-entire surface, and then a fiber fabric is bonded through the polyurethane adhesive. Manufacturing method. 7. After the third step, a polyurethane adhesive is uniformly applied to the entire surface of the resin film from which the release cloth has been peeled off, and then the fiber cloth is bonded via the polyurethane adhesive. 5. The method for producing a highly moisture-permeable and highly waterproof laminated fabric according to claim 4, further comprising a fourth step of performing the following.